Compound having structural unit of polysiloxane, coating composition curable by active energy ray, and material having curing film of the composition

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to novel compounds having a given polysiloxane structural unit. Further, the present invention has excellent hardness / abrasion resistance, transparency, excellent stain resistance, particularly fingerprint resistance, and curing capable of providing excellent antistatic property and peelability as required. The present invention relates to an active energy ray-curable coating composition capable of forming a coating. Furthermore, the present invention relates to a material (film, sheet, resin plate, etc.) having a cured coating having excellent hardness, abrasion resistance, transparency, and fingerprint resistance.

【0002】

[Conventional technology]

Plastic products such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, styrene resins such as ABS, vinyl chloride resins, cellulose acetate, etc. are particularly excellent in lightness, ease of processing, impact resistance, etc. Therefore, it is used for various purposes such as containers, instrument panels, packaging materials, and various housing materials.

【0003】

However, these plastic products have low surface hardness and are easily damaged. Therefore, a transparent resin such as polycarbonate or polyethylene terephthalate has a drawback that the original transparency and appearance of the resin are significantly impaired by repeated use. Therefore, it is difficult to use such a plastic product in a field where wear resistance is required.

【0004】

Therefore, an active energy ray-curable hard coat material (coating material) is provided for the purpose of imparting abrasion resistance to the surface of the plastic product. However, the cured layer of a commercially available active energy ray-curable hard coat material has a drawback that static electricity is likely to be generated because the surface specific resistance value is high. The generated static electricity promotes the adhesion of dust and dirt to the product, which has been a cause of spoiling the aesthetics and transparency of the product.

【0005】

In order to avoid the problems of abrasion resistance and adhesion of dust and dust due to the generation of static electricity, active energy ray curing capable of giving a coating having abrasion resistance and antistatic property to the surface of a plastic product. Various methods for applying the sex coating material have been studied. Further, a method has been devised in which an antistatic layer having abrasion resistance is provided on the front surface side of the plastic product and a transparent film having an adhesive layer is attached on the back surface side. However, even these conventional methods still have insufficient wear resistance.

【0006】

Therefore, recently, various active energy ray-curable coating agents capable of achieving hardness and wear resistance superior to those of conventional methods have been proposed. For example, Japanese Patent Application Laid-Open No. 11-309814 states that the surface of a resin base material is coated with two or more layers of a coating agent, and an inorganic film-forming coating agent such as polysilazane is used for the outermost layer to withstand abrasion. A transparent coated molded product with significantly improved properties is disclosed. However, since the coating agent used on the surface of this coated molded product is an inorganic coating agent, there are problems that it is difficult to thicken the film and that productivity is poor because two or more layers need to be applied. there were. In addition, the stain resistance has not been improved so much, and once the product becomes dirty, it is difficult to wipe it off.

【0007】

Attempts have also been made to improve hardness and wear resistance by coating two or more layers of coating agents having different elastic moduli. For example, Japanese Patent Application Laid-Open No. 2000-52472 shows that a coating film having a high hardness can be obtained by increasing the elastic modulus of the coating agent of the second layer as compared with the coating agent of the first layer. Further, Japanese Patent Application Laid-Open No. 2000-214791 shows that a coating film having high hardness can be obtained by making the elastic modulus of the coating agent of the second layer smaller than that of the coating agent of the first layer. All of these coating agents can increase the apparent hardness by avoiding shock absorption and stress concentration. However, there is a problem that the total thickness of the coating film becomes 10 μm or more and the productivity is poor because two or more layers need to be applied. In addition, there is also a problem that the stain resistance of the coating film of this coating agent has not been improved so much.

【0008】

Further, in Japanese Patent Application Laid-Open No. 2000-219845, a methacrylic polymer is applied to the first layer, and a coating layer obtained by curing an organosiloxane resin composed of colloidal silica and a hydrolyzed condensate of a specific silicate is laminated on the second layer. Thereby, it is disclosed that a coating film having an excellent abrasion resistance having a total thickness of 10 μm or less can be realized. However, since this technique requires coating of two or more layers, there is a problem in productivity and the like. In addition, this coating also has a problem that the stain resistance is not very good.

【0009】

On the other hand, various coating agents that can achieve excellent hardness and wear resistance even with a single layer coating have been studied. For example, as disclosed in JP-A-5-287215 and JP-A-9-100111, active energy ray-curable coating agents based on a compound obtained by reacting a polyfunctional acrylate with colloidal silica have been conventionally used. Compared to the organic / inorganic composite coating agent of No. 1, the hardness and wear resistance are improved to some extent even by single-layer coating. However, it is difficult to impart antistatic properties, and there are still problems with the stability of the coating agent, so there is a drawback that there are large practical restrictions. Moreover, the stain resistance was not sufficient.

【0010】

Further, Japanese Patent Application Laid-Open No. 2000-15734 states that the hardness can be improved by using a coating agent in which a low elastic modulus component such as urethane acrylate oligomer is blended with a polyfunctional acrylate, and ITO is further applied to the coating film. Conductive layer such as (indium tin oxide) layer and SiO₂It has been shown that antistatic properties can be imparted by coating an inorganic layer such as a layer in multiple layers. However, when the antistatic layer is included, it still becomes a multi-layer coating, and there are many problems in productivity and inferior in stain resistance.

【0011】

Further, as a coating agent having an antistatic property, for example, a technique of blending an organic cationic substance such as a quaternary ammonium salt structure shown in JP-A-10-279833 is known. Further, a technique of blending an anionic substance such as an organic sulfonate shown in JP-A-2000-95970 is also known. In addition, a technique for dispersing an inorganic conductive filler and a technique for blending an organic π-electron conjugate polymer are also being studied. However, even with these techniques, it was not possible to achieve sufficiently high hardness and wear resistance. In addition, it is difficult to uniformly mix the organic cationic substance with colloidal silica, and the organic anionic substance has problems such as low solubility in an organic solvent and low transparency. It is an obstacle to achieving both improvement of antistatic property.

【0012】

Further, for example, as shown in JP-A-2000-80169, a composition containing a polymer having a polydimethylsiloxane structure introduced at a specific site as an organic cationic substance having a quaternary ammonium salt structure. According to this, it is possible to form a film having excellent antistatic property, stain resistance and abrasion resistance as compared with other conventional techniques. However, further improvements have been required for pencil hardness and abrasion resistance. Further, in terms of stain resistance, it cannot be said that fingerprint resistance (suppression of fingerprint adhesion, easy wiping of adhered fingerprints) is not always sufficient.

【0013】

On the other hand, the addition reaction of a hydrogen siloxane group to a double bond in the presence of a transition metal catalyst such as Pt has been widely studied academically and industrially in the field of organosilicon chemistry as a hydrosylation reaction. There is. This hydrosyllation reaction is generally used for the preparation of a peelable paint and the cross-linking high molecular weight reaction. However, the reaction with polyfunctional acrylate is difficult to control and gelation reaction is likely to occur. Therefore, Japanese Patent Application Laid-Open No. 7-149906 and Journal of Applied Polymer Science, Vol. 47, 1309 As shown on page 1314 (1993), etc., it is only applied to the reaction with a specific polymer siloxane having a relatively low content of hydrogen siloxane group.

【0014】

[Problems to be Solved by the Invention]

Thus, the present invention has been made in view of the above prior art, and the solution of the present invention is to cure by irradiating with active energy rays, resulting in a high contact angle with water and organic matter, excellent. An active energy ray-curable coating composition capable of forming a film having hardness, abrasion resistance, transparency, and, if necessary, excellent antistatic properties, and achieving excellent stain resistance (particularly fingerprint resistance). Is to provide. Another object of the present invention is to provide a novel compound that can be used as an active ingredient of such an active energy ray-curable coating composition. Further, another problem to be solved by the present invention is a material having excellent hardness, abrasion resistance, transparency and fingerprint resistance, and a material having antistatic properties as required (particularly a film or a sheet). And a resin plate).

【0015】

[Means for solving problems]

As a result of diligent studies in order to solve the above problems, the present inventors have found that an excellent active energy ray-curable coating composition can be provided by using the following compounds. That is, the present invention provides a compound having a polysiloxane structural unit represented by the following general formula (1).

【0016】

[Chemical 3]

<img file="JP2002194084A_D0001.tif" />【0017】

In the general formula (1), R is a hydrogen atom (however, the ratio of hydrogen atom to n R is 20% or less), methyl group, -R.¹-COO-R²(R¹Is an alkylene group with 2 or 3 carbon atoms, R²Is a group with a molecular weight of 2000 or less containing two or more acryloyl groups, or a group having a metal oxide or an inorganic oxide), -R³-COO-R⁴(R³Is an alkylene group with 2 or 3 carbon atoms, R⁴Is a group having a (meth) acrylic polymer having a molecular weight of 3000 or more), or a group consisting of a metal oxide or an inorganic oxide, n represents an integer of 2 or more, and at least one of n Rs is -R¹-COO-R²And at least one other is -R³-COO-R⁴Alternatively, it is a group composed of a metal oxide or an inorganic oxide.

【0018】

The present invention further provides an active energy ray-curable coating composition having a polysiloxane structural unit represented by the following general formula (2).

【0019】

[Chemical 4]

<img file="JP2002194084A_D0002.tif" />【0020】

In the general formula (2), R'is a hydrogen atom (however, the ratio of hydrogen atom to n R'is 20% or less), methyl group, -R.¹-COO-R²(R¹Is an alkylene group with 2 or 3 carbon atoms, R²Is a group with a molecular weight of 2000 or less containing two or more acryloyl groups, or a group containing a metal oxide or an inorganic oxide), -R³-COO-R⁴(R³Is an alkylene group with 2 or 3 carbon atoms, R⁴Is a group having a (meth) acrylic polymer with a molecular weight of 3000 or more), or a group consisting of a metal oxide or an inorganic oxide, n indicates an integer of 2 or more, and n R's are different from each other. There may be at least one R'-R¹-COO-R²Is.

【0021】

However, all n R's are -R³-COO-R⁴And when it is not a group having a metal oxide or an inorganic oxide, the active energy ray-curable coating composition contains a compound having a polysiloxane structural unit represented by the general formula (2) in the molecule. It contains a (meth) acrylic polymer having a molecular weight of 3000 or more, which contains an acryloyl group and / or a methacryloyl group, or a metal oxide or an inorganic oxide.

【0022】

Further, in the present invention, an acrylate group contained in a polyfunctional acrylate (A) having a molecular weight of 2000 or less having three or more acryloyl groups in the molecule is contained in a polysiloxane (B) having a methylhydrogensiloxane group. Hydrosilylation with Si-H groups to reduce the residual ratio of Si-H groups present in the polysiloxane (B) to 20% or less (however, before, during, or after the hydrosilylation reaction, in the molecule. Contains a composition obtained from a (meth) acrylic polymer (C) having an acryloyl group and / or a methacryloyl group and having a molecular weight of 3000 or more (adding / or a metal oxide or an inorganic oxide (D)). An active energy ray-curable coating composition is provided.

【0023】

The weight ratio of the polyfunctional acrylate (A) to the polysiloxane (B) is preferably (A) :( B) = 85: 15 to 99.5: 0.5. The weight ratio of the polyfunctional acrylate (A), the polysiloxane (B), and the (meth) acrylic polymer (C) is (A) :( C) = 65: 35 to 95 :. It is 5, and it is preferable that ((A) + (C)): (B) = 85: 15 to 99.5: 0.5. Further, the weight ratio of the polyfunctional acrylate (A), the polysiloxane (B), and the metal oxide or the inorganic oxide (D) is (A) :( D) = 90: 10 to 10 :. It is 90, and it is preferable that (A): (B) = 85: 15 to 99.5: 0.5.

【0024】

Further, as the polysiloxane (B), a homopolymer of polymethylhydrogensiloxane having both ends having a trimethylsilyl group or a polysiloxane having a methylhydrogensiloxane group of 50 mol% or more in the polysiloxane structural unit may be used. it can. Further, as the (meth) acrylic polymer (C), in addition to an acryloyl group and / or a methacryloyl group, an aryl group, an aralkyl group, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 6 or more carbon atoms, and a poly A (meth) acrylic polymer having at least one hydrophobic group selected from a dimethylsiloxane group and a perfluoroalkyl group can be used. Further, as the (meth) acrylic polymer (C), a (meth) acrylic polymer having an acryloyl group and / or a methacryloyl group and a quaternary ammonium base can be used. Further, the (meth) acrylic polymer (C) has an acryloyl group and / or a methacryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and a quaternary ammonium base (meth). Acrylic polymers can be used. Further, as the metal oxide or the inorganic oxide (D), a silica sol dispersible in an organic solvent can be used. Further, as the polyfunctional acrylate (A) and / or the metal oxide or inorganic oxide (D), the polyfunctional acrylate (A) and the metal oxide or inorganic oxide (D) are directly or as a bonding group. Those bonded via the above can be used.

【0025】

Furthermore, the present invention provides a material having a cured film formed by applying the active energy ray-curable coating composition and irradiating with active energy rays, and the material is a film, a sheet or a sheet. It can be a resin plate.

【0026】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail. First, the compound having the polysiloxane structural unit of the present invention and each component constituting the active energy ray-curable coating composition will be described, and then the application of the composition will be described.

【0027】

The compound of the present invention is characterized by having a polysiloxane structural unit represented by the above general formula (1). Further, the active energy ray-curable coating composition of the present invention contains a compound having a polysiloxane structural unit represented by the above general formula (2), and if necessary, an acryloyl group and / or a methacryloyl group in the molecule. It is characterized by containing a (meth) acrylic polymer having a molecular weight of 3000 or more, or a metal oxide or an inorganic oxide.

【0028】

The ratio of hydrogen atoms in n R or R'constituting the general formulas (1) and (2) is 20% or less. When the ratio of the hydrogen atom is 20% or less, the storage stability and transparency of the compound or composition of the present invention can be ensured, which is preferable. The method of reducing the proportion of hydrogen atoms to 20% or less is not particularly limited. A method of reducing the proportion of hydrogen atoms in the polysiloxane to 20% or less by using a hydrosyllation reaction is preferable. The ratio of hydrogen atoms to n R or R'is more preferably 15% or less, even more preferably 12% or less, and particularly preferably 10% or less. Further, the polysiloxane structural unit of the above general formulas (1) and (2) may contain dimethylsiloxane in which R or R'is a methyl group.

【0029】

R or R'in the above general formulas (1) and (2) is -R¹-COO-R²If, then R¹Is an alkylene group with 2 or 3 carbon atoms and R²Is a group having a molecular weight of 2000 or less containing two or more acryloyl groups, or a group having a metal oxide or an inorganic oxide. This -R¹-COO-R²The group can be introduced, for example, by hydrosilylating a polyfunctional acrylate having three or more acryloyl groups in the molecule and having a molecular weight of 2000 or less with a SiH group of a polysiloxane structural unit. Further, by further reacting the polyfunctional acrylate group introduced in this manner with a metal oxide or an inorganic oxide, R²A group having a metal oxide or an inorganic oxide can be formed as a base.

【0030】

In addition, R or R'in the above general formulas (1) and (2) is -R.³-COO-R⁴If, then R³Is an alkylene group with 2 or 3 carbon atoms, R⁴Is a group having a (meth) acrylic polymer having a molecular weight of 3000 or more. This -R³-COO-R⁴The group can be introduced, for example, by hydrosilylating a (meth) acrylic polymer having a molecular weight or more containing an acryloyl group and / or a methacryloyl group with a SiH group of a polysiloxane structural unit. Further, R or R'of the above general formulas (1) and (2) may be a group composed of a metal oxide or an inorganic oxide. The metal oxide or inorganic oxide is introduced into the surface by, for example, a Si-OH group existing on the surface of the metal oxide or the inorganic oxide (in the absence of the -OH group, a silane coupling agent or a titanium coupling agent). It can be introduced by a dehydrogenation condensation reaction between the obtained -OH group) and the Si-H group of the polysiloxane structural unit. Further, an acryloyl group and / or a methacryloyl group may be bonded in advance to the surface of a metal compound or an inorganic oxide, and the polysiloxane structural unit can be introduced by hydrosyllation with a SiH group.

【0031】

A polyfunctional acrylate having a molecular weight of 2000 or less having three or more acryloyl groups in the molecule, a (meth) acrylic polymer having a molecular weight of 3000 or more containing an acryloyl group and / or a methacryloyl group, and a metal oxide or an inorganic substance. Specific examples of the oxide will be described later. The method for introducing the functional group is not particularly limited, and the compound and composition of the present invention are as long as they have the polysiloxane structural unit represented by the general formulas (1) and (2). Included within range.

【0032】

N in the above general formulas (1) and (2) is not particularly limited as long as it is an integer of 2 or more. n is preferably 3 or more, more preferably 5 or more, and particularly preferably 10 or more. Also, of the n Rs in general formula (1), at least one R is -R.¹-COO-R²And at least one other R is -R³-COO-R⁴Alternatively, it is a group composed of a metal oxide or an inorganic oxide. Other Rs may be the same or different from each other as long as they satisfy this condition. Further, the repeating units having the same R may or may not be continuous.

【0033】

On the other hand, in the R'of the general formula (2), at least one R'is -R.¹-COO-R²If so, the other R's may be the same or different from each other. Further, the repeating units having the same R'may be continuous or may not be continuous.

【0034】

However, all n R's are -R³-COO-R⁴And when it is not a group consisting of metal oxides or inorganic oxides, that is, in the polysiloxane structural unit represented by the above general formula (2), -R at all.³-COO-R⁴When the active energy ray-curable coating composition does not contain a group or a group composed of a metal oxide or an inorganic oxide, the active energy ray-curable coating composition includes a compound having a polysiloxane structural unit represented by the above general formula (2) and an intracellular compound. Contains a (meth) acrylic polymer having a molecular weight of 3000 or more, which contains an acryloyl group and / or a methacryloyl group, or a metal oxide or an inorganic oxide. That is, -R³-COO-R⁴A group consisting of a group and a metal oxide or an inorganic oxide is a composition in the form of a (meth) acrylic polymer having a molecular weight of 3000 or more or a metal oxide or an inorganic oxide containing an acryloyl group and / or a methacryloyl group in the molecule. It is contained in.

【0035】

Further, the active energy ray-curable coating composition of the present invention contains an acrylate group contained in a polyfunctional acrylate (A) having three or more acryloyl groups in the molecule and a molecular weight of 2000 or less, and a methylhydrogensiloxane group. Hydrosilylate with the Si-H group contained in the polysiloxane (B) having, and reduce the residual ratio of the Si-H group present in the polysiloxane (B) to 20% or less (however, before the hydrosilylation reaction). , A (meth) acrylic polymer (C) having an acryloyl group and / or a methacryloyl group having a molecular weight of 3000 or more in the molecule, and / or a metal oxide or an inorganic oxide (D) is added during or after the reaction. ) Can also be obtained. Therefore, these (A) to (D) components will be described below.

【0036】

Polyfunctional acrylate (A) having a molecular weight of 2000 or less and having 3 or more acryloyl groups in the molecule This polyfunctional acrylate (A) has three or more acryloyl groups in one molecule. If the number of acryloyl groups is less than 3, it is difficult to obtain sufficient wear resistance (scratch resistance). The molecular weight of (A) needs to be at least 2000 or less in order to suppress a decrease in reactivity and an increase in liquid viscosity, preferably 1500 or less, and even more preferably 1000 or less. The polyfunctional acrylate may contain a polymerized moiety such as an oligomer. Examples of such a polyfunctional acrylate (A) include trimethylol propane triacrylate, ethylene oxide-modified trimethylol propane triacrylate, propylene oxide-modified trimethylol propane triacrylate, tris (acryloxyethyl) isocyanurate, and caprolactone-modified tris (caprolactone-modified tris). Acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol tetraaacrylate, ditrimethylolpropanetetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl Obtained by reacting modified dipentaerytritor tetraacrylate, alkyl-modified sidipentaerytritor pentaacrylate, caprolactone-modified sidipentaerytritor hexaacrylate, and polyisocyanate with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule. Urethane acrylate, tetracarboxylic acid dianhydride, carboxyl group-containing polyfunctional acrylate obtained by reacting hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, and a mixture of two or more of these. Can be mentioned.

【0037】

Polysiloxane (B) with a methylhydrogensiloxane group When polysiloxane (B) having a methylhydrogensiloxane group is used in combination with the above (A), the toughness of the coating film can be improved and stain resistance (stain resistance; especially fingerprint resistance) is imparted. can do. The type of the polysiloxane (B) is not particularly limited as long as it is a polysiloxane compound having a methylhydrogensiloxane group. Polymeric polyhydrogensiloxanes, such as methylhydrogensiloxane polymers or copolymers of methylhydrogensiloxane and dimethylsiloxane, are preferred in view of improving toughness and crosslinkability. Specifically, a homopolymer of a polymethylhydrogensiloxane having a trimethylsilyl group at both ends, or a polysiloxane in which 50 mol% or more of the polysiloxane structural unit is a methylhydrogensiloxane group is particularly preferable.

【0038】

A (meth) acrylic polymer (C) having a molecular weight of 3000 or more and having an acryloyl group and / or a methacryloyl group in the molecule. By using this (meth) acrylic polymer (C) in combination with the polyfunctional acrylate (A), the toughness of the coating film can be improved. Since the (meth) acrylic polymer (C) has an acryloyl group and / or a methacryloyl group in the molecule, it is copolymerized with other acrylate components and cured when irradiated with active energy rays to form a film. It is possible to impart excellent transparency and the like. Further, when it is desired to impart antistatic properties to the film, it is preferable to use a (meth) acrylic polymer (C) having an antistatic property-imparting group such as a quaternary ammonium salt. The molecular weight of the (meth) acrylic polymer (C) is 3000 or more, and more preferably 5000 or more.

【0039】

The type of such a (meth) acrylic copolymer (C) is not particularly limited as long as it has an acryloyl group and / or a methacryloyl group and contains (meth) acrylate as a copolymerization component. For example, a copolymer of an aromatic ring such as a benzene ring, an (meth) acrylate having a hydrophobic group such as an alkyl group having 6 or more carbon atoms, a polydimethylsiloxane group, and a perfluoroalkyl group, and a hydroxyalkyl (meth) acrylate. Acryloyl group and / or methacryloyl group-containing isocyanate is added to the acryloyl group and / or methacryloyl group-containing copolymer, one or more (meth) acrylates, and hydroxyalkyl (meth) acrylates. Acryloyl group and / or methacryloyl group-containing isocyanate was added to a copolymer with a vinyl group-containing aromatic compound such as (meth) acrylamide or styrene derivative to contain acryloyl group and / or methacryloyl group. Copolymers, one or more (meth) acrylates, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, and vinyl group-containing aromatic compounds such as (meth) acrylamide and styrene derivatives. Examples thereof include a copolymer obtained by adding acryloyl acid and / or methacrylate to the coalescence and containing an acryloyl group and / or a methacryloyl group.

【0040】

On the other hand, as the antistatic property-imparting group, those having a quaternary ammonium base structure are preferable. Although there are various methods for introducing such a group, a tertiary amine-containing methacrylate such as dimethylaminoethyl methacrylate is copolymerized with an alkyl such as an alkyl halide, an alkyl halocarboxylate, a dialkyl sulfate, or an alkyl organic sulfonate. Examples thereof include a method of alkylating a tertiary amine with an agent to form a quaternary ammonium base structure. Those having an antistatic property-imparting group will be described in more detail below.

【0041】

Polymer with acryloyl group and quaternary ammonium base (C-1) This polymer contains a compound (a1) having one radically polymerizable group and a hydroxyl group in one molecule, (meth) acrylic acid esters (a2) having a tertiary amino group, and (a1) and (a2). ), And a compound (a4) having an acryloyl group and an isocyanato group is added to the hydroxyl group-containing polymer composition obtained by copolymerizing other (meth) acrylic acid esters (a3). It is obtained by obtaining a polymer (a5) having an acryloyl group in the side chain and then adding an alkylating agent (a6) to a tertiary amino group.

【0042】

Examples of the compound (a1) having one radically polymerizable group and a hydroxyl group in one molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Examples thereof include acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, caprolactone-modified -2-hydroxyethyl (meth) acrylate, and 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid.

【0043】

Typical examples of (meth) acrylic acid esters (a2) having a tertiary amino group include esters of (meth) acrylic acid and N, N-dialkylaminoalkyl alcohols. For example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl methacrylate, N, N-dibutylaminoethyl methacrylate and the like can be mentioned.

【0044】

The other (meth) acrylic acid esters (a3) that can be copolymerized with the above (a1) and (a2) have one radically polymerizable group in one molecule. Examples of such (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate. , T-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) ) Acrylate, cyanoethyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, polymerizable silane (eg, trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate) , Methyldimethoxysilylpropyl (meth) acrylate, etc.), polymerizable fluoroalkyl compounds (eg, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2 -(Perfluorooctyl) ethyl (meth) acrylate, etc.), polydimethylsiloxane having a terminal methacryloyl group, etc. can be mentioned.

【0045】

Examples of the compound (a4) having an acryloyl group and an isocyanate group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxypropyl acrylate, and caprolactone. Denatured 2-hydroxyethyl acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and other hydroxyl group acrylates, tolylene diisocyanate, isophorone diisocyanate, xylylene Examples thereof include adducts having a molar ratio of 1: 1 of isocyanate compounds such as isocyanate and hexamethylene diisocyanate.

【0046】

When copolymerizing (a1), (a2) and (a3), the amount of the compound (a1) having one radically polymerizable group and a hydroxyl group in one molecule is 100 weight by weight of the copolymerizable monomer. In%, it is 1 to 40% by weight, preferably 3 to 15% by weight. If it is 1% by weight or less, sufficient transparency and adhesion cannot be exhibited. On the other hand, if it is 40% by weight or more, cross-linked gel formation is likely to occur at the time of polymerization or (a4) addition, which is not preferable. The amount of (a2) + (a3) used is 60 to 99% by weight, preferably 85 to 97% by weight. Further, (a3) may be copolymerized by using two or more kinds. The weight ratio of (a2) and (a3) is (a2) :( a3) = 10: 90 to 98: 2, preferably (a2) :( a3) = 50: 50 to 96: 4.

【0047】

The above-mentioned copolymerization of (a1), (a2) and (a3) is carried out in a solvent using a usual radical polymerization initiator. Solvents include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethylene glycol dimethyl ether and ethylene glycol diethyl ether. , Ethers such as diethylene glycol dimethyl ether, ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, and these can be mixed and used. ..

【0048】

Examples of the radical polymerization initiator used in the polymerization reaction include organic peroxides such as benzoyl peroxide, di-t-butyl peroxide and cumene hydroperoxide, 2,2'-azobisisobutyronitrile, and 2,2'-azobis. Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferably used. The monomer concentration in the polymerization solution is usually 10 to 60% by weight, and the polymerization initiator can be used in an amount of 0.1 to 10% by weight, preferably 0.3 to 2% by weight, based on the usual monomer mixture. ..

【0049】

An acryloyl group obtained by adding a compound (a4) having an acryloyl group and an isocyanate group to the copolymer (a5) obtained by the copolymerization of the above-mentioned monomers (a1), (a2) and (a3). In the copolymer having the above, the ratio of the copolymer (a5) and the component (a4) to the hydroxyl group (-OH group) of the copolymer (a5) / the isocyanate group (-NCO group) of the (a4) 1 It is obtained by mixing with and stirring at 60 to 110 ° C for 1 to 20 hours. In this reaction, in order to prevent polymerization by acryloyl groups during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, and the amount used is a reaction mixture. With respect to this, it is 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight. Also, known reaction catalysts such as dibutyltin dilaurate and 1,4-diazabicyclo [2.2.2] octane may be added to promote the reaction.

【0050】

The desired polymer (a6) can be obtained by further converting the copolymer (a5) having an acryloyl group into a quaternary ammonium salt with an alkylating agent (quaternary agent). Examples of the alkylating agent (quaternary agent) include alkyl chlorides such as methyl chloride (methyl chloride) and butyl chloride (butyl chloride), methyl bromide (methyl bromide), methyl iodide (methyl iodide), and benzyl chloride (methyl iodide). Benzyl chloride), halides such as chloroacetic acid derivatives, alkylsulfate esters such as dimethylsulfate and diethylsulfate, and sulfonic acid esters such as methyl p-toluenesulfonate and methyl benzenesulfonate can be mentioned. In the reaction of converting the tertiary amine moiety in the polymer into a quaternary ammonium salt with a quaternary agent, equimolar compounds of the tertiary amine and the quaternary agent are mixed and stirred at 20 to 80 ° C for 1 to 20 hours. It is done by. In carrying out the quaternization reaction, alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol, etc.), 2-methoxyethanol, 2-ethoxyatanol, 2- It is desirable to add ethers such as butoxyethanol, water, or a mixture thereof.

【0051】

Polymer with acryloyl group and / or methacryloyl group, organopolysiloxane unit bonded to the main chain via nitrogen atom and quaternary ammonium base structure (C-2) This polymer can be obtained by adding an amino group-containing organopolysiloxane to the polymer (a6). As the amino group-containing organopolysiloxane, polyalkylaminoalkylpolysiloxane having an amine equivalent of 500 to 10000 is preferable. The reaction of Michael addition of this compound to an acryloyl group and / or a methacryloyl group is carried out by mixing at a ratio of (acryloyl group and / or methacryloyl group) / amino group&gt; 1 and mixing at 60 to 110 ° C for 1 to 20 hours. It is done by stirring. In this reaction, an acryloyl group and / or a methacryloyl group is added to the polymer, and an adduct unit of an organopolysiloxane having an acryloyl group and / or a methacryloyl group and an amino group is introduced.

【0052】

Metal oxide or colloidal inorganic oxide (D) As the metal oxide or inorganic oxide, it is preferable to use a colloidal metal oxide or inorganic oxide that can be uniformly dispersed. Examples of such metal oxides or inorganic oxides (D) include oxides such as silicon, aluminum, titanium, zirconium, tin, zinc, and tantalum (for example, silica sol dispersible in an organic solvent), or these. Also included are composites of and other metals and metal oxides (eg, antimony compounds, indium compounds, etc.). Further, when these oxides, a polyfunctional acrylate (A) having an acryloyl group and / or a methacryloyl group, and a metal oxide or an inorganic oxide (D) are previously bonded via an organic bonding group, they are transparent. It may be particularly preferable from the viewpoint of properties, hardness and the like. Examples of such a bond include a urethane bond, an ester bond, a siloxane bond, an ether bond, and the like. Further, a metal oxide or an inorganic oxide is treated with a known silane coupling agent or titanium coupling agent and hydrolyzed to contain an OH group on the surface, whereby a Si-H group and an OH group of a polysiloxane structural unit are contained. Dehydrolysis condensation with and on occurs at the same time, which may be particularly preferable.

【0053】

In the activation energy curable coating composition of the present invention, the weight ratio of (A) to (B) is preferably (A) :( B) = 85: 15 to 99.5: 0.5. If (B) is less than 0.5, the effect of improving stain resistance and hardness is small, and if (B) is more than 15, the hardness tends to decrease and gelation during the reaction tends to be observed. The weight ratio of (A) to (C) is preferably (A) :( C) = 65: 35 to 95: 5. When (C) is less than 5, the effect of adding (C) is small, and when (C) is 35 or more, the hardness tends to decrease.

【0054】

The weight ratio of ((A) + (C)) to (B) is preferably ((A) + (C)) :( B) = 85: 15 to 99.5: 0.5. If (B) is less than 0.5, the stain resistance and hardness improving effect are small, while if it is more than 15, the polysiloxane concentration tends to be too high, and conversely, the hardness tends to decrease. The weight ratio of (A) to (D) is preferably (A) :( D) = 90: 10 to 10:90. When (D) is less than 10, the effect of adding (D) becomes small, and when (D) is more than 90, the adhesion of the coating film tends to decrease or the hardness tends to decrease.

【0055】

It is desirable that the polysiloxane (B) be reacted with the polyfunctional acrylate (A) and the (meth) acrylic polymer (C) in advance. For this reaction, a hydrosyllation reaction between the hydrogen siloxane group (B) and the acryloyl group (A) or the acryloyl group or methacryloyl group (C) is preferable. The (meth) acrylic polymer (C) can be added before, during, or after the hydrosyllation reaction, but it is preferable to add the (meth) acrylic polymer (C) before the hydrosyllation reaction. Further, a metal oxide or an inorganic oxide (D) can be added before and after the hydrosyllation reaction, and it is preferable to bond with the polyfunctional acrylate (A) before the hydrosyllation reaction.

【0056】

As a preferred embodiment of the reaction, a hydrosilylation reaction is carried out by adding a hydrosilicate-capable fiber metal catalyst to the mixture of (A), (B) and (C), and the SiH group present in (B) is carried out. A method of reducing the residual rate of the above to 20% or less can be mentioned. Further, as another preferred embodiment, a hydrosilylation reaction is carried out by adding a hydrosilizable fiber metal catalyst to the mixture of (A), (B) and (D), and Si- present in (B) is carried out. A method of reducing the residual rate of H groups to 20% or less can be mentioned. In yet another preferred embodiment, the hydrosilylation reaction is carried out by adding a hydrosilizable fibrous metal catalyst to the mixture of (A), (B), (C) and (D) and is present in (B). A method of reducing the residual ratio of SiH groups to 20% or less can be mentioned.

【0057】

In order to proceed the hydrosylation reaction, a commonly used transition metal catalyst (Pt catalyst, Rh catalyst, Pd catalyst, Ru catalyst, etc.) is added, and the temperature is from several hours at room temperature to 100 ° C for several hours. It can be reacted by stirring for several tens of hours while paying attention to gelation. The appropriate amount of catalyst in this case is several tens of ppm to several thousand ppm. When the catalyst concentration is high, the reaction is quick, but side reactions are likely to occur, and there is a problem in terms of cost. On the other hand, if the addition is suppressed to about several ppm, side reactions can be suppressed and there is a great merit in terms of cost, but the reaction progress is slowed down, which is not preferable.

【0058】

When the reaction rate of the hydrosylation reaction is low, unreacted polyhydrogensiloxane exists, which causes many problems such as phase separation and deterioration of transparency. Further, this functional group has particularly high reactivity with an OH group-containing compound such as water or alcohol, and may cause dehydrogenation or gelation due to excessive cross-linking. Therefore, if a large amount of hydrogen siloxane group remains, it gradually reacts with the moisture in the air, the moisture in the solvent, the OH-containing component in the solvent and the monomer, etc., and generates volatile by-products and gas. Often not particularly desirable. Therefore, in order to maintain the transparency and other stability of the physical properties of the coating film and improve the storage stability of the liquid, absorption of hydrogen siloxane characteristics by IR (2180 cm)^-1) Should be continued until 20% or less, preferably 10% or less of the total. However, the reaction time may be significantly long with the above catalyst of several tens of ppm, so after reducing it to 50% or less of the total, it is reacted with alcohol by transesterification reaction such as Sn-based catalyst to prevent specific absorption of IR. A method of reducing to 20% or less of the total may be adopted.

【0059】

The active energy ray-curable coating composition of the present invention may contain other components other than the above (A) to (D) as long as the characteristics of the present invention are not impaired. As such a component, for example, any one or more of monofunctional acrylate, bifunctional acrylate, acrylate having an alkylene ether group, epoxy acrylate, urethane acrylate, ester acrylate, polysiloxane, and silicate may be blended. .. The preferable range differs depending on each substance, but for example, when the total weight of (A) is 100, it is desirable to keep it within 50 of them. This is because if more than that is added, the characteristics of the present invention are often impaired, which may be unfavorable.

【0060】

When ultraviolet rays are used as the active energy rays in curing the active energy ray-curable coating composition of the present invention, a photopolymerization initiator is used. Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, and benzophenone. , 2,4,6-trimethylbenzoin diphenylphosphenyl oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanol, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butane-1-one, Michler's ketone, N, N-dimethylaminobenzoate isoamyl, 2-chlorothioxanthone, 2,4-diethylthioxanthone, etc., and two or more of these photopolymerization initiators are appropriately used. It can also be used together. The addition of the photopolymerization initiator is preferably 10% by weight or less, preferably 1 to 5% by weight, based on the sum of the components (A) to (C).

【0061】

The active energy ray-curable coating composition of the present invention includes an ultraviolet absorber (for example, a benzotriazole-based, a benzophenol-based, a salicylic acid-based, a cyanoacrylate-based ultraviolet absorber) and an antioxidant (for example, an antioxidant) for the purpose of improving the physical characteristics of the coating. , Hindered phenol-based, sulfur-based, phosphorus-based antioxidants), light stabilizers (eg, hindered amine-based photostabilizers), blocking inhibitors, slip agents, leveling agents, etc. When the various additives are formed into the film, they can be blended in a proportion of 0.01 to 2% by weight, respectively. Further, in the active energy ray-curable coating composition of the present invention, the same solvent as that used in the production of the polymer can be used for adjusting the viscosity of the coating composition.

【0062】

The active energy ray-curable coating composition of the present invention includes, for example, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, styrene resin such as MS resin, AS resin and ABS, vinyl chloride resin, triacetyl cellulose and the like. Directly on a resin base material such as cellulose acetate, or covered with other coatings such as other curable resin layers (thermosetting resin, active energy ray curable resin), inorganic oxide layers, and vapor-deposited layers of inorganic substances and metals. The resin substrate is coated with a dipping method, a flow coating method, a spray method, a bar coating method, and a coating tool such as a gravure coating, a roll coating, a blade coating, and an air knife coating. After the line irradiation, the surface of the plastic substrate can be coated so as to obtain a film having a thickness of 1 to 50 μm, preferably 1 to 20 μm.

【0063】

Next, in order to cross-cure the coated coating composition layer, ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp, or usually 20 to 2000 kV. A film can be formed by irradiating with active energy rays such as electron beams, α rays, β rays, and γ rays taken out from the electron beam accelerator of the above and curing them.

【0064】

The active energy ray-curable coating composition of the present invention can be formed as a material having various coatings by a specific coating method and irradiation with active energy rays. As a material having such a coating, for example, surface scratch treatment and / or simultaneously antistatic property and fingerprint resistance and the like imparted with the functionality of polyethylene terephthalate and over preparative, polycarbonate, PMMA, MS resins, triacetyl cellulose Various materials such as, etc. can be mentioned, and can be used as a film material, a sheet material, and a resin plate.

【0065】

[Example]

Synthesis examples and examples will be described below, and the present invention will be described in more detail. The components, ratios, procedures, etc. described in the following synthesis examples and examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. The "parts" and "%" described in Synthesis Examples and Examples mean parts by weight and% by weight, respectively.

【0066】

(Synthesis Example 1) 10 parts of an organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Co., Ltd .: FM0725), 30 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, and N, N-dimethylaminoethyl. A mixture of 50 parts of methacrylate and 200 parts of methyl ethyl ketone is heated to add 2,2'-azobis (2,4-dimethylvaleronitrile) at 65 ° C and 2 hours after the temperature rise at 65 ° C, respectively. 0.6 parts were added and reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to obtain a copolymer having a solid content of 33%. Next, 22.2 parts of isophoron diisocyanate and 57.1 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Viscote 300, hydroxyl value 131 mgKOH / g) were added at 25 ° C to 80. 79.3 parts of the adduct obtained by reacting at ° C for 8 hours was added to the copolymer having a solid content of 33%, reacted at 80 ° C for 5 hours, and the infrared absorption spectrum was 2250 cm.^-1The disappearance of the absorption spectrum of the isocyanate group was confirmed, and a copolymer solution having an acryloyl group and a solid content of 45% was obtained.

【0067】

Next, the obtained copolymer solution was diluted with isopropyl alcohol to a solid content of 20%, methyl chloride was introduced into the reaction system, and the reaction was carried out at 50 ° C. for 6 hours, and then an amino group-containing organopoly was added. 10 parts of siloxane (manufactured by Toshiba Silicon Co., Ltd .: TSF4700 amine equivalent 3000) is added to 100 parts of solid content and reacted at 80 ° C for 1.5 hours to obtain an acryloyl group and an organopolysiloxane having an acryloyl group and an amino group. A polymer (X-1) (solid content 28%) having the unit of the adduct of the above was obtained.

【0068】

(Synthesis Example 2) A mixture of 30 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, and 60 parts of N, N-dimethylaminoethyl methacrylate and 200 parts of methyl ethyl ketone is heated to raise the temperature to 65 ° C. Two hours after the temperature rises at 65 ° C, 0.6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) are added, and the mixture is reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to solidify. A copolymer of 33% min was obtained. Next, 22.2 parts of isophoron diisocyanate and 57.1 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Viscote 300, hydroxyl value 131 mgKOH / g) were added at 25 ° C to 80. 79.3 parts of the adduct obtained by reacting at ° C for 8 hours was added to the copolymer having a solid content of 33%, reacted at 80 ° C for 5 hours, and the infrared absorption spectrum was 2250 cm.^-1The disappearance of the absorption spectrum of the isocyanate group was confirmed, and a copolymer solution having an acryloyl group and a solid content of 45% was obtained.

【0069】

Next, the obtained copolymer solution was diluted with isopropyl alcohol to a solid content of 20%, methyl chloride was introduced into the reaction system, and the reaction was carried out at 50 ° C. for 6 hours, and then an amino group-containing organopoly was added. 10 parts of siloxane (manufactured by Toshiba Silicon Co., Ltd .: TSF4700 amine equivalent 3000) is added to 100 parts of solid content and reacted at 80 ° C for 1.5 hours to make an acryloyl group and an organopoly having an acryloyl group and an amino group. A polymer (X-2) (solid content 27%) having a unit of an adduct of siloxane was obtained.

【0070】

(Synthetic Example 3) 30 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Co., Ltd .: FM0725), and N, N-dimethylaminoethyl. A mixture of 50 parts of methacrylate and 200 parts of methyl ethyl ketone is heated to add 2,2'-azobis (2,4-dimethylvaleronitrile) at 65 ° C temperature rise and 2 hours after 65 ° C temperature rise, respectively. 0.6 parts were added and reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to obtain a copolymer having a solid content of 33%. Next, 22.2 parts of isophoron diisocyanate and 57.1 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Viscote 300, hydroxyl value 131 mgKOH / g) were added at 25 ° C to 80. 79.3 parts of the adduct obtained by reacting at ° C for 8 hours was added to the copolymer having a solid content of 33%, and the reaction was carried out at 80 ° C for 5 hours.^-1The disappearance of the absorption spectrum of the isocyanate group was confirmed, and a copolymer solution having a solid content of 45% having an acryloyl group in the side chain was obtained.

【0071】

Next, the obtained copolymer solution was diluted with isopropyl alcohol to a solid content of 20%, and then 0.95 mol of methyl chloroacetate was added per 1 mol of N, N-dimethylaminoethyl methacrylate to add 60 ° C. For 8 hours, add 10 parts of amino group-containing organopolysiloxane (manufactured by Toshiba Silicon Co., Ltd .: TSF4700 amine equivalent 3000) to 100 parts of solid content, react at 80 ° C for 1.5 hours, and side chain. A polymer (X-3) (solid content 26%) having an acryloyl group unit and an adduct unit of an organopolysiloxane having an acryloyl group and an amino group in the side chain was obtained.

【0072】

(Synthetic Example 4) 30 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Co., Ltd .: FM0725), and N, N-dimethylaminoethyl. A mixture of 50 parts of methacrylate and 200 parts of methyl ethyl ketone is heated to add 2,2'-azobis (2,4-dimethylvaleronitrile) at 65 ° C temperature rise and 2 hours after 65 ° C temperature rise, respectively. 0.6 parts were added and reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to obtain a copolymer having a solid content of 33%. Next, 22.2 parts of isophorone diisocyanate and 57.1 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Viscote 300, hydroxyl value 131 mgKOH / g) were added at 25 ° C to 80. 79.3 parts of the adduct obtained by reacting at ° C for 8 hours was added, and the reaction was carried out at 80 ° C for 5 hours, and the infrared absorption spectrum was 2250 cm.^-1The disappearance of the absorption spectrum of the isocyanate group was confirmed, and a copolymer solution having a solid content of 45% having an acryloyl group in the side chain was obtained.

【0073】

Next, the obtained copolymer solution was diluted with methyl ethyl ketone to a solid content of 20%, and then an amino group-containing organopolysiloxane (manufactured by Toshiba Silicon Co., Ltd .: TSF4700 amine equivalent 3000) was added to 100 parts of the solid content. , 10 parts added, reacted at 80 ° C for 1.5 hours, polymer (X-4) (solid content 24) having an acryloyl group and an adduct unit of an organopolysiloxane having an acryloyl group and an amino group in the side chain. %) Was obtained.

【0074】

(Synthesis Example 5) When a mixture of 20 parts of glycidyl methacrylate, 80 parts of styrene, and 300 parts of methyl isobutyl ketone is heated and heated to 65 ° C, and 2 hours after the temperature is raised to 65 ° C, 2 respectively. 0.6 parts of, 2'-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to obtain a copolymer with a solid content of 33% (P). -7). To this, 1.03 mol of acrylic acid and 0.5 g of 4-dimethylaminopyridine as a catalyst were added per 1 mol of glycidyl methacrylate, reacted at 100 ° C for 12 hours, and a polymer having an acryloyl group in the side chain (X). -5) (solid content 35%) was obtained.

【0075】

(Synthesis Example 6) A mixture of 30 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 60 parts of N, N-dimethylaminoethyl methacrylate, and 200 parts of methyl ethyl ketone is heated to raise the temperature to 65 ° C and 65. Two hours after the temperature rises to ° C, 0.6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to solidify. A copolymer of 33% min was obtained (P-3). Next, 22.2 parts of isophorone diisocyanate and 57.1 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Viscote 300, hydroxyl value 131 mgKOH / g) were added at 25 ° C to 80. 79.3 parts of the adduct obtained by reacting at ° C for 8 hours was added, and the reaction was carried out at 80 ° C for 5 hours, and the infrared absorption spectrum was 2250 cm.^-1After confirming the disappearance of the absorption spectrum of the isocyanate group of the above, the solid content was adjusted to 20% with isopropyl alcohol, and then 0.95 mol of methyl chloroacetate was added per 1 mol of N, N-dimethylaminoethyl methacrylate to add 60 ° C. Reacted in 1 for 8 hours to obtain a polymer (X-6) (solid content 24%) having an acryloyl group and a quaternary amino group.

【0076】

(Comparative Synthesis Example 1) 60 parts of methyl methacrylate, 10 parts of trimethoxysilylpropyl methacrylate, 60 parts of N, N-dimethylaminoethyl methacrylate, organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Co., Ltd .: FM0725) A mixture of 30 parts and 200 parts of methyl ethyl ketone is heated to add 0.6 of 2,2'-azobis (2,4-dimethylvaleronitrile) at 65 ° C and 2 hours after the temperature rise at 65 ° C, respectively. The mixture was added in portions and reacted at 65 ° C for 5 hours and at 80 ° C for 2 hours to obtain a copolymer having a solid content of 33%.

【0077】

(Examples 1 to 9 and Comparative Examples 1 to 3) A composition having a composition as shown in Table 1 (containing an alcohol component in the solvent) and a Pt catalyst (SRX212CAT) of 0.1 part per 100 parts of the solid content of the composition. (Pt-based catalyst solution manufactured by Toray Dow Corning Silicon Co., Ltd.) is heated at 80 ° C and 2180 cm.^-1It was heated until the absorption of nearby SiH was reduced to less than 50% of that before the reaction. After that, in Example 7, 0.1 part of Pt catalyst (SRX212CAT; Pt-based catalyst solution manufactured by Toray Corning Silicon Co., Ltd.), and in Examples 1 to 6, 8 and 9, 0.2 part of Sn catalyst (dibutyltin dilaurate). ) Are added, 2180 cm^-1Heating was performed until the absorption of nearby SiH was reduced to 20% or less (preferably 10% or less) before the reaction. In Comparative Examples 1 to 3, no catalyst was used. The SiH residual ratio of the obtained composition is as shown in Table 1. Next, an active energy ray-curable coating composition in which 3 parts of Irgacure 907 was added per 100 parts of solid content and the solid content concentration was adjusted to about 35% with a predetermined solvent was applied to a transparent biaxial film having a haze value of 1.5%. Apply to stretched polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd .: T600E, 100 μm thickness) using a bar coater so that the film coating thickness after drying is 5 to 7 μm, and heat dry at 80 ° C for 2 minutes. did. For this, a high-pressure mercury lamp with an output density of 120 W / cm was used, and 300 mJ / cm at a position 15 cm below the light source.²A cured film was formed by irradiating with ultraviolet rays.

【0078】

[table 1]

<img file="JP2002194084A_D0003.tif" />Note: All are adjusted with a solid content concentration of 35%. For every 100 parts of the component containing an acryloyl group or a methacryloyl group as an initiator, 3 parts of Irgacure 907 is contained. DPHA: Dipentaerythritol Hexa / Pentaacrylate (manufactured by Nippon Kayaku) SH1107: Polymethylhydrogensiloxane with terminal trimethylsilyl (manufactured by Toray Dow Corning Silicon) MEK-ST: Organosilica sol in MEK solvent (manufactured by Nissan Chemical Industries, Ltd.) [0079]

(Comparative Example 4) A mixture containing 90 parts of DPHA, 10 parts of X-2, 5 parts of SH1107, 0.1 part of SRX212CAT, and a solid content of 35% using MEK and IPA as a solvent was heated at 80 ° C for 2 hours. .. The SiH survival rate at this point was 50% of the original. After dissolving 3 parts of Irgacure 907 per 100 parts of solid content at 25 ° C in this solution, a transparent biaxially stretched polyethylene terephthalate film with a haze value of 1.5% (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd .: T600E, 100 μm thickness) ) Was coated with a bar coater so that the film coating thickness after drying was 5 to 7 μm, and the film was dried by heating at 80 ° C. for 2 minutes. For this, a high-pressure mercury lamp with an output density of 120 W / cm was used, and 300 mJ / cm at a position 15 cm below the light source.²A cured film was formed by irradiating with ultraviolet rays.

【0080】

(Test Example) The cured coatings formed in Examples 1 to 9 and Comparative Examples 1 to 4 were tested for transparency, abrasion resistance, contact angle, fingerprint resistance, and antistatic property. The details of the test are as follows. 1) Transparency Evaluated by haze value (JIS K-7105). 2) Pencil hardness The measurement was performed based on the conditions of JIS K-5400 using a JIS-compliant pencil hardness tester manufactured by Tayu Kikai Co., Ltd., and the number of the hardest pencil without scratches was displayed.

【0081】

3) Abrasion resistance Using a wear wheel of CS-10F manufactured by Calibrase, a 100-turn Taber wear test was performed under a load of 500 g, and the difference between the haze value after the Taber wear test and the haze value before the Taber wear test was evaluated as ΔH%. 4) Surface resistance value The evaluation sample was left in a thermostatic chamber at 23 ° C. and a relative humidity of 65% for 24 hours, and then measured using a TR-8601 type (manufactured by Takeda Riken) at an applied voltage of 100 V and a 1-minute value. 5) Contact angle For the contact angle, use a P-type contact angle measuring device manufactured by Kyowa Kagaku Co., Ltd., and drop 0.002 ml of water onto the measurement surface of a sample left at 23 ° C and 65% relative humidity for 24 hours or more to bring it to 23 ° C. Measured (unit; degree).

【0082】

6) Fingerprint resistance For fingerprint adhesion, the thumb wiped with the JK wiper 150-S immediately before was pressed vertically for 3 seconds, and the adhesion at that time was visually evaluated relative (the standard is , the one with less adhesion is , most or Those that do not adhere at all are , those with high adhesion are ×). As a reference, a 0.3% methyl ethyl ketone solution of the polymer prepared in Comparative Synthesis Example 1 was used, and the film was applied to a polyethylene terephthalate film (the film is the same as that used in the above Examples and Comparative Examples) with a thickness of 0.03 μm, and 80 After curing at ° C for 2 hours, a sample left at 23 ° C and a relative humidity of 65% for 24 hours or longer was used. For fingerprint wiping property, after leaving the above sample for 1 hour, wipe it 3 times with JK wiper 150-S, if it is completely wiped, if it is completely wiped 4 to 5 times, will it take 5 times or more to wipe? Or, if some fingerprint marks remain even after wiping, it was marked as x. The test results are summarized in Table 2.

【0083】

[Table 2]

<img file="JP2002194084A_D0004.tif" />【0084】

The examples within the range of the present invention shown in Examples 1 to 9 are excellent in transparency, hardness (pencil hardness), abrasion resistance, and antifouling property (fingerprint resistance), and if a material is selected, antistatic property can be obtained. Can also obtain an excellent cured film. On the other hand, when only (A) is used as in Comparative Example 1, when only (A) + (C) is used as in Comparative Example 2, and when only (A) + (D) is used as in Comparative Example 3. In both cases, a coating film having excellent transparency and abrasion resistance can be obtained, but the hardness (pencil hardness) and fingerprint resistance are not high. Further, as shown in Comparative Example 4, the cured film obtained from a composition having a high SiH residual ratio and outside the scope of the present invention does not have sufficient transparency and wear resistance, and is characterized by hardness of the present invention. Features such as (pencil hardness) and fingerprint resistance cannot be utilized.

【0085】

[Effect of the invention]

When the compound having the polysiloxane structural unit of the present invention and the active energy ray-curable coating composition are used, the transparency, hardness (pencil hardness), abrasion resistance, and stain resistance (particularly fingerprint resistance) are excellent. At the same time, a film having a high level of antistatic property can be formed. Further, the material having a cured film formed by the compound or composition of the present invention is a material having excellent transparency, hardness (pencil hardness), abrasion resistance, and stain resistance (particularly fingerprint resistance).