JP5543439B2

Adhesive compositions with multiple tackifiers

Abstract

This record has no abstract on file.

Term

Projected expiry 28 April 2029.

1 claim: 1 independent, 0 dependent

1
接着剤組成物であって、ａ）ブロックコポリマーであって、それぞれが、（メタ）アクリレート、スチレン、又はこれらの組み合わせを含む第１モノエチレン性不飽和モノマーから誘導される、少なくとも２つのＡエンドブロックポリマー単位であって、それぞれのＡエンドブロックが、少なくとも５０℃のガラス転移温度を有するもの、及び（メタ）アクリレート、ビニルエステル、又はこれらの組み合わせを含む第２モノエチレン性不飽和モノマーから誘導される少なくとも１つのＢミッドブロックポリマー単位であって、それぞれのＢミッドブロックが、２０℃以下のガラス転移温度を有するもの、を含み、並びにｂ）粘着付与剤混合物であって、１）０個又は１個の炭素−炭素結合を有する、３０〜７０重量％の第１ロジン酸、第１ロジンエステル、又はこれらの混合物、２）２個の炭素−炭素二重結合を有する、１０〜４０重量％の第２ロジン酸、第２ロジンエステル、又はこれらの混合物、及び３）３個の炭素−炭素二重結合を有する、１０〜５０重量％の第３ロジン酸、第３ロジンエステル、又はこれらの混合物、を含む組成物。

136 paragraphs, as filed

The adhesive composition and the article containing these adhesive compositions will be described.

Pressure sensitive adhesives are used in many applications and often contain polymers prepared from various (meth) acrylic monomers. The (meth) acrylic monomers selected to prepare this polymer often include polar monomers such as (meth) acrylic acid. Polar monomers tend to increase the bond strength and shear adhesion performance of the adhesive composition. When a methacrylic acid monomer is included, the resulting polymer often has relatively strong adhesion to substrates with polar surfaces, but relatively weak to other substrates with non-polar surfaces. Has adhesiveness.

In order to increase the adhesiveness to various substrates, the adhesive composition often contains a tackifier. Many tackifiers suitable for adhesive compositions are known.

The adhesive composition and the article containing these adhesive compositions will be described. More specifically, the adhesive composition comprises (a) a block copolymer prepared from a monoethylenically unsaturated monomer and (b) a mixture of tackifiers. The adhesive composition can be adhered to many substrates, including those having a non-polar surface. In the first aspect, an adhesive composition is provided. The adhesive composition comprises (a) a block copolymer and (b) a mixture of tackifiers. Block copolymers have at least two A-end block polymer units and at least one B mid-block polymer unit. Each A-end block polymer unit is derived from a first monoethylenically unsaturated monomer selected from methacrylate, styrene, or a mixture thereof. The glass transition temperature of each A-end block is at least 50 ° C. Each B midblock polymer unit is derived from a second monoethylene unsaturated monomer selected from (meth) acrylates, vinyl esters, or mixtures thereof. The glass transition temperature of each B midblock is 20 ° C. or lower. The tackifier mixture contains a first solid tackifier, a second solid tackifier, and a third liquid tackifier. The first solid tackifier has a glass transition temperature corresponding to at least 20 ° C. and has 0 or 1 carbon-carbon double bonds, at least 70% by weight of the first rosin, the first rosin. Contains esters or mixtures thereof. The second solid tackifier has a glass transition temperature corresponding to at least 20 ° C. and has 0 or 1 carbon-carbon double bonds, and is 50% by weight or less of the first rosin, the first rosin. Contains esters or mixtures thereof. The third liquid tackifier has a glass transition temperature of 0 ° C. or lower. In the second aspect, an article containing a substrate and an adhesive composition adhered to the surface of the substrate is provided. The adhesive composition comprises (a) a block copolymer and (b) a mixture of tackifiers containing 1) a first solid tackifier, 2) a second solid tackifier, and 3) a third liquid tackifier. Same as above, including. In a third aspect, an adhesive composition is provided. The adhesive composition comprises (a) a block copolymer and (b) a mixture of tackifiers. Block copolymers have at least two A-end block polymer units and at least one B mid-block polymer unit. Each A-end block polymer unit is derived from a first monoethylenically unsaturated monomer selected from methacrylate, styrene, or a mixture thereof. The glass transition temperature of each A-end block is at least 50 ° C. Each B midblock polymer unit is derived from a second monoethylene unsaturated monomer selected from (meth) acrylates, vinyl esters, or mixtures thereof. The glass transition temperature of each B midblock is 20 ° C. or lower. The tackifier mixture is (1) 30-70% by weight of the first rosin acid, the first rosin ester, or a mixture thereof, having 0 or 1 carbon-carbon bond, (2) 2 carbons. 10 to 40% by weight of secondary rosin acid, second rosin ester, or a mixture thereof having a carbon-carbon double bond, and (3) 10 to 50% by weight having 3 carbon-carbon double bonds. Includes a tertiary rosin ester, a tertiary rosin ester, or a mixture thereof. In a fourth aspect, an article comprising a substrate and an adhesive composition adhered to the surface of the substrate is provided. The adhesive composition comprises (a) a block copolymer and (b) (1) 30-70% by weight of the first rosin acid, the first rosin ester, or these having 0 or 1 carbon-carbon bonds. Mixtures, (2) 10-40% by weight second rosin acid, second rosin ester, or mixtures thereof, having two carbon-carbon double bonds, and (3) three carbon-carbon doubles. It is the same as described above, which comprises 10 to 50% by weight of a tertiary rosin ester having a bond, a tertiary rosin ester, or a tackifier mixture containing a mixture thereof. The above-mentioned outline of the present invention is not intended to explain each embodiment or all implementations of the present invention. The following figures, embodiments for carrying out the invention, and examples more specifically illustrate these embodiments.

The invention can be more fully understood by examining the detailed description of the various embodiments of the invention below along with the accompanying drawings.<figref num="1">Plot of shear modulus with respect to temperature for a representative adhesive composition and two comparative adhesive compositions.</figref>

An adhesive composition and an article containing the adhesive composition are provided. More specifically, the adhesive composition comprises a block copolymer in addition to the tackifier mixture. The tackifier mixture can be selected to alter the glass transition temperature of the block copolymer while maintaining the transparency of the adhesive composition. The tackifier mixture comprises a rosin acid, a rosin ester, or a mixture thereof having various degrees of unsaturation. Adhesive compositions can generally be adhered to a variety of substrates, including those with non-polar or low energy surfaces. For example, the adhesive composition can be adhered to the polyolefin surface.

The terms "a", "an", and "the" are used interchangeably with "at least one" and mean one or more of the described elements.

Any of the above ranges usually include endpoints and all numbers between endpoints. For example, the range 1-10 includes all numbers 1, 10, and 1-10. Numbers are often integers.

The term "room temperature" refers to temperatures in the range of 20-25 ° C.

The term "and / or" means one or both. For example, the notation, rosin acid and / or rosin ester means rosin acid, rosin ester, or both rosin acid and rosin ester (eg, a mixture of rosin acid and rosin ester).

Block copolymer As used in the present invention, the terms "polymer" and "polymeric" mean a polymeric unit such as a polymeric material or a polymer block that is a homopolymer or copolymer. Similarly, the terms "polymerize" and "polymerize" mean the process of manufacturing a polymer material or polymer unit. The term "homopolymer" means a polymeric unit, such as a polymeric block, which is a reaction product of a polymeric material or one type of monomer. That is, the homopolymer is derived from a single monomer. The term "copolymer" means a polymeric unit such as a polymeric material or a polymeric block that is the reaction product of at least two different monomers. That is, the copolymer is derived from multiple types of monomers.

As used in the present invention, the term "block copolymer" means a polymeric material that contains a variety of polymeric blocks that are covalently bonded to each other. Block copolymers usually contain at least two different polymer blocks called A blocks and B blocks. Blocks A and B usually have different chemical compositions and different glass transition temperatures. The A-block polymer unit and the B-block polymer unit are derived from monoethylenically unsaturated monomers. Each polymer block and the resulting block copolymer has a saturated polymer backbone that does not require subsequent hydrogenation.

Block copolymers have at least two A-end block polymer units and at least one B mid-block polymer unit. As used in the present invention, the term "end block" means the terminal region of a block copolymer, and the term "mid block" means the central portion of a block copolymer. Each unit of the A-end block polymer is covalently attached to the B mid-block polymer unit. The terms "A block" and "A end block" are used interchangeably herein. Similarly, the terms "B block" and "B end block" are used interchangeably herein.

A block copolymer having at least two A blocks and at least one B block is a ternary block copolymer of formula ABA or a star block copolymer having at least three segments of formula (AB). possible. A ternary block copolymer usually has a linear structure with a B block in the center and an A block in the terminal region. Star-shaped block copolymers often have a central part from which various branches extend. The B block is usually in the central part of the star block copolymer and the A block is in the terminal region of the star block copolymer.

The A block tends to be more rigid than the B block. That is, the A block has a higher glass transition temperature and tends to be harder than the B block. As used in the present invention, the term "glass transition temperature" or "T"g"" Means the temperature at which the polymer material transitions from the glass state to the rubber state. The glassy state usually involves a material, eg, brittle, hard, rigid, or a combination thereof. In contrast, rubber states usually involve materials, such as those of flexible and elastomeric origin. The glass transition temperature can be determined using methods such as differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA). The A block has a glass transition temperature of at least 50 ° C., and the B block has a glass transition temperature of 20 ° C. or less. In many typical block copolymers, the A block is a T at at least 60 ° C, at least 80 ° C, at least 100 ° C, or at least 120 ° C.gOn the other hand, the B block has a glass transition temperature of 10 ° C. or lower, 0 ° C. or lower, -5 ° C. or lower, or -10 ° C. or lower.

The A-block polymer unit tends to be a thermoplastic material, whereas the B-block polymer unit tends to be an elastomer material. As used in the present invention, the term "thermoplastic" means a polymeric material that flows when heated and returns to its initial state when cooled to room temperature. As used in the present invention, the term "elastomeric" means a polymeric material that can be stretched to at least twice its initial length and shrinks to approximately its initial length upon release. Normally, the B block is considered to be a soft block, whereas the A block is considered to be a hard block.

Typically, the solubility parameter of the A block is very different from the solubility parameter of the B block. In other words, the A block is usually neither compatible nor miscible with the B block, resulting in the A block being phase separated from the B block. Block copolymers have polyphasic morphology in the temperature range of at least about 20 ° C to 150 ° C. Block copolymers can have different regions that reinforce the A-block domain (eg, nanodomain) within the softer, elastomeric B-block matrix. For example, block copolymers can have separate, discontinuous A-block phases within a substantially continuous B-block phase. In some such examples, the concentration of A block polymer units is less than or equal to about 35% by weight of the block copolymer. A-blocks typically provide block copolymers with structural strength and binding strength.

Monoethylenically unsaturated monomers suitable for A-block polymer units are usually at least 50 ° C. T when reacted to form homopolymers.gHave. In many examples, suitable monomers for A-block polymer units are T at at least 60 ° C, at least 80 ° C, at least 100 ° C, or at least 120 ° C when reacted to form homopolymers.gHave. T of these homopolymersgCan be 200 ° C. or 150 ° C. or lower. T of these homopolymersgCan be, for example, in the range of 50 ° C. to 200 ° C., 50 ° C. to 150 ° C., 60 ° C. to 150 ° C., 80 ° C. to 150 ° C., or 100 ° C. to 150 ° C. T at least 50 ° C. when reacted to form homopolymersgIn addition to these monomers havinggOther monomers can be included in the A block as long as it maintains at least 50 ° C.

The A-block polymer unit is usually derived from a methacrylate monomer, a styrene-based monomer, or a mixture thereof. That is, the A-block polymer unit is a reaction product of a first monoethylenically unsaturated monomer selected from a methacrylate monomer, a styrene-based monomer, or a mixture thereof. As used in the present invention to describe the monomers used to form the A-block polymer unit, the term "mixture of these" refers to two or more types of monomers (eg, methacrylate and styrene) or This means that two or more monomers of the same type (eg, two different methacrylates) can be mixed. At least two of the A blocks of a block copolymer can be the same or different. In many block copolymers, all of the A block polymer units are derived from the same monomer or monomer mixture.

In many embodiments, the methacrylate monomers react to form the A block. That is, the A block is derived from the methacrylate monomer. Obtained A block TgAny methacrylate monomer can be used as long as it is at least 50 ° C. The methacrylate monomer can be, for example, an alkyl methacrylate, an aryl methacrylate, or an aralkyl methacrylate of the formula (I).

In formula (I), R１Is an alkyl, aryl, or aralkyl (ie, an alkyl substituted with an aryl group). Suitable alkyl groups often have 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. If the alkyl group has more than two carbon atoms, the alkyl group can be branched or cyclic. Suitable aryl groups often have 6-12 carbon atoms. Suitable aralkyl groups often have 7-18 carbon atoms.

Representative alkyl methacrylates of formula (I) include, but are not limited to, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, butyl tertiary methacrylate, and cyclohexyl methacrylate. In addition to the monomer of formula (I), isobornyl methacrylate can be used. Typical aryl (meth) acrylates of formula (I) include, but are not limited to, phenyl methacrylate. Representative aralkyl methacrylates of formula (I) include, but are not limited to, benzyl methacrylate and 2-phenoxyethyl methacrylate (methacarylate).

In other embodiments, the A-block polymer unit is derived from a styrene-based monomer. Typical styrene-based monomers capable of reacting to form an A block include styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, ethylstyrene, tertiary butylstyrene, isopropylstyrene, and Examples include, but are not limited to, various alkyl-substituted styrenes such as dimethylstyrene.

For A block In addition to the monomers described above, these polymer units are 5% by weight or less of polar monomers such as methacrylic acid, methacrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide, or hydroxyalkylmethacrylate. Can be prepared using. For example, these polar monomers can be used to regulate the binding strength of the A block and the glass transition temperature. However, even when polar monomers are added, the T of each A blockgMaintains at least 50 ° C. The polar groups resulting from the polar monomers in the A block can function as reaction sites for chemical or ionic cross-linking, if desired. The A-block polymer unit can be prepared using 4% by weight or less, 3% by weight or less, or 2% by weight or less of polar monomers. However, in many examples, the A-block polymer unit is essentially free or completely free of polar monomers. As used in the present invention, the term "essentially free" refers to one of the selected monomers in which any polar monomer present is used to form an A-block polymer unit. It means that it is an impurity in. The amount of polar monomer is less than 1% by weight, less than 0.5% by weight, less than 0.2% by weight, or less than 0.1% by weight of the monomer in the reaction mixture used to form the A-block polymer unit. is there.

A-block polymer units are often homopolymers. In some typical A blocks, the polymer units are derived from 1-6, 1-4, 1-3, 1-2, or alkyl methacrylate monomers having an alkyl group with one carbon atom. In some more specific examples, the A-block polymer unit is derived from methyl methacrylate (ie, the A-block is poly (methyl methacrylate)).

Monoethylenically unsaturated monomers suitable for use in B-block polymer units usually have a T of 20 ° C or lower when reacted to form homopolymers.gHave. In many examples, the suitable monomer for the B-block polymer unit is a T of 10 ° C or lower, 0 ° C or lower, -5 ° C or lower, or -10 ° C or lower when reacted to form a homopolymer.gHave. T of these homopolymersgIs often 80 ° C. or higher, 70 ° C. or higher, 60 ° C. or higher, or 50 ° C. or higher. T of these homopolymersgCan be, for example, in the range of 80 ° C. to 20 ° C., 70 ° C. to 10 ° C., 60 ° C. to 0 ° C., or 60 ° C. to 10 ° C. T below 20 ° C when reacted to form homopolymersgIn addition to these monomers with B block TgOther monomers can be included in the B block as long as the temperature is maintained below 20 ° C.

B midblock polymer units are usually derived from (meth) acrylate monomers, vinyl ester monomers, or combinations thereof. That is, the B midblock polymer unit is a reaction product of a second monomer selected from a (meth) acrylate monomer, a vinyl ester monomer, or a mixture thereof. As used in the present invention, the term "(meth) acrylate" means both methacrylate and acrylate. As used in the present invention to describe the monomers used to form the B midblock polymer unit, the term "mixtures of these" refers to two or more types of monomers (eg, (meth) acrylates). And vinyl ester) or two or more monomers of the same type (eg, two different (meth) acrylates) can be mixed.

In many embodiments, the acrylate monomers react to form a B block. The acrylate monomer can be, for example, an alkyl acrylate or a heteroalkyl acrylate. The B block is often derived from the acrylate monomer of formula (II).

In formula (II), R２Is an alkyl having 1 to 22 carbons or a heteroalkyl having 2 to 20 carbons and 1 to 6 heteroatoms selected from oxygen or sulfur. The alkyl or heteroalkyl group can be linear, branched, cyclic, or a combination thereof.

Representative alkyl acrylates of formula (II) that can be used to form B-block polymer units include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-. Pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylbutyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2-pentyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate , Lauryl acrylate, isotridecyl acrylate, octadecyl acrylate, and dodecyl acrylate, but are not limited thereto.

Representative heteroalkyl acrylates of formula (II) that can be used to form B-block polymer units include, but are not limited to, 2-methoxyethyl acrylates and 2-ethoxyethyl acrylates.

Several alkyl methacrylates can be used to prepare B blocks such as alkyl methacrylates having alkyl groups with more than 6 to 20 carbon atoms. Representative alkyl methacrylates include, but are not limited to, 2-ethylhexyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, isodecyl methacrylate, and lauryl methacrylate. Similarly, some heteroalkyl methacrylates such as 2-ethoxyethyl methacrylate can also be used.

Suitable polymer units for the B block can be prepared from the monomers of formula (II). Commercially unavailable or directly non-polymerizable (meth) acrylate monomers can be obtained by esterification or transesterification reactions. For example, a commercially available (meth) acrylate can be hydrolyzed and then esterified with an alcohol to give the (meth) acrylate of interest. This process may leave some residual acid in the B block. Alternatively, the higher alkyl (meth) acrylate can be derived from the lower alkyl (meth) acrylate by directly transesterifying the lower alkyl (meth) acrylate with the higher alkyl alcohol.

In yet other embodiments, the B-block polymer unit is derived from the vinyl ester monomer. Representative vinyl esters include, but are not limited to, vinyl acetate, vinyl 2-ethyl-hexanoate, and vinyl neodecanoate.

For B block In addition to the above-mentioned monomers, this polymer unit contains 5% by weight or less of acrylic acid, acrylamide, N-alkylacrylamide (eg, N-methyl-acrylamide), N, N-dialkylacrylamide (N, N). It can be prepared using polar monomers such as dimethylacrylamide) or hydroxyalkyl acrylates. These polar monomers can be used, for example, to regulate the glass transition temperature (ie, even in this case, the T in the B block.gMaintains below 20 ° C). In addition, these polar monomers can provide polar groups within the polymer unit to be able to function as reaction sites for chemical or ionic cross-linking, if desired. The polymer unit can be prepared using 4% by weight or less, 3% by weight or less, or 2% by weight or less of polar monomers. However, in many examples, the B-block polymer unit is essentially free or completely free of polar monomers. As used in the present invention, the term "essentially free" refers to one of the selected monomers in which any polar monomer present is used to form a B-block polymer unit. It means that it is an impurity in. The amount of polar monomer is less than 1% by weight, less than 0.5% by weight, less than 0.2% by weight, or less than 0.1% by weight of the monomer used to form the B-block polymer unit.

In many cases, the B-block polymer unit is a homopolymer. In some examples of the B block, the polymer unit is an alkyl group having 1-22, 2-20, 3-20, 4-20, 4-18, 4-10, or 4-6 carbon atoms. It can be derived from an alkyl acrylate having. Acrylate monomers such as alkyl acrylate monomers tend to be less rigid than their alkyl methacrylate counterparts.

In some adhesive compositions, the block copolymer is a (meth) acrylate block copolymer having an A block polymer unit derived from a methacrylate monomer and a B block polymer unit derived from an acrylate monomer. For example, the A-block polymer unit can be derived from an alkyl methacrylate monomer and the B-block polymer unit can be derived from an alkyl acrylate monomer. In some more specific embodiments, the A block is derived from an alkyl methacrylate having an alkyl group having 1-6, 1-4, 1-3, or 1-2 carbon atoms, and the B block is It is derived from an alkyl acrylate having an alkyl group having 3, 20, 4 to 20, 4 to 18, 4 to 10, 4 to 6, or an alkyl group having 4 carbon atoms. For example, the A block can be derived from methyl methacrylate, and the B block can be derived from an alkyl acrylate having an alkyl group having 4 to 10, 4 to 6, or 4 carbon atoms. In a more specific example, the A block can be derived from methyl methacrylate and the B block can be derived from n-butyl acrylate. That is, the A block is poly (methyl methacrylate) and the B block is poly (n-butyl acrylate).

The weight percent of the B block is usually equal to or greater than the weight percent of the A block in the block copolymer. Larger amounts of A block tend to increase the modulus of elasticity of the block copolymer. However, if the amount of A block is too large, the morphology of the block copolymer may be reversed from the desired arrangement, where the B block forms a continuous phase and the block copolymer is an elastomeric material. That is, if the amount of A block is too large, the copolymer tends to have more similar properties to the thermoplastic material than to the elastomeric material. Block copolymers typically contain 10 to 50% by weight of A block polymer units and 50 to 90% by weight of B block polymer units. For example, block copolymers are 10-40% by weight A-block polymer units and 60-90% by weight B-block polymer units, 10-35% by weight A-block polymer units and 65-90% by weight B-block polymer units. 15-50% by weight A-block polymer unit and 50-85% by weight B-block polymer unit, 15-35% by weight A-block polymer unit and 65-85% by weight B-block polymer unit, 10-30% by weight A-block polymer units and 70-90% by weight B-block polymer units, 15-30% by weight A-block polymer units and 70-85% by weight B-block polymer units, 15-25% by weight A-block polymer units and 75 It can contain up to 85% by weight of B-block polymer units, or 10 to 20% by weight of A-block polymer units and 80-90% by weight of B-block polymer units.

Block copolymers can have any suitable molecular weight. In many embodiments, the molecular weight of the block copolymer is at least 2,000 g / mol, at least 3,000 g / mol, at least 5,000 g / mol, at least 10,000 g / mol, at least 15,000 g / mol, at least 20, 000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, at least 40,000 g / mol, or at least 50,000 g / mol. Block copolymers often have a molecular weight of 500,000 g / mol or less, 400,000 g / mol or less, 200,000 g / mol or less, 100,000 g / mol or less, 50,000 g / mol or less, or 30,000 g / mol. It is as follows. For example, the molecular weight of block copolymers is in the range of 1,000 to 500,000 g / mol, in the range of 3,000 to 500,000 g / mol, in the range of 5,000 to 100,000 g / mol, in the range of 5,000 to 50, It can be in the range of 000 g / mol or in the range of 5,000 to 30,000 g / mol. The molecular weight is usually expressed as a weight average molecular weight.

Block copolymers can be prepared using any well-known technique. In some methods of block copolymer preparation, European Patent No. 0 349 232 As described in B1 (Andrus et al.), Iniferter is used. However, for some applications, block copolymer preparation methods that do not include the use of initiators may be preferred, which tend to leave residues that are particularly problematic in photopolymerization reactions. Because there is. For example, in the presence of thiocarbamate (commonly used in initiators), the resulting block copolymer may be more susceptible to outdoor exposure degradation. Outdoor exposure degradation can result from relatively weak carbon-sulfur bonds in the thiocarbamate residue. For example, elemental or mass spectrometry can often be used to detect the presence of thiocarbamate. For this reason, in some applications it is desirable to use methods that do not form this weak carbon-sulfur bond to prepare block copolymers. That is, some block copolymers were prepared using a synthetic method that was independent of the use of initiators and that the block copolymers did not contain these weak carbon-sulfur bonds.

Some suitable methods for producing block copolymers are living polymerization methods. As used in the present invention, the term "living polymerization" means a polymerization technique, polymerization step, or polymerization reaction in which the propagating species does not stop or migrate. After 100% conversion, the addition of additional monomers can result in further polymerization. The molecular weight of the living polymer increases linearly with conversion because the number of propagating species does not change. Examples of the living polymerization method include a living free radical polymerization method and a living anion polymerization method. Specific examples of the living-free radical polymerization reaction include an atomic transfer polymerization reaction and a reversible addition cleavage chain transfer polymerization reaction.

Block copolymers prepared using the living polymerization method tend to have well-controlled blocks. As used in the present invention, the term "well controlled" means that when it comes to the method of making blocks and block copolymers, the block polymer units have the following properties: controlled molecular weight, low polydispersity, well defined. It means having at least one of a block or a block having high purity.

Some blocks and block copolymers have a well-controlled molecular weight close to the theoretical molecular weight. The theoretical molecular weight means a calculated molecular weight based on the molar packing amount of the monomer and reaction initiator used to form each block. Well-controlled blocks and block copolymers often have a weight average molecular weight (M) of about 0.8-1.2 times the theoretical molecular weight, or about 0.9-1.1 times the theoretical molecular weight.w). As such, the molecular weight of the block and the molecular weight of the total block can be selected and prepared.

Some blocks and block copolymers have low polydispersity. As used in the present invention, the term "polydispersity" is a measure of molecular weight distribution and is the number average molecular weight of the polymer (M).n) Divided by weight average molecular weight (M)w) Means. Materials with the same molecular weight have a polydispersity of 1.0, whereas materials with multiple molecular weights have a polydispersity greater than 1.0. The degree of polydispersity can be determined using, for example, gel permeation chromatography. Well-controlled blocks and block copolymers often have a polydispersity of 2.0 or less, 1.5 or less, or 1.2 or less.

Some block copolymers have well-defined blocks. That is, the boundaries of the continuous phase containing the A block and the B block are sufficiently defined. These well-defined blocks have boundaries that are essentially free of tapered structures. As used in the present invention, the term "tapered structure" means a structure derived from the monomers used in both A and B blocks. The tapered structure can increase the mix of A-block and B-block phases and reduce the overall bond strength of block copolymers or adhesives containing block copolymers. Block copolymers prepared using methods such as living anionic polymerization tend to provide boundaries that are free or substantially free of tapered structures. The clear boundary between the A and B blocks often results in the formation of physical crosslinks that can increase the overall bond strength without the need for chemical crosslinks. In contrast to these well-defined blocks, some block copolymers prepared using iniferters have less clear blocks with a tapered structure.

Some A and B blocks have high purity. For example, the A block can be substantially free or completely free of segments derived from the monomers used in the preparation of the B block. Similarly, the B block can be substantially free or completely free of the monomers derived from the monomers used in the preparation of the A block.

Living polymerization methods usually result in a more stereoregular block structure than blocks prepared using non-living or pseudo-living polymerization methods (eg, polymerization reactions using initializers). The stereoregularity exhibited by highly syndiotactic or isotactic structures tends to result in a well-controlled block structure and also tends to affect the glass transition temperature of the block. For example, syndiotactic poly (methyl methacrylate) (PMMA) synthesized using the living polymerization method is about 20 ° C. to more than similar PMMA synthesized using conventional (ie, non-living) polymerization methods. It can have a glass transition temperature as high as about 25 ° C. Tacticity can be detected using, for example, nuclear magnetic resonance spectroscopy. Structures with stereoregularity greater than about 75% can often be obtained using the living polymerization method.

When the living polymerization method is used to form the block, the monomer is contacted with the reaction initiator in the presence of an inert diluent. The Inactive Diluent can promote heat transfer and mixing of the reaction initiator with the monomer. Any suitable Inactive Diluent can be used, but saturated hydrocarbons, aromatic hydrocarbons, ethers, esters, ketones, or combinations thereof are often selected. Typical diluents include saturated aliphatic hydrocarbons such as hexane, octane and cyclohexane and alicyclic hydrocarbons; aromatic hydrocarbons such as toluene; and aliphatic ethers and cyclic ethers such as dimethyl ether, diethyl ether and tetrahydrofuran. Examples include, but are not limited to, esters such as ethyl acetate and butyl acetate; and ketones such as acetone and methyl ethyl ketone.

When a block copolymer is prepared using the living anion polymerization method, the living A block can be represented by a simplified structure AM, where M is a I, such as lithium, sodium, or potassium. It is a reaction initiator fragment selected from Group metals. For example, the A block can be a polymerization reaction product of the first monomer composition containing the methacrylate monomer of the formula (I). A second monomer composition containing a monomer used to form a B block can be added to AM to form a living diblock structure ABM. For example, the second monomer composition can contain a monomer of formula (II). A ternary block structure ABA is formed by adding another filling of the first monomer composition that can contain the monomer of formula (I) followed by elimination of the living anion moiety. be able to. Alternatively, the living binary block ABM structure can be coupled using a bifunctional or polyfunctional coupling agent to the ternary block structure ABA copolymer or (AB). )n-A star-shaped block copolymer can be formed.

Any reaction initiator known in the art can be used for the living anionic polymerization reaction. Typical reaction initiators include organic lithium compounds (eg, ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, tertiary octyllithium, n-decyllithium, phenyllithium). , 2-naphthyllithium, 4-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, etc.) and other alkali metal hydrocarbons. Such monofunctional reaction initiators may be useful in the production of living A blocks or living B blocks. In the living anionic polymerization of (meth) acrylate, the reactivity of the anion can be suppressed by adding a complexing ligand selected from materials such as lithium chloride, crown ether, and lithium ethoxylate.

Examples of the bifunctional reaction initiator suitable for the living anionic polymerization reaction include 1,1,4,4-tetraphenyl-1,4-dilithiobutane; 1,1,4,4-tetraphenyl-1,4-dilithio. Isobutane; and, but are not limited to, lithium naphthalene, sodium naphthalene, potassium naphthalene, and their homologues. Other suitable bifunctional reaction initiators include dilithium compounds such as those prepared by the addition reaction of alkyllithium with a divinyl compound. For example, alkyllithium can react with 1,3-bis (1-phenylethenyl) benzene or m-diisopropenylbenzene.

For a living anionic polymerization reaction, it is usually desirable to add a small amount (eg, one drop at a time) of the reaction initiator to the monomer while the characteristic color due to the anion of the reaction initiator is observed. A calculated amount of reaction initiator can then be added to produce a polymer of the desired molecular weight. In many cases, by adding a small amount in advance, the contaminants that react with the reaction initiator are destroyed, and the polymerization reaction can be better controlled.

The polymerization temperature used depends on the monomer being polymerized and the type of polymerization method used. Generally, the reaction can be carried out at a temperature of about -100 ° C to about 150 ° C. For living anionic polymerization reactions, the temperature is often from about 80 ° C. to about 20 ° C. For living radical polymerization reactions, the temperature is often from about 20 ° C to about 150 ° C. Living-free radical polymerization reactions tend to be less sensitive to temperature changes than living anionic polymerization reactions.

Block copolymer preparation methods using the living anion polymerization method include, for example, US Pat. Nos. 6,734,256 B1 (Everaerts et al.), 7,084,209 B2 (Everaerts et al.), 6,806. It is further described in 320 B2 (Everaerts et al.) And 7,255,920 B2 (Everaerts et al.), All of which are incorporated herein by reference. This polymerization method is described, for example, in US Pat. Nos. 6,630,554 B1 (Hamada et al.) And 6,984,114 B2 (Kato et al.), And Japanese Patent Application Publication No. 1999-302617 (Uchiumi). Et al.) And 1999-No. 323072 (Uchiumi et al.).

Generally, the polymerization reaction is carried out under controlled conditions in order to eliminate substances that can destroy the reaction initiator or living anion. Usually, the polymerization reaction is carried out in an inert atmosphere such as nitrogen, argon, helium, or a combination thereof. If the reaction is living anionic polymerization, anhydrous conditions may be required.

Suitable block copolymers are Kuraray Co., Ltd. , LTD. It can be purchased from (Tokyo, Japan) under the trade name of LA Polymer (LA POLYMER). Some of these block copolymers, such as LA 2140, LA 2250, and LA 410, are ternary block copolymers with poly (methyl methacrylate) end blocks and poly (n-butyl acrylate) mid blocks.

In some embodiments, two or more block copolymers are included in the adhesive composition. For example, multiple block copolymers having different weight average molecular weights or multiple block copolymers having different concentrations of A block polymer units can be used. By using a plurality of block copolymers having different weight average molecular weights or a plurality of block copolymers having different amounts of A block polymer units, for example, the shear strength of the adhesive composition can be improved.

When multiple block copolymers with different weight average molecular weights are included in the adhesive composition, the weight average molecular weight can vary in any suitable amount. In some cases, the molecular weight of the first block copolymer is at least 25%, at least 50%, at least 75%, at least 100%, at least 150%, or at least 200% from the second block copolymer having the higher weight average molecular weight. Can be changed. The block copolymer mixture is 10 to 90% by weight of the first block copolymer and 10 to 90% by weight of the second block copolymer having a larger weight average molecular weight, 20 to 80% by weight of the first block copolymer and 20 to 80% by weight. Can contain a second block copolymer having a higher weight average molecular weight of, or a second block copolymer having a weight average molecular weight of 25-75% by weight and a second block copolymer having a weight average molecular weight of 25-75% by weight.

When multiple block copolymers with different concentrations of A-block polymer units are included in the adhesive composition, the concentrations can vary in any suitable amount. In some cases, the concentration can vary by at least 20%, at least 40%, at least 60%, at least 80%, or at least 100%. The block copolymer mixture is a first block copolymer having 10 to 90% by weight and a second block copolymer having 10 to 90% by weight of a larger amount of A block or a first block copolymer of 20 to 80% by weight and 20 to 80% by weight. Can contain a second block copolymer having a larger amount of A block or a 25-75% by weight first block copolymer and a second block copolymer having a larger amount of 25-75% by weight of A block.

Adhesive-imparting agent mixture The adhesive composition comprises a tackifier mixture in addition to the block copolymer. Adhesive compositions containing higher concentrations of tackifiers often better adhere to certain substrates such as those with non-polar surfaces or low surface energy. Higher concentrations of tackifiers often improve the adhesiveness of the adhesive composition to substrates such as polyolefins. However, if the amount of certain tackifiers is too high, the adhesive composition often tends to be opaque rather than transparent. For many articles containing an adhesive composition, a transparent adhesive composition is desirable. The tackifier mixture can be used to provide an adhesive composition with the desired transparency and adhesiveness.

The adhesive composition usually contains at least 30% by weight of the block copolymer and at least 30% by weight of the tackifier mixture, based on the total weight of the block copolymer and the tackifier mixture in the adhesive composition. For example, the adhesive composition contains 30-70% by weight of the block copolymer and 30-70% by weight of the tackifier mixture based on the total weight of the block copolymer and the tackifier mixture in the adhesive composition. it can. In other examples, the adhesive composition is 35-65% by weight block copolymer and 35-65% by weight tackifier based on the total weight of the block copolymer and tackifier mixture in the adhesive composition. Can contain an agent mixture. In yet another embodiment, the adhesive composition is 40-60% by weight block copolymer and 40-60% by weight adhesive based on the total weight of the block copolymer and tackifier mixture in the adhesive composition. It can contain an additive mixture.

The tackifier mixture includes loginic acid, rosin ester, or a mixture thereof having various degrees of unsaturation. Each of the resin acid and rosin ester contained in the tackifier mixture has 3 condensed carbon rings and 0, 1, 2, or 3 carbon-carbon double bonds.

Examples of rosin acids having three carbon-carbon double bonds include those such as isomers of formula (III) or formula (III).

The rosin acid of formula (III) is commonly referred to as dehydroabietic acid.

Examples of rosin acids having two carbon-carbon bonds include those having isomers of formulas (IV) to (X) or formulas (IV) to (X).

The rosin of formula (IV) is commonly referred to as abietic acid, the rosin of formula (V) is commonly referred to as levopimaric acid, and the rosin of formula (VI) is commonly referred to as pulsetriic acid. The rosin of formula (VII) is commonly referred to as neo-abietic acid, the rosin of formula (VIII) is commonly referred to as pimaric acid, the rosin of formula (IX) is commonly referred to as sandalacopimaric acid, and The rosin acid of formula (X) is commonly referred to as isopimaric acid.

Examples of the rosin acid having one carbon-carbon double bond include any of the rosin acids shown in FIGS. (IV) to (X), hydrogenated (that is, dihydro). For example, one carbon-carbon bond of formula (IV) can be hydrogenated to the rosin acid of formula (XI) or an isomer thereof.

Similarly, a single carbon-carbon bond of formula (VIII) can be hydrogenated to a rosin acid of formula (XII) or (XIII) or an isomer thereof.

The two double bonds of the rosin acid of formula (III) having an aromatic ring are hydrogenated to form any of the following rosin acids of formula (XI), (XIV), or (XV): be able to.

Examples of the rosin acid having no carbon-carbon double bond include any rosin acid represented by the formulas (IV) to (X) or an isomer thereof, which has been hydrogenated (that is, tetrahydro). Be done. For example, both carbon-carbon bonds of formula (IV) can be hydrogenated to a compound of formula (XVI) or an isomer thereof.

This identical rosin acid is obtained by hydrogen-completed the rosin acid of formula (III). Similarly, both carbon-carbon bonds of formula (VIII) can be hydrogenated to a compound of formula (XVII) or an isomer thereof.

Esters corresponding to any of these rosin acids are usually formed by reacting alcohols or polyols with rosin acids. Typical alcohols or polyols often have 1 to 20 carbon atoms and 1 to 5 hydroxyl groups. Alcohols or polyols can be saturated or unsaturated. The polyol is often an aliphatic polyol such as an alkane substituted with multiple hydroxy groups. The polyol can be, for example, glycerol, ethylene glycol, diethylene glycol, or pentaerythritol. When a polyol is used, the rosin acid can react with all or any portion of the hydroxyl groups on the polyol. For example, a rosin ester formed using glycerol as a polyol can be a monoester, a diester, or a ternary ester, whereas a rosin ester formed using pentaerythritol as a polyol can be a monoester, a diester, or a ternary ester. , Monoesters, diesters, ternary esters, or quaternary esters. Monoesters are formed by reacting rosin acid with one of the hydroxyl groups of an alcohol or polyol. Diesters, ternary esters, and quaternary esters can be formed by reacting rosinic acid with 2, 3, or 4 hydroxy groups of the polyol, respectively. A mixture of rosin esters can be present.

In one aspect, the adhesive composition comprises at least three tackifiers, each of which is a loginic acid, a rosin ester, or a mixture thereof. Often, each tackifier is a mixture of rosin acids and / or rosin esters with different degrees of saturation (ie, different degrees of unsaturation). The adhesive composition comprises a first tackifier and a second tackifier that are solid at room temperature and a third tackifier that is liquid at room temperature.

The two solid tackifiers in the adhesive composition have a glass transition temperature corresponding to at least 20 ° C. These two tackifiers differ from each other in their saturation. The first solid tackifier is more cured than the second solid tackifier. In other words, the first solid tackifier has a higher degree of saturation and a lower degree of unsaturation than the second solid tackifier. Due to this difference in saturation or hydrogenation, the two solid tackifiers have different solubilities in block copolymers and in the various polymer units of block copolymers. The first solid tackifier is less compatible or miscible with the elastomeric region of the block copolymer than the second solid tackifier.

Both the first and second solid tackifiers can contain a plurality of logonic acids, rosin esters, or mixtures thereof, having 0, 1, 2, or 3 carbon-carbon double bonds. Each of the first and second solid tackifiers can contain, for example, a mixture of rosin acids of formulas (III)-(XVII) and / or isomers thereof and / or rosin esters thereof. However, the distribution of these logonic acids and / or rosin esters in the first solid tackifier and the second solid tackifier is usually different. Compared to the second solid tackifier, the first solid tackifier usually contains a higher amount of the first rosin acid and / or the first rosin ester with 0 or 1 carbon-carbon double bond. To do. Compared to the first solid tackifier, the second solid tackifier usually contains a third rosin acid and / or a third rosin ester with a larger amount of three carbon-carbon double bonds. In addition, compared to the first solid tackifier, the second solid tackifier often contains a second rosin acid and / or a second rosin ester with a larger amount of two carbon-carbon double bonds. Contains, but not always. The first and second solid tackifiers are in the amount of a third rosin acid and / or a third rosin ester with three carbon-carbon double bonds and with zero or one carbon-carbon double bond. The most different in the amount of the first rosin acid and / or the first rosin ester having.

The first solid tackifier often contains more hydrogenated logonic acid and / or rosin ester than the second solid tackifier. Usually, at least 70% by weight of the first solid tackifier is a first rosin acid and / or a first rosin ester having 0 or 1 carbon-carbon double bonds. In other words, at least 70% by weight of the first solid tackifier is a rosin acid and / or a rosin ester thereof corresponding to the hydrogenation equivalents of formulas (III)-(X) and / or isomers thereof. is there. For example, at least 70% by weight of the first solid tackifier can be a rosin ester of formulas (XI)-(XVII) and / or a rosin ester and / or an isomer thereof. Some representative first solid tackifiers have at least 75% by weight, at least 80% by weight, or at least 85% by weight of the first rosin acid and / or 0 or 1 carbon-carbon double bond. Contains the first rosin ester having.

In contrast, 50% by weight or less of the second solid tackifier is a first logic acid and / or a first rosin ester having 0 or 1 carbon-carbon double bonds. In other words, the second solid tackifier in an amount of 50% by weight or less is a rosin acid and / or a rosin ester corresponding to the hydrogenation equivalents of the formulas (III) to (X) and / or an isomer thereof. .. Some typical second solid tackifiers are 0 or 1 of 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, or 20% by weight or less. It contains a first logic acid and / or a first rosin ester having carbon-carbon double bonds.

The first solid tackifier often contains no more than 20% by weight of a second rosin acid and / or a second rosin ester having two carbon-carbon double bonds. Some typical first solid tackifiers are two carbon-carbon double bonds of 18% by weight or less, 16% by weight or less, 15% by weight or less, 14% by weight or less, or 12% by weight or less. Contains a second rosin acid and / or a second rosin ester.

The second solid tackifier often contains at least 5% by weight of a second rosin acid and / or a second rosin ester having two carbon-carbon double bonds. For example, some second solid tackifiers are at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45%. It has a second rosin acid and / or a second rosin ester having two carbon-carbon double bonds in weight%, or at least 50% by weight. When the amount of the second rosin acid and / or the second rosin ester is relatively small, such as less than 20% by weight, the first rosin acid and / or the first rosin ester having 0 or 1 carbon-carbon bond. The amount of increases correspondingly.

Compared to the second solid tackifier, the first solid tackifier usually contains a smaller amount of the third rosin acid and / or a third rosin ester with three carbon-carbon double bonds. The tertiary rosin acid and / or rosin ester is often a dehydroabietic acid and / or rosin ester of formula (III) in which all three carbon-carbon double bonds are in the same 6-membered carbon ring. And / or their isomers. The first solid tackifier often contains a third rosin acid and / or a third rosin ester having three carbon-carbon double bonds of 20% by weight or less, whereas the second solid tackifier contains a second. Solid tackifiers often contain at least 25% by weight of a tertiary logonic acid and / or a tertiary rosin ester having three carbon-carbon double bonds. Some typical first solid tackifiers have 3 carbon-carbon double bonds of 18% by weight or less, 16% by weight or less, 15% by weight or less, 14% by weight or less, or 12% by weight or less. Contains a tertiary rosin acid and / or a tertiary rosin ester. In contrast, some typical second solid tackifiers have three carbon-carbon double bonds of at least 30% by weight, at least 35% by weight, at least 40% by weight, or at least 45% by weight. Contains a tertiary logic acid and / or a tertiary rosin ester.

Some representative first solid tackifiers are first rosin acid and / or first rosin ester having at least 70% by weight of 0 or 1 carbon-carbon double bond, 20% by weight or less. A second rosin acid and / or a second rosin ester having two carbon-carbon double bonds, and a third rosin acid and / or a first rosin having three carbon-carbon double bonds of 20% by weight or less. Contains ester. Other typical first solid tackifiers are at least 70% by weight of the first rosin acid and / or the first rosin ester, 15% by weight or less of the second rosin acid and / or the second rosin ester, and 15% by weight. % Or less of a tertiary rosin acid and / or a tertiary rosin ester. Further other representative first solid tackifiers are at least 75% by weight of the first rosin acid and / or the first rosin ester, 12% by weight or less of the second rosin acid and / or the second rosin ester, and 12 Contains less than or equal to% by weight tertiary rosin acid and / or tertiary rosin ester.

In some embodiments, the first solid tackifier is a first rosin acid and / or a first rosin ester having 70-100% by weight of 0 or 1 carbon-carbon double bond, 0-15. A second rosin acid and / or a second rosin ester with 2% by weight of carbon-carbon double bonds, and a third rosin acid and / with 3% by weight of 3 carbon-carbon double bonds. Alternatively, it contains a third rosin ester. For example, the first solid tackifier is 70-98% by weight of the first rosin acid and / or the first rosin ester, 1-15% by weight of the second rosin acid and / or the second rosin ester, and 1-15. It can contain% by weight of the tertiary rosin acid and / or the tertiary rosin ester. In another embodiment, the first solid tackifier is 70-96% by weight of the first rosin acid and / or the first rosin ester, 1-15% by weight of the second rosin acid and / or the second rosin ester. It can also contain 3 to 15% by weight of a tertiary rosin acid and / or a tertiary rosin ester.

Some typical second solid tackifiers are first rosin acid and / or first rosin ester with 0 or 1 carbon-carbon double bond of 50% by weight or less, at least 5% by weight. Contains a second rosin acid and / or a second rosin ester with two carbon-carbon double bonds, and a rosin acid and / or rosin ester with at least 25% by weight of three carbon-carbon double bonds. .. Other typical second solid tackifiers are 40% by weight or less of the first rosin acid and / or the first rosin ester, at least 5% by weight of the second rosin acid and / or the second rosin ester, and at least 30. Contains% by weight of the tertiary rosin acid and / or the tertiary rosin ester. The combined amount of the first rosin acid and / or the first rosin ester plus the second rosin acid and / or the second rosin ester is often at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45%. % By weight, or at least 50% by weight.

In some embodiments, the second solid tackifier is a first rosin acid and / or a first rosin ester having 0 to 50% by weight of 0 or 1 carbon-carbon double bonds, 5 to 70. A second rosin acid and / or a second rosin ester with 2% by weight carbon-carbon double bonds, and a third rosin acid and / with 25-70% by weight 3 carbon-carbon double bonds. Alternatively, it contains a third rosin ester. For example, the second solid tackifier is 0 to 45% by weight of the first rosin acid and / or the first rosin ester, 5 to 70% by weight of the second rosin acid and / or the second rosin ester, and 25 to 60% by weight. It can contain% by weight of the tertiary rosin acid and / or the tertiary rosin ester. Other representative secondary rosin acids and / or rosin esters thereof are 0 to 20% by weight of the first rosin acid and / or the first rosin ester, and 35 to 70% by weight of the second rosin acid and / or the second. It contains a rosin ester and 30-60% by weight of a tertiary rosin acid and / or a tertiary rosin ester. Further other representative rosin esters and / or rosin esters thereof are 20 to 50% by weight of rosin and / or rosin esters, and 5 to 20% by weight of rosin and / or rosin esters. It contains 2 rosin esters and 30-70% by weight of tertiary rosin acid and / or tertiary rosin ester.

Suitable first solid tackifiers include Eastman Chemicals (Kingsport, TN) under the trade name FORAL or Hercules, Inc. Some are commercially available from (Wilmington, Delaware), but are not limited to these. For example, Foral 85, Foral 85E, and Foral 85LB (LB means low bromine) are glycerol esters of rosin acid. Foral 105 and Foral 105E are pentaerythritol esters of rosin acid. Foral AX and Foral AX-E are rosin acids.

Suitable second solid tackifiers are, for example, commercially available from Arakawa Chemical, USA under the trade name SUPER ESTER, and Eastman Chemicals (Kingsport, TN) under the trade name PERMALYN. Examples include various glycerol esters of rosin acid commercially available from Kingsport)). Examples include, but are not limited to, Super Ester W-100, Super Ester A-75, Super Ester W-100, Super Ester KE-100, Super Ester KE-300, and Permarin 5095-C. Superester KE-100 and Superester KE-300 are considered to be optically transparent.

In addition to the first and second tackifiers, both solid at room temperature, the tackifier mixture comprises a third tackifier, which is a liquid or viscous fluid at room temperature or near room temperature. .. The third liquid tackifier has a glass transition temperature of 0 ° C. or lower. Like the first solid tackifier and the second solid tackifier, the third liquid tackifier is a loginic acid, a rosin ester, or a mixture thereof. The third liquid tackifier can be a single logic acid or a single rosin ester. Alternatively, the third liquid tackifier can be a mixture of logonic acid and / or rosin ester.

In many embodiments, the third liquid tackifier contains a mixture of rosin acids and / or rosin esters with varying numbers of carbon-carbon double bonds. The same type of logonic acid and / or rosin ester present in the first solid tackifier and the second solid tackifier can be present in the third liquid tackifier. Compared to the first solid tackifier, the third liquid tackifier often has a larger amount of logonic acid and / or rosin ester with two carbon-carbon double bonds, and a smaller amount of zero. Alternatively, it contains a loginic acid and / or a rosin ester having one carbon-carbon bond. Compared to the second solid tackifier, the third liquid tackifier often has a smaller amount of logonic acid and / or rosin ester with three carbon-carbon double bonds, and a larger amount of zero. Alternatively, it contains a loginic acid and / or a rosin ester having one carbon-carbon double bond.

Some representative third liquid tackifiers are at least 20% by weight of the first rosin acid and / or the first rosin ester having 0 or 1 carbon-carbon double bond, at least 20% by weight. A second rosin acid and / or a second rosin ester having two carbon-carbon double bonds, and a third rosin acid and / or a third rosin having three carbon-carbon double bonds of 20% by weight or less. Contains ester. The amount of the first rosin acid and / or the first rosin ester in the third liquid tackifier can be at least 25% by weight, at least 30% by weight, at least 35% by weight, or at least 40% by weight. The amount of the second rosin acid and / or the second rosin ester in the third liquid tackifier can be at least 25% by weight, at least 30% by weight, at least 35% by weight, or at least 40% by weight. The amount of the third rosin acid and / or the third rosin ester in the third liquid tackifier can be less than 18% by weight, less than 15% by weight, less than 12% by weight, or less than 10% by weight.

For example, the third liquid tackifier is a first rosin acid and / or a first rosin ester having 20-80% by weight of three carbon-carbon double bonds, and 20-80% by weight of two carbon-. It can contain a second rosin acid and / or a second rosin ester with a carbon double bond, and a third rosin acid and / or a third rosin ester with 3 carbon-carbon double bonds of 0-20% by weight. .. In other embodiments, the third liquid tackifier is 20 to 70% by weight of the first rosin acid and / or the first rosin ester, 20 to 70% by weight of the second rosin acid and / or the second rosin ester. It can also contain 0 to 15% by weight of a tertiary rosin acid and / or a tertiary rosin ester. In yet another embodiment, the third liquid tackifier is 30-60% by weight of the first rosin acid and / or the first rosin ester, 30-60% by weight of the second rosin acid and / or the second rosin ester. , And 1 to 15% by weight of the tertiary rosin acid and / or the tertiary rosin ester.

Examples of the third liquid tackifier include, but are not limited to, those commercially available from Eastman Chemicals (Kingsport, TN) under the trade name STAYBELITE. An example is Staverite Ester 3-E.

In one of the three tackifiers commonly included in tackifier mixtures, the first solid tackifier is a loginate and / or rosin with 0 or 1 carbon-carbon double bond. It has the maximum amount of ester. The first solid tackifier is usually mostly a loginic acid and / or a rosin ester having 0 or 1 carbon-carbon double bond. The second solid tackifier has a maximum amount of logonic acid and / or rosin ester with three carbon-carbon double bonds. In most cases, the second solid tackifier is mostly a mixture of rosin acid and / or a rosin ester thereof having two and three carbon-carbon double bonds. The third liquid tackifier is often a mixture of 0, 1, or 2 carbon-carbon double bonds of rosin acid and / or its rosin ester.

One of the main reasons for adding the tackifier is to raise the glass transition temperature of the B block polymer unit of the block copolymer. When a tackifier is added, T of B blockgUsually increases, and the modulus of elasticity of the B block usually decreases. Decreasing the elastic modulus tends to make the B block softer. The first solid tackifier and the second solid tackifier are often B-block T.gEquivalent in their ability to raise. However, if too much of the first solid tackifier is added, the adhesive composition can change from transparent to opaque. Being opaque means that the compatibility or solubility of the first solid tackifier in the block copolymer has exceeded the limit. Even if the first solid tackifier is further added beyond the point at which the adhesive composition becomes opaque, the glass transition temperature of the B block hardly rises. That is, once the solubility of the first solid tackifier in the B block exceeds the limit, the glass transition temperature of the B block does not change significantly even if the first solid tackifier is further added.

Although any amount of the first solid tackifier can be used, the amount of the first solid tackifier is usually selected so that the solubility of the first solid tackifier in the block copolymer does not exceed the limit. .. The adhesive composition often contains 25% by weight or less or 20% by weight or less of the first solid tackifier. The weight% of the first solid tackifier in the adhesive composition is based on the total weight of the block copolymer and the tackifier mixture. For example, the adhesive composition can contain a first solid tackifier of 18% by weight or less, 15% by weight or less, 12% by weight or less, 10% by weight or less, 8% by weight or less, or 5% by weight or less. The amount of the first solid tackifier in the adhesive composition is at least 1% by weight. For example, the adhesive composition can contain at least 2% by weight, at least 5% by weight, or at least 10% by weight of the first solid tackifier. The concentrations of the first solid tackifier in the adhesive composition are often 1-25% by weight, 1-20% by weight, 2-20% by weight, 3-20% by weight, 5-20% by weight, Alternatively, it is in the range of 5 to 15% by weight.

The second solid tackifier can be added in larger amounts into the adhesive composition as compared to the first solid tackifier without changing the transparency of the composition, but the second solid tackifier can be added. In addition to being miscible with B-block polymer units, the agent is somewhat compatible with A-block polymer units. The second solid tackifier is T in B block.gHowever, the solubility of the second solid tackifier in the A block reduces the shear modulus and bonding force of the adhesive composition at high temperatures. obtain. Therefore, a mixture of the first and second solid tackifiers is used to optimize the tackiness without adversely affecting the transparency of the adhesive composition and without adversely affecting the shear modulus and binding force. Can be transformed into.

The amount of the second solid tackifier is usually selected to adjust the glass transition temperature of the B block and the flat modulus of the block copolymer. The adhesive composition often contains 40% by weight or less or 50% by weight or less of the second solid tackifier. The weight% of the second solid tackifier in the adhesive composition is based on the total weight of the block copolymer and the tackifier mixture. The adhesive composition can contain, for example, a second solid tackifier of 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less. Adhesive compositions often contain at least 1% by weight, at least 2% by weight, or at least 4% by weight of a second solid tackifier. Some adhesive compositions contain at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 12% by weight, or at least 15% by weight of the second solid tackifier. The amount of the second solid tackifier is often in the range of 4-40% by weight, 5-35% by weight, 5-30% by weight, 5-25% by weight, or 5-20% by weight.

The third liquid tackifier is usually added to reduce the flat modulus or modulus at room temperature. If the elastic modulus at room temperature is small, the wetting of the base material by the adhesive composition is usually good. The adhesive composition can contain 50% by weight or less of the third liquid tackifier. The weight% of the third liquid tackifier in the adhesive composition is based on the total weight of the block copolymer and the tackifier mixture. The adhesive composition can contain, for example, a third liquid tackifier of 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, or 25% by weight or less. Some adhesive compositions contain at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, or at least 30% by weight of a third liquid tackifier. The amount of the third liquid tackifier is often in the range of 1-50% by weight, 5-50% by weight, 10-50% by weight, 10-40% by weight, or 10-30% by weight.

The tackifier mixture in the adhesive composition is typically 1 to 45% by weight of the first solid tackifier, 5 to 55% by weight of the second solid tackifier, and 5 to 70% by weight of the third liquid tack. Contains an imparting agent. For example, the tackifier mixture may include 5 to 45% by weight of the first solid tackifier, 5 to 50% by weight of the second tackifier, and 5 to 60% by weight of the third liquid tackifier. it can. In other embodiments, the tackifier mixture is 5 to 40% by weight of the first solid tackifier, 5 to 50% by weight of the second solid tackifier, and 10 to 60% by weight of the third liquid tackifier. Can include agents.

Adhesive compositions are often 30-70% by weight (meth) acrylate block copolymers, 1-25% by weight first solid tackifiers, 1-50% by weight second solid tackifiers, and 1 Contains ~ 50% by weight of a third liquid tackifier. For example, the adhesive composition comprises 30-70% by weight (meth) acrylate block copolymer, 1-20% by weight first solid tackifier, 5-50% by weight second solid tackifier, and 5-5. It can contain 50% by weight of the third liquid tackifier. In other examples, the adhesive composition is 40-60% by weight (meth) acrylate block copolymer, 1-20% by weight first solid tackifier, 5-40% by weight second solid tackifier. , And 10 to 50% by weight of a third liquid tackifier. The weight percentage of each of the block copolymer and the tackifier in the adhesive composition is based on the total weight of the block copolymer and the tackifier mixture.

In another aspect, an adhesive composition comprising a (meth) acrylate block copolymer and a tackifier mixture of loginic acid, rosin ester, or a mixture thereof is provided. The tackifier mixture contains 30-75% by weight of 0 or 1 carbon-carbon double bond primary rosin acid and / or 1st rosin ester, 10-40% by weight of 2 carbon-carbons. It contains a second rosin acid and / or a second rosin ester having a double bond, and a third rosin acid and / or a third rosin ester having 10 to 50% by weight of three carbon-carbon double bonds.

The tackifier mixture comprises a first logic acid and / or a first rosin ester having 30-75% by weight of 0 or 1 carbon-carbon double bond. For example, the tackifier mixture is 30 to 70% by weight, 35 to 70% by weight, 40 to 70% by weight, 45 to 70% by weight, 30 to 65% by weight, 35 to 65% by weight, 40 to 65% by weight, It can contain 30-60% by weight, 35-60% by weight, or 40-60% by weight of the first logonic acid and / or the first rosin ester.

The tackifier mixture comprises a second rosin acid and / or a second rosin ester having 10-40% by weight of two carbon-carbon double bonds. For example, the tackifier mixture is 15-40% by weight, 20-40% by weight, 10-35% by weight, 15-35% by weight, or 20-35% by weight of the dilogic acid and / or the second rosin ester. Can be contained.

The tackifier mixture comprises a tertiary logic acid and / or a tertiary rosin ester having 10 to 50% by weight of three carbon-carbon double bonds. For example, the tackifier mixture is 15 to 50% by weight, 20 to 50% by weight, 10 to 45% by weight, 15 to 45% by weight, 20 to 45% by weight, 10 to 40% by weight, 15 to 40% by weight, It can contain 20-40% by weight, 10-35% by weight, 15-35% by weight, or 20-35% by weight of a tertiary logonic acid and / or rosin ester.

Adhesive compositions containing 30-70% by weight (meth) acrylate block copolymers often have a first rosin acid and / or a first rosin having 10-50% by weight of 0 or 1 carbon-carbon bond. 1 Contains rosin ester. For example, the adhesive composition comprises 15-50% by weight, 15-45% by weight, 15-40% by weight, 15-35% by weight, 20-40% by weight, 20-40% by weight of the first rosin acid and /. Alternatively, it can contain a first rosin ester. The weight percentage of the block copolymer and any logic acid and / or rosin ester in the adhesive composition is based on the total weight of the block copolymer and tackifier mixture.

Adhesive compositions containing 30-70% by weight (meth) acrylate block copolymers often have a second rosin acid and / or a second with 3-30% by weight of two carbon-carbon double bonds. Contains rosin ester. For example, the adhesive composition is 4 to 30% by weight, 4 to 25% by weight, 5 to 30% by weight, 5 to 25% by weight, or 5 to 20% by weight of the second rosin acid and / or the second rosin ester. Can be contained. The weight percentage of the block copolymer and any rosin acid and / or rosin ester in the adhesive composition is based on the total weight of the block copolymer and tackifier mixture.

Adhesive compositions containing 30-70% by weight (meth) acrylate block copolymers often have a third rosin acid and / or a third with 3 to 35% by weight of three carbon-carbon double bonds. Contains rosin ester. For example, the adhesive composition is 3 to 30% by weight, 3 to 25% by weight, 4 to 35% by weight, 4 to 30% by weight, 4 to 25% by weight, 5 to 35% by weight, 5 to 30% by weight, Alternatively, it can contain 5 to 25% by weight of a tertiary rosin acid and / or a tertiary rosin ester. The weight percentage of the block copolymer and any rosin acid and / or rosin ester in the adhesive composition is based on the total weight of the block copolymer and tackifier mixture.

The adhesive composition is, for example, 30-70% by weight (meth) acrylate block copolymer, a first rosin acid having 10 to 50% by weight of 0 or 1 carbon-carbon double bond and / or a first. Rosin ester. A second rosin acid and / or a second rosin ester having 3 to 30% by weight of two carbon-carbon double bonds, and a third rosin having 3 to 35% by weight of three carbon-carbon double bonds. Acids and / or tertiary rosin esters can be included. Some typical adhesive compositions are 30-70% by weight (meth) acrylate block copolymers, 15-50% by weight of the first rosinic acid and / or the first rosin ester, 5-25% by weight of the first rosin ester. 2 Contains rosin acid and / or rosin ester, and 3-30% by weight of rosin acid and / or rosin ester. The weight percentage of the block copolymer and any rosin acid and / or rosin ester in the adhesive composition is based on the total weight of the block copolymer and tackifier mixture.

Other components of the adhesive composition The adhesive composition may optionally contain a solvent. Such adhesive compositions can be applied to substrates using coating methods. Once the coating is formed, the solvent can be removed. Examples of suitable solvents include, but are not limited to, ethyl acetate, tetrahydrofuran, methyl ethyl ketone, and toluene. The solvent can be present in any amount required, eg, in the amount required to coat the adhesive composition. In some applications, the solvent is present in an amount of 40% by weight or less of the adhesive composition. For example, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less can be the solvent.

Various plasticizers can be added to the adhesive composition. Typical plasticizers include hydrocarbon oils (eg, aromatic or paraffinic oils), polyalkylene oxides such as phthalates, polyethylene oxides and polypropylene oxides, phosphate esters, aliphatic carboxylic acid esters, and benzoic acid esters. However, it is not limited to these. The plasticizer can be added in any desired amount, but in most cases it is 20% by weight or less of the adhesive composition.

Fillers can be added. The filler can usually change the storage modulus of the adhesive composition. When transparency is desired, fillers with relatively small particle sizes, for example less than 1 micrometer (1000 nanometers), are often selected. The filler can be used in any desired amount, but is often 20% by weight or less of the adhesive composition.

Various other polymeric materials can be added to the adhesive composition. For example, in addition to the block copolymers described above, which are often ternary block or star block copolymers, binary block copolymers can be added. Binary block copolymers usually include hard polymer units and soft polymer units. The hard polymer units of binary block copolymers are often selected to be compatible with or miscible with the A block end blocks of ternary blocks or star block copolymers. Similarly, the soft polymer units of binary blocks are often selected to be compatible with or miscible with the B midblocks of ternary blocks or star block copolymers.

A ternary block or star block copolymer having an A block derived from an alkyl methacrylate such as methyl methacrylate and a B block derived from an alkyl acrylate such as n-butyl acrylate is an A block derived from an alkyl methacrylate such as methyl methacrylate. It can be mixed with a binary block having the above and a B block derived from an alkyl acrylate such as n-butyl acrylate. The binary block of 50% by weight or less can be a hard polymer unit. For example, some binary blocks have 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less of hard polymer units, and the rest of the binary blocks are soft polymer units. ..

By adding a binary block copolymer, the adhesiveness of the adhesive composition can often be further increased. The binary block copolymer can be added in any desired amount, but in most cases, it is added in an amount of 50% by weight or less based on the total weight of the binary block copolymer and the ternary block or star block copolymer. For example, the amount of binary block is 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 20% by weight or less, based on the total weight of the binary block copolymer and the ternary block or star block copolymer. It can be 15% by weight or less.

Other optional additives include, for example, stabilizers such as antioxidants and UV stabilizers, dyes, and radiation cross-linking agents.

Goods and goods manufacturing method Articles containing an adhesive composition are provided. The adhesive composition (same as described above) is usually attached to the substrate. In most embodiments, the adhesive composition is a pressure sensitive adhesive. As used in the present invention, the term "pressure sensitive adhesive" means strong and durable adhesiveness, adhesion to a substrate under finger pressure, and sufficient binding force to be removed cleanly from the substrate. Means an adhesive that indicates.

Any suitable substrate can be used. Some suitable substrates include paper, fabrics, polymer materials, glass materials, ceramic materials, metal-containing materials such as metals or metal oxides, or combinations thereof. The substrate can have any suitable thickness and surface texture. The substrate can be flexible or rigid. The base material may include a single layer or a multi-layer such as a support layer, an undercoat layer, a hard coat layer, a decorative layer and the like. The substrate can be visually transparent, colored but permeable, or opaque (ie, opaque).

Examples of polymer materials that can be used as substrates include polyvinyl chloride, polyester (eg polyethylene terephthalate), polyolefins, poly (meth) acrylates, polyurethanes, polycarbonates, fluorinated polymers with perfluoro groups, polyethylene. Vinyl acetate, cellulose acetate, ethyl cellulose and the like can be mentioned, but the present invention is not limited thereto. Typical polyolefins include polyethylene (eg, high density polyethylene) and polypropylene (eg, high density polypropylene). Some polymer materials have metallized surfaces such as metallized polymer films. Other polymeric materials have an outer layer that forms a release surface (eg, the release surface can contain a silicone material). The polymeric material substrate can be in any suitable form, such as, for example, a sheet or foam. Some typical foam substrates contain polyolefins (eg polyethylene), polyurethanes, poly (meth) acrylates, or neoprene.

Examples of fabrics that can be used as a substrate include non-woven fabrics in addition to woven fabrics. These fabrics can be made using yarns that are natural (eg, cotton, wool, or silk) or synthetic (eg, nylon, polyester, or rayon). The fabric can also be made from ceramic materials or glass.

Some substrates include metals. Some typical metal substrates are films containing aluminum or copper.

The article can include two substrates with an adhesive composition placed between the two substrates. For example, an adhesive film containing an adhesive composition attached to a first base material is bonded to the second base material so that the adhesive composition is arranged between the first base material and the second base material. Can be made to. Any suitable second substrate can be used, but in some applications the second substrate is a low surface energy substrate, such as those containing polyolefins.

For example, the adhesive composition can be adhered to one main surface of the first substrate, and the opposite main surface of the first substrate can have a graphic design or label. The layer of the adhesive composition can be placed between the first substrate and the release liner. By removing the release liner, the adhesive composition can be adhered to the second substrate. For example, the second substrate can be a low surface energy substrate, such as one containing polyolefin.

Some more specific articles are transfer tapes. The transfer tape can include an adhesive layer placed between the two release liners, or can include an adhesive layer placed adjacent to a single release liner. Another specific article is a single-sided tape in which a substrate (eg, backing material or carrier) is placed adjacent to a single adhesive layer. A further specific article is a double-sided tape in which a substrate (eg, backing material or carrier) is placed between two adhesive layers. The substrate of the single-sided or double-sided tape can be, for example, a film, a non-woven fabric, a woven fabric, or a foam.

In many articles, the adhesive composition is optically transparent. As used in the present invention, the term "visually transparent" means at least 90% visual transmission, less than about 2% haze, and less than about 1% in the wavelength band of 400-700 nanometers. It means an adhesive composition in the form of a film having a thickness of about 0.05 mm (2 mils) with opacity. Both visual transmittance and haze can be measured using, for example, ASTM-D 1003-95. Optically transparent adhesive compositions are often aesthetically bubble-free. Optical transparency is measured when the adhesive composition is in film form, but the optically transparent adhesive composition does not have to be in film form.

The optical transparency of the adhesive composition may depend on the size of the A block domain. The A block domain often has an average size of less than 200 nanometers, less than 150 nanometers, or less than 100 nanometers. The size of the A block domain can be changed, for example, by varying the amount of A block or by changing the monomer composition used to form the A block within the block copolymer. Unless the indices of refraction of both the A block and the B block are well matched, the larger size A block domain tends to cause light scattering.

Articles containing the substrate and the adhesive layer attached to the substrate can be made, for example, using coating techniques. When using coating techniques, the adhesive composition often contains a solvent. Suitable coating methods include, but are not limited to, knife coating, die coating, spray coating and the like. The substrate is often a flexible backing material that can be supplied from the roll for coating. After coating, the solvent can be removed by evaporation or drying.

Alternatively, the substrate and the article containing the adhesive layer attached to the substrate can be made by applying the adhesive composition to the substrate using a hot melt process. The adhesive composition can be applied, for example, by spraying or extruding the solution.

These examples are for the purpose of exemplification only, and do not mean that they are limited to the scope of the attached document name claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are per weight unless otherwise stated. Solvents and other reagents used were obtained from Sigma-Aldrich Chemical Company (Milwaukee, Wisconsin), unless otherwise stated.<tables num="1"><img id="000011" he="192" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> Test method 180 degree peel strength Adhesive tape samples (ie, adhesive compositions coated on a polymer backing) are available from Imass, Inc. Analysis was performed using an IMASS slip / peel tester available from (Accord, Mass.). A 1.27 cm wide strip of adhesive tape was applied to the horizontal surface of a clean polypropylene test plate fixed to a peeling tester. The adhesive was placed between the polypropylene test plate and the polymer backing. Firm contact between the adhesive and the polypropylene test plate was performed by pressure molding on a polymer backing material by passing it through a 2 kg hard rubber roller once. The free end of the strip was attached to the peel tester scale. The strip was removed at a constant rate of 30.5 cm / min (12 inch / min). Peeling adhesion is measured in ounces and expressed in Newton / decimeter (N / dm). The data reported in Table 2 are the averages of multiple tests. If the tape showed an irregular response (ie, jerky), it was reported as a shokky peel. 90 degree peel strength of acrylic foam tape Foam tape samples were evaluated by measuring their peeling adhesive strength to various surfaces. Foam tapes were made as described in Example 14. Applicable to strip polypropylene (PP), high density polyethylene (HDPE), or stainless steel (SS) test panels of foam tape with dimensions of 1.25 cm width x 12.7 cm length, and 0.13 mm thick anode treated The aluminum foil was laminated on the exposed adhesive layer. Since the aluminum foil is larger in size than the foam tape, there was an aluminum foil portion that was not laminated on the adhesive layer. The assembly was then roller pressed using a 6.8 kg steel roller four times at a speed of 61 cm / min (24 inch / min) and left at room temperature (about 22 ° C.) for 24 hours. did. Aluminum strip at 90 degree angle, Instron type 4465 tensile tester (Instron) Foam tape was stripped from the test panel at a crosshead speed of 30.5 cm / min (12 inch / min) within Corporation (available from Norwood, Mass.). The average peeling adhesive force required to remove the foam tape from the panel is measured in pounds and expressed in Newton / decimeter (N / dm). Gel permeation chromatography analysis The weight average molecular weight of block copolymers was measured using gel permeation chromatography (GPC). 10.0 mL aliquot of tetrahydrofuran was added to about 25.0 mg of each sample. The block copolymer was dissolved in tetrahydrofuran overnight. After lysis, the sample was filtered through a 0.25 micron Teflon® syringe filter. The GPC apparatus (model 2695 separation module) was obtained from Waters Corporation (Milford, Mass.) With a PL gel mixed B column (Polymer Labs Varian, Inc. (Amherst, Mass.)). The eluate was tetrahydrofuran, the injection volume was 100 microliters, the temperature was 35 ° C., and the detector was a model 100 dual detector (refractive index portion) (from Viscotec Corporation (Houston, Texas)). The molecular weight calculation was based on a calibration curve made using a narrow dispersible polystyrene standard in the molecular weight range of 7.50E + 06 grams / mol to 580 grams / mol. The actual calculation was completed with Cirrus GPC software (from Polymer Labs). Dynamic mechanical analysis The adhesive composition was tested by dynamic mechanical analysis (DMA) in a parallel plate rheometer, marketed as Model A2000 from TA Instruments (New Castle, Delaware). Samples were heated at 50 ° C. to 150 ° C. at a rate of 2 ° C. per minute at a frequency of 1 radian / sec and a maximum strain of 1%. The storage modulus (G') value as a function of temperature was recorded. Nuclear magnetic resonance analysis The tackifier was analyzed by proton 1H nuclear magnetic resonance (NMR) spectroscopy on a Varian INOVA 400 NMR spectrometer. The tackifier was dissolved in chloroform.<tables num="2"><img id="000012" he="136" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> Differential scanning calorimetry (DSC) analysis The glass transition temperatures of the various tackifiers were measured using a differential scanning calorimeter (Model Q200) commercially available from TA Instruments (New Castle, Delaware). The sample was heated by increasing the temperature at a rate of 10 ° C. per minute. The glass transition temperature was characterized as the midpoint of the inflection point in the heat transfer vs. temperature curve.<tables num="3"><img id="000013" he="55" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> Compatibility of tackifiers with ternary block copolymers The compatibility of various tackifiers with ternary block copolymers was determined by preparing various compositions having different ratios of tackifier to ternary block copolymers, as shown in Table 4 below. The film was cast from the composition. The clear film indicates that the tackifier is soluble in the ternary block copolymer. The opaque film indicates that the solubility of the ternary block copolymer in the tackifier has exceeded the limit. Various compositions containing 55% by weight of solids in toluene were prepared. The ternary block copolymer used was LA Polymer 410. The composition was cast as a thick film and the solvent was removed by evaporation. The amount of the ternary block polymer (% by weight), the tackifier, and the amount of the tackifier (% by weight) are shown in Table 4 for the resulting film. The opacity or permeability of the resulting film was recorded.<tables num="4"><img id="000014" he="74" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> Various adhesive compositions containing 55% by weight of solids in toluene were prepared. The ternary block copolymer (which was LA polymer 410) was mixed with various tackifiers as shown in Table 5. Each adhesive composition contained 60% by weight of the ternary block copolymer and 60% by weight of the tackifier based on the total weight of the adhesive composition. The adhesive composition is knife-coated on a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to obtain an approximately 50 micrometer (2 mil) thick dry adhesive coating. It was. Haze measurements were performed using a BYK Gardner haze meter.<tables num="5"><img id="000015" he="71" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> (Example 1) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 40% by weight LA Polymer 2140 ternary block copolymer, 5% by weight Foral 85 solid tackifier, 35% by weight Superester A-75 solid tackifier, and 20% by weight Staverite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 2) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 40% by weight LA Polymer 2140 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 30% by weight Superester A-75 solid tackifier, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 3) An adhesive composition containing 62% by weight of solids in toluene was prepared. The solid content was 40% by weight LA polymer 2140 ternary block copolymer, 30% by weight Foral 85 solid pressure-imparting agent, 10% by weight Superester A-75 solid pressure-imparting agent, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 4) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 50% by weight LA Polymer 2140 ternary block copolymer, 5% by weight Foral 85 solid pressure-imparting agent, 25% by weight Superester A-75 solid pressure-imparting agent, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 5) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 50% by weight LA Polymer 2140 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 20% by weight Superester A-75 solid tackifier, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 6) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 50% by weight LA Polymer 2140 ternary block copolymer, 15% by weight Foral 85 solid pressure-imparting agent, 15% by weight Superester A-75 solid pressure-imparting agent, and 20% by weight Staverite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 7) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 60% by weight LA polymer 2140 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 10% by weight Superester A-75 solid tackifier, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. This adhesive composition was also knife coated on a silicone release liner and dried in an oven at 90 ° C. The obtained film was laminated to a thickness of about 2 to 3 mm and subjected to a dynamic mechanical test. The results are shown in FIG. (Example 8) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 60% by weight LA Polymer 2140 ternary block copolymer, 15% by weight Foral 85 solid tackifier, 5% by weight Superester A-75 solid tackifier, and 20% by weight Stevelite ester. It contained a 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 9) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solid content is 10% by weight LA Polymer 410 ternary block copolymer, 30% by weight LA polymer 2250 ternary block copolymer, 5% by weight Foral 85 solid tackifier, 35% by weight Superester A-75 solid adhesive. It contained an imparting agent and a 20% by weight Stevelite ester 3-E liquid tackifier. This adhesive composition is knife-coated on a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to obtain a dry adhesive coating about 50 micrometer (2 mil) thick. It was. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 10) An adhesive composition containing 62% by weight of solids in toluene was prepared. The solids were 30% by weight LA Polymer 410 ternary block copolymer, 10% by weight LA Polymer 2250, 5% by weight Foral 85 solid tackifier, 35% by weight Superester A-75 solid tackifier, and It contained 20% by weight of the Staverite ester 3-E liquid tackifier. This adhesive composition was knife-coated on a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to obtain a dry adhesive coating about 50 micrometer (2 mil) thick. It was. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 11) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 33% by weight LA Polymer 2140 ternary block copolymer, 7% by weight LA polymer 410 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 30% by weight Superester A-75 solid adhesive. It contained an imparting agent and a 20% by weight Stevelite ester 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 12) An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids were 27% by weight LA Polymer 2140 ternary block copolymer, 13% by weight LA polymer 410 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 30% by weight Superester A-75 solid adhesive. It contained an imparting agent and a 20% by weight Stevelite ester 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. (Example 13) An adhesive composition containing 62% by weight of solids in toluene was prepared. The solids were 20% by weight LA Polymer 2140, 20% by weight LA Polymer 410 ternary block copolymer, 10% by weight Foral 85 solid tackifier, 20% by weight Superester A-75 solid tackifier, and 20% by weight Superester A-75 solid tackifier. It contained 20% by weight of the Staverite ester 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. Comparative Example 1 An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids contained 40% by weight LA polymer 2140 ternary block copolymer, 40% by weight Foral 85 solid tackifier, and 20% by weight Staverite ester 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9. Comparative Example 2 An adhesive composition containing 62% by weight of solids in toluene was prepared. The solid content contained 50% by weight LA2140 ternary block copolymer, 40% by weight Foral 85 solid tackifier, and 10% by weight Staverite ester 3-E liquid tackifier. The adhesive composition was knife coated onto a 50 micrometer (2 mil) thick polyester film and dried in an oven at 90 ° C. for 15 minutes to approximately 27-30 micrometers (1.1-1.2 mils). A thick dry adhesive coating was obtained. The 180 degree peeling test data of this example is shown in Table 6. The contents of the tackifier mixture and the adhesive composition are shown in Tables 7-9.<tables num="6"><img id="000016" he="106" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables><tables num="7"><img id="000017" he="107" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables><tables num="8"><img id="000018" he="110" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables><tables num="9"><img id="000019" he="107" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables><tables num="10"><img id="000020" he="107" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables> Comparative Example 3 An adhesive composition containing 62% by weight of solids in toluene was prepared. Solids contained 60% by weight LA polymer 2140 ternary block copolymer, 20% by weight Foral 85 solid tackifier, and 20% by weight Staverite ester 3-E liquid tackifier. The adhesive composition was knife-coated on a silicone release liner and dried in an oven at 90 ° C. The obtained film was laminated to a thickness of about 2 to 3 mm and subjected to a dynamic mechanical test. The results are shown in FIG. Comparative Example 4 An adhesive composition containing 62% by weight of solids in toluene was prepared. The solid content contained 60% by weight LA polymer 2140 ternary block copolymer, 20% by weight Superester A-75 solid tackifier, and 20% by weight Stevelite ester 3-E liquid tackifier. The adhesive composition was knife-coated on a silicone release liner and dried in an oven at 90 ° C. The obtained film was laminated to a thickness of about 2 to 3 mm and subjected to a dynamic mechanical test. The results are shown in FIG. (Example 14) 50% by weight LA Polymer 410 ternary block copolymer, 10% by weight Foral 85 solid adhesive, 20% by weight Superester A-75 solid adhesive, and 20% by weight Staverite ester 3E liquid adhesive. An adhesive composition containing the agent was prepared. The adhesive composition was compounded in a 25 mm biaxial extruder manufactured by Thermo Scientific Hake Corporation (Milwakee, Wisconsin). The melting temperature was maintained at 149 ° C. (300 ° F) and the adhesive was coated as a transfer adhesive on the silicone release liners listed in Table 1 as an adhesive with a thickness of approximately 50 micrometers (2 mils). .. (Example 15) Using a transfer adhesive as described in Example 14, a 45 mil (1.1 mm) thick acrylic foam tape having the adhesive layers of the present invention on both sides of the foam was made. A foam containing a primer, a 10% solids solution of a polyamide resin (Macromelt 6240 from Henkel, Inc.) in a solvent blend with 47.5 parts of isopropanol, 47.5 parts of n-propanol and 5 parts of water. Using a brush, it was applied to the top of the adhesive transfer tape and dried at ambient temperature for 10 minutes to give a 0.00033 inch (0.0083 mm) thick dry primer. The primed transfer tape was manually rolled down to each side of the acrylic foam (primer surface to foam) and then placed in a laminating machine heated to 45 ° C (115 ° F) at 2.3 m / min (7). Feed at a rate of .5 ft / min) to obtain a foam tape structure. Acrylic foams were made as described in Example 7 of US Pat. No. 4,749,590 (Klingen et al.), Except for the following: After partial polymerization and prior to foaming, 0.19 parts of additional 2,2-dimethoxy-2-phenylacetophenone (available from Ciba Specialty Chemicals (Tarrytown, NY) as Irgacare 651), 0.55 parts of 1,6-hexanediol diacrylate (available from Sartomer (Exton, PA) as SR-238), 2 parts of hydrophobic fumed silica (Wacker-Chemie as HDK H15P) GMBH (available from Munich, NY), 8 parts of glass microspheres (available as K-15 from 3M (St. Paul, PA)), 0. 57 parts of black dye and 1.54 parts of surfactant were added to 100 parts of syrup. The black pigment is 4.6 parts of carbon black (Cabot as Monarch 120). A dispersion in 80.0 parts polypropylene glycol and 15.4 parts anhydrous tin chloride from Corporation (available from Billerica, Mass.). Surfactants are described in Example 1 of US Pat. No. 5,024,880. Therefore, in order to evaluate the 90-degree peel strength, a pressure-sensitive foamed tape was attached to various substrates. Adhesive data for polypropylene (PP), high density polyethylene (HDPE), and stainless steel (SS) are shown in Table 11.<tables num="11"><img id="000021" he="41" wi="158" file="0005543439.tif" img-format="tif" img-content="drawing" /></tables>

12 members in 6 offices

This recordMember, by publication datePriority claim

Priority claims6

Priority claims
Document	Office	Kind	Date
5753208	United States of America	P	2008-05-30
2009041875	United States of America	W	2009-04-28
2008057532	–	–	–
2009041875	–	–	–
US20080057532P	–	–	–
WO2009US41875	–	–	–

Members12

Family members, oldest first
Document	Office	Kind
WO2009146227A1	World Intellectual Property Organization (WIPO)	A1	2009-12-03
KR20110010810A	Republic of Korea	A	2011-02-07
EP2291481A1	European Patent Office (EPO)	A1	2011-03-09
US2011135922A1	United States of America	A1	2011-06-09
CN102099433A	China	A	2011-06-15
JP2011522088A	Japan	A	2011-07-28
US8551616B2	United States of America	B2	2013-10-08
CN102099433B	China	B	2013-10-23
EP2712904A1	European Patent Office (EPO)	A1	2014-04-02
JP5543439B2This record	Japan	B2	2014-07-09
EP2291481B1	European Patent Office (EPO)	B1	2014-10-01
KR101617479B1	Republic of Korea	B1	2016-05-02

13 legal events, as the office reported them to INPADOC

Over the term

Point at a mark for the event

Events

Legal events, newest first
	Event	Code
2020-05-16	Cancellation because of no payment of annual feesLAPS	LAPS
2019-05-14	Receipt of annual feesJAPANESE INTERMEDIATE CODE: R250R250	R250
2018-05-08	Receipt of annual feesJAPANESE INTERMEDIATE CODE: R250R250	R250
2017-05-09	Receipt of annual feesJAPANESE INTERMEDIATE CODE: R250R250	R250
2014-05-16	Certificate of patent or registration of utility modelJAPANESE INTERMEDIATE CODE: R150R150	R150
2014-05-15	First payment of annual fees (during grant procedure)JAPANESE INTERMEDIATE CODE: A61A61	A61
2014-04-09	Written decision to grant a patent or to grant a registration (utility model)JAPANESE INTERMEDIATE CODE: A01A01	A01
2014-04-01	Decision of grant or rejection writtenTRDD	TRDD
2013-12-10	Written amendmentJAPANESE INTERMEDIATE CODE: A523A521	A521
2013-09-11	Notification of reasons for refusalJAPANESE INTERMEDIATE CODE: A131A131	A131
2013-09-06	Report on retrievalJAPANESE INTERMEDIATE CODE: A971007A977	A977
2012-04-03	Written amendmentJAPANESE INTERMEDIATE CODE: A523A521	A521
2012-04-03	Written request for application examinationJAPANESE INTERMEDIATE CODE: A621A621	A621