CN114958053A - Active energy ray-curable resin composition, cured product, laminate, and curing method - Google Patents

Abstract

The present invention addresses the problem of providing an active energy ray-curable resin composition that can produce a cured product having a certain processability, viscosity, and scratch resistance, a cured product containing the composition, a laminate, and a curing method. The solution provided in the present invention is an active energy ray-curable resin composition comprising: a (meth) acrylic copolymer (A) which is a reaction product of a radical polymer (a1) which is a monomer component containing an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2), a polyfunctional (meth) acrylate (B), and a melamine resin (C).

Description

Active energy ray-curable resin composition, cured product, laminate, and curing method

Technical Field

The present invention relates to an active energy ray-curable resin composition, a cured product, a laminate, and a curing method.

Background

Various plastics have been used in various fields such as the main bodies of household electric appliances such as refrigerators, televisions, air conditioners, remote controllers thereof, housings and displays of information terminals such as mobile phones, smartphones, input boards, personal computers, automobile parts, and automobile interior materials. Plastics have advantages such as processability, transparency, lightweight property, and low cost, but have disadvantages such as softness and easy scratching compared to glass materials.

In order to improve these disadvantages, a hard coating agent is applied to the surface of the plastic material to improve the scratch resistance of the surface without impairing the advantages of the plastic material. As such a hard coating agent, silicone-based, acrylic-based, melamine-based resins, and the like can be used. Among these, from the viewpoint of curing time, raw material cost, and the like, active energy ray-curable resin compositions using acrylic resins curable by active energy rays such as ultraviolet rays have become the mainstream.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2004-

Disclosure of Invention

[ problems to be solved by the invention ]

In the case of using the active energy ray-curable resin composition, when the active energy ray-curable resin composition is applied before the molding of the plastic and is irradiated with an active energy ray to crosslink and cure the resin, the crosslinking density of the resin can be increased to improve the chemical resistance and the scratch resistance. On the other hand, the active energy ray-curable resin composition cross-cured in such a manner has poor processability. In order to cope with such a problem of processability, an active energy ray-curable resin composition is applied by coating or the like after the plastic is molded (patent document 1). However, the above method has problems that the number of coating steps is increased, uneven coating occurs on the curved surface portion of the processed product, and the yield is poor.

Therefore, a hard coating agent which can be applied before molding of a plastic or film and has coating film hardness such as processability and scratch resistance is required.

The present invention addresses the problem of providing an active energy ray-curable resin composition that can produce a cured product having a certain processability, viscosity, and scratch resistance, and a cured product and a laminate containing the composition.

[ means for solving problems ]

As a result of diligent research, the present inventors have found that the above problems can be solved by using a predetermined active energy ray-curable resin composition.

That is, the present invention relates to the following items 1 to 11.

(item 1)

An active energy ray-curable resin composition comprising: a (meth) acrylic copolymer (A) which is a reaction product of a radical polymer (a1) containing monomer components of an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2), a polyfunctional (meth) acrylate (B), and

a melamine resin (C).

(item 2)

The active energy ray-curable resin composition according to item 1, wherein

(A) The hydroxyl group concentration of the component (B) is 1.1 to 5mmol/g,

(A) component (B) has a (meth) acrylic acid equivalent of 150 to 1,000g/eq, and

(B) the component (A) has 3 or more and 30 or less (meth) acryloyl groups.

(item 3)

The active energy ray-curable resin composition according to item 1 or 2, wherein the mass ratio (in terms of solid content) of the component (A) to the component (B) is 10/90 to 99/1.

(item 4)

The active energy ray-curable resin composition according to any one of items 1 to 3, wherein the content (in terms of solid content) of the component (C) is 1% by mass or more and 25% by mass or less, relative to 100% by mass of the total amount of the components (A) and (B).

(item 5)

The active energy ray-curable resin composition according to any one of items 1 to 4, which contains a photopolymerization initiator (D).

(item 6)

The active energy ray-curable resin composition according to any one of items 1 to 5, which contains a fluorine-containing compound (E).

(item 7)

The active energy ray-curable resin composition according to any one of items 1 to 6, which contains the inorganic fine particles (F).

(item 8)

A partially cured product obtained by heating the active energy ray curable resin composition according to any one of items 1 to 7, and having an elongation at break of 40% or more.

(item 9)

A cured product of the active energy ray-curable resin composition according to any one of items 1 to 7.

(item 10)

A laminate having the partially cured product according to item 8 or the cured product according to item 9 on at least one surface of a substrate surface.

(item 11)

A method wherein after the active energy ray-curable resin composition according to any one of items 1 to 7 is heated to be partially cured, an active energy ray is irradiated to be further cured.

[ Effect of the invention ]

The active energy ray-curable resin composition, and the cured product and laminate containing the same of the present invention have a certain processability, tackiness, and scratch resistance.

Detailed Description

In the present invention, the ranges of the numerical values such as the physical property values and the contents may be appropriately set (for example, selected from the upper and lower limits described in the following items). Specifically, as for the numerical value α, when the lower limit of the numerical value α is exemplified by a1, a2, A3, and the like, and the upper limit of the numerical value α is exemplified by B1, B2, B3, and the like, the range of the numerical value α can be exemplified by a1 or more, a2 or more, A3 or more, B1 or less, B2 or less, B3 or less, a1 to B1, a1 to B2, a1 to B3, a2 to B1, a2 to B2, a2 to B3, A3 to B1, A3 to B2, A3 to B3, and the like. In the present invention, "to" is used to include numerical values described before and after the "to" as the lower limit value and the upper limit value.

The present invention relates to an active energy ray-curable resin composition (hereinafter also referred to as "resin composition") comprising: a (meth) acrylic copolymer (a) (hereinafter also referred to as "component a"), a polyfunctional (meth) acrylate (B) (hereinafter also referred to as "component B"), and a melamine resin (C) (hereinafter also referred to as "component C"), which is a reaction product of a radical polymer (a1) (hereinafter also referred to as "component a 1") containing a monomer component of an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2) (hereinafter also referred to as "component a 2"). Furthermore, (meth) acrylate refers to acrylate and/or methacrylate. Further, (meth) acrylic acid means acrylic acid and/or methacrylic acid.

< component (A) >

(A) Component (a) is a (meth) acrylic copolymer which is a reaction product of component (a1) and component (a 2). The copolymer (a) may be a copolymer of two or more kinds.

< (a1) component

(a1) The component (A) is a radical polymer of a monomer component containing an epoxy group-containing mono (meth) acrylate. As the epoxy group-containing mono (meth) acrylate (hereinafter, also referred to as "component a 1-1"), various known ones can be used.

Examples of the component (a1-1) include glycidyl (meth) acrylate, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and [ (3, 4-epoxycyclohexane) -1-yl ] methyl (meth) acrylate. The substances exemplified as the component (a1-1) and the substances known as the component (a1-1) may be used alone or in combination of two or more. The component (a1-1) is preferably glycidyl (meth) acrylate in terms of ease of obtaining and scratch resistance.

(a1) The constituent monomer of component (A) may contain a copolymerizable monomer having no epoxy group (hereinafter also referred to as "component (a 1-2)") in addition to component (a 1-1). As the component (a1-2), various known substances can be used.

Examples of the component (a1-2) include: aromatic mono (meth) acrylates such as styrene, α -methylstyrene, t-butylstyrene and dimethylstyrene; aliphatic unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, alkenylsuccinic anhydride and dienylsuccinic anhydride; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate; acrylonitrile, acrylamide, vinyl acetate, a macromonomer having one or more unsaturated double bonds at any one end and containing no epoxy group or carboxyl group, and the like. Examples of the macromonomer having one or more unsaturated double bonds at any one end and containing no epoxy group or carboxyl group include a (meth) acryloyl group-containing macromonomer, polysiloxane macromonomer, (meth) acrylate macromonomer, styrene macromonomer, (meth) acrylamide macromonomer, and acrylonitrile macromonomer. The substances exemplified as the component (a1-2) and the substances known as the component (a1-2) may be used alone or in combination of two or more. As the macromonomer, a commercially available product can also be used. The product is not particularly limited, and examples thereof include (meth) acryloyl group-containing macromonomers (product names "Macromonomer (Macromonomer) AA-6", "Macromonomer (Macromonomer) AB-6", manufactured by tokyo synthesis (stock)), polysiloxane macromonomers (product names "selaplane FM-0711", "selaplane FM-0721", manufactured by Jenzhi (JNC) (stock)), and (meth) acrylate macromonomers (product names "blanmomer PME-4000", "blanmomer PSE-1300", manufactured by solar oil (stock)), and the like.

< (a2) component

(a2) The component (B) is an alpha, beta-unsaturated carboxylic acid. In the present invention, the α, β -unsaturated carboxylic acid means a substance having an unsaturated bond between a carbon (α carbon) located beside a carboxyl group and a further adjacent carbon (β carbon).

The component (a2) is not particularly limited, and various known substances can be used. Examples of the component (a2) include α, β -unsaturated monocarboxylic acids, α, β -unsaturated dicarboxylic acids, and the like. Examples of the α, β -unsaturated monocarboxylic acid include (meth) acrylic acid. Examples of the α, β -unsaturated dicarboxylic acid include itaconic acid and maleic acid. The substances exemplified as the component (a2) and the substances known as the component (a2) may be used alone or in combination of two or more. The component (a2) is preferably an α, β -unsaturated monocarboxylic acid, and more preferably (meth) acrylic acid, from the viewpoint of satisfactory scratch resistance of a coating film (hereinafter also referred to as "cured product") obtained by completely curing the resin composition.

(a1) The upper limit of the mass ratio of the component (a2) to the component (a1)/(a2) (in terms of solid content), (a1)/(a2)) may be 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, etc., and the lower limit thereof may be 95/5, 90/10, 85/15, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, etc. In one embodiment, the mass ratio of the component (a1) to the component (a2) (in terms of solid content, (a1)/(a2)) is preferably about 10/90 to 99/1.

(A) Examples of the upper limit of the hydroxyl group concentration of the component (B) include 5mMol/g, 4.9mMol/g, 4.8mMol/g, 4.7mMol/g, 4.6mMol/g, 4.5mMol/g, 4.4mMol/g, 4.3mMol/g, 4.2mMol/g, 4.1mMol/g, 4mMol/g, 3.9mMol/g, 3.8mMol/g, 3.7mMol/g, 3.6mMol/g, 3.5mMol/g, 3.4mMol/g, 3.3mMol/g, 3.2mMol/g, 3.1mMol/g, 3mMol/g, 2.9mMol/g, 2.8mMol/g, 2.7mMol/g, 2.6mMol/g, 2.5mMol/g, 2.4mMol/g, 2.3mMol/g, 2.2mMol/g, 2.1mMol/g, 2.5mMol/g, 4mMol/g, 4.3mMol/g, 4mMol/g, 4.9mMol/g, 2.1mMol/g, 4mMol/g, 4.9mMol/g, 4mMol/g, 4.7mmol/g, 4.6mmol/g, 4.5mmol/g, 4.4mmol/g, 4.3mmol/g, 4.2mmol/g, 4.1mmol/g, 4mmol/g, 3.9mmol/g, 3.8mmol/g, 3.7mmol/g, 3.6mmol/g, 3.5mmol/g, 3.4mmol/g, 3.3mmol/g, 3.2mmol/g, 3.1mmol/g, 3mmol/g, 2.9mmol/g, 2.8mmol/g, 2.7mmol/g, 2.6mmol/g, 2.5mmol/g, 2.4mmol/g, 2.3mmol/g, 2.2.2 mmol/g, 2.1mmol/g, 2mmol/g, 1.5mmol/g, 1.1mmol/g, etc. In one embodiment, the hydroxyl group concentration of the component (A) is preferably about 1.1 to 5 mmol/g. When the hydroxyl group concentration of the component (a) is not less than the lower limit, the scratch resistance of the cured product is favorable, and therefore, it is preferable. In the present invention, the hydroxyl group concentration indicates the amount of substance of the hydroxyl group contained in one or more components 1g for which calculation of the hydroxyl group concentration is desired.

(A) Examples of the upper limit of the (meth) acrylic acid equivalent of the component (A) may include 1,000g/eq, 900g/eq, 800g/eq, 700g/eq, 600g/eq, 500g/eq, 400g/eq, 390g/eq, 380g/eq, 370g/eq, 360g/eq, 350g/eq, 340g/eq, 330g/eq, 320g/eq, 310g/eq, 300g/eq, 290g/eq, 280g/eq, 270g/eq, 260g/eq, 250g/eq, 240g/eq, 230g/eq, 220g/eq, 210g/eq, 200g/eq, 190g/eq, 180g/eq, 170g/eq, 160g/eq, etc., and examples may include the lower limit of the (meth) acrylic acid equivalent of the component (A), 900g/eq, 800g/eq, etc, 700g/eq, 600g/eq, 500g/eq, 400g/eq, 390g/eq, 380g/eq, 370g/eq, 360g/eq, 350g/eq, 340g/eq, 330g/eq, 320g/eq, 310g/eq, 300g/eq, 290g/eq, 280g/eq, 270g/eq, 260g/eq, 250g/eq, 240g/eq, 230g/eq, 220g/eq, 210g/eq, 200g/eq, 190g/eq, 180g/eq, 170g/eq, 160g/eq, 150g/eq, etc. In one embodiment, the equivalent weight of (meth) acrylic acid in the component (A) is preferably about 150g/eq to 1,000 g/eq. When the (meth) acrylic acid equivalent of the component (a) is not more than the upper limit, the scratch resistance of the cured product is good, and therefore, it is preferable. In the present invention, the (meth) acrylic acid equivalent is represented by the solid mass g of the (A) component per (meth) acrylic acid group.

The upper limit of the content of the component (a) having a hydroxyl group concentration outside the above-mentioned numerical range and a (meth) acrylic acid equivalent outside the above-mentioned numerical range may be, for example, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 1 mass%, or the like, with respect to 100 mass% of the total amount of the component (a), and the lower limit may be, for example, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 1 mass%, 0 mass%, or the like. The content of the component (a) having a hydroxyl group concentration outside the above numerical range and a (meth) acrylic acid equivalent outside the above numerical range is not more than the above numerical value with respect to 100% by mass of the total amount of the component (a), and therefore is particularly preferable in terms of excellent scratch resistance.

(A) The upper limit of the weight average molecular weight of the component (a) may be 200,000, 150,000, 100,000, 50,000, 30,000, 10,000, etc., and the lower limit may be 150,000, 100,000, 50,000, 30,000, 10,000, 5,000, etc. In one embodiment, the weight average molecular weight of the component (a) is preferably 5,000 or more and 200,000 or less. When the weight average molecular weight of the component (A) is within the above range, the cured product has excellent blocking resistance, and the resin composition has a preferred viscosity. In the present invention, the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography.

The upper limit of the content (in terms of solid content) of the component (a) may be 99 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass% or the like, and the lower limit may be 95 mass%, 90 mass%, 85 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (a) is preferably about 10% by mass to 99% by mass relative to 100% by mass of the total amount of the resin composition.

Synthesis method of component (A)

The method for synthesizing the component (a) is not particularly limited, and various known methods can be used. Examples of the method for synthesizing component (A) include a method in which component (a1) and component (a2) are reacted at 50 ℃ to 200 ℃ for 30 minutes to 12 hours.

< ingredient (B) >

(B) The component (A) is other than the component (A), and is a polyfunctional (meth) acrylate.

Examples of the component (B) include a polyfunctional (meth) acrylate having two (meth) acryloyl groups, a polyfunctional (meth) acrylate having three (meth) acryloyl groups, a polyfunctional (meth) acrylate having four (meth) acryloyl groups, a polyfunctional (meth) acrylate having five (meth) acryloyl groups, and a polyfunctional (meth) acrylate having six (meth) acryloyl groups. Examples of the polyfunctional (meth) acrylate having two (meth) acryloyl groups include dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and hexanediol di (meth) acrylate. Examples of the polyfunctional (meth) acrylate having three (meth) acryloyl groups include glycerol tri (meth) acrylate, sorbitol tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate, Propylene Oxide (PO) -modified trimethylolpropane tri (meth) acrylate, EO-modified phosphoric acid tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and ethoxylated isocyanuric acid tri (meth) acrylate. Examples of the polyfunctional (meth) acrylate having four (meth) acryloyl groups include 1, 2, 3-cyclohexane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and sorbitol tetra (meth) acrylate. Examples of the polyfunctional (meth) acrylate having five (meth) acryloyl groups include sorbitol penta (meth) acrylate, di-trimethylolpropane penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Examples of the polyfunctional (meth) acrylate having six (meth) acryloyl groups include ditrimethylolpropane hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Examples of the other component (B) include polyurethane (meth) acrylate, polyester (meth) acrylate, and epoxy poly (meth) acrylate.

As a method for synthesizing the polyurethane (meth) acrylate, various known methods can be exemplified. Examples of known methods for synthesizing the polyurethane (meth) acrylate include:

(1) a method in which a hydroxyl group-containing (meth) acrylate is further subjected to a urethanization reaction with an isocyanate group-terminated prepolymer obtained by urethanizing a polyol and a polyisocyanate;

(2) a method of reacting an isocyanate group-containing (meth) acrylate with a hydroxyl-terminated prepolymer obtained by urethanizing a polyol and a polyisocyanate;

(3) a method of reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate;

(4) a method of reacting a polyol with an isocyanate group-containing (meth) acrylate;

(5) a method of reacting a hydroxyl group-containing (meth) acrylate with an isocyanate group-containing (meth) acrylate, and the like.

In these methods, various known catalysts (e.g., dibutyltin dilaurate) can be suitably used as needed.

Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, neopentyl glycol, 3-methyl-1, 5-pentanediol, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol, bis- [ hydroxymethyl ] -cyclohexane, and the like. The polyhydric alcohol exemplified above and the polyhydric alcohol known per se can be used alone or in combination of two or more.

Examples of the polyether polyol include polyalkylene glycol (such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol). As the polyether polyol, commercially available products can also be used. Examples of the product include products such as "adi Polyether (ADEKA Polyether) P series", "adi Polyether (ADEKA Polyether) G series", "adi Polyether (ADEKA Polyether) EDP series" (manufactured by adi (ADEKA) (stock)), and the like.

Examples of the polyester polyol include those obtained by the reaction of a polyol with a polycarboxylic acid (succinic acid, phthalic acid, malonic acid, maleic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc.), ring-opened polymers of cyclic esters (propiolactone, β -methyl- δ -valerolactone, e-caprolactone, etc.), and three-component reaction products of a polyol with a polycarboxylic acid and a cyclic ester. As the polyester polyol, a commercially available product can be used. Examples of the product include the product names "Colorado Polyol (Kuraray Polyol) P series", "Colorado Polyol (Kuraray Polyol) F series" (manufactured by Colorado (Kuraray) (Co., Ltd.), the product name "Placcel (Placcel) 205" (manufactured by Daicel (Daicel) (Co., Ltd.), and the product name "Polilet (Polylite) OD-X-2155" (manufactured by Di Egyo (DIC) (Co., Ltd.).

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene (phosgene), a ring-opened polymer of a cyclic carbonate (e.g., alkylene carbonate), and the like. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. As the polycarbonate polyol, a commercially available product can be used. The product may be named "kola Polyol (Kuraray Polyol) C series" (manufactured by kola corporation), and the like.

Examples of the acrylic polyol include homopolymers or copolymers of acrylic monomers having one or more hydroxyl groups in one molecule, and copolymers obtained by copolymerizing these copolymers with other monomers. As the acrylic polyol, a commercially available product can be used. The product may be named "Yajiaofeng UH-2000 series" (manufactured by east Asia corporation), for example.

Examples of the polyolefin polyol include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof having two or more hydroxyl groups. As the polyolefin polyol, commercially available products can also be used. Examples of the product include "Nissan (NISSO) -PB GI series" (manufactured by Nissan Co., Ltd.).

Examples of the polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 3-methyldiphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclopentyl isocyanate. Examples of the other polyisocyanate include the above-mentioned exemplified polyisocyanates, adducts of various known polyisocyanates, and polymers of these isocyanates. Examples of such polyisocyanates include biuret, urethanate, adduct, allophanate (allophanate), and the like. Examples of biurets as polyisocyanates include those known by the trade names "Duranate (Duranate) 24A-100", "Biuret (Biuret) 22A-75P" and "Biuret (Biuret) 21S-75E" (all manufactured by Asahi chemical Co., Ltd.). Examples of the uric acid ester of polyisocyanate include those having the trade names "crotonate HK" and "crotonate HXR" (all manufactured by tokoa (stock)). Examples of the adduct of polyisocyanate include "crotonate HL" (manufactured by tokyo (r) ") and the like. Examples of the allophanate of the polyisocyanate include "crotonate" 2770 "(manufactured by Tosoh corporation). The polyisocyanate of the present invention may have an average number of isocyanate groups of 3 to 10. The average number of isocyanate groups can be calculated by the following formula. Average isocyanate group number ═ (number average molecular weight (Mn) × isocyanate group concentration (%)/(42.02 × 100). The isocyanate group concentration (%) in the formula (I) is determined by the following method in accordance with Japanese Industrial Standards (JIS) K1603-1: a value measured by the method described in 2007. The polyisocyanate exemplified above and the polyisocyanate known per se can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate include: 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, methyl 4- (hydroxymethyl) cyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, hydroxyphenyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. The hydroxyl group-containing (meth) acrylate exemplified above and the hydroxyl group-containing (meth) acrylate known per se may be used alone or in combination of two or more.

Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1, 1- (bisacryloxymethyl) ethyl isocyanate. The isocyanate group-containing (meth) acrylate exemplified above and the isocyanate group-containing (meth) acrylate known in the art may be used alone or in combination of two or more.

Various known methods can be exemplified as a method for synthesizing the polyester (meth) acrylate. Examples of the various known synthetic methods for polyester (meth) acrylate include:

(1) a method of reacting a carboxyl group-containing (meth) acrylate (carboxyethyl (meth) acrylate, carboxypolycaprolactone mono (meth) acrylate, etc.) with a hydroxyl group-terminated polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol;

(2) a method of reacting a carboxyl-terminated polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol with a hydroxyl-containing (meth) acrylate.

In these methods, various known catalysts can be suitably used as needed.

Examples of the epoxy poly (meth) acrylate include those obtained by addition reaction of a carboxyl group-containing (meth) acrylate and an epoxy resin having at least two epoxy groups in one molecule (such as a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol type epoxy resin).

In these methods, various known catalysts can be suitably used as needed.

(B) Commercially available products can be used as the components. As the product, there can be exemplified: pentaerythritol triacrylate ((product name "a-TMM-3", "a-TMM-3L", manufactured by maizhou chemical industry (stock)), (product name "Miramer) M301", manufactured by Meiyuan (MIWON) corporation), (product name "arinexus (Aronix) M-309", manufactured by east asian synthesis (stock)), di-trimethylolpropane tetraacrylate (product name "arinexus (Aronix) M-408", manufactured by east asian synthesis (stock)), ethoxylated pentaerythritol tetra (meth) acrylate (product name "SR 494", manufactured by Sartomer), dipentaerythritol penta (meth) acrylate (product name "SR 399", manufactured by Sartomer), a mixture of dipentaerythritol poly (meth) acrylate (dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate) ((product name "yakara (ka) DPHA", manufactured by Nippon chemical industries, manufactured by, Urethane (meth) acrylates ((product names "UV 1700B", "UV 7620 EA", "UV 7610B", "UV 7600B", "UV 7650B", manufactured by Mitsubishi Chemical Co., Ltd.), "DPHA 40H", "UX 5003", manufactured by Nippon Chemical Co., Ltd.), "BiAMSET (BEAMSET) 577", manufactured by Mitsuwa Chemical Co., Ltd.), "8 UX-015A", manufactured by Mitsubishi Chemical Co., Ltd.), "U15 HA", manufactured by Newzhongmura Chemical Co., Ltd.), "Milamor Miramer PU 610", manufactured by Miwon Specialty Chemical Co., Ltd., "Etercure (Etercure)6196 + 100", manufactured by Long Materials (Eternal Materials Co., Ltd.), and the like).

The substances exemplified as the component (B) and the substances known as the component (B) may be used alone or in combination of two or more.

(B) Examples of the upper limit of the number of (meth) acryloyl groups in the component (a) may include 30, 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, 3, etc., and examples of the lower limit thereof may include 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, 3, 2, etc. In one embodiment, the number of (meth) acryloyl groups contained in component (B) is preferably about 2 to 30, and more preferably 3 to 30. When the number of (meth) acryloyl groups in the component (B) is in the above range, the viscosity of the partially cured product, the scratch resistance of the cured product, and the pencil hardness tend to be excellent.

(B) Examples of the upper limit of the molecular weight of the component (a) include 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250 and the like, and examples of the lower limit thereof include 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, 100 and the like. In one embodiment, the molecular weight of the component (B) is preferably about 100 to 50,000. In the present invention, the term "molecular weight" refers to a numerical value calculated on an atomic weight basis.

(A) Examples of the upper limit of the mass ratio of the component (B) to the component (B) (converted as a solid component, (a)/(B)) include 99/1, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 60/40, 50/50, 40/60, 30/70, 25/75, 20/80, 15/85 and the like, and examples of the lower limit thereof include 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 60/40, 50/50, 40/60, 30/70, 25/75, 20/80, 15/85, 10/90 and the like. In one embodiment, the mass ratio of the component (A) to the component (B) (in terms of solid content, (A)/(B)) is preferably about 10/90 to 99/1.

The upper limit of the content (in terms of solid content) of the component (B) may be, for example, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 3 mass%, etc., with respect to 100 mass% of the total amount of the resin composition, and the lower limit may be, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 3 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (B) is preferably about 1 to 90% by mass based on 100% by mass of the total amount of the resin composition.

The upper limit of the total content (in terms of solid content) of the component (a) and the component (B) may be 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass% or the like, and the lower limit may be 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the total content (in terms of solid content) of the component (a) and the component (B) is preferably about 50 to 99% by mass based on 100% by mass of the total amount of the resin composition.

Production method of mixture of component (A) and component (B)

(A) The mixture of the component (a) and the component (B) is usually obtained by mixing the component (a) and the component (B) at normal temperature.

< ingredient (C) >

(C) The component is melamine resin. The melamine resin is not particularly limited, and various known melamine resins can be used. Examples of the resin include resins containing a structural unit derived from a compound represented by the following general formula (1).

General formula (1):

[ solution 1]

(in the general formula (1), R ¹ ～R ⁶ May be the same or different from each other, and each represents a hydrogen atom or a hydroxymethyl group (-CH) ₂ OH), methoxymethyl (-CH) ₂ OCH ₃ ) Ethoxymethyl (-CH) ₂ OCH ₂ CH ₃ ) N-butoxymethyl (-CH) ₂ OCH ₂ CH ₂ CH ₂ CH ₃ ) And isobutoxymethyl (-CH) ₂ OCH(CH ₃ )CH ₂ CH ₃ ) The material in)

(C) Commercially available products can be used as the components. As the product, there can be exemplified: the manufactured products have the names "Saimel (Cymel) 300", "Saimel (Cymel) 301", "Saimel (Cymel)303 LF", "Saimel (Cymel) 350", "Saimel (Cymel) 370N", "Saimel (Cymel) 771", "Saimel (Cymel) 325", "Saimel (Cymel) 327", "Saimel (Cymel) 703", "Saimel (Cymel) 712", "Saimel (Cymel) 701", "Saimel (Cymel) 266", "Saimel (Cymel) 267", "Saimel (Cymel) 285", "Saimel (Cymel) 232", "Saimel (Cymel) 235", "Saimel (Cymel) 236", "Saimel (Cymel) 238", "Saimel (Cymel) 272", "Saimel (Cymel) 232", "Saimel (Cymel) 235", "Mimex" (Mikan) 202 "," MW Hazel) 202 "," Mikan Mei (Cymel)202 "," Mikani (Cymel)253 "," Saimel (Cymel)202 "," Mikan Mei (Cymel)202 "," Mikan Mei (Cyel) 202 "," Saimel (Cymel)202 "," Saimel (Mikan Mei (Cyle) 202 "," Saimel (Cyanel) 202 "," Saimel (Cyanel) and Mikanai (Cyanel) 202 "," Saimel) and Mikanel) 500 "" Saimel (Cyanel) 500 "" Saimel) and Mikanai Mei Mikanai (Cyanel) 202 "" Saimel) products "Nikalac" (Nikalac) MW-390 "," Nikalac (Nikalac) MW-100LM "," Nikalac (Nikalac) MX-750LM "," Nikalac (Nikalac) MW-22 "," Nikalac (Nikalac) MS-21 "," Nikalac (Nikalac) MS-11 "," Nikalac (Nikalac) MW-24X "," Nikalac (Nikalac) MS-001 "," Nikalac (Nikalac) MX-002 "," Nikalac (Nikalac) MX-730 "," Nikalac (Nikalac) MX-750 "," Nikalac (Nikalac) MX-708-Nikalac (Nikalac) MX-706 "," Nikalac (Nikalac) MX-042 "," Nikalac (Nikalac) MX-708 "," Nikalac (Nikalac) MX-417 "," Nikalac (Nikalac) MX-410 ", and the like.

The substances exemplified as component (C) and the substances known as component (C) may be used alone or in combination of two or more.

(C) The component (C) is preferably a fully ether-type methylated melamine resin because of its excellent curability at low temperature in a short time.Further, in the present invention, the "full ether type methylated melamine resin" means R of the methylated melamine represented by the above formula ¹ ～R ⁶ All are methoxymethyl (-CH) ₂ OCH ₃ ) The melamine resin of (1). Examples of the fully ether-type methylated melamine resin include 2, 4, 6-tris [ bis (methoxymethyl) amino group]Examples of the products include 1, 3, 5-triazine, and semel (Cymel)303LF and nicaraga (Nikalac) MW-30M.

The upper limit of the content (in terms of solid content) of the component (C) may be 25 mass%, 20 mass%, 15 mass%, 10 mass%, 8 mass%, 5 mass%, 3 mass%, etc., with respect to 100 mass% of the total amount of the components (a) and (B), and the lower limit may be 20 mass%, 15 mass%, 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (C) is preferably about 1 to 25% by mass relative to 100% by mass of the total amount of the components (a) and (B). The content (in terms of solid content) of the component (C) is not more than the upper limit with respect to 100 mass% of the total amount of the components (a) and (B), and is particularly preferable in view of excellent processability.

The upper limit of the content (in terms of solid content) of the component (C) may be, for example, 25 mass%, 20 mass%, 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, etc. with respect to 100 mass% of the total amount of the resin composition, and the lower limit may be, for example, 20 mass%, 15 mass%, 14 mass%, 13 mass%, 12 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (C) is preferably about 1 to 25% by mass relative to 100% by mass of the total amount of the resin composition.

< ingredient (D) >

The resin composition may further contain a photopolymerization initiator (D) (hereinafter also referred to as "component (D)"). By containing the component (D) in the resin composition, the resin composition has excellent curing performance (hereinafter, also referred to as "curability").

The component (D) is not particularly limited, and various known substances can be used. Examples of the component (D) include a radical photopolymerization initiator, a cationic photopolymerization initiator, and an anionic photopolymerization initiator.

Examples of the radical photopolymerization initiator include a phenylalkyl ketone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator, and an oxime ester type photopolymerization initiator.

Examples of the phenylalkyl ketone type photopolymerization initiator include benzyl dimethyl ketal such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one; α -hydroxybenzylalkyl ketones such as 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and 1-hydroxy-cyclohexyl-phenyl-ketone; and α -aminophenylalkyl ketones such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone.

Examples of the acylphosphine oxide type photopolymerization initiator include 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

Examples of the hydrogen abstraction-type photopolymerization initiator include methyl phenylglyoxylate and the like.

Examples of the oxime ester type photopolymerization initiator include 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime), and the like.

Examples of the cationic photopolymerization initiator include a mixture of iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate (1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrakis- (pentafluorophenyl) borate, and the like.

Examples of the anionic photopolymerization initiator include a cobalamin complex, o-nitrobenzyl alcohol carbamate, and oxime ester.

The substances exemplified as the component (D) and the substances known as the component (D) may be used alone or in combination of two or more.

The component (D) is preferably a radical photopolymerization initiator, more preferably a phenylalkyl ketone photopolymerization initiator, further preferably an α -hydroxybenzylalkyl ketone, particularly preferably 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and/or 1-hydroxy-cyclohexyl-phenyl-one, in order to provide particularly excellent curing properties.

As the component (D), commercially available products can also be used. The product is not particularly limited, and examples thereof include: 2, 2-dimethoxy-1, 2-diphenylethan-1-one (product name "ohm nidad (Omnirad) 651", manufactured by IGM Resins Co., Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (product name "ohm nidad (Omnirad) 2959", manufactured by IGM Resins Co., Ltd.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one (product name "ohm nidad (Omnirad) 127", manufactured by IGM Resins Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl ketone (product name "ohm nidad (Omnirad) 184", IGM resins, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (product name "Omnirad (Omnirad) 907", IGM resins), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (product name "Omnirad (Omnirad) 369E", IGM resins), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (product name "Omnirad (Omnirad)379 EG", IGM resins), 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (product name "Omnirad (TPO H"), IGM resins, Inc.), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (product name "Omnirad (Omnirad) 819", IGM resins, Inc.), methyl phenylglyoxylate (product name "Omnirad (Omnirad) MBF", IGM resins, Inc.), 1, 2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime) ] (product name "Bright good (IRGACURE) OXE 01", manufactured by BASF Japan, acetone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (product name "Bright good (IRGACURE) OXE 02", manufactured by Japan, Ba Fu (Japan), Iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate (1-), and propylene carbonate (product name "ohm nikat (Omnicat) 250", manufactured by IGM resins Co., Ltd.), triaryl sulfonium hexafluorophosphate (product name "ohm nikat (Omnicat) 270", manufactured by IGM resins Co., Ltd.), triaryl sulfonium tetrakis- (pentafluorophenyl) borate (product name "Irgacure (IRGACURE) 290", manufactured by BASF (BASF) Co., Ltd.), and the like.

The upper limit of the content (in terms of solid content) of the component (D) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, etc., with respect to 100 mass% of the total amount of the resin composition, and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (D) is preferably about 1% by mass to 10% by mass based on 100% by mass of the total amount of the resin composition.

< ingredient (E) >

The resin composition may further contain a fluorine-containing compound (E) (hereinafter also referred to as "component (E)"). By containing the component (E) in the resin composition, the cured product is particularly excellent in scratch resistance, and further excellent in leveling property (coating property), water repellency, oil repellency, stain resistance and finger sliding property.

The component (E) is not particularly limited, and various known substances can be used. Examples of the component (E) include: perfluoroalkyl-containing compounds such as perfluoroalkyl-containing carboxylic acids or salts thereof, perfluoroalkyl-containing sulfonic acids or salts thereof, or perfluoroalkyl-containing phosphoric acids or phosphoric acid esters thereof, perfluoroalkenyl-containing compounds in which the perfluoroalkyl group is substituted with a perfluoroalkenyl group, perfluoroether-containing compounds in which the perfluoroalkyl group is substituted with a perfluoroether group, fluoro-lipophilic group-containing oligomers, fluoro-hydrophilic group-lipophilic group-carboxyl group-containing oligomers, fluoro-Ultraviolet (UV) -reactive group-containing oligomers, and the like.

The substances exemplified as the component (E) and the substances known as the component (E) may be used alone or in combination of two or more. In addition, these may use one kind of polymer each other or two or more kinds of polymers.

The component (E) is preferably an oligomer containing a fluorine-containing group-UV reactive group, because the cured product is excellent in scratch resistance, water repellency, oil repellency, stain resistance, and the like.

As the component (E), commercially available products can also be used. As the product, there can be exemplified: perfluorobutanesulfonate (product name "Meijia method (Megafac) F-114", manufactured by DIC (R)), carboxylate containing perfluoroalkyl group (product name "Meijia method (Megafac) F-410", manufactured by DIC (R)), phosphate ester containing perfluoroalkyl group-phosphoric acid group (product name "Meijia method (Megafac) F-510", manufactured by DIC (R)), modified perfluoropolyether (product name "OPTOOL (OPTOOL) DAC-HP", manufactured by Dajin industry (R)), (product names "KY-108", "KY-164", "X-71-195", "KY-1900", manufactured by shin-Etsu chemical industry (R)), oligomer containing fluoro group-lipophilic group (product name "Meijia method (Megafac) F-281", "Meijia method (Megafac) F-253", "Meijiafac (Megafac) F-251", the above-mentioned oligomer may be produced by DIC (Strand), the fluorine-containing hydrophilic group-containing oligomer (product name "Meijia method (Megafac) F-430", "Meijia method (Megafac) F-551", "Meijia method (Megafac) F-552", produced by DIC (Strand)), the fluorine-containing hydrophilic group-lipophilic group-containing oligomer (product name "Meijiafac method (Megafac) F-477", produced by DIC (Strand)), the fluorine-containing hydrophilic group-lipophilic group-carboxyl group-containing oligomer (product name "Meijiafac method (Megafac) F-570", produced by DIC (Strand)), the fluorine-containing UV reactive group-containing oligomer ((product name "Meijiafac method (Megafac) RS-56", "Meijiafac method (Megafac) RS-90", "Megafac method (Megafac) RS-75-A", produced by DIC (Strand), (product names "KY-1203", "KY-1207" and "KY-1211", manufactured by shin-Etsu chemical industries, Ltd.), and the like.

The upper limit of the content (in terms of solid content) of the component (E) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, etc., and the lower limit may be 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, 0.05 mass%, 0.01 mass%, etc., with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (E) is preferably about 0.01 to 10% by mass relative to 100% by mass of the total amount of the resin composition.

< ingredient (F) >

The resin composition may further contain inorganic fine particles (F) (hereinafter also referred to as "component (F)"). By containing the component (F) in the resin composition, the cured product and the laminate are excellent in scratch resistance.

The component (F) is not particularly limited, and various known substances can be used. Examples of the component (F) include zinc oxide nanoparticles, silica nanoparticles, alumina nanoparticles, cerium oxide nanoparticles, iron oxide nanoparticles, titanium oxide nanoparticles, zirconium oxide nanoparticles, and cuprous oxide nanoparticles.

The substances exemplified as the component (F) and the substances known as the component (F) may be used alone or in combination of two or more.

The component (F) is preferably alumina nanoparticles, because the cured product has excellent scratch resistance.

As the component (F), commercially available products can also be used. As the product, there can be exemplified: silica nanoparticles (manufactured by name of "nano-bike (NANOBYK) -3650", "nano-bike (NANOBYK) -3652", manufactured by bike Chemical (BYK-chemie)), alumina nanoparticles (manufactured by name of "nano-bike (NANOBYK) -3603", "nano-bike (NANOBYK) -3610", manufactured by bike Chemical corporation), (manufactured by name of "armb (alminb) -H06", manufactured by CIK nanotechnology (thigh)), cerium oxide nanoparticles (manufactured by name of "cerium (IV) oxide nanoparticles (10 nm)", manufactured by fuji film and photochemistry (FUJIFILM Wako Chemical) (thigh)), iron oxide nanoparticles (manufactured by name of "iron (II, III), magnetic nanoparticle solution", manufactured by SIGMA ALDRICH-ALDRICH (SIGMA-ALDRICH), titanium oxide nanoparticles (manufactured by name of "TTO-51 (a)", and, "TTO-55 (C)", manufactured by stone industries (stock), zirconia nanoparticles (product names "zekeley (zircono) -Cp", "zekeley (zircono) -Rp", "zekeley (zircono) -Cw", "zekeley (zircono) -Ck", manufactured by ITEC (stock)), cuprous oxide nanoparticles (product name "FRC-N10", manufactured by gulewa Chemicals (stock)), and the like.

The upper limit of the content (in terms of solid content) of the component (F) may be 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass% or the like, and the lower limit may be 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.01 mass% or the like, with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (F) is preferably about 0.01 to 10% by mass relative to 100% by mass of the total amount of the resin composition.

< ingredient (G) >

The resin composition may further contain an acid catalyst (G) (hereinafter also referred to as "component (G)").

Examples of the component (G) include: examples of the organic sulfonic acid include a dinonylnaphthalene disulfonic acid catalyst, a dinonylnaphthalene (mono) sulfonic acid catalyst, a dodecylbenzenesulfonic acid catalyst (a blocked acid catalyst), a p-toluenesulfonic acid catalyst (a blocked acid catalyst), and an organic phosphoric acid (a phosphoric acid catalyst, a phosphoric acid blocked catalyst, and the like).

The substances exemplified as the component (G) and the substances known as the component (G) may be used alone or in combination of two or more.

As the component (G), commercially available products can also be used. As the product, there can be exemplified: dinonylnaphthalene disulfonic acid catalyst (manufactured under the names "nacres (nacre) 155", "nacres (nacre) 3525", "nacres (nacre) X49-110", manufactured by KING INDUSTRIES (KING INDUSTRIES), dinonylnaphthalene mono-sulfonic acid catalyst (manufactured under the names "nacres (nacre) 1051", manufactured by KING INDUSTRIES (KING INDUSTRIES), dodecylbenzene sulfonic acid catalyst (manufactured under the names "nacres) 5076", manufactured by KING INDUSTRIES (KING INDUSTRIES), dodecylbenzene sulfonic acid catalyst (blocking acid catalyst) (manufactured under the names "nacres (nacre) 5225", "nacres (nacre) 5528", "keyre (ure) 5925", manufactured by KING INDUSTRIES (KING) 2500 ", manufactured by KING INDUSTRIES, p-toluenesulfonic acid catalyst (blocking acid catalyst) (manufactured under the names" nacres (nacre) 4025 ", manufactured under the names" KING catalysts "(KING INDUSTRIES, 4000)", "gold phosphoric acid catalyst (KING) 4000", king INDUSTRIES, Inc.), phosphoric acid blocking catalysts (product name "Nakrare (NACURE) 4167", King INDUSTRIES, Inc.), and the like.

In the component (G), it is preferable that a strong acid (for example, an organic sulfonic acid) is used as a catalyst for the "full ether type methylated melamine resin" and the "methylol type methylated melamine resin", and a weak acid (for example, an organic phosphoric acid) is used as a catalyst for the "imino type methylated melamine resin" and the "imino-methylol type methylated melamine resin", from the viewpoint of excellent hardening properties.

The upper limit of the content (in terms of solid content) of the component (G) may be 10 mass%, 8 mass%, 6 mass%, 4 mass%, 2 mass%, etc., and the lower limit may be 8 mass%, 6 mass%, 4 mass%, 2 mass%, 1 mass%, etc., with respect to 100 mass% of the total amount of the resin composition. In one embodiment, the content (in terms of solid content) of the component (G) is preferably about 1 to 10% by mass relative to 100% by mass of the total amount of the resin composition.

< method for producing resin composition >

The method for producing the resin composition containing the component (a), the component (B), and the component (C), and the component (D), the component (E), the component (F), and the component (G) added as needed is not particularly limited, and various known methods can be used. Examples of such a method include a method in which the component (A), the component (B), and the component (C), and if necessary, the component (D), the component (E), the component (F), and the component (G) are mixed in appropriate amounts, and the mixture is diluted with an organic solvent to adjust nonvolatile components, and then uniformly mixed.

As the organic solvent, those exemplified below and those known as organic solvents can be used alone or in combination of two or more. Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol ether solvents, ester solvents, alkyl halide solvents, amide solvents, and other petroleum solvents.

Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

Examples of the aromatic solvent include toluene, xylene, and products such as "Tinsol (T-SOL) 100" and "Tinsol (T-SOL) 150" (manufactured by Yineng New (ENEOS) ").

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol, and cresol.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

Examples of the glycol ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, and bis (2-methoxyethyl) ether.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

Examples of the alkyl halide solvent include chloroform.

Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam.

Examples of the other petroleum solvent include dimethyl sulfoxide and methylcyclohexane.

Other Agents capable of formulation

The resin composition may further contain one or more agents selected from various known resins such as acrylic resins, epoxy resins, urethane resins, etc., reactive diluent monomers, ultraviolet absorbers, antioxidants, silicone additives (silicone or siloxane), silane compounds, antistatic agents, antifogging agents, rheology control agents, fillers, mold release agents, flame retardants, viscosity control agents, plasticizers, antibacterial agents, antifungal agents, antifoaming agents, colorants, stabilizers, pigments, surface control agents, various solvents, various catalysts, and photosensitizers.

< partially cured product >

A resin composition that is partially cured by heating (hereinafter, the treatment is also referred to as "heat treatment") is also one aspect of the present invention. The partially cured product of the present invention can be laminated on the surface of a molded product having a complicated shape such as deep drawing without causing cracks.

By heating the resin composition, the resin composition becomes a product of a thermal crosslinking reaction (also referred to as "partially cured product"). Since the thermal crosslinking reaction product is in a non-viscous state, it is easy to print another layer on the film-shaped thermal crosslinking reaction product or to wind the film. In the stage of the heating, the ethylenically unsaturated group contained in the resin composition is not crosslinked, and thus the resin composition is not completely crosslinked and hardened. In other words, the cured product is partially cured. Therefore, the film-like thermally crosslinked reaction product can be adapted to the curved surface of the molded article and has flexibility to such an extent that no crack is generated. Further, a film having a pad shape may be attached to the film-like product of the thermal crosslinking reaction to transfer the shape, or a protective film for preventing stains may be attached.

The upper limit of the thickness of the film-like thermal crosslinking reaction product may be 1,000. mu.m, 500. mu.m, 250. mu.m, 100. mu.m, 50. mu.m, 10. mu.m, 3. mu.m, 1. mu.m, 0.5. mu.m, etc., and the lower limit thereof may be 500. mu.m, 250. mu.m, 100. mu.m, 50. mu.m, 10. mu.m, 3. mu.m, 1. mu.m, 0.5. mu.m, 0.1. mu.m, etc. In one embodiment, the thickness of the film-like thermal crosslinking reaction product is preferably 0.1 μm or more and 1,000 μm or less. By setting the thickness in the above range, the workability of the partially cured product and the scratch resistance of the cured product can be improved.

Examples of the method for applying the resin composition include bar coater coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and flow coating. The upper limit of the coating amount (mass after drying) is 1,000g/m ² 、500g/m ² 、250g/m ² 、100g/m ² 、50g/m ² 、10g/m ² 、3g/m ² Etc., the lower limit may be 500g/m ² 、250g/m ² 、100g/m ² 、50g/m ² 、10g/m ² 、3g/m ² 、1g/m ² And the like. In one embodiment, the coating amount (mass after drying) is preferably 1g/m ² Above and 1,000g/m ² About the following.

As a method of heat treatment, various known methods can be used. As a method of the heat treatment step, a method of heating the resin composition at 80 ℃ to 150 ℃ for 1 minute to 30 minutes, or the like is preferably exemplified from the viewpoint of reactivity of the component (a) and the component (B) with the component (C).

The lower limit of the elongation at break of the film-like thermally crosslinked reaction product is, for example, 250%, 200%, 150%, 100%, 90%, 80%, 70%, 60%, 50%, 40%, etc. The film-like thermally crosslinked reaction product may not be broken even if it is elongated to more than the object to which the film is laminated, that is, to the limit. Therefore, the upper limit of the elongation at break of the film-like thermal crosslinking reaction product is not particularly limited, and examples thereof include 600%, 550%, 500%, 450%, 400%, 350%, 300%, 250%, 200%, and 150%.

In the present invention, the elongation at break of the film-like thermal crosslinking reaction product is a ratio of a length (cm) of the coating film which is elongated from 0% of the length (cm) of the coating film when the state before the film is elongated is 0%. Specifically, a commercially available tensile tester such as Tensilon Universal tester (product name "RTG-1250", manufactured by Anden (A & D) Inc.) is used to perform stretching at a speed of 100mm/min while heating at 150 ℃, and the length of the sample when a crack is visible and the length of the sample before stretching are used to calculate the tensile tester from the following formula.

Elongation at break (%) < 100 × ((L-Lo)/Lo)

Lo: length of specimen before stretching

L: length of specimen at which cracking started to be visible

< hardening substance >

A cured product obtained by irradiating a partially cured product with an active energy ray such as ultraviolet ray is also one aspect of the present invention.

As a method for hardening by irradiation with an active energy ray, various known methods can be used. Examples of the method of curing by ultraviolet rays during irradiation with active energy rays include irradiation with 10mJ/cm using a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, a light-emitting diode (LED) or the like that emits light in a wavelength range of 150nm to 450nm, and the like ² Above and 10,000mJ/cm ² The following methods are used. When a high-pressure mercury lamp is used, a method of curing a lamp having a light quantity of usually 80W/cm to 160W/cm at a transport speed of 2 m/min to 50 m/min, and the like can be exemplified. Examples of the method of curing by an electron beam include a method of curing at a transport speed of 5 m/min to 50 m/min by using an electron beam accelerator usually having an acceleration voltage of 10kV to 300 kV.

< laminate >

The present invention also relates to a laminate comprising a partially cured product or cured product and a substrate. Examples of the laminate include a laminate obtained by applying a partially cured product to at least one surface of a substrate and then completely curing the partially cured product by irradiation with an active energy ray such as ultraviolet light. By completely curing the partially cured product, the substrate can be given scratch difficulty.

Examples of the substrate include metal, plastic, glass, and other resins. Examples of the metal include iron, aluminum-plated steel sheet, tin-free steel sheet (TFS), stainless steel sheet, zinc phosphate-treated steel sheet, and treated steel sheet of zinc-zinc alloy-plated steel sheet (corrosion-resistant steel sheet). Examples of the plastic include thermoplastic substrates and thermosetting plastic substrates. Examples of the thermoplastic base material include general-purpose plastic base materials and engineering plastic base materials. Examples of the general-purpose plastic base material include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based materials. Examples of the olefin-based polymer include polyethylene, polypropylene, and norbornene. Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the like. Examples of the acrylic include polymethyl methacrylate (PMMA). Examples of the vinyl group include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrenes include Polystyrene (PS) resin, styrene-Acrylonitrile (AS) resin, styrene-butadiene-Acrylonitrile (ABS) resin, and the like. Examples of the engineering plastic substrate include general-purpose engineering plastics and super engineering plastics. Examples of the general-purpose engineering plastic include polycarbonate, polyamide (nylon), and the like. Examples of the super engineering plastic include Polyetheretherketone (PEEK). Examples of the thermosetting plastic substrate include polyimide, epoxy resin, and melamine resin. As another plastic substrate, triacetyl cellulose resin and the like can be exemplified. The base material in the laminate of the present invention is preferably a thermoplastic base material, more preferably at least one selected from polyester-based, acrylic-based and general-purpose engineering plastics, and even more preferably polyester-based or acrylic-based and general-purpose engineering plastics.

The substrate may be in the form of a film. When the substrate is in the form of a film, the upper limit of the thickness thereof may be 1,000. mu.m, 750. mu.m, 500. mu.m, 300. mu.m, 100. mu.m, 50. mu.m, 25 μm, etc., and the lower limit thereof may be 750. mu.m, 500. mu.m, 300. mu.m, 100. mu.m, 50. mu.m, 25. mu.m, 10 μm, etc. In one embodiment, the film-like substrate preferably has a thickness of about 10 μm to 1,000. mu.m.

For the purpose of improving the adhesion and adhesion between the substrate and the cured product, the surface of the substrate may be subjected to various surface treatments such as corona treatment, plasma treatment, primer coating, degreasing treatment, and surface roughening treatment. In addition, another layer (for example, an easy adhesion layer, an adhesive layer, or the like) may be disposed between the substrate and the cured product for the purpose of improving the adhesion and the close contact between the substrate and the cured product.

As a specific example of the laminate of the present invention, a laminate having various layers in the following order can be exemplified. In addition, various known layers such as a pattern layer may be appropriately disposed before and after each layer.

(1) A cured product/substrate,

(2) Cured product/easy-to-adhere layer or adhesive layer/substrate,

(3) A partially cured product/substrate,

(4) Partially cured/easy-to-bond or adhesive/substrate

< shaped article >

Examples of applications of the resin composition include forming a hard coat layer on various known articles.

As the article, various known articles can be exemplified. Examples of the articles include a main body of a home appliance such as a refrigerator, a television, or an air conditioner, a remote controller thereof, a housing and a display of an information terminal such as a mobile phone, a smartphone, an input board, or a personal computer, and a plastic molded article such as an automobile part or an automobile interior material.

[ examples ]

The present invention will be described in more detail below by reference to synthesis examples, comparative examples, evaluation examples and comparative evaluation examples, but the present invention is not limited to these examples. In the following description, parts and% are based on mass.

In this example, the weight average molecular weight (Mw) was measured by Gel Permeation Chromatography (GPC) under the following conditions.

(GPC measurement conditions)

The machine is as follows: the product name is "HLC-8220" (manufactured by Tosoh)

Pipe column: the product name "TSK gel Super (TSKgel Super) HM-L" (manufactured by Tosoh corporation) × 3

Developing solvent: tetrahydrofuran (hereinafter, also referred to as "THF")

< Synthesis example 1: synthesis of component (A-1)

A reaction apparatus including a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube was charged with 32.6 parts of glycidyl methacrylate (hereinafter, also referred to as "GMA"), 48.6 parts of butyl acetate, and 1.5 parts of azobisisobutyronitrile (hereinafter, also referred to as "AIBN"), and then heated to about 100 ℃ under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 16.6 parts of acrylic acid (hereinafter, also referred to as "AA"), 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to react for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-1") having a resin solid content of 50%. The obtained (meth) acrylic acid copolymer had a hydroxyl group concentration of 4.7mmol/g, an acrylic acid equivalent of 214g/eq, and a weight-average molecular weight (in terms of polystyrene obtained by GPC) of 30,000.

< Synthesis example 2: (A-2) Synthesis of component >

A reaction apparatus including a stirrer, a cooling tube, a thermometer, and a nitrogen inlet tube was charged with 16.3 parts of GMA, 16.3 parts of methyl methacrylate, 48.6 parts of butyl acetate, and 2.0 parts of AIBN, and then heated to about 100 ℃ under a nitrogen stream, and the temperature was maintained for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 8.3 parts of AA, 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to carry out a reaction for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-2") having a resin solid content of 50%. The obtained (meth) acrylic acid copolymer had a hydroxyl group concentration of 2.8mmol/g, an acrylic acid equivalent of 356g/eq, and a weight-average molecular weight (calculated as polystyrene by GPC) of 10,000.

< example 1: preparation of resin composition (1)

50.0 parts of dipentaerythritol polyacrylate (product name "Aronix M-403", manufactured by Toyo Synthesis (Ltd.), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 50.0 parts of full ether type methylated melamine resin (product name "Saimel 303 LF", manufactured by Nippon Kalim corporation) 10.0 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (product name "Omnirad" 184 ", manufactured by IGM resins Co., Ltd.) as a photopolymerization initiator, 2.0 parts of a fluorine-containing compound (product name" Meijia method (Megafac) RS-90 ", manufactured by DIC (Ltd.), 4.0 parts of P-Toluene Sulfonic acid (P-Toluene sulfoacid, PTS) as a catalyst were blended with 50.0 parts of the (A-1) component, and the mixture was diluted with methyl ethyl ketone so that the nonvolatile component became 20%, and uniformly mixed to obtain the resin composition.

< example 2 to example 12: preparation of resin compositions (2) to (12)

Resin compositions (2) to (12) were prepared in the same manner as in example 1, except that the compositions were changed to the compositions shown in table 1 below.

< example 13: preparation of resin composition (13)

50.0 parts of dipentaerythritol polyacrylate (product name "Aronix M-403", manufactured by Toyo Synthesis (Ltd.), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 50.0 parts of full-ether methylated melamine resin (product name "Saumel 303 LF", manufactured by Nippon Kalim corporation), 15.0 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (product name "ohmic Nirad (Omnirad) 184", manufactured by IGM resin Co., Ltd.) as a photopolymerization initiator, 2.0 parts of a fluorine-containing compound (product name "Meigafac) RS-90", manufactured by DIC (Ltd.), 1.0 part of alumina nanoparticles (product name "Nanibok OBYK) -3610", manufactured by Pick Chemicals Co., Ltd.), and 4.0 parts of PTS (p-toluenesulfonic acid) as a catalyst were blended in 50.0 parts of the component (A-1), the resin composition was prepared by diluting methyl ethyl ketone so that the nonvolatile content became 20%, and uniformly mixing the components.

< example 14: preparation of resin composition (14)

A resin composition (14) was prepared in the same manner as in example 13, except that the composition was changed to the composition shown in table 1 below.

< comparative example 1 to comparative example 5: preparation of resin compositions (C1) to (C5)

Resin compositions (C1) to (C5) were prepared in the same manner as in example 1, except that the compositions shown in table 2 were changed.

< production of partially cured coating film >

The resin compositions ((1) to (14), (C1) to (C5)) prepared in the examples and comparative examples were applied to the surface of a substrate (made of polymethyl methacrylate and having a thickness of 0.400mm) to a film thickness of about 5 μm using a bar coater (model No.24 ", first physical and chemical (stock) manufacture), dried in a circulating air dryer at 100 ℃ for 5 minutes, and heated to form a partially cured coating film.

< production of cured article >

The partially cured coating films of examples and comparative examples were irradiated at an irradiation distance of 15cm, a belt speed of 7m/min, and a cumulative irradiation dose of 300mJ/cm using a high-pressure mercury lamp (output 120W/cm) ² And (3) curing under the condition (1) to prepare a cured product.

< evaluation of Performance: processability >

Test pieces obtained by cutting out the partially cured coating films of examples and comparative examples at a length of 13cm and a width of 1.5cm were stretched in a circulating air dryer at 150 ℃ to evaluate the elongation at break.

Very good: an elongation at break of 100% to 300%

O: the elongation at break is more than 40% and less than 100%

X: elongation at break of less than 40%, or failure to form a thermosetting film

< evaluation of Performance: viscosity >

The partially cured coating films of the examples and comparative examples were touched with a finger to evaluate the presence or absence of a finger mark on the surface of the coating film.

O: no finger mark

X: with finger marks

< evaluation of Performance: scratch resistance

The cured products of the examples and comparative examples were set in a commercially available measuring apparatus (product name "plane abrasion tester", manufactured by Daorhizi Seiki Seisaku-Sho Ltd.), and the surface of the cured product was subjected to reciprocal abrasion 1000 times with a load of 1kg using Steel Wool (count "# 0000", grade "ultra-fine", manufactured by Japan Steel Wool (stock). The scratch resistance of the laminate was evaluated according to the number of formed scratches according to the following criteria.

AAAA: without any scratch

AAA: the number of the scars is more than 1 and less than 3

AA: the number of the scars is more than 3 and less than 5

A: the number of the scars is more than 5 and less than 10

B: the number of the scars is more than 10

The compositions of the resin compositions (1) to (14) of the examples and the results of the performance evaluations are shown in table 1. The compositions and the performance evaluation results of the resin compositions (C1) to (C5) of the comparative examples are shown in table 2.

[ Table 2]

The meanings of the terms in tables 1 to 2 are as follows.

(A-1): synthesis of the (meth) acrylic copolymer solution obtained in example 1 (hydroxyl group concentration 4.7mmol/g, acrylic acid equivalent 214g/eq)

(A-2): synthesis of the (meth) acrylic copolymer solution obtained in example 2 (hydroxyl group concentration 2.8mmol/g, acrylic acid equivalent 356g/eq)

Aronix (Aronix) M-403: dipentaerythritol poly (meth) acrylate (manufactured by TOYA SYNTHESIS (PULSE), 5-6-FUNCTIONAL)

Aronix (Aronix) M-402: dipentaerythritol poly (meth) acrylate (manufactured by TOYA SYNTHESIS (PULSE), 5-6-FUNCTIONAL)

Siriwu (SIRIUS) -501: multifunctional acrylate having dendritic polymer structure (product name "Sirius-501", manufactured by Osaka organic chemical industry (stock), 16-20 functions)

Melamor (Miramer) PU 610: aliphatic urethane (meth) acrylate (6-functional, manufactured by Meiyuan Special chemical Co., Ltd.)

IBXA: isobornyl acrylate (manufactured by Osaka organic chemical industry (jet), 1 function)

Semel (Cymel)303 LF: full-ether type methylated melamine resin (manufactured by Zhanxin (stock Co., Ltd., 5-6 functional.)

Semel (Cymel) 300: full-ether type methylated melamine resin (manufactured by Zhanxin (stock Co., Ltd., 6-functional))

Crotamide (Coronate) HK: uroacetate of hexamethylene diisocyanate (product name "Crosstide (Konate) HK", manufactured by Tosoh)

Ohm nidad (Omnirad) 184: 1-hydroxy-cyclohexyl-phenyl ketone (product name "Omnirad) 184", manufactured by IGM resins Co.)

RS-90: fluorine-containing compound (product name "Meijia method (Megafac) RS-90", manufactured by DIC (stock Co Ltd.))

Nano bike (NANOBYK) -3610: alumina nanoparticles (product name "Nanobike (NANOBYK) -3610", manufactured by Bik chemical Co., Ltd.)

PTS: p-toluenesulfonic acid

DOTL: dioctyltin dilaurate

< reference example 1: preparation of resin composition (α)

50.0 parts of dipentaerythritol polyacrylate (product name "Aronix M-403", manufactured by Toyo Seiyaku K.K., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 50.0 parts of full-ether methylated melamine resin (product name "Seimel 303 LF", manufactured by Zhan Mikan K.K.), 30.0 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (product name "Omnirad) 184", manufactured by IGM resins K.K.) as a photopolymerization initiator, 2.0 parts of a fluorine-containing compound (product name "Meigafac (Megafac) RS-90", manufactured by DIC (K.K.), 4.0 parts of PTS (p-toluenesulfonic acid) as a catalyst, and diluted with methyl ethyl ketone so that the nonvolatile content becomes 20% were added to 50.0 parts of the component (A-1), and uniformly mixed to obtain the resin composition. In the same manner as in each of examples and comparative examples, the adhesion and scratch resistance were evaluated, and the results were respectively "o" and "AAA".

< reference example 2: preparation of resin composition (. beta.)

25.0 parts of (A-1) component, 25.0 parts of the following (A-3) component, 50.0 parts of dipentaerythritol polyacrylate (product name "Aronix) M-403", manufactured by Toyo Synthesis (Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), 5.0 parts of all-ether methylated melamine resin (product name "Saumel (Cymel)303 LF", manufactured by Nippon Kalim corporation), 15.0 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (product name "Omnirad (Omnirad) 184", manufactured by IGM resins Co., Ltd.), 2.0 parts of a fluorine-containing compound (product name "Meijia method (Megafac) RS-90", manufactured by Nippon Kalim), 4.0 parts of PTS (p-toluenesulfonic acid) as a catalyst, and diluting with methylethylketone so that the nonvolatile component becomes 20%, and uniformly mixed to obtain the resin composition. As a result of evaluating the workability and the tackiness in the same manner as in each of examples and comparative examples, the results were £ and.

< reference example 3: preparation of resin composition (. gamma.)

50.0 parts of the component (A-1), 50.0 parts of dipropylene glycol diacrylate (product name "Milamer M222", manufactured by Meiyuan specialty Chemicals Co., Ltd.), 15.0 parts of all-ether type methylated melamine resin (product name "Semel 303 LF", manufactured by Japan Zhanxin (Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (product name "Omnirad) 184", manufactured by IGM resins Co., Ltd.), 5.0 parts of a fluorine-containing compound (product name "Meigafac RS-90", manufactured by DIC (Co., Ltd.), and 4.0 parts of PTS (p-toluenesulfonic acid) as a catalyst were blended, diluted with methyl ethyl ketone so that the nonvolatile content became 20%, and mixed uniformly to obtain a resin composition. The workability was evaluated in the same manner as in each of examples and comparative examples, and the result was "excellent".

< Synthesis example 3: (A-3) Synthesis of component >

After 4.9 parts of GMA, 27.9 parts of methyl methacrylate, 48.6 parts of butyl acetate and 2.0 parts of AIBN were charged into a reaction apparatus equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas inlet tube, the temperature was raised to about 100 ℃ under a nitrogen gas flow, and the temperature was maintained for 10 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and charged with 2.5 parts of AA, 0.5 part of methoxyphenol and 0.1 part of triphenylphosphine, and the temperature was raised to 110 ℃ under bubbling of air to carry out a reaction for 9 hours, thereby obtaining a (meth) acrylic copolymer solution (hereinafter, also referred to as "component A-3") having a resin solid content of 50%. The resulting (meth) acrylic copolymer had a hydroxyl group concentration of 1.0mmol/g, an acrylic acid equivalent of 1,017g/eq, and a weight-average molecular weight (in terms of polystyrene obtained by GPC) of 10,000.

Claims (11)

1. An active energy ray-curable resin composition comprising: a (meth) acrylic copolymer (A) which is a reaction product of a radical polymer (a1) which is a monomer component containing an epoxy group-containing mono (meth) acrylate and an α, β -unsaturated carboxylic acid (a2), a polyfunctional (meth) acrylate (B), and a melamine resin (C).

2. The active energy ray-curable resin composition according to claim 1, wherein

(A) The hydroxyl group concentration of the component (B) is 1.1 to 5mmol/g,

(A) component (B) has a (meth) acrylic acid equivalent of 150g/eq or more and 1,000g/eq or less, and

(B) the component (A) has 3 or more and 30 or less (meth) acryloyl groups.

3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the mass ratio of the component (A) to the component (B) in terms of solid content is (A)/(B) of 10/90 to 99/1.

4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the content of the component (C) is 1% by mass or more and 25% by mass or less in terms of solid content, relative to 100% by mass of the total amount of the components (A) and (B).

5. The active energy ray-curable resin composition according to any one of claims 1 to 4, containing a photopolymerization initiator (D).

6. The active energy ray-curable resin composition according to any one of claims 1 to 5, containing a fluorine-containing compound (E).

7. The active energy ray-curable resin composition according to any one of claims 1 to 6, containing inorganic fine particles (F).

8. A partially cured product obtained by heating the active energy ray curable resin composition according to any one of claims 1 to 7, and having an elongation at break of 40% or more.

9. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 7.

10. A laminate having the partially cured product according to claim 8 or the cured product according to claim 9 on at least one surface of a substrate.

11. A curing method wherein after the active energy ray-curable resin composition according to any one of claims 1 to 7 is heated to be partially cured, an active energy ray is irradiated to be further cured.