Acrylic block copolymer and thermoplastic resin composition

The present invention is rich in flexibility, excellent in mechanical strength, molding processability, oil resistance, heat resistance, heat decomposition resistance, weather resistance, compression set, and highly reactive acrylic block, which has not existed in the past. With respect to polymers and compositions.

Further, the present invention relates to a seal product for automobiles, household electric products or office electric products using the acrylic block copolymer and a composition composed of the acrylic block copolymer, and an automobile / electric / Regarding electronic parts.

Furthermore, the present invention relates to a method for producing the acrylic block copolymer.

Vulcanized rubber has excellent flexibility and rubber elasticity, but since it is necessary to add an additive to the rubber and vulcanize it at the time of molding, the molding cycle time is long and the process is complicated. There is a problem with moldability. Further, since the vulcanized rubber does not melt even if it is molded and vulcanized and then reheated, there is a problem that post-processing such as joining cannot be performed and it is difficult to recycle after use.

From this point of view, in recent years, thermoplastic elastomers have come to be used in place of vulcanized rubber. For example, in automobile vehicles, various sealing parts such as glass run channels, weather strips, various boots, and draining moldings are used. Vulcanized rubber is used for most of them, but in recent years, lightweight and recyclable olefin-based thermoplastic elastomers have begun to be used for some of the sealing parts from the viewpoint of improving fuel efficiency and environmental problems.

In general, thermoplastic elastomers have an alloy structure consisting of a rubber component (soft segment) that exhibits entropy elasticity and a restraining component (hard segment) that flows at high temperatures but prevents plastic deformation at room temperature and gives a reinforcing effect to the rubber component. taking it. For example, in a styrene-based elastomer, styrene blocks aggregate to act as hard segments, and butadiene-based blocks or isoprene-based blocks form a matrix and act as soft segments. Further, the olefin-based elastomer has an alloy structure in which rubber such as ethylene-propylene-diene copolymer rubber (EPDM) is dispersed in a resin such as polypropylene (PP). In both cases, the hard segment flows at a high temperature, so that thermoplastic processing such as injection molding is possible. However, conventional styrene-based or olefin-based thermoplastic elastomers do not have sufficient rubber elasticity and heat resistance (heat resistance in this case means compression set characteristics at high temperatures) as compared with vulcanized rubber, and also have oil resistance. It has the drawback of poor sex. On the other hand, as a thermoplastic elastomer having excellent oil resistance, an acrylic block body having a methacrylic block and an acrylic block has been disclosed in recent years as disclosed in Japanese Patent No. 2553134. The moldability is very good, but it has a drawback of being inferior in heat resistance. Further, since the hard segment of the thermoplastic elastomer flows at a high temperature, it is possible to perform thermoplastic processing such as injection molding. However, when the thermal decomposition temperature of the thermoplastic elastomer is lower than the injection molding temperature, the heat is generated. Thermal deterioration of thermoplastic elastomers may occur, and in particular, many methacrylic polymers decompose into monomers by depolymerization at 170 to 250 ° C (Polymer Handbook Third Edition: Wiley-Interscience 1989). It also has the disadvantage that it cannot be used when high temperature thermal stability is required.

On the other hand, it is already known that the thermoplastic elastomer is added for the purpose of resin modification such as enhancing the impact resistance of the thermoplastic resin, or is compounded with the thermoplastic resin and used as a soft material (for example, patent). Reference 1). However, since styrene-based elastomers and olefin-based elastomers are non-polar resins, it is possible to modify other non-polar resins, but since they have poor compatibility with polar resins, the purpose is to modify polar resins. In this case, it is necessary to add a compatibilizer separately or to graft and add a compound such as maleic anhydride to the thermoplastic elastomer to modify it (for example, Patent Documents 2 and 3). .. In this case, although modification can be performed, the oil resistance is lowered due to the characteristics of the styrene-based or olefin-based thermoplastic elastomer itself. Further, in the case of the acrylic block body as well, the oil resistance and compatibility were better than those of the styrene-based or olefin-based thermoplastic elastomer, but the levels were insufficient. Therefore, it has been desired to develop a thermoplastic elastomer which is excellent in oil resistance, heat resistance, and heat decomposition resistance, and further excellent in modification of a thermoplastic resin and compound characteristics.

For example, conventional materials with oil resistance, heat resistance, and rubber elasticity include nitrile rubber (NBR), acrylic rubber (ACM), silicone rubber (VMQ), and chloroprene rubber (CR), which are seal products for automobiles. It is used for seal products for household electric products, seal products for office electric products, automobiles, electric parts, electronic parts, etc. As mentioned above, the kneaded product obtained by blending and kneading additives is gold. Since it is necessary to supply the material into a mold and then vulcanize it, a special molding machine is required, the molding cycle time is long, and the process is complicated. Therefore, a promising thermoplastic elastomer has been desired.

<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 10-279738</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 7-173390</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2000-265033</text></patcit></p>

<p> The present invention is a novel acrylic block copolymer which is highly flexible, has excellent mechanical strength, molding processability, oil resistance, heat resistance, heat decomposition resistance, weather resistance and compression set, and is also highly reactive. An object of the present invention is to provide a method for producing the acrylic block copolymer.</p><p> Further, the present invention provides a seal for the acrylic block copolymer, a composition using the acrylic block copolymer, a seal product for automobiles, a seal product for household electric products, a seal product for office electric products, and the like. The purpose is to provide products, automobiles, and electrical / electronic parts.</p><p> As a result of studies to solve the above problems, it is composed of a methacrylic polymer block (a) and an acrylic polymer block (b), and a specific acid anhydride group is contained in the main chain of at least one of the polymer blocks. The acrylic block copolymer characterized by having is highly flexible, excellent in mechanical strength, molding processability, oil resistance, heat resistance, heat decomposition property and compression set, and further excellent in reactivity. The present invention has been completed.</p>

<p> That is, the present invention comprises (a) a methacrylic polymer block and (b) an acrylic polymer block, and the general formula (1): is contained in the main chain of at least one of the polymer blocks.<chemistry num="1"><img file="JP4493498B2_D0001.tif" /></chemistry>(In the formula, R¹Are hydrogen or methyl groups, which may be the same or different from each other. It relates to an acrylic block copolymer characterized by having at least one (c) acid anhydride group represented by (n is an integer of 0 to 3 and m is an integer of 0 or 1).</p><p> It is preferable that the acrylic block copolymer has (d) a carboxyl group of 0.1 to 50% by weight.</p><p> (ab)_nType, b- (ab)_nType and (ab)_nIt is preferably composed of at least one acrylic block copolymer selected from the group consisting of -a type.</p><p> The number average molecular weight of the acrylic block copolymer is preferably 30,000 to 500,000.</p><p> The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic block copolymer measured by gel permeation chromatography is preferably 1 to 1.8.</p><p> The acrylic block copolymer may be composed of 5 to 80% by weight of the methacrylic polymer block (a) and 95 to 20% by weight of the acrylic polymer block (b) in the entire acrylic block copolymer. preferable.</p><p> It is preferable that the acid anhydride group (c) is contained in the methacrylic polymer block (a).</p><p> It is preferable that the acrylic anhydride group (c) is contained in the acrylic polymer block (b).</p><p> It is preferable that the acid anhydride group (c) is contained in an amount of 0.1 to 99.9% by weight based on the total amount of the acrylic block copolymer (A).</p><p> It is preferable to have the carboxyl group (d) in the same block as the block having the acid anhydride group (c).</p><p> The acrylic copolymer block (b) is 50 to 100% by weight of at least one acrylic acid ester selected from the group consisting of n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, and these. It is preferably composed of 0 to 50% by weight of other acrylic acid ester and / or other vinyl-based monomer copolymerizable with.</p><p> The acrylic polymer block (b) is preferably composed of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate.</p><p> The acrylic polymer block (b) is preferably composed of n-butyl acrylate and 2-methoxyethyl acrylate.</p><p> The acrylic polymer block (b) is preferably composed of n-butyl acrylate and 2-ethylhexyl acrylate.</p><p> It is preferable that the acrylic block copolymer is hydrolyzed to open a ring-opening acid anhydride group and have a (e) carboxyl group in the side chain.</p><p> It is preferable that the acrylic block copolymer is a block copolymer produced by atom transfer radical polymerization.</p><p> From (A) acrylic block copolymer, (B) crosslinked rubber, (C) thermoplastic resin, (D) thermoplastic elastomer, (E) lubricant, (F) inorganic filler and (G) stabilizer Concerning a composition consisting of one or more selected from the group consisting of.</p><p> The composition comprises 0.5 to 99.5% by weight of the acrylic block copolymer (A) and 99.5 to 0.5% by weight of the thermoplastic resin (C) and / or the thermoplastic elastomer (D) in the entire composition. Is preferable.</p><p> The thermoplastic resin (C) is selected from the group consisting of polyvinyl chloride resin, polymethylmethacrylate resin, acrylonitrile-styrene copolymer resin, methylmethacrylate-styrene copolymer resin, polycarbonate resin, polyester resin and polyamide resin. It is preferable that the resin is a thermoplastic elastomer (D) selected from the group consisting of styrene elastomers, olefin elastomers, urethane elastomers, vinyl chloride elastomers, amide elastomers, ester elastomers and acrylic elastomers.</p><p> The composition preferably contains 0.01 to 50 parts by weight of the lubricant (E) and / or 0.01 to 300 parts by weight of the inorganic filler (F) with respect to 100 parts by weight of the acrylic block copolymer (A). ..</p><p> The acrylic block copolymer (A) may contain one or more acrylic acid ester units selected from the group consisting of n-butyl acrylate units, ethyl acrylate units and 2-methoxyethyl acrylate units. preferable.</p><p> In the main chain of at least one of the methacrylic polymer block (a) and the acrylic polymer block (b), the general formula (2):<chemistry num="2"><img file="JP4493498B2_D0002.tif" /></chemistry>(In the formula, R²Represents a hydrogen or methyl group. R³Represents a hydrogen, methyl group, or phenyl group and may be the same or different from each other except that it contains at least one methyl group) (A') Acrylic block copolymer having at least one unit. The present invention relates to a method for producing the acrylic block copolymer, which comprises melt-kneading at a temperature of 180 to 300 ° C.</p><p> It is preferable that the acrylic block copolymer (A') is produced by controlled radical polymerization.</p><p> It is preferable to melt-knead the acrylic block copolymer (A) with water.</p><p> The present invention relates to a seal product obtained by molding the acrylic block copolymer (A).</p><p> The present invention relates to a seal product comprising the above composition.</p><p> The present invention relates to automobile, electric, and electronic parts made of the acrylic block copolymer (A).</p>

<p> The acrylic block copolymer of the present invention is highly flexible, has excellent mechanical strength, molding processability, oil resistance, heat resistance, heat decomposition resistance, weather resistance, and is also rich in reactivity. It can be suitably used as a plastic elastomer, a compatibilizer, and the like. The novel acrylic block copolymer of the present invention and the composition using the same can be used for automobiles, electric / electronic parts (for example, seal products for automobiles, seal products for household electric products, or office work) by taking advantage of their characteristics. It can be widely used for sealing products such as sealing products for electrical products.</p>

The present invention is an acrylic block copolymer (A), which comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and is contained in the main chain of at least one of the polymer blocks. , General formula (1):<chemistry num="3"><img file="JP4493498B2_D0003.tif" /></chemistry>(In the formula, R¹Are hydrogen or methyl groups, which may be the same or different from each other. It relates to an acrylic block copolymer characterized by having at least one acid anhydride group (c) represented by (n is an integer of 0 to 3 and m is an integer of 0 or 1).

Hereinafter, the present invention will be described in detail.

&lt;Acrylic block copolymer (A)&gt; The structure of the acrylic block copolymer (A) of the present invention is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer is required for the physical properties of the acrylic block copolymer (A), the processing required for the composition with the crosslinked rubber (B), the thermoplastic resin (C), and the like. Although it can be used properly according to the needs such as characteristics and mechanical characteristics, the linear block copolymer is preferable from the viewpoint of cost and easiness of polymerization.

The linear block copolymer may have any structure. When the methacrylic polymer block (a) is expressed as a and the acrylic polymer block (b) is expressed as b from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, (ab)_nType, b- (ab)_nType and (ab)_nIt is preferably composed of at least one acrylic block copolymer selected from the group consisting of -a type (n is an integer of 1 or more, for example, an integer of 1 to 3). Although not particularly limited, among these, ab-type diblock copolymers, aba-type triblock copolymers, or mixtures thereof are preferable from the viewpoint of ease of handling during processing and physical characteristics of the composition.

The acid anhydride group (c) is characterized in that at least one is introduced per at least one polymer block of the methacrylic polymer block (a) and the acrylic polymer block (b). When the number is two or more, the mode in which the monomer is polymerized can be random copolymerization or block copolymerization. Taking the aba-type triblock copolymer as an example, (a / z) -ba-type, (a / z) -b- (a / z)-type, zaba-type, zabaz-type, a- (b / z) ) -A type, abza type, azbza type, (a / z)-(b / z)-(a / z) type, zazbzaz type, etc. may be used. Here, z represents a monomer or polymer block containing an acid anhydride group (c), and (a / z) means an acid anhydride group (c) in a methacrylic polymer block (a). Indicates that the monomer containing the acid anhydride group (c) is copolymerized with (b / z), which means that the acrylic polymer block (b) is copolymerized with the monomer containing the acid anhydride group (c). Represents that.

Further, the site where z is contained and the mode in which z is contained in the methacrylic polymer block (a) or the acrylic polymer block (b) can be freely set, and can be used properly according to the purpose.

The number average molecular weight of the acrylic block copolymer (A) is not particularly limited, and may be determined from the molecular weights required for the methacrylic polymer block (a) and the acrylic polymerization system block (b), respectively. If the molecular weight is small, it may not be possible to exhibit sufficient mechanical properties as an elastomer, and conversely, if the molecular weight is larger than necessary, the processing properties may be deteriorated. From the above viewpoint, the number average molecular weight of the acrylic block copolymer (A) is preferably 30,000 to 500,000, more preferably 40,000 to 4,00000, and even more preferably 50,000 to 300,000.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is also not particularly limited, but is 1 to 1.8. It is preferably present, and more preferably 1 to 1.5. If Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer may decrease.

The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is not particularly limited, and the physical properties and composition required for the intended use are not particularly limited. It may be determined from the moldability required at the time of processing and the molecular weights required for the methacrylic polymer block (a) and the acrylic polymer block (b), respectively. To exemplify the range of the composition ratio of the preferable methacrylic polymer block (a) and acrylic polymer block (b), the methacrylic polymer block (a) is 5 to 80% by weight, and the acrylic polymer block ( b) is preferably 95 to 20% by weight. More preferably, the methacrylic polymer block (a) is 10 to 70% by weight, and the acrylic polymer block (b) is 90 to 30% by weight. More preferably, the methacrylic polymer block (a) is 10 to 60% by weight, and the acrylic polymer block (b) is 90 to 40% by weight. Particularly preferably, the methacrylic polymer block (a) is 20 to 50% by weight, and the acrylic polymer block (b) is 80 to 50% by weight. If the proportion of the methacrylic polymer block (a) is less than 5% by weight, the rubber elasticity at high temperature may decrease, and if it is more than 80% by weight, the mechanical properties as an elastomer, particularly the elongation at break, decrease. Or, the flexibility of the composition with the thermoplastic resin may decrease.

The relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is the glass transition of the methacrylic polymer block (a). Temperature Tg_a, Tg the glass transition temperature of the acrylic polymer block (b)_{b b}Therefore, it is preferable to satisfy the relationship of the following equation. Tg_a&gt; Tg_{b b}

The glass transition temperature (Tg) of the polymers (methacrylic polymer block (a) and acrylic polymer block (b)) is set according to the following Fox formula, and the weight of the monomer of each polymer portion is set. This can be done by setting the ratio. 1 / Tg = (W₁/ Tg₁) + (W₂/ Tg₂) + ... + (W_m/ Tg_m) W₁+ W₂+ ... + W_m=1

In the formula, Tg represents the glass transition temperature of the polymer part, and Tg₁, Tg₂, ..., Tg_mRepresents the glass transition temperature of each polymerization monomer. Also, W₁, W₂, ..., W_mRepresents the weight ratio of each polymerized monomer.

For the glass transition temperature of each polymerized monomer in the Fox formula, for example, the value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

The glass transition temperature can be measured by DSC (differential scanning calorimetry) or the tanδ peak of dynamic viscoelasticity, but of the methacrylic polymer block (a) and the acrylic polymer block (b). If the polarities are too close or the number of chained polymers of the block is too small, the measured values may deviate from the calculation formula by the Fox formula.

The general formula (1):<chemistry num="4"><img file="JP4493498B2_D0004.tif" /></chemistry>(In the formula, R¹Are hydrogen or methyl groups, which may be the same or different from each other. The method for introducing the acid anhydride group (c) represented by (n is an integer of 0 to 3 and m is an integer of 0 or 1) into the block copolymer is not particularly limited, but the ease of introduction and purification after introduction are not particularly limited. In terms of convenience, etc., it was introduced into the acrylic block copolymer (A) in the form of a functional group that is a precursor of the acid anhydride group (c), for example, in the form of the general formula (2), and then introduced into the acrylic block copolymer (A). It is preferably introduced by cyclization.

N in the general formula (1) is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. When n is 4 or more, polymerization may be complicated or cyclization of an acid anhydride group may be difficult.

In general formula (1), m is 0 or an integer of 1, and when n is 0, m is also 0, and when n is 1 to 3, m is preferably 1.

The acid anhydride group (c) may be contained in only one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. The reaction site of the acrylic block copolymer (A) or the blocks constituting the acrylic block copolymer (A) (methacrylic polymer block (a) and acrylic polymer block (b)) may be used. ) Aggregation power, glass transition temperature, and required physical properties of the acrylic block copolymer (A), etc., can be used according to the purpose so that the conditions for introducing the acid anhydride group (c) are suitable. .. For example, a methacrylic polymer block (a) or an acrylic polymer block (b) is selectively modified or reacted using a compound having an amino group, a hydroxyl group, or the like with an acid anhydride group as a reaction point. If desired, the acid anhydride group (c) may be introduced into the block to be modified or reacted. Further, in terms of improving the heat resistance and heat-decomposability of the acrylic block copolymer (A), the acid anhydride group (c) may be introduced into the methacrylic polymer block (a), and both the acrylic block and the acrylic block copolymer. From the viewpoint of imparting oil resistance to the polymer (A), further rubber elasticity and compressive permanent strain characteristics, a reaction site (crosslinking point) in which the acid anhydride group (c) is crosslinked to the acrylic polymer block (b), etc. It should be introduced as. Although not particularly limited, it is preferable to have it in either the methacrylic polymer block (a) or the acrylic polymer block (b) in terms of control of the reaction point, heat resistance, rubber elasticity, and the like. ..

Further, although not particularly limited, when it is contained in the methacrylic polymer block (a), R of the general formula (1)¹Is preferably a methyl group, and when it is contained in the acrylic polymer block (b), R in the general formula (1)¹Is preferably hydrogen. R when included in the methacrylic polymer block (a)¹R when is hydrogen or when it is contained in the acrylic polymer block (b)¹When is a methyl group, the polymerization operation of the acrylic block copolymer (A) becomes complicated, or the difference in glass transition temperature between the methacrylic polymer block (a) and the acrylic polymer block (b). Tends to decrease, and the rubber elasticity of the acrylic block copolymer (A) tends to decrease.

The preferred range of the content of the acid anhydride group (c) is the cohesiveness and reactivity of the acid anhydride group (c), the structure and composition of the acrylic block copolymer (A), and the acrylic block copolymer. It depends on the number of blocks constituting (A), the glass transition temperature, and the site and mode in which the acid anhydride group (c) is contained. To exemplify a preferable range of the content of the acid anhydride group (c), it is preferably 0.1% by weight or more and 99.9% by weight or less, 0.5% by weight or more and 99.9% by weight in the entire acrylic block copolymer (A). % Or less is more preferable. If it is less than 0.1% by weight, the reactivity of the acrylic block copolymer (A) and the compatibility with the thermoplastic resin may be insufficient. Further, for the purpose of improving the heat resistance and heat-decomposability of the acrylic block copolymer (A), an acid anhydride group (c) having a high Tg was introduced into the methacrylic polymer block (a) which is a hard segment. If it is less than 0.1% by weight, the improvement of heat resistance and heat decomposability is insufficient, and the development of rubber elasticity at high temperature may decrease. On the other hand, if it exceeds 99.9% by weight, it may be difficult to introduce it, or the cohesive force may become too strong, resulting in a decrease in workability. When an acid anhydride group (c) is introduced into the acrylic block copolymer (b) for the purpose of imparting oil resistance and rubber elasticity to the acrylic block copolymer (A), it is less than 0.1% by weight. , Oil resistance is imparted, cohesive force is insufficient, and even when used as a reaction point, the reaction is insufficient, so rubber elasticity and compressive permanent strain characteristics tend to decrease, 99.9% by weight. If it exceeds the above, it tends to be difficult to introduce, and the flexibility and mechanical properties tend to decrease.

The content of the acid anhydride group (c) represents a weight% as a monomer having an acid anhydride group (c) from the beginning or a monomer having an acid anhydride group by a reaction or the like. This content is¹³C (¹H)-Can be calculated by NMR analysis.

The content block or content of the anhydride group (c) is the required cohesive force, glass transition temperature, crosslinked rubber (B), thermoplastic resin (C) and / or phase with the thermoplastic elastomer (D). It may be appropriately determined according to the solubility, the reaction point, and the like.

The acrylic block copolymer (A) may contain a carboxyl group (d) from the viewpoint of further improving heat resistance and cohesive force. The carboxyl group (d) can be generated in the process of introducing the acid anhydride group (c) into the acrylic block copolymer (A).

The carboxyl group (d) may be contained in only one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. , The reaction point of the acrylic block copolymer (A), the cohesive force of the blocks constituting the acrylic block copolymer (A), the glass transition temperature, and the required acrylic block copolymer (A). From the viewpoint of the physical properties of)), it can be used properly so that the conditions for introducing the carboxyl group (d) are suitable according to the purpose. Although not particularly limited, an acid anhydride group (an acid anhydride group (d) can be easily introduced into the acrylic block copolymer (A) and the reaction point of the acrylic block copolymer (A) can be controlled. It is preferably contained in the same block as the block having c), and more preferably contained in the methacrylic polymer block (a) in terms of heat resistance and cohesiveness. This is because by introducing Tg and a carboxyl group (d) having a high cohesive force into the hard segment, it becomes possible to exhibit more rubber elasticity even at a high temperature. When the acrylic polymer block (b) has a carboxyl group (d), it is used as a crosslinkable reaction site (crosslink point) for imparting oil resistance and further imparting rubber elasticity and compressive permanent strain characteristics. It is preferable in terms of improving compatibility with crosslinked rubber, thermoplastic resin and / or thermoplastic elastomer.

The content of the carboxyl group (d) can be at least one per polymer block, and if the number is two or more, the mode in which the monomer is polymerized is random copolymerization or block. It can be copolymerized. Taking the aba-type triblock copolymer as an example, (a / y) -ba-type, (a / y) -b- (a / y)-type, yaba-type, yabay-type, a- (b / y) ) -A type, abya type, aybya type, (a / y)-(b / y)-(a / y) type, yaybyay type, etc. may be used. Here, y represents a monomer or polymer block containing a carboxyl group (d), and (a / y) is a single amount containing a carboxyl group (d) in a methacrylic polymer block (a). The body is copolymerized, and (b / y) means that the acrylic polymer block (b) is copolymerized with a monomer containing a carboxyl group (d).

Further, the site where y is contained and the mode in which y is contained in the methacrylic polymer block (a) or the acrylic polymer block (b) can be freely set, and can be used properly according to the purpose.

The preferred range of the content of the carboxyl group (d) is the cohesive force of the carboxyl group (d), the structure and composition of the acrylic block copolymer (A), the number of blocks constituting the acrylic block copolymer, and , Varies depending on the location and mode of inclusion of the carboxyl group (d).

To exemplify a preferable range of the content of the carboxyl group (d), it is preferably 0 to 50% by weight of the monomers constituting the acrylic block copolymer (A). It is more preferably 0.1 to 50% by weight, and particularly preferably 0.5 to 40% by weight. When the acrylic block copolymer (A) is further required to have heat resistance and cohesive force, it is preferable to introduce the carboxyl group (d) in the range of up to 50% by weight. If it exceeds 50% by weight, the carboxyl group (d) tends to be easily cyclized with the adjacent ester unit at a high temperature, so that the operation of introducing the carboxyl group (d) tends to be complicated. Incidentally, carboxy case of generating Le group (d) is in process of introducing an acid anhydride group (c), typically produce more than 0.1 wt%. If it is less than 0.1% by weight, the introduction of the carboxyl group (d) into the hard segment may result in insufficient improvement in heat resistance and cohesive force. The content of the carboxyl group (d) represents a weight% of a monomer having a carboxyl group (d) from the beginning or a monomer having a carboxyl group due to a reaction or the like. This content is¹³C (¹H)-Can be calculated by NMR analysis.

&lt;Metaacrylic polymer block (a)&gt; The monomer constituting the methacrylic polymer block (a) is the glass of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A). Relationship of transition temperature, Tg_a&gt; Tg_{b b}From the methacrylic acid ester and other vinyl-based monomers copolymerizable therewith, from the viewpoint of easy obtaining, cost and availability of an acrylic block copolymer having desired physical properties. Is preferable. Further, a monomer having an acid anhydride group (c) and a carboxyl group (d) may be contained as a methacrylic acid ester. The proportion of the methacrylic acid ester is preferably 50% by weight or more, and more preferably 75% by weight or more in the entire methacrylic polymer block (a). If it is less than 50% by weight, the characteristics of the methacrylic acid ester, such as weather resistance, high glass transition point, and compatibility with the resin, may be impaired. The proportion of the other copolymerizable vinyl-based monomer is preferably 0 to 50% by weight, more preferably 0 to 25% by weight.

The molecular weight required for the methacrylic polymer block (a) may be determined from the cohesive force required for the methacrylic polymer block (a) and the time required for its polymerization.

It is said that the cohesive force depends on the degree of interaction and entanglement between molecules, and as the molecular weight is increased, the entanglement point increases and the cohesive force increases. That is, the molecular weight required for the methacrylic polymer block (a) is M._aThe molecular weight between the entangled points of the polymers constituting the methacrylic polymer block (a) is Mc._aAs M_aTo exemplify the range of, preferably M when cohesive force is required._a&gt; Mc_aIs. To give a further example, if more cohesive force is required, preferably M_a&gt; 2 Mc_aOn the contrary, if you want to achieve both cohesive force and creep property to some extent, Mc_a&lt;M_a&lt;2Mc_aIs preferable. For the molecular weight between entangled points, refer to the literature of Wu et al. (Polym. Eng. And Sci., 1990, Vol. 30, p. 753).

For example, assuming that the methacrylic polymer block (a) is entirely composed of methyl methacrylicate, the range of the number average molecular weight of the methacrylic polymer block (a) when cohesive force is required is illustrated. Then, it is preferably 9200 or more. However, if the acid anhydride group (c) is contained in the methacrylic polymer block (a), the cohesive force of the acid anhydride group (c) is imparted, so the molecular weight may be set lower than this. it can. Further, since the polymerization time tends to be long when the number average molecular weight is large, it may be set according to the required productivity, but it is preferably 200,000 or less, more preferably 100,000 or less.

Trifluoromethyl methacrylic acid, trifluoromethylmethyl methacrylic acid, 2-trifluoromethylethyl methacrylic acid, 2-trifluoroethyl methacrylic acid, 2-perfluoroethyl ethyl methacrylic acid, 2-per methacrylic acid Fluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl methacrylic acid, perfluoromethyl methacrylic acid, diperfluoromethylmethyl methacrylic acid, 2-perfluoromethyl-2-perfluoroethylmethyl methacrylic acid , 2-Perfluorohexyl ethyl methacrylic acid, 2-perfluorodecylethyl methacrylic acid, 2-perfluorohexadecylethyl methacrylic acid and other methacrylic acid fluorinated alkyl esters. At least one of these is used. Among these, methyl methacrylate is preferable in terms of compatibility with the thermoplastic resin to be combined, cost, and availability.

Examples of the vinyl-based monomer copolymerizable with the methacrylic acid ester constituting the methacrylic acid polymer block (a) include an acrylic acid ester, an aromatic alkenyl compound, a vinyl cyanide compound, and a conjugated diene compound. Examples thereof include halogen-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, and maleimide compounds.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, and the like. Acrylic acid aliphatic hydrocarbon (for example, alkyl having 1 to 18 carbon atoms) ester such as n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate; cyclohexyl acrylate Acrylic acid alicyclic hydrocarbon ester such as isobornyl acrylate; Acrylic acid aromatic hydrocarbon ester such as phenyl acrylate and toluyl acrylate; Acrylic acid aralkyl ester such as benzyl acrylate; 2-methoxyethyl acrylate, acrylic Acrylic acid such as 3-methoxybutyl acid and ester of functional group-containing alcohol having ether oxygen; trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethyl ethyl acrylate, acrylic acid 2-Perfluoroethyl-2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, Acrylic acid fluoride alkyl esters such as 2-perfluorohexyl ethyl acrylate, 2-perfluorodecyl ethyl acrylate, and 2-perfluorohexadecyl ethyl acrylate can be mentioned.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

Examples of the conjugated diene compound include butadiene and isoprene.

Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.

Examples of the unsaturated carboxylic acid compound include methacrylic acid and acrylic acid.

Examples of the unsaturated dicarboxylic acid compound include maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyl esters, fumaric acid, fumaric acid monoalkyl esters and dialkyl esters, and the like.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamic acid and the like.

Examples of the maleimide-based compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

At least one of these is used. These vinyl-based monomers are selected depending on the compatibility when the acrylic-based block copolymer is combined with the crosslinked rubber (B), the thermoplastic resin (C) and / or the thermoplastic elastomer (D). be able to. In addition, the polymer of methyl methacrylate is almost quantitatively depolymerized by thermal decomposition, but in order to suppress it, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-acrylic acid It is possible to copolymerize methoxyethyl or a mixture thereof, styrene, or the like. Further, acrylonitrile can be copolymerized for the purpose of further improving oil resistance.

The glass transition temperature of the methacrylic polymer block (a) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. If the glass transition temperature is less than 100 ° C, the rubber elasticity at high temperature decreases.

The glass transition temperature (Tg) of the methacrylic polymer block (a) can be set by setting the weight ratio of the monomer of each polymer portion according to the Fox formula described above. Here, the glass transition temperature is a Fox formula using the values described in Polymer Handbook Third Edition (Wiley-Interscience 1989) as the glass transition temperature of each polymerization monomer and the polymerization ratio of each monomer. Therefore, it is assumed that it is calculated.

&lt;Acrylic polymer block (b)&gt; The monomer constituting the acrylic polymer block (b) is a glass transition between the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A). Temperature relationship, Tg_a&gt; Tg_{b b}It is preferably composed of an acrylic acid ester and a vinyl-based monomer copolymerizable therewith, from the viewpoints of easily obtaining a composition having desired physical properties, cost and availability. Further, a monomer having an acid anhydride group (c) and a carboxyl group (d) may be contained as an acrylic acid ester. The proportion of the acrylic ester is preferably 50% by weight or more, and more preferably 70% by weight or more in the entire acrylic polymer block (b). If it is less than 50% by weight, the physical characteristics of the composition, which are the characteristics when the acrylic ester is used, particularly impact resistance, flexibility, and oil resistance may be impaired. The proportion of the other copolymerizable vinyl-based monomer is preferably 0 to 50% by weight, more preferably 0 to 30% by weight.

The molecular weight required for the acrylic polymer block (b) may be determined from the elastic modulus and rubber elasticity required for the acrylic polymer block (b), the time required for the polymerization, and the like.

The elastic modulus is closely related to the mobility of the molecular chain and its molecular weight, and does not show the original elastic modulus unless the molecular weight is above a certain level. The same applies to rubber elasticity, but from the viewpoint of rubber elasticity, it is desirable that the molecular weight is large. That is, the molecular weight required for the acrylic polymer block (b) is M._{b b}To exemplify the range as, preferably M_{b b}&gt; 3000, more preferably M_{b b}&gt; 5000, more preferably M_{b b}&gt; 10000, especially preferably M_{b b}&gt; 20000, most preferably M_{b b}&gt; 40000. However, since the polymerization time tends to be long when the number average molecular weight is large, it may be set according to the required productivity, but it is preferably 500,000 or less, and more preferably 300,000 or less.

Examples of the acrylic acid ester constituting the acrylic polymer block (b) include the same acrylic acid esters used in the methacrylic polymer block (a). At least one of these is used.

Among these, n-butyl acrylate is preferable in terms of impact resistance, compression set, cost, and availability. When oil resistance is required, ethyl acrylate is preferable. In addition, 2-ethylhexyl acrylate is preferable when a material having flexibility, low temperature characteristics, and lower hardness is required. In addition, a mixture of n-butyl acrylate and 2-ethylhexyl acrylate is preferable when a balance between flexibility and mechanical strength and a material having a lower hardness are required. Further, when it is desired to achieve both oil resistance and low temperature characteristics, a mixture of ethyl acrylate, n-butyl acrylate and 2-methoxyethyl acrylate is preferable. When oil resistance and flexibility are required, a mixture of n-butyl acrylate and 2-methoxyethyl acrylate is preferable.

Examples of the vinyl-based monomer copolymerizable with the acrylic acid ester constituting the acrylic polymer block (b) include methacrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, and halogen. Examples thereof include unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, etc., and specific examples thereof are the same as those used for the methacrylic polymer block (a). I can give you something.

At least one of these is used. These vinyl-based monomers have the glass transition temperature, elastic modulus, and polarity required for the acrylic polymer block (b), as well as the physical characteristics, crosslinked rubber, thermoplastic resin, and / or heat required for the composition. A preferable one can be selected from the viewpoint of compatibility with the plastic elastomer. For example, acrylonitrile can be copolymerized for the purpose of improving the oil resistance of the composition.

The glass transition temperature of the acrylic polymer block (b) is preferably 50 ° C. or lower, more preferably 0 ° C. or lower. If the glass transition temperature is higher than 50 ° C, the rubber elasticity of the acrylic block copolymer (A) may decrease.

The glass transition temperature (Tg) of the acrylic polymer block (b) can be set by setting the weight ratio of the monomer of each polymer portion according to the Fox formula described above. Here, the glass transition temperature uses the value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) as the glass transition temperature of each polymerization monomer, and uses the polymerization ratio of each monomer according to the Fox formula. It is assumed that it has been calculated.

&lt;Acid anhydride group (c)&gt; Since the acid anhydride group (c) has reactivity with a compound having an amino group, a hydroxyl group, an epoxy group, etc., a crosslinked rubber, a thermoplastic resin and / or heat can be used as a reaction point when modifying the polymer. As a compatibility improving site when blended with a plastic elastomer, it has a feature that it can be used as a cross-linking point when further imparting rubber elasticity to a soft segment. Further, since the acid anhydride group (c) has a high glass transition temperature (Tg), it has an effect of improving the heat resistance of the acrylic block copolymer (A) when it is introduced into the hard segment. For example, the glass transition temperature of a polymer having an acid anhydride group is as high as 159 ° C for polymethacrylic acid anhydride, and the heat resistance of the acrylic block copolymer is improved by introducing the units constituting these. can do.

As a method for introducing the acid anhydride group (c), it is preferable to introduce the acid anhydride group (c) into an acrylic block copolymer in the form of a precursor of the acid anhydride group, and then cyclize it. Although not particularly limited, the general formula (2):<chemistry num="5"><img file="JP4493498B2_D0005.tif" /></chemistry>(In the formula, R²Represents a hydrogen or methyl group. R³Represents a hydrogen, methyl group, or phenyl group and may be the same or different from each other except that they contain at least one methyl group). An acrylic block copolymer (A') characterized by having at least one in any of the polymer blocks (b) can be melt-kneaded and introduced by cyclization at a temperature of 180 to 300 ° C. preferable.

The unit represented by the general formula (2) can be introduced into an acrylic block copolymer by copolymerizing an acrylic acid ester or a methacrylic acid ester monomer derived from the general formula (2). Can be done.

The unit represented by the general formula (2) is desorbed and cyclized from the adjacent ester unit at high temperature to form an acid anhydride group (for example, Hatada et al., JMS-PURE APPL.CHEM., See A30 (9 &amp; 10), PP.645-667 (1993)). According to these, in general, in a polymer having a bulky ester unit and β-hydrogen, the ester unit is decomposed at a high temperature, followed by cyclization to form an acid anhydride group. By using these methods, an acid anhydride group can be easily introduced into the acrylic block copolymer.

Although not particularly limited, specific examples of such monomers include t-butyl acrylate, isopropyl acrylate, α, α-dimethylbenzyl acrylate, α-methylbenzyl acrylate, and t-butyl methacrylate. Examples thereof include isopropyl methacrylic acid, α, α-dimethylbenzyl methacrylic acid, and α-methylbenzyl methacrylic acid. Among these, t-butyl acrylate and t-butyl metaacrylate are preferable from the viewpoints of availability, polymerization, and formation of an acid anhydride group.

The formation of the acid anhydride group is preferably performed by heating the acrylic block copolymer (A') at a high temperature, and is not particularly limited, but is preferably heated at 180 to 300 ° C. If it is lower than 180 ° C, the formation of acid anhydride groups may be insufficient, and if it is higher than 300 ° C, the polymer (A') itself may be decomposed.

&lt;Carboxyl group (d) and Carboxyl group (e)&gt; The carboxyl group has a strong cohesive force, and the monomer having a carboxyl group has a high glass transition temperature (Tg), and has an effect of improving the heat resistance of the acrylic block copolymer. Functional groups such as hydroxyl groups also have hydrogen bonding ability, but their Tg is lower than that of monomers having a carboxyl group, and the effect of improving heat resistance is small. Therefore, the carboxyl group (d) and / or the carboxyl group (e) may be contained from the viewpoint of further improving the heat resistance and the cohesive force of the acrylic block copolymer (A).

The method for introducing the carboxyl group (d) is not particularly limited, but it is preferable to generate the carboxyl group (d) in the process of introducing the acid anhydride group (c) into the acrylic block copolymer (A) from the viewpoint of ease of introduction. ..

The method will be described below.

In the acrylic block copolymer (A') having the unit represented by the general formula (2), the unit represented by the general formula (2) is desorbed, cyclized, and acid anhydride from the adjacent ester unit at high temperature. Generate a base (c). At this time, the ester unit decomposes to generate a carboxyl group (d), and subsequently, cyclization occurs to form an acid anhydride group (c). Utilizing this, the carboxyl group (d) can be introduced by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by the general formula (2). Specifically, the acrylic block copolymer (A') may be heated under pressure in the state of a polymer solution, or the acrylic block copolymer (A') may be directly heated and melted. Good. It is more preferable to melt-knead the acrylic block copolymer (A') from the viewpoint of ease of production and the like. When melt-kneading an acrylic block copolymer (A'), the melt-kneading time (residence time in the extruder when an extruder is used) is the temperature at which the acrylic block copolymer (A') is melt-kneaded, the screw configuration, and L / D (screw). It may be appropriately determined according to the ratio of the effective length L and the screw diameter D), the screw rotation speed, and the like. In this method, the carboxyl group (d) tends to be easily cyclized with the adjacent ester unit at a high temperature. Therefore, when the carboxyl group (d) is introduced in an amount of more than 50% by weight, the introduction operation becomes complicated. Tends to be. In addition, the physical properties after the molding process change, and it tends to be difficult to obtain a product having stable physical properties.

Further, when the acrylic block copolymer (A) is required to have further heat resistance, a carboxyl group (e) can be introduced. As a method for introducing the carboxyl group (e), it is possible to introduce it by hydrolyzing the acid anhydride group of the acrylic block copolymer (A) and opening the ring, in terms of cost and ease of production. preferable. As described above, in the method of generating the carboxyl group (d) in the process of introducing the acid anhydride group (c) into the acrylic block copolymer (A), the carboxyl group (d) is associated with the adjacent ester unit. This is because it tends to be easily cyclized, and if it exceeds 50% by weight, the operation of introducing the carboxyl group (d) tends to be complicated. On the other hand, when a monomer having a carboxyl group is directly polymerized under polymerization conditions and introduced, the monomer having a carboxyl group may inactivate the catalyst during polymerization. In JP-A-2001-234147, JP-A-10-298248, etc., the carboxyl group is protected by an appropriate protecting group, or the acrylic block is in the form of a functional group that is a precursor of the carboxyl group. A method of introducing a carboxyl group by introducing it into a coalescence and then performing selective decomposition is described, but there is a tendency that there is a problem in terms of cost and the production becomes complicated.

The carboxyl group (e) means a product produced by hydrolyzing an acid anhydride group (c), but is distinguished from a carboxyl group (d) generated in the process of introducing the acid anhydride group (c). It is not necessary, and the total of the monomer having a carboxyl group (d) and the monomer having a carboxyl group (e) is 50% by weight of the monomers constituting the acrylic block copolymer (A). % Or more can be easily introduced. Further, by hydrolyzing all the acid anhydride groups (c), a block copolymer having only a carboxyl group as a functional group can be obtained.

Such an acrylic block copolymer can be suitably produced by hydrolyzing the acid anhydride group (c) of the acrylic block copolymer (A) to open the ring. The method of hydrolyzing to introduce the carboxyl group (e) is not particularly limited, and the acrylic block copolymer (A) may be heated with water under pressure, and the acrylic block copolymer (A) may be heated. May be melt-kneaded with water. From the viewpoint of ease of production and cost, it is preferable to melt and knead (A) with water.

As a method of heating the acrylic block copolymer (A) together with water under pressure, a pressure-resistant reaction vessel can be used. Further, as a method of melt-kneading the acrylic block copolymer (A) together with water, it can be carried out in various devices capable of simultaneously performing heating and kneading, for example, for ordinary rubber processing. Examples include rubberies, kneaders, single-screw or multi-screw extruders used. An extruder is preferably used, and a closed type extruder is more preferably used in terms of reactivity to a carboxyl group, ease of production, and the like. When the acrylic block copolymer (A) is melt-kneaded, the melt-kneading time (residence time in the extruder when an extruder is used) is the temperature at which the acrylic block copolymer (A) is melt-kneaded, the screw configuration, and L / D (screw). It may be appropriately determined according to the ratio of the effective length L and the screw diameter D), the screw rotation speed, and the like.

The glass transition temperature of a polymer having a carboxyl group (d) and / or a carboxyl group (e) is as high as 228 ° C for polymethacrylic acid, for example, and by introducing a monomer constituting these, an acrylic system is used. The heat resistance of the block copolymer (A) can be improved.

Further, the content of the carboxyl group may be appropriately set according to the physical characteristics required for the acrylic block copolymer (A).

&lt;Manufacturing method of acrylic block copolymer (A')&gt; The method for producing the acrylic block copolymer (A') is not particularly limited, but it is preferable to use controlled polymerization using a polymer initiator. Examples of controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization developed in recent years. Of these, living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the acrylic block copolymer.

Living radical polymerization is a radical polymerization in which the activity of the polymerization terminal is maintained without being lost. In a narrow sense, living polymerization refers to polymerization in which the terminal is always active, but in general, it also includes pseudo-living polymerization in which an inactivated terminal and an activated terminal are in an equilibrium state. .. The definition here is also the latter. Living radical polymerization has been actively studied by various groups in recent years.

Examples include radicals that use chain transfer agents such as polysulfides, cobalt porphyrin complexes (J.Am.Chem.Soc., 1994, Vol. 116, p. 7943) and nitroxide compounds. Atom Transfer Radical Polymerization (ATRP) using a trapping agent (Macromolecules, 1994, Vol. 27, p. 7228), using an organic halide as an initiator and using a transition metal complex as a catalyst. ) Etc. can be given. In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of ease of control.

Atom transfer radical polymerization is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a group 7, 8, 9, 10 or 11 element of the periodic table as a central metal as a catalyst. (For example, Matyjaszewski et al., Journal of American Chemical Society (J.Am.Chem.Soc.), 1995, Vol. 117, p. 5614, Macromolecules, 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721).

According to these methods, the polymerization rate is generally very high, and the polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw /), although the polymerization is radical polymerization in which a termination reaction such as coupling between radicals is likely to occur. A polymer of Mn = 1.1 to 1.5) is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

As the organic halide or sulfonyl halide compound used as an initiator in the atom transfer radical polymerization method, a monofunctional, bifunctional or polyfunctional compound can be used. These may be used properly according to the purpose, but when producing a diblock copolymer, a monofunctional compound is preferable from the viewpoint of easy availability of an initiator, and an aba-type triblock copolymer, When producing a bab-type triblock copolymer, it is preferable to use a bifunctional compound from the viewpoint of shortening the number of reaction steps and time, and when producing a branched block copolymer, the number of reaction steps. , It is preferable to use a polyfunctional compound from the viewpoint of shortening the time.

It is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound composed of a polymer in which a halogen atom is bonded to the end of a molecular chain among organic halides or sulfonyl halide compounds. Since such a polymer initiator can be produced by a controlled polymerization method other than the living radical polymerization method, it is characterized in that a block copolymer obtained by binding polymers obtained by different polymerization methods can be obtained. ..

1 As a functional compound, for example C₆H₅-CH₂X, C₆H₅-C (H) (X) -CH₃, C₆H₅-C (X) (CH₃)₂, R⁴-C (H) (X) -COOR⁵, R⁴-C (CH)₃) (X)-COOR⁵, R⁴-C (H) (X) -CO-R⁵, R⁴-C (CH)₃) (X) -CO-R⁵, R⁴-C₆H₄-SO₂X Examples thereof include compounds indicated by.

In the formula, C₆H₅Is a phenyl group, C₆H₄Represents a phenylene group (either ortho-substituted, meta-substituted, or para-substituted). R⁴Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. R⁵Represents a monovalent organic group having 1 to 20 carbon atoms.

R⁴As a specific example of an alkyl group having 1 to 20 carbon atoms (including an alicyclic hydrocarbon group), for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t- Examples thereof include a butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group and an isobornyl group. Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a triyl group, and a naphthyl group. Specific examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

R⁵As a specific example of a monovalent organic group having 1 to 20 carbon atoms, for example, R⁴The same group as above can be mentioned.

Specific examples of the monofunctional compound include tosyl bromide, methyl 2-propionate bromide, ethyl 2-propionate bromide, butyl 2-propionate bromide, methyl 2-isobutyrate bromide, 2-. Examples thereof include ethyl bromide isobutyrate and butyl 2-isobutyrate bromide. Of these, ethyl 2-propionate and butyl 2-propionate are preferable because they have a structure similar to that of the acrylic acid ester monomer and therefore polymerization can be easily controlled.

Bifunctional compounds include, for example. X-CH₂-C₆H₄-CH₂-X, X-CH (CH)₃)-C₆H₄-CH (CH)₃) -X, XC (CH)₃)₂-C₆H₄-C (CH)₃)₂-X, X-CH (COOR)⁶)-(CH₂)_n-CH (COOR⁶) -X, XC (CH)₃) (COOR⁶)-(CH₂)_n-C (CH)₃) (COOR⁶) -X X-CH (COR)⁶)-(CH₂)_n-CH (COR)⁶) -X, XC (CH)₃) (COR⁶)-(CH₂)_n-C (CH)₃) (COR⁶) -X, X-CH₂-CO-CH₂-X, X-CH (CH)₃)-CO-CH (CH₃) -X, XC (CH)₃)₂-CO-C (CH)₃)₂-X, X-CH (C₆H₅)-CO-CH (C₆H₅) -X, X-CH₂-COO- (CH₂)_n-OCO-CH₂-X, X-CH (CH)₃) -COO- (CH₂)_n-OCO-CH (CH)₃) -X, XC (CH)₃)₂-COO- (CH₂)_n-OCO-C (CH)₃)₂-X, X-CH₂-CO-CO-CH₂-X, X-CH (CH)₃)-CO-CO-CH (CH)₃) -X, XC (CH)₃)₂-CO-CO-C (CH)₃)₂-X, X-CH₂-COO-C₆H₄-OCO-CH₂-X, X-CH (CH)₃)-COO-C₆H₄-OCO-CH (CH)₃) -X, XC (CH)₃)₂-COO-C₆H₄-OCO-C (CH)₃)₂-X, X-SO₂-C₆H₄-SO₂-X Examples thereof include compounds indicated by.

In the formula, R⁶Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. n represents an integer from 0 to 20. C₆H₅, C₆H₄, X are the same as described above.

R⁶Specific examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms are R.⁴It is the same as the specific example of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms.

Specific examples of the bifunctional compound include bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, dimethyl 2,3-dibromosuccinate, and 2,3-dibromosuccinate. Diethyl acid, dibutyl 2,3-dibromosuccinate, dimethyl 2,4-dibromoglutarate, diethyl 2,4-dibromoglutarate, dibutyl 2,4-dibromoglutarate, dimethyl 2,5-dibromoadipate, 2, Diethyl 5-dibromoadipate, dibutyl 2,5-dibromoadipate, dimethyl 2,6-dibromopimerate, diethyl 2,6-dibromopimerate, dibutyl 2,6-dibromopimerate, dimethyl 2,7-dibromosberate, 2 , 7-Dibromosverinate diethyl, 2,7-dibromosberate dibutyl, and the like. Of these, bis (bromomethyl) benzene, diethyl 2,5-dibromoadipate, and diethyl 2,6-dibromopimelate are preferable from the viewpoint of availability of raw materials.

As a polyfunctional compound, for example C₆H₃-(CH₂-X)₃, C₆H₃-(CH (CH)₃)-X)₃, C₆H₃-(C (CH)₃)₂-X)₃, C₆H₃-(OCO-CH₂-X)₃, C₆H₃-(OCO-CH (CH)₃)-X)₃, C₆H₃-(OCO-C (CH)₃)₂-X)₃, C₆H₃-(SO₂-X)₃Examples thereof include compounds indicated by.

In the formula, C₆H₃Is a trivalent phenyl group (the positions of the three bonds may be any combination at the 1st to 6th positions), and X is the same as above.

Specific examples of the polyfunctional compound include tris (bromomethyl) benzene, tris (1-bromoethyl) benzene, tris (1-bromoisopropyl) benzene and the like. Of these, tris (bromomethyl) benzene is preferable from the viewpoint of availability of raw materials.

If an organic halide having a functional group or a sulfonyl halide compound is used in addition to the group that initiates polymerization, a polymer in which a functional group other than the group that initiates polymerization is easily introduced at the terminal or in the molecule can be obtained. Be done. Examples of the functional group other than the group that initiates such polymerization include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a silyl group.

In the organic halide or sulfonyl halide compound that can be used as the initiator, the carbon to which the halogen group (halogen atom) is bonded is bonded to a carbonyl group, a phenyl group, or the like, and the carbon-halogen bond is activated. Then the polymerization starts. The amount of the initiator to be used may be determined from the molar ratio with the monomer according to the required molecular weight of the acrylic block copolymer. That is, the molecular weight of the acrylic block copolymer can be controlled by how many molecules of the monomer are used per initiator molecule.

The transition metal complex used as a catalyst for the atom transfer radical polymerization is not particularly limited, but preferably monovalent and zero-valent copper, divalent ruthenium, divalent iron, and divalent nickel. Complex of.

Among these, a copper complex is preferable from the viewpoint of cost and reaction control. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. Among them, cuprous chloride and cuprous bromide are preferable from the viewpoint of controlling polymerization. When monovalent copper compounds are used, 2,2'-bipyridyl, derivatives thereof (eg 4,4'-dinolyl-2,2'-bipyridyl, 4,4'-di (5-), are used to enhance catalytic activity. 2,2'-bipyridyl compounds such as (nolyl) -2,2'-bipyridyl, etc .; 1,10-phenanthroline, derivatives thereof (eg 4,7-dinolyl-1,10-phenanthroline, 5,6-dynolyl- 1,10-Phenanthroline compounds such as 1,10-phenanthroline; polyamines such as tetramethyldiethylenetriamine (TMEDA), pentamethyldiethylenetriamine, hexamethyl (2-aminoethyl) amine may be added as ligands. ..

In addition, a triphenylphosphine complex of divalent ruthenium chloride (RuCl)₂(PPh₃)₃) Is also preferable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides may be added as an activator. In addition, a divalent iron bistriphenylphosphine complex (FeCl)₂(PPh₃)₂), Divalent nickel bistriphenylphosphine complex (NiCl₂(PPh₃)₂) And divalent nickel bistributylphosphine complex (NiBr)₂(PBu₃)₂) Is also preferable as a catalyst.

The catalyst, ligand and activator to be used are not particularly limited, but may be appropriately determined from the relationship between the initiator, monomer and solvent used and the required reaction rate. For example, in the polymerization of an acrylic monomer such as an acrylic acid ester, it is preferable that the growth end of the polymer chain has a carbon-bromine bond from the viewpoint of controlling the polymerization. Therefore, the initiator used is an organic bromide or It is a sulfonyl bromide compound, preferably acetonitrile, and a ligand such as pentamethyldiethylenetriamine using a metal complex catalyst having copper as a central metal contained in copper bromide, preferably cuprous bromide. Is preferably used. Further, in the polymerization of a methacrylic monomer such as a methacrylic acid ester, it is preferable that the growth end of the polymer chain has a carbon-chloride bond from the viewpoint of controlling the polymerization, so that the initiator used is organic. It is a chloride or sulfonyl chloride compound, and the solvent is preferably a mixed solvent with acetonitrile, if necessary, toluene or the like, and a metal complex catalyst having copper chloride, preferably cuprous chloride contained in copper chloride as a central metal. It is preferable to use a ligand such as pentamethyldiethylenetriamine.

The amount of catalyst and ligand used may be determined from the relationship between the amount of initiator, monomer and solvent used and the required reaction rate. For example, when trying to obtain a polymer with a high molecular weight, the initiator / monomer ratio must be smaller than when trying to obtain a polymer with a low molecular weight. In addition, the reaction rate can be increased by increasing the number of catalysts and ligands. Further, when a polymer having a glass transition point higher than room temperature is produced, the reaction rate tends to decrease when an appropriate organic solvent is added to lower the viscosity of the system and increase the stirring efficiency. In such a case, the reaction rate can be increased by increasing the number of catalysts and ligands.

The atom transfer radical polymerization can be carried out in a solvent-free environment (bulk polymerization) or in various solvents. Further, in bulk polymerization and polymerization performed in various solvents, the polymerization can be stopped in the middle.

As the solvent, for example, a hydrocarbon solvent, an ether solvent, a halogenated hydrocarbon solvent, a ketone solvent, an alcohol solvent, a nitrile solvent, an ester solvent, a carbonate solvent and the like can be used.

Examples of the hydrocarbon solvent include benzene and toluene. Examples of the ether solvent include diethyl ether and tetrahydrofuran. Examples of the halogenated hydrocarbon solvent include methylene chloride and chloroform. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol and the like. Examples of the nitrile solvent include acetonitrile, propionitrile, benzonitrile and the like. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the carbonate solvent include ethylene carbonate and propylene carbonate.

At least one of the above-mentioned solvents can be used.

When a solvent is used, the amount used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency. Further, even when the polymerization is stopped in the middle of bulk polymerization or polymerization performed in various solvents, the conversion rate of the monomer at the point of stopping the reaction is the relationship between the viscosity of the entire system and the required stirring efficiency. It may be decided appropriately from.

The polymerization can be carried out in the range of 23 ° C to 200 ° C, preferably in the range of 50 to 150 ° C.

In order to produce an acrylic block copolymer by the above polymerization, a method of sequentially adding monomers, a method of polymerizing the next block using a pre-synthesized polymer as a polymer initiator, or a separately polymerized polymer. Can be mentioned as a method of binding by reaction. Any of these methods may be used, and may be used properly according to the purpose. From the viewpoint of simplicity of the manufacturing process, the method of sequentially adding monomers is preferable. Further, when it is desired to prevent the monomer of the previous block from remaining and copolymerizing with the next block, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator is preferable. ..

Hereinafter, in the case of sequential addition of monomers, the case of polymerizing the next block using a polymer synthesized in advance as a polymer initiator will be described in detail, but the method for producing an acrylic block copolymer of the present invention will be described. It is not limited at all.

In the case of sequential addition of monomers, it is desirable to charge the monomer to be polymerized next when the conversion rate of the monomer prepared to be polymerized first is 80 to 95%. When the polymerization is allowed to proceed until the conversion rate exceeds 95%, the growth reaction of the polymer chain is suppressed with high probability. In addition, since polymer radicals are likely to react with each other, side reactions such as disproportionation, coupling, and chain transfer tend to occur easily. When the monomer to be polymerized next is charged when the conversion rate is less than 80%, the monomer prepared to be polymerized first is mixed with the monomer to be polymerized next and copolymerized. It can be a problem.

Further, in this case, as the order of addition of the monomers, a method (p1) in which an acrylic monomer is first charged and polymerized, and then a methacrylic monomer is charged and polymerized, and a methacrylic single is first added. A method (q1) in which an acrylic monomer is charged and polymerized after the weight is charged and polymerized can be considered. First, an acrylic monomer is charged and polymerized, and then a methacrylic monomer is charged. (P1) is preferable from the viewpoint of controlling the polymerization. This is because it is preferable to grow the methacrylic polymer block from the end of the acrylic polymer block.

As a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, for example, the polymerization of the first block is carried out at a desired time by temporarily lowering the temperature in a living state, stopping the polymerization, and then 1 A method of adding the monomer of the second block after distilling off the monomer of the second block under reduced pressure can be mentioned. If you want to polymerize the third and subsequent blocks, you can operate in the same way as for the second block. In this method, it is possible to prevent the remaining monomer of the previous block from copolymerizing during the polymerization of the second and subsequent blocks.

In this case, the order of polymerization of the blocks is as follows: first, the acrylic block is polymerized and then the methacrylic block is polymerized (p2), and first, the methacrylic block is polymerized and then the acrylic block is polymerized. A method of polymerizing (q2) can be considered, but a method of first polymerizing an acrylic block and then polymerizing a methacrylic block (p2) is preferable from the viewpoint of controlling polymerization. This is because it is preferable to grow the methacrylic polymer block from the end of the acrylic polymer block.

Here, a method for obtaining the conversion rate of an acrylic monomer, a methacrylic monomer, etc. will be described. A gas chromatograph (GC) method, a gravimetric method, or the like can be applied to obtain the conversion rate. In the GC method, the reaction solution of the polymerization system is sampled at any time before the start of the reaction and during the reaction, and GC measurement is performed. This is a method for calculating the consumption rate. The advantage of this method is that even when a plurality of monomers are present in the system, the conversion rate of each can be determined independently. The gravimetric method is a method in which a polymerization reaction solution is sampled, the solid content concentration is determined from the weight before drying and the weight after drying, and the conversion rate of the monomer as a whole is determined. The advantage of this method is that the conversion rate can be easily determined. Among these methods, the GC method is used when a plurality of monomers are present in the system, for example, when the acrylic monomer is contained as a copolymerization component of the methacrylic monomer. preferable.

The reaction solution obtained by the polymerization contains a mixture of a polymer and a metal complex, and a metal complex and a metal salt are generated by adding an organic acid containing a carboxyl group or a sulfonyl group to generate the metal complex. The solid content is removed by filtration, etc., and then impurities such as basic active alumina, basic adsorbent, solid inorganic acid, anion exchange resin, and acid remaining in the solution by the cellulose anion exchanger adsorption treatment are removed. By removing it, an acrylic block copolymer solution can be obtained.

From the polymer solution thus obtained, the polymerization solvent and unreacted monomers are subsequently removed by an evaporation operation to isolate an acrylic block copolymer. As the evaporation method, a thin film evaporation method, a flash evaporation method, a horizontal evaporation method provided with an extrusion screw, or the like can be used. Since the acrylic block copolymer has adhesiveness, efficient evaporation is possible by using the horizontal evaporation method alone equipped with an extrusion screw or in combination with other evaporation methods among the above evaporation methods.

&lt;Manufacturing method of acrylic block copolymer (A)&gt; As the acrylic block copolymer (A), a method of heating the acrylic block copolymer (A') at a high temperature of 180 to 300 ° C. is preferably used. At that time, the acrylic block copolymer (A') may be heated under pressure in the state of the polymer solution, or may be heated while evaporating and removing the solvent from the polymer solution. The polymer (A') may be directly heated and melted, but the acrylic block copolymer (A') is directly heated in terms of reactivity to acid anhydride groups and ease of production. It is preferable to melt. Furthermore, it is more preferable to melt-knead the acrylic block copolymer (A').

As a method of heating the acrylic block copolymer (A') in the state of the polymer solution, it can be carried out in a pressure-resistant reaction vessel. Further, as a method of heating the acrylic block copolymer (A') while evaporating and removing the solvent from the polymer solution, a horizontal evaporation method provided with an extrusion screw or the like can be used. As a method of directly heating and melting the acrylic block copolymer (A'), a press machine, an injection molding machine, or the like can be used.

In order to further efficiently proceed the reaction, a method of melt-kneading the acrylic block copolymer (A') can be mentioned, and it can be carried out in various devices capable of simultaneously heating and kneading. Examples include Banbury, Kneader, single-screw or multi-screw extruders used for normal rubber processing. Although not particularly limited, an extruder is preferably used in terms of reactivity to an acid anhydride group and ease of production. When melt-kneading an acrylic block copolymer (A'), the melt-kneading time (residence time in the extruder when an extruder is used) is the temperature at which the acrylic block copolymer (A') is melt-kneaded, the screw configuration, and L / D (screw). It may be appropriately determined according to the ratio of the effective length L and the screw diameter D), the screw rotation speed, and the like.

&lt;Composition&gt; The acrylic block copolymer (A) of the present invention is a crosslinked rubber (B), a thermoplastic resin (C), a thermoplastic elastomer (D), a lubricant (E), an inorganic filler (F), and a stabilizer (G). ) Can be used as a composition containing at least one selected from the group consisting of. Moreover, those compositions can be suitably used as a sealing product or the like.

Although not particularly limited, for example, in the following cases, the acrylic block copolymer (A), the crosslinked rubber (B), the thermoplastic resin (C), the thermoplastic elastomer (D), the lubricant (E), and the inorganic material are used. A filler (F) and a stabilizer (G) can be blended and used suitably.

When cross-linked rubber (B) is added to the acrylic block copolymer (A) to impart rubber elasticity to the acrylic block copolymer (A), to improve physical properties such as low temperature characteristics, or when cross-linked rubber (B) is used. ) To impart thermoplasticity by adding an acrylic block copolymer (A) to improve the processability and recyclability of the crosslinked rubber (B); a thermoplastic resin to the acrylic block copolymer (A). When adjusting the hardness of the acrylic block copolymer (A) by adding (C) and / or the thermoplastic elastomer (D), improving physical properties such as mechanical properties and low temperature properties, or when using a thermoplastic resin (C) ) And / or the thermoplastic block copolymer (A) was added as a softening agent to the thermoplastic elastomer (D) to maintain the high elasticity of the thermoplastic resin (C) and / or the thermoplastic elastomer (D). While adjusting the hardness or improving the compression set characteristics; utilizing the reactivity of the acrylic block copolymer (A), two or more crosslinked rubbers (B) and / or thermoplastic resins (C) ) And / or the thermoplastic block copolymer (A) may be added as a compatibilizer to the thermoplastic elastomer (D) to improve the mechanical properties. Further, by adding a lubricant (E) and an inorganic filler (G) to the acrylic block copolymer (A) or its composition, the friction property of the surface of the acrylic block copolymer (A) or its composition is added. May be reduced, mechanical properties such as elastic modulus may be improved, and workability may be improved. Stabilizer (G) can be used to prevent thermal deterioration and acid deterioration during processing, and to improve the heat resistance and weather resistance of products.

Acrylic block copolymer (A) and crosslinked rubber (B), thermoplastic resin (C) and / or thermoplastic elastomer (D), as well as lubricant (E) and / or inorganic filler (F) and / or stable The blending ratio of the agent (G) may be appropriately determined according to the physical characteristics required for the obtained composition, for example, the characteristics of the sealing product.

Acrylic block copolymer (A) is added to impart rubber elasticity to the acrylic block copolymer (A), when it is necessary to improve low temperature characteristics, or to impart thermoplasticity to the crosslinked rubber. In this case, it is preferably composed of 0.5 to 99.5% by weight of the acrylic block copolymer (A) and 99.5 to 0.5% by weight of the crosslinked rubber (B), and 0.5 to 90% by weight of the acrylic block copolymer (A) and It is more preferable that the crosslinked rubber (B) is composed of 99.5 to 10% by weight. If the amount of the acrylic block copolymer (A) is less than 0.5% by weight, the thermoplasticity imparted to the crosslinked rubber tends to be insufficient, and if the amount of the crosslinked rubber (B) is less than 0.5% by weight, the acrylic block copolymer weight tends to be insufficient. There is a tendency that the rubber elasticity imparted to the coalesced (A) and the improvement of low temperature characteristics are insufficient.

The blending ratio of the acrylic block copolymer (A) and the thermoplastic resin (C) and / or the thermoplastic elastomer (D) may be appropriately determined as necessary, and is not particularly limited, but is an acrylic block copolymer. It is preferably composed of (A) 0.5 to 99.5% by weight, the thermoplastic resin (C) and / or the thermoplastic elastomer (D) 99.5 to 0.5% by weight, and the acrylic block copolymer (A) 0.5 to 90% by weight. And, more preferably, it is composed of 99.5 to 10% by weight of the thermoplastic resin (C) and / or the thermoplastic elastomer (D).

The hardness of the acrylic block copolymer (A) can be adjusted by adding a thermoplastic resin (C) and / or a thermoplastic elastomer (D) to the acrylic block copolymer (A), and mechanical properties, mechanical properties, etc. can be adjusted. When improving the physical properties, the acrylic block copolymer (A) is preferably 99.5 to 50% by weight, and the thermoplastic resin (C) and / or the thermoplastic elastomer (D) is preferably 0.5 to 50% by weight. If the amount of the thermoplastic resin (C) and / or the thermoplastic elastomer (D) is less than 0.5% by weight, the adjustment of the hardness of the acrylic block copolymer and the improvement of physical properties such as mechanical properties may be insufficient.

Further, an acrylic block copolymer (A) is added as a softening agent to the thermoplastic resin (C) and / or the thermoplastic elastomer (D), and the thermoplastic resin (C) and / or the thermoplastic elastomer (D) is added. When adjusting the hardness or improving the compressive permanent strain characteristics while maintaining the high elasticity of the acrylic block copolymer (A), 0.5 to 50% by weight of the acrylic block copolymer (A), the thermoplastic resin (C) and / or The thermoplastic elastomer (D) is preferably 99.5 to 50% by weight. If the amount of acrylic block copolymer (A) is less than 0.5% by weight, the adjustment of the hardness of the thermoplastic resin (C) and / or the thermoplastic elastomer (D) and the improvement of physical properties such as mechanical properties are insufficient. Acrylic block copolymer (A) is added as a compatibilizer to two or more types of crosslinked rubber (B) and / or thermoplastic resin (C) and / or thermoplastic elastomer (D), and mechanical properties Acrylic block copolymer (A) is 0.5 to 20% by weight, crosslinked rubber (B) and / or thermoplastic resin (C) and / or thermoplastic elastomer (D) is 80 to 99.5% by weight. Is preferable. If the amount of the acrylic block copolymer (A) is less than 0.5% by weight, the improvement of mechanical properties and the improvement of compatibility may be insufficient.

When the acrylic block copolymer (A) or its composition is mixed with the lubricant (E), the inorganic filler (F), and the stabilizer (G), the acrylic block copolymer (A) or its composition 100 It is preferably composed of 0.01 to 50 parts by weight of the lubricant (E), 0.01 to 300 parts by weight of the inorganic filler (F), and 0.01 to 15 parts by weight of the stabilizer (G) with respect to the parts by weight, and more preferably the lubricant (E). ) 0.1 to 30 parts by weight, inorganic filler (F) 0.1 to 100 parts by weight. If the lubricant (E) is less than 0.01 parts by weight, the frictional property of the surface may not be reduced, and if it is more than 50 parts by weight, it may bleed out from the acrylic block copolymer (A) or its composition, or it may be oil resistant. Sex may be reduced. If the amount of the inorganic filler (F) is less than 0.01 parts by weight, the improvement of mechanical properties such as elastic modulus may be insufficient, and if it is more than 300 parts by weight, the elongation during tension is reduced or the compression set is permanent. The characteristics may deteriorate. In addition, if the amount of stabilizer (G) is less than 0.01 parts by weight, the effect of preventing heat deterioration and acid deterioration during processing and improving the heat resistance and weather resistance of the product may be insufficient, and the weight is 15 weight. If the amount is more than the portion, the mechanical properties of the acrylic block copolymer (A) or its composition may be deteriorated or colored.

&lt;Crosslinked rubber (B)&gt; In the present invention, the crosslinked rubber (B) is a vulcanized rubber or a core-shell type that is crosslinked by adding a graft crosslinker or the like, and the core-shell type is a phase with the acrylic block copolymer (A). It is preferable in terms of solubility and the like.

Specific examples of the crosslinked rubber (B) include acrylic rubber (ACM), ethylene-acrylic acid ester copolymer rubber (AEM), acrylic nitrile-acrylic acid ester copolymer rubber (ANM), and chlorinated polyethylene (CM). Chlorosulphonized polyethylene (CSM), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), ethylene-vinyl acetate copolymer rubber (EVA), ethylene tetrafluoride-propylene rubber (FEPM) ), Ethylene-propylene-vinylidene fluoride rubber, fluororubber (FKM), polyisobutylene (PIB), epichlorohydrin rubber (CO), acrylate butadiene rubber (ABR), styrene-butadiene rubber (SBR), butadiene Rubber (BR), natural rubber (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), butyl rubber (IIR), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), acrylonitrile-butadiene copolymer rubber (NBR), hydride nitrile rubber (H-NBR), chloroprene rubber, norbornen rubber (NOR), polyester urethane rubber (AU), polyether urethane rubber (EU), silicone rubber (VMQ), fluorosilicone rubber (FVMQ) , Polydimethylsiloxane (MQ), polysulfide rubber, ethylene-methylacrylate copolymer rubber (EMA), ethylene-ethylacrylate copolymer rubber (EEA), ethylene-methylmethacrylate copolymer rubber (EMMA) and the like. The core-shell type crosslinked rubber characterized by excellent compatibility with other resins is not particularly limited, but is a methyl methacrylate-butadiene-styrene copolymer (MBS resin), an acrylic graft copolymer, and an acrylic. -Acrylic composite rubber-based graft copolymers can be mentioned. As MBS resin, Kaneka B series, Kaneka M series (both manufactured by Kaneka Chemical Industry Co., Ltd.), and as acrylic graft copolymer, Kaneka FM series (Kaneka Chemical Industry Co., Ltd.)

At least one of these may be used. Of these, silicone rubber (VMQ) is preferable because it is excellent in low temperature characteristics and high temperature characteristics (heat resistance) required for various sealing products. Further, from the viewpoint of also having mechanical properties, a core-shell type crosslinked silicone rubber in which silicone is used as the core portion and methyl methacrylate or the like is used for the shell portion is preferable. In addition to this, rubber having good compatibility with the acrylic block copolymer (A) can be preferably used.

&lt;Thermoplastic resin (C)&gt; The thermoplastic resin (C) that can be used in the present invention is not particularly limited, and for example, a polyvinyl chloride resin, a polyethylene resin, a polypropylene resin, a cyclic olefin copolymer resin, a polymethyl methacrylate resin, a styrene-methyl methacrylate resin, and the like. Acrylonitrile-styrene copolymer resin, polystyrene resin, polyphenylene ether resin, polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone Examples thereof include resins and polyamideimide resins. At least one of these can be used. Although not particularly limited, those having good compatibility with the acrylic block copolymer (A) are preferably used, and those having a functional group capable of reacting with an acid anhydride group are more preferably used. Examples of the functional group capable of reacting with the acid anhydride group include an amino group and a hydroxyl group, and examples of the thermoplastic resin having these include a polyester resin and a polyamide resin. In addition to this, a thermoplastic resin containing a functional group that reacts with an acid anhydride group can also be preferably used. When a polyvinyl chloride resin, a polymethyl methacrylate resin, an acrylonitrile-styrene copolymer resin, a methyl methacrylate-styrene copolymer resin, or a polycarbonate resin is used, the compatibility with the acrylic block copolymer (A) is good. Therefore, it has the effect of improving the hardness while maintaining the mechanical strength, and effectively acting as a compatibilizer between the resin and the polyester resin or polyamide resin.

&lt;Thermoplastic Elastomer (D)&gt; The thermoplastic elastomer (D) that can be used in the present invention is not particularly limited, and for example, a thermoplastic elastomer such as a styrene elastomer, an olefin elastomer, a urethane elastomer, a vinyl chloride elastomer, an ester elastomer, an amide elastomer, or an acrylic elastomer is used. be able to. At least one of these can be used. Among them, ester elastomers and amide elastomers are preferable in that acrylic elastomers have oil resistance, heat resistance and compatibility, and have functional groups capable of reacting with oil resistance, heat resistance and acid anhydride groups. In addition to this, a thermoplastic elastomer containing a functional group that reacts with an acid anhydride group can also be preferably used. When a styrene elastomer, an olefin elastomer, a urethane elastomer, or a vinyl chloride elastomer is used, it has effects such as being able to impart oil resistance, heat resistance, weather resistance, and scratch resistance while maintaining properties such as rubber elasticity and flexibility. ..

&lt;Glidant (E)&gt; Examples of the lubricant (E) that can be used in the present invention include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate, and sodium palmitate, and polyethylene wax. , Polypropylene wax, waxes such as montanic acid wax, low molecular weight polyolefin such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxane such as dimethylpolysiloxane, octadecylamine, alkyl phosphate, fatty acid ester, ethylene bisstearylamide, etc. Examples thereof include amide-based lubricants, fluororesin powders such as tetrafluoroethylene resin, molybdenum disulfide powder, silicone resin powders, silicone rubber powders, and silica. At least one of these can be used. Of these, stearic acid, calcium stearate, zinc stearate, and magnesium stearate are preferable from the viewpoint of cost and processability. When the obtained composition is used for various sealing products, stearic acid, zinc stearate, and calcium stearate are preferable from the viewpoint of imparting the required low frictional property.

&lt;Inorganic filler (F)&gt; Examples of the inorganic filler (F) that can be used in the present invention include titanium oxide, zinc sulfide, zinc oxide, carbon black, calcium carbonate, calcium silicate, clay, kaolin, silica, mica powder, alumina, and glass fiber. Examples include, but are not limited to, metal fibers, potassium silicate whisker, asbestos, wollastonite, mica, talc, glass flakes, milled fibers, and metal powders. At least one of these can be used. Of these, titanium oxide, carbon black, calcium carbonate, silica, and talc are preferable from the viewpoints of improving mechanical properties, reinforcing effect, cost, and the like. When the obtained composition is used in various sealing products, carbon black or titanium oxide is preferable because it has a required high elastic modulus, weather resistance, and can also be used as a pigment.

&lt;Stabilizer (G)&gt; Examples of the stabilizer (G) that can be used in the present invention include an anti-aging agent, a light stabilizer, and an ultraviolet absorber. Specific examples of the anti-aging agent include, but are not limited to, phenyl-α-naphthylamine (PAN), octyldiphenylamine, N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-di-. β-Phenyl-p-phenylenediamine (DNPD), N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine (IPPN), N, N'-diallyl-p-phenylenediamine, phenothiazine derivative, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N-phenyl-N' -(3-Methacryloxy-2-hydropropyl) -p-phenylenediamine, diallyl phenylenediamine mixture, diallyl-p-phenylenediamine mixture, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine , Amine-based anti-aging agents such as diphenylamine derivatives, imidazole-based anti-aging agents such as 2-mercaptobenzoimidazole (MBI), 2,6-di-t-butyl-4-methylphenol, pentaerythrityltetrakis [3-( 5-Di-t-butyl-4-hydroxyphenol) -propinate] and other phenolic anti-aging agents, nickel diethyl-dithiocarbamate and other phosphate-based anti-aging agents, and triphenylphosphite and other secondary anti-aging agents. , 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-t-) Pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate and the like. In addition, as a light stabilizer and an ultraviolet absorber, 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2,

As industrial products, Irganox1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (manufactured by Sankyo Lifetech Co., Ltd.), Adecastab LA-57 (manufactured by Asahi Denka Kogyo Co., Ltd.), Adecastab LA-68 (manufactured by Asahi Denka Kogyo Co., Ltd.) , Chimassorb944 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS765 (manufactured by Sankyo Lifetech Co., Ltd.), Adecaster LA-62 (manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN144 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Adecastab LA-63 (manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN622 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Adecastab LA-32 (manufactured by Asahi Denka Kogyo Co., Ltd.), Adecastab LA-36 (manufactured by Asahi Denka Kogyo Co., Ltd.) , TINUVIN571 (manufactured by Ciba Specialty Chemicals Co., Ltd.), TINUVIN234 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Adecaster LA-31 (manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN1130 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Adekastab AO-20 (manufactured by Asahi Denka Kogyo Co., Ltd.), Adekastab AO-50 (manufactured by Asahi Denka Kogyo Co., Ltd.), Adekastab 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.), Adekastab PEP-36 made by Asahi Denka Kogyo Co., Ltd. Examples include GM (Sumitomo Chemical Industry Co., Ltd.), Sumilyzer GS (Sumitomo Chemical Industry Co., Ltd.), and Sumilyzer TP-D (Sumitomo Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more. Among them, Sanol LS770, Irganox1010, Sumilyzer GS, and TINUVIN234 are preferable in terms of the effect of preventing deterioration of the acrylic block body due to heat and light and the cost.

&lt;Manufacturing method of thermoplastic elastomer composition&gt; Acrylic block copolymer (A) of the present invention, acrylic block copolymer (A) and crosslinked rubber (B), thermoplastic resin (C), thermoplastic elastomer (D), lubricant (E), The method for processing or producing a composition containing at least one selected from the group consisting of an inorganic filler (F) and a stabilizer (G) is not particularly limited, and for example, a Banbury mixer, a roll mill, a kneader, or a simple compound. Existing methods such as a method of mechanically mixing and shaping into pellets using a known device such as a shaft or multi-screw extruder can be used. The temperature at the time of kneading is the productivity and the acrylic block copolymer (A), crosslinked rubber (B), thermoplastic resin (C), thermoplastic elastomer (D), lubricant (E), stabilizer (G) to be used. ), The acrylic block copolymer (A) to be obtained, and the mechanical properties of the composition should be adjusted. For example, it can be produced by melt-kneading at 100 to 300 ° C. 130 to 300 ° C is more preferable, and 150 to 250 ° C is even more preferable. If it is lower than 100 ° C, the acrylic block copolymer (A) will not melt sufficiently, and the crosslinked rubber (B), thermoplastic resin (C), thermoplastic elastomer (D), lubricant (E), and inorganic filling will be insufficient. Kneading with the agent (F), stabilizer (G), etc. may become non-uniform. If the temperature is higher than 300 ° C, the acrylic block copolymer (A) itself may be decomposed.

Acrylic block copolymer (A), acrylic block copolymer (A) and crosslinked rubber (B), thermoplastic resin (C), thermoplastic elastomer (D), lubricant (E), inorganic filler The composition containing at least one selected from the group consisting of (F) and stabilizer (G) is a flexibility-imparting agent, flame-retardant agent, pigment, mold release agent, antistatic agent, antibacterial antifungal, if necessary. Agents, compatibilizers and the like may be added. The optimum additives may be appropriately selected according to the required physical properties, the intended use, and the like.

Examples of the flexibility-imparting agent include plasticizers usually blended in thermoplastic resins and rubbers; softeners such as process oils; oligomers; oils such as animal oils and vegetable oils; petroleum distillates such as kerosene, heavy oil, light oil, and naphtha. Examples include, but are not limited to, compounds such as fractions. Examples of the softening agent include process oils, and more specifically, paraffin oils; naphthenic process oils; petroleum-based process oils such as aromatic process oils.

Polyester plasticizer, which is a polymer of dibasic acids such as adipic acid, azelaic acid, and phthalic acid and glycol and monohydric alcohol, glucol derivative, glycerin derivative, paraffin derivative such as chlorinated paraffin, epoxy derivative polyester polymer type Plasticizers, polyether-based polymerizable plasticizers, carbonate derivatives such as ethylene carbonate and propylene carbonate, sulfonamide derivatives such as N-butylbenzenesulfonamide, N-ethyltoluenesulfonamide and N-cyclohexyltoluenesulfonamide; acrylic plasticizer Examples thereof include vinyl-based polymers obtained by polymerizing vinyl-based monomers such as agents by various methods. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those widely marketed as plasticizers for rubber or thermoplastic resins can also be used. Commercially available plasticizers include Thiocol TP (manufactured by Morton), Adeka Sizar O-130P, C-79, UL-100, P-200, RS-735 (manufactured by Asahi Denka Co., Ltd.), Sun Sosizer N. -400 (Shin Nihon Rika Co., Ltd.), BM-4 (Dahachi Chemical Industry Co., Ltd.), EHPB (Ueno Fine Chemicals Industry Co., Ltd.), UP-1000 (Toa Synthetic Co., Ltd.), etc. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, and tall oil. Examples thereof include vinyl-based polymers obtained by polymerizing vinyl-based monomers such as acrylic plasticizers by various methods. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those widely marketed as plasticizers for rubber or thermoplastic resins can also be used. Commercially available plasticizers include Thiocol TP (manufactured by Morton), Adeka Sizar O-130P, C-79, UL-100, P-200, RS-735 (manufactured by Asahi Denka Co., Ltd.), Sun Sosizer N. -400 (Shin Nihon Rika Co., Ltd.), BM-4 (Dahachi Chemical Industry Co., Ltd.), EHPB (Ueno Fine Chemicals Industry Co., Ltd.), UP-1000 (Toa Synthetic Co., Ltd.), etc. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, and tall oil. Examples thereof include vinyl-based polymers obtained by polymerizing vinyl-based monomers such as acrylic plasticizers by various methods. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those widely marketed as plasticizers for rubber or thermoplastic resins can also be used. Commercially available plasticizers include Thiocol TP (manufactured by Morton), Adeka Sizar O-130P, C-79, UL-100, P-200, RS-735 (manufactured by Asahi Denka Co., Ltd.), Sun Sosizer N. -400 (Shin Nihon Rika Co., Ltd.), BM-4 (Dahachi Chemical Industry Co., Ltd.), EHPB (Ueno Fine Chemicals Industry Co., Ltd.), UP-1000 (Toa Synthetic Co., Ltd.), etc. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, and tall oil.

It is preferable to use the flexibility-imparting agent having excellent affinity with the acrylic block copolymer (A), the crosslinked rubber (B), the thermoplastic resin (C), and the thermoplastic elastomer (D). Although not particularly limited, among these, adipic acid derivative, phthalic acid derivative, glutaric acid derivative, trimellitic acid derivative, pyromeritic acid derivative, polyester plasticizer, glycerin derivative, epoxy derivative, which are plasticizers having low volatility and low heat loss. Polyester-based polymerizable plasticizers, polyether-based polymerized plasticizers, acrylic-based plasticizers, and the like are preferably used. The above flexibility-imparting agents are for at least one type<u style="single">I</u>Can be

The flame retardants mentioned above include, but are not limited to, the following compounds: triphenylphosphine, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, antimony trioxide and the like. These may be used alone or in combination of two or more.

The pigments mentioned above include, but are not limited to, the following compounds: titanium oxide, zinc sulfide, zinc oxide and the like. These may be used alone or in combination of two or more.

The compatibilizers include Clayton series (manufactured by Shell Japan Co., Ltd.), Tough Tech series (manufactured by Asahi Kasei Kogyo Co., Ltd.), Dynaron (manufactured by Nippon Synthetic Rubber Co., Ltd.), and Epofriend (manufactured by Daicel Chemical Industry Co., Ltd.). ), Septon (manufactured by Claret Co., Ltd.), Nof Alloy (manufactured by Nippon Oil &amp; Fats Co., Ltd.), Lexpearl (manufactured by Nippon polyolefin Co., Ltd.), Bond First (manufactured by Sumitomo Chemical Co., Ltd.), Bondine (manufactured by Sumitomo Chemical Co., Ltd.) (Manufactured by Mitsui Chemicals Co., Ltd.), Admer (manufactured by Mitsui Chemicals Co., Ltd.), Umex (manufactured by Sanyo Kasei Kogyo Co., Ltd.), VMX (manufactured by Mitsubishi Chemical Co., Ltd.), Modiper (manufactured by Nippon Oil &amp; Fats Co., Ltd.), Staphyroid (Takeda) Commercial products such as Yakuhin Kogyo Co., Ltd. and Rezeta (Toa Synthetic Co., Ltd.) can be mentioned.

The acrylic block copolymer (A) of the present invention has a wide hardness range depending on the types of the constituent monomers, the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b), and the like. Those having low hardness and flexibility may be blocked when produced in the form of powder or pellets. Therefore, the acrylic block copolymer (A) of the present invention, the acrylic block copolymer (A), the crosslinked rubber (B), the thermoplastic resin (C), the thermoplastic elastomer (D), and the lubricant ( In a composition containing at least one selected from the group consisting of E), an inorganic filler (F), and a stabilizer (G), when produced in the form of powder or pellets, various lubricants are used to prevent blocking. It may be applied. Specific examples of the lubricant include the above-mentioned lubricant (E), calcium carbonate, talc, kaolin, alumina, aluminum hydroxide, acrylic polymer fine particles, and the like. It is preferably at least one selected from these groups. Calcium carbonate and talc are preferable from the viewpoint of cost, and especially when the methacrylate-based polymer block (a) in the methacrylic block copolymer uses methyl methacrylate as a main component, a methyl polymethacrylic acid resin. It is preferable to use the powder as a lubricant because the effect of the addition of the lubricant on the product properties is hardly considered.

In the present invention, as a method of applying a lubricant to the powder or pellet, the powder or pellet may be produced without the lubricant, and the lubricant may be applied to the obtained powder or pellet, or the lubricant may be applied at the same time in the powder or pellet manufacturing process. You may.

As a method of producing pellets without a lubricant and applying the lubricant to the obtained pellets, a method of dispersing the polymer pellets in a solvent containing a lubricant, a method of spraying a solvent containing a lubricant on the pellets, or a method of spraying the pellets with a solvent containing a lubricant can be used. Examples include a method of directly mixing pellets and lubricants. Further, as a method of applying at the same time in the pellet manufacturing process, for example, an underwater cut method and a strand cut method can be mentioned. In pellet production by the underwater cut method, it may be necessary to prevent blocking of pellets near the die and cutter. In this case, since the polymer is cut in the circulating cooling water, the blocking property can be improved by adding one or more lubricants to the circulating cooling water. Further, in the strand cut method, the resin discharged from the die has a high temperature, and a general method is to cool the strands in the aqueous phase, solidify the resin, and then cut the resin. It is also possible to exhibit the blocking prevention effect of pellets by adhering the lubricant to the surface by adding and dispersing the lubricant and immersing the strands in the aqueous phase.

&lt;Automotive, electrical / electronic parts&gt; The acrylic block copolymer (A) of the present invention, the acrylic block copolymer (A), the crosslinked rubber (B), the thermoplastic resin (C), the thermoplastic elastomer (D), and the lubricant (E). The composition containing at least one selected from the group consisting of an inorganic filler (F) and a stabilizer (G) has oil resistance and heat resistance while maintaining the original characteristics of the acrylic block copolymer. Due to its improved thermal decomposition resistance, weather resistance, mechanical properties, compression set, etc., automobiles, electrical and electronic parts, such as automobile seal products, household electric product seal products, office electric product seal products Can be used more preferably. The sealing product of the present invention has excellent oil resistance, heat resistance, etc., and is superior in simplification and recyclability of the molding process as compared with conventional sealing products such as vulcanized rubber type, and is olefin type. It can have better oil resistance and weather resistance as compared with thermoplastic elastomers.

Specifically, the types are various oil seals such as oil seals and reciprocating oil seals, various packings such as gland packing, lip packing, and squeeze packing, constant velocity joint boots, strut boots, rack &amp; opinion boots, and brakes. Various boots such as booster boots and steering ball joint boots, dust covers for suspensions, dust covers for suspension tie rods, dust covers for stabilizers and die rods, resin intake manifold gaskets, gaskets for throttle bodies, power steering Vane pump gasket, head cover gasket, water dispenser self-contained pump gasket, filter gasket, pipe joint (ABS &amp; HBB) gasket, HDD top cover gasket, HDD connector gasket, cylinder head gasket combined with metal, car cooler compressor Various gaskets such as gaskets, engine peripheral gaskets, AT separate plates, general-purpose gaskets (industrial sewing machines, nailers, etc.), needle valves, plunger valves, water / gas valves, brake valves, drinking valves, aluminum electrolytic capacitors. Various valves such as safety valves, diaphragms for vacuum boosters and water / gas, seal washers, bore plugs, various stoppers mainly for cushioning performance such as high-precision stoppers, plug tube seals, injection pipe seals, oil receivers , Brake drum seals, light-shielding seals, plug seals, connector seals, keyless entry covers and other precision seal rubbers. In addition, various weather strips such as door weather strips for automobile supplies, trunk seals, and seal products such as glass run channels can be mentioned.

Acrylic block copolymer (A), acrylic block copolymer (A), crosslinked rubber (B), thermoplastic resin (C), thermoplastic elastomer (D), lubricant (E), inorganic filling Compositions containing at least one selected from the group consisting of agents (F) and stabilizers (G) are used in fields such as packaging materials, construction, civil engineering materials, and miscellaneous goods, in addition to automobiles and electrical / electronic parts. It can be widely and suitably used as a hose, a sheet, a film material, a vibration damping material, a vibration isolating material, a grip, a cushioning material, an adhesive base polymer, a resin modifier, and the like.

For molding of the product, the acrylic block copolymer (A) or its composition is extruded, compression molded, blow molded, calendar molded, vacuum molded, foam molded, injection molded, powder slush molded, injection blow. It can be molded by any molding method such as. Of these, injection molding is preferable because it is simple.

Next, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

In the examples, BA, EA, MEA, 2EHA, MMA, TBMA, and TBA are n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate, respectively. Represents t-butyl metaacrylate and t-butyl acrylate.

&lt;Test method&gt; (Molecular weight) The molecular weight shown in this example was measured by the GPC analyzer shown below, and GPC measurement was performed using a polystyrene gel column using chloroform as a mobile phase to determine the polystyrene-equivalent molecular weight. GPC measurement was performed with a GPC analyzer (system: GPC system manufactured by Wacker (Waters), column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK). Chloroform was used as the mobile phase, and the polystyrene-equivalent molecular weight was determined.

(Acid anhydride group conversion analysis) The acid anhydride group conversion reaction of the acrylic block copolymer was confirmed using an infrared spectrum (FTIR-8100, manufactured by Shimadzu Corporation) and a nuclear magnetic resonance (AM400, manufactured by BRUKER).

As a solvent for nuclear magnetic resonance analysis, deuterated chloroform was used for the block body having a carboxylic acid ester structure, and deuterated acetone was used for the block body containing an acid anhydride group.

(Carboxyl group conversion analysis) The carboxyl group conversion reaction of the acrylic block copolymer was confirmed using infrared spectrum (FTIR-8100, manufactured by Shimadzu Corporation) and nuclear magnetic resonance (AM400, manufactured by BRUKER).

As a solvent for nuclear magnetic resonance analysis, deuterated chloroform was used for the block body having a carboxylic acid ester structure, and deuterated methanol was used for the block body containing a carboxyl group.

(hardness) The hardness at 23 ° C (immediately after, JIS A) was measured according to JIS K6253. However, if the hardness exceeds 90 by the type A durometer, it was measured by the type D durometer (JIS D).

(Mechanical strength) The measurement was performed using the Autograph AG-10TB type manufactured by Shimadzu Corporation, applying the method described in JIS K7113 mutatis mutandis. The measurement was performed at n = 3, and the average value of the strength (MPa) and elongation (%) values when the test piece broke was adopted. The test piece used was a 2 (1/3) shape with a thickness of about 2 mm. The test was performed at a test speed of 500 mm / min at 23 ° C. As a general rule, the test piece used was adjusted to a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5% for 48 hours or more before the test.

(Compressive permanent strain) In accordance with JIS K6301, hold the cylindrical molded product at 70 ° C, 100 ° C or 120 ° C for 22 hours or 72 hours under the condition of a compression ratio of 25%, leave it at 23 ° C for 30 minutes, and then mold it. The body thickness was measured and the residual strain was calculated. That is, it corresponds to the fact that the compression set is 0% and the strain is completely recovered, and the compression set is 100% and the strain is not recovered at all.

(Oil resistance) The weight change rate (% by weight) was determined by immersing the molded product of the composition in ASTM Oil No. 3 kept at 150 ° C for 72 hours in accordance with ASTM D638.

In addition, the shape after immersion was evaluated according to the following criteria. Shape: Retention = , Slightly swelling = ~ , Swelling = , Severe swelling or partial dissolution = ×, Complete dissolution = XX

(Heat-resistant) This was done by comparing the flow start temperatures. The flow start temperature is 60 kgf / cm with a load of resin heated at a heating rate of 5 ° C / min using a high-grade flow tester CFT-500C manufactured by Shimadzu Corporation.²Under the above conditions, the temperature at which the resin extrusion piston of the flow tester clearly begins to drop when extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm (indicated as Tfb in this measuring instrument).

(Thermogravimetric analysis) The heat-decomposability of the acrylic block copolymer was measured with a differential thermogravimetric simultaneous measuring device (DTG-50) manufactured by Shimadzu Corporation (SHIMADZU). The measurement was performed under a nitrogen flow rate of 50.0 ml / min and a heating rate of 10.0 ° C / min. The 5% weight loss temperature was determined based on the weight at 100 ° C.

(Insoluble fraction (% by weight)) Insoluble content (% by weight) is obtained by wrapping 1 g (Wu) of a sample in a 100 mesh wire mesh and immersing it in toluene at 80 ° C or acetone at 60 ° C for 24 hours (toluene or acetone is an acrylic block copolymer). (Select the one that is soluble), toluene or acetone soluble content is separated, the residual solid content is vacuum dried at 60 ° C, and the weight g (Wc) of the residual solid content after drying is measured to measure the sample. For 1g (Wu)<u style="single">Remaining</u>It was determined from the weight of the retained solid content (Wc). The progress of the reaction can be confirmed from the insoluble fraction (% by weight).

(Friction) In accordance with JIS K7215, in order to measure the frictional property due to rubbing between the same materials, a 2 mm thick sheet was cut into a shape of 20 x 20 mm as a mating material and 80 x 200 mm as a test piece, and SURFACE PROPERTY TESTER (HEIDON TYPE) The dynamic friction coefficient was calculated using: 14DR). The test conditions were a load of 100 gf and a speed of 50 mm / min. When it was not possible to measure due to strong adhesiveness, etc., it was judged as x.

(Recyclability) The sheet obtained for evaluation of the tensile properties and the like is kneaded again with a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) at the processing temperature used to prepare the sheet, and press processing is performed at each temperature. I did.

In the evaluation of recyclability, if the same sheet as before kneading is obtained, it is judged that the recyclability is good, and if the same sheet as before kneading is not obtained, the recyclability is judged to be poor. It was judged as x.

(Low temperature embrittlement) In accordance with JIS K7216, a 2 mm thick molded sheet was cut into 38 x 6 mm and the low temperature embrittlement temperature was measured with a low temperature embrittlement temperature measuring device (manufactured by Toyo Seiki Co., Ltd.).

(Workability) The 2 mm-thick molded sheet obtained for evaluating the tensile properties and the like was finely pelletized, and the processing temperature with respect to the melt viscosity (1500 poise) was measured with a capillograph (manufactured by Toyo Seiki Co., Ltd.). The measurement conditions are as follows. Capillary length 10 mm, capillary diameter 1 mm, barrel diameter 9.55 mm.

&lt;Manufacturing of acrylic block copolymer&gt; Manufacturing example 1 (MMA-co-TBMA) -b-BA-b- (MMA-co-TBMA) (MMA / TBMA = 50 / 50mol%, BA / (MMA-co-TBMA) = 70/30% by weight) type acrylic Synthesis of block copolymer (hereinafter referred to as 50TBA7) The following operations were performed to obtain 50 TBA7. After replacing the inside of the polymerization vessel of the 5 L separable flask with nitrogen, 11.3 g (78.5 mmol) of copper bromide was weighed, and 180 mL of acetonitrile (nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, 5.65 g (15.7 mmol) of diethyl 2,5-dibromoadipate and 900 ml (6.28 mol) of BA were added. The mixture was heated and stirred at 85 ° C, and 1.64 ml (7.85 mmol) of the ligand diethylenetriamine was added to initiate polymerization.

At regular intervals from the start of polymerization, about 0.2 mL of the polymerization solution was withdrawn from the polymerization solution for sampling, and the conversion rate of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. At a BA conversion of 95%, add TBMA 351 ml (2.16 mol), MMA 232 ml (2.16 mol), copper chloride 7.77 g (78.5 mmol), diethylenetriamine 1.64 ml (7.85 mmol) and toluene (nitrogen bubbling) 1148 ml. It was. Similarly, the conversion rates of TBMA and MMA were determined. When the conversion rate of TBMA was 70% and the conversion rate of MMA was 62%, 1500 ml of toluene was added and the reactor was cooled in a water bath to terminate the reaction.

The reaction solution was diluted with 2.0 L of toluene, 17.9 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. 12.0 g of the adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the polymer solution, and the mixture was further stirred at room temperature for 3 hours. The adsorbent was filtered through a Kiriyama funnel to obtain a colorless and transparent polymer solution. This solution was dried to remove the solvent and residual monomers to obtain the desired acrylic block copolymer 50TBA7.

GPC analysis of the obtained acrylic block copolymer 50TBA7 revealed that the number average molecular weight Mn was 108240 and the molecular weight distribution Mw / Mn was 1.49.

Manufacturing example 2 (MMA-co-TBMA) -b-BA-b- (MMA-co-TBMA) (MMA / TBMA = 95 / 5mol%, BA / (MMA-co-TBMA) = 70/30% by weight) type acrylic Synthesis of block copolymer (hereinafter referred to as 5TBA7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.80 g (16.1 mmol) of diethyl 2,5-dibromoadipate and 900 ml (6.28 mol) of BA, and when the conversion rate of BA was 95%, TBMA was 40.9 ml (16.1 mmol). 0.25 mol) and MMA 512.6 ml (4.82 mol) were added. The reaction was terminated when the conversion rate of TBMA was 60% and the conversion rate of MMA was 57%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 5TBA7.

GPC analysis of the obtained acrylic block copolymer 5TBA7 revealed that the number average molecular weight Mn was 107312 and the molecular weight distribution Mw / Mn was 1.58.

Manufacturing example 3 (MMA-co-TBMA) -b-BA-b- (MMA-co-TBMA) (MMA / TBMA = 80 / 20mol%, BA / (MMA-co-TBMA) = 70/30% by weight) type acrylic Synthesis of block copolymer (hereinafter referred to as 20TBA7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.65 g (15.7 mmol) of diethyl 2,5-dibromoadipate and 900 ml (6.28 mol) of BA, and TBMA 151.9 ml (TBMA 151.9 ml) when the conversion rate of BA was 95%. 0.94 mol) and MMA 400.9 ml (3.77 mol) were added. The reaction was terminated when the conversion rate of TBMA was 70% and the conversion rate of MMA was 64%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 20TBA7.

GPC analysis of the obtained acrylic block copolymer 20TBA7 revealed that the number average molecular weight Mn was 122858 and the molecular weight distribution Mw / Mn was 1.46.

Manufacturing example 4 Synthesis of TBMA-b-BA-b-TBMA (BA / TBMA = 70/30% by weight) type acrylic block copolymer (hereinafter referred to as 100TBA7) Polymerization was carried out using a 2 L separable flask at a charging ratio of 2.26 g (6.3 mmol) of diethyl 2,5-dibromoadipate and 360 ml (2.51 mol) of BA. When the conversion rate of BA was 95%, 243 ml (1.50 mol) of TBMA was used. ) Was added. The reaction was terminated when the conversion rate of TBMA was 70% and the conversion rate of MMA was 68%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 100TBA7.

GPC analysis of the obtained acrylic block copolymer 100TBA7 revealed that the number average molecular weight Mn was 95491 and the molecular weight distribution Mw / Mn was 1.44.

Manufacturing example 5 (MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 95 / 5mol%, (BA-co-EA-co- Synthesis of MEA) / (MMA-co-TBMA) = 70/30% by weight) type acrylic block copolymer (hereinafter referred to as 5T3A7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 6.04 g (16.8 mmol) of diethyl 2,5-dibromoadipate, 362 ml (2.52 mol) of BA, 344 ml (3.17 mol) of EA, and 195 ml (1.51 mol) of MEA. When the conversion rate was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 97%, 42.5 ml (0.26 mol) of TBMA and 534 ml (5.02 mol) of MMA were added. The reaction was terminated when the conversion rate of TBMA was 63% and the conversion rate of MMA was 58%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 5T3A7.

GPC analysis of the obtained acrylic block copolymer 5T3A7 revealed that the number average molecular weight Mn was 12400 and the molecular weight distribution Mw / Mn was 1.45.

Manufacturing example 6 (MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 80 / 20mol%, (BA-co-EA-co- Synthesis of MEA) / (MMA-co-TBMA) = 70/30% by weight) type acrylic block copolymer (hereinafter referred to as 20T3A7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.89 g (16.4 mmol) of diethyl 2,5-dibromoadipate, 362 ml (2.52 mol) of BA, 344 ml (3.17 mol) of EA, and 195 ml (1.51 mol) of MEA. When the conversion rate was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 97%, 158 ml (0.98 mol) of TBMA and 418 ml (3.92 mol) of MMA were added. The reaction was terminated when the conversion rate of TBMA was 64% and the conversion rate of MMA was 59%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 20T3A7.

GPC analysis of the obtained acrylic block copolymer 20T3A7 revealed that the number average molecular weight Mn was 111000 and the molecular weight distribution Mw / Mn was 1.47.

Manufacturing example 7 (MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 80 / 20mol%, (BA-co-EA-co- Synthesis of MEA) / (MMA-co-TBMA) = 60/40% by weight) type acrylic block copolymer (hereinafter referred to as 20T3A6) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.31 g (14.8 mmol) of diethyl 2,5-dibromoadipate, 281 ml (1.96 mol) of BA, 267 ml (2.47 mol) of EA, and 151 ml (1.18 mol) of MEA. When the conversion rate was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 97%, 193 ml (1.20 mol) of TBMA and 509 ml (4.78 mol) of MMA were added. The reaction was terminated when the conversion rate of TBMA was 64% and the conversion rate of MMA was 61%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic-based acrylic block copolymer 20T3A6.

GPC analysis of the obtained acrylic block copolymer 20T3A6 revealed that the number average molecular weight Mn was 118927 and the molecular weight distribution Mw / Mn was 1.49.

Manufacturing example 8 (MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 50 / 50mol%, (BA-co-EA-co- Synthesis of MEA) / (MMA-co-TBMA) = 60/40% by weight) type acrylic block copolymer (hereinafter referred to as 50T3A6) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.31 g (14.8 mmol) of diethyl 2,5-dibromoadipate, 281 ml (1.96 mol) of BA, 267 ml (2.47 mol) of EA, and 151 ml (1.18 mol) of MEA. When the conversion rate was 95%, the conversion rate of EA was 95%, and the conversion rate of MEA was 98%, 435 ml (2.70 mol) of TBMA and 287 ml (2.70 mol) of MMA were added. The reaction was terminated when the conversion rate of TBMA was 67% and the conversion rate of MMA was 59%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 50T3A6.

GPC analysis of the obtained acrylic block copolymer 50T3A6 revealed that the number average molecular weight Mn was 96778 and the molecular weight distribution Mw / Mn was 1.46.

Manufacturing example 9 TBMA-b- (BA-co-EA-co-MEA) -b-TBMA ((BA-co-EA-co-MEA) / TBMA = 60/40% by weight) type acrylic block copolymer (hereinafter 100T3A6) ) Synthesis Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.69 g (15.8 mmol) of diethyl 2,5-dibromoadipic acid, 301 ml (2.10 mol) of BA, 286 ml (2.64 mol) of EA, and 162 ml (1.26 mol) of MEA. When the conversion rate was 96%, the conversion rate of EA was 96%, and the conversion rate of MEA was 98%, 636 ml (3.94 mol) of TBMA was added. The reaction was terminated when the conversion rate of TBMA was 77%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 100T3A6.

GPC analysis of the obtained acrylic block copolymer 100T3A6 revealed that the number average molecular weight Mn was 90416 and the molecular weight distribution Mw / Mn was 1.43.

Manufacturing example 10 TBMA-b- (BA-co-MEA) -b-TBMA (BA / MEA = 50 / 50mol%, (BA-co-MEA) / TBMA = 60/40 (% by weight)) type block copolymer (hereinafter , Described as 100T2A6) Polymerization was performed using a 5 L separable flask at a charging ratio of 5.45 g (15.1 mmol) of diethyl 2,5-dibromoadipate, 369 ml (2.57 mol) of BA, and 331 ml (2.57 mol) of MEA, and the conversion rate of BA was 94%. , TBMA 503 ml (3.10 mol) was added when the conversion rate of MEA was 97%. The reaction was terminated when the conversion rate of TBMA was 72%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target block copolymer (100T2A6).

GPC analysis of the obtained block copolymer (100T2A6) revealed that the number average molecular weight (Mn) was 80400 and the molecular weight distribution (Mw / Mn) was 1.55.

Production example 11 (MMA-co-TBMA) -b- (BA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 60 / 40mol%, BA / MEA = 67 / 33mol%<u style="single">、(</u>Synthesis of BA-co-MEA) / (MMA-co-TBMA) = 65/35 wt%) type block copolymer (hereinafter referred to as 40T2A'6.5) Polymerization was performed using a 5 L separable flask at a charging ratio of 5.34 g (14.8 mmol) of diethyl 2,5-dibromoadipate, 518 ml (3.61 mol) of BA, and 232 ml (1.80 mol) of MEA, and the conversion rate of BA was 95%. , TBMA 311 ml (1.93 mol) and MMA 308 ml (2.90 mol) were added when the conversion rate of MEA was 97%. The reaction was terminated when the conversion rate of TBMA was 68% and the conversion rate of MMA was 62%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target block copolymer (40T2A'6.5).

GPC analysis of the obtained block copolymer (40T2A'6.5) revealed that the number average molecular weight Mn was 102500 and the molecular weight distribution Mw / Mn was 1.36.

Manufacturing example 12 (MMA-co-TBMA) -b- (BA-co-2EHA) -b- (MMA-co-TBMA) (MMA / TBMA = 50 / 50mol%, BA / 2EHA = 70/30% by weight, (BA- Synthesis of co-2EHA) / (MMA-co-TBMA) = 80/20% by weight) type acrylic block copolymer (hereinafter referred to as 50TEBA8) Polymerization was performed using a 5 L separable flask at a charging ratio of 5.55 g (15.4 mmol) of diethyl 2,5-dibromoadipate, 696 ml (4.85 mol) of BA, and 304 ml (1.46 mol) of 2EHA, and the conversion rate of BA was 95%. When the conversion rate of 2EHA was 95%, 126 ml (1.39 mol) of TBMA and 124 ml (1.39 mol) of MMA were added. The reaction was terminated when the conversion rate of TBMA was 83% and the conversion rate of MMA was 80%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 50TEBA8.

GPC analysis of the obtained acrylic block copolymer 50TEBA8 revealed that the number average molecular weight Mn was 95830 and the molecular weight distribution Mw / Mn was 1.34.

Production example 13 Synthesis of MMA-BA-MMA (BA / MMA = 70/30% by weight) type acrylic block copolymer (hereinafter abbreviated as BA7) The following operations were performed to obtain BA7.

After replacing the inside of the polymerization vessel of the 5 liter separable flask with nitrogen, 11.3 g (78.5 mM) of copper bromide was weighed, and 180 mL of acetonitrile (dried with Molecular Sieves 3A and then nitrogen bubbling) was added. After heating and stirring at 70 ° C for 5 minutes, the mixture was cooled to room temperature again, and the initiator 2,5-dibromoadipate diethyl 5.7 g (15.7 mM) and acrylate-n-butyl 804.6 g (900.0 ml) were added. .. The mixture was heated and stirred at 80 ° C., and 1.6 ml (7.9 mM) of the ligand diethylenetriamine was added to initiate polymerization. At regular intervals from the start of polymerization, about 0.2 ml of the polymerization solution was withdrawn from the polymerization solution for sampling, and the conversion rate of butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of -n-butyl acrylate is 95%, methyl methacrylate 345.7 g (369.3 ml), copper chloride 7.8 g (78.5 m mol), diethylene triamine 1.6 ml (7.9 m mol), toluene (molecular sieves) After drying at 3A and bubbling with nitrogen) 1107.9 ml was added. Similarly, the conversion rate of methyl methacrylate was determined. When the conversion rate of methyl methacrylate was 85% and the conversion rate of butyl acrylate-n-ate was 98%, 1500 ml of toluene was added and the reactor was cooled in a water bath to terminate the reaction. The polymerization solution was always green during the reaction.

The reaction solution was diluted with 4000 mL of toluene, 22.1 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 23 ° C. for 3 hours. After removing the precipitated insoluble part by filtering with a Kiriyama funnel, 9.7 g of the adsorbent Kyoward 500SH was added to the polymer solution, and the mixture was further stirred at 23 ° C. for 3 hours. The adsorbent was filtered through a Kiriyama funnel to obtain a colorless and transparent polymer solution. The solution was dried to remove the solvent and residual monomers to give the desired BA7.

When the obtained BA7 was analyzed by GPC, the number average molecular weight Mn was 119200 and the molecular weight distribution Mw / Mn was 1.51. Moreover, when the composition analysis by NMR was performed, it was BA / MMA = 72/28 (% by weight).

Production example 14 MMA-b- (BA-co-EA-co-MEA) -b-MMA ((BA-co-EA-co-MEA) / MMA = 70/30% by weight) type acrylic block copolymer (hereinafter 3A7) (Abbreviated as) The following operations were performed to obtain 3A7.

Using a 500 mL separable flask, 1.37 g (9.5 mmol) of copper bromide, 20 mL of acetonitrile (nitrogen bubbling), 0.69 g (1.9 mmol) of diethyl dibromoadipate, 40.2 ml (280 mmol), After adding 38.2 ml (352 mmol) of EA and 21.6 ml (168 mmol) of MEA in the same procedure as in Example 1, 0.20 ml (1.0 mmol) of the ligand diethylenetriamine was added to initiate the polymerization.

MMA 42.8 ml (400 mmol), copper chloride 1.82 g (18.5 mmol), diethylenetriamine 0.20 ml (1.0 mmol) at a BA conversion rate of 95%, an EA conversion rate of 95% and a MEA conversion rate of 96%. ) And 128.5 ml of toluene (nitrogen bubbling) were added, and when the conversion rate of BA was 97%, the conversion rate of EA was 97%, the conversion rate of MEA was 98%, and the conversion rate of MMA was 82%, toluene was added. 150 ml was added and the reactor was cooled in a water bath to terminate the reaction.

The reaction solution was diluted with 400 mL of toluene, 2.21 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 23 ° C. for 3 hours. After removing the precipitated insoluble part by filtering with a Kiriyama funnel, 0.97 g of the adsorbent Kyoward 500SH was added to the polymer solution, and the mixture was further stirred at 23 ° C. for 3 hours. The adsorbent was filtered through a Kiriyama funnel to obtain a colorless and transparent polymer solution. The solution was dried to remove the solvent and residual monomers to give the desired 3A7.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 113000 and the molecular weight distribution Mw / Mn was 1.49. When the composition was analyzed, it was EA / BA / MEA / MMA = 24/33/15/28 (% by weight).

Production example 15 MMA-b- (BA-co-MEA) -b-MMA (BA / MEA = 67 / 33mol%)<u style="single">、(</u>Synthesis of BA-co-MEA) /MMA=65/35% by weight) type block copolymer (hereinafter referred to as 2A'6.5) After replacing the 5 L separable flask with nitrogen, weigh 10.4 g (72.2 mmol) of copper bromide, 10.4 g (28.9 mmol) of diethyl 2,5-dibromoadipate, BA691 ml (4.82 mol), MEA 309 ml (2.41 mol), 100 ml (1.91 mol) of acetonitrile was added, and the mixture was heated and stirred at 85 ° C. for 30 minutes, and 1.64 ml (7.85 mmol) of the ligand diethylenetriamine was added to initiate polymerization. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA was 97% and the conversion rate of MEA was 98%, 1050 ml (9.86 mol) of toluene, 7.15 g (72.2 mmol) of copper chloride, and 535 ml (5.00 mol) of MMA were added. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of MMA was 89%, 1500 ml of toluene was added and cooled to terminate the reaction.

The reaction solution was diluted with 4.0 l of toluene, 20.6 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours, and then the solid content was filtered through a Kiriyama funnel. To the obtained polymer solution, 14.4 g of the adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The adsorbent was filtered through a Kiriyama funnel to obtain a colorless and transparent polymer solution. This solution was dried to remove the solvent and residual monomers to obtain the desired acrylic block copolymer 2A'6.5.

GPC analysis of the obtained block copolymer (2A'6.5) revealed that the number average molecular weight Mn was 71416 and the molecular weight distribution Mw / Mn was 1.40.

Manufacturing example 16 MMA-b- (BA-co-2EHA) -b-MMA (BA / 2EHA = 70/30% by weight, (BA-co-2EHA) / MMA = 80/20% by weight) type acrylic block copolymer ( Synthesis of (hereinafter referred to as EBA8) Polymerization was performed using a 5 L separable flask at a charging ratio of 5.55 g (15.4 mmol) of diethyl 2,5-dibromoadipate, 695 ml (4.85 mol) of BA, and 305 ml (1.46 mol) of 2EHA, and the conversion rate of BA was 95%. 2 MMA 299 ml (3.35 mol) was added when the conversion of EHA was 95%. The reaction was terminated when the conversion rate of MMA was 70%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer EBA8.

GPC analysis of the obtained acrylic block copolymer EBA8 revealed that the number average molecular weight Mn was 109184 and the molecular weight distribution Mw / Mn was 1.33.

Production example 17 Synthesis of 50TBA7-B1 A solution in which 6272 g of acetonitrile and 8940 g of BA and 8940 g were mixed in advance was charged into a 500 L reactor vacuum devolatile after nitrogen substitution in a state where the inside of the reactor was depressurized. Next, 813.7 g of cuprous bromide was charged, the temperature was raised to 68 ° C, and the mixture was stirred for 30 minutes. Then, a mixed solution of BA, 57216.0 g and butyl acetate 1305.4 g, and a solution prepared by dissolving 408.4 g of diethyl 2,5-dibromoadipate in acetonitrile 3528.0 g were prepared, and the mixture was stirred for another 30 minutes while raising the temperature to 75 ° C. Was done. 98.2 g of pentamethyldiethylenetriamine was added to initiate the polymerization of butyl acrylate, which is the first block. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA reached 95%, toluene 100249.6g, cuprous chloride 561.5g, MMA, 17459.8g, TBMA, 24797.4g were added, and pentamethyldiethylenetriamine 98.2g was added to form the second block of MMA. / TBMA copolymerization was started. When the conversion of MMA reached 58%, 77940 g of toluene was added to dilute the reaction solution and the reactor was cooled to terminate the polymerization. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 104800 and the molecular weight distribution Mw / Mn was 1. It was 25. Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 25 wt%, and 728 g of p-toluenesulfonic acid was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled and neutralized, and the reaction was stopped after confirming that the solution was colorless and transparent. After that, the solution was discharged and solid-liquid separation was performed to remove the solid content. To this block copolymer solution, 1200 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 1 hour. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. After that, the solution was discharged and solid-liquid separation was performed to remove the adsorbent. The polymer was isolated by supplying the above polymer solution to a horizontal evaporator with a vent port (Kurimoto, Ltd., horizontal evaporator SCP-100) and evaporating the solvent and unreacted monomer. The temperature of the body jacket and screw of the evaporator was adjusted to 180 ° C with a heat medium, and the inside of the evaporator was kept under reduced pressure of about 0.01 MPa or less by a vacuum pump. In this way, pellets of the title block copolymer were prepared.

Production example 18 Synthesis of 20T3A6.8-B1 After nitrogen substitution, a solution prepared by premixing 7056 g of acetonitrile and 8046 g of BA was charged into a vacuum devolatile 500 L reactor in a state where the inside of the reactor was depressurized. Next, 851.5 g of cuprous bromide was charged, the temperature was raised to 68 ° C, and the mixture was stirred for 30 minutes. Then, a mixed solution of BA, 14588.8 g, EA, 22226.9 g, MEA, 13789.9 g and butyl acetate 1111.3 g, and a solution prepared by dissolving 427.4 g of diethyl 2,5-dibromoadipate in 2822.4 g of acetonitrile were charged and 75 ° C. Stirring was performed for another 30 minutes while raising the temperature to C. 102.9 g of pentamethyldiethylenetriamine was added to initiate the copolymerization of BA / EA / MEA, which is the first block. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA reaches 95%, 96202.9 g of toluene, 587.7 g of cuprous chloride, MMA, 30513.5 g, TBMA, 10834.2 g are added, and 102.9 g of pentamethyldiethylenetriamine is added to form the second block of MMA. / TBMA copolymerization was started. When the conversion of MMA reached 59%, 69280 g of toluene was added to dilute the reaction solution and the reactor was cooled to terminate the polymerization. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 95900 and the molecular weight distribution Mw / Mn was 1. It was 36. Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 24 wt%, and 847 g of p-toluenesulfonic acid was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled and neutralized, and the reaction was stopped after confirming that the solution was colorless and transparent. After that, the solution was discharged and solid-liquid separation was performed to remove the solid content. To this block copolymer solution, 940 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 2 hours. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. Other than that, pellets of the title block copolymer were prepared in the same manner as in Production Example 17.

Manufacturing example 19 Synthesis of 20T3A6.8-B2 A solution prepared by mixing BA, 32694.7 g, EA, 32105.6 g, MEA, 19918.7 g, acetonitrile 2430.4 g and butyl acetate 1605.2 g in a vacuum devolatile 500 L reactor after nitrogen substitution was placed in the reactor. It was charged under reduced pressure. Next, 615.0 g of cuprous bromide was charged and stirred for 15 minutes. Then, a solution prepared by dissolving 617.4 g of diethyl 2,5-dibromoadipate in 4704.0 g of acetonitrile was prepared, and the mixture was further stirred for 50 minutes while raising the temperature to 75 ° C. 74.3 g of pentamethyldiethylenetriamine was added to initiate the copolymerization of BA / EA / MEA, which is the first block. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA reaches 96%, add toluene 73751.1 g, cuprous chloride 424.4 g, MMA, 29530.3 g, TBMA, 10485.1 g, and add pentamethyldiethylenetriamine 74.3 g to form the second block of MMA. / TBMA copolymerization was started. The polymerization rate was controlled by adding triamine as needed. When the conversion of MMA reached 91%, 220,000 g of toluene was added to dilute the reaction solution and the reactor was cooled to terminate the polymerization. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 110200 and the molecular weight distribution Mw / Mn was 1. It was 27. Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 25 wt%, and 1468 g of p-toluenesulfonic acid was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sampled and neutralized, and the reaction was stopped after confirming that the solution was colorless and transparent. After that, the solution was discharged and solid-liquid separation was performed to remove the solid content. To this block copolymer solution, 1680 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the inside of the reactor was replaced with nitrogen, and the mixture was stirred at room temperature for 1 hour. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. Other than that, pellets of the title block copolymer were prepared in the same manner as in Production Example 17.

Production example 20 Synthesis of 20T3A6-B1 Polymerization was performed at a charging ratio of 371.8 g of diethyl 2,5-dibromoadipate, BA17604.8, EA17287.6 g, and MEA10725.4 g, and when the conversion rate of BA reached 95%, MMA33333.3 g and TBMA11835.4 g were added. did. The reaction was terminated when the conversion rate of MMA reached 58%. Other than that, the same production as in Production Example 18 was carried out to prepare pellets of the title block copolymer. GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 103400 and the molecular weight distribution Mw / Mn was 1.36.

Production example 21 Synthesis of 50T3A6.5-B1 Polymerization was performed at a preparation ratio of diethyl 2,5-dibromoadipate (483.0 g, BA24431.2, EA23991.0 g, MEA14884.3 g), and when the conversion rate of BA reached 95%, MMA21046.7 g and TBMA29891.6 g were added. did. The reaction was terminated when the conversion rate of MMA reached 58% . Other than that, the same production as in Production Example 18 was carried out to prepare pellets of the title block copolymer.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 98900 and the molecular weight distribution Mw / Mn was 1.28.

Production example 22 Synthesis of 50T3A6-B1 Polymerization was carried out at a charging ratio of 424.9 g of diethyl 2,5-dibromoadipate, BA20119.8 g, EA19757.3 g, and MEA12257.7 g, and when the BA conversion rate reached 94%, MMA21516.7 g and TBMA30559.2 g were added. did. The reaction was terminated when the conversion rate of MMA reached 56%. Other than that, the same production as in Production Example 18 was carried out to prepare pellets of the title block copolymer. GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 101200 and the molecular weight distribution Mw / Mn was 1.28.

Production example 23 Synthesis of 40T2A'6.5-B1 Polymerization was carried out at a charging ratio of 421.7 g of diethyl 2,5-dibromoadipate, BA37031.5 g and MEA18800.7 g, and when the conversion rate of BA reached 95%, MMA23103.6 g and TBMA21875.3 g were added. The reaction was terminated when the conversion rate of MMA reached 61%. Other than that, the same production as in Production Example 19 was carried out to prepare pellets of the title block copolymer.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 93700 and the molecular weight distribution Mw / Mn was 1.36.

Production example 24 Synthesis of 50TEBA8-B1 Polymerization was carried out at a charging ratio of 377.1 g of diethyl 2,5-dibromoadipate, BA42289.3 g, and 2EHA18337.1 g, and when the conversion rate of BA reached 95%, MMA7865.0 g and TBMA11170.3 g were added. The reaction was terminated when the conversion rate of MMA reached 71%. Other than that, the same production as in Production Example 18 was carried out to prepare pellets of the title block copolymer.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 91800 and the molecular weight distribution Mw / Mn was 1.29.

Production example 25 Synthesis of BA7-B1 Synthesis was carried out in a 500 L reactor, polymerization was carried out at a charging ratio of 339.0 g of diethyl 2,5-dibromoadipate and BA48276.0 g, and MMA31094.8 g was added when the conversion rate of BA reached 96%. The reaction was terminated when the conversion rate of MMA reached 60%. Other than that, the same production as in Production Example 17 was carried out to prepare pellets of the title block copolymer.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 105300 and the molecular weight distribution Mw / Mn was 1.38.

Production example 26 3A6-B1 synthesis Polymerization was carried out at a charging ratio of 360.4 g of diethyl 2,5-dibromoadipate, BA16167.7 g, EA15876.4 g, and MEA9849.9 g, and MMA41887.0 g was added when the conversion rate of BA reached 96%. The reaction was terminated when the conversion rate of MMA reached 61%. Other than that, the same production as in Production Example 18 was carried out to prepare pellets of the title block copolymer.

GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 104200 and the molecular weight distribution Mw / Mn was 1.36.

Production example 27 Synthesis of 2A'6.5-B1 Polymerization was carried out at a charging ratio of 611.5 g of diethyl 2,5-dibromoadipate, BA53720.6 g, and MEA27232.8 g, and MMA43528.4 g was added when the conversion rate of BA reached 96%. The reaction was terminated when the conversion rate of MMA reached 92%. Other than that, the same production as in Production Example 19 was carried out to prepare pellets of the title block copolymer. GPC analysis of the obtained acrylic block copolymer revealed that the number average molecular weight Mn was 108300 and the molecular weight distribution Mw / Mn was 1.33.

Production example 28 MMA-b- (BA-co-TBA) -b-MMA (BA / TBA = 97.5 / 2.5mol%, (BA-co-TBA) / MMA = 70/30% by weight) type acrylic block copolymer ( Synthesis of (hereinafter referred to as 2.5STBA7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.65 g (15.7 mmol) of diethyl 2,5-dibromoadipic acid, 877 ml (6.12 mol) of BA, and 22.9 ml (0.16 mol) of TBA, and the conversion rate of BA was 95. %, MMA 369 ml (3.45 mol) was added when the conversion rate of TBA was 95%. The reaction was terminated when the conversion rate of MMA was 65%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 2.5STBA7.

GPC analysis of the obtained acrylic block copolymer 2.5STBA7 revealed that the number average molecular weight Mn was 116000 and the molecular weight distribution Mw / Mn was 1.52.

Production example 29 MMA-b- (BA-co-TBA) -b-MMA (BA / TBA = 90 / 10mol%, (BA-co-TBA) / MMA = 70/30% by weight) type acrylic block copolymer (hereinafter Synthesis of (described as 10STBA7) Polymerization was carried out using a 5 L separable flask at a charging ratio of 5.64 g (15.7 mmol) of diethyl 2,5-dibromoadipic acid, 808 ml (5.64 mol) of BA, and 91.6 ml (0.63 mol) of TBA, and the conversion rate of BA was 95. %, MMA 461 ml (4.31 mol) was added when the conversion rate of TBA was 96%. The reaction was terminated when the conversion rate of MMA was 79%. Other than that, it was produced in the same manner as in Production Example 1 to obtain the target acrylic block copolymer 10STBA7.

GPC analysis of the obtained acrylic block copolymer 10STBA7 revealed that the number average molecular weight Mn was 113408 and the molecular weight distribution Mw / Mn was 1.35.

Example 1 Acid anhydride reaction and characterization of acrylic block copolymer 50TBA7 Laboplast Mill 50C150 (blade shape: roller type) with acrylic block copolymer 50TBA7, 45g and Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.09g obtained in Production Example 1 set at 240 ° C. R60, manufactured by Toyo Seiki Co., Ltd.) was melt-kneaded at 100 rpm for 20 minutes to obtain the desired acid anhydride group-containing acrylic block copolymer (the obtained polymer is hereinafter referred to as 50ANBA7).

Conversion of the t-butyl ester moiety to acid anhydride and carboxyl groups is performed by IR (Infrared Absorption Spectrum) and¹³C (¹It was confirmed by H) -NMR (nuclear magnetic resonance spectrum). That is, in IR, 1800 cm after conversion^-1It was confirmed from the fact that the absorption spectrum derived from the acid anhydride group can be seen around.¹³C (¹In H) -NMR, the 82 ppm signal derived from the quaternary carbon of the t-butyl group and the 28 ppm signal derived from the methyl carbon disappeared after the conversion, and 172 to 173 ppm (m) newly derived from the carbonyl carbon of the acid anhydride group. ) And a signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group appeared. The amounts of the monomer having an acid anhydride group and the monomer having a carboxyl group were 24% by weight and 21% by weight, respectively, in the methacrylic polymer block of the obtained acrylic block copolymer. The content of each¹³C (¹H)-Calculated from the integrated value of the above signals in NMR analysis.

Further, the obtained massive sample was heat-press molded at 240 ° C. to obtain a cylindrical compact for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Moreover, the obtained sheet-shaped molded product was kneaded again with a lab plast mill, and the recyclability was evaluated.

A thermogravimetric analysis of the acid anhydride group-containing acrylic block copolymer 50ANBA7 revealed that the 5% weight loss temperature was 357 ° C.

Examples 2-12 Acid anhydride reaction and characterization The acrylic block copolymers (5TBA7, 20TBA7, 100TBA7, 5T3A7, 20T3A7, 20T3A6, 50T3A6, 100T3A6, 100T2A6, 40T2A'6.5, 50TEBA8) obtained in Production Examples 2 to 11 and Production Examples 12 were used as Example 1. An acrylic block copolymer containing an acid anhydride group was synthesized by the same formulation (hereinafter, the obtained acrylic block copolymers were 5ANBA7, 20ANBA7, 100ANBA7, 5AN3A7, 20AN3A7, 20AN3A6, 50AN3A6, 100AN3A6, 100AN2A6, respectively. , 40AN2A'6.5, 50ANEBA8).

Further, as in Example 1, the content of the monomer having an acid anhydride group and the monomer having a carboxyl group is adjusted.¹³C (¹H)-Calculated by NMR analysis.

The content of the monomer having an acid anhydride group and the monomer having a carboxyl group in the methacrylic polymer block of the obtained acrylic block copolymer is the monomer having an acid anhydride group and the carboxyl group. The monomers having a group are described below in this order.

5ANBA7 was 2% by weight and 4% by weight, respectively, in the methacrylic polymer block.

20ANBA7 was 11% by weight and 19% by weight, respectively, in the methacrylic polymer block.

100ANBA7 was 69% by weight and 31% by weight, respectively, in the methacrylic polymer block.

5AN3A7 was 2% by weight and 7% by weight, respectively, in the methacrylic polymer block.

20AN3A6 was 3% by weight and 17% by weight, respectively, in the methacrylic polymer block.

50AN3A6 was 22% by weight and 18% by weight in the methacrylic polymer block.

100AN3A6 was 45% by weight and 55% by weight, respectively, in the methacrylic polymer block.

40AN2A'6.5 was 20% by weight and 20% by weight, respectively, in the methacrylic polymer block.

50ANEBA8 was 26% by weight and 27% by weight, respectively, in the methacrylic polymer block.

Further, by the same formulation as in Example 1, a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm was obtained. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Further, the obtained sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated.

Example 13 Carboxylation reaction and property evaluation by hydrolysis of acrylic anhydride group-containing acrylic block copolymer 20g of 20AN3A6 was placed in a pressure-resistant container together with 40g of water and heated at 200 ° C. for 2 hours to obtain the desired carboxyl group-containing acrylic block copolymer (the obtained polymer is hereinafter referred to as 20C3A6).

Conversion of acid anhydride groups to carboxyl groups is performed by IR (Infrared Absorption Spectrum) and¹³C (¹It was confirmed by H) -NMR analysis (nuclear magnetic resonance spectrum).

That is, in IR analysis, it is 1800 cm after conversion.^-1It was confirmed from the disappearance of the absorption spectrum derived from the acid anhydride group. Also,¹³C (¹In H) -NMR analysis, the signal of 172 to 173 ppm (m) derived from the carbonyl carbon of the acid anhydride group is quantitatively converted into the signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group. I was able to confirm.

The heat resistance of the obtained carboxyl group-containing acrylic block copolymer was measured by an enhanced flow. In addition, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 100 parts by weight of the obtained carboxyl group-containing acrylic block copolymer, and the temperature was set to 240 ° C. A lumpy sample was obtained by melt-kneading at 50 rpm for 20 minutes using a mill (manufactured by Toyo Seiki Co., Ltd.). The obtained sample was heat-press molded at a set temperature of 240 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties.

Example 14 A target carboxyl group-containing acrylic block copolymer (the obtained polymer is hereinafter referred to as 50C3A6) was obtained by the same method as in Example 13 except that 50AN3A6 was used. Further, a sample for character evaluation was prepared by the same method as in Example 13.

Example 15 A target carboxyl group-containing acrylic block copolymer (the obtained polymer is hereinafter referred to as 100C3A6) was obtained by the same method as in Example 13 except that 100AN3A6 was used. Further, a sample for character evaluation was prepared by the same method as in Example 13.

Comparative Examples 1 to 4 Labplast mill (Toyo Seiki) set to 190 ° C by blending 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) with 100 parts by weight of the polymer produced in Production Examples 13 to 16. A massive sample was obtained by melt-kneading at 50 rpm for 20 minutes using (manufactured by Co., Ltd.).

The obtained sample was hot-press molded at a set temperature of 190 ° C. to obtain a cylindrical molded body for compression permanent strain evaluation having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Further, the obtained sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated.

When the thermogravimetric analysis of this acrylic block copolymer BA7 having no acid anhydride group obtained in Comparative Example 1 was measured, the 5% weight loss temperature was 280 ° C. From the above results, it was shown that the introduction of the acid anhydride group has the effect of remarkably improving its heat-decomposability.

Comparative example 5 The olefin elastomer Santoprene 211-55 (manufactured by AS Japan Co., Ltd.) is melt-kneaded using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C at a screw rotation speed of 100 rpm. I got a sample.

The obtained sample was hot press molded at a set temperature of 170 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Similarly, hot press molding was performed at a set temperature of 170 ° C. to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. It can be seen that the olefin-based elastomer has good compression set, but the level of oil resistance is insufficient.

Comparative example 6 Ester-based elastomer Perprene P-30B (manufactured by Toyobo Co., Ltd.) is melt-kneaded using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C at a screw rotation speed of 50 rpm to prepare a sample. Obtained.

The obtained sample was hot press molded at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Although the polyester-based elastomer shows good mechanical properties, it can be seen that even a low-hardness grade has insufficient flexibility, as well as insufficient oil resistance and compression set.

Comparative example 7 A circular product having a diameter of 30 mm was cut out from a crosslinked chloroprene sheet (CR) -shaped molded product having a thickness of 2 mm, and six of them were stacked to obtain a molded product for compression permanent strain evaluation. And the compression set was measured. In addition, dumbbells and the like were cut out from the sheet-shaped molded product, and the oil resistance and tensile properties were measured. Further, the sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated. It can be seen that the crosslinked chloroprene exhibits good mechanical properties, oil resistance, and compression set characteristics, but cannot be recycled.

<tables num="1"><img file="JP4493498B2_D0006.tif" /></tables>

<tables num="2"><img file="JP4493498B2_D0007.tif" /></tables>

<tables num="3"><img file="JP4493498B2_D0008.tif" /></tables>

The test results of Examples 1 to 12 are shown in Table 1, the test results of Examples 13 to 15 are shown in Table 2, and the test results of Comparative Examples 1 to 7 are shown in Table 3.

The block copolymer containing an acid anhydride group introduced with an acid anhydride group has better compression set at high temperature than the block copolymer without an acid anhydride group, and has good heat resistance and heat resistance. It can be seen that the decomposability is improved (Examples 1 to 12). Moreover, it can be seen that the strength required for molding and the like is maintained. Further, it is flexible due to the composition of the acrylic polymer block in the acid anhydride group-containing acrylic block copolymer, the composition ratio of the acrylic block and the methacrylic polymer block, and the content of the acid anhydride group. However, it can be seen that materials having various hardnesses from low hardness to high hardness can be obtained.

It can be seen that the acid anhydride group-containing block copolymer in which the acrylic polymer block is made of BA is a material that is flexible and has an excellent balance of heat resistance, mechanical properties, and low temperature properties.

It can be seen that the acid anhydride group-containing block copolymer in which the acrylic polymer block is composed of BA, EA, and MEA is extremely excellent in oil resistance, and is also a material having an excellent balance of heat resistance and mechanical properties.

It can be seen that the acid anhydride group-containing block copolymer in which the acrylic polymer block is composed of BA and MEA is a material having an excellent balance of oil resistance, heat resistance and mechanical properties.

It can be seen that the acid anhydride group-containing block copolymer in which the acrylic polymer block is composed of BA and 2EHA is a material that is flexible and has extremely low hardness, and has an excellent balance of heat resistance, mechanical properties, and low temperature properties.

It can be seen that the carboxyl group-containing block obtained by hydrolyzing the acid anhydride group has good compression set at high temperature and further improved heat resistance (Examples 13 to 15). Moreover, it can be seen that the strength required for molding and the like is maintained. In addition, although the cohesive force is improved by the introduction of the carboxyl group, the hardness hardly changes, and it can be seen that the material exhibits good compressive permanent strain and mechanical strength with low hardness.

On the other hand, it can be seen that all of Comparative Examples 1 to 4 have recyclability, but have insufficient compression set, heat resistance, and heat decomposition. In the case of Comparative Example 5, it can be seen that it has recyclability and has good compression set, but its oil resistance is insufficient. In the case of Comparative Example 6, it is found that it has recyclability and shows good tensile properties, but its oil resistance and compression set are insufficient. Also, it lacks flexibility. In the case of Comparative Example 7, it can be seen that the tensile properties and the compression set are good, but since it is a crosslinked rubber, it cannot be recycled.

As is clear from Tables 1 to 3, the thermoplastic elastomer composition of the present invention has recyclability, good compression set, oil resistance, and heat resistance, and has the strength required for molding and the like. You can see that it is maintained. In addition, it can be seen that the material exhibits low hardness, flexibility, and good compression set and mechanical strength, even though the cohesive force is improved by the introduction of the functional group.

Example 16 Acid anhydride reaction of 20T3A6 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed with 100 parts by weight of the polymer 20T3A6 obtained in Production Example 7, and a twin-screw extruder with a vent (44 mm, L /). Using D = 42.25) (manufactured by Japan Steel Works, Ltd.), extrude and knead at a rotation speed of 50 rpm and a set temperature of 240 ° C to obtain the desired acid anhydride group-containing acrylic block copolymer (20AN3A6). It was. The conversion of the t-butyl ester moiety to an acid anhydride group is the same as in Example 1 with IR (infrared absorption spectrum) and¹³It was confirmed by C-NMR (nuclear magnetic resonance spectrum). From this, it was confirmed that an acid anhydride group-containing acrylic block copolymer can be obtained using various processing machines. Moreover, since it can be manufactured by an extruder, it can be seen that the manufacturing process is simplified.

Example 17 Acid anhydride reaction and characterization Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 parts by weight was mixed with 100 parts by weight of the polymer 50TBA7-B1 obtained in Production Example 17, and a twin-screw extruder with a vent (44 mm, Using L / D = 42.25) (manufactured by Japan Steel Works, Ltd.), extrude and knead at a rotation speed of 300 rpm and a set temperature of 240 ° C to obtain the desired acid anhydride group-containing acrylic block copolymer (50ANBA7-). B1) was obtained. At this time, a submersible cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Was connected to the tip of the twin-screw extruder, and Alflo H-50ES (as an adhesive in the circulating water of the submersible cut pelletizer) ( By adding (manufactured by NOF CORPORATION), spherical pellets without adhesion resistance were obtained.

The conversion of the t-butyl ester moiety to an acid anhydride group is the same as in Example 1 with IR (infrared absorption spectrum) and¹³It was confirmed by C-NMR (nuclear magnetic resonance spectrum). The obtained pellets were melt-kneaded at 100 rpm for 10 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C, and then heat-press molded at 220 ° C to have a diameter of 30 mm and a thickness of 30 mm. A cylindrical compact for evaluation of permanent strain of compression with a diameter of 12 mm was obtained. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Moreover, the obtained sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated.

Examples 18-24 Acid anhydride reaction and characterization Acrylic block copolymers obtained in Production Examples 18 to 24 (20T3A6.8-B1, 20T3A6.8-B2, 20T3A6-B1, 50T3A6.5-B1, 50T3A6-B1, 40T2A'6.5-B1, 50TEBA8- Using B1), an acid anhydride group-containing acrylic block copolymer was synthesized by the same formulation as in Example 17 (hereinafter, the obtained acrylic block copolymers are 20AN3A6.8-B1 and 20AN3A6, respectively. .8-B2, 20AN3A6-B1, 50AN3A6.5-B<u style="single">1、</u>Described as 50AN3A6-B1, 40AN'2A6.5-B1, 50ANEBA8-B1).

Further, by the same formulation as in Example 17, a cylindrical molded body for evaluation of compression set having a diameter of 30 mm and a thickness of 12 mm was obtained. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Further, the obtained sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated.

Comparative example 8 ~ 10 100 parts by weight of the acrylic block copolymers (BA7-B1, 3A6-B1, 2A'6.5-B1) obtained in Production Examples 25 to 27, manufactured by Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.) ) 0.3 parts by weight was blended and extruded and kneaded using a twin-screw extruder with a vent (44 mm, L / D = 42.25) (manufactured by Japan Steel Works, Ltd.) at a rotation speed of 300 rpm and a set temperature of 190 ° C. At this time, a submersible cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Was connected to the tip of the twin-screw extruder, and Alflo H-50ES (as an adhesive in the circulating water of the submersible cut pelletizer) ( By adding (manufactured by NOF CORPORATION), spherical pellets without adhesion resistance were obtained.

The obtained spherical pellets were melt-kneaded at 50 rpm for 10 minutes using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C. to obtain a massive sample.

The obtained sample was hot-press molded at a set temperature of 190 ° C. to obtain a cylindrical molded body for compression permanent strain evaluation having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, mechanical strength and heat resistance were measured on these sheets. Further, the obtained sheet-shaped molded product was kneaded again with a plast mill, and the recyclability was evaluated.

<tables num="4"><img file="JP4493498B2_D0009.tif" /></tables>

Table 4 shows the test results of Examples 17 to 24 and the test results of Comparative Examples 8 to 10.

It is possible to pelletize while performing the acid anhydride reaction with an extruder, and even the acid anhydride group-containing block produced by the extruder is compared with the block without acid anhydride group introduced. Therefore, it can be seen that the compression set is good at high temperature, and the heat resistance and the compression set property are improved. Moreover, it can be seen that the strength required for molding and the like is maintained. Further, it is flexible depending on the composition of the acrylic polymer block in the acid anhydride group-containing acrylic block copolymer, the composition ratio of the acrylic polymer block and the methacrylic polymer block, and the content of the acid anhydride group. However, it can be seen that materials having various hardnesses from low hardness to high hardness can be obtained.

As is clear from Table 4, the thermoplastic elastomer composition of the present invention has recyclability, good compression set, oil resistance, and heat resistance, and maintains the strength required for molding and the like. You can see that. In addition, it can be seen that the material exhibits low hardness, flexibility, and good compression set and mechanical strength, even though the cohesive force is improved by the introduction of the functional group.

Example 25 Carboxylation reaction by hydrolysis of block copolymer containing acid anhydride group 20AN3A6, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is mixed with 100 parts by weight, and a thermomixer (30 mm, L / D = 12) (manufactured by Noritake Co., Ltd.) is used at the tip. Using a visualization extruder (30 mm, L / D = 36) (manufactured by Plastic Engineering Laboratory Co., Ltd.), which was installed in two units, set the rotation speed at 25 rpm while press-fitting water at 0.14 kg / hour. Extrusion kneading was performed at a temperature of 200 ° C. to obtain the desired carboxyl group-containing block (20C3A6).

Conversion of acid anhydride groups to carboxyl groups is performed by IR (Infrared Absorption Spectrum) and¹³C (¹It was confirmed by H) -NMR analysis (nuclear magnetic resonance spectrum).

That is, in IR analysis, it is 1800 cm after conversion.^-1It was confirmed from the disappearance of the absorption spectrum derived from the acid anhydride group. Also,¹³C (¹In H) -NMR analysis, the signal of 172 to 173 ppm (m) derived from the carbonyl carbon of the acid anhydride group is quantitatively converted into the signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group. I was able to confirm.

From this, it was confirmed that the acid anhydride group can be ring-opened using various processing machines to obtain a carboxyl group-containing acrylic block copolymer. Moreover, since it can be manufactured by an extruder, it can be seen that the manufacturing process is simplified.

&lt;Thermoplastic resin composition&gt; Example 26 Acid anhydride reaction of acrylic block copolymer 2.5STBA7 Laboplast Mill (Toyo Seiki Co., Ltd.) in which the acrylic block copolymer 2.5STBA7, 45g obtained in Production Example 28 and 0.09g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) were set at 240 ° C. The product was melt-kneaded at 100 rpm for 20 minutes to obtain the desired acid anhydride group-containing acrylic block copolymer (the obtained polymer is hereinafter referred to as 2.5 SANBA7).

Conversion of the t-butyl ester moiety to acid anhydride and carboxyl groups is performed by IR (Infrared Absorption Spectrum) and¹³C (¹It was confirmed by H) -NMR (nuclear magnetic resonance spectrum). That is, in IR, 1800 cm after conversion^-1It was confirmed from the fact that the absorption spectrum derived from the acid anhydride group can be seen around. The amounts of the monomer having an acid anhydride group and the monomer having a carboxyl group were 0.6% by weight and 1.9% by weight, respectively, in the acrylic polymer block of the obtained acrylic block copolymer.

The content of the monomer having an acid anhydride group and the monomer having a carboxyl group is determined by methylating the carboxyl group in the acrylic block with diazomethane and then thermally decomposing it by GC Co., Ltd. Shimadzu Corporation. Calculated by GC-9A).

To the obtained 2.5 SANBA7, 100 parts by weight, add 30 parts by weight of Uvesta 3012U (manufactured by Ube Industries, Ltd.), set 190 ° C, and rotate at 100 rpm for 20 minutes. The mixture was kneaded with a bulk sample. The obtained massive sample was heat-press molded at 190 ° C. to obtain a cylindrical compact for evaluation of permanent compression strain having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance and mechanical strength were measured with these sheets.

Example 27 Acid anhydride reaction of acrylic block copolymer 10STBA7 The acid anhydrideization reaction was carried out in the same manner as in Example 26 except that the acrylic block copolymer 10STBA7 obtained in Production Example 29 was used, and the target acid anhydride group-containing acrylic block copolymer (the obtained polymer) was subjected to the acid anhydrideization reaction. Is described below as 10SANBA7). Further, in the same manner as in Example 26, a sample for evaluation was obtained by kneading with Uvesta 3012U. The amounts of the monomer having an acid anhydride group and the monomer having a carboxyl group were 2% by weight and 7% by weight, respectively, in the acrylic polymer block of the obtained acrylic block copolymer. The content of each¹³C (¹H)-Calculated from the integrated value of the above signals in NMR analysis.

Further, in the same manner as in Example 26, a sample for evaluation was obtained by kneading with Uvesta 3012U.

Comparative Example 11 Add 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 30 parts by weight of Uvesta 3012U (manufactured by Ube Industries, Ltd.) to 100 parts by weight of BA7 obtained in Production Example 13, and set 190. A massive sample was obtained by kneading with a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) for 20 minutes at ° C and a rotation speed of 100 rpm. The obtained massive sample was heat-press molded at 190 ° C. to obtain a cylindrical compact for evaluation of permanent compression strain having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured for these compacts. Further, heat press molding was performed in the same manner to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance and mechanical strength were measured with these sheets.

<tables num="5"><img file="JP4493498B2_D0010.tif" /></tables>

Examples 26 and 27 and Comparative Example 11 are shown in Table 5. As is clear from Table 5, the composition using the acrylic block copolymer having an acid anhydride group in the acrylic polymer block used the acrylic block copolymer having no acid anhydride group. It can be seen that it is flexible and has excellent mechanical strength, oil resistance, and compression set characteristics as compared with the composition.

Further, since the insoluble content (wt%) in acetone increases, it can be seen that the polyamide resin reacts with the acid anhydride group-containing block copolymer. Therefore, the composition with the acid anhydride group-containing acrylic block copolymer and the thermoplastic resin can be suitably used as a compatibilizer.

Example 28 Add 100 parts by weight of polybutylene terephthalate resin (Duranex 2002, manufactured by Polyplastics Co., Ltd.) to 20ANBA7, 100 parts by weight, and set temperature 240 ° C, rotation speed 100 rpm for 20 minutes Labplast Mill (Toyo) It was kneaded with Seiki Co., Ltd. to obtain a massive sample. The obtained sample was heat-press molded at a set temperature of 240 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties. The physical characteristics of the obtained molded product were punched into a predetermined shape and evaluated.

Example 29 Add 100 parts by weight of Diamide E47-S1 (manufactured by Daiselhurus) to 100 parts by weight of 20ANBA7, an acid anhydride type acrylic block copolymer, and labplast mill for 20 minutes at a set temperature of 190 ° C and a rotation speed of 100 rpm. A molded product was prepared and evaluated in the same manner as in Example 28, except that it was kneaded with (manufactured by Toyo Seiki Co., Ltd.) and hot-press molded at a set temperature of 190 ° C.

Example 30 A molded product was prepared and evaluated in the same manner as in Example 28, except that 100 parts by weight of Uvesta 3012U (manufactured by Ube Industries, Ltd.) was added to 20ANBA7 and 100 parts by weight.

Comparative Example 12 Polybutylene terephthalate resin (Duranex 2002, manufactured by Polyplastics Co., Ltd.) is kneaded with a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) at a set temperature of 240 ° C. and a rotation speed of 100 rpm for 20 minutes to prepare a massive sample. Obtained. The obtained sample was heat-press molded at a set temperature of 240 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties.

The physical characteristics of the obtained molded product were punched into a predetermined shape and evaluated.

Comparative Example 13 A molded product was prepared and evaluated in the same manner as in Comparative Example 12 except that Daiamide E47-S1 (manufactured by Daicel Huls) was used.

Comparative Example 14 A molded product was prepared and evaluated in the same manner as in Comparative Example 12 except that Uvesta 3012U (manufactured by Ube Industries, Ltd.) was used.

Comparative Example 15 A molded product was prepared and evaluated in the same manner as in Comparative Example 12 except that 20ANBA7 was used.

<tables num="6"><img file="JP4493498B2_D0011.tif" /></tables>

Table 6 shows the test results of Examples 28 to 30 and Comparative Examples 12 to 15. As is clear from Table 6, it was found that in the present invention, a desired flexible molded product can be obtained. In Examples 29 and 30, the insoluble content (wt%) in toluene increases, indicating that the resin and the acid anhydride group-containing acrylic block are reacting. Therefore, the composition with the acid anhydride group-containing acrylic block copolymer and the thermoplastic resin can be suitably used as a compatibilizer.

&lt;Rubber composition and thermoplastic elastomer composition&gt; Example 31 Crosslinked rubber 1 (20AN3A6) for 100 parts by weight of acid anhydride group-containing block body (20AN3A6)<u style="single">silicone</u>-Acrylic composite rubber, manufactured by Mitsubishi Rayon Co., Ltd., S-2001) is added by 10 parts by weight, and kneaded with a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes at a set temperature of 180 ° C and a rotation speed of 100 rpm to form a lump. Composition was obtained.

Using the obtained composition, a columnar molded body having a diameter of 30 mm and a thickness of 12 mm was produced, and the hardness and compression set were measured. Further, the obtained composition was heat-press molded at a set temperature of 180 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties. Oil resistance, tensile properties, and low temperature embrittlement were measured using the obtained molded product.

Examples 32, 33 Crosslinked rubber 2 (powdered NBR, manufactured by JSR Co., Ltd., PN20HA) in Example 32 and crosslinked rubber 1 (in Example 33) with respect to 100 parts by weight of the carboxyl group-containing block copolymer (20C3A6).<u style="single">silicone</u>-Acrylic composite rubber, manufactured by Mitsubishi Rayon Co., Ltd., S-2001) were added by 10 parts by weight, and kneaded with a plastomill at a set temperature of 180 ° C. and a rotation speed of 100 rpm for 10 minutes to obtain a massive composition. Evaluation was performed in the same manner as in Example 32.

Example 34 Crosslinked rubber 1 (100 parts by weight) of block copolymer containing carboxyl group (100C3A6)<u style="single">silicone</u>-Acrylic composite rubber, manufactured by Mitsubishi Rayon Co., Ltd., S-2001) Add 57 parts by weight, knead with Labplast Mill (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes at a set temperature of 230 ° C and a rotation speed of 100 rpm, and set. A molded product was prepared and evaluated in the same manner as in Example 31 except that the molded product was hot press molded at a temperature of 230 ° C.

Example 35 Crosslinked rubber 1 (100 parts by weight) of block copolymer containing carboxyl group (100C3A6)<u style="single">silicone</u>-Acrylic composite rubber, manufactured by Mitsubishi Rayon Co., Ltd., S-2001) 64.5 parts by weight, lubricant 1 (stearic acid, manufactured by Nacalai Tesque Co., Ltd.) 0.6 parts by weight and inorganic filler 1 (carbon black, Asahi Carbon Co., Ltd.) Asahi # 15) Add 1.6 parts by weight, knead with a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes at a set temperature of 230 ° C and a rotation speed of 100 rpm, and heat press mold at a set temperature of 230 ° C. Prepared a molded product in the same manner as in Example 31 and evaluated it.

Example 7B The low temperature brittleness was measured using a sheet-shaped molded product having a thickness of 2 mm that was press-molded in Example 7.

Example 13B Raboplast Mill (Toyo Seiki Co., Ltd.) set to 180 ° C by blending 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) with 100 parts by weight of block copolymer 20C3A6 containing a carboxyl group. (Manufactured) was melt-kneaded at 100 rpm for 20 minutes to obtain a massive sample. The obtained sample was heat-press molded at 180 ° C. to produce a columnar molded body having a diameter of 30 mm and a thickness of 12 mm, and the hardness and compression set were measured. Further, the obtained composition was heat-press molded at a set temperature of 180 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties. Oil resistance, tensile properties, and low temperature embrittlement were measured using the obtained molded product.

Example 15B Raboplast Mill (Toyo Seiki Co., Ltd.) set to 230 ° C by blending 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) with 100 parts by weight of block copolymer 100C3A6 containing a carboxyl group. (Manufactured) was melt-kneaded at 100 rpm for 20 minutes to obtain a massive sample.

The obtained sample was evaluated in the same manner as in Comparative Example 13B except that it was hot press molded at 230 ° C.

<tables num="7"><img file="JP4493498B2_D0012.tif" /></tables>

Table 7 shows the test results of Examples 31 to 35 and Examples 7B, 13B, and 15B. As is clear from the results in Table 7, in Examples 31 to 35, it can be seen that even if the crosslinked rubber is added, a molded product having desired flexibility, compression set, oil resistance, tensile properties, etc. can be obtained. .. Further, it can be seen that the low temperature embrittlement property can be improved without impairing the oil resistance by adding the crosslinked rubber having a low Tg.

&lt;Filler-containing composition&gt; Example 36 For 100 parts by weight of the carboxyl group-containing block copolymer (20C3A6), 5 parts by weight of lubricant 1 (stearic acid, manufactured by Nacalai Tesque Co., Ltd.) and 1 inorganic filler (carbon black, manufactured by Asahi Carbon Co., Ltd., Asahi) # 15) 0.25 parts by weight was added and kneaded with a laboplast mill (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes at a set temperature of 180 ° C. and a rotation speed of 100 rpm to obtain a massive composition.

The obtained composition was heat-press molded at 180 ° C. to obtain a columnar molded product having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured using the obtained molded product. Further, the composition obtained in the same manner was heat-press molded to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance, tensile properties and frictional properties were measured using the obtained sheet-shaped molded product. Furthermore, the workability was measured.

Example 37 For 100 parts by weight of block copolymer (20AN3A6) containing an acid anhydride group, 20 parts by weight of lubricant 1 (stearic acid, manufactured by Nacalai Tesque Co., Ltd.) and 1 inorganic filler (carbon black, Asahi Carbon Co., Ltd.) Asahi # 15) 1.25 parts by weight was added, and a molded product was prepared and evaluated in the same manner as in Example 36.

Example 38 For 100 parts by weight of the carboxyl group-containing block copolymer (20C3A6), 2 parts by weight of lubricant 2 (zinc stearate, manufactured by Nippon Yushi Co., Ltd.) and 2 parts by weight of inorganic filler 2 (carbon black, manufactured by Asahi Carbon Co., Ltd.) Asahi # 60HN) A molded product was prepared and evaluated in the same manner as in Example 36 except that 10 parts by weight was added.

Example 39 For 100 parts by weight of the carboxyl group-containing block copolymer (20C3A6), 5 parts by weight of lubricant 3 (calcium stearate, manufactured by Sakai Chemical Industry Co., Ltd., SC-100) and inorganic filler 2 (carbon black, Asahi carbon (carbon black, Asahi carbon) A molded product was prepared and evaluated in the same manner as in Example 36, except that 0.25 parts by weight of Asahi # 60HN) manufactured by Asahi Co., Ltd. was added.

Comparative Examples 1B and 2B The frictional properties were evaluated using the sheet-shaped molded products having a thickness of 2 mm that were press-molded in Comparative Example 1 and Comparative Example 2, but the frictional properties were too high to be measured because of their high adhesiveness.

Example 13C The frictional property was evaluated using a sheet-shaped molded product having a thickness of 2 mm that was press-molded in Example 13B. Further, the sheet-shaped molded product was cut into pellets and the processing temperature was measured.

Example 40 25 parts by weight of plasticizer (butylpolyacrylic acid, manufactured by Toa Synthetic Co., Ltd., UP-1000), lubricant 2 (Zn stearate, Sakai Kagaku) for 100 parts by weight of block copolymer (20C3A6) containing a carboxyl group. Add 3 parts by weight of SZ-2000) and 15 parts by weight of inorganic filler 2 (carbon black, Asahi Carbon Co., Ltd., Asahi # 60HN), set temperature 180 ° C, rotation speed 100 rpm for 10 minutes. It was kneaded with a plasticizer (manufactured by Toyo Seiki Co., Ltd.) to obtain a massive composition. The obtained composition was heat-press molded at 180 ° C. to obtain a columnar molded product having a diameter of 30 mm and a thickness of 12 mm. Hardness and compression set were measured using the obtained molded product. Further, the composition obtained in the same manner was heat-press molded to obtain a sheet-shaped molded product having a thickness of 2 mm. Oil resistance and tensile properties were measured using the obtained sheet-shaped molded product. It can be seen that even if a plasticizer is added, a molded product having desired flexibility, compression set, oil resistance, tensile properties, etc. can be obtained.

<tables num="8"><img file="JP4493498B2_D0013.tif" /></tables>

Table 8 shows the test results of Examples 36 to 40, Comparative Examples 1B and 2B, and Example 13C. As is clear from the results in Table 8, the acrylic block copolymer used in the present invention to which a lubricant and an inorganic filler are added has desired flexibility, oil resistance, compressive permanent strain and tensile properties. However, it can be seen that the dynamic friction of the resin surface is small.

Further, as is clear from the comparison between Example 36 and Example 13C, the processing temperature can be lowered by adding a lubricant and an inorganic filler to the acrylic block copolymer used in the present invention. It can be seen that good molding can be performed in the case of injection molding.

&lt;Solution agent&gt; Example 41 Ubesta 3012U (manufactured by Ube Industries, Ltd.) 25 parts by weight, 20ANBA7, 4 parts by weight is mixed with BA7, 100 parts by weight, kneaded with a plast mill for 20 minutes at a set temperature of 240 ° C. I got a sample of. The obtained sample was heat-press molded at a set temperature of 240 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties. The physical characteristics of the obtained molded product were punched into a predetermined shape and evaluated.

Comparative example 16 25 parts by weight of Uvesta 3012U (manufactured by Ube Industries, Ltd.) was mixed with 100 parts by weight of BA7 and kneaded with a plast mill for 20 minutes at a set temperature of 240 ° C. and a rotation speed of 100 rpm to obtain a massive sample. The obtained sample was heat-press molded at a set temperature of 240 ° C. to obtain a molded product having a thickness of 2 mm for evaluation of physical properties. The physical characteristics of the obtained molded product were punched into a predetermined shape and evaluated.

<tables num="9"><img file="JP4493498B2_D0014.tif" /></tables>

The test results of Example 41 and Comparative Example 16 are shown in Table 9. As is clear from Table 9, in the present invention, it can be seen that the one to which the acid anhydride group-containing block body is added has improved elongation at break and acts suitably as a compatibilizer between Uvesta 3012U and MBAM. ..

From the above results, it can be seen that the acrylic block copolymer of the present invention is rich in flexibility, excellent in mechanical strength, molding processability, oil resistance, heat resistance, and thermal decomposition property, and further rich in reactivity. Further, it can be seen that by combining the acrylic block copolymer of the present invention with a rubber or a thermoplastic resin and / or a thermoplastic elastomer, a novel composition rich in flexibility, oil resistance, heat resistance and the like can be obtained. Further, since it is particularly excellent in oil resistance, heat resistance and compression set, it can be seen that it can be widely used in automobiles and electric / electronic parts.