TW201940541A - Active energy ray-curable resin composition, cured product and thin film especially providing a plastic product applied to automotive interior parts, and home appliances - Google Patents

Abstract

Provided herein are an active energy ray-curable resin composition, a cured product, and a thin film. The present invention provides an active energy ray-curable resin composition characterized in that the active energy ray-curable resin composition contains, with respect to 100 parts by mass of polycarbonate urethane (meth) acrylate, 1.0 to 15.0 parts by mass of a triazine-containing ultraviolet absorber, and 0.3 to 2.0 parts by mass of a light stabilizer containing a hindered amine structure. The present invention also provides a cured product of the active energy ray-curable resin composition and a thin film comprising the cured product.

Description

   Active energy ray-curable resin composition, cured product and film   

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

For automotive interior parts, plastic parts of home appliances, etc., in order to show a high-grade feeling, an active energy ray-curable resin composition capable of providing a coating film (cured material) having a soft feeling (wet feeling) may be used.

In order to impart a touch to the hardened material, the resin needs to have a certain degree of flexibility. However, such a soft resin has the problems of poor durability such as acid resistance, alkali resistance, light yellowing resistance, and light adhesion resistance of the cured product.

Therefore, the technical problem to be solved by the present invention is to provide an active energy ray-curable resin composition. The cured product has a good touch, and can make the cured product resistant to acid, alkali, light yellowing, and light density. Either of the adhesion properties was good.

The inventors have conducted intensive studies and found that the above-mentioned problems can be solved by an active energy ray-curable resin composition containing a specific component.

According to the present invention, the following items are provided.

(Item 1)

An active energy ray-curable resin composition, characterized in that the active energy ray-curable resin composition contains 1.0 to 15.0 parts by mass of 100 parts by mass of a polycarbonate urethane (meth) acrylate. A triazine structure-containing ultraviolet absorber and 0.3 to 2.0 parts by mass of a hindered amine structure-containing light stabilizer.

(Item 2)

The active energy ray-curable resin composition according to the above item, wherein the polycarbonate urethane (meth) acrylate is a polycarbonate diol, an alicyclic diisocyanate, and a hydroxyl group-containing ( The reaction product of a meth) acrylate.

(Item 3)

The hardened | cured material is a hardened | cured material of the active-energy-ray-curable resin composition as described in any one of the said items.

(Item 4)

A film characterized by including a hardened material as described in the above item.

In the present invention, in addition to the combinations explicitly stated, further combinations of one or more of the above features may also be provided.

When the active energy ray-curable resin composition is used, the cured product exhibits a good feel, and the cured product exhibits excellent effects on acid resistance, alkali resistance, light yellowing resistance, and light adhesion. .

Throughout the specification, ranges of numerical values such as physical properties and contents can be appropriately set (for example, selected from values of upper and lower limits described in each of the following items). Specifically, when the value α is exemplified as A1, A2, A3, A4 (setting A1> A2> A3> A4) as the upper limit and lower limit of the value α, the range of the value α is, for example, A1 or less and A2 or less , Below A3, above A2, above A3, above A4, A2 ~ A1, A3 ~ A1, A4 ~ A1, A3 ~ A2, A4 ~ A2, A4 ~ A3, etc.

[Active energy ray-curable resin composition (also referred to as a composition)]

The present invention provides an active energy ray-curable resin composition, characterized in that the active energy ray-curable resin composition contains 1.0 to 15.0 based on 100 parts by mass of a polycarbonate urethane (meth) acrylate. The mass absorber contains a triazine structure-containing ultraviolet absorber and 0.3 to 2.0 mass parts of a hindered amine structure-containing light stabilizer.

<Polycarbonate urethane (meth) acrylate (also known as urethane (meth) acrylate)>

Polycarbonate urethane (meth) acrylates are reaction products of polycarbonate polyols, polyisocyanates, and hydroxyl-containing (meth) acrylates. Any of the polyisocyanate and the hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.

In the present invention, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". Similarly, "(meth) acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid".

(Polycarbonate polyol)

In the present invention, the "polycarbonate polyol" is, for example, a polyol having a plurality of carbonate groups. The polycarbonate polyol can be produced by a reaction of a diol with a carbonate or phosgene.

In one embodiment, the polycarbonate polyol is represented by Formula 1: (In the formula, R ^{1a ′} and R ^{1b ′} are each independently a hydrocarbon group, and a1 ′ is an integer of 1 or more.)

A hydrocarbon group is a group consisting only of a carbon atom and a hydrogen atom. Moreover, the substituent which replaces a hydrocarbon group may contain an atom which is neither a carbon atom nor a hydrogen atom.

The carbon number of the hydrocarbon group is not particularly limited, and its upper limit and lower limit are, for example, 30, 29, 25, 20, 16, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. . In one embodiment, the carbon number of the hydrocarbon group is preferably about 1 to 30, more preferably about 1 to 20, even more preferably about 1 to 16, and particularly preferably about 1 to 12.

The hydrocarbon group is, for example, an aliphatic group or an aromatic group.

The aliphatic group is, for example, an acyclic aliphatic group, an alicyclic group, or the like.

Acyclic aliphatic group means an aliphatic group having no cyclic structure.

Monovalent acyclic aliphatic groups are, for example, alkyl, alkenyl, alkynyl and the like.

The alkyl group is, for example, a linear alkyl group or a branched alkyl group.

A linear alkyl group can be represented by the general formula -C _n H _{2n + 1} (n is an integer of 1 or more). The linear alkyl group is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decamethyl group, and the like.

A branched alkyl group is a group in which at least one hydrogen of a linear alkyl group is substituted with an alkyl group. The branched alkyl group is, for example, isopropyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

The divalent acyclic aliphatic group is, for example, an alkylene group, an alkenylene group, an alkynylene group, or the like.

Examples of the alkylene group include a linear alkylene group and a branched alkylene group.

The linear alkylene group can be represented by the general formula-(CH ₂ ) _n- (n is an integer of 1 or more). Linear alkylene, for example, methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decyl Methylene (n-decylene) and the like.

A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group. The branched alkylene group is, for example, diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene, or the like.

An alicyclic group refers to an aliphatic group having a cyclic structure.

The monovalent alicyclic group is, for example, a cycloalkyl group, a cycloalkylalkyl group, an alkylcycloalkylalkyl group, or the like.

The cycloalkyl group is, for example, a monocyclic cycloalkyl group, a bridged cyclocycloalkyl group, or a fused cyclocycloalkyl group. In addition, one or more hydrogens of a cycloalkyl group may be substituted by a linear or branched alkyl group.

A monocyclic ring is, for example, a cyclic structure having no internal bridge structure formed by carbon covalent bonds. The fused ring is, for example, a cyclic structure in which two or more monocyclic rings have two atoms in common (that is, only one side of each ring is shared (condensed) with each other). A bridge ring is, for example, a cyclic structure in which two or more monocyclic rings share three or more atoms.

Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

The bridged cyclocycloalkyl group is, for example, tricyclodecyl group, adamantyl group, norbornyl group, or the like.

Cycloalkylalkyl, by ^R calkyl -R ^alkyl - ^(wherein, R calkyl represents a cycloalkyl group, R ^alkyl represents an alkyl group) a group represented.

Divalent alicyclic groups, such as cycloalkylene group, cycloalkylene alkylene group, and alkylene cycloalkylene alkylene group .

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged cycloalkylene group, and a fused ring cycloalkylene group. In addition, one or more hydrogens of the cycloalkylene group may be substituted by a linear or branched alkyl group.

Monocyclic cycloalkylene is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5,5-trimethylcyclohexylene and the like.

The bridged ring cycloalkylene group is, for example, a tricyclodecylene group, an adamantylene group, a norbornylene group, or the like.

The fused ring cycloalkylene group is, for example, a bicyclodecylene group.

The cycloalkylene alkylene group is a group represented by -R ^calkylene -R ^alkylene- (where R ^calkylene represents a cycloalkylene group, and R ^alkylene represents an alkylene group).

The alkylene cycloalkylene group is a group represented by -R ^alkylene -R ^calkylene -R ^alkylene- (where R ^calkylene represents a cycloalkylene group, and R ^alkylene represents an alkylene group).

The monovalent aromatic group is, for example, an aryl group.

Examples of the aryl group include phenyl, naphthyl, and fluorenyl.

The divalent aromatic group is, for example, an arylene group.

Examples of the arylene group include phenylene, naphthylene, and fluorenylene.

The upper limit and lower limit of the weight average molecular weight (Mw) of the polycarbonate polyol are, for example, 20,000, 19000, 17500, 15000, 12500, 10000, 9000, 5000, 2500, 1500, 1000, and the like. In one embodiment, the weight average molecular weight (Mw) of the polycarbonate polyol is preferably 1000 to 20,000.

The upper limit and lower limit of the number average molecular weight (Mn) of the polycarbonate polyol are, for example, 5000, 4000, 2500, 1500, 1000, 900, 750, 500, and the like. In one embodiment, the number average molecular weight (Mn) of the polycarbonate polyol is preferably 500 to 5000.

The upper limit and lower limit of the molecular weight distribution (Mw / Mn) of the polycarbonate polyol are, for example, 2.8, 2.7, 2.5, 2.2, 2.0, 1.9, 1.8, and the like. In one embodiment, the molecular weight distribution (Mw / Mn) of the polycarbonate polyol is preferably 1.8 to 2.8.

The weight-average molecular weight and the number-average molecular weight can be obtained by using a gel permeation chromatography (for example: Tosoh Corporation, trade name "HLC-8220"; column: manufactured by Tosoh Corporation, Trade name "TSKgel superHZM-M") and the like (hereinafter the same).

The upper limit of the content of the structural unit derived from the polycarbonate polyol in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate is, for example, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, etc .; lower limits, such as 85% by mass, 80% by mass, 75% by mass, 70% by mass Mass%, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, etc. In one embodiment, the content of the structural unit derived from the polycarbonate polyol in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate is desirably 35 to 90% by mass. .

The upper limit and the lower limit of the content of the structural unit derived from a polycarbonate polyol in 100 mol% of all the structural units of the polycarbonate urethane (meth) acrylate are, for example, 35 mol% and 30 mol% , 25 mole%, 20 mole%, 15 mole%, 10 mole%, 9 mole%, 5 mole%, etc. In one embodiment, the content of the structural unit derived from the polycarbonate polyol in 100 mol% of all the structural units of the polycarbonate urethane (meth) acrylate is preferably 5 mol% to 35. Mohr%.

(Polyisocyanate)

In the present invention, "polyisocyanate" means a compound having two or more isocyanate groups (-N = C = O). The number of isocyanate groups contained in the polyisocyanate may be two or more, for example, two, three, four, and the like.

In one embodiment, the polyisocyanate is represented by the general formula 2: O = C = NR ^{2a '} -N = C = O

(Wherein R ^{2a ′} is a hydrocarbon group).

The polyisocyanate is, for example, an aliphatic polyisocyanate, an aromatic polyisocyanate, or the like.

The aliphatic polyisocyanate is, for example, an acyclic aliphatic polyisocyanate, an alicyclic polyisocyanate, or the like.

The acyclic aliphatic polyisocyanate is, for example, an alkylene polyisocyanate, or an adduct or modification thereof.

The alkylene polyisocyanate is, for example, a linear alkylene polyisocyanate or a branched alkylene polyisocyanate.

The linear alkylene polyisocyanate is, for example, hexamethylene diisocyanate (HMDI), decamethylene diisocyanate, or the like.

The branched alkylene polyisocyanate is, for example, trimethylhexamethylene diisocyanate (TMXDI).

The alicyclic polyisocyanate is, for example, a monocyclic alicyclic polyisocyanate, a bridged alicyclic polyisocyanate, a fused cycloalicyclic polyisocyanate, and the like.

The monocyclic alicyclic polyisocyanate is, for example, a monocyclic alkylene polyisocyanate. The monocyclic alkylene polyisocyanate is, for example, hydrogenated diphenylmethane diisocyanate (H12MDI), hydrogenated xylylene diisocyanate (HXDI), isophorone diisocyanate (IPDI), and the like.

The bridged alicyclic polyisocyanate is, for example, a bridged cycloalkylene polyisocyanate. The bridged alkylene polyisocyanate is, for example, norbornene diisocyanate (NBDI) and the like.

The fused-ring alicyclic polyisocyanate is, for example, a fused-ring alkylene polyisocyanate. The fused ring alkylene polyisocyanate is, for example, a bicyclodecyl diisocyanate and the like.

The aromatic polyisocyanate is, for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and the like.

The upper limit and lower limit of the content of the structural unit derived from polyisocyanate in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate are, for example, 45% by mass, 40% by mass, 35% by mass, 30% Mass%, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, etc. In one embodiment, the content of the structural unit derived from polyisocyanate in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate is preferably 5 to 45% by mass.

The upper limit and the lower limit of the content of the structural unit derived from polyisocyanate in 100 mol% of all the structural units of the polycarbonate urethane (meth) acrylate are, for example, 55 mol%, 50 mol%, and 45 mol. Ear mole%, 40 mole%, 35 mole%, 30 mole%, 29 mole%, 25 mole%, etc. In one embodiment, the content of the structural unit derived from polyisocyanate in 100 mol% of all the structural units of the polycarbonate urethane (meth) acrylate is preferably 25 mol% to 55 mol%. .

(Hydroxy-containing (meth) acrylate)

In the present invention, the "hydroxyl-containing (meth) acrylate" means a compound having a hydroxyl group and a (meth) acrylate moiety.

In one embodiment, a hydroxyl-containing (meth) acrylate is represented by Formula 3: (In the formula, R ^{3a ′} is an alkylene group or a cycloalkylene group, and R ^{3b ′} is a hydrogen atom or a methyl group).

The hydroxyl-containing (meth) acrylate is, for example, a hydroxyl-containing mono (meth) acrylate or the like.

Hydroxyl-containing mono (meth) acrylates are, for example, β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, ε-caprolactone-modified β-hydroxyethyl (meth) acrylate, and the like.

The upper limit and the lower limit of the content of the structural unit derived from the hydroxyl-containing (meth) acrylate in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate are, for example, 30% by mass and 29% by mass %, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 3% by mass, etc. In one embodiment, the content of the structural unit derived from the hydroxyl-containing (meth) acrylate in 100% by mass of all the structural units of the polycarbonate urethane (meth) acrylate is preferably 3% by mass ~ 30% by mass.

The upper limit and lower limit of the content of the structural unit derived from the hydroxyl group-containing (meth) acrylate in 100 mol% of all the structural units of the polycarbonate urethane (meth) acrylate are, for example, 55 mol%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 29 mole%, 25 mole%, etc. In one embodiment, the content of the structural unit derived from the hydroxyl-containing (meth) acrylate in 100% by mole of all the structural units of the polycarbonate urethane (meth) acrylate is preferably 25 mol. Ear% ~ 55mol%.

In one embodiment, the polycarbonate urethane (meth) acrylate is a reaction product of a polycarbonate diol, an alicyclic diisocyanate, and a hydroxyl group-containing (meth) acrylate.

The upper limit and lower limit of the (meth) acrylfluorenyl group contained in the polycarbonate urethane (meth) acrylate are, for example, 9, 8, 7, 6, 5, 4, 3, 2, 1 etc. In one embodiment, the number of (meth) acrylfluorenyl groups contained in the polycarbonate urethane (meth) acrylate is preferably 1 to 9, more preferably 1 to 3, and more It is preferably 1-2.

In one embodiment, the polycarbonate urethane (meth) acrylate is represented by the following general formula: ( ^Wherein R ^1a , R ^1b , R ^2a1 , R ^2a2 , R ^3a1, and R ^3a2 are each independently a hydrocarbon group, R ^3b1 and R ^3b2 are each independently a hydrogen atom or a methyl group, and a1 and n are integers of 1 or more (Also, ideally, a1 is 2 to 23, and n is ideally 1 to 2).

(Relative proportions among constituent components)

The mass ratio of the structural unit derived from the polycarbonate polyol to the structural unit derived from the polyisocyanate in the polycarbonate urethane (meth) acrylate (the mass of the structural unit derived from the polycarbonate polyol / The upper and lower limits of the mass of the structural unit derived from the polyisocyanate are, for example, 20, 19, 15, 14, 10, 9, 7, 5, 4, 2, 1, 0.9, 0.6, 0.5, and the like. In one embodiment, the mass ratio (mass of the structural unit derived from the polycarbonate polyol / mass of the structural unit derived from the polyisocyanate) is preferably 0.5 to 20.

The mass ratio of the structural unit derived from the polycarbonate polyol to the structural unit derived from the polyisocyanate in the polycarbonate urethane (meth) acrylate (a substance derived from the structural unit of the polycarbonate polyol) The upper limit and lower limit of the amount / the amount of the structural unit derived from the polyisocyanate) are, for example, 1.5, 1.4, 1.0, 0.9, 0.5, 0.4, 0.1, 0.09, 0.05, and the like. In one embodiment, the above-mentioned substance-to-mass ratio (substance mass from a structural unit derived from a polycarbonate polyol / substance mass from a structural unit derived from a polyisocyanate) is preferably 0.05 to 1.5.

Mass ratio of the structural unit derived from a polycarbonate polyol to the structural unit derived from a hydroxyl group-containing (meth) acrylate in the polycarbonate urethane (meth) acrylate (derived from a polycarbonate polyol The upper and lower limits of the mass of the structural unit of the alcohol / the mass of the structural unit derived from the hydroxyl-containing (meth) acrylate) are, for example, 30, 29, 25, 24, 20, 19, 15, 14, 10, 9, 5, 4, 2, 1, etc. In one embodiment, the mass ratio (mass of a structural unit derived from a polycarbonate polyol / mass of a structural unit derived from a hydroxyl group-containing (meth) acrylate) is preferably 1 to 30.

The weight ratio of the structural unit derived from a polycarbonate polyol to the structural unit derived from a hydroxyl group-containing (meth) acrylate in the polycarbonate urethane (meth) acrylate (derived from polycarbonate The upper limit and lower limit of the amount of the structural unit of the polyol / the amount of the structural unit derived from the hydroxyl group-containing (meth) acrylate) are, for example, 1.5, 1.4, 1.0, 0.9, 0.5, 0.4, 0.1, 0.09, 0.05 Wait. In one embodiment, the above-mentioned substance-to-mass ratio (physical substance from a structural unit derived from a polycarbonate polyol / substance mass from a structural unit derived from a hydroxyl group-containing (meth) acrylate) is preferably from 0.05 to 1.5.

Mass ratio of structural units derived from polyisocyanate to structural units derived from hydroxyl-containing (meth) acrylate in the polycarbonate urethane (meth) acrylate (mass of structural unit derived from polyisocyanate) / The upper limit and the lower limit of the mass of the structural unit derived from the hydroxyl-containing (meth) acrylate are, for example, 15, 14, 10, 9, 5, 4, 1, 0.9, 0.5, 0.4, 0.1, and the like. In one embodiment, the mass ratio (mass of a structural unit derived from a polyisocyanate / mass of a structural unit derived from a hydroxyl group-containing (meth) acrylate) is desirably 0.1 to 15.

The mass ratio of the structural unit derived from the polyisocyanate to the structural unit derived from the hydroxyl group-containing (meth) acrylate in the polycarbonate urethane (meth) acrylate (the amount of the structural unit derived from the polyisocyanate The upper limit and lower limit of the physical amount / the physical amount derived from the hydroxyl-containing (meth) acrylate structural unit) are, for example, 2.5, 2.4, 2.0, 1.9, 1.5, 1.4, 1.0, 0.9, 0.5, 0.4, and the like. In one embodiment, the above-mentioned weight ratio (the weight of the structural unit derived from the polyisocyanate / the weight of the structural unit derived from the hydroxyl-containing (meth) acrylate) is preferably 0.4 to 2.5.

(Physical properties of polycarbonate urethane (meth) acrylate, etc.)

The upper limit and lower limit of the weight average molecular weight (Mw) of the polycarbonate urethane (meth) acrylate are, for example, 1.5 million, 1.25 million, 1 million, 750,000, 500,000, 250,000, 100,000, 5 Million, 10,000, 9000, 7500, 6000 and so on. In one embodiment, the weight average molecular weight (Mw) of the polycarbonate urethane (meth) acrylate is preferably 60 to 1.5 million.

The upper limit and lower limit of the number average molecular weight (Mn) of the polycarbonate urethane (meth) acrylate are, for example, 500,000, 400,000, 300,000, 250,000, 100,000, 50,000, 10,000, 9000 , 7500, 6000, 5000, 4500, etc. In one embodiment, the number average molecular weight (Mn) of the polycarbonate urethane (meth) acrylate is preferably from 4500 to 500,000.

The upper and lower limits of the molecular weight distribution (Mw / Mn) of the polycarbonate urethane (meth) acrylate are, for example, 2.1, 2.0, 1.9, 1.8, 1.7, and the like. In one embodiment, the molecular weight distribution (Mw / Mn) of the polycarbonate urethane (meth) acrylate is preferably 1.7 to 2.1.

The upper limit and the lower limit of the (meth) acryl group concentration of the polycarbonate urethane (meth) acrylate are, for example, 1.82 mmol / g, 1.8 mmol / g, 1.7 mmol / g, 1.5 mmol / g, 1.25mmol / g, 1.0mmol / g, 0.9mmol / g, 0.75mmol / g, 0.5mmol / g, 0.25mmol / g, 0.15mmol / g, 0.14mmol / g, etc. In one embodiment, the (meth) acrylfluorenyl group concentration of the polycarbonate urethane (meth) acrylate is preferably 0.14 mmol / g to 1.82 mmol / g.

The method for producing a polycarbonate urethane (meth) acrylate is not particularly limited as long as it is a method for reacting a polycarbonate polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. A method for producing a polycarbonate urethane (meth) acrylate, for example, a method of mixing a polycarbonate polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate; a method of mixing a polycarbonate A method for producing a polyol and a polyisocyanate by reacting them with a hydroxyl group-containing (meth) acrylate.

The upper and lower limits of the content of the polycarbonate urethane (meth) acrylate in the active energy ray-curable resin composition are, for example, 99.2% by mass, 99% by mass, 95% by mass, 90% by mass, and 85% by mass. %, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, etc. In one embodiment, the content of the polycarbonate urethane (meth) acrylate in the active energy ray-curable resin composition is preferably 40.0% to 99.2% by mass.

<Ultraviolet absorbent containing a triazine structure>

The ultraviolet absorber having a triazine structure is, for example, a compound represented by the following general formula (B1): B ¹ -B ² -OH. In the formula, B ¹ represents a 1,3,5-triazine ring, and B ² represents an aromatic ring.

The triazine structure-containing ultraviolet absorber represented by the general formula (B1) is, for example, a compound represented by the following general formula (B1-A): [Chem 4] ( ^Wherein R ^b1 to R ^b14 are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group, Aryloxy, -C (= O) OR ^ba , -NR ^bb R ^bc , -C (= O) NR ^bd R ^be, etc .; R ^ba ~ R ^be each independently are, for example, a hydrogen atom, a hydroxyl group, a carboxyl group, a substitution Or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, etc.).

Substituted alkyl, substituted aryl, substituted alkoxy, substituted aryloxy substituents such as hydroxy, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted Substituted alkoxy, -C (= O) OR ^{ba '} , -NR ^bb' R ^{bc '} , -C (= O) NR ^bd' R ^{be ',} and the like. R ^{ba ′} to R ^{be ′} are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and the like.

Triazine-containing ultraviolet absorbers, such as 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl -6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3, 5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy- 4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2 , 4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (1 -Isooctyloxycarbonylethoxy)]-1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3, 5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and the like.

Commercial products of the triazine-containing ultraviolet absorber are, for example, TINUVIN 400, 405, 460, 477, and 479 (the above are manufactured by BASF Japan Ltd.).

The upper limit and lower limit of the content of the ultraviolet absorber containing a triazine structure with respect to 100 parts by mass of the polycarbonate urethane (meth) acrylate are, for example, 15 parts by mass, 14 parts by mass, 10 parts by mass, 9 Parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, and the like. In one embodiment, the content of the ultraviolet absorber having a triazine structure is preferably 1.0 to 15.0 parts by mass relative to 100 parts by mass of the polycarbonate urethane (meth) acrylate.

The upper limit and lower limit of the content of the ultraviolet absorber containing a triazine structure in the active energy ray-curable resin composition are, for example, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, and 7% by mass. , 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.7 mass%, 0.5 mass%, etc. In one embodiment, the content of the ultraviolet absorber containing a triazine structure in the active energy ray-curable resin composition is preferably 0.5% by mass to 15.0% by mass.

<Light stabilizer with hindered amine structure>

In the present invention, a light stabilizer containing a hindered amine structure refers to a compound having a 2,2,6,6-tetramethylpiperidine skeleton.

A light stabilizer having a hindered amine structure, for example, a compound having one hindered amine structure, a compound having two hindered amine structures, a compound having three hindered amine structures, a compound having four hindered amine structures, and a hindered amine. Structure of polymers, etc.

A compound having a hindered amine structure, such as 4-ethoxymethyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl Piperidine, 4-propenyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenethylfluorenyloxy) -2,2,6,6-tetramethylpiperidine, 4 -Benzyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethyl Piperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylaminemethaneoxy) -2,2,6,6-tetramethylpiperidine, 4- (Cyclohexylamine formamyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylamineformamyloxy) -2,2,6,6-tetramethylpiperidine, etc. .

Compounds having two hindered amine structures, such as bis (2,2,6,6-tetramethyl-4-piperidine) carbonate, bis (2,2,6,6-tetramethyl-4-oxalate) Piperidine) ester, malonate bis (2,2,6,6-tetramethyl-4-piperidine) ester, sebacate bis (2,2,6,6-tetramethyl-4-piperidine) ) Ester, bis (2,2,6,6-tetramethyl-4-piperidine) adipate, bis (2,2,6,6-tetramethyl-4-piperidine) terephthalate) Ester, bis (1,2,2,6,6-pentamethyl-4-piperidine) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidine) oxalate, Bis (1,2,2,6,6-pentamethyl-4-piperidine) malonate, bis (1,2,2,6,6-pentamethyl-4-piperidine) sebacate Ester, bis (1,2,2,6,6-pentamethyl-4-piperidine) adipate, bis (1,2,2,6,6-pentamethyl-4-terephthalate) Piperidine) ester, N, N'-bis (2,2,6,6-tetramethyl-4-piperidine) -1,3-xylylenediamine, 1,2-bis (2,2, 6,6-tetramethyl-4-piperidinyloxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidinyloxy) p-xylene, bis (2, 2,6,6-tetramethyl-4-piperidine) toluene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidine) -hexamethylene -1,6-dicarbamate and the like.

Compounds having three hindered amine structures, such as tris (2,2,6,6-tetramethyl-4-piperidinyl) -benzene-1,3,5-tricarboxylic acid ester, tris (2,2 , 6,6-tetramethyl-4-piperidinyl) -benzene-1,3,4-tricarboxylic acid ester and the like.

Compounds with 4 hindered amine structures, such as N, N ', N ", N' ''-tetra (4,6-bis (butyl- (N-methyl-2,2,6,6-tetra Methylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine (N, N ', N ", N' '' -tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecane-1,10- diamine), tetra (2,2,6,6-tetramethyl-4-piperidinyl) -butane-1,2,3,4-tetracarboxylic acid ester, tetra (1,2,2,6, 6-pentamethyl-4-piperidinyl) -butane-1,2,3,4-tetracarboxylic acid ester and the like.

A polymer with a hindered amine structure, such as dibutylamine, 1,3,5-triazine or N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1 Polycondensate of 1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidinyl) butylamine, poly [{6- (1,1,3,3 -Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} Hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl) imine}], and 1,2,3,4-butanetetracarboxylic acid, 1,2,2 , 6,6-pentamethyl-4-piperidinol and β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5 ) Undecane] condensate of diethanol and the like.

Commercial products of light stabilizers containing hindered amine structures are, for example, Tinuvin 622, 123, 144 (the above are manufactured by BASF); ADK STAB ( ) LA-52, 57, 63P, 68, 72, 77Y, 77G, 81, 82, 87, 402AF, 502XP (the above are manufactured by ADEKA Corporation), etc.

The upper limit and lower limit of the content of the light stabilizer containing a hindered amine structure with respect to 100 parts by mass of the polycarbonate urethane (meth) acrylate are, for example, 2 parts by mass, 1.9 parts by mass, 1.5 parts by mass, 1.4 Parts by mass, 1 part by mass, 0.9 parts by mass, 0.5 parts by mass, 0.3 parts by mass, and the like. In one embodiment, the content of the light stabilizer containing a hindered amine structure is preferably 0.3 to 2.0 parts by mass relative to 100 parts by mass of the polycarbonate urethane (meth) acrylate.

The upper limit of the mass ratio of the triazine structure-containing ultraviolet absorber to the hindered amine structure-containing light stabilizer (the mass of the triazine structure-containing ultraviolet absorber / the hindered amine structure-containing light stabilizer) in the composition, and Lower limit, for example, 50, 49, 45, 44, 40, 39, 35, 34, 30, 29, 25, 24, 20, 19, 15, 14, 14, 10, 9, 5, 4, 1, 0.9, 0.5, etc. . In one embodiment, the mass ratio of the triazine structure-containing ultraviolet absorber to the hindered amine structure-containing light stabilizer in the above composition (the mass of the triazine structure-containing ultraviolet absorber / the hindered amine structure-containing light stability) The mass of the agent is preferably 0.5 to 50.

The upper and lower limits of the content of the light stabilizer containing a hindered amine structure in the active energy ray-curable resin composition are, for example, 30% by mass, 29% by mass, 27% by mass, 25% by mass, 23% by mass, and 20% by mass. , 19% by mass, 17% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0.9 Mass%, 0.7% by mass, 0.5% by mass, 0.4% by mass, 0.2% by mass, 0.1% by mass, 0.09% by mass, 0.05% by mass, 0.03% by mass, 0.02% by mass, 0.01% by mass, etc. In one embodiment, the content of the light stabilizer containing a hindered amine structure in the active energy ray-curable resin composition is preferably 0.01% by mass to 30.0% by mass.

<Photopolymerization initiator>

In one embodiment, the composition includes a photopolymerization initiator. The photopolymerization initiator may be contained in the composition alone or in combination of two or more.

The photopolymerization initiator is, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, and the like.

Photo-radical polymerization initiator, such as α-hydroxyalkylphenone, benzoin ether, substituted or unsubstituted alkyl phenone, substituted or unsubstituted benzil, substituted Or unsubstituted benzophenone, fluorenylphosphine oxide, oxime ester, substituted thioxanthone, intramolecular hydrogen abstraction type photopolymerization initiator, and the like.

α-Hydroxyalkyl benzophenone, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4 '-(2-hydroxyethoxy) -2-methyl Phenylacetone (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylacetone), 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl Propargyl) benzyl) phenyl) -2-methylpropan-1-one and the like.

The benzoin ether is, for example, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, and the like.

Substituted or unsubstituted alkyl phenones, such as acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl- 2- (p-toluenesulfonyloxy) acetophenone, benzoin, 2-benzyl-2- (dimethylamino) -4'-morpholinophenone, 2-methyl-4 ' -(Methylthio) -2-morpholinophenylacetone, 2-isonitrosophenylacetone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, and the like.

The substituted or unsubstituted benzophenone is, for example, benzophenone, p-anisyl, and the like.

Substituted or unsubstituted benzophenones, such as benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) diphenyl Methyl ketone, 4,4'-dichlorobenzophenone, 1,4-dibenzofluorenylbenzene, 2-benzylbenzoic acid, 4-benzylbenzoic acid, 2-benzylmethyl Methyl benzoate and so on.

Fluorenylphosphine oxide, such as 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine Oxides, etc.

Oxime esters, such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylideneoxime)], ethyl ketone, 1- [9-ethyl-6 -(2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) and the like.

The substituted thioxanthone is, for example, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthiazolone and the like.

Intramolecular hydrogen abstraction-type photopolymerization initiators, such as oxyphenyl acetic acid, 2- [2-oxo-2-phenylethoxyethoxy] ethyl ester, and oxyphenylacetic acid , A mixture of 2- (2-hydroxyethoxy) ethyl esters, methyl phenylglyoxylate, and the like.

The upper limit and lower limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the composition are, for example, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, and 2 parts by mass , 1 part by mass, 0 parts by mass, etc. In one embodiment, from the viewpoint of hardenability, the content of the photopolymerization initiator is desirably 0 to 10 parts by mass relative to 100 parts by mass of the composition.

The upper limit and lower limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the urethane (meth) acrylate are, for example, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, and 4 parts by mass , 3 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, and the like. In another embodiment, the content of the photopolymerization initiator is desirably 0 to 10 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate.

<Silicone resin>

In one embodiment, the composition includes a silicone resin. The silicone resin may be contained in the above composition alone or in combination of two or more.

The silicone resin is, for example, a polysiloxane-modified acrylic resin, a polyether-modified polydimethylsiloxane, a polyester-modified polydimethylsiloxane, or a polyether-modified silicone.

The upper limit and lower limit of the content of the silicone resin with respect to 100 parts by mass of the composition are, for example, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, and the like. In one embodiment, from the viewpoint of hardenability, the content of the silicone resin is desirably 0 to 5 parts by mass relative to 100 parts by mass of the above composition.

The upper limit and lower limit of the content of the silicone resin with respect to 100 parts by mass of the urethane (meth) acrylate are, for example, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass. In another embodiment, the content of the silicone resin is desirably 0 to 5 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate.

<Silicon dioxide>

In one embodiment, the composition includes silicon dioxide. Silicon dioxide may be contained in the above-mentioned composition alone or in combination of two or more.

The silica is, for example, dry silica, pulverized silica, fused silica, fumed silica, and the like.

The upper limit and lower limit of the content of silicon dioxide with respect to 100 parts by mass of the above composition are, for example, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, and the like. In one embodiment, from the viewpoint of hardenability, the content of silicon dioxide is desirably 0 to 20 parts by mass relative to 100 parts by mass of the above composition.

The upper limit and lower limit of the content of silicon dioxide with respect to 100 parts by mass of the urethane (meth) acrylate are, for example, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, and the like. In another embodiment, the content of silicon dioxide is preferably 0 to 20 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate.

<Diluted solvent>

In one embodiment, the composition includes a diluent solvent. The diluent solvent may be contained in the above-mentioned composition alone or in combination of two or more.

Diluent solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl Alcohol, diacetone alcohol, acetone acetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methylcellulose, ethylcellulose, 1 , 4-dioxane, propylene glycol methyl ether, ethylene glycol ether acetate, propylene glycol methyl ether acetate and the like.

The upper limit and lower limit of the content of the diluent solvent with respect to 100 parts by mass of the above composition are, for example, 80 parts by mass, 70 parts by mass, 60 parts by mass, 50 parts by mass, 40 parts by mass, 30 parts by mass, 20 parts by mass, 10 Parts by mass, 5 parts by mass, 1 part by mass, 0 parts by mass, and the like. In one embodiment, from the viewpoint of viscosity suitable for coating, the content of the diluent solvent is preferably about 0 to 80 parts by mass relative to 100 parts by mass of the composition.

The upper limit and lower limit of the content of the dilution solvent with respect to 100 parts by mass of the urethane (meth) acrylate are, for example, 70 parts by mass, 60 parts by mass, 50 parts by mass, 40 parts by mass, 30 parts by mass, 20 Parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, 0 parts by mass, and the like. In another embodiment, the content of the diluting solvent is preferably about 0 to 70 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate.

<Additives>

The above composition may contain polycarbonate urethane (meth) acrylate, a UV absorber containing a triazine structure, a light stabilizer containing a hindered amine structure, a photopolymerization initiator, a silicone resin, Reagents other than silica and diluent are used as additives. The additives may be contained in the above-mentioned composition alone or in combination of two or more.

The additives include, for example, a hardening aid, a defoaming agent, a surface conditioner, an antifouling agent, an inorganic filler, a pigment, an antistatic agent, and a metal oxide fine particle dispersion.

In one embodiment, the content of the additive is, for example, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc., relative to 100 parts by mass of the composition. .

In another embodiment, the content of the additive is, for example, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, and less than 100 parts by mass of the polycarbonate urethane (meth) acrylate. 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, and the like.

The active energy ray-curable resin composition can be obtained by mixing the following components: a polycarbonate urethane (meth) acrylate; a UV absorber containing a triazine structure; and a light stabilizer containing a hindered amine structure. ; And photopolymerization initiators, silicone resins, silicon dioxide, diluent solvents, and / or additives as needed. The mixing means and mixing order are not particularly limited.

The said composition can also be used suitably as an active-energy-ray-curable resin composition for coating, and a coating agent.

[Hardened matter]

The present invention provides a cured product of the active energy ray-curable resin composition. The cured product can be obtained by a method including a step of irradiating the composition with active energy rays such as ultraviolet rays, electron beams, and radiation.

The ultraviolet light source is, for example, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or an LED lamp. The amount of ultraviolet rays can be appropriately adjusted according to the thickness of the cured product. In addition, the light quantity, light source configuration, and conveyance speed can be adjusted as required. For example, when using a high-pressure mercury lamp, it is ideal for a lamp with a lamp output of about 80 ~ 160W / cm to be about 5 ~ 50m / min. The conveying speed hardens it. On the other hand, in the case of an electron beam, an electron beam acceleration device having an acceleration voltage of about 10 to 300 kV is preferably hardened at a conveying speed of about 5 to 50 m / min.

[Film]

The present invention provides a film including the cured product. In one embodiment, the thin film is an article including the hardened material and various base films as constituent elements.

As the base film (base material), various conventional base films (base materials) can be used. Base film, for example, polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, cellulose triacetate film , ABS film, AS film, norbornene resin film, cycloolefin film, polyvinyl alcohol film, etc. The thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.

The above-mentioned film can be produced by various conventional methods. A method for producing a thin film is, for example, a method of applying the active energy ray-curable resin composition to at least one surface of the base film, drying the base film as necessary, and then irradiating the active energy ray. In addition, a laminated film can also be produced by coating the non-coated surface of the obtained base film with the resin composition provided in this embodiment, bonding another base film thereon, and then irradiating active energy rays.

Coating methods such as bar coater coating, wire bar coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, lithography, flexographic printing Flexo printing, screen printing, etc.

The coating amount is not particularly limited, but the mass after drying is preferably about 0.1 to 30 g / m ² , and more preferably 1 to 20 g / m ² .

[Example]

Hereinafter, the present invention will be specifically described using examples and comparative examples. However, the descriptions in the above-mentioned ideal implementation modes and the following examples are provided for the purpose of example only, and not for the purpose of limiting the invention. Therefore, the scope of the present invention is not limited to the implementation modes specifically described in this specification, nor is it limited to the embodiments specifically described in this specification. The scope of the present invention is limited only by the scope of patent application. In addition, unless otherwise stated, in each Example and a comparative example, numerical values, such as a part and%, are mass standards.

<Synthesis Example 1> (Synthesis of polycarbonate urethane (meth) acrylate)

A three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 10.4 parts of hydrogenated xylylene diisocyanate (hereinafter referred to as H-XDI) and 53.4 parts of polycarbonate diol (trade name "ETERNACOLL" "PH-200" (manufactured by Ube Kosan Co., Ltd.) (hereinafter referred to as PH-200), 30.0 parts of methyl isobutyl ketone, and 0.01 parts of tin octoate were reacted at 80 ° C. When the residual isocyanate group reaches 2.4%, 6.2 parts of hydroxyethyl acrylate (hereinafter referred to as HEA), 0.01 part of tin octoate, and 0.07 part of hydroquinone monomethyl ether are added for reaction until the isocyanate group remains When it is 0.1% or less, a solution (A-1) containing a polycarbonate urethane (meth) acrylate having a resin content of 70% is obtained.

<Synthesis example 2 to synthesis example 5>

Hereinafter, based on the raw materials and compounding amounts in Table 1, synthesis of urethane (meth) acrylate was performed in the same manner as in Synthesis Example 1.

【Table 1】

H-XDI: hydrogenated xylylene diisocyanate

IPDI: isophorone diisocyanate

4-HBA: 4-hydroxybutyl acrylate

T6002: Polycarbonate glycol "DURANOLT6002" manufactured by Asahi Kasei Corporation

PTMG2000: Mitsubishi Chemical Corporation, polyether polyol

PLACCELL220AL: Polycaprolactone polyol manufactured by Daicel Corporation

<Example 1>

66.7 parts of the solution containing a polycarbonate urethane (meth) acrylate obtained in Synthesis Example 1, 1.4 parts of a triazine structure-containing ultraviolet absorber TINUVIN400 (manufactured by BASF), and 0.5 parts of a light containing a hindered amine structure Stabilizer TINUVIN123 (manufactured by BASF), 0.05 parts of polyether-modified dimethylpolysiloxane BYK-333 (manufactured by BYK Additives & Instruments), 1.4 parts of photopolymerization initiator Irgacure907 (manufactured by BASF, hereinafter referred to as Irg.907) ), 30.0 parts of methyl ethyl ketone (hereinafter referred to as MEK), stir, then mix 2.5 parts of silicon dioxide ACEMATT 3300 (manufactured by EVONIK) and 5 parts of methyl ethyl ketone, and use a homomixer to homogenize the dispersion Thus, an active energy ray-curable resin composition having a solid content of 50% was obtained.

<Example 2 to Example 5, Comparative Example 1 to Comparative Example 9>

Hereinafter, in the same manner as in Example 1, the active energy ray-curable resin composition was prepared by diluting with MEK so that the total solid content was 50% according to the mixing ratio in the following table. In addition, the value of (A) component in a table | surface is a value as a solution (70% of solid content).

(A) Ingredient: Polyurethane (meth) acrylate

(B) Ingredient: UV absorber containing triazine structure

(C) Ingredient: Light stabilizer with hindered amine structure

(D) component: Photopolymerization initiator

TINUVIN 479: UV absorber with triazine structure made by BASF

DAINSORB T-53: benzotriazole UV absorber manufactured by Daiwa Chemical Co., Ltd.

SEESORB 712: Made by Shiplow Chemical Co., Ltd., benzophenone-based UV absorber

ADK STABLA-52: Light stabilizer with hindered amine structure, manufactured by Aidike Co., Ltd.

ADK STABAO-60: Antioxidant with hindered phenol structure, manufactured by Aidike Co., Ltd.

ADK STABPEP-36: manufactured by Idecco Co., Ltd., phosphite-based antioxidant

<Preparation of hardened material>

Using a bar coater No. 20, the active energy ray-curable resin compositions of the examples and comparative examples were manually coated on an easily adhered polyethylene terephthalate film so that the dry film thickness was 15 μm; After it was dried at 80 ° C. for 1 minute, it was irradiated with a high-pressure mercury lamp (120W, 1 lamp) at a cumulative irradiation amount of 300 mJ / cm ² to make a cured product, and the following evaluations were performed.

<Evaluation of Touch>

The tactile sensation was evaluated by the sensation of touching the surface of the hardened body with the hand. Those who feel soft are good; those who feel hard and tack on the plastic surface are not suitable.

<Evaluation of acid resistance>

On the surface of the hardened material, a droplet having a diameter of about 10 mm was prepared with a 0.1 N sulfuric acid aqueous solution, the droplet was covered with a glass container, and left at 20 ° C. After 24 hours, the surface of the cured film was rinsed with water, and the presence of droplets was visually confirmed. If there are no traces of droplets, it is ○, and if traces of droplets can be confirmed, it is X.

<Evaluation of Alkali Resistance>

On the surface of the hardened material, a droplet having a diameter of about 10 mm was prepared with a 0.1 N aqueous sodium hydroxide solution, the droplet was covered with a glass container, and left at 20 ° C. After 24 hours, the surface of the cured film was rinsed with water, and the presence of droplets was visually confirmed. If there are no traces of droplets, it is ○, and if traces of droplets can be confirmed, it is X.

<Evaluation of light resistance>

The yellowing degree (yellowing degree) ΔYI and adhesion after irradiating the hardened product with a metal halide lamp (illumination 55 mJ / cm ² , manufactured by Iwasaki Electric Co., Ltd.) for 96 hours were evaluated. The degree of yellowing ΔYI was measured using a color difference meter (trade name: ZE 6000 manufactured by Nippon Denshoku Industries Co., Ltd.). For the adhesion, a peel test was performed using a cellophane tape using the following method.

<Adhesion: Peel Test>

A cross-cut test was performed based on JIS-K-5400. Introduce 100-grid 1mm square cuts on the surface of the produced hardened product, and stick cellophane tape (NICHIBAN Co., Ltd., trade name: LpackLP-24); tear off from the hardened product instantly In the case of the cellophane tape, the case where the cured film was not adhered to the cellophane tape side and the cured film remained on the substrate side was marked as ○, and the case where peeling was confirmed was marked as ×.

The evaluation results of the examples and comparative examples are shown in the following table.

Claims (4)

    An active energy ray-curable resin composition, characterized in that the active energy ray-curable resin composition contains 1.0 to 15.0 parts by mass of 100 parts by mass of a polycarbonate urethane (meth) acrylate. A triazine structure-containing ultraviolet absorber and 0.3 to 2.0 parts by mass of a hindered amine structure-containing light stabilizer.         The active energy ray-curable resin composition according to item 1 of the scope of application, wherein the polycarbonate urethane (meth) acrylate is a polycarbonate diol, an alicyclic diisocyanate, and Reaction product of a hydroxyl-containing (meth) acrylate.         A hardened product characterized in that it is a hardened product of an active energy ray-curable resin composition as described in the first or second scope of the patent application.         A thin film comprising a hardened material as described in item 3 of the patent application scope.