JP5539605B2 - Active energy ray-curable coating agent and use thereof - Google Patents

Description

  The present invention relates to an active energy ray-curable coating agent. More specifically, in the present invention, the cured coating film (coating layer) has transparency, adhesion, oil resistance, chemical resistance, excellent wear resistance, and the coating film is hardly damaged. Optical materials, automobile bodies, and plastic parts that can be applied to thermoforming and in-molding applications such as vacuum forming because they have self-healing properties even after they are scratched, and they are extensible. The present invention relates to a coating agent suitable for surface protection applications such as plastic films. The present invention also relates to an automotive clear paint, a plastic film top coat agent, and a plastic component protective coat agent using the coating agent. Furthermore, the present invention relates to a topcoat film having a topcoat layer coated and cured with the topcoat agent, and a molded product obtained by thermoforming the topcoat film or a laminate obtained by laminating the topcoat film and another substrate. .

  In recent years, a coating layer (hard coat layer) made of synthetic resin with excellent scratch resistance has been provided for the purpose of protecting the surface of optical materials such as color filters, flat panel displays, and automobile bodies (scratch prevention and antifouling, etc.). Or a plastic film with a hard coat applied. These coating layers are required to have scratch resistance as an essential characteristic from the viewpoint of surface protection, and various characteristics such as chemical resistance, oil resistance, and vacuum formability are required depending on applications. As for scratch resistance, simply hardening the coating film easily causes “cracking” to deformation and lowers the vacuum formability, etc., so that it is difficult to scratch but is flexible. (Extensibility) is required.

  In order to solve the above problems, as a protective film having flexibility and extensibility, a so-called self-healing protective film in which a scratch generated on the surface recovers with time is attracting attention. Optical films having repairability are known (for example, Patent Documents 1 and 2). However, hard coating agents composed of radically polymerizable compounds such as urethane acrylate have poor operability due to odor, oxygen curing inhibition, high viscosity, etc., large curing shrinkage, warping of the film, and insufficient adhesion to plastic (especially polyethylene terephthalate). (Insufficient adhesion to (PET) film) was a problem.

  On the other hand, as active energy ray-curable resins used for optical applications and the like, in addition to the above, epoxy resins are known. Epoxy resin has advantages such as high heat resistance, high hardness, high transparency, and low curing shrinkage at the time of curing, but it is inferior in stretchability, easily cracked against deformation, and vacuum formability. Therefore, it has been difficult to use for thin film coating, top coat of a film requiring flexibility, vacuum forming application, and the like. Therefore, improvements such as blending a polyol compound and imparting flexibility have been made. For example, in the field of resin molded products, it is composed of a compound having an epoxy group, a specific carbonate diol, and an active energy ray active catalyst. An active energy ray-curable composition is known (for example, Patent Document 3). However, in the composition, the miscibility, oil resistance, and chemical resistance of the epoxy resin and polyol may be reduced, and there has been no study applied to a thin film coating such as a protective layer. In addition, there has been no study on scratch resistance such as self-repairability.

JP 2003-4939 A JP 2003-84102 A JP-A-9-71636

  The object of the present invention is to provide excellent wear resistance without impairing transparency, adhesion, oil resistance (gasoline resistance) and chemical resistance, which are the characteristics of epoxy resin, and excellent self-repair and scratch resistance. In addition, it is an object of the present invention to provide an active energy ray-curable coating agent that is effective for protecting optical materials, flat panel displays, automobile bodies, etc. Further, a clear paint for automobiles comprising the coating agent, a top coat agent for plastic films, a coating agent for protecting plastic parts, and a resin cured layer obtained by curing the coating agent with active energy rays (hereinafter referred to as a coating layer). An object of the present invention is to provide a topcoat film having a molded product obtained by thermoforming or in-molding them.

  As a result of intensive studies, the inventor has obtained at least one resin selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, and a coating agent comprising a polyol having a specific structure and characteristics and an active energy ray-sensitive catalyst. The inventors have found that the above object can be achieved and completed the present invention.

That is, the present invention includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is a polyol (B1) having a main chain composed of a carbon-carbon bond,
The polyol (B1) having a main chain composed of carbon-carbon bonds is a polyolefin-based polyol,
Polyolefin polyol, Ri Oh in polyolefin polyol hydrogenated to produce a polydiene-based polyol having hydroxyl groups at both ends of the molecular chain,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight .

  Furthermore, the present invention provides the active energy ray-curable coating agent, wherein the polydiene-based polyol having hydroxyl groups at both ends of the molecular chain is polyisoprene having hydroxyl groups at both ends of the molecular chain.

The present invention also includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). A coating agent as a component, wherein the polyol (B) is a polyol (B1) having a main chain composed of carbon-carbon bonds,
Carbon - polyol having a main chain consisting of carbon bonds (B1) is, Ri vinyl ether oligomer der having hydroxyl groups at both ends,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight .

（式中、Ｒ¹は水素原子、アルキル基またはアリール基を示し、ｎは１〜５０の整数である。） Furthermore, the present invention provides the active energy ray-curable coating agent, wherein the vinyl ether oligomer is an oligomer represented by the following chemical formula (I).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 1 to 50.)

The present invention also includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). A coating agent as a component, wherein the polyol (B) is a polyol (B1) having a main chain composed of carbon-carbon bonds,
Carbon - polyol having a main chain consisting of carbon bonds (B1) is, Ri (meth) acrylic copolymer der having a hydroxyl group,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight .

  Furthermore, the present invention provides the active energy wherein the (meth) acrylic copolymer having a hydroxyl group is a (meth) acrylic copolymer having an ethylenically unsaturated monomer having a hydroxyl group as at least one monomer component. A line curable coating agent is provided.

  Furthermore, the present invention provides the active energy ray-curable coating agent, wherein the (meth) acrylic copolymer having a hydroxyl group is a (meth) acrylic copolymer having a lactone-modified hydroxyl group.

Furthermore, the present invention, the a lactone-modified hydroxyl (meth) acrylic copolymer, lactone-modified obtained by adding a lactone monomer with a hydroxyl group (meth) acrylate and at least one monomer component (meth) acrylic The active energy ray-curable coating agent which is a copolymer is provided.

The present invention also includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). A coating agent as a component, wherein the polyol (B) is a polycarbonate polyol (B2),
Polycarbonate polyol (B2) is another diol represented by 1,6-hexanediol and HO—R ² —OH (wherein R ² has 2 to 14 carbon atoms and is linear or branched) Any of these may contain 1 to 3 cyclic structures, which may further contain oxygen, nitrogen and sulfur atoms in the molecule) and a carbonate component, which is 1,6-hexane. the molar ratio of diol and other diol 10: 1 to 1: 9, Ri number average molecular weight of 400 to 3000 der,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight .

The present invention also includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). A coating agent as a component, wherein the polyol (B) is a polyester polyol (B3);
The polyester polyol (B3) is a polycaprolactone polyol ,
The resin (A) includes an epoxy resin and a vinyl ether resin,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight.

The present invention also includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C). A coating agent as a component, wherein the polyol (B) is a polyether polyol (B4);
The polyether polyol (B4) is a ring- opening polymer of a cyclic ether,
The polyether polyol (B4) has a molecular weight of 400 to 3000,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). An active energy ray-curable coating agent is provided, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight.

Furthermore, this invention provides the said active energy ray-curable coating agent whose ratio (epoxy group / hydroxyl group) of an epoxy group and a hydroxyl group in an active energy ray-curable coating agent is 1.5-20.
Further, in the present invention, a coating layer obtained by applying a coating agent on a substrate (polyethylene terephthalate film having a thickness of 100 μm) and curing it with an active energy ray is subjected to an abrasion test (load: 200 gf / 20 cm) with steel wool (# 0000). ² ) The difference ΔH (ΔH = H ₂ −H ₁ ) between the haze value (Haze value) H ₁ of the coating layer immediately after the test and the haze value H ₂ after 2 hours is less than 0. The active energy ray-curable coating agent is provided.

  Furthermore, in the present invention, a coating layer formed by applying a coating agent on a base material (polyethylene terephthalate film having a thickness of 100 μm) and curing with an active energy ray is heated together with the base material at 130 ° C., and the drawdown reaches the lower limit. The active energy ray-curable coating agent has an elongation percentage of 50% or more when immediately stretched.

  Furthermore, the present invention relates to a Taber abrasion test (JIS K 5400 8.9, wear wheel: S) of a coating layer obtained by applying a coating agent on a base material (polyethylene terephthalate film having a thickness of 100 μm) and curing with an active energy ray. -42 / CS-0, the above-mentioned active energy ray-curable coating agent, wherein the number of rotations required for the substrate to be exposed at a rotation number of 60 rpm, a load of 500 gf, and a coating thickness of 5 μm is 1500 times or more. .

  Furthermore, this invention provides the clear coating material for motor vehicles which consists of said active energy ray hardening coating agent.

  Furthermore, this invention provides the topcoat agent for plastic films which consists of said active energy ray curable coating agent.

  Furthermore, the present invention provides a coating agent for protecting plastic parts comprising the above active energy ray-curable coating agent.

  Furthermore, the present invention provides the above active energy ray-curable coating agent that is used for a protective film of a color filter.

  Furthermore, the present invention provides a cured resin obtained by curing the active energy ray-curable coating agent, the clear paint for automobiles, the plastic component protecting coating agent or the plastic film topcoat agent with active energy rays. .

  Furthermore, this invention provides the topcoat film which has the topcoat layer formed by apply | coating the said topcoat agent for plastic films to said at least one surface of a plastic film, and carrying out active energy ray hardening.

Furthermore, the present invention provides a molded product obtained by drawing the top coat film or a laminate obtained by laminating the top coat film on another substrate by thermoforming.
In the present specification, as the invention described in the specification, at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an activity A resin composition comprising an energy ray-sensitive catalyst (C), wherein the polyol (B) has a main chain comprising a carbon-carbon bond, a polyol (B1), a polycarbonate polyol (B2), a polyester polyol (B3), and a polyether An active energy ray-curable coating agent is described which is at least one polyol selected from polyols (B4).
In the active energy ray-curable coating agent, the blending amount of the resin (A) is 20 to 75 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The blending amount of B) is preferably 25 to 80 parts by weight and the blending amount of the catalyst (C) is preferably 0.5 to 10 parts by weight.
The polyol (B1) having a main chain composed of carbon-carbon bonds is preferably a polydiene polyol or polyolefin polyol having hydroxyl groups at both ends of the molecular chain.
The polydiene polyol is preferably polybutadiene.
The polydiene polyol is preferably a polydiene polyol in which a part of the double bond of the main chain is epoxidized.
The polydiene-based polyol in which a part of the double bond in the main chain is epoxidized is preferably polybutadiene in which a part of the double bond in the main chain is epoxidized.

  The active energy ray-curable coating agent of the present invention uses at least one resin selected from an epoxy resin, an oxetane resin, and a vinyl ether resin and a specific polyol, so that it has transparency, adhesion, oil resistance, and chemical resistance. It has a coating layer with excellent wear resistance, scratch resistance, and self-repairability. Moreover, since this coating layer has extensibility, it is excellent in vacuum moldability. Reflecting the above characteristics, the automotive clear paint, the plastic film topcoat agent and the like comprising the coating agent have excellent surface protection. Furthermore, the top coat film using the top coat agent and the molded product thereof have excellent scratch resistance.

  The active energy ray-curable coating agent of the present invention includes at least one resin (A) selected from an epoxy resin, an oxetane resin, and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray sensitive material. The catalyst (C) is an essential component. In addition to (A) to (C), other resins, antifoaming agents, acid diffusion control agents, reactive diluents, photosensitizers, and dehydrating agents may be used as long as the effects of the present invention are not impaired. Contains various additives such as surfactants, antistatic agents, leveling agents, silane coupling agents, wetting improvers, antioxidants, UV absorbers, plasticizers and lubricants, inorganic fine particles, and organic fine particles. Also good. Moreover, it can dilute and use to a suitable viscosity with a solvent.

  The resin (A) used in the coating agent of the present invention is selected from epoxy resins, oxetane resins, and vinyl ether resins from the viewpoints of coating film hardness, oil resistance, chemical resistance, transparency, and reactivity with polyols. Or a mixture of two or more resins. Among these, it is preferable to include at least one epoxy resin.

The epoxy resin used as the resin (A) of the present invention is not particularly limited, but preferably an alicyclic epoxy resin having a cyclic aliphatic skeleton and one or more, preferably two or more epoxy groups in the molecule. It is. More preferably, it is a case where two epoxy groups are contained in one molecule. Examples of the alicyclic epoxy resin containing two epoxy groups in one molecule include compounds having the following structural formula.

  The compound represented by the general formula (II) is produced by oxidizing a corresponding alicyclic olefin compound with an aliphatic percarboxylic acid or the like. Among these, those produced using substantially anhydrous aliphatic percarboxylic acid are preferable in that they have a high epoxidation rate (see, for example, JP-A-2002-275169).

  In the general formula (II), Y represents a linking group. For example, a single bond, an alkylene group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-) and a group in which a plurality of these are linked. The alkylene group preferably has 1 to 18 carbon atoms, and includes a linear or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene group, 1,2-cyclopentylene, Divalent alicyclic hydrocarbon groups such as 3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene group ( Particularly, a divalent cycloalkylene group) and the like are exemplified.

Specific examples of the compound described above include the following compounds.

  Note that m is an integer of 1 to 30.

As the epoxy resin, in addition to the above, for example, limonene diepoxide may be used in which only one of the two epoxy groups includes two carbon atoms constituting the cycloaliphatic skeleton. Moreover, the following glycidyl ethers in which the epoxy group does not contain the carbon atom constituting the cycloaliphatic skeleton can also be used.

In addition, polyfunctional epoxy having three or more epoxy groups and monoepoxy having only one epoxy group can be used as follows.

In addition, said l, p, q is an integer of 1-30, and said a, b, c, d, e, f are integers of 0-30. R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aryl group.

  The epoxy resin of this invention may use only 1 type, and may mix and use 2 or more types.

  The epoxy resin of the present invention can also be obtained on the market. For example, “Celoxide 2021P”, “Celoxide 2081”, “Epolide GT401”, “Epolide PB3600”, “Epolide PB4700”, “EHPE3150”, “Epolide GT301” ”,“ Celoxide 3000 ”(all manufactured by Daicel Chemical Industries, Ltd.),“ ERL-4221 ”,“ UVR-6128 ”,“ UVR-6105 ”(produced by Dow Chemical Co., Ltd.). Among these, “Celoxide 2021P” (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate) is particularly preferable.

  The epoxy resin of the present invention is preferably liquid. The term “liquid” as used in the present application means that the viscosity measured at 25 ° C. is 100000 mPa · s or less (preferably 50000 mPa · s or less). The viscosity (70 ° C.) is preferably 3000 mPa · s or less, more preferably 500 mPa · s or less. When two or more kinds of epoxy resins are mixed and used, the above-described viscosity may be satisfied after mixing. In the case of solid or pasty or high viscosity after mixing, when used for coating as it is, the workability is reduced or the miscibility with the polyol (B) is lowered, and the transparency of the coating agent is reduced. May decrease. When the viscosity is high, the coating can be carried out by lowering the viscosity to an appropriate level with a solvent.

  The oxetane resin used in the resin (A) of the present invention is not particularly limited as long as it is a curable compound having an oxetane ring in the molecule and is, for example, 3-ethyl-3-hydroxymethyloxetane, 1 , 4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane and the like. As these compounds, for example, “OXT-101, 121, 211, 221, 212, 610” manufactured by Toagosei Co., Ltd. is commercially available.

  The vinyl ether resin used in the resin (A) of the present invention is not particularly limited as long as it is a curable vinyl ether compound, and examples thereof include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like. . Commercially available products such as Maruzen Petrochemical Co., Ltd. “HEVE, HBVE, DEGV” are available for these compounds.

  The polyol (B) used in the coating agent of the present invention is a compound having two or more hydroxyl groups in one molecule, and preferably has three or more hydroxyl groups per molecule. The polyol (B) of the present invention is at least one polyol selected from a polyol (B1) having a main chain composed of carbon-carbon bonds, a polycarbonate polyol (B2), a polyester polyol (B3), and a polyether polyol (B4). It is.

  When the coating agent of the present invention is photocured, the resin (A) and the polyol (B) form a copolymer (cured product) by cationic polymerization. In the coating agent of the present invention, by adding a specific polyol component to the resin (A) having properties such as high transparency, high hardness, adhesion, and chemical resistance, abrasion resistance, scratch resistance, Self-repairability, stretchability, vacuum formability, etc. can be imparted. Among these, by setting the molecular weight of the polyols (B1) to (B4) to 400 or more, when the number of hydroxyl groups is 3 or more, the length of the unit necessary for developing flexibility can be secured, and Since the number of cross-linking points increases, it becomes possible to achieve both wear resistance, scratch resistance, self-repairability and chemical resistance.

  In addition, in the copolymer (cured product) of the resin (A) and the polyol, when the ether chain is included in the main chain of the polyol component, the cured product is easily thermally decomposed, and the ester bond is included. Since hydrolysis tends to occur, the stability may be lowered when the cured product is used in a high-temperature and high-humidity environment. For this reason, when the polyol (B1) or the polycarbonate polyol (B2) having a stable structure not containing an ether bond, an ester bond or the like in the main chain is used as the polyol (B), the stability in a use environment of high temperature and high humidity. The property is further improved.

  The number average molecular weight of the polyol (B) of the present invention is 400 or more (for example, 400 to 30000), preferably 450 to 25000, more preferably 500 to 23000, and still more preferably 600 to 20000. When the molecular weight of the polyol (B) is less than 400, the amount of the hydroxyl group of the polyol (B) with respect to the cationically polymerizable functional group of the resin (A) is relatively large, so that in the cationic polymerization for forming a cured product. Since the length of the molecular chain is shortened and the curing degree (polymerization degree) of the coating layer is lowered, chemical resistance and coating film hardness are lowered. When the molecular weight exceeds 30000 and is excessive, the miscibility with the resin (A) may decrease or the coating property may decrease. In addition, the amount of the hydroxyl group relative to the cationically polymerizable functional group of the resin (A) is relatively small, the curing reaction rate of the coating agent is slowed, and workability may be reduced.

  When the polyol (B) of the present invention is a polyol (B1) having a main chain composed of carbon-carbon bonds, 60% or more of the main chain (however, excluding end groups) are carbon atoms, preferably 65 % Or more is a carbon atom, and more preferably, the main chain consists only of carbon atoms. As the polyol (B1), a saturated or unsaturated linear or branched polyol having 25 to 700 carbon atoms is preferably exemplified from the viewpoint of molecular weight control. The position of the hydroxyl group is not particularly limited at the end of the main chain and the side chain. Of these, polydiene-based polyols or polyolefin-based polyols are preferred as those having hydroxyl groups at both ends of the molecular chain, and (meth) acrylic copolymers having hydroxyl groups (hereinafter referred to as poly (poly) polyols) having hydroxyl groups in the side chain. (Referred to as acrylic polyol).

  As the polydiene polyol having hydroxyl groups at both ends of the molecular chain, polybutadiene or polyisoprene having hydroxyl groups at both ends of the molecular chain, or having hydroxyl groups at both ends of the molecular chain, and a double bond of the main chain A polydiene-based polyol (for example, polybutadiene) partially epoxidized is preferable.

  Examples of the polyolefin-based polyol having hydroxyl groups at both ends of the molecular chain include polyethylene and polypropylene having hydroxyl groups at both ends of the molecular chain. Preferably, the polydiene having hydroxyl groups at both ends of the molecular chain described above. What was manufactured by hydrogenating a system polyol is preferable. For example, hydrogenated polybutadiene or polyisoprene having hydroxyl groups at both ends of the molecular chain is preferable.

  The polyacryl polyol is a (meth) acrylic copolymer having a hydroxyl group, for example, a (meth) acrylic copolymer having an ethylenically unsaturated monomer having a hydroxyl group as at least one monomer component. Among the polyacryl polyols, polyacryl polyols in which the hydroxyl group is a hydroxyl group derived from lactone modification are preferable, and such a polyacryl polyol has, for example, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate (meth). Examples include (meth) acrylic copolymers having, as a monomer component, a lactone-modified (meth) acrylic monomer (for example, ε-caprolactone-modified acrylic monomer) obtained by adding a lactone monomer to the hydroxyl group of the acrylic monomer. Furthermore, a polyacryl polyol in which the lactone-modified (meth) acryl monomer is 30% by weight or more of the whole monomer component is preferable.

  Examples of the monomer component having a hydroxyl group constituting the polyacryl polyol include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε- Preferred examples include hydroxyalkyl esters of (meth) acrylic acid such as caprolactone-modified acrylic monomers. Examples of the monomer component having a hydroxyl group such as the above-mentioned ε-caprolactone-modified acrylic monomer include, for example, “Placcel F (Placcel FM1D, FM2D, FM3, FM3X, FM5, FM5L, FA1DDM, FA2D, FA3, FA5” manufactured by Daicel Chemical Industries, Ltd. , FA10L) "etc. are available on the market.

  Examples of copolymer components that can be used include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate (Meth) acrylic acid alkyl ester or (meth) acrylic acid cycloalkyl ester having 1 to 24 carbon atoms in the alkyl group or cycloalkyl group such as cyclohexyl (meth) acrylic acid; (meth) acrylic acid, maleic acid, itacon Α, β-ethylenically unsaturated carboxylic acids such as acid and crotonic acid; (meth) acrylamide, N -(Meth) acrylamide or derivatives thereof such as methyl (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide; styrene, vinyltoluene, α-methylstyrene Aromatic vinyl monomers such as vinyl propionate, vinyl acetate, (meth) acrylonitrile, and other vinyl monomers. In addition, methacrylate having a methyl glycidyl group ("M-GMA" manufactured by Daicel Chemical Industries, Ltd.) and (meth) acrylate having an alicyclic epoxy group ("Cyclomer M100, A400" manufactured by Daicel Chemical Industries, Ltd.) Etc.) are also preferably used.

As the polyol (B1) of the present invention, in addition to the above, vinyl ether oligomers having hydroxyl groups at both ends are also preferable. For example, vinyl ether oligomers represented by the above formula (I) can be used. In the formula (I), R ¹ represents hydrogen, an alkyl group or an aryl group, and n is an integer of 1 to 50. Examples of the alkyl group herein include linear or branched alkyl groups having about 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and hexyl groups. Can be mentioned. Examples of the aryl group include phenyl and naphthyl groups. The aromatic ring of the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, but are not limited thereto.

  Examples of the polyol (B1) listed above include, for example, “Epolide PB3600”, “Cell Top D446”, “Placcel DC2009”, “Placcel DC2016”, “Placcel DC2209”, “Placcel EPA2250”, “Placcel EPA5860” (any) Also manufactured by Daicel Chemical Industries, Ltd.), “TOE-2000H” (manufactured by Kyowa Hakko Chemical Co., Ltd.), “Poly bd R-45HT”, “Poly bd R-15HT”, “Poly ip”, “Epol” ( Idemitsu Kosan Co., Ltd.), “Kurapol” (Kuraray Co., Ltd.) and the like are available as commercial products.

  When the polyol (B) of the present invention is a polycarbonate polyol (B2), the polycarbonate polyol (B2) is liquid. When the polycarbonate polyol is solid (wax, paste, etc.), the miscibility with the resin (A) is poor, and the effect of adding the polyol is reduced. That is, the copolymer composition is biased, the chemical resistance is lowered, and the coating film hardness and the self-repairing property are locally lowered. In addition, unevenness of curing may occur at the time of curing, resulting in a decrease in productivity such as generation of “wrinkles”, or a decrease in transparency due to poor dispersion, which may not be used for optical materials.

  As the above-mentioned polycarbonate polyol (B2), the phosgene method or the carbonate exchange reaction using dialkyl carbonate or diphenyl carbonate such as dimethyl carbonate and diethyl carbonate (Japanese Patent Laid-Open No. 62-187725) is the same as the method for producing ordinary polycarbonate polyol. JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420 and the like.

  Examples of the polyol used in the carbonate exchange reaction together with dialkyl carbonate and the like include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol And dipropylene glycol.

  Examples of the polycarbonate polyol (B2) include “Placcel CD205PL, CD205HL, CD210PL, CD210HL, CD220, CD220PL, CD220HL, CD220EC, CD221T” manufactured by Daicel Chemical Industries, Ltd., “UH-CARB50” manufactured by Ube Industries, Ltd. , UH-CARB100, UH-CARB300, UH-CARB90 (1/3), UH-CARB90 (1/1), UC-CARB100 "," PCDL T4671, T4672, T5650J, T5651 and T5652 "manufactured by Asahi Kasei Chemicals Corporation Etc. are available as commercial products.

Among the above, the polycarbonate polyol (B2) of the present invention is a 1,6-hexanediol component, and other diols represented by the chemical formula HO—R ² —OH, from the viewpoints of self-healing effect and production cost. In the case of an oligomer composed of a component and a carbonate component, it is particularly preferable from the viewpoint of compatibility with the epoxy resin (A). In the above case, the molar ratio of the 1,6-hexanediol component to other diol components is preferably 10: 1 to 1: 9, more preferably 9: 1 to 2: 8. R ² represents a divalent organic group. R ² has, for example, 2 to 14 carbon atoms and may contain oxygen, nitrogen and sulfur atoms, and may be linear or branched. Furthermore, it may have 1 to 3 cyclic structures, and may contain oxygen, nitrogen, and sulfur atoms in the ring. Among these, a divalent hydrocarbon group having 2 to 14 carbon atoms (in particular, an alkylene group, a cycloalkylene group, or a group in which these are bonded) in which an oxygen atom may be interposed is preferable as R ² . The number average molecular weight is preferably 400 to 3000.

  When the polyol (B) of the present invention is a polyester polyol (B3), the polyester polyol is composed of a polyol component and a carboxylic acid component, and is a dehydration esterification reaction, a transesterification reaction, a lactone ring-opening polymerization, or a combination thereof. Can be synthesized. Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, Examples include propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, and pentaerythritol. As the carboxylic acid component, oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, Citralaconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, lactic acid, malic acid Glycolic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Examples of lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

  Among these, as the polyester polyol (B3) of the present invention, polycaprolactone polyol is particularly preferable. Examples of the polycaprolactone polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, methylpentanediol, 2, 4-diethylpentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, ethylene oxide or propylene oxide adduct of bisphenol A, glycerin, etc. Examples include polycaprolactone polyols obtained by ring-opening addition polymerization of ε-caprolactone in the presence of a known polyhydric alcohol. Among them, particularly preferred are polycaprolactone polyols obtained by ring-opening addition polymerization of ε-caprolactone to trimethylolpropane, and polycaprolactone polyols obtained by ring-opening addition polymerization of ε-caprolactone to pentaerythritol. These can be used alone or in admixture of two or more.

  The number of hydroxyl groups per molecule of the polyester polyol (B3) of the present invention is preferably 2 or more, more preferably 3 or more, from the viewpoint of achieving both scratch resistance, extensibility and chemical resistance. From the same viewpoint, the molecular weight is preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less.

  Examples of the polyester polyol (B3) include “Placcel 205, 205H, 205U, 205BA, 208, 210, 210CP, 210BA, 212, 212CP, 220, 220CPB, 220NP1, 220BA, 220ED, manufactured by Daicel Chemical Industries, Ltd. 220EB, 220EC, 230, 230CP, 240, 240CP, 210N, 220N, L205AL, L208AL, L212AL, L220AL, L230AL, 220ED, 220EB, 220EC, 205BA, 210BA, 220BA, 305, 308, 312, L312AL, 320, L320AL , L330AL, 410, 410D, 610, P3403, CDE9P, etc. are commercially available.

  When the polyol (B) of the present invention is a polyether polyol (B4), examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. These are produced by ring-opening polymerization of cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran.

  The number of hydroxyl groups per molecule of the polyether polyol (B4) of the present invention is preferably 2 or more, more preferably 3 or more, from the viewpoint of achieving both scratch resistance, elongation and chemical resistance. The molecular weight is preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less from the same viewpoint.

  As the polyether polyol (B4), “P-400, P-700, P-1000, P-2000, P-3000, G-300, G-400, G-700, G manufactured by Asahi Denka Kogyo Co., Ltd. -1500, G-3000, G-4000, EDP-450, EDP-550, DG-500, DG-575, SP-600, SP-690SC-800, SC-1000, SC-1001, quadrol ", Nippon Oil & Fats Polyethylene glycol “PEG # 200, 400, 600, 1000, 1500, 2000, 4000, 6000” manufactured by Co., Ltd., Bisol “2EN-6, 4EN, 10EN, 2P, 2PN, 3PN” manufactured by Toho Chemical Industry Co., Ltd., “Poly-G 420P, 720PG, 1020P, 2020P, 3020P, 630PG, 10” manufactured by Asahi Glass Co., Ltd. 0PG, 1530PG, 2530PG, 3030PG, 4030PG, 5030PG, 210PG, 212PG, 448PG, 412PG, 439PG, 216PG, X-213, X-301, X-302, X-303, 400P, 415P, 419P, 423P, 443P, 427P, 441P, 442P, 610PG, 357SA, 465SA, 480SA, 530SA, X-71-531, X-71-532, 375S, 531S, RF-64, RF-66 ", Sanyo Chemical Industries, Ltd." PEG200 " , PEG300, PEG400, PEG600, PEG1000, PEG1500, PEG1540, PEG2000, PEG4000S, PEG4000N, PEG6000S, PEG6000P "," Sanix GP-200, G E-250, TP-700, TE-700, EP-400, HE-400, HE-560, HE-600, RA-530, RX-401, RX-300, RX-403, RX-500, HR- 460A "," Sanix Triol GP-250, GP-400, GP-600, GP-1000, TP-400 "," Sanix Polyol RP-410A, HR-450P, HS-209 "," Sanix Hexatriol "SP-750" etc. are available as a commercial item.

  Among the above, the polyol (B) of the present invention is particularly preferably a polyol (B1) having a main chain composed of a carbon-carbon bond such as polyacryl polyol or a polyester polyol (B3) such as polycaprolactone polyol.

  In the coating agent of the present invention, the blending amount of the resin (A) is preferably 20 to 75 parts by weight, more preferably relative to the total amount (100 parts by weight) of the resin (A) and the polyol (B). 30 to 70 parts by weight. Moreover, the blending amount of the polyol (B) is preferably 25 to 80 parts by weight, more preferably 30 to 70 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). . When the blending amount of the resin (A) exceeds 75 parts by weight, the effect of adding the polyol (B) is small, the scratch resistance and abrasion resistance of the coating layer after curing is reduced, stretchability and self-healing May decrease. When the content is less than 20 parts by weight, curing may not proceed, or chemical resistance, scratch resistance, and wear resistance may decrease.

  The catalyst (C) used in the coating agent of the present invention is not particularly limited as long as it is a catalyst that generates protons, anions, radicals, and the like upon irradiation with active energy rays such as ultraviolet rays. Cationic polymerization initiator, radical polymerization Although it may be a catalyst or an anionic polymerization catalyst, a cationic polymerization catalyst is preferred. The active energy rays are not particularly limited, such as ultraviolet rays and electron beams, but ultraviolet rays are preferably used from the viewpoint of reactivity and the like. Specific examples of the catalyst (C) differ depending on the combination with the resin (A) and the polyol (B), but examples of the photocationic polymerization initiator include diaryliodonium salts and triarylsulfonium salts. In addition, the catalyst (C) may be used in combination with different photocationic polymerization initiators, may be used in combination with a photocationic polymerization initiator and a photoradical polymerization initiator, and may generate protons by photocationic polymerization initiator and heat. A generated thermal cationic polymerization initiator may be used in combination. As the catalyst (C), an existing commercial product can be used. “CYRACURE UVI-6922, UVI-6976” manufactured by The DOW Chemical Company, “Adekatopmer SP-” manufactured by Asahi Denka Kogyo Co., Ltd. 150, SP-152, SP-170, SP-172 "," Shin-Aid SI-60L, SI-80L, SI-100L, SI-110L, SI-180L "manufactured by Sanshin Chemical Industry Co., Ltd., GE Toshiba Silicone ( "UV9380c" manufactured by Co., Ltd., "Rhodorsil 2074" manufactured by Rhodia Japan Co., Ltd., "IRGACURE250" manufactured by Ciba Specialty Chemicals Co., Ltd., and "Uvacure 1590" manufactured by Daicel-Cytec Co., Ltd. are available on the market.

  The blending amount of the catalyst (C) of the present invention in the coating agent is preferably 0.5 to 10 parts by weight, more preferably based on the total amount (100 parts by weight) of the resin (A) and the polyol (B). Is 1 to 8 parts by weight. When the content of the catalyst (C) is less than 0.5 parts by weight, the initiation efficiency of the polymerization reaction at the time of active energy ray irradiation is poor, resulting in local polymerization and unevenness, or decreased productivity If the content exceeds 10 parts by weight, the transparency may decrease. Moreover, it may be difficult to control the curing reaction, or the coating layer after curing may turn yellow.

  For the purpose of adjusting the reaction rate, a compound having a hydroxyl group (including a low molecular weight polyol having a number average molecular weight of less than 400) may be added to the coating agent of the present invention, if necessary. In that case, examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, and glycerin. As described above, the addition of a hydroxyl group can increase the curing reaction rate. However, when a large amount of the above compound is added, a chain transfer reaction is likely to occur, so that the degree of curing is lowered, and the wear resistance and scratch resistance of the coating layer after curing may be lowered. For this reason, a preferable addition amount is about 0.1 to 5 weight% with respect to the total amount (100 weight part) of resin (A) and a polyol (B).

  From the viewpoint of adjusting the refractive index of the coating layer after curing, a fluorine-containing alcohol, an aromatic ring, or an epoxy resin having a bromine and an aromatic ring may be added to the coating agent of the present invention. The refractive index can be adjusted to be low by adding a fluorine-containing alcohol, while the refractive index can be adjusted to be high by adding an epoxy resin having the aromatic ring or bromine and aromatic ring. These addition amounts can be appropriately changed according to the desired refractive index within a range not impairing the effects of the present invention, but 10 to 10 parts by weight relative to the total amount (100 parts by weight) of the resin (A) and the polyol (B). About 50% by weight is preferable. In addition, when the epoxy resin having an aromatic ring or bromine and an aromatic ring is used in combination with the other resin (A), the addition amount of the aromatic ring or the epoxy resin having a bromine and an aromatic ring is the aromatic ring or bromine and aromatic. What is necessary is just to satisfy | fill said relationship with respect to resin (A) other than the epoxy resin which has a ring, and the total amount (100 weight part) of a polyol (B).

  The fluorine-containing alcohol is preferably a linear or branched alcohol having 3 to 15 carbon atoms and 1 to 23 fluorine atoms. For example, 1H, 1H-trifluoroethanol, 1H, 1H-pentafluoropropanol 6- (perfluoroethyl) hexanol, 1H, 1H-heptafluorobutanol, 2- (perfluorobutyl) ethanol, 3- (perfluorobutyl) propanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy -2,3,3,3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 2- (perfluorooctyl) ethanol, 3 -(Perfluorooctyl) propano 6- (perfluorooctyl) hexanol, 2- (perfluorodecyl) ethanol, 1H, 1H-2,5-di (trifluoromethyl) -3,6-dioxaundecafluorononanol, 6- ( Perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl) ethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexadecafluorononanol, 2H-hexafluoro-2-propanol 1H, 1H, 3H-hexafluorobutanol, 2,2,3,3 4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8- Examples include octanediol and 2,2-bis (trifluoromethyl) propanol.

  As the epoxy resin having an aromatic ring or bromine and aromatic ring, it is possible to use an existing commercial product. For example, as a commercially available product, bisphenol A type epoxy resin may be Japan Epoxy Resin Co., Ltd. “Epicoat 828, 1001, 1004, 1009” manufactured by Dainippon Ink & Chemicals, Inc., “Epicron 850-S, 860, 1055”, and bisphenol F type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc. "830-S", bisphenol S type epoxy resin "Epiclon EXA1514" manufactured by Dainippon Ink & Chemicals, Ltd .; phenylglycidyl ether "Denacol EX-141" manufactured by Nagase ChemteX Corporation; Is "Epico" manufactured by Japan Epoxy Resin Co., Ltd. 152, 157S65, 1031S, 604 "and" Epicron N-665, HP-7200 "manufactured by Dainippon Ink & Chemicals, Inc .; Naphthalene type epoxy resins include" Epicron HP- "manufactured by Dainippon Ink & Chemicals, Inc. 4032, EXA-4701 ”;“ Epicoat YX4000 ”manufactured by Japan Epoxy Resin Co., Ltd. as the biphenol type epoxy resin;“ Epicoat 1256, 4250 ”manufactured by Japan Epoxy Resin Co., Ltd. as the phenoxy resin; Epoxy resin "Epicoat 5050, 5051", Dainippon Ink & Chemicals "Epicron 152,153", Nagase ChemteX "Denacol EX-147" (dibromophenylglycidyl ether), etc. Be mentioned .

  In the coating agent of the present invention, it is preferable to use a solvent such as an organic solvent for the purpose of adjusting coating properties and the like. The solvent varies depending on the types of the resin (A) and the polyol (B), and is not particularly limited. For example, methyl ethyl ketone, methyl isobutyl ketone, toluene, butyl acetate, methoxypropanol, methoxypropyl acetate, methobuta (3-methoxy Butanol), methoacetate (3-methoxybutyl acetate), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl Chromatography ether acetate, diethylene glycol such as monobutyl ether acetate is preferably used. As an addition amount of a solvent, 5-500 weight part is preferable with respect to the total amount (100 weight part) of resin (A) and a polyol (B). Moreover, when using a solvent, the drying conditions of the coating layer after application | coating are set according to a solvent, and it does not specifically limit, For example, it is preferable to carry out on the conditions for 1 to 30 minutes at 60-200 degreeC.

  In addition to the above, the coating agent of the present invention includes other resins, antifoaming agents, acid diffusion control agents, reactive diluents, photosensitizers, and dehydrating agents as long as the effects of the present invention are not impaired. Contains various additives such as surfactants, antistatic agents, leveling agents, silane coupling agents, wetting improvers, antioxidants, UV absorbers, plasticizers, lubricants, inorganic fine particles, and organic fine particles. Also good.

  The ratio of epoxy group to hydroxyl group (epoxy group / hydroxyl group) in the coating agent of the present invention is preferably 1.5 to 20, and more preferably 2 to 15. When there are more hydroxyl groups than the above range, the length of the polymer chain is shortened by cationic polymerization for forming a cured product, the degree of curing (polymerization degree) of the coating layer is lowered, and chemical resistance and coating film hardness are lowered. There is a case. In addition, due to the inhibition of curing by moisture, the curing rate (reaction rate) may decrease and productivity may decrease. Even in the case where the number of hydroxyl groups is small, the curing rate is lowered, and thus productivity may be lowered.

  The viscosity (25 ° C.) of the coating agent of the present invention is preferably 1 to 1000 mPa · s, more preferably 2 to 500 mPa · s, from the viewpoints of applicability and workability. The viscosity of the coating agent can be controlled by the resin (A), the composition of the polyol, the molecular weight, the number of hydroxyl groups, the amount of diluent, and the like.

  The coating agent of the present invention can form a coating layer excellent in transparency, oil resistance, chemical resistance, abrasion resistance, scratch resistance, self-repairability, and extensibility (vacuum formability) by active energy curing. . For this reason, the coating agent of this invention is preferably used for the protective layer formation which protects a to-be-coated article from a damage. The article to be coated is not particularly limited, and can be used for metal products such as automobiles, plastic products such as films and molded products, glass products such as optical materials, wood products such as furniture, and paper. Among them, coating agents for forming protective layers for optical materials such as color filters that require transparency, clear paints to be applied to the body of automobiles, topcoat agents for protecting the surface of plastic films, and coating agents for protecting plastic parts It is particularly preferably used as a coating agent used for thermoforming such as vacuum forming or in-mold forming by top-coating a plastic film.

  The coating method of the present invention can be applied by a known method, and varies depending on the object to be coated, and is not particularly limited. For example, spin coating, brush coating, spraying (spraying), dip coating , Blade coating method, roll coating method, ink jet printing, gravure printing, screen printing, flexographic printing, bar coating method, die coating method and the like. Above all, in the case of automotive applications, spraying methods such as air spray and airless spray, methods using rotary atomizing coating machines, electrostatic coating machines, etc .; when applying to plastic films, gravure printing, flexographic printing, etc. The printing method, dip coating method, blade coating method, roll coating method, bar coating method and the like are preferable. In applying the coating agent, an undercoat layer may be provided on the article to be coated from the viewpoint of adhesion or the like. Moreover, when the coating agent of this invention uses a solvent, it is preferable to dry on the said conditions after the said application | coating.

The coating agent curing method of the present invention is based on active energy ray irradiation from the viewpoints of workability, productivity, and a wide range of applicable objects. Visible light, infrared rays, ultraviolet rays, X-rays, α-rays, β-rays, γ-rays, electron beams and the like can be used as the active energy rays to be irradiated. Among these, ultraviolet rays are most preferably used from the viewpoint of industrial properties such as safety and reaction efficiency. Preferably 200~400nm wavelength of ultraviolet light used, as the preferred irradiation conditions, for example, illuminance 1~1000mW / cm ^2, an irradiation amount 0.1~10000mJ / cm ^2. As an active energy ray irradiation device, for example, a lamp light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp, a pulse such as an argon ion laser or a helium neon laser, or a continuous laser light source can be used. It is.

  Furthermore, it is preferable to perform a heat treatment in addition to the above-described curing treatment, since the curing is likely to proceed sufficiently. The heat treatment is preferably after the curing treatment, and the conditions vary depending on the type of substrate to which the coating agent is applied, but are preferably performed at a temperature of room temperature to 180 ° C. for about 10 minutes to 1 week, for example.

  Although the thickness of a coating layer changes with uses and is not specifically limited, For example, 3-100 micrometers is preferable, More preferably, it is 5-40 micrometers. Among these, 10 to 100 μm is preferable for automobile applications, and 3 to 50 μm is preferable for top coats for plastic films. If the coating layer is thinner than the above preferred range, the scratch resistance may be reduced, and if it is thick, it may be disadvantageous in terms of cost, and the design property may be reduced, or the coating layer itself may be easily peeled off. .

The coating layer of the present invention has excellent self-healing properties. The self-repairing property represents a characteristic that a scratch generated on the surface of the coating layer can disappear over time. Specifically, in an atmosphere of 23 ° C. and 50% RH, a 200 gf weight was placed on steel wool (# 0000) manufactured by Nippon Steel Wool Co., Ltd. (load area 20 cm ² ), and the coating surface (coating layer surface) was applied. The test can be carried out by reciprocating 20 times, and evaluation can be made by the change in haze value (decrease with time) of the coating film surface immediately after the test. It is preferable that the haze value after 2 hours is reduced with respect to the haze value immediately after abrasion, and more preferably 3% or more. Self-healing results from the occurrence of scratches in a reversible deformation (elastic deformation). The excellent self-repairing property is achieved by the fact that the resin forming the coating layer has an elastic deformation region up to a high stress, that is, excellent toughness (toughness).

  The coating layer of the present invention has excellent wear resistance. The abrasion resistance can be evaluated by, for example, a Taber type abrasion tester (based on JIS K 5400 8.9). The above-mentioned wear resistance of the coating layer of the present invention is 1500 rotations until the substrate surface is exposed under the conditions of wear wheel S-42 / CS-0, rotation speed 60 rpm, load 500 gf, coating layer thickness 5 μm. It is preferable that it is above, more preferably 1800 rotations or more. When the wear resistance is 1500 revolutions or less, the surface is likely to be damaged, and the surface protection may not be sufficient.

  The coating layer of the present invention has excellent scratch resistance. The scratch resistance can be evaluated by, for example, observing the degree of scratching immediately after the test in steel wool rubbing similar to the self-repairing property.

  Since the coating layer of the present invention has scratch resistance and self-healing properties, it is difficult to be scratched, and scratches once generated are easy to recover, so that scratches are hardly left on the surface overall. In the coating agent of the present invention, the resin (A) mainly contributes to improving the hardness, and the polyol (B) contributes to imparting toughness.

  The coating layer of the present invention has excellent oil resistance (including gasoline resistance). Oil resistance is evaluated by stain resistance (conforming to JIS K 5400 8.10). For example, regular gasoline is dropped on the coating surface, wiped after a certain period of time, and evaluated by observing the degree of contamination of the coating surface. Is possible.

  The coating layer of the present invention has excellent chemical resistance. Chemical resistance is evaluated by stain resistance (conforming to JIS K 5400 8.10). For example, 99% ethanol is dropped on the coating surface, wiped off after a certain period of time, and surface contamination is observed. Can be evaluated.

  The coating layer of the present invention has excellent vacuum formability. The vacuum formability can be replaced with the stretchability of the coating film corresponding to the target deep drawing. For example, when deep drawing is performed so as to be half of the original thickness, it corresponds to an elongation rate of 100%. Specifically, for example, a cured coating film is formed on a substrate to produce a strip-shaped test piece. Fix both ends of the test piece and heat with a far infrared heater. When the drawdown reaches the lower limit, slowly pull both ends of the test piece. It can be evaluated by the rate of elongation relative to the length of the original strip. The coating agent of the present invention copolymerizes a flexible polyol (B) component with a resin (A) that is a hard cured product, imparts flexibility to the copolymer (cured product), and the polyol is trifunctional or higher. If it exists, since the extensional viscosity of the cured product is increased, resulting in toughness, excellent vacuum formability is exhibited. If the vacuum formability is poor, problems such as cracking, peeling, cracking, and whitening may occur on the coating film when thermoforming or in-mold forming is performed.

  The light transmittance of the coating layer (manufactured by Shimadzu Corporation, spectrophotometer “UV-2450”, wavelength 400 nm, cured product (coating layer) thickness 5 μm, base material is polyethylene terephthalate film and thickness 100 μm) is 90T% or more is preferable. When the light transmittance is less than 90 T%, it may be difficult to use as an optical material or the design may be deteriorated.

  The coating layer preferably has good bending resistance. The bending resistance can be evaluated by, for example, the absence of cracks or peeling of the coating layer in a bending test (JIS K 5400). When it is inferior in bending resistance, when a coating layer is provided on a substrate that is easily deformed, such as a plastic film, the coating layer may be cracked or peeled off.

  The curing shrinkage of the coating layer is preferably smaller from the viewpoint of workability when the hard-coated substrate is further processed, and there is no deformation such as warpage or curl when a cured film is formed on the substrate. Those are preferred.

  The adhesion between the coating layer and the substrate is economically desirable without using a substrate that has been subjected to an easy adhesion treatment, and even polyethylene terephthalate that has not been subjected to an easy adhesion treatment is particularly preferred.

  A top coat film (hard coat film) is obtained by applying and curing a top coat agent comprising the coating agent of the present invention on at least one surface of a plastic film to form a top coat layer.

  The resin of the plastic film used for the top coat film varies depending on the application and is not particularly limited. For example, polyester resin such as polyethylene terephthalate, PBT, and PEN, polyolefin resin such as polyethylene and polypropylene, and norbornene-based cyclic polyolefin resin , Polystyrene resins such as polystyrene, ABS, styrene-butadiene copolymer, polyvinyl chloride, polyvinyl alcohol, fluorine resin, polycarbonate resin, acrylic resin, polyamide resin, aramid, polyphenylene sulfide resin, polyimide resin, cellulose triacetate (TAC) And cellulose acetate, polyetherimide, polyarylate, polyethersulfone and the like. Among these, polyethylene terephthalate, polycarbonate, cyclic polyolefin resin, and TAC are preferable. These plastic films can be produced by a method such as melt film formation or solution film formation, or a polyester film, polystyrene film, polyolefin film or the like sold in the market can be used.

  The plastic film used for the top coat film may be an unstretched sheet or a stretched and oriented film such as uniaxially stretched or biaxially stretched depending on the application. Moreover, a single layer film may be used and a laminated film by co-extrusion or bonding may be used. Moreover, according to a use, you may provide functional layers, such as an adhesion layer, an ultraviolet absorption layer, a printing layer, an antistatic layer, on the surface on the opposite side to the topcoat layer of this invention. The film thickness of the plastic film also varies depending on the application and is not particularly limited, but is generally preferably 10 μm to 2 mm, more preferably 25 to 200 μm.

  The top coat film may be thermoformed either alone or by laminating (bonding) other base materials such as a plastic film or sheet that can be thermoformed on the surface opposite to the coating layer. it can. Thermoforming is a method of forming after plasticizing by applying heat, and is not particularly limited. For example, hot plate pressure forming, vacuum forming, vacuum pressure forming, press forming drawing forming or in-mold forming may be used. Can be mentioned.

  The top coat film of the present invention has excellent scratch resistance. Therefore, protective films for daily necessities such as cosmetics, building interiors such as building materials, joinery and flooring, automobiles and parts of automobiles, electric products such as mobile phones and televisions, and electronic devices such as display parts of flat panel displays It is preferably used for window pasting film for crime prevention, packaging film and the like. Among these, liquid crystal displays, automobile parts, and flooring are particularly preferable.

  The haze of the top coat film is preferably 10% or less, more preferably 5% or less, from the viewpoint of keeping the scattered light transmittance low.

[Methods for measuring physical properties and methods for evaluating effects]
Below, the measuring method used by this application and the evaluation method of an effect are illustrated.

(1) Scratch resistance (steel wool resistance test)
The coating agent obtained in Examples and Comparative Examples was applied to an untreated polyethylene terephthalate film (“HMW” manufactured by Teijin DuPont Films Ltd., thickness 100 μm, haze value 2.2%) at a thickness of 5 μm, Using a UV irradiation device (trade name “ECS-301” manufactured by Eye Graphics Co., Ltd.), the coating film was irradiated with ultraviolet rays (integrated light amount 500 mJ / cm ² ), and the condition was 23 ° C. and 50% RH. The coating was cured by leaving for 2 days to prepare a test piece.
In an atmosphere of 23 ° C. and 50% RH, a weight of 200 gf (per 20 cm ² area) is placed on steel wool (# 0000) manufactured by Nippon Steel Wool Co., Ltd., and the coating (coating layer) surface of the test piece is reciprocated 20 times. The degree of scratching immediately after rubbing was visually observed. Those with no scratches were judged as having good scratch resistance (O), and those that could be confirmed as scratches were judged as poor (X).

(2) Self-healing property A test piece was prepared in the same manner as (1) above.
Under an atmosphere of 23 ° C. and 50% RH, a steel wool (# 0000) manufactured by Nippon Steel Wool Co., Ltd. was placed with a weight of 200 gf (per 20 cm ² area), and the coating surface was rubbed 20 times back and forth (after about 5 minutes). The haze value measured in [ _1] was defined as H1. Further haze value measured again after 2 hours was H _2.
The difference ΔH (ΔH = H ₂ −H ₁ ) between H ₂ and H ₁ is obtained. If the value of ΔH is less than 0, it is judged that there is self-healing (◯), and if it is 0 or more, self-healing is Not (x) judged.
In addition, in the above, haze value was measured based on JIS K 7361-1 using Nippon Denshoku Industries Co., Ltd. haze meter "NDH-300A".

(3) Oil resistance (gasoline resistance)
A test piece was prepared in the same manner as (1) above.
The oil resistance was evaluated according to the stain resistance (JIS K 5400 8.10). Specifically, regular gasoline was dropped on the coating surface, wiped off after 3 minutes, and dried at 80 ° C. for 5 minutes. The surface of the coated film after drying was observed. If the coating film was not contaminated, it was judged as good (◯), and if the coating film was found contaminated, it was judged as poor (x).

(4) Chemical resistance A test piece was prepared in the same manner as in (1) above.
The chemical resistance was evaluated according to the contamination resistance (JIS K 5400 8.10). Specifically, a 50% ethanol aqueous solution was prepared from distilled water and 99.5% ethanol, dropped onto the coating surface, wiped off after 3 minutes, and dried at 80 ° C. for 5 minutes. The surface of the coated film after drying was observed. If the coating film was not contaminated, it was judged as good (◯), and if the coating film was found contaminated, it was judged as poor (x).

(5) Extensibility (vacuum formability)
The top-coated polyethylene terephthalate film was bonded to an ABS sheet having a thickness of 200 μm in the same manner as in the above (1) to prepare a test piece having a width of 10 mm and a length of 150 mm.
A marked line was marked at a position of 25 mm toward the both ends from the center of the test piece (the distance between the initial marked lines was 50 mm). Fix both ends of the test piece, heat with a far infrared heater (130 ° C), and when the drawdown ("sag" due to its own weight during heating) reaches the lower limit, slowly peel off both ends of the test piece. Pull until cracked or whitened. The distance between the marked lines at that time was L (mm), and the value obtained by the formula of (L-50) / 50 × 100 was defined as the elongation percentage (%). When the elongation was 50% or more, extensibility was good (◯), and when it was less than 50%, extensibility was poor (x).

(6) Abrasion resistance (Taber abrasion test)
A test piece was prepared in the same manner as (1) above.
Abrasion resistance is measured according to JIS K 5400 8.9 using a Taber-type Ablaser (“Taber's ABRASION TESTER” manufactured by Yasuda Seiki Seisakusho Co., Ltd.) specified in JIS K 6902 2.9.1. did. The wear wheel was S-42 / CS-0, and the number of rotations until the base polyethylene terephthalate film began to be exposed was evaluated under the conditions of a rotation number of 60 rpm and a load of 500 gf. If the rotational speed was 1500 revolutions or more, it was judged that the abrasion resistance was good (◯), and if it was less than 1500 revolutions, it was judged that the abrasion resistance was poor (x).

(7) Adhesiveness Test pieces were produced in the same manner as (1) above.
The adhesion was measured by a cross-cut tape method according to JIS K 5400 8.5.2. Specifically, the coating film of the test piece was cut at intervals of 1 mm in length and breadth, and after a 100 square grid cut was made on the coating film, an adhesive tape was applied and peeled off. The state of adhesion of the coated film after peeling was observed with the naked eye, and the case where peeling was less than 10 squares out of 100 squares was judged as good adhesion (◯). The case where peeling was 10 squares or more was judged as poor adhesion (x).

(8) Warpage An A4 size test piece was produced in the same manner as in (1) above.
The test piece was placed on a flat table and allowed to stand at 23 ° C. and 50% RH for 24 hours. When the amount of lift (maximum value at the four corners) was less than 1.0 mm, it was judged as good (◯), and 1.0 mm or more was judged as bad (x).

(9) Transparency (light transmittance)
A test piece was prepared in the same manner as (1) above.
Using a spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), the light transmittance (T%) at a wavelength of 400 nm was measured. A light transmittance of 90 T% or more was judged as good transparency (◯), and less than 90 T% was judged as poor transparency (x).

Example 1 (referred to as a reference example)
As shown in Table 1, as the resin (A), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (trade name “manufactured by Daicel Chemical Industries, Ltd.”, which is an alicyclic epoxy resin. 60 parts by weight of Celoxide 2021P ”) as a polyol, 36.5 parts by weight of a hydroxyl-terminated epoxidized polybutadiene (manufactured by Daicel Chemical Industries, Ltd., trade name“ Epolide PB3600 ”) as a UV-sensitive catalyst, and triarylsulfonium hexa Fluorophosphate salt (manufactured by Daicel Cytec Co., Ltd., 3 parts by weight of trade name “Uvacure 1590”), BYK CHEMIE 0.5 parts by weight as leveling agent, 100 parts by weight of methyl ethyl ketone as solvent at a temperature of 60 parts by weight Stir and mix for 1 hour at ℃, active It was produced energy ray-curable coating agent.
As shown in Table 1, the cured product of the obtained coating agent had excellent transparency, adhesion, abrasion resistance, scratch resistance, self-repairability, oil resistance, chemical resistance, and extensibility. . Also, the warpage was small.

Example 2
As shown in Table 1, the active energy ray-curable coating was carried out in the same manner as in Example 1, except that hydroxyl-terminated hydrogenated polyisoprene (made by Idemitsu Kosan Co., Ltd., trade name “Epol”) was used as the polyol. An agent was prepared.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 3
As shown in Table 1, as a polyol, both terminal hydroxyl group type vinyl ether oligomer (manufactured by Kyowa Hakko Chemical Co., Ltd., trade name “TOE-2000H”: HO (CH ₂ ) ₂ (CH (OC ₂ H ₅ ) CH ₂ ) _n An active energy ray-curable coating agent was prepared in the same manner as in Example 1 except that (CH ₂ OH) was used.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 4
As shown in Table 1, a polyacryl polyol (produced by Daicel Chemical Industries, trade name “Cell Top D446”) containing a lactone-modified (meth) acrylic monomer as a monomer component is used as a polyol, and the addition amount of each component is changed. In the same manner as in Example 1, an active energy ray-curable coating agent was produced.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 5
As shown in Table 1, as the polyol, a polyacryl polyol containing a lactone-modified (meth) acryl monomer as a monomer component (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel EPA5860”) was used, and the amount of each component added was changed. In the same manner as in Example 1, an active energy ray-curable coating agent was produced.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 6
As shown in Table 1, as the polyol, a polyacryl polyol containing a lactone-modified (meth) acryl monomer as a monomer component (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel EPA5860”) was used, and the amount of each component added was changed. In the same manner as in Example 1, an active energy ray-curable coating agent was produced.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 7
As shown in Table 1, the active energy ray-curable coating was carried out in the same manner as in Example 1 except that a liquid polycarbonate polyol (trade name “Placcel CD220PL” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. An agent was prepared.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 8 (referred to as a reference example)
As shown in Table 1, the active energy ray curability was the same as in Example 1 except that a trifunctional polyester polyol (trade name “Placcel PCL305” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. A coating agent was prepared.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 9 (referred to as a reference example)
As shown in Table 1, the active energy ray curability was the same as in Example 1 except that a trifunctional polyester polyol (trade name “Placcel PCL308” manufactured by Daicel Chemical Industries, Ltd.) was used as the polyol. A coating agent was prepared.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 10 (referred to as a reference example)
As shown in Table 1, a trifunctional polyester polyol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel PCL308”) was used as the polyol, and the addition amount of each component was changed in the same manner as in Example 1. An active energy ray-curable coating agent was prepared.
As shown in Table 1, the obtained coating agent had excellent characteristics.

Example 11 (referred to as a reference example)
As shown in Table 2, as a polyol, a tetrafunctional polyester polyol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel PCL410D”) was used, and the addition amount of each component was changed, as in Example 1, An active energy ray-curable coating agent was prepared.
As shown in Table 2, the obtained coating agent had excellent characteristics.

Example 12 (referred to as a reference example)
As shown in Table 2, as the polyol, a hexafunctional polyester polyol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel PCL610”) was used, and the addition amount of each component was changed, as in Example 1, An active energy ray-curable coating agent was prepared.
As shown in Table 2, the obtained coating agent had excellent characteristics.

Example 13
As shown in Table 2, an active energy ray-curable coating agent was produced in the same manner as in Example 1 except that polyethylene glycol (trade name “PEG1000” manufactured by Sanyo Chemical Industries, Ltd.) was used as the polyol. did.
As shown in Table 2, the obtained coating agent had excellent characteristics.

Example 14 (referred to as a reference example)
As shown in Table 2, exactly the same as Example 9 except that half of the epoxy resin was replaced with oxetane resin (trade name “OXT-221” manufactured by Toagosei Co., Ltd.) as the resin (A). An active energy ray-curable coating agent was prepared.
As shown in Table 2, the obtained coating agent had excellent characteristics.

Example 15
As shown in Table 2, the resin (A) was exactly the same as Example 9 except that half of the epoxy resin was replaced with vinyl ether resin (manufactured by Maruzen Petrochemical Co., Ltd., trade name “diethylene glycol monovinyl ether DEGV”). Thus, an active energy ray-curable coating agent was produced.
As shown in Table 2, the obtained coating agent had excellent characteristics.

Comparative Example 1
As shown in Table 2, as the polyol, the molecular weight was 300, and a trifunctional polyester polyol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel PCL303”) was used in exactly the same manner as in Example 8, An active energy ray-curable coating agent was prepared.
As shown in Table 2, the cured product of the obtained coating agent was inferior in wear resistance, easily scratched, and inferior in extensibility.

Comparative Example 2
As shown in Table 2, the polyol had a molecular weight of 300, and a trifunctional polyester polyol (trade name “Placcel PCL303” manufactured by Daicel Chemical Industries, Ltd.) was used in exactly the same manner as in Example 10, A coating agent was prepared.
As shown in Table 2, the obtained coating agent was slowly cured, and a cured coating film could not be obtained under the above-mentioned curing conditions.

Comparative Example 3
As shown in Table 2, an active energy ray-curable coating agent was produced in the same manner as in Example 1 except that the polyol was not added and the addition amount of each component was changed.
As shown in Table 2, the obtained cured product of the coating agent was inferior in abrasion resistance, easily scratched, self-healing property was not seen, and the extensibility was inferior.

Comparative Example 4
As shown in Table 2, curing was carried out in the same manner as in Example 1 using a commercially available UV-curable specially modified urethane acrylate (manufactured by NATCO, trade name “UV self-healing clear”) having self-healing properties. The product was evaluated.
As shown in Table 2, the commercially available self-healing UV curable specially modified urethane acrylate has poor adhesion to the polyester terephthalate film as a base material, and has a quality in which warping of the film due to curing shrinkage is observed. It was.

Claims (22)

A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is a polyol (B1) having a main chain composed of a carbon-carbon bond,
The polyol (B1) having a main chain composed of carbon-carbon bonds is a polyolefin-based polyol,
The polyolefin-based polyol is a polyolefin-based polyol prepared by hydrogenating a polydiene-based polyol having hydroxyl groups at both ends of the molecular chain,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight.   2. The active energy ray-curable coating agent according to claim 1, wherein the polydiene-based polyol having hydroxyl groups at both ends of the molecular chain is polyisoprene having hydroxyl groups at both ends of the molecular chain. A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is a polyol (B1) having a main chain composed of a carbon-carbon bond,
The polyol (B1) having a main chain composed of carbon-carbon bonds is a vinyl ether oligomer having hydroxyl groups at both ends,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight. The active energy ray-curable coating agent according to claim 3, wherein the vinyl ether oligomer is an oligomer represented by the following chemical formula (I).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 1 to 50.) A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is a polyol (B1) having a main chain composed of a carbon-carbon bond,
The polyol (B1) having a main chain composed of carbon-carbon bonds is a (meth) acrylic copolymer having a hydroxyl group,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight.   6. The active energy ray curing according to claim 5, wherein the (meth) acrylic copolymer having a hydroxyl group is a (meth) acrylic copolymer having an ethylenically unsaturated monomer having a hydroxyl group as at least one monomer component. Coating agent.   The active energy ray-curable coating agent according to claim 5, wherein the (meth) acrylic copolymer having a hydroxyl group is a (meth) acrylic copolymer having a lactone-modified hydroxyl group. Claims wherein a lactone-modified hydroxyl (meth) acrylic copolymer is a hydroxyl group and at least one monomer component a lactone-modified (meth) acrylate obtained by adding lactone monomer (meth) acrylic copolymer Item 8. The active energy ray-curable coating agent according to Item 7. A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is the polycarbonate polyol (B2),
Polycarbonate polyol (B2) is another diol represented by 1,6-hexanediol and HO—R ² —OH (wherein R ² has 2 to 14 carbon atoms and is linear or branched) Any of these may contain 1 to 3 cyclic structures, which may further contain oxygen, nitrogen and sulfur atoms in the molecule) and a carbonate component, which is 1,6-hexane. The molar ratio of diol to other diol is 10: 1 to 1: 9, the number average molecular weight is 400 to 3000,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight. A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is the polyester polyol (B3),
The polyester polyol (B3) is a polycaprolactone polyol ,
The resin (A) includes an epoxy resin and a vinyl ether resin,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight. A coating agent comprising at least one resin (A) selected from an epoxy resin, an oxetane resin and a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst (C) as essential components. The polyol (B) is a polyether polyol (B4),
The polyether polyol (B4) is a ring- opening polymer of a cyclic ether,
The polyether polyol (B4) has a molecular weight of 400 to 3000,
The blending amount of the resin (A) is 20 to 70 parts by weight and the blending amount of the polyol (B) is 30 to 80 parts by weight with respect to the total amount (100 parts by weight) of the resin (A) and the polyol (B). The active energy ray-curable coating agent, wherein the compounding amount of the catalyst (C) is 0.5 to 10 parts by weight.   The active energy ray-curable coating agent according to claim 1, wherein the ratio of epoxy group to hydroxyl group (epoxy group / hydroxyl group) in the active energy ray-curable coating agent is 1.5-20. When a coating layer formed by applying a coating agent on a substrate (polyethylene terephthalate film having a thickness of 100 μm) and curing with an active energy ray was subjected to an abrasion test (load: 200 gf / 20 cm ² ) with steel wool (# 0000), The difference ΔH (ΔH = H ₂ −H ₁ ) between the haze value (haze value) H ₁ of the coating layer immediately after the test and the haze value H ₂ after 2 hours is less than 0. The active energy ray-curable coating agent according to -12.   When the coating agent is applied on a base material (polyethylene terephthalate film with a thickness of 100 μm) and cured with active energy rays, the coating layer is heated at 130 ° C. together with the base material and stretched immediately after the drawdown reaches the lower limit. The active energy ray-curable coating agent according to claim 1, which has an elongation of 50% or more.   A Taber abrasion test (JIS K 5400 8.9, wear wheel: S-42 / CS-0) of a coating layer formed by applying a coating agent on a substrate (polyethylene terephthalate film having a thickness of 100 μm) and curing with an active energy ray The number of rotations required for the substrate to be exposed at a rotation number of 60 rpm, a load of 500 gf, and a coating thickness of 5 μm is 1500 times or more.   The clear paint for motor vehicles consisting of the active energy ray hardening coating agent in any one of Claims 1-15.   The topcoat agent for plastic films which consists of an active energy ray hardening coating agent in any one of Claims 1-15.   A coating agent for protecting plastic parts comprising the active energy ray-curable coating agent according to any one of claims 1 to 15.   The active energy ray-curable coating agent according to any one of claims 1 to 15, which is used for a protective film of a color filter.   A resin obtained by curing the active energy ray-curable coating agent according to any one of claims 1 to 19, a clear paint for automobiles, a coating agent for protecting plastic parts or a topcoat agent for plastic film with an active energy ray. Cured product.   The topcoat film which has a topcoat layer formed by apply | coating the topcoat agent for plastic films of Claim 17 to at least one surface of a plastic film, and hardening | curing active energy ray.   The molded article which carried out the draw molding of the topcoat film of Claim 21, or the laminated body obtained by laminating | stacking this topcoat film on another base material by thermoforming.