TWI702240B - Urethane (meth)acrylate resin and laminated film - Google Patents

Abstract

The subject of the present invention is to provide a urethane (meth)acrylate resin having excellent properties such as scratch resistance, curl resistance, flexibility, and impact resistance in a cured coating film, and a curable composition containing it Object and its hardened material, and laminated film. Specifically, by using polyisocyanate compound (A) and di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials, urethane (meth)acrylate resin contains the curing The sexual composition, its cured product, and laminated film solve the aforementioned problems.

Description

Urethane (meth)acrylate resin and laminated film

The present invention relates to a urethane (meth)acrylate resin with excellent properties such as scratch resistance, curl resistance, flexibility, and impact resistance in a cured coating film, a curable composition containing it, and The hardened material and laminated film.

Plastic films made of polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc., are mostly used for polarizing plate protective films incorporated into flat panel displays and Industrial applications such as surface protection films for touch panels. These plastic films, when they are alone, are vulnerable to surface damage, have low workability and are prone to cracks and cracks. Therefore, a coating composed of active energy ray-curable resin is usually provided on the surface to compensate for this. Use it for performance.

As for the coating agent for reinforcing plastic film, it is known that, for example, it contains polyurethane polycarbonate obtained by reacting isophorone diisocyanate, neopentyl erythritol diacrylate, and neopentyl erythritol triacrylate. Acrylate active energy ray-curable coating composition (refer to Patent Document 1), and urethane acrylic acid obtained by reacting an aliphatic diisocyanate with an acrylate having a hydroxyl value of 173 mgKOH/g of neopentaerythritol An ultraviolet curable composition of ester (see Patent Document 2) and the like. These paints are Although it is excellent in damage properties, the toughness and flexibility of the coating film are not sufficient, and it is easy to cause cracks due to external impact.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2011-144309

Patent Document 2: Japanese Patent Application Publication No. 2015-021089

In view of the above-mentioned actual situation, the problem to be solved by the present invention is to provide a urethane (meth)acrylic acid with excellent properties such as scratch resistance, curl resistance, flexibility, and impact resistance in the cured coating film. Ester resin, curable composition containing it and its cured product, and laminated film.

In order to solve the above-mentioned problems, the inventors have conducted in-depth investigations and found that by using a di(meth)acrylate dihydroxy ester compound as a reaction raw material for a urethane (meth)acrylate resin, the above-mentioned problem can be solved. Problem, and completed the present invention.

That is, the present invention relates to a urethane (meth)acrylate resin, which uses a polyisocyanate compound (A) and a di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials.

The present invention further relates to a curable composition containing the aforementioned urethane (meth)acrylate resin and a photopolymerization initiator.

The present invention further relates to a kind of the aforementioned curable composition Hardened object.

The present invention further relates to a laminated film having a layer composed of the aforementioned cured product and another plastic film layer.

According to the present invention, it is possible to provide a urethane (meth)acrylate resin with excellent properties such as scratch resistance, curl resistance, flexibility, and impact resistance in a cured coating film, and curability containing it. The composition, its cured product, and laminated film. The curable composition containing the urethane (meth)acrylate resin of the present invention can be suitably used as a reinforcing coating agent for various plastic films. In addition, the laminated film obtained by using the curable composition of the present invention has excellent scratch resistance and curl resistance, and has high flexibility and is not prone to cracks during bending or winding. In addition, when there is a drop on the film It also has impact resistance that is not easy to break when falling objects.

[The form of implementing the invention]

The urethane (meth)acrylate resin of the present invention uses a polyisocyanate compound (A) and a di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials.

If the aforementioned polyisocyanate compound (A) is a compound having a plurality of isocyanate groups in the molecular structure, the detailed structure is not particularly limited, and any one of various compounds may be used. Among them, as the polyisocyanate compound (A) that can be particularly preferably used in the present invention, exemplified by The following five polyisocyanate compounds (A).

1. Aliphatic polyisocyanate compound (A1)

2. The polyisocyanate compound (A2) represented by any of the following structural formulas (A2-1) or (A2-2)

(In the formula, R ^{1 is} each independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and m is 0 or an integer of 1 to 4. R ^{2 is} each independently a hydrogen atom and 1 to 4 carbon atoms Any of the alkyl groups.)

3. The polyisocyanate compound (A3) represented by any of the following structural formulas (A3-1) ~ (A3-4)

(In the formula, R ^{3 is} each independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and n is 0 or an integer of 1 to 4. R ^{4 is} each independently a hydrogen atom, and each having 1 to 4 carbon atoms Any of the alkyl groups.)

4. Polyisocyanate compound having an isocyanurate ring structure in the molecular structure (A4)

5. Polyisocyanates with urethane bonding sites in the molecular structure Ester compound (A5)

When the aforementioned polyisocyanate compound (A) is any one of the aforementioned polyisocyanate compounds (A1) to (A5), the preferred form of the urethane (meth)acrylate resin of the present invention will be described in detail below .

A description will be given when the aforementioned polyisocyanate compound (A) is the aforementioned aliphatic polyisocyanate compound (A1). The urethane (meth)acrylate resin of the present invention in this situation is called urethane (meth)acrylate resin (1).

The aliphatic polyisocyanate compound (A1) includes, for example, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, etc. These may be used alone, or two or more of them may be used in combination.

The aforementioned di(meth)acrylate dihydroxy ester compound (B) includes, for example, the di(meth)acrylate (B1) of a diglycidyl ether compound or the di(meth)acrylate (B2) of a tetraol compound ).

The di(meth)acrylate (B1) of the aforementioned diglycidyl ether compound includes: reacting the diglycidyl ether of various diol compounds with (meth)acrylic acid or its derivatives to form (meth)acrylate Chemical compound. The aforementioned diol compounds include, for example, aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, neopentyl glycol, and hexanediol; hydroquinone, 2-methylhydroquinone, and benzenedimethanol , Biphenyldiol, biphenyldimethanol, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthalenediol, naphthalene dimethanol and other diols containing aromatic rings; by the aforementioned aliphatic or aromatic Cyclic diol, and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl Polyether modified glycol obtained by ring-opening polymerization of various cyclic ether compounds such as glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; by the aforementioned aliphatic or aromatic Cyclic diols, lactone modified diols obtained by polycondensation of lactone compounds such as ε-caprolactone; make malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and other aliphatic Dicarboxylic acid or phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, phthalic acid and other aromatic dicarboxylic acids or these anhydrides, etc., and the aforementioned aliphatic or aromatic ring-containing dicarboxylic acids Polyester diol obtained by alcohol reaction.

The di(meth)acrylate (B2) of the aforementioned tetraol compound includes, for example, methanetetraol, 1,1,2,2-ethanetetraol, 1,1,3,3-propanetetraol, 1 ,2,3,4-butanetetraol, 1,1,4,4-butanetetraol, neopentylerythritol, 1,1,5,5-pentaerythritol, pentane-1,2, 4,5-tetraol, 1,2,5,6-hexanetetraol, 1,1,6,6-hexanetetraol, 2,2-bis(hydroxymethyl)-1,4-butanedi Di(meth)acrylate of aliphatic tetraol compound such as alcohol. The di(meth)acrylate dihydroxy ester compound (B) may be used independently, respectively, and may use 2 or more types together.

When the aforementioned polyisocyanate compound (A) is the aforementioned aliphatic polyisocyanate compound (A1), it is based on the need to be a urethane (meth)acrylate with excellent curl resistance, flexibility, and impact resistance in the cured product The resin (1) and the di(meth)acrylate dihydroxy ester compound (B) are preferably the di(meth)acrylate (B2) of the aforementioned tetraol compound. Moreover, it is preferable to use the (meth)acrylate (β) of a tetraol compound as a reaction raw material of the di(meth)acrylate (B2) containing the said tetraol compound. That is, the aforementioned urethane (meth)acrylate resin (1) is preferably made of the aforementioned aliphatic poly The isocyanate compound (A1) and the (meth)acrylate (β) of the tetraol compound are the necessary raw materials for the reaction, and the (meth)acrylate (β) of the tetraol compound is based on the bis(meth)acrylate (β) of the tetraol compound (B2) as an essential component.

The tetraol compound which is the raw material of the (meth)acrylate (β) of the aforementioned tetraol compound includes, for example, methanetetraol, 1,1,2,2-ethanetetraol, 1,1,3,3- Propanetetraol, 1,2,3,4-butanetetraol, 1,1,4,4-butanetetraol, neopentaerythritol, 1,1,5,5-pentaerythritol, pentane -1,2,4,5-tetraol, 1,2,5,6-hexanetetraol, 1,1,6,6-hexanetetraol, 2,2-bis(hydroxymethyl)-1 , 4-Butanediol and so on. These may be used alone, or two or more of them may be used in combination.

The (meth)acrylate (β) of the aforementioned tetraol compound may be the di(meth)acrylate (B2) of the tetraol compound alone, or the di(meth)acrylate (B2) of the tetraol compound ) A composition with mono(meth)acrylate, tri(meth)acrylate, or tetra(meth)acrylate of a tetraol compound. Among them, the urethane (meth)acrylate resin (1) that is to be excellent in curl resistance, flexibility, and impact resistance in the cured product is preferably a (meth)acrylate of a tetraol compound 25 mol% or more in (β) is di(meth)acrylate (B2).

Based on the need to become a urethane (meth)acrylate resin (1) with excellent curl resistance, flexibility, and impact resistance in the cured product, the (meth)acrylate (β) of the aforementioned tetraol compound The hydroxyl value is preferably in the range of 150 to 500 mgKOH/g, more preferably in the range of 180 to 500 mgKOH/g, further preferably in the range of 190 to 500 mgKOH/g, particularly preferably in the range of 210 to 500 mgKOH/g.

The aforementioned urethane (meth)acrylate resin (1) is based on The aforementioned aliphatic polyisocyanate compound (A1) and di(meth)acrylate dihydroxy ester compound (B) are necessary reaction materials, but other reaction materials other than these may be further used. The aforementioned other reaction raw materials, specifically, include: other polyisocyanate compounds (A1') other than the aforementioned aliphatic polyisocyanate compound (A1), (meth)acrylic monohydroxy ester compound (C), and the aforementioned two ( Other polyol compounds (D) and the like other than the dihydroxy meth)acrylate compound (B).

The aforementioned other polyisocyanate compounds (A1') include, for example, isocyanurate-modified products, biuret-modified products, and allophanate-modified products of the aforementioned aliphatic polyisocyanate compound (A1), and Examples include: isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other alicyclic diisocyanate compounds; toluene diisocyanate, xylylene diisocyanate, tetramethyl Aromatic diisocyanate compounds such as xylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1) ; These isocyanurate modified products, biuret modified products, allophanate modified products, etc. These may be used alone, or two or more of them may be used in combination.

[In the formula, R ^{5 is} each independently any one of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms. R ^{6 is} each independently an alkyl group having 1 to 4 carbon atoms or a bonding point to the structural part represented by the structural formula (1) via a methylene group marked with *. m is 0 or an integer of 1 to 3, and n is an integer of 1 or more. ]

When the aforementioned other polyisocyanate compound (A1') is used, in order to fully exhibit the effects of the present invention, the aforementioned aliphatic polyisocyanate compound (A1) has a difference with respect to the aforementioned aliphatic polyisocyanate compound (A1) and the aforementioned other polyisocyanate The ratio of the total mass of the compound (A1′) is preferably 50% by mass or more, and more preferably 80% by mass or more.

The aforementioned (meth)acrylate monohydroxy ester compound (C) includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxy (meth)acrylate Butyl ester, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylerythritol tri(meth)acrylate, dineopentylerythritol penta(meth)acrylate And other aliphatic (meth)acrylate compounds; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, (Meth)acrylate compounds containing aromatic rings, such as 3-hydroxy-4-acetylphenyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate; by the aforementioned (meth)acrylate compound , And various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc. Polyether modified (meth)acrylate compound obtained by ring-opening polymerization; lactone modified (former) obtained by polycondensation of the aforementioned (meth)acrylate compound with lactone compounds such as ε-caprolactone Base) acrylic Ester compounds, etc. These may be used alone, or two or more of them may be used in combination. Among them, the urethane (meth)acrylate resin (1) is preferably an aliphatic (meth)acrylate compound or its polyether modified resin (1) based on the flexibility and impact resistance of the cured product. Properties, modified lactones. Furthermore, in order to become a urethane (meth)acrylate resin (1) with excellent curability and high surface hardness of a cured coating film, it is preferable that it is a trifunctional or more (meth)acrylate compound.

The aforementioned other polyol compound (D) includes, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl -1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, neopentylerythritol, Polyol monomers such as dineopentaerythritol; through the aforementioned polyol monomers, and succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, Obtained by the co-condensation of dicarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid The polyester polyol; the lactone type obtained by the polycondensation reaction of the aforementioned polyol monomer and various lactones such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone, etc. Polyester polyol; polyether obtained by ring-opening polymerization of the aforementioned polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether Polyols, etc. These polyol compounds may be used alone, respectively, or two or more types may be used in combination.

The method for producing the aforementioned urethane (meth)acrylate resin (1) includes, for example, combining the aforementioned aliphatic polyisocyanate compound (A1) and di(meth)acrylate dihydroxy ester compound (B) to The aforementioned aliphatic poly The molar ratio [(NCO)/(OH)] of the isocyanate group possessed by the isocyanate compound (A1) and the hydroxyl group possessed by the di(meth)acrylate dihydroxy ester compound (B) is 1/0.95~1/1.05 Use the ratio of the range and perform the method in the temperature range of 20~120℃. A well-known and customary urethane catalyst may be used as needed.

In addition, when the aforementioned aliphatic polyisocyanate compound (A1) and di(meth)acrylate dihydroxy ester compound (B) are used together, the aforementioned other polyisocyanate compound (A1') and the aforementioned (meth)acrylate monohydroxy ester When the compound (C) and the aforementioned other polyol compound (D) are reacted, it may be a method of reacting the raw materials at once, or the polyisocyanate component and the polyol component may be reacted to obtain an intermediate product, and then A method of reacting the monool component, and a method of first reacting the polyisocyanate component and the monool component to obtain an intermediate product, and then reacting the polyol component. The reaction ratio of each component is preferably such a ratio that the total molar ratio [(NCO)/(OH)] of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1/0.95 to 1/1.05 .

To become a urethane (meth)acrylate resin with excellent curability and high hardness on the surface of the cured coating film, the urethane (meth)acrylate resin obtained in this way (1) The (meth)acrylic acid equivalent is preferably in the range of 100 to 500 g/eq, more preferably in the range of 100 to 300 g/eq. In addition, in the present invention, the (meth)acrylic equivalent of the urethane (meth)acrylate resin is a value calculated from the reaction raw material as a theoretical value.

In addition, based on the need to become a urethane (meth)acrylate resin with an excellent balance of properties in the cured product, the aforementioned urethane ( The weight average molecular weight (Mw) of the meth)acrylate resin (1) is preferably in the range of 2,000 to 60,000, and more preferably in the range of 2,000 to 30,000.

Furthermore, in the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Co., Ltd.

Column: TSK- manufactured by Tosoh Co., Ltd.

GUARDCOLUMN SuperHZ-L+Tosoh Co., Ltd. TSK-GEL SuperHZM-M×4

Detector: RI (differential refractometer)

Data processing: Multi Station GPC-8020modelII manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40℃, solvent tetrahydrofuran flow rate 0.35ml/min

Standard: Monodisperse Polystyrene

Sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content is filtered with a microfilter (100μl)

The case where the aforementioned polyisocyanate compound (A) is a polyisocyanate compound (A2) represented by either of the following structural formulas (A2-1) or (A2-2) will be described. The urethane (meth)acrylate resin of the present invention at this time is referred to as urethane (meth)acrylate resin (2).

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, and m is 0 or an integer of 1 to 4. R ^{2 is} each independently a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.)

In the aforementioned structural formula (A2-1) or (A2-2), R ¹ is any one of an alkyl group having 1 to 4 carbon atoms, and m is 0 or an integer of 1 to 4. In addition, R ^{2 is} each independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Among them, in order to be a urethane (meth)acrylate resin (2) excellent in the balance of surface hardness, flexibility, and impact resistance of the cured coating film, it is preferable that m is 0 and all R ² is a hydrogen atom. In addition, the bonding position of the isocyanate group in the structural formula (A2-1) or (A2-2) is preferably 4,4'-position.

The aforementioned di(meth)acrylate dihydroxy ester compound (B) includes, for example, the di(meth)acrylate (B1) of a diglycidyl ether compound and the di(meth)acrylate (B2) of a tetraol compound ). Specific examples of these compounds are the same as the various compounds exemplified in the description about the urethane (meth)acrylate resin (1). The di(meth)acrylate dihydroxy ester compound (B) may be used independently, respectively, and may use 2 or more types together. Among them, based on the urethane (meth)acrylate resin (2) that is to be excellent in curl resistance, flexibility, and impact resistance in the cured product, an aliphatic diol diglycidyl ether compound is preferred. Di(meth)acrylate or di(meth)acrylate of aliphatic tetraol compound.

In the aforementioned urethane (meth)acrylate resin (2), the di(meth)acrylate (B2) of a tetraol compound is used as the aforementioned di( For the dihydroxy meth)acrylate compound (B), the (meth)acrylate (β) of the tetraol compound can also be used as the reaction material of the di(meth)acrylate (B2) containing the tetraol compound . The (meth)acrylate (β) of the tetraol compound is the same as that described in the description of the urethane (meth)acrylate resin (1).

The aforementioned urethane (meth)acrylate resin (2) uses the aforementioned polyisocyanate compound (A2) and di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials, but it can also be used further Reaction raw materials other than these. The aforementioned other reaction materials, specifically, include: other polyisocyanate compounds (A2') other than the aforementioned polyisocyanate compound (A2), (meth)acrylic monohydroxy ester compound (C), and the aforementioned di(meth)acrylic acid Polyol compounds (D) other than the dihydroxy ester compound (B), etc.

The aforementioned other polyisocyanate compound (A2') includes, for example, an isocyanurate-modified product, a biuret-modified product, and a allophanate-modified product of the aforementioned polyisocyanate compound (A2), in addition to : Aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. ; Alicyclic diisocyanate compounds such as isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate; toluene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5- Aromatic diisocyanate compounds such as naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the aforementioned structural formula (1); these isocyanurate modified products and biuret modified Properties, modified allophanate, etc. These can be separated Used alone or in combination of two or more kinds.

When the aforementioned other polyisocyanate compound (A2') is used, in order to fully exhibit the effects of the present invention, the aforementioned polyisocyanate compound (A2) is relative to the aforementioned polyisocyanate compound (A2) and the aforementioned other polyisocyanate compound (A2') The ratio of the total mass is preferably 50% by mass or more, more preferably 80% by mass or more.

The aforementioned (meth)acrylate monohydroxy ester compound (C) and the aforementioned other polyol compound (D) include those exemplified in the description of the aforementioned urethane (meth)acrylate resin (1) All compounds are the same.

The aforementioned urethane (meth)acrylate resin (2) can be produced by the same method as the aforementioned urethane (meth)acrylate resin (1).

To become a urethane (meth)acrylate resin with excellent curability and high hardness on the surface of the cured coating film, the urethane (meth)acrylate resin obtained in this way (2) The equivalent weight of the (meth)acrylic acid group is preferably in the range of 100 to 500 g/eq, more preferably in the range of 100 to 300 g/eq.

The weight average molecular weight (Mw) of the aforementioned urethane (meth)acrylate resin (2) is higher than the weight average molecular weight (Mw) of the urethane (meth)acrylate resin to be an excellent balance of properties in the cured product. Preferably, it is in the range of 2,000 to 60,000, more preferably in the range of 2,000 to 30,000.

The situation where the aforementioned polyisocyanate compound (A) is a polyisocyanate compound (A3) represented by any one of the following structural formulas (A3-1) to (A3-4) will be described. In this situation, the carbamate of the present invention (A Base) acrylate resin, called urethane (meth)acrylate resin (3).

(In the formula, R ^{3 is} each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 or an integer of 1 to 4. R ^{4 is} each independently any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms .).

In the aforementioned structural formulas (A3-1) to (A3-4), R ^{3 is} each independently any one of an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 4. In addition, R ^{4 is} each independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Among them, in order to be the urethane (meth)acrylate resin (3) that is excellent in the balance of surface hardness, flexibility, and impact resistance of the cured coating film, it is preferable that n is 0 and all R ⁴ is a hydrogen atom. In addition, the polyisocyanate compound (A3) is preferably a compound represented by any one of (A3-1) to (A3-3).

The aforementioned di(meth)acrylate dihydroxy ester compound (B) includes, for example, the di(meth)acrylate (B1) of a diglycidyl ether compound and the di(meth)acrylate (B2) of a tetraol compound ). Specific examples of these compounds are the same as the various compounds exemplified in the description about the urethane (meth)acrylate resin (1). Bis(methyl) The dihydroxy acrylate compound (B) may be used individually, respectively, and may use 2 or more types together. Among them, the urethane (meth)acrylate resin (3) is preferably an aliphatic diol diglycidyl ether compound based on the urethane (meth)acrylate resin (3) having excellent curl resistance, flexibility, and impact resistance in the cured product. Di(meth)acrylate or di(meth)acrylate of aliphatic tetraol compound.

When the di(meth)acrylate (B2) of the tetraol compound is used as the dihydroxy di(meth)acrylate compound (B) in the aforementioned urethane (meth)acrylate resin (3) In other words, the (meth)acrylate (β) of the tetraol compound can also be used as a reaction material of the di(meth)acrylate (B2) containing the tetraol compound. The (meth)acrylate (β) of the tetraol compound is the same as that described in the description of the aforementioned urethane (meth)acrylate resin (1).

The aforementioned urethane (meth)acrylate resin (3) is based on the aforementioned polyisocyanate compound (A3) and di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials, but it can be further Use reaction materials other than these. The aforementioned other reaction raw materials, specifically, include: other polyisocyanate compounds (A3') other than the aforementioned polyisocyanate compound (A3), (meth)acrylic acid monohydroxy ester compound (C), and the aforementioned bis(methyl) Polyol compounds (D) other than the dihydroxy acrylate compound (B), etc.

The aforementioned other polyisocyanate compound (A3') includes, for example, an isocyanurate-modified product, a biuret-modified product, and a allophanate-modified product of the aforementioned polyisocyanate compound (A3), in addition to : Butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and other aliphatic diisocyanates Isocyanate compounds; alicyclic diisocyanate compounds such as hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; having the repetition shown in the aforementioned structural formula (1) Structure polymethylene polyphenyl polyisocyanate; these isocyanurate modified products, biuret modified products, allophanate modified products, etc. These may be used alone, or two or more of them may be used in combination.

When the aforementioned other polyisocyanate compound (A3') is used, the aforementioned polyisocyanate compound (A3) is relative to the aforementioned polyisocyanate compound (A3) and the aforementioned other polyisocyanate compound (A3') in order to fully exhibit the effects of the present invention. The ratio of the total mass is preferably 50% by mass or more, more preferably 80% by mass or more.

The aforementioned (meth)acrylate monohydroxy ester compound (C) and the aforementioned other polyol compound (D) include various examples exemplified in the description of the aforementioned urethane (meth)acrylate resin (1) The same compound.

The aforementioned urethane (meth)acrylate resin (3) can be produced by the same method as the aforementioned urethane (meth)acrylate resin (1).

To become a urethane (meth)acrylate resin with excellent curability and high hardness on the surface of the cured coating film, the urethane (meth)acrylate resin obtained in this way (3) The equivalent weight of the (meth)acrylic acid group is preferably in the range of 100 to 500 g/eq, more preferably in the range of 100 to 300 g/eq.

Based on the need to be a urethane (meth)acrylate resin with an excellent balance of properties in the cured product, the aforementioned urethane (meth) The weight average molecular weight (Mw) of the acrylic resin (3) is preferably in the range of 2,000 to 60,000, and more preferably in the range of 2,000 to 30,000.

The case where the aforementioned polyisocyanate compound (A) is a polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure will be described. The urethane (meth)acrylate resin of the present invention in this situation is referred to as urethane (meth)acrylate resin (4).

The aforementioned polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure includes, for example, various diisocyanate monomers or polymethylene having a repeating structure represented by the aforementioned structural formula (1) The polyphenyl polyisocyanate compound is obtained by modifying isocyanurate in the presence of monool or diol. The aforementioned diisocyanate monomers include, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliphatic diisocyanate monomers such as diisocyanate; isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other alicyclic diisocyanate monomers; toluene diisocyanate, Aromatic diisocyanate monomers such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc. These may be used alone, or two or more of them may be used in combination.

In addition, the aforementioned monoalcohols include: hexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n- Stearyl alcohol, n-nonadecanol, etc. Furthermore, glycols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanedi Alcohol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. These monoalcohols and diols may be used alone, respectively, or two or more of them may be used in combination.

The aforementioned polyisocyanate compound (A4) having an isocyanurate ring structure in its molecular structure may be used alone, or two or more of them may be used in combination. Among them, based on the urethane (meth)acrylate resin (4) that is to be an excellent balance of various properties in the cured product, isocyanuric acid which is an aliphatic or alicyclic diisocyanate monomer is preferred Modified acid ester.

In addition, the isocyanate group content of the polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure is preferably in the range of 13-30% by mass, more preferably in the range of 15-25% by mass.

The aforementioned di(meth)acrylate dihydroxy ester compound (B) includes, for example, the di(meth)acrylate (B1) of a diglycidyl ether compound and the di(meth)acrylate (B2) of a tetraol compound ). Specific examples of these compounds include the same compounds as those exemplified in the description of the aforementioned urethane (meth)acrylate resin (1). The di(meth)acrylate dihydroxy ester compound (B) may be used independently, respectively, and may use 2 or more types together. Among them, based on the urethane (meth)acrylate resin (4) that is to be excellent in curl resistance, flexibility, and impact resistance in the cured product, an aliphatic diol diglycidyl ether compound is preferred. Di(meth)acrylate or di(meth)acrylate of aliphatic tetraol compound.

When the di(meth)acrylate (B2) of the tetraol compound is used as the dihydroxy di(meth)acrylate compound (B) in the aforementioned urethane (meth)acrylate resin (4) In other words, the (meth)acrylate (β) of the tetraol compound can also be used as the two (Meth)acrylate (B2) reaction material. The (meth)acrylate (β) system of the tetraol compound is the same as that described in the description of the aforementioned urethane (meth)acrylate resin (1).

The aforementioned urethane (meth)acrylate resin (4) uses the aforementioned polyisocyanate compound (A4) and di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials, but it can also be further used Reaction raw materials other than these. The aforementioned other reaction raw materials, specifically, include: other polyisocyanate compounds (A4') other than the aforementioned polyisocyanate compound (A4), (meth)acrylic monohydroxy ester compound (C), and the aforementioned bis(methyl) Polyol compounds (D) other than the dihydroxy acrylate compound (B), etc.

The aforementioned other polyisocyanate compounds (A4') include, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic diisocyanate compounds such as hexamethylene diisocyanate; alicyclic diisocyanate compounds such as isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate Aromatic diisocyanate compounds such as isocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; having the repeating structure shown in the aforementioned structural formula (1) Polymethylene polyphenyl polyisocyanate; these biuret modified products, allophanate modified products, etc. These may be used alone, or two or more of them may be used in combination. Among these, in order to fully exhibit the effects of the present invention, the aforementioned aliphatic diisocyanate compound or alicyclic diisocyanate compound is preferred.

When these other polyisocyanate compounds (A4') are used, in order to fully exhibit the effects of the present invention, compared to the aforementioned polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure, and the aforementioned other polyisocyanate compounds The total mass of the isocyanate compound (A4') is preferably 20% by mass or more, more preferably 30% by mass or more of the polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure.

The aforementioned (meth)acrylate monohydroxy ester compound (C) and the aforementioned other polyol compound (D) include those exemplified in the description of the aforementioned urethane (meth)acrylate resin (1) All compounds are the same.

The aforementioned urethane (meth)acrylate resin (4) can be produced by the same method as the aforementioned urethane (meth)acrylate resin (1).

To become a urethane (meth)acrylate resin with excellent curability and high hardness on the surface of the cured coating film, the urethane (meth)acrylate resin (4) thus obtained The equivalent weight of the (meth)acrylic acid group is preferably in the range of 100 to 500 g/eq, more preferably in the range of 100 to 300 g/eq.

The weight average molecular weight (Mw) of the aforementioned urethane (meth)acrylate resin (4) is higher than the weight average molecular weight (Mw) of the urethane (meth)acrylate resin to be an excellent balance of properties in the cured product. Preferably, it is in the range of 2,000 to 60,000, more preferably in the range of 2,000 to 30,000.

A description will be given when the aforementioned polyisocyanate compound (A) is a polyisocyanate compound (A5) having a urethane bonding site in the molecular structure. The carbamate of the present invention (methyl ) Acrylate resin is called urethane (meth)acrylate resin (5).

The aforementioned polyisocyanate compound (A5) having a urethane bonding site in the molecular structure includes, for example, a reaction product of various polyisocyanate raw materials and polyol raw materials. That is, the aforementioned polyisocyanate compound (A5) having a urethane bonding site in the molecular structure has the following molecular structure: a urethane bond separated by a structural site derived from a polyol raw material , A molecular structure formed by bonding structural parts derived from polyisocyanate raw materials to each other. In addition, such polyisocyanate compounds are generally called adduct-modified polyisocyanates.

The polyisocyanate raw material constituting the polyisocyanate compound (A5) having a urethane bonding site in the molecular structure includes, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-tri Aliphatic diisocyanate compounds such as methylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, Alicyclic diisocyanate compounds such as hydrogenated diphenylmethane diisocyanate; aromatics such as toluene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, etc. Group diisocyanate compounds; polymethylene polyphenyl polyisocyanate compounds having the repeating structure represented by the aforementioned structural formula (1); these isocyanurate modified products, biuret modified products, and ureas Modified formate, etc. These may be used alone, or two or more of them may be used in combination.

Among the aforementioned polyisocyanate raw materials, urethane (meth)acrylate is based on a good balance of the properties of the cured product. The resin (5) is preferably an aliphatic or alicyclic diisocyanate compound.

The polyol raw material constituting the polyisocyanate compound (A5) having a urethane bonding site in the molecular structure may be a compound having two or more hydroxyl groups in one molecule, and it is not particularly limited, and various types can be used. Compound. Specifically, examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3-isopropyl-1 ,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5 -Pentylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol, etc. Aliphatic diol compound; trimethylolethane, trimethylolpropane, glycerin, hexanetriol, neopentylerythritol, di-trimethylolpropane, dineopentaerythritol and other tri-functional aliphatic Polyol compounds; aromatic diol compounds such as dihydroxybenzene, dihydroxynaphthalene, biphenyl, and bisphenol; aromatic polyol compounds with three or more functions such as benzenetriol; various diol compounds mentioned above or polybasic with three or more functions Alcohol compounds, and malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid (anhydride), fumaric acid, hexahydrophthalic acid, Aliphatic dibasic acids such as tetrahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid, aromatic dibasic acids such as phthalic acid (anhydride), isophthalic acid and terephthalic acid, 1, 2, Aliphatic tribasic acids such as 5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2, 5,7-Naphthalene tricarboxylic acid and other aromatic tribasic acids and other polybasic acids The polyester polyol compound of the condensation reaction product; has ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether in the molecular structure Polyoxyalkylene-modified polyol compounds with ring-opening polymerization structure of various cyclic ether compounds such as allyl glycidyl ether; those with ring-opening polymerization structure of various lactone compounds such as ε-caprolactone in the molecular structure A lactone-modified polyol compound; a polyoxyalkylene-modified polylactone polyol compound having both a polyoxyalkylene structure and a lactone ring-opening structure in the molecular structure; Carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and other polycondensed polycarbonate polyol compounds of carbonylation agents. These cocoa can be used individually, respectively, and two or more types can also be used together.

The method of reacting the polyisocyanate raw material with the polyol raw material to obtain the polyisocyanate compound (A5) having a urethane bonding site in the molecular structure, for example, includes: The molar number of the hydroxyl group and the molar number of the isocyanate group contained in the polyisocyanate compound described above are used to be excessive, and both are used, and the reaction is performed in the temperature range of 20 to 120°C.

For this reaction, a well-known and customary urethane catalyst such as zinc octoate can also be used as needed. Moreover, this reaction can also be carried out in a solvent as needed. Examples of the aforementioned solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cyclic ether solvents such as tetrahydrofuran and dioxolane, methyl acetate, ethyl acetate, and acetic acid. Ester solvents such as butyl ester, aromatic hydrocarbon solvents such as toluene and xylene, carbitol, cellosolve, alcohol solvents such as methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination of two or more types.

The reaction ratio of the polyisocyanate raw material and the polyol raw material is not particularly limited, and is appropriately adjusted according to the desired molecular weight and isocyanate group content. Among them, it is preferable that the urethane (meth)acrylate resin (5) that is to be an excellent balance of the properties of the cured product should have an isocyanate group content of 5 in the obtained polyisocyanate compound (A5). The ratio in the range of ~15% by mass reacts.

The end point of the reaction of the polyisocyanate raw material and the polyol raw material can be confirmed by, for example, the rate of change over time of the isocyanate group content in the reaction mixture.

When the polyisocyanate compound (A) is a polyisocyanate compound (A5) having a urethane bonding site in the molecular structure, it can also be used in combination in addition to the aforementioned polyisocyanate compound having a urethane bonding site in the molecular structure. In addition to the isocyanate compound (A5), other polyisocyanate compounds (A5'). Other polyisocyanate compounds (A5') include various polyisocyanate compounds exemplified as the polyisocyanate raw material of the aforementioned polyisocyanate compound (A5). Among them, it is preferable to use a diisocyanate compound other than the aforementioned polyisocyanate compound (A5) as the aforementioned urethane (meth)acrylate resin (5) which is to be an excellent balance of various properties of the cured product. Polyisocyanate compound (A5'). The isocyanate group content of the aforementioned diisocyanate compound is preferably 20% by mass or more, more preferably 25% by mass or more. Furthermore, the aforementioned diisocyanate compound is particularly preferably an aliphatic or alicyclic diisocyanate compound.

When the aforementioned other polyisocyanate compound (A5') is used, it is based on the need to be a urethane (meth)acrylate resin (5) that has an excellent balance of properties in the cured product. Among the aforementioned polyisocyanate compounds (A5) The ratio of the isocyanate group to the total isocyanate group of the aforementioned polyisocyanate compound (A5) and the aforementioned other polyisocyanate compound (A5′) is preferably 3 mol% or more, preferably in the range of 3 to 90 mol%, Especially preferred is the range of 5-30 mol%.

In addition, when a diisocyanate compound other than the polyisocyanate compound (A5) is used as the other polyisocyanate compound (A5'), the polyisocyanate compound having a urethane bonding site in the molecular structure ( The ratio of the isocyanate group in A5) to the total isocyanate group of the polyisocyanate compound (A5) and the diisocyanate compound is preferably 3 mol% or more, preferably in the range of 3 to 90 mol%, particularly preferably It is in the range of 5-30 mole%.

In addition, with respect to the total mass of the polyisocyanate compound (A5) and the other polyisocyanate compound (A5'), it is preferable that 50% by mass or more is other than the polyisocyanate compound (A5) or the polyisocyanate compound (A5) The diisocyanate compound is more preferably 80% by mass or more of a diisocyanate compound other than the polyisocyanate compound (A5) or the polyisocyanate compound (A5).

The aforementioned di(meth)acrylate dihydroxy ester compound (B) includes, for example, the di(meth)acrylate (B1) of a diglycidyl ether compound and the di(meth)acrylate (B2) of a tetraol compound ). Specific examples of these compounds are the same as the various compounds exemplified in the description of the aforementioned urethane (meth)acrylate resin (1). Bis(methyl)propane The enoic acid dihydroxy ester compound (B) may be used alone, or two or more kinds may be used in combination. Among them, the urethane (meth)acrylate resin (5) is preferably an aliphatic diol diglycidyl ether compound that is to be excellent in curl resistance, flexibility, and impact resistance in the cured product. Di(meth)acrylate or di(meth)acrylate of aliphatic tetraol compound.

When the di(meth)acrylate (B2) of the tetraol compound is used as the dihydroxy di(meth)acrylate compound (B) in the aforementioned urethane (meth)acrylate resin (5) In other words, the (meth)acrylate (β) of the tetraol compound can also be used as a reaction material of the di(meth)acrylate (B2) containing the tetraol compound. The (meth)acrylate (β) system of the tetraol compound is the same as that described in the description of the aforementioned urethane (meth)acrylate resin (1).

The aforementioned urethane (meth)acrylate resin (5) is based on the aforementioned polyisocyanate compound (A5) and di(meth)acrylate dihydroxy ester compound (B) as necessary reaction materials, but it can be further Use reaction materials other than these. The aforementioned other reaction raw materials, specifically, include: (meth)acrylate monohydroxy ester compound (C), and other polyol compounds (D) other than the aforementioned di(meth)acrylate dihydroxy ester compound (B), etc. .

The aforementioned (meth)acrylate monohydroxy ester compound (C) and the aforementioned other polyol compound (D) include various exemplified in the description of the aforementioned urethane (meth)acrylate resin (1) The same compound.

The aforementioned urethane (meth)acrylate resin (5) can use the same method as the aforementioned urethane (meth)acrylate resin (1). Method to manufacture.

To become a urethane (meth)acrylate resin with excellent curability and high hardness on the surface of the cured coating film, the urethane (meth)acrylate resin (5) thus obtained The equivalent weight of the (meth)acrylic acid group is preferably in the range of 100 to 500 g/eq, more preferably in the range of 100 to 300 g/eq.

In addition, based on the need to be a urethane (meth)acrylate resin having an excellent balance of properties in the cured product, the weight average molecular weight (Mw) of the aforementioned urethane (meth)acrylate resin (5) ) Is preferably in the range of 2,000 to 60,000, more preferably in the range of 2,000 to 10,000.

啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二基苯基)-2-羥基-2-甲基丙烷-1-酮、4-苯甲醯基-4’-甲基二甲基硫化物、2,2’-二乙氧基苯乙酮、苄基二甲基縮酮、苄基-β-甲氧基乙基縮醛、鄰苯甲醯基安息香酸甲酯、雙(4-二甲胺基苯基)酮、對二甲胺基苯乙酮、α,α-二氯-4-苯氧基苯乙酮、4-二甲胺基苯甲酸戊酯、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物、2,4-雙-三氯甲基-6-[二-(乙氧基羰基甲基)胺基]苯基-S-三

、2,4-雙-三氯甲基-6-(4-乙氧基)苯基-S-三

、2,4-雙-三氯甲基-6-(3-溴-4-乙氧基)苯基-S-三

蒽醌、2-三級丁基蒽醌、2-戊基蒽醌、β-氯蒽醌等。該等可分別單獨使用，亦可併用二種類以上。 The curable composition of the present invention contains the aforementioned urethane (meth)acrylate resin and a photopolymerization initiator. Examples of the aforementioned photopolymerization initiator include: benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone , 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, Michele ketone, 3,3',4,4'-tetra(tertiary butyl) Peroxycarbonyl) benzophenone and other benzophenones; xanthone (xanthone), thioxanthone (thioxanthone), 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethyl Xanthones and thioxanthones such as thioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl; benzyl Alpha-diketones such as diacetyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; 4-dimethylaminobenzoic acid, 4-disulfide Various benzoic acids such as ethyl methylaminobenzoate; 3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy -1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-

Linylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-

(Hydroxyphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide , Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2- Methyl propan-1-one, 4-benzyl-4'-methyl dimethyl sulfide, 2,2'-diethoxy acetophenone, benzyl dimethyl ketal, benzyl- β-Methoxy ethyl acetal, o-benzoyl benzoate methyl ester, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α-dichloro-4 -Phenoxyacetophenone, pentyl 4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethane Group-6-[bis-(ethoxycarbonylmethyl)amino]phenyl-S-tri

, 2,4-Bis-trichloromethyl-6-(4-ethoxy)phenyl-S-tri

, 2,4-Bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-tri

Anthraquinone, 2-tertiary butyl anthraquinone, 2-pentyl anthraquinone, β-chloroanthraquinone, etc. These may be used alone, or two or more types may be used in combination.

啉基-1-丙酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁烷-1-酮之群組的1種或二種以上的混合系，可對更廣 範圍的波長的光顯示活性，成為硬化性高的硬化性組成物，故而較佳。 Among the aforementioned photopolymerization initiators, by using 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2- Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2- Diphenylethane-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-

Linyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-

One or a mixture of two or more of the group of (alolinylphenyl)-butan-1-one can show activity to light of a wider range of wavelengths and become a curable composition with high curability. good.

Commercial products of the aforementioned photopolymerization initiator include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", manufactured by Ciba Specility Chemicals, "Irgacure-651", "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure -1800", "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "Darocur-1173"; "Lucirin TPO" manufactured by BASF; Nippon Kayaku Co., Ltd. ) "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA"; "Vicure-10" and "Vicure-55" manufactured by Stauffer Chemical; AKZO "Trigonal P1" made by Sandoz; "Sandoray 1000" made by Sandoz; "Deep" made by Upjohn; "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" made by Ward Blenkinsop, etc.

The addition amount of the aforementioned photopolymerization initiator is preferably an amount that can fully exhibit the function of the photopolymerization initiator without crystal precipitation and deterioration of the coating film properties. Specifically, relative to the curable composition 100 parts by mass of the substance are preferably used in the range of 0.05 to 20 parts by mass, and particularly preferably used in the range of 0.1 to 10 parts by mass.

The curable composition of the present invention may contain various photosensitizers together with the aforementioned photopolymerization initiator. Photosensitizers, for example, amines, urea, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds or nitriles Class or other nitrogen-containing compounds.

The curable composition of the present invention may further contain: other photocurable compounds other than the urethane (meth)acrylate resin of the present invention, and organic solvents, ultraviolet absorbers, antioxidants, and silicon Additives, fluorine-based additives, silane coupling agents, organic beads, inorganic particles, inorganic fillers, rheology control agents, defoamers, anti-fogging agents, colorants, etc.

The aforementioned other photocurable compounds include, for example, various (meth)acrylate monomers and other urethane (meth)acrylates other than the aforementioned urethane (meth)acrylate resin of the present invention Ester, epoxy (meth)acrylate, etc.

啉、N-乙烯基吡咯啶酮、四氫糠基丙烯酸酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異莰基酯、(甲基)丙烯酸異癸基酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸十三基酯、(甲基)丙烯酸鯨蠟基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸2-乙氧基乙基酯、(甲基)丙烯酸3-甲氧基丁基酯、乙基卡必醇(甲基)丙烯酸酯、磷酸(甲基)丙烯酸酯、環氧乙烷改性磷酸(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基酯、環氧乙烷改性(甲基)丙烯酸苯氧基酯、環氧丙烷改性(甲基)丙烯酸苯氧基酯、壬基酚(甲 基)丙烯酸酯、環氧乙烷改性壬基酚(甲基)丙烯酸酯、環氧丙烷改性壬基酚(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基-2-羥基丙基苯二甲酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙基酯、酞酸氫2-(甲基)丙烯醯氧基乙酯、酞酸氫2-(甲基)丙烯醯氧基丙酯、六氫酞酸氫2-(甲基)丙烯醯氧基丙酯、四氫酞酸氫2-(甲基)丙烯醯氧基丙酯、(甲基)丙烯酸二甲基胺基乙基酯、(甲基)丙烯酸三氟乙基酯、(甲基)丙烯酸四氟丙基酯、(甲基)丙烯酸六氟丙基酯、(甲基)丙烯酸八氟丙基酯、單(甲基)丙烯酸金剛烷基酯等單(甲基)丙烯酸酯；丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、丙氧基化己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯；三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯 、二新戊四醇三(甲基)丙烯酸酯等三(甲基)丙烯酸酯；新戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二-三羥甲基丙烷五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二-三羥甲基丙烷六(甲基)丙烯酸酯等4官能以上的(甲基)丙烯酸酯；以及，上述各種多官能(甲基)丙烯酸酯的一部分或全部經以聚氧伸烷基鏈或聚酯鏈所改性的(甲基)丙烯酸酯等。 The aforementioned (meth)acrylate monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, N-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, glycidyl (meth)acrylate, acryloyl

Morpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (meth) Base) isodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, (meth) ) Benzyl acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (methyl) )Acrylate, ethylene oxide modified phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide modified phenoxy (meth)acrylate, propylene oxide modified ( Meth) phenoxy acrylate, nonylphenol (meth)acrylate, ethylene oxide modified nonylphenol (meth)acrylate, propylene oxide modified nonylphenol (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, methoxypolyglycol (meth)acrylate, methoxypropanediol (meth)acrylate, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloxyethyl hydrogen phthalate, hydrogen phthalate 2 -(Meth) propylene oxypropyl ester, hexahydrophthalic acid hydrogen 2-(meth) acryloxy propyl ester, tetrahydrophthalic acid hydrogen 2-(meth) acryloxy propyl ester, (former Base) dimethylaminoethyl acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, (meth)acrylic acid Mono(meth)acrylates such as octafluoropropyl ester and adamantyl mono(meth)acrylate; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxy Hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di( Di(meth)acrylates such as meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylerythritol di(meth)acrylate; trihydroxy Methylpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate )Acrylate, di-trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, dineopentaerythritol tri(meth)acrylate and other tri(meth)acrylic acid Esters; neopentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dineopentaerythritol tetra (meth) acrylate, dineopentaerythritol five (meth) Base) acrylate, di-trimethylolpropane penta(meth)acrylate, dineopentol hexa(meth)acrylate, di-trimethylolpropane hexa(meth)propylene (Meth)acrylates with four or more functions such as acid esters; and (meth)acrylates in which part or all of the above-mentioned various polyfunctional (meth)acrylates are modified with polyoxyalkylene chains or polyester chains Acrylic etc.

Examples of the aforementioned other urethane (meth)acrylate compounds include urethane (meth)acrylates composed of various polyisocyanate compounds and (meth)acrylate monohydroxy ester compounds. The aforementioned polyisocyanate compound includes, for example, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate; cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate Alicyclic diisocyanates such as isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, etc.; 1,5-naphthalene diisocyanate , 4,4'-diphenylmethane diisocyanate, 2,2'-bis(p-phenylisocyanate) propane, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraoxane Diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate and other aromatic diisocyanates, and various diisocyanate monomers, and these isocyanurate modifications Properties, adducts Modified product, biuret modified product.

On the other hand, the (meth)acrylate monohydroxy ester compound includes various compounds exemplified as the (meth)acrylate monohydroxy ester compound (C).

The epoxy (meth)acrylate compound includes various compounds exemplified as the di(meth)acrylate (B1) of the diglycidyl ether compound.

These other photocurable compounds may be used alone, or two or more of them may be used in combination. Among them, it is preferable to use various (meth)acrylate monomers in order to be a composition having excellent curability. When these other photocurable compounds are used, it is preferable to use the urethane (meth)acrylate resin of the present invention and other photocurable compounds in 100 parts by mass in total. The ester (meth)acrylate resin is used in a ratio of 5 parts by mass or more, and is particularly preferably used in a ratio of 20 parts by mass or more.

Examples of the aforementioned organic solvent include: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; Aromatic solvents such as toluene and xylene; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether Glycol ether solvents such as ether and propylene glycol monopropyl ether. These may be used alone, or two or more of them may be used in combination.

These organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition. Generally, it is preferable to adjust the non-volatile components to a range of 10 to 80% by mass.

、2-[4-{(2-羥基-3-十三基氧基丙基)氧基}-2-羥苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

等三

衍生物、2-(2’-呫噸羧基-5’-甲基苯基)苯并三唑、2-(2’-鄰硝基苄氧基-5’-甲基苯基)苯并三唑、2-呫噸羧基-4-十二基氧基二苯甲酮、2-鄰硝基苄氧基-4-十二基氧基二苯甲酮等。該等可分別單獨使用，亦可併用二種以上。 Examples of the aforementioned ultraviolet absorbers include: 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-tri

, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-Three

Wait three

Derivatives, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole Azole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These may be used alone, or two or more of them may be used in combination.

Examples of the aforementioned antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These may be used alone, or two or more of them may be used in combination.

The aforementioned silicon-based additives, for example, include: dimethyl polysiloxane, methyl phenyl polysiloxane, cyclic dimethyl polysiloxane, methyl hydrogen polysiloxane, polyether modified two Methylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amine-modified dimethylpolysiloxane copolymer, etc. Polyorganosiloxanes with alkyl or phenyl groups, polyether-modified polydimethylsiloxanes with acryl groups, polyester-modified polydimethylsiloxanes with acryl groups, etc. . These may be used alone, or two or more of them may be used in combination.

Examples of the aforementioned fluorine-based additives include DIC Co., Ltd. "Megafac" series. These may be used alone, or two or more of them may be used in combination.

Examples of the aforementioned silane coupling agent include: vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3 -Glycidyloxypropyl three Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylic acid Oxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methylpropene Glyoxypropyl triethoxysilane, 3-propenoxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N -2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureido Propyl triethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropane) Group) tetrasulfide, 3-isocyanatopropyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethyl vinyl Silane, trichlorovinylsilane, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl ginseng (2-methoxyethoxy) silane and other vinyl silane coupling Agent; diethoxy (glycidyloxypropyl) methyl silane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, Epoxy silane coupling agents such as 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; Styryl trimethoxysilane and other styrene-based silane coupling agents; 3-methacryloxy propyl methyl dimethoxy silane, 3-acryloxy propyl trimethoxy silane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (methyl )Acryloxy-based silane coupling agent; N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethyl Oxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Amino-based silane coupling agents such as triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine and N-phenyl-3-aminopropyl trimethoxysilane; 3 -Urea-based silane coupling agents such as ureidopropyltriethoxysilane; chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyl trimethoxysilane and other mercapto-based silane coupling agents; bis(triethoxysilylpropyl) tetrasulfide and other sulfide-based silane coupling agents; 3-isocyanate propyl triethoxy Isocyanate-based silane coupling agents such as base silane. These may be used alone, or two or more of them may be used in combination.

The aforementioned organic beads, for example, include: polymethyl methacrylate Beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester Series resin beads, polyamide resin beads, polyimide resin beads, polyvinyl fluoride resin beads, polyethylene resin beads, etc. These may be used alone, or two or more of them may be used in combination. The average particle diameter of the organic beads is preferably in the range of 1-10 μm.

Examples of the aforementioned inorganic fine particles include fine particles such as silica, alumina, zirconia, titanium oxide, barium titanate, and antimony trioxide. These may be used alone, or two or more of them may be used in combination. The average particle diameter of the inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm. In addition, when the inorganic fine particles are contained, a dispersing aid may be further used, such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide. Phosphate compounds such as alkyl-modified phosphoric acid dimethacrylate. These may be used alone, or two or more of them may be used in combination.

Commercial products of the aforementioned dispersion aid include, for example, "Kayamer PM-21" and "Kayamer PM-2" manufactured by Nippon Kayaku Co., Ltd., "Lightester P-2M" manufactured by Kyoeisha Chemical Co., Ltd., and the like.

The curable composition of the present invention can be used for coating applications. The coating can be applied to various substrates and cured by irradiating active energy rays to be used as a coating for protecting the surface of the substrate. In this case, the curable composition of the present invention can be directly coated on the surface-protected member and used, or the one obtained by coating on a plastic film can be used as a protective film. Alternatively, the curable composition of the present invention may be coated on a plastic film, and the coated film may be used as an anti-reflection film, a diffusion film, a sheet, etc. Optical film is used. Since the cured coating film of the curable composition of the present invention has the characteristics of high surface hardness and excellent flexibility and impact resistance, it can be coated on various types of plastic films with the film thickness due to the application for protection Film applications and film-like molded products are used.

The aforementioned plastic film includes, for example, polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetyl cellulose resin, Plastic film or sheet made of ABS resin, AS resin, norbornene resin, polyimide resin, etc.

Among the above-mentioned plastic films, cellulose triacetate film is particularly suitable for use in polarizing plates of liquid crystal displays. Generally, the thickness is as thin as 40~100μm, even when a hard coat layer is provided. , It is also difficult to sufficiently increase the surface hardness, and it has the characteristics of being easy to curl greatly. The coating film composed of the curable composition of the invention of this application achieves high surface hardness and excellent curl resistance, flexibility, transparency, and impact resistance even when a triacetate cellulose film is used as a substrate. Such effects can be suitably used. When the cellulose triacetate film is used as a substrate, the coating amount when the curable composition of the present invention is applied is preferably applied so that the film thickness after drying is in the range of 1 to 20 μm, and is preferably The range of 2~10μm. Coating methods at this time include, for example, bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing (offset printing). ), flexographic printing, screen printing, etc.

Among the above plastic films, polyester films, for example, can include: The thickness of polyethylene terephthalate is generally about 20 to 300 μm. Because it is cheap and easy to process, it can be used for various applications such as touch panel displays, but it is very soft, and it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided. When the polyethylene film is used as a substrate, the coating amount when coating the curable composition of the invention of the present application is based on its application. It is preferably coating so that the film thickness after drying is in the range of 1 to 100 μm, preferably To be in the range of 1-20μm. Generally speaking, a cured coating film exceeding 20 μm tends to curl greatly compared with a thin film thickness. However, the curable composition of the invention of this application also has the characteristics of excellent curl resistance. Even when it is coated with a relatively high film thickness exceeding 30 μm, curling is difficult to occur, and it can be suitably used. The coating method in this case includes, for example, bar coater coating, wire-wound coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

Among the above-mentioned plastic films, polymethyl methacrylate film is generally relatively thick and strong due to a thickness of about 50 to 2,000 μm, and can be suitably used for front panel applications of liquid crystal displays, etc., especially Films for applications requiring high surface hardness. When the polymethyl methacrylate film is used as a substrate, the coating amount when coating the curable composition of the invention of this application depends on its use. It is preferable to coat so that the film thickness after drying becomes 1~ The range of 100 μm is preferably the range of 1 to 20 μm. The coating method in this case includes, for example, bar coater coating, wire-wound coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

In addition, among the above-mentioned plastic films, cycloolefin polymer films are generally known to be not resistant to forces from the transverse direction such as tearing, and have poor folding resistance. On the other hand, from the viewpoint of transparency and heat resistance, it has been The field of use is gradually expanding. The cured coating film obtained from the curable composition of the present invention can effectively improve its flexibility and impact resistance even for such a fragile film. From the viewpoint that such an effect can be suitably expressed, the thickness of the cured coating film is preferably adjusted in the range of 1 to 10 μm. The coating method in this case includes, for example, bar coater coating, wire-wound coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

Examples of the active energy rays irradiated when the curable composition of the present invention is cured and formed into a coating film include ultraviolet rays and electron beams. When curing by ultraviolet light, use an ultraviolet irradiation device with a xenon lamp, high-pressure mercury lamp, metal halide lamp, LED, etc. as the light source, and adjust the amount of light and the configuration of the light source as needed. When a high-pressure mercury lamp is used, it is generally preferable to harden the lamp with a light quantity in the range of 80 to 160 W/cm with respect to a lamp with a conveying speed of 5 to 50 m/min. On the other hand, when curing by an electron beam, it is preferable to use an electron beam acceleration device that usually has an acceleration voltage in the range of 10 to 300 kV, and to perform curing at a conveying speed of 5 to 50 m/min.

In addition, the substrate coated with the curable composition of the present invention can be suitably used not only as a plastic film, but also as a surface coating agent for various plastic molded products, such as mobile phones, household appliances, and automobile bumpers. In this case, the method of forming the coating film includes, for example, a coating method, a transfer method, and a sheet bonding method.

The coating method includes spraying the coating material; or a method in which a printing machine such as a curtain coater, a roll coater, or a gravure coater is used to coat the molded product as a top coat, and then irradiate active energy rays to harden it.

The laminated film of the present invention has a cured coating film of the curable composition of the present invention and a plastic film layer. In addition, it may have a functional film layer such as an antireflection film, a diffusion film, and a polarizing film. These various layer configurations can be formed by a method of directly applying a resin raw material and drying or curing, or can be formed by a method of bonding through an adhesive layer.

[Example]

Specific manufacturing examples and examples are given below to explain the present invention more specifically, but the present invention is not limited to these examples. The parts and% in the examples are quality standards unless otherwise stated.

Furthermore, in the examples of the present invention, the weight average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Co., Ltd.

Column: Protection column H _XL made by Tosoh Co., Ltd. -H+TSKgelG5000HXL made by Tosoh Co., Ltd.+TSKgelG4000HXL made by Tosoh Co., Ltd.+TSKgelG3000HXL made by Tosoh Co., Ltd.+TSKgelG2000HXL made by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data processing: SC-8010 manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40℃, solvent tetrahydrofuran flow rate 1.0ml/min

Standard: Polystyrene

Sample: obtained by filtering 0.4% by mass of a tetrahydrofuran solution in terms of resin solid content with a microfilter (100μl)

Production Example 1 Production of neopentylerythritol diacrylate

136 parts by mass of neopentylerythritol and 600 parts by mass of N,N-dimethylformamide were charged into a flask equipped with a thermometer, stirrer, and condenser, and 3.7 parts by mass of p-toluenesulfonic acid was added as a catalyst . The temperature was raised to 80°C while stirring to dissolve the neopentylerythritol in N,N-dimethylformamide, and then the mass parts of cyclohexanone was added. While maintaining the reaction temperature at 80°C, the pressure in the reaction system was reduced to 140 mmHg, and the reaction was continued while distilling off the generated water. When it became impossible to confirm the generation of water, it was further refluxed for 1 hour. While continuing to stir, it was cooled to room temperature and returned to normal pressure, and unreacted neopentylerythritol was removed by filtration under reduced pressure. After the N,N-dimethylformamide was removed under reduced pressure from the obtained filtrate, ethyl acetate was added, and the deposited neopentylerythritol was removed by filtration again. After the obtained filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution, it was further washed with a saturated aqueous sodium chloride solution, and the organic layer was dehydrated with magnesium sulfate. The reaction product after dehydration was concentrated to obtain a ketal compound (x1).

The previously obtained ketal compound (x1) 21.6 parts by mass, 120 parts by mass of dichloromethane, and 46.5 parts by mass of triethylamine were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and cooled to -5°C. While keeping the inside of the reaction system below 0°C, drop the 3-chloropropane It is obtained by dissolving 29 parts by mass of chlorine in 40 parts by mass of dichloromethane. After the dripping was completed, the temperature was gradually raised to room temperature, and the reaction was further carried out for 4 hours. After confirming the disappearance of the ketal compound (x1) as a raw material by gas chromatography, the triethylamine hydrochloride was removed by filtration under reduced pressure. After the obtained filtrate was washed with a saturated sodium bicarbonate aqueous solution, it was further washed with a saturated sodium chloride aqueous solution, and dehydrated with anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of (meth)acrylate compound (x2).

The previously obtained (meth)acrylate compound (x2) 6.5 parts by mass and 30 parts by mass of acetone were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and were cooled to 0° C. while stirring. 10 mass parts of 10% sulfuric acid aqueous solution was dropped in small amounts at a time so that the inside of the reaction system did not exceed 10°C, and after adding the total amount, the reaction was allowed to react at room temperature for 16 hours. After confirming the disappearance of the (meth)acrylate compound (x2) as a raw material by gas chromatography, 10 parts by mass of water was added, and acetone was removed under reduced pressure. The obtained water layer was extracted with ethyl acetate, and washed with a saturated aqueous sodium hydrogen carbonate solution until the pH became 7. After the organic layer was dehydrated with magnesium sulfate, it was concentrated under normal temperature and reduced pressure conditions to obtain 4.1 parts by mass of neopentylerythritol diacrylate.

Example 1 Production of urethane (meth)acrylate resin (1-1) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 parts by mass of dibutyltin and 0.1 parts by mass of hydroquinone were added to the four-necked flask to complete Homogeneous solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 84 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (1-1) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (1-1) is 3,000, and the acryl equivalent calculated from the charged raw materials is 130 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

In addition, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 2 Production of urethane (meth)acrylate resin (1-2) composition

173.9 parts by mass of a mixture of neopentylerythritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 81.07 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 84 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, adjust the non-volatile content to 80% using butyl acetate , The mixture of urethane (meth)acrylate resin (1-2) and neopentylerythritol tetraacrylate was obtained. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (1-2) is 4,000, and the acryl equivalent calculated from the charged raw materials is 136 g/eq.

Furthermore, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 220 mgKOH/g.

Example 3 Production of urethane (meth)acrylate resin (1-3)

125.9 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g) obtained in Production Example 1, 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone were added to a four-necked flask to make uniform Solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 84 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (1-3). The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (1-3) is 15,000, and the acryl equivalent calculated from the charged raw materials is 208 g/eq.

Example 4 Production of urethane (meth)acrylate resin (2-1) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 parts by mass of dibutyltin and 0.1 parts by mass of hydroquinone were added to the four-necked flask to complete Homogeneous solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 131.2 parts by mass of 4,4-methylenedicyclohexyl-diisocyanate ("VESTANATH12MDI" manufactured by Evonik Degussa Japan) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (2-1) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (2-1) was 3,000, and the acryl equivalent calculated from the charged raw materials was 148 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

The hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 5 Production of urethane (meth)acrylate resin (2-2)

130.9 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g) obtained in Production Example 1, 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone were added to a four-necked flask to make uniform Solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 131.2 parts by mass of 4,4-methylenedicyclohexyl-diisocyanate ("VESTANATH12MDI" manufactured by Evonik Degussa Japan) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (2-2). Aminomethyl The weight average molecular weight (Mw) of the acid ester (meth)acrylate resin (2-2) was 19,000, and the acryl equivalent calculated from the charged raw materials was 250 g/eq.

Example 6 Production of urethane (meth)acrylate resin (3-1) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the internal temperature of the flask became 50°C, and then, it took about one hour to divide 97 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals Co., Ltd.) Invest. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (3-1) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (3-1) was 3,000, and the acryl equivalent calculated from the charged raw materials was 136 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

In addition, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 7 Production of urethane (meth)acrylate resin (3-2)

130.9 mass of neopentylerythritol diacrylate to be obtained in manufacturing example 1 Parts (hydroxyl value 450 mgKOH/g), 0.1 parts by mass of dibutyl tin dilaurate, and 0.1 parts by mass of hydroquinone were added to a four-neck flask to form a uniform solution. It was heated until the internal temperature of the flask became 50°C, and then, it took about one hour to divide 97 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals Co., Ltd.) Invest. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (3-2). The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (3-2) was 18,000, and the acryl equivalent calculated from the charged raw materials was 218 g/eq.

Example 8 Production of urethane (meth)acrylate resin (3-3) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the internal temperature of the flask became 50°C, and it took about one hour to remove 2,5(2,6)-bis(isocyanatemethyl)bicyclo[2,2,1]heptane (manufactured by Mitsui Chemicals Co., Ltd. "Cosmonet NBDI”) 103 parts by mass were added in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (3-3) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (3-3) was 4,000, and the acryl equivalent calculated from the charged raw materials was 138 g/eq.

Furthermore, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 9 Production of urethane (meth)acrylate resin (3-4)

130.9 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g) obtained in Production Example 1, 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone were added to a four-necked flask to make uniform Solution. It was heated until the internal temperature of the flask became 50°C, and then it took about one hour to remove 2,5(2,6)-bis(isocyanatemethyl)bicyclo[2,2,1]heptane (manufactured by Mitsui Chemicals Co., Ltd.) Cosmonet NBDI”) 103 parts by mass were put in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, the non-volatile components were adjusted to 80% using butyl acetate to obtain a urethane (meth)acrylate resin ( 3-4). The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (3-4) was 18,500, and the acryl equivalent calculated from the charged raw materials was 223 g/eq.

Example 10 Production of urethane (meth)acrylate resin (4-1) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the inner temperature of the flask became 50°C, and then, it took about one hour to convert the polyisocyanate (DIC Co., Ltd. "Burnock DN-901S" hexamethylene diisocyanate modified isocyanurate, Isocyanate group content 23.5 mass %) 44.7 mass parts, hexamethylene bis 63 parts by mass of isocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) were introduced in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (4-1) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (4-1) is 10,000, and the acryl equivalent calculated from the charged raw materials is 139 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

In addition, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 11 Production of urethane (meth)acrylate resin (5-1) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the internal temperature of the flask reached 50°C, and then it took about one hour to add 63 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) and hexamethylene diisocyanate. The modified product ("Duranate E405-70B" manufactured by Asahi Kasei Chemical Co., Ltd.: 70% by mass of non-volatile components and 10.1% by mass of the isocyanate group content of the resin solid content) was charged in 148 parts by mass in batches. Make the reaction at 80℃ After 3 hours, the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy, the non-volatile content was adjusted to 80% using butyl acetate, and the urethane (meth)acrylate resin (5-1) and A mixture of neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (5-1) is 6,000, and the acryl equivalent calculated from the charged raw materials is 180 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

In addition, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 12 Production of urethane (meth)acrylate resin (5-2)

124.67 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g), 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone obtained in Production Example 1 were added to a four-necked flask to make a uniform Solution. It was heated until the inner temperature of the flask became 50°C, and then it took about one hour to add 78.5 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) and hexamethylene diisocyanate The modified substance ("Duranate E405-70B" manufactured by Asahi Kasei Chemical Co., Ltd.: 70% by mass of non-volatile components and 10.1% by mass of isocyanate group content of resin solids) was added in 38.7 parts by mass in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (5-2). Urethane (meth)acrylate tree The weight average molecular weight (Mw) of the fat (5-2) is 5,600, and the acryl equivalent calculated from the charged raw materials is 242 g/eq.

Example 13 Production of urethane (meth)acrylate resin (5-3) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the inner temperature of the flask became 50°C, and then it took about one hour to add 63 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) and hexamethylene diisocyanate 150 parts by mass of the modified substance ("Burnock DN-921S" manufactured by DIC Corporation: 100% by mass of non-volatile components and 7% by mass of isocyanate group) was added in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (5-3) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (5-3) was 6,500, and the acryl equivalent calculated from the charged raw materials was 177 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

Furthermore, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 14 Urethane (meth)acrylate resin (5-4) Manufacturing

124.67 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g), 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone obtained in Production Example 1 were added to a four-necked flask to make a uniform Solution. It was heated until the inner temperature of the flask became 50°C, and then it took about one hour to add 78.5 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) and hexamethylene diisocyanate The modified substance ("Burnock DN-921S" manufactured by DIC Corporation: 100% by mass of non-volatile components and 7% by mass of isocyanate group) was added in 39.2 parts by mass. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (5-4). The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (5-4) was 3,800, and the acryl equivalent calculated from the charged raw materials was 243 g/eq.

Example 15 Production of urethane (meth)acrylate resin (5-5) composition

208 parts by mass of a mixture of neopenteritol triacrylate and tetraacrylate ("Aronics M-305" manufactured by Toagosei Co., Ltd.), 75.2 parts by mass of neopenteritol diacrylate obtained in Production Example 1, and dilauric acid 0.1 part by mass of dibutyltin and 0.1 part by mass of hydroquinone were added to the four-neck flask to make a uniform solution. It was heated until the internal temperature of the flask became 50°C, and then, it took about one hour to remove 1,3-bis(isocyanatomethyl)cyclohexane (72.8 parts by mass of "Takenate 600" manufactured by Mitsui Chemicals Co., Ltd., Liuya) Modified product of adduct of methyl diisocyanate (Burnock DN-955S made by DIC Corporation: non-volatile 75% by mass of the sexual component and 9.3% by mass of the isocyanate group content of the resin solid content) 150.5 parts by mass were added in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (5-5) Mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (5-5) was 4,500, and the acryl equivalent calculated from the charged raw materials was 167 g/eq.

Furthermore, the hydroxyl value of "Aronics M-305" is 112.8 mgKOH/g, and the mixing ratio of neopentyl erythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.

In addition, the hydroxyl value of the mixture of "Aronics M-305" and neopentylerythritol diacrylate is 200 mgKOH/g.

Example 16 Production of urethane (meth)acrylate resin (5-6)

124.67 parts by mass of neopentylerythritol diacrylate (hydroxyl value 450mgKOH/g), 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone obtained in Production Example 1 were added to a four-necked flask to make a uniform Solution. It was heated until the internal temperature of the flask became 50°C, and then, it took about one hour to remove 1,3-bis(isocyanatomethyl)cyclohexane (Mitsui Chemicals "Takenate 600" 90.7 parts by mass, Liuya The modified product of the adduct of methyl diisocyanate (“Burnock DN-955S” manufactured by DIC Corporation: 75% by mass of non-volatile components, 9.3% by mass of the isocyanate group content of the resin solid content) 39.3 parts by mass was added in batches. After reacting at 80°C for 3 hours, after confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, the non-volatile The hair component was adjusted to 80%, and a urethane (meth)acrylate resin (5-6) was obtained. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (5-6) was 3,300, and the acryl equivalent calculated from the charged raw materials was 246 g/eq.

Comparative Production Example 1 Production of urethane (meth)acrylate resin (1') composition

A mixture of neopentyl erythritol diacrylate, neopentyl erythritol triacrylate, and neopentyl erythritol tetraacrylate ("Aronics M-306" manufactured by Toagosei Co., Ltd., hydroxyl value 165 mgKOH/g) 350.63 parts by mass, dilauric acid 0.2 parts by mass of dibutyltin and 0.2 parts by mass of hydroquinone were added to the four-neck flask to form a homogeneous solution. After heating until the inner temperature of the flask became 50° C., it took about one hour to add 84 parts by mass of hexamethylene diisocyanate ("Duranate 50M-HDI" manufactured by Asahi Kasei Chemical Co., Ltd.) in batches. After reacting at 80°C for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectroscopy, butyl acetate was used to adjust the non-volatile content to 80% to obtain a urethane (meth)acrylate resin (1') A mixture with neopentylerythritol tetraacrylate. The weight average molecular weight (Mw) of the urethane (meth)acrylate resin (1') is 1,500, and the acryl equivalent calculated from the charged raw materials is 122 g/eq.

Examples 17 to 32, Comparative Example 1

125 parts by mass of the urethane (meth)acrylate resin composition or urethane (meth)acrylate resin obtained in Examples 1 to 16 and the comparative production example, a photoinitiator (Ciba specility "Irgacure # 184" manufactured by Chemicals Corporation) 4 parts by mass and 75 parts by mass of methyl ethyl ketone were mixed to obtain a curable composition. This was applied to a 125 μm-thick PET film using a bar coater, and dried at 80°C for 2 minutes. Next, under an air atmosphere, an 80W high-pressure mercury lamp was irradiated with ultraviolet rays of 300 mJ/cm ² to obtain a laminate film having a cured coating film with a thickness of 5 μm on the PET film. For this laminated film, various evaluation tests were conducted by the following methods. The results are shown in Table 1.

Surface hardness test

Regarding the aforementioned laminated film, in accordance with JISK5600-5-4, the pencil hardness of the surface of the cured coating film of the curable composition was measured under a load of 500g. The measurement was performed 5 times with a pencil of hardness H, and the measurement without scratches was evaluated as A when it was 4 or more times, and B when it was 3 times or less was evaluated.

Scratch resistance test

A disc-shaped indenter with a diameter of 2.4 cm was coated with 0.5 g of steel wool (made by STEEL WOOL Co., Ltd., Japan). A load of 500 g was applied to the indenter to harden the laminated film. Abrasion test of 200 reciprocating film surface. The haze value of the coating film before and after the abrasion test was measured using an automatic haze computer ("HZ-2" manufactured by Suga Tester Co., Ltd.), and the scratch resistance was evaluated by the difference (dH).

Softness test

Use a mandrel testing machine (“Bending Tester” manufactured by TP Giken Co., Ltd.) to wind the aforementioned laminated film on a test rod, and conduct a test to visually confirm whether cracks occur. The minimum diameter of the test rod that does not produce cracks (mm) ) Let be the evaluation result. The test rod system used a scale of 1mm from 2mm to 6mm in diameter.

Curl resistance test

A 5 cm square coating film was cut out from the above-mentioned laminated film to obtain a test piece, and the horizontal lift from four corners of the test piece was measured, and the average value (mm) was evaluated.

Impact resistance test

The test was conducted with reference to JISK5600-5-3. Specifically as follows.

[Device]

Weight: A ball bearing steel ball (mass 300.0±0.5g, diameter 25.40mm, grade 60) specified in JISB1501 "Steel Balls for Ball Bearings" is suspended by a wire at the tip.

Steel platform: A steel platform with a length of 300mm, a width of 200mm, and a thickness of 30mm is installed horizontally on the concrete floor.

[operating]

1. Place the hardened coating film surface of the laminated film upward and fix it on the steel table.

2. Hang the weight at a position where the distance from the surface of the laminate film to the lower end of the weight is 50mm, and after confirming that the swing and rotation have stopped, let it fall onto the laminate film.

3. After the laminated film after the drop test was allowed to stand in a room for 1 hour, the damage of the coating surface was investigated.

4. The test was continued every 50 mm from the surface of the laminated film to the lower end of the weight, and the evaluation was performed with the maximum distance that does not cause cracks or peeling of the cured coating film.

Claims (5)

A kind of urethane (meth)acrylate resin, which is a urethane (meth)acrylate using polyisocyanate compound (A) and (meth)acrylate (β) of tetraol compound as necessary reaction materials. Meth) acrylate resin, the (meth)acrylate (β) hydroxyl value of the tetraol compound is in the range of 190 to 500 mgKOH/g and the di(meth)acrylate (B2) of the tetraol compound is required Component, the aforementioned polyisocyanate compound (A) is: a polyisocyanate compound (A2) represented by any one of the following structural formulas (A2-1) and (A2-2),

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, and m is 0 or an integer of 1 to 4; R ^{2 is} each independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms); The polyisocyanate compound (A3) represented by any one of the following structural formulas (A3-1) to (A3-4),

(In the formula, R ^{3 is} each independently an alkyl group with 1 to 4 carbon atoms, n is 0 or an integer of 1 to 4; R ^{4 is} each independently any one of a hydrogen atom and an alkyl group with 1 to 4 carbon atoms ); a polyisocyanate compound (A4) having an isocyanurate ring structure in the molecular structure; or a polyisocyanate compound (A5) having a urethane bonding site in the molecular structure. A urethane (meth)acrylate resin, which uses a polyisocyanate compound (A) and (meth)acrylate (β) with a tetraol compound as necessary reaction materials. The ( The meth)acrylate (β) system has a hydroxyl value in the range of 190 to 500 mgKOH/g and contains the di(meth)acrylate (B2) of the tetraol compound as an essential component; the aforementioned polyisocyanate compound (A) is an aliphatic poly Isocyanate compound (A1). A curable composition containing the urethane (meth)acrylate resin of claim 1 or 2 and a photopolymerization initiator. A hardened product of the hardenable composition of claim 3. A laminated film having a layer containing a cured product as claimed in Claim 4 and other plastic film layers.