WO2012032588A1 - Coating and laminate - Google Patents

Abstract

This coating comprises (a) 20-40 mass% of a vinyl ester resin or an unsaturated polyester resin, (b) 50-70 mass% of a vinyl monomer and/or a (meth)acrylate monomer, (c) 1-20 mass% of a modifying agent (the total of the components (a) to (c) being 100 mass%), (d) 0.1-15 parts by mass of at least one type of a radical polymerization initiator selected from the group consisting of an organic peroxide, an ultraviolet reaction initiator and an electron beam reaction initiator per 100 parts by mass of the total of the components (a) to (c), and (e) 0.5-10 parts by mass of an ionic liquid as an antistatic material per 100 parts by mass of the total of the components (a) to (c). The coating can be applied with excellent adhesiveness to a polyester resin, a polycarbonate, an acrylic resin, glass, a rigid vinyl chloride resin, a soft vinyl chloride resin, or a styrene resin.

Description

Paints and laminates

The present invention relates to a paint and a laminate, and is a layer of polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin (particularly polycarbonate, acrylic resin, polyester resin). The coating layer that exhibits antistatic properties is obtained, and the balance of hardness, water resistance, abrasion resistance, transparency, surface smoothness, flexibility, and impact resistance is sufficient. The present invention relates to a paint and a laminate.

Vinyl ester resins (urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate), reactive diluents, adhesives and paints consisting of curing agents, packaging materials, display materials such as labels, electronic parts Widely used in various fields such as precision equipment and construction materials. In recent years, the thermosetting type has been used for the purpose of speeding up the manufacturing process and improving productivity, but recently, an active energy ray curable liquid curable adhesive or paint that is cured by ultraviolet rays or electron beams has been used instead. Is also widely used. Thus, as the field of use expands and the requirements for the purpose of use increase, the demand for higher performance is also increasing for active energy ray-curable liquid curable adhesives and paints.

Patent Document 1 below includes a (meth) acrylate compound having an acryloyl group or methacryloyl group in the molecule, a conductive fine powder containing tin oxide, a photopolymerization initiator, dimethylformamide, and a cellosolve solvent. A photocurable antistatic coating composition containing an organic solvent is disclosed. However, such paints have a problem of requiring a solvent, and glass, polycarbonate, acrylic resin, polyester resin, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin (especially polycarbonate, acrylic resin). The adhesiveness with the layer of the resin or polyester resin was insufficient, and the transparency was inferior. Further, when an antistatic material was blended in the paint, the cured paint layer could not exhibit both antistatic properties and adhesiveness as expected. Further, none of the balance of water resistance, abrasion resistance, transparency, surface smoothness, flexibility and impact resistance was sufficient.

JP-A-9-302268

The object of the present invention is to adhere to a layer of polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin (especially polycarbonate, acrylic resin, polyester resin). Paints and laminates with sufficient balance of hardness, water resistance, abrasion resistance, transparency, surface smoothness, flexibility, and impact resistance. Is to provide.

As a result of intensive studies, the present inventor has solved the above-mentioned problems with a paint containing the following components (a), (b), (c), (d) and (e) in a specific quantitative relationship. The present invention was completed.

That is, the present invention is as follows.
1. (A) Vinyl ester resin or unsaturated polyester resin 20 to 40% by mass
(B) Vinyl monomer and / or (meth) acrylate monomer 50 to 70% by mass
(C) modifying agent 1 to 20% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
(D) At least one radical polymerization initiator selected from the group consisting of an organic peroxide, an ultraviolet reaction initiator, and an electron beam initiator is 0.1% relative to a total of 100 masses of the components (a) to (c). 15 to 15 parts by mass and (e) an ionic liquid as an antistatic material containing 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) Paint for polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin.
2. 2. The paint according to 1 above, wherein the component (a) is at least one selected from the group consisting of urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
3. The component (b) is at least one selected from (b-1) a compound having a cyclic structure and one ethylenically unsaturated group; (b-2) a diacrylate compound; and (b-3) a triacrylate compound. 3. The paint according to 1 or 2 above, which is a seed monomer.
4). The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g; 4. The modified rubber (c-3); and at least one selected from the group consisting of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol. Paint.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The paint as described in 4 above, which is at least one selected from the group consisting of a polyisoprene polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof.
6). 6. The coating material according to 5 above, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mg KOH / g.
7. The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. The paint described in 1.
8). 5. The paint according to 4 above, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. 5. The coating material as described in 4 above, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. 5. The paint according to 4 above, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. 11. The coating material as described in any one of 1 to 10 above, wherein the ionic liquid (e) contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium. .
12 The ionic liquid (e) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. 12. The paint according to 11 above.
13. Further, it contains an antistatic improver (f), and the antistatic enhancer (f) comprises an acidic phosphate ester (f-1), a carbodiimide compound (f-2), and a vinyl ether compound (f-3). And at least one selected from the group, and the blending amount of the antistatic improver (f) is in the range of 0.02 to 30 when the mass of the ionic liquid (e) is 1. 13. The paint according to any one of 1 to 12 above, wherein
14 14. The paint according to any one of 1 to 13 above, which is used on the surface of a display.
15. 15. The paint as described in 14 above, which is used on the surface of a display of a portable mobile terminal.
16. (A) Vinyl ester resin or unsaturated polyester resin 20 to 40% by mass
(B) Vinyl monomer and / or (meth) acrylate monomer 50 to 70% by mass
(C) modifying agent 1 to 20% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
(D) At least one radical polymerization initiator selected from the group consisting of an organic peroxide, an ultraviolet reaction initiator, and an electron beam initiator is 0.1% relative to a total of 100 masses of the components (a) to (c). And (e) an ionic liquid as an antistatic material, and a coating layer (A) containing 0.5 to 10 parts by mass with respect to 100 parts in total of the components (a) to (c);
Polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin layer (B) was formed so that the layer (A) and layer (B) were in contact with each other. Laminated body.
17. 17. The laminate according to 16 above, wherein the thickness of the paint layer (A) is 2 to 200 μm.
18. 18. The laminate according to 16 or 17 above, wherein the ionic liquid (e) contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium.
19. The ionic liquid (e) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. The laminate as described in 18 above.
20. The coating layer (A) further contains an antistatic improver (f), and the antistatic improver (f) comprises an acidic phosphate ester (f-1), a carbodiimide compound (f-2), and a vinyl ether. And at least one selected from the group consisting of the compound (f-3) and the blending amount of the antistatic improver (f) is 0 when the mass of the ionic liquid (e) is 1. 20. The laminate according to any one of 16 to 19, wherein the laminate is in the range of 02 to 30.
21. 21. The laminate according to any one of 16 to 20, which is used on the surface of a display.
22. The laminate as described in 21 above, which is used on the surface of a display of a portable mobile terminal.

Since the paint of the present invention contains the specific components (a) to (e) in a specific amount, the polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or Adhesiveness with a layer of styrene resin (especially polycarbonate, acrylic resin, polyester resin) is sufficient, and a coating layer exhibiting antistatic properties is obtained, and hardness, water resistance, abrasion resistance, Transparency, surface smoothness, flexibility and impact resistance are balanced at a high level. Moreover, since the coating material of this invention has a viscosity suitable for application | coating, it is not necessary to dilute with an organic solvent and can provide a favorable working environment.
The laminate of the present invention comprises a coating layer (A) of the present invention and a polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin (in particular, polycarbonate, Since the layer (A) and the layer (B) are in contact with the layer (B) of the acrylic resin or polyester resin), the adhesiveness of both layers is excellent (the layer (B) Direct coating is possible without primer treatment), antistatic properties, hardness, water resistance, abrasion resistance, transparency, surface smoothness, flexibility, and impact resistance are balanced at a high level.

Hereinafter, the present invention will be described in more detail.
Component (a) Vinyl ester resin or unsaturated polyester resin Component (a) of the paint of the present invention is a vinyl ester resin or an unsaturated polyester resin.
Specifically, the vinyl ester resin is selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably high hardness expression, quick drying property, Examples thereof include epoxy (meth) acrylate and urethane (meth) acrylate resins that are particularly excellent in adhesiveness, non-yellowing property, and low viscosity expression. Epoxy (meth) acrylate is a preferred component in the present invention because it is particularly excellent in low shrinkage, adhesiveness and water resistance after the coating is cured. In addition, the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.

Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.

The polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.

As used herein, the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.

Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene. A diisocyanate, a triphenylmethane triisocyanate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.

Examples of the method for producing the urethane (meth) acrylate resin include: (1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a terminal isocyanate compound, and then a hydroxyl group is produced. A method of reacting the containing (meth) acrylate so that the hydroxyl groups are approximately equal to the isocyanate group, and (2) reacting the polyisocyanate compound and the hydroxyl-containing (meth) acrylate at NCO / OH = 2 or more, Examples include a method in which a compound of a terminal isocyanate is produced and then a polyol is added to react.

The epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.

Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.

Here, as a typical example of the bisphenol type epoxy resin, a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used. An epoxy resin, a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like. Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.

Examples of the esterification catalyst include a known catalyst such as a tertiary amine such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine, or diethylamine hydrochloride. Can be used as is.

The polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. A compound is reacted. The number average molecular weight of such a resin is preferably 500 to 5,000.

The saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction. In addition, the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.

Examples of the saturated dibasic acid herein include the compounds shown in the above-mentioned polyester polyol, and examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride. Moreover, the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.

The (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there. Preferably, glycidyl (meth) acrylate is used.

The unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin. . As the acid component, for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to. Examples of the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.

Component (b) Vinyl monomer and / or (meth) acrylate monomer Component (b) of the paint of the present invention is a vinyl monomer and / or (meth) acrylate monomer. Specific examples include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.

Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isode (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, iso Butoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmo Examples include ruphorin and vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.

The component (b) vinyl monomer and / or (meth) acrylate monomer of the paint of the present invention is preferably (b--) in terms of high hardness development, quick drying, adhesion, non-yellowing, and low viscosity development. 1) at least one monomer selected from a compound having a cyclic structure and one ethylenically unsaturated group; (b-2) a diacrylate compound; and (b-3) a triacrylate compound, More preferably, 1) is used in combination with (b-2) or (b-3). In particular, when (b-1) and (b-3) are used in combination, the balance between the hardness and the adhesive strength of the coating film made of the resulting paint is improved.

(B-1) Compound having a cyclic structure and one ethylenically unsaturated group Component (b-1) used in the present invention is a compound having a cyclic structure and one ethylenically unsaturated group.
Examples of the component (b) include alicyclic structure-containing (meth) acrylates such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; Examples include benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like.
Furthermore, compounds represented by the following formulas (1) to (3) can be given.

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and p is preferably Shows the number from 1 to 4.)

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are independent of each other and are H or CH ₃ , and q is an integer of 1 to 5)

Examples of the component (b) include monomers having an N-vinyl group in that they are excellent in high hardness development, quick drying, adhesion, non-yellowing, and low viscosity development. For example, N-vinyl pyrrolidone, N -Vinylcaprolactam, N-vinylformamide, N-vinylimidazole, N-vinylcarbazole and the like. Of these, N-vinylcaprolactam is preferred because of its excellent adhesiveness and low viscosity.

The component (b-2) used in the present invention is a diacrylate monomer.
Examples of the diacrylate monomer used in the present invention include ethylene glycol diacrylate, dipropylene glycol diacrylate (DPGDA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate, and tetraethylene glycol diacrylate. Examples include acrylate, tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, and modified bisphenol A diacrylate. Dipropylene glycol diacrylate and tripropylene glycol diacrylate are preferred in terms of high hardness development, quick drying properties, and no yellowing.

The component (b-3) used in the present invention is a triacrylate monomer.
(B-3) has a function of improving the balance between the hardness and adhesion of the coating film made of the resulting coating.
Examples of the triacrylate monomer include three glycols such as ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, hexanediol, trimethylolpropane, tetramethylolpropane, pentaerythritol, and dipentaerythritol. The thing which esterified acrylic acid is mentioned.
Of these, trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and pentaerythritol triacrylate are preferred because they are excellent in the balance between the hardness and adhesion of the coating film made of the resulting coating.

When (b-1) and (b-2) are used in combination, when the blending ratio is (b-1) + (b-2) = 100 parts by mass, (b-1) is 80 -20 parts by mass, preferably 75-25 parts by mass, and (b-2) is 20-80 parts by mass, preferably 25-75 parts by mass.

When (b-1) and (b-3) are used in combination, when the blending ratio is (b-1) + (b-3) = 100 parts by mass, (b-1) is 80 -20 parts by mass, preferably 75-25 parts by mass, and (b-3) is 20-80 parts by mass, preferably 25-75 parts by mass.

In the paint of the present invention, when a cycloalkene or an alicyclic vinyl compound is used as the component (b), the cured paint layer (A) is hard-coated. These compounds are blended, and it is preferable not to blend these compounds for undesired uses.
Examples of the cycloalkene include cycloalkenes such as cyclobutene, cyclopentene, cycloheptene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, cyclooctene, and the like. . The number of carbon atoms of the cycloalkene is, for example, 4 to 20. Moreover, a dicyclopentadiene monomer can be mentioned. The dicyclopentadiene-based monomer is dicyclopentadiene or a substituted product thereof. Examples of the substituted product include alkyl substituted products, alkylidene substituted products, and aromatic substituted products. And may have a polar group such as a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group or a silyl group. The carbon number of the dicyclopentadiene monomer is, for example, 4 to 20. Specific examples include dicyclopentadiene, 2-methyldicyclopentadiene, 2-ethyldicyclopentadiene, 5-methyldicyclopentadiene, 5,5-dimethyldicyclopentadiene, 2,3-dihydrodicyclopentadiene, and the like. It is done.
Examples of the alicyclic vinyl compound include a cycloalkene vinyl compound and a cycloalkane vinyl compound. Examples of the cycloalkene vinyl compound include compounds having an aliphatic ring having 5 to 8 carbon atoms having a double bond and having a polymerizable vinyl group. The aliphatic ring includes 1 to 4 carbon atoms. The above-described alkyl group or halogen atom group can be substituted. Examples of the cycloalkene vinyl compound include, for example, cyclopentene vinyl compounds such as 2-vinylcyclopentene, 2-methyl-4-vinylpentene, 3-vinylcyclopentene, and 3-t-butyl-4-vinylpentene; 4-vinylcyclohexene Cyclohexene such as 4-isopropenyl vinylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenyl vinylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenyl vinylcyclohexene Vinyl compounds; 2-vinylcycloheptene, 3-vinylcycloheptene, 4-vinylcycloheptene, 3-methyl-6-vinylcycloheptene, 4-ethyl-6-vinylcycloheptene, 3-t- Butyl-5-vinylcyclo Cycloheptene vinyl compounds such as butene; 2-vinylcyclooctene, 3-vinylcyclooctene, 4-vinylcyclooctene, 2-methyl-5-vinylcyclooctene, 4-ethyl-6-vinylcyclooctene, 3-t And cyclooctene vinyl compounds such as -butyl-7-vinylcyclooctene. The cycloalkene vinyl compound can have a (meth) acryloyl group as a vinyl bond.
Examples of the cycloalkane vinyl compound include compounds having a saturated aliphatic ring having 5 to 8 carbon atoms and having a polymerizable vinyl group. The aliphatic ring can have an alkyl group having 1 to 4 carbon atoms or a halogen atom group as a substituent. Examples of cycloalkane vinyl compounds include cyclopentane vinyl compounds such as 2-vinylcyclopentane, 2-methyl-4-vinylpentane, 3-vinylcyclopentane, 3-t-butyl-4-vinylpentane; 4-vinyl Cyclohexane, 4-isopropenyl vinylcyclohexane, 1-methyl-4-vinylcyclohexane, 1-methyl-4-isopropenyl vinylcyclohexane, 2-methyl-4-vinylcyclohexane, 2-methyl-4-isopropenyl vinylcyclohexane, etc. Cyclohexane vinyl compound; 2-vinylcycloheptane, 3-vinylcycloheptane, 4-vinylcycloheptane, 3-methyl-6-vinylcycloheptane, 4-ethyl-6-vinylcycloheptane, 3-t-butyl-5- Vinylcycloheptane Cycloheptane vinyl compounds: 2-vinylcyclooctane, 3-vinylcyclooctane, 4-vinylcyclooctane, 2-methyl-5-vinylcyclooctane, 4-ethyl-6-vinylcyclooctane, 3-t-butyl- Cyclooctane vinyl compounds such as 7-vinylcyclooctane, 1,4-cyclohexanedimethanol divinyl ether, cyclopentane vinyl ether, cyclohexane vinyl ether, cycloheptane vinyl ether, cyclooctane vinyl ether, 4-methylcyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, etc. Examples thereof include cycloalkane vinyl ether compounds having a saturated aliphatic ring having 5 to 8 carbon atoms. The cycloalkene vinyl compound can have a (meth) acryloyl group as a vinyl bond.

Component (c) Modifier Component (c) of the paint of the present invention is a modifier.
(C) Examples of the modifier include a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g (c— 2); modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol.

(I) The polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

The hydroxyl value of component (c) is the adhesion of the paint of the present invention to a substrate (B) made of glass, polycarbonate, acrylic resin, polyester resin, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin. Contributes to improvement.

The (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the adhesion to the substrate (B) (polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin) is good.
(I) The hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of adhesiveness, and more preferably 150 to 300 mgKOH / g.

(I) As a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g, it is more preferable in terms of adhesiveness to the substrate (B),
(I) Castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polyisoprene polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3)
(I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
Is mentioned.

In the present invention, the polyol of component (c) can be used as a mixture of two or more if necessary.

(I) A castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

The “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds. The ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound. Further, the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).

The “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.

Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.

The polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols. These are fatty acid ester polyols derived from castor oil, such as a mixture of these and castor oil.

Examples of polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A). A vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.

Among the castor oil-based polyols, castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of adhesion to the base material (B).
Further, from the viewpoint of adhesiveness to the substrate (B), (i) an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g is preferable. More preferably, it is 150 to 240 mg KOH / g.

The component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A). The component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.). Among these, an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid has preferable adhesion to the substrate (B), and can be represented by, for example, the following formula (4).

In the formula (4), m represents an average number of 2 to 5, and n represents an average number of 2 to 5.

Modified polyols derived from castor oil represented by the formula (4) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mgKOH / mg, viscosity 700 to 1500 mPa · s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa · s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa · s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.

(I) A polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

Examples of the polybutadiene-based polyol used in the present invention include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene / butadiene) polyol, poly (butadiene / styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
Polybutadiene-based polyols are commercially available. For example, “Poly bd R-15HT (hydroxyl value 102.7 mgKOH / mg, Mw1200)” and “Poly bd R-45HT (hydroxyl value 46.6 mgKOH / manufactured by Idemitsu Kosan Co., Ltd.) are available. mg, Mw2800) "and the like.
From the viewpoint of adhesion to the substrate (B), the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g. .
(C-1-2) The weight average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.

(I) A polyisoprene-based polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3) will be described.

Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu. “Epol®” (hydroxyl value 50.5 mg KOH / mg, Mn 2500) is a liquid polyolefin obtained by hydrogenating “Poly ip®”. Almost no double bonds remain in the molecule.

(I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g will be described.

(I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.

Examples of the epoxy resin used here include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak, terpene diphenol; Polyglycidyl ether compound of ethylene oxide and / or propylene oxide adduct of the above mononuclear polyhydric phenol compound or polynuclear polyhydric phenol compound; polyglycidyl ether compound of hydrogenated mononuclear polyhydric phenol compound; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin Polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, Aliphatic and aromatic such as sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Or homopolymers or copolymers of glycidyl esters of alicyclic polybasic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, etc. Glycidylami An epoxy compound having a hydrogen group; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6- Epoxidized products of cyclic olefin compounds such as methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, Examples include heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be internally crosslinked by a prepolymer of terminal isocyanate.

Among these epoxy resins, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, Use of bisphenol type epoxy resins such as polyglycidyl ether compounds such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) It is preferable because an excellent coating film can be formed.

(I) An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what

Examples of the carboxylic acid compound include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.

Examples of the polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol Like low molecular weight polyols is.

Examples of the amino compounds include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as

Among the above active hydrogen compounds, alkanolamine compounds such as diethanolamine are preferable.

Also, the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.

When the active hydrogen compound is reacted with the epoxy resin, a normal method of adding the active hydrogen compound to the epoxy resin can be employed. For example, the presence of a known catalyst such as a tertiary amine compound or a phosphonium salt. Below, a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.

(I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g preferably has a hydroxyl value of 100 to 140 mgKOH / g from the viewpoint of the effects of the present invention.

Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.

(I) A polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g will be described.

(I) Polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g may be aromatic, aliphatic or castor oil-based. Even if the hydroxyl value of (i) and the acid value of (ii) are satisfied, the adhesion to the substrate (B) is improved.
The hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
The acid value of (ii) is more preferably 4 to 15 mgKOH / g.

If (i) and (ii) are met,
As the polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g,
(I) a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g
Is exemplified.

(I) A castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.

The Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa · s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent adhesion to the substrate (B).
The Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa · s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent adhesion to the substrate (B).

The modified rubber (c-3) will be described.
Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.

(C-3-1) Carboxylated Polyisoprene The carboxylated polyisoprene (c-3-1) used in the present invention fulfills the function of improving the adhesion of the substrate (B).
Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.

(C-3-2) Carboxylated polybutadiene The carboxylated polybutadiene (c-3-2) used in the present invention functions to improve the adhesion to the substrate (B).
Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the storage stability to be obtained is deteriorated, which is not preferable. Further, the cis 1,4-bond is preferably 40% by weight or more, and if the cis 1,4-bond is less than 40% by weight, the resulting adhesiveness is lowered, which is not preferable.

The carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by weight of butadiene and 2 to 20% by weight of the carboxyl group-introducing compound are preferred.

The liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution. The liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance. Furthermore, the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.

As the carboxyl group-introducing compound, an ethylenically unsaturated dicarboxy compound such as an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester can be used. Specific examples of the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleate or monoethyl maleate. Can be mentioned. Of these, maleic anhydride is preferred for reasons of safety, economy and reactivity. (Maleed polybutadiene is preferred.)

Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.

The acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g). When the acid value is less than 50 (mgKOH / g), the adhesiveness with the base material (B) decreases, and when it exceeds 120 (mgKOH / g), the viscosity increases and the workability decreases.

Furthermore, the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.

Further, the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa · s, more preferably 5 to 13 Pa · s, and further preferably 6 to 9 Pa · s.

In addition, maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the paint obtained is rich in adhesiveness with the substrate (B).
Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Moreover, the paint obtained is excellent in terms of decorating properties.

Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.

The compound (c-4) having an epoxy equivalent of 150 to 700 g / mol will be described.

One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .

Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; Dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4- Hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxy) Phenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, polyglycidyl ether compounds of polyphenols such as terpene phenol; ethylene Polyglycidyl ethers of polyhydric alcohols such as glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumarate Acid, itaconic acid, succinic acid, glutaric acid, suberic acid, azide Acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, etc. Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) ) Phenyl) Epoxy compounds having a glycidylamino group such as methane, diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, Epoxidized products of cyclic olefin compounds such as 4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene Examples thereof include epoxidized conjugated diene polymers such as copolymers, and heterocyclic compounds such as triglycidyl isocyanurate.

Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferred in view of adhesion to substrates (B).

Examples of polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).

Another form of the compound (d-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is. A polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.

A specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID ™ L-207 POLYMER). L-207 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of −53 ° C. It is a coalescence and is preferred in terms of adhesion to the substrate (B).

Component (d) At least one radical polymerization initiator selected from the group consisting of organic peroxides, ultraviolet reaction initiators and electron beam reaction initiators. Component (d) of the paint of the present invention comprises organic peroxides, ultraviolet rays It is at least one radical polymerization initiator selected from the group consisting of a reaction initiator and an electron beam reaction initiator.

Examples of the ultraviolet reaction initiator and electron beam reaction initiator include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl Ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, benzyl sulfide, thioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.

When the reaction is allowed to proceed by heating in the paint of the present invention, it is preferable to use an organic peroxide.
Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2, 5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p chlorobenzoyl peroxide, 2,4 dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert -Butyl peroxyisopropyl carbonate, diaceti Examples include ruperoxide, lauroyl peroxide, tert-butylcumyl peroxide, succinic acid peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide.

Of these, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl are used for efficient thermosetting at a general thermosetting temperature of 100 ° C to 150 ° C. -2,5-di (tert-butylperoxy) hexyne-3 is most preferred.

The paint of the present invention contains an ionic liquid (e) as an antistatic material. The ionic liquid (e) is a salt composed of a cation and an anion and is a liquid.
The ionic liquid (e) used in the present invention preferably contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium. Examples of the cation are as follows.

The ionic liquid (e) used in the present invention includes an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. Those are preferred. Examples of the anion are as follows.

The ionic liquid is preferably water-soluble.
In the present invention, preferred ionic liquids are combinations of cations and anions, such as (1-1) and (10-1), (1-1) and (10-4), (1-1) and (11-1 ), (1-2) and (8-3), (1-2) and (10-1), (1-2) and (10-2), (1-2) and (10-4), (1-2) and (11-1), (1-6) and (7-11), (1-6) and (8-3), (1-6) and (8-5), (1 -6) and (8-6), (1-6) and (9-1), (1-6) and (9-2), (1-6) and (9-3), (1-6) ) And (10-1), (1-6) and (10-4), (1-6) and (10-7), (1-6) and (11-1), (1-6) (12-5), (1-6) and (12-6), (1-8) and (8-2), (1-8) and (8-5), (1- ) And (8-6), (1-8) and (9-1), (1-8) and (10-4), (1-12) and (10-4), (1-13) (10-4), (1-17) and (10-4), (2-1) and (9-1), (2-1) and (9-2), (3-1) and (8 -2), (3-1) and (8-3), (3-1) and (11-1), (3-5) and (8-3), (3-6) and (10-4) ), (3-8) and (9-2), (5-8) and (12-5), (5-9) and (10-4) ionic liquids are mentioned. From the viewpoint of satisfactorily expressing the effects of the invention (having both adhesion to the substrate (B) and antistatic properties), (1-2) and (8-3), (1-2) and (10-1 ), An ionic liquid having an ion pair of (1-2) and (10-2) is more preferred, ) And (8-3) when using ionic liquids having an ion pair is particularly high adhesion to the base material (B) it is, and preferably from the viewpoint of excellent antistatic property.

The paint of the present invention can further contain an antistatic improver (f) as necessary. Examples of the antistatic improver (f) include at least one selected from the group consisting of an acidic phosphate ester (f-1), a carbodiimide compound (f-2), and a vinyl ether compound (f-3).

As the acidic phosphate ester (f-1) in the present invention, any acidic phosphate ester generally used as an additive for plastics can be used. For example, one obtained by substituting 1 to 3 or more active hydrogens of phosphoric acids. Examples of phosphoric acids include phosphoric acid, metaphosphoric acid, orthophosphoric acid, phosphorous acid, phosphonic acid, pyrophosphoric acid, diphosphinic acid, diphosphoric acid, and diphosphonic acid. Examples of the group that substitutes active hydrogen include an alkyl group, an aryl group, an alkenyl group, and a hydroxyalkyl group (all of which have 1 to 30 carbon atoms). Examples of the above include monoalkyl esters, monoaryl esters, dialkyl esters, diaryl esters, monoalkyl esters of phosphorous acid, and trialkyl esters of pyrophosphoric acid. Of these, preferred are those represented by the formula (f-1-1).

(R ₁ is a monovalent hydrocarbon group having 1 to 30 carbon atoms, n is 1 or 2, and when n is 2, R ₁ may be the same or different.) In (f-1-1), the alkyl group having 1 to 30 carbon atoms represented by R ₁ includes methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl. , Amyl, tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and triancontyl Group and the like. When n is 2, two R _{1 s} may be the same or different. More preferable as the acidic phosphate ester is an acidic phosphate having the above R ₁ having 8 to 30 carbon atoms, and particularly preferable ones are monolauryl ester of phosphoric acid, monostearyl ester of phosphoric acid, and phosphoric acid. Distearyl ester, or a combination thereof.

The acidic phosphate ester is, for example, a method of hydrolyzing a corresponding trialkyl phosphate or a corresponding triester or tetraester of phosphoric acid, a method of hydrolyzing after reacting phosphorus oxychloride with a corresponding alkanol, or It can be synthesized by a known method such as a method of reacting phosphorus pentoxide with the corresponding alkanol.

As the carbodiimide compound (f-2) in the present invention, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.
Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
Diisocyanates include 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

The carbodiimidization catalysts include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

As such a high molecular weight polycarbodiimide, there is a carbodilite series manufactured by Nisshinbo Co., Ltd. Among them, Carbodilite V-01, 03, 05, 07, 09 is preferable because it is excellent in antistatic improvement.

The vinyl ether compound (f-3) in the present invention contributes to the improvement of the conductive function in the cured paint (coating film).

Examples of such vinyl ether compound (f-3) include ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, and n-octyl vinyl ether. , Vinyl ethers of alkyl or alkenyl alcohols such as 2-ethylhexyl vinyl ether, octadecyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, oleyl vinyl ether; for example, aliphatics such as cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, benzyl vinyl ether Monoalcohol vinyl ethers having a ring or an aromatic ring;

For example, 1,4-cyclohexanedimethanol divinyl ether (CHDM) glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether , Pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane monovinyl ether Mono-polyvinyl ethers of polyhydric alcohols such as 1,4-dihydroxymethylcyclohexane divinyl ether;

For example, polyalkylene glycol mono-divinyl ethers such as diethylene glycol divinyl ether, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol monobutyl monovinyl ether; and other vinyl ethers such as glycidyl vinyl ether and ethylene glycol vinyl ether methacrylate; Examples thereof include hydroxybutyl vinyl ether.

Preferred are triethylene glycol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether (CHDM).

A preferable blending ratio of the components (a), (b), (c), (d), and (e) is as follows when the total amount of the components (a), (b), and (c) is 100% by mass. Component (a) 20 to 40% by mass, Component (b) 50 to 70% by mass, Component (c) 1 to 20% by mass, and the component (a) to (c) in total 100 parts by mass d) is 0.1 to 15 parts by mass. The component (e) is 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the components (a) to (c).
When the upper limit of the component (a) is exceeded, pencil hardness, Taber abrasion, surface smoothness, flexibility, impact resistance are deteriorated, and solvent resistance is also deteriorated. If it is less than the lower limit, it becomes brittle and the Taber wear resistance, flexibility, and impact resistance deteriorate. Moreover, water resistance also deteriorates.
When the upper limit of the component (b) is exceeded, the adhesiveness deteriorates and becomes brittle, the pencil hardness and the Taber abrasion resistance deteriorate, and the water resistance, flexibility and impact resistance also deteriorate. If it is less than the lower limit, the adhesiveness deteriorates, and the water resistance, pencil hardness, Taber abrasion, and surface smoothness deteriorate.
When it exceeds the upper limit of the component (c), it softens and pencil hardness and Taber abrasion deteriorate. Moreover, water resistance also deteriorates. Moreover, adhesiveness deteriorates and total light transmittance also deteriorates. If it was less than the lower limit, it became brittle and the Taber abrasion deteriorated. Moreover, adhesiveness and water resistance are also deteriorated.
When the upper limit of the component (d) is exceeded, the shrinkage becomes too large and the water resistance deteriorates. Moreover, adhesiveness deteriorates and surface smoothness also deteriorates. It is not cured below the lower limit.
When the upper limit of the component (e) is exceeded, the wear resistance, adhesiveness, and bleed resistance deteriorate. Below the lower limit, the antistatic properties deteriorate.

A more preferable blending ratio of the components (a), (b), (c), (d), and (e) is when the total amount of the components (a), (b), and (c) is 100% by mass. , Component (a) 25 to 35% by mass, component (b) 55 to 65% by mass, component (c) 3 to 15% by mass, and components relative to a total of 100 parts by mass of the components (a) to (c). When (d) is selected from an ultraviolet reaction initiator and an electron beam reaction initiator, it is 5 to 10 parts by mass, and when it is an organic peroxide, it is 0.1 to 5 parts by mass.
In addition, the component (e) is 2 to 7 parts by mass with respect to 100 parts by mass in total of the components (a) to (c).

The more preferable lower limit of the component (c) is 5% by mass or more from the viewpoint of adhesiveness with the substrate (B).

As a method for producing the coating material of the present invention, the above components (a) to (e) are mixed at a predetermined ratio, and then a suitable stirrer (for example, Mazerustar KK-250S (manufactured by Kurabo Industries Co., Ltd.) in which a stirrer and a defoaming device are fused). ).

The paint of the present invention has a viscosity that is advantageous in terms of operation without being diluted in an organic solvent. For example, the paint of the present invention has a viscosity at 25 ° C. (measured with a B-type viscometer) of, for example, 20 to 2000 mPa · s, preferably 100 to 1500 mPa · s. In addition, dilution with an organic solvent can also be performed as needed.
Moreover, a polymerization accelerator, a pigment, etc. can be suitably mix | blended with the coating material of this invention as needed.

The paint of the present invention can be applied on a substrate and cured. Application methods include spin coating, (doctor) knife coating, micro gravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meyer) bar coating, die coating, and spraying. Examples thereof include a coating method, a dip coating method, etc. (for example, ASS-301 model manufactured by Manual Spinner Co., Ltd. as a spin coating method). In addition, when an ultraviolet reaction initiator or an electron beam reaction initiator is used as the component (d), the coating material can be cured by irradiating with an ultraviolet ray or an electron beam. As irradiation conditions, for example, when ultraviolet rays are used, irradiation intensity of 150 to 1000 mJ / cm ² and irradiation time of 1 to 60 seconds can be mentioned. When an organic peroxide is used as the component (d), the paint can be cured by heating to 100 to 150 ° C., for example.

The thickness of the cured coating is, for example, 2 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 100 μm from the viewpoint of price and performance.

The coating material of the present invention can be applied to various substrates that cannot be conventionally adhered and cured unless a special primer or the like is used, such as polyester resin (for example, polyethylene terephthalate PET); polycarbonate; acrylic resin (for example, polymethyl resin). (Methacrylate PMMA); glass; soft and hard vinyl chloride resin; or styrenic resin (for example, acrylonitrile-butadiene-styrene copolymer ABS or polystyrene resin PS) on a base material (B) without using a primer or the like The coating layer (A) cured with good adhesion can be formed. (If it is possible in terms of cost and the like, a stronger adhesion can be obtained when using a primer on the substrate.)

Such a laminate formed by contacting the layer (A) and the base material (B) of the paint of the present invention so that the layer (A) and the layer (B) are in contact with each other, for example, for display panels and various devices. Useful for panel covers, vehicle glass, and various plastic products.
Since it is particularly excellent in transparency and wear resistance, it is suitable for a display, particularly a display part of a portable mobile terminal.

Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

The raw materials used in the examples and comparative examples are as follows.
Component (a-1) Vinyl ester resin (i) Urethane acrylate CN975 aromatic urethane acrylate, type = polyester, viscosity at 60 ° C. = 500, number of functional groups = 6
(Ii) Polyester acrylate CN292 polyester acrylate manufactured by Sartomer, type = aliphatic polyester, viscosity at 25 ° C. = 630, number of functional groups = 4
(Iii) Epoxy acrylate Sartomer CNUVE151 epoxy acrylate, type = polyester, viscosity at 25 ° C. = 150,000, number of functional groups = 2
(Iv) Urethane acrylate CN963B80 Urethane acrylate (1,6-hexanediol diacrylate HDDA blend), type = polyester, viscosity at 60 ° C. = 1,100, number of functional groups = 2
Component (a-2) Unsaturated polyester resin RIGOLAC 21E-A-2 (trademark) manufactured by Showa Polymer Co., Ltd.

Component (b-1) Compound having a cyclic structure and one ethylenically unsaturated group (i) N-vinylcaprolactam boiling point 117 ° C. (10 mm Hg) manufactured by BASF
Vapor pressure <0.1 mm Hg (20 ℃)
Flash point 110 ° C
Melting point 35 ℃
Viscosity 3.5 cps (40 ° C)
Component (b-2) Diacrylate monomer (i) Dipropylene glycol diacrylate (DPGDA) manufactured by BASF
(Ii) BASF, tripropylene glycol diacrylate (TPGDA)
(Iii) SR238NS from Sartomer, 1,6 hexanediol diacrylate, 25 ° C. viscosity = 9, number of functional groups = 2, fast-curing property, low volatility, Class 4 3 stone, skin irritation (PII) = 4.1

Component (b-3) Triacrylate monomer SR351NS (manufactured by Sartomer), trimethylolpropane triacrylate, 25 ° C. viscosity = 106 mPa · s, number of functional groups = 3, fast curing, low volatility, Class 4 3 stone, skin irritation Sex (PII) = 3.0

Component (c) Modifier (c-1-2) Polybutadiene Polyol Idemitsu Kosan Co., Ltd., Poly bd R-15HT
Viscosity: 1.5 Pa · s / 30 ° C., hydroxyl value: 102.7 mg KOH / g
(C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa · s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g
(C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd. Polyip (registered trademark), a polyisoprene-type liquid polymer having a highly reactive hydroxyl group at the molecular end (hydroxyl value 46.6 mgKOH / mg, number average) Molecular weight Mn = 2500)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-1262
Polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit mgKOH / g), hydroxyl value : 240-290 (unit mgKOH / g)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-2151U
A polyol containing a castor oil-based polyol, an acidic phosphate ester compound having 12 or more carbon atoms and terpene phenols Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit: mgKOH / g), hydroxyl value: 240 to 290 (unit: mgKOH / g)
(C-1-3) Hydrogenation product of polyisoprene-based polyol Epol (trademark) hydroxyl-terminated liquid polyolefin (viscosity (Pa · s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average, manufactured by Idemitsu Kosan Co., Ltd. Molecular weight 2500)
(C-3-1) Maleated polyisoprene Kuraray Co., Ltd. LIR-420 (Acid value (mgKOH / g) 40)
(C-3-2) Maleic acid-modified polybutadiene SARTOMER Ricon130MA8 (viscosity (Pa · s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700)
(C-3-2) Maleic acid-modified polybutadiene POLYVEST ™ OC 800 S manufactured by EVONIK (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bond: 24%, vinyl bond 1%, maleation rate: 7.5%, number average molecular weight: 3300 (GPC), weight average molecular weight: 13,600 (GPC), viscosity (20 ° C.): 6 to 9 Pa · s (measured at DIN 53214) Acid value: 70 to 90 mg KOH / g, Iodine value: 380 to 420 g / 100 g (polymerized with Ziegler-Natta catalyst)
(C-1-4) Epoxy polyol resin DIC Corporation EPICLON (trademark) U-125-60BT
(Viscosity (Pa · s / 30 ° C) 70, hydroxyl value (mgKOH / g) 120)
(C-4-1) Polyepoxy compound having an epoxy equivalent of 150 to 250 g / mol Adeka Resin EP-4100E (manufactured by ADEKA; bisphenol A diglycidyl ether, epoxy equivalent 190)
(C-4-2) Polymer having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol Kuraray L-207 (KRATON LIQUID ™) (epoxy equivalent is 590 g / mol, hydroxyl equivalent is 7000 g / mol) , Glass transition temperature -53 ° C, polymer with fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure))

The characteristics of each polyol were measured as follows.
-Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1.
1. A 500ml beaker (standard) is used for the measuring instrument.
2. The standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity. Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.

A: Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
B: 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
f: Factor

-Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils. According to JIS K 1557-5,
(1) End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
(2) Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker.
2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
Result of (1) 11.72 Set pH as the end point and calculate the acid value by the following formula. Moreover, a blank is calculated | required in the same procedure.
Acid value (mgKOH / g) = (D−B) × K × F × M / S
D: Titration value (mL)
B: Blank (0.085mL)
K: Molecular weight of KOH (56.1)
F: Factor of titrant (1.000)
M: Molar concentration of titrant (0.1 mol / L)
S: Sampling amount (g)

Component (d) Component radical polymerization initiator (i) Photopolymerization initiator IRBACURE ™ 819 manufactured by CIBA
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (ii) Thermal polymerization initiator manufactured by NOF Corporation, Perhexa 25B (1-minute half-life: 179 ° C.), 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane

Component (e) Ionic liquid (i) Basific LQ 01 (1-ethyl-3-methyl-1H-imidazolium ethyl sulfate, manufactured by BASF, having the ion pairs (1-2) and (8-3) above Ionic liquid)
(Ii) Basicic AC 09 (1-ethyl-3-methyl-imidazolium tetrachloroaluminate, an ionic liquid having an ion pair of (1-2) and (10-2)) manufactured by BASF
(Iii) Basion VS 01 (1-ethyl-3-methyl-imidazolium thiocyanate, an ionic liquid having an ion pair of (1-2) and (10-1)) manufactured by BASF
(Iv) manufactured by Lion Akzo Co., Ltd., TMAC-100 (tetramethylammonium chloride (ionic liquid having ion pairs (5-10) and (7-2))

Component (f-1) Acidic phosphate ester (i) Adekstab AX-71 manufactured by ADEKA Corporation, monostearyl phosphate and distearyl phosphate mixture (ii) Monolauryl phosphate manufactured by Daihachi Chemical Industry Co., Ltd.

Component (f-2) Carbodiimide compound Carbodilite V-05 manufactured by Nisshinbo Chemical Co., Ltd., NCO group 8.2%

Vinyl ether compounds (f-3)
(I) Triethylene glycol divinyl ether, DVE-3 (manufactured by BASF), 25 ° C. viscosity = 2.6 mPa · s
(ii) 1,4-cyclohexanedimethanol divinyl ether (CHDM), manufactured by BASF

Examples 1 to 38, Comparative Examples 1 to 8
In the mixing ratios (parts by mass) shown in Tables 1 to 13 below, the components (a) to (b) are placed in a container equipped with a stirrer and stirred sufficiently at room temperature. When the liquid temperature reaches room temperature, add the component (d) and stir well so as not to remain undissolved, then add the component (e), and if necessary, add (f) and stir. A paint was obtained. The viscosity (mPa · s) at 25 ° C. of the obtained adhesive composition was measured. That is, using a handy type digital viscometer TVC-7 type rotational viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are also shown in Tables 1 to 13.

Next, a coating material was applied by spin coating on various base materials (B) (dimensions: 150 mm × 25 mm × thickness 1 mm) shown in each table (applied thickness 10 μm), and this was applied in air at 500 mJ / cm ^2. The laminate was prepared by irradiating with ultraviolet rays having the energy of 2 to cure. When a thermal polymerization initiator was used, 0-0.05 parts by mass of 6% naphthene cobalt was added to the composition as necessary, and the composition was cured by heat treatment at 100 ° C. for 30 minutes.

Each base material (B) used is as follows.
・ Glass (slide glass for microscope preparation)
・ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.)
・ PMMA: Mitsubishi Rayon Acrypet VH
・ PET: Unitika Unitika polyester resin MA-2103
・ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844)
-Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N)
・ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114)
・ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.)

Evaluation (viscosity)
According to JIS K7233, the measurement was performed at 25 ° C. using a total TVC-7 rotational viscometer. The viscosity of the curing agent composition was evaluated as follows from the viewpoint of maintaining workability in a solvent-free unit with mPa · S.
○: Viscosity that can be used practically at a viscosity of 1000 mPa · s / 25 ° C. or less.
Δ: Viscosity is 1000 to 2000 mPa · s / 25 ° C., and the working air temperature is restricted, which is not practically preferable.
X: Since the viscosity is 2000 mPa · s / 25 ° C. or higher and workability is poor, it is necessary to dilute with a solvent at room temperature or lower.

(Measurement of haze value and total light transmittance)
Using a coating sample on a glass substrate, measurement was performed using a measuring instrument (trade name “COH-300A”) manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement of pencil hardness)
Using a coating sample on a glass substrate, measurement was performed according to the pencil hardness measurement method described in Japanese Industrial Standard K5400.
In addition, the determination of the presence or absence of scratches on the sample is made with the naked eye of the measurer in accordance with the above-mentioned standard. When the average value of the depth measured at five different locations was 0.2 μm or more, it was determined that “scratches had occurred”.

(Measurement of Taber abrasion)
Using a sample coated on a PC (polycarbonate) substrate, after a Taber abrasion test (CS-10 abrasive paper, 500 g, 20 times), the coating haze value obtained from the following formula was evaluated by the difference before and after abrasion (ΔH). .
Haze (%) = (diffuse transmittance / total light transmittance) × 100

(Adhesion test)
Each substrate was measured as follows in accordance with a cross-cut tape test method described in Japanese Industrial Standard K5400.
Cross-cut test (Cross-cut Test, coating thickness 10 μm (spin coating method)): A 1 × 1 mm square cut is made on the test surface (hard coat layer (A) side) using a cutter knife. Use the cutter guide. The number of grids is 10 vertical x 10 horizontal = 100. Strongly press the cellophane tape into the grid, and peel off the end of the tape rapidly at an angle of 45 ° to see the grid pattern (number of grids remaining without peeling).

(Water resistance test)
For each substrate, the sample was immersed in boiling water (pure water) for 1 hour and then naturally dried indoors, and visually observed for the presence or absence of deterioration of the appearance of the hard coat layer.
○: No peeling or cracking (immersion for 1 hour)
×: Peeling or cracking occurred (immersion for 1 hour)

Impact resistance test Test method: Apply a paint with a thickness of 15 to 20μm on a 25mm wide and 1mm thick steel plate by spin coating, drop a 1kgw spherical weight from 1m height after curing, and evaluate according to the following criteria went.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked

Flexibility Test method: A paint was applied to a steel sheet of 25 mm width and 1 mm thickness by a spin coating method to a thickness of 15 to 20 μm, and after curing, a 90-degree bending test was performed and evaluation was performed according to the following criteria.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked

Surface resistance The surface resistance was applied to a PC (polycarbonate) base material (dimensions: 150 mm x 25 mm x thickness 1 mm) as a sample by spin coating (coating thickness 10 µm). High resistance manufactured by Mitsubishi Chemical Corporation The surface resistivity (Ω / sq.) Was measured with an applied voltage of 500 V according to ASTM D257 using a rate meter Hi-Lester UP (MCP-HT450 type). The resistivity of each sample was an average value (n = 5) of five measured values.

Bleed resistance Test method: A coating sample on a glass substrate was visually confirmed and evaluated according to the following criteria.
○: No bleed / bloom ×: With bleed / bloom

The results are shown in the table.

Referring to the results of the examples in the table, since the paints of the examples are blended with specific amounts of the components (a) to (e), glass, polycarbonate, acrylic resin, polyester resin, Adhesiveness with layers of hard vinyl chloride resin, soft vinyl chloride resin or styrene resin (especially polycarbonate, acrylic resin, polyester resin) is sufficient, antistatic property, hardness, water resistance, abrasion resistance, transparent It can be seen that performance, flexibility and impact resistance are balanced at a high level.
In Comparative Example 1, since the blending amount of the component (a) is less than the lower limit specified in the present invention and the blending amount of the component (b) exceeds the upper limit defined in the present invention, the adhesiveness deteriorates. It became brittle and the Taber abrasion deteriorated. In addition, water resistance, impact resistance, and flexibility deteriorated.
In Comparative Example 2, the compounding amount of the component (a) exceeds the upper limit specified by the present invention, and the compounding amount of the component (b) is less than the lower limit specified by the present invention. Worsened. In addition, water resistance, impact resistance, and flexibility deteriorated.
In Comparative Example 3, since the component (c) was not blended, the adhesiveness deteriorated and became brittle and the Taber wear resistance deteriorated. In addition, water resistance, impact resistance, and flexibility deteriorated.
In Comparative Example 4, since the blending amount of the component (c) exceeded the upper limit specified in the present invention, the shrinkage was too large and the water resistance was deteriorated. Moreover, adhesiveness deteriorated and total light transmittance and surface hardness also deteriorated.
In Comparative Example 5, since the amount of component (d) was less than the lower limit specified in the present invention, curing was insufficient.
In Comparative Example 6, since the blending amount of the component (d) exceeded the upper limit defined in the present invention, the shrinkage was too large and the water resistance was deteriorated. Adhesiveness, water resistance, impact resistance, and flexibility also deteriorated.
Since the comparative example 7 did not mix | blend a component (e), surface resistance deteriorated.
In Comparative Example 8, since the blending amount of the component (e) exceeds the upper limit specified in the present invention, bleeding was observed.
Even when the coating thickness of the paint of the present invention was tested at 5 μm, good results were obtained as in Examples 1 to 25.

Claims (22)

1. (A) Vinyl ester resin or unsaturated polyester resin 20 to 40% by mass
   (B) Vinyl monomer and / or (meth) acrylate monomer 50 to 70% by mass
   (C) modifying agent 1 to 20% by mass,
   (However, the total of the components (a) to (c) is 100% by mass)
   (D) At least one radical polymerization initiator selected from the group consisting of an organic peroxide, an ultraviolet reaction initiator, and an electron beam initiator is 0.1% relative to a total of 100 masses of the components (a) to (c). 15 to 15 parts by mass and (e) an ionic liquid as an antistatic material containing 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) Paint for polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin.
2. The paint according to claim 1, wherein the component (a) is at least one selected from the group consisting of urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
3. The component (b) is at least one selected from (b-1) a compound having a cyclic structure and one ethylenically unsaturated group; (b-2) a diacrylate compound; and (b-3) a triacrylate compound. The paint according to claim 1, wherein the paint is a seed monomer.
4. The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g; 4. The modified rubber (c-3); and at least one selected from the group consisting of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol. The paint described.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; The paint according to claim 4, wherein the paint is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof.
6. The paint according to claim 5, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g.
7. The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 4. The paint according to 4.
8. The paint according to claim 4, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. The paint according to claim 4, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. The paint according to claim 4, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. The ionic liquid (e) contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium, according to any one of claims 1 to 10. paint.
12. The ionic liquid (e) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. The paint according to claim 11.
13. Further, it contains an antistatic improver (f), and the antistatic enhancer (f) comprises an acidic phosphate ester (f-1), a carbodiimide compound (f-2), and a vinyl ether compound (f-3). And at least one selected from the group, and the blending amount of the antistatic improver (f) is in the range of 0.02 to 30 when the mass of the ionic liquid (e) is 1. The paint according to any one of claims 1 to 12, wherein:
14. The paint according to any one of claims 1 to 13, which is used on the surface of a display.
15. 15. The paint according to claim 14, which is used on the surface of a display of a portable mobile terminal.
16. (A) Vinyl ester resin or unsaturated polyester resin 20 to 40% by mass
    (B) Vinyl monomer and / or (meth) acrylate monomer 50 to 70% by mass
    (C) modifying agent 1 to 20% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    (D) At least one radical polymerization initiator selected from the group consisting of an organic peroxide, an ultraviolet reaction initiator, and an electron beam initiator is 0.1% relative to a total of 100 masses of the components (a) to (c). And (e) an ionic liquid as an antistatic material, and a coating layer (A) containing 0.5 to 10 parts by mass with respect to 100 parts in total of the components (a) to (c);
    Polyester resin, polycarbonate, acrylic resin, glass, hard vinyl chloride resin, soft vinyl chloride resin or styrene resin layer (B) was formed so that the layer (A) and layer (B) were in contact with each other. Laminated body.
17. The laminate according to claim 16, wherein the coating layer (A) has a thickness of 2 to 200 µm.
18. The laminate according to claim 16 or 17, wherein the ionic liquid (e) contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium. .
19. The ionic liquid (e) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. The laminate according to claim 18.
20. The coating layer (A) further contains an antistatic improver (f), and the antistatic improver (f) comprises an acidic phosphate ester (f-1), a carbodiimide compound (f-2), and a vinyl ether. And at least one selected from the group consisting of the compound (f-3) and the blending amount of the antistatic improver (f) is 0 when the mass of the ionic liquid (e) is 1. The laminate according to any one of claims 16 to 19, which is in a range of 0.02 to 30.
21. The laminate according to any one of claims 16 to 20, wherein the laminate is used on a surface of a display.
22. The laminate according to claim 21, wherein the laminate is used on a surface of a display of a portable mobile terminal.