Active energy ray curable urethane (meth)acrylate composition

Abstract

The present invention provides a urethane (meth)acrylate composition that exhibits excellent release properties from molds, a high refractive index, and good adhesion to the substrate in the cured product (film) after UV curing. [Solution] An active energy ray curable urethane (meth)acrylate composition (X) is used, comprising urethane (meth)acrylate (A), a monomer (B) having a chemical formula weight of 100 or more and a number average molecular weight of 1,000 or less that does not have a urethane bond, and a tertiary amine salt of a phosphate ester (C), wherein (C) consists of a salt of a phosphate ester (c1) and a tertiary amine (c2), and (c2) consists of a tertiary aliphatic amine or an alkylene oxide adduct of a primary or secondary aliphatic amine, and satisfying all of the following requirements. (1) Solution viscosity at 25°C is 2,500-5,000 mPa·s (2) Double bond content is 3.2-3.8 mmol / g based on the weight of (X) (3) Aromatic content is 4.2-5.0 mmol / g based on the weight of (X)

Description

[Technical Field]

[0001] This invention relates to an active energy ray curable urethane (meth)acrylate composition. [Background technology]

[0002] Active energy ray curable compositions harden quickly upon irradiation with active energy rays and provide coatings with excellent scratch resistance, elastic modulus, weather resistance, and chemical resistance. Therefore, they are widely used as paints, coatings, sealants, and adhesives for optical components, electrical products, electronic components, and the interior and exterior of aircraft and automobiles. Among these curable compositions, active energy ray curable compositions containing urethane (meth)acrylate have recently been proposed for shaping applications, from the viewpoint of curability and yield. (Patent Documents 1 and 2) [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6816790 [Patent Document 2] Japanese Patent Publication No. 2017-210579 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0004] However, with the above compositions, when molding using a mold, it is necessary to design a highly flexible curable composition to satisfy the need for conformability to the mold. As a result, there is a problem in that the mold release properties do not reach a satisfactory level. Furthermore, when prioritizing mold release properties, there are problems such as insufficient adhesion to the film substrate. [Means for solving the problem]

[0005] The inventors of this invention arrived at this present invention as a result of diligent research to solve the above problems. In other words, the present invention relates to an active energy ray-curable urethane (meth)acrylate composition comprising urethane (meth)acrylate (A), a monomer (B) having a chemical formula weight of 100 or more and a number average molecular weight of 1,000 or less that does not have a urethane bond, and a tertiary amine salt of a phosphate ester (C), wherein (C) is a salt of a phosphate ester (c1) and a tertiary amine (c2), and (c2) is a tertiary aliphatic amine or an alkylene oxide adduct of a primary or secondary aliphatic amine, and satisfies all of the following requirements (1) to (3); a coating agent comprising the composition; an optical component or electrical / electronic component comprising a cured product obtained by curing the composition; and a method for producing a coating characterized by applying the composition to at least a part of at least one side of a substrate and curing it by irradiation with active energy rays. Requirements: (1) The viscosity of the solution at 25°C is 2,500 to 5,000 mPa·s. (2) The double bond content is 3.2 to 3.8 mmol / g based on the weight of (X) (3) Aromatic content is 4.2-5.0 mmol / g based on the weight of (X) [Effects of the Invention]

[0006] The active energy ray curable urethane (meth)acrylate composition of the present invention exhibits the following effects. (1) Excellent adhesion to the substrate. (2) The cured product obtained by curing the composition has excellent mold release properties. [Modes for carrying out the invention]

[0007] In the present invention, urethane (meth)acrylate (A) is a (meth)acrylate having a urethane group. (A) includes a hydroxyl group-containing (meth)acrylate (a) having 1 to 6 or more hydroxyl groups and 1 to 10 or more (meth)acryloyl groups, which is formed by reacting it with a polyisocyanate (hereinafter sometimes abbreviated as PI) (b).

[0008] (a) includes (meth)acrylic acid adducts of polyglycidyl ethers (a1) and reaction products of (meth)acrylic acid with divalent to octavalent or higher polyols [formula weight of 116 or more and number average molecular weight [hereinafter abbreviated as Mn. Measurement is by gel permeation chromatography (GPC)] of 5,000 or less] (a2).

[0009] The polyglycidyl ethers constituting (a1) include polyglycidyl ethers of polyvalent (2-6 or more) phenols or their alkylene oxide (hereinafter abbreviated as AO) adducts, as shown below.

[0010] (1) Diglycidyl ether of divalent phenol Diglycidyl ethers of divalent phenols having 6 to 30 carbon atoms (hereinafter abbreviated as C), such as monocyclic phenols (catechol, resorcinol, etc.) and polycyclic phenols [condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenols (bisphenol A, -F, -AF, and -S, etc.), halogenated bisphenols (dichlorobisphenol A, tetrachlorobisphenol A, etc.), biphenyls (1,4-dihydroxybiphenyl, etc.)], diglycidyl ethers obtained from the reaction of 2 moles of bisphenol A and 3 moles of epichlorohydrin, etc. (2) Polyglycidyl ethers of trivalent to hexavalent or higher polyvalent phenols Polyglycidyl ethers of trivalent to hexavalent or higher polyhydric phenols with C6 or higher and Mn 5,000 or lower, such as triglycidyl ethers of trivalent phenols [pyrogallol, dihydroxynaphthylcresol, tris(hydroxyphenyl)methane, etc.], tetraglycidyl ethers of tetravalent phenols [tetrakis(4-hydroxyphenyl)ethane, etc.], and polyglycidyl ethers of hexavalent or higher polyhydric phenols [phenol or cresol novolac resin (Mn 200-5,000), polyhydric phenols obtained by the condensation reaction of resorcinol and acetone (Mn 400-5,000), etc.]. (3) Polyglycidyl ethers of AO adducts of polyvalent (divalent to hexavalent or more) phenols Polyglycidyl ethers of compounds obtained by adding C2-4 AO to polyhydric phenols and mixtures thereof, as exemplified in (1) and (2) above. Examples of AO for C2-4 include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3-, 1,3- and isobutylene oxides, tetrahydrofuran, and mixtures thereof. Of these, EO is preferred from the viewpoint of adhesion of the cured product to the plastic substrate. The number of moles of AO added to polyvalent phenols, etc., is preferably 1 to 20 moles, more preferably 2 to 15 moles, and especially preferably 2 to 10 moles, from the viewpoint of mold release properties and adhesion to plastic substrates of the cured product, which will be described later.

[0011] (a2) includes hydroxyethyl (meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di-, tri- and tetra-(meth)acrylate and their AO (1-100 mol) adducts, etc. Of the above (a), (a1) is preferred from the viewpoint of the high refractive index of the cured product of the present invention, which will be described later.

[0012] (a) The number of hydroxyl groups in (a) is 1 to 6 or more, preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3, from the viewpoint of adhesion of the cured product to the resin substrate and mold release properties. (a) The number of (meth)acryloyl groups is 1 to 10 or more, preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 4, from the viewpoint of curability and adhesion to the plastic substrate.

[0013] The polyisocyanate (b) in this invention includes the following, and mixtures of two or more of these. (b1) Aromatic PI with 6-20 carbon atoms (excluding carbon in the NCO group, the same applies below) Diisocyanates (hereinafter abbreviated as DI), such as 1,3- or 1,4-phenylene DI, 2,4- or 2,6-tolylene DI (TDI), 4,4'- or 2,4'-diphenylmethane DI (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- or p-isocyanatophenylsulfonyl isocyanate, etc.; polyisocyanates (trisocyanates, etc.) having three or more functional groups, such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate), and 4,4',4''-triphenylmethane triisocyanate

[0014] (b2) aliphatic polyisocyanates having 2 to 18 carbon atoms DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl caproate, 2,6-diisocyanatoethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and trimethylhexamethylene diisocyanate (TMDI); polyisocyanates (trisocyanates, etc.) having three or more functional groups, such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, and lysine ester triisocyanate (phosgenated product of the reaction product of lysine and alkanolamine, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- or 3-isocyanatopropyl-2,6-diisocyanatohexanoate)

[0015] (b3) alicyclic polyisocyanates having 4 to 45 carbon atoms DIs, such as isophorone DI (IPDI), 2,4- or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4'-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, 2,5- or 2,6-norbornane DI, and dimer acid DI (DDI); trifunctional or more PIs (triisocyanates, etc.), such as bicycloheptane triisocyanate. (b4) C8~15 Aromatic aliphatic PI m- and p-xylylene DI (XDI), diethylbenzene DI, and α,α,α',α'-tetramethylxylylene DI (TMXDI) (b5) Nulates of (b1) to (b4) above Of these, (b1), (b3), and (b5) are preferred from the viewpoint of the high refractive index of the cured product of the present invention, as described later, and (b3) is even more preferred.

[0016] The NCO / OH equivalent ratio in the reactions of (a) and (b) is not particularly limited, but from the viewpoint of storage stability, it is preferably 1 / 10 to 1 / 0.5, more preferably 1 / 5 to 1 / 0.7, and especially preferably 1 / 2 to 1 / 1.

[0017] In the production of (A) obtained by reacting (a) and (b), a urethane catalyst may be used. Urethane catalysts include metal compounds (organobismuth compounds, organotin compounds, organotitanium compounds, etc.) and quaternary ammonium salts.

[0018] Among metal compounds, organobismuth compounds include organobismuth carboxylates, organobismuth alkoxides, and chelate compounds of bismuth with compounds having a dicarbonyl group. Organic bismuth carboxylates are represented by the general formula Bi(OCOR)3, where R is a monovalent aliphatic hydrocarbon group [C1-20, e.g., alkyl (methyl, ethyl, n- or i-propyl, n-, i-, sec- or t-butyl, octyl, 2-ethylhexyl, decyl, and dodecyl) and alkenyl (1-, 2- or i-propenyl, 1-, 2- or 3-butenyl) group], an aromatic (ali) hydrocarbon group (C6-20, e.g., phenyl, toluyl, xylenyl, benzyl, phenethyl, and hexylphenyl group), or an alicyclic hydrocarbon group (C3-10, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl group). Of these R groups, C2-12 aliphatic groups and C5-10 alicyclic hydrocarbon groups are preferred from the viewpoint of hydrolysis resistance. Specific examples of organic bismuth carboxylates include bismuthtri(2-ethylhexanoate), bismuthtri(decanoate), and bismuthtri(cyclohexanoate).

[0019] Organic bismuth alkoxides are represented by the general formula Bi(OR)3, where R is the same as above, and the preferred R from the viewpoint of hydrolysis resistance is also the same as above. Specific examples of organic bismuth alkoxides include tri-2-ethylhexyloxybismuth and tri-cyclohexyloxybismuth.

[0020] In chelate compounds of a compound having a dicarbonyl group and bismuth, the compound having a dicarbonyl group includes C4-C15 compounds such as acetylacetone, acetylacetic acid, and acetoacetoxyethyl (meth)acrylate, and the chelate compounds include chelate compounds of these compounds and bismuth. Specific examples of chelate compounds of a compound having a dicarbonyl group and bismuth include bis(acetylacetone)bismuth.

[0021] Organotin compounds include divalent tin compounds (such as stanus octoate) and tetravalent tin compounds (such as trimethyltin laurate, trimethyltin hydrooxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin maleate).

[0022] Organic titanium compounds include tetraalkyl (C2-12) titanates and alkylenedicarboxylic acid (C2-12) titanium. Examples of quaternary ammonium salts include tetraalkyl(C1-4)ammonium bromide and tetraalkyl(C1-4)ammonium perchlorate.

[0023] The amount of urethane catalyst used is preferably 1% or less, more preferably 0.001 to 0.5%, and even more preferably 0.05 to 0.2%, based on the total weight of (a) and (b), from the viewpoint of reactivity and transparency.

[0024] The conditions for the urethane reaction of (a) and (b) are not particularly limited. For example, (A) can be produced by mixing (a) and (b) and reacting them at a temperature of preferably 40 to 100°C, more preferably 60 to 95°C, for 2 to 20 hours, from the viewpoint of reactivity and the stability of the mixture. Alternatively, the mixture may be diluted with a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.) as needed before reaction. The amount of solvent used is preferably 5,000% or less based on the total weight of (a) and (b), with a lower limit of preferably 10% from the viewpoint of ease of handling the mixture and an upper limit of preferably 1,000% from the viewpoint of reaction rate.

[0025] The urethane reaction can be carried out under atmospheric pressure, reduced pressure, or increased pressure. The progress of the urethane reaction can be determined, for example, by measuring the NCO% and hydroxyl value of the reaction system.

[0026] The benzene skeleton content (by weight) in (A) is preferably 15-50%, more preferably 18-45%, and particularly preferably 20-40% from the viewpoint of the refractive index and light resistance of the cured product. Here, the benzene skeleton refers only to the carbon atoms constituting the benzene ring or its fused ring (naphthalene ring, etc.). The benzene skeleton may be derived from (a) or from (b). The benzene skeleton content is 1 H and 13 It can be measured by 13C-NMR (nuclear magnetic resonance spectroscopy) or IR (infrared absorption spectroscopy) analysis. for example, 1 When determining the benzene skeleton content using 1H-NMR, an internal standard is added, and the internal standard is used to determine the content derived from the internal standard. 1 The integral value of the H peak and the benzene skeleton in (A) 1 The number of moles of benzene skeletons in (A) can be determined from the ratio of the integral values ​​of the H peak (around 7-8 ppm), and the benzene skeleton content can be determined by multiplying this by the molecular weight.

[0027] The Mn in (A) is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, and particularly preferably 2,000 to 20,000, from the viewpoint of curability and ease of handling.

[0028] The content (by weight) of (A) is, based on the total weight of the composition of the present invention, preferably a lower limit of 5%, more preferably 7%, and particularly preferably 10% from the viewpoint of adhesion to the substrate, and preferably an upper limit of 50%, more preferably 40%, and particularly preferably 30% from the viewpoint of mold release properties.

[0029] In the present invention, (B) is a monomer having a chemical formula weight of 100 or more (preferably 150 or more) and Mn of 1,000 or less (preferably 800) and not having a urethane bond. If the chemical formula weight of (B) is less than 100, the curability decreases, and if the Mn exceeds 1,000, the adhesion to the plastic substrate decreases. (B) includes the following (B1), (B2), and mixtures thereof.

[0030] (B1) Aromatic unsaturated hydrocarbons C8-C18, for example, those containing one ethylenically unsaturated group (such as styrene), and those containing two ethylenically unsaturated groups (such as divinylbenzene). (B2) (meth)acryloyl group-containing monomer (B2-1) A monomer containing one (meth)acryloyl group C4-18, for example, aliphatic (meth)acrylates [methyl (meth)acrylate, ethyl (meth)acrylate, octyl acrylate, 2-ethylhexyl acrylate, etc.], alicyclic (meth)acrylates [cyclohexyl (meth)acrylate, etc.], aromatic (meth)acrylates [benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.], heterocyclic compounds [tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, etc.], and (meth)acrylates of AO1-10 molar adducts of alkyl (C1-20) phenols (C6-30) [for example, (meth)acrylate of PO8 molar adduct of phenol, (meth)acrylate of EO8 molar adduct of nonylphenol, etc.] (B2-2) A monomer containing two (meth)acryloyl groups C8-30, for example, aliphatic di(meth)acrylates [ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc.], alicyclic-containing di(meth)acrylates [dimethylol cyclotridecane diacrylate, etc.], and di(meth)acrylates of 2-10 molar AO adducts of bisphenol (Mn400) [for example, di(meth)acrylates of 2 molar EO of bisphenol A, and 4 molar PO adducts of bisphenol A, -F, and -S]. (B2-3) monomers containing 3 to 6 or more (meth)acryloyl groups Poly(meth)acrylates of polyhydric (trihydric to hexahydric or higher) alcohols (C3 to 40), such as trimethylolpropane (hereinafter abbreviated as TMP) tri(meth)acrylate, glycerin (hereinafter abbreviated as GR) tri(meth)acrylate, TMP-PO3 molar adduct tri(meth)acrylate, TMP-EO3 molar adduct tri(meth)acrylate, pentaerythritol (hereinafter abbreviated as PE) tri(meth)acrylate, PE-tetra(meth)acrylate, PE-EO4 molar adduct tetra(meth)acrylate, diPE-penta(meth)acrylate, and diPE-hexa(meth)acrylate.

[0031] Of the above (B1) to (B2) [(B2-1) to (B2-3)], (B2) is preferred from the viewpoint of adhesion to the plastic substrate and mold release properties, and (B2-1) and (B2-2) are even more preferred. Of (B), those containing active hydrogen atoms may be added after the urethane formation reaction is complete, while those without active hydrogen atoms may be added at either the urethane formation reaction or after the reaction is complete, or at both stages.

[0032] The content (by weight) of (B) is, based on the total weight of the composition of the present invention, preferably a lower limit of 25% from the viewpoint of the strength of the cured product, more preferably 30%, and especially preferably 35%, and preferably an upper limit of 85%, more preferably 80%, and especially preferably 70% from the viewpoint of curability.

[0033] In the present invention, the phosphate ester tertiary amine salt (C) is a composition comprising a salt of a phosphate ester (c1) and a tertiary amine (c2).

[0034] Examples of phosphate esters (c1) include those represented by the following general formula (1).

[0035] [ka] [In the formula, R 1[where is a C1-20 or larger alkoxy group, a C1-20 or larger alcohol AO1-30 molar adduct with active hydrogen removed, or a C1-20 or larger alcohol AO1-30 molar adduct with active hydrogen removed; m and n represent integers of 1 or 2 satisfying m+n=3.] In (c1), if it includes (c1-1) where n is 1 and (c1-2) where n is 2 as described in the general formula (1) above, the molar ratio of (c1-1) to (c1-2) ((c1-1) / (c1-2)) is preferably 0.5 / 1 to 2 / 1, more preferably 0.6 / 1 to 1.7 / 1, and particularly preferably 0.7 / 1 to 1.4 / 1, from the viewpoint of substrate adhesion and mold release properties.

[0036] A tertiary amine (C2) is a compound consisting of a tertiary aliphatic amine or an alkylene oxide adduct of a primary or secondary aliphatic amine. Examples of tertiary aliphatic amines, or alkylene oxide adducts of primary or secondary aliphatic amines, include tertiary aliphatic amines with 3 to 30 C atoms, 2 to 30 molar AO(C2 to 4) adducts of primary aliphatic (C4 to 30) amines, or 1 to 30 molar AO(C2 to 4) adducts of secondary aliphatic (C4 to 30) amines. Examples of tertiary aliphatic amines with C3-30 include triethylamine, tributylamine, lauryldimethylamine, and dimethylstearylamine. Examples of primary aliphatic (C4-30) amine AO(C2-4) 2-30 molar adducts or secondary aliphatic (C4-30) amine AO(C2-4) 1-30 molar adducts include butylamine EO4 molar and EO10 molar adducts, laurylamine EO10 molar adducts, stearylamine EO10 molar and EO15 molar adducts, diethylamine EO4 molar and EO10 molar adducts, dibutylamine EO4 molar and EO10 molar adducts, laurylmethylamine EO10 molar adduct, and methylstearylamine EO15 molar adduct.

[0037] (C) includes a salt produced by the neutralization reaction of (c1) and (c2), and a mixture of the salt and an excess of (c1) and / or (c2). There are no particular limitations on the equivalent ratio (c1 / c2) of (c1) and (c2) when manufacturing (C). However, from the viewpoint of storage stability of the composition and mold release properties of the cured product, the ratio is preferably 0.5 / 1 to 3 / 1, more preferably 0.7 / 1 to 2.5 / 1, and particularly preferably 0.8 / 1 to 2.0 / 1. Methods for incorporating (C) into the composition of the present invention include a method of first generating (C) from (c1) and (c2) and then adding it to the composition, and a method of adding (c1) and (c2) separately to the composition.

[0038] Specific examples of (C) include the salt of tetradecanol EO10 molar adduct phosphate ester / lauryldimethylamine, the salt of tetradecanol EO10 molar adduct phosphate ester / dimethylstearylamine, the salt of lauryl alcohol EO2 molar adduct phosphate ester / laurylamine EO10 molar adduct, the salt of tetradecanol EO2 molar adduct phosphate ester / stearylamine EO10 molar adduct, and the salt of stearyl alcohol EO10 molar adduct phosphate ester / stearylamine EO15 molar adduct.

[0039] The content (by weight) of (C) is preferably 0.001 to 3%, more preferably 0.01 to 2%, particularly preferably 0.05 to 1%, and most preferably 0.07 to 0.30%, based on the total weight of the composition of the present invention, from the viewpoint of imparting mold release properties, adhesion to plastic substrates, and increasing the refractive index of the cured product.

[0040] The composition of the present invention is an active energy ray curable urethane (meth)acrylate composition that satisfies the following requirement (1). Requirements: (1) The viscosity of the solution at 25°C is 2,500 to 5,000 mPa·s.

[0041] The composition of the present invention preferably satisfies the following requirements (1-2) from the viewpoint of substrate adhesion, and more preferably satisfies the following requirements (1-3). The solution viscosity at 25°C can be adjusted by the types and compositional ratios of (A), (B), and (C) that constitute composition (X). Requirements; (1-2) Solution viscosity at 25°C is 2,750-4,750 mPa·s (1-3) Solution viscosity at 25℃ is 2,800~4,500 mPa·s

[0042] The method for measuring the solution viscosity of the composition of the present invention at 25°C is as follows. <Method for measuring solution viscosity> The composition of the present invention is temperature-controlled at 25°C for 120 minutes, and the solution viscosity (mPa·s) is measured using a Type B viscometer [VISCOMETER TVB-10M manufactured by Toki Sangyo Co., Ltd.] under the following conditions. [Measurement conditions] Rotor: TM3 Measurement temperature: 25℃ Rotation speed: 12 rpm

[0043] The composition of the present invention is an active energy ray curable urethane (meth)acrylate composition that satisfies the following requirement (2). Requirements; (2) Double bond content is 3.2-3.8 mmol / g based on the weight of (X)

[0044] The composition of the present invention preferably satisfies the following requirement (2-2) from the viewpoint of mold release properties and substrate adhesion, and more preferably satisfies the following requirement (2-3). The double bond content can be adjusted depending on the types and compositional ratios of (A) and (B) that constitute composition (X). Requirements; (2-2) Double bond content is 3.25-3.75 mmol / g based on the weight of (X) (2-3) The double bond content is 3.3-3.7 mmol / g based on the weight of (X).

[0045] The double bond content of the composition of the present invention was calculated according to the formulation of the obtained composition (X) using the following method. The double bond content of (X) (mmol / g) = (Amount of (A) (g) × Double bond content of (A) (mmol / g) + Amount of (B) (g) × Double bond content of (B) (mmol / g)) ÷ (Weight of composition (X) (g))

[0046] The composition of the present invention is an active energy ray curable urethane (meth)acrylate composition that satisfies the following requirement (3). Requirements; (3) Aromatic content of 4.2-5.0 mmol / g based on the weight of (X)

[0047] The composition of the present invention preferably satisfies the following requirement (3-2) from the viewpoint of a high refractive index of the cured product, and more preferably satisfies the following requirement (3-3). The aromatic content can be adjusted by the types and compositional ratios of (A), (B), and (C) that constitute composition (X). Requirements; (3-2) Aromatic content of 4.25-4.95 mmol / g based on the weight of (X) (3-3) Aromatic content is 4.3-4.9 mmol / g based on the weight of (X)

[0048] The aromatic content of the composition of the present invention was calculated according to the formulation of the obtained composition (X) using the following method. Aromatic content of (X) (mmol / g) = (Amount of (A) (g) × Aromatic content of (A) (mmol / g) + Amount of (B) (g) × Aromatic content of (B) (mmol / g) + Amount of (C) (g) × Aromatic content of (C) (mmol / g)) ÷ (Weight of composition (X) (g))

[0049] The composition of the present invention may further contain various additives (E) used in paints and inks, as necessary, to the extent that they do not impair the effects of the present invention. (E) includes inorganic fine particles (E1), organic pigments (E2), dispersants (E3), defoamers (E4), leveling agents (E5), silane coupling agents (E6), thixotropy imparting agents (thickeners) (E7), slip agents (E8), antioxidants (E9), and ultraviolet absorbers (E10). The total content (by weight) of (E) is preferably 60% or less, and more preferably 0.005 to 50%, based on the total weight of the composition of the present invention.

[0050] (E1) includes alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (alumina and silica fusion, alumina coated with silica, etc.)], zirconia, tungsten carbide, titanium carbide, silicon carbide, boron carbide, diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (fine silica, hydrated silica, diatoms, colloidal silica, etc.), silicates (fine magnesium silicate, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), and carbonates. Examples include [settling (active, dry, heavy or light) calcium carbonate, magnesium carbonate, etc.], clay (kaolin clay, sericite clay, byrophyllite clay, montmorillonite clay, bentonite, acid clay, etc.), sulfates [aluminum sulfate (sulfate, satin white, etc.), barium sulfate (barite powder, precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (plaster) (anhydrous plaster, hemihydrate plaster, etc.)], lead white, mica powder, zinc oxide, titanium dioxide, activated calcium fluoride, cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, rock fiber, and microballoons.

[0051] Of these, alumina, silica, silicates, carbonates, sulfates, and titanium oxide are preferred from the viewpoint of scratch resistance and composition of the cured product, and suppression of discoloration of the cured product, while silica, calcium carbonate, barium sulfate, and titanium oxide are even more preferred. (E1) may be a combination of two or more types, or a composite of two or more types (for example, titanium oxide fused to silica). The shape of (E1) is not particularly limited and may be any of the following: irregular shape, spherical, hollow, porous, petal-shaped, aggregated, or granular. The volume-average particle size of (E1) is preferably 0.01 to 1 μm. The content (by weight) of (E1) is preferably 50% or less, more preferably 30% or less, and even more preferably 3-25%, based on the total weight of the composition of the present invention, from the viewpoint of the flexibility of the cured product.

[0052] Examples of organic pigments (E2) include the following: (1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine 6B, etc.), condensed azo pigments, chelate azo pigments, etc. (2) Polycyclic pigments Phthalocyanine blue, indanthron blue, quinacridone red, dioxazine violet, etc. (3) Dyeing rake Basic dyes (such as Victoria Pure Blue BO Lake), acid dyes (such as Alkali Blue Toner), etc. (4) Others Adin pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments The content (by weight) of (E2) is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less, based on the total weight of the composition, from the viewpoint of the flexibility of the cured product.

[0053] Examples of dispersants (E3) include organic dispersants [high molecular weight dispersants (Mn 2,000 to 500,000) and low molecular weight dispersants (chemical formula weight of 100 or more and Mn less than 2,000)] and inorganic dispersants.

[0054] Examples of polymeric dispersants include formalin condensates of naphthalene sulfonates [alkali metal (Na and K, etc.) salts, ammonium salts, etc.], polystyrene sulfonates (same as above), polyacrylates (same as above), poly(2-4)carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salts (same as above), carboxymethylcellulose (Mn 1,000-10,000), and polyvinyl alcohol (Mn 1,000-100,000).

[0055] Examples of low molecular weight dispersants include the following: (1) Polyoxyalkylene type AO(C2-4) 1-30 molar adducts of aliphatic alcohols (C4-30), alkyl(C1-30) phenols, aliphatic(C4-30) amines, and aliphatic(C4-30) amides Examples of aliphatic alcohols include n-, i-, sec-, and t-butanol, octanol, and dodecanol; examples of (alkyl)phenols include phenol, methylphenol, and nonylphenol; examples of aliphatic amines include laurylamine and methylstearylamine; and examples of aliphatic amides include stearic acid amide. (2) Polyhydric alcohol type Monoester compounds of C4-C30 fatty acids (lauric acid, stearic acid, etc.) and polyhydric (dihydric to hexahydric or higher) alcohols (e.g., GR, PE, sorbitol, and sorbitan) (3) Carboxylate type Alkali metal salts (same as above) of fatty acids C4-C30 (same as above) (4) Sulfate ester type Alkali metal (SALES) salts of C4-C30 aliphatic alcohols (same as above) and 1-30 molar AO(C2-C4) adducts of aliphatic alcohols, etc. (5) Sulfonate type Alkyl(C1~30) phenol (same as above) alkali metal sulfonates (same as above) (6) Phosphate ester type Salts of mono- or diphosphate esters of C4-30 aliphatic alcohols (same as above) and 1-30 molar adducts of aliphatic alcohols AO(C2-4) [alkali metal (same as above) salts, quaternary ammonium salts, etc.], excluding the aforementioned tertiary amine phosphate salts (C). (7) Primary to tertiary amine salt type Hydrochloride salts of C4-30 aliphatic amines [primary (e.g., laurylamine), secondary (e.g., dibutylamine), and tertiary (e.g., dimethylstearylamine)], and inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, etc.) salts of triethanolamine and monoesters of C4-30 fatty acids (same as above). (8) Quaternary ammonium salt type Inorganic acid salts (same as above) of quaternary ammonium compounds of C4-30 (butyltrimethylammonium, diethyllaurylmethylammonium, dimethyldistearylammonium, etc.) These are some examples.

[0056] Examples of inorganic dispersants include alkali metal salts (as described above) of polyphosphate and phosphate-based dispersants (phosphoric acid, monoalkyl phosphate esters, dialkyl phosphate esters, etc.). The content (by weight) of (E3) is preferably 10% or less, and more preferably 0.05 to 5%, based on the total weight of the composition of the present invention.

[0057] Examples of defoaming agents (E4) include lower alcohols (C1-6) (methanol, butanol, etc.), higher alcohols (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acids (C10-20) (oleic acid, stearic acid, etc.), higher fatty acid esters (C11-30) (glycerin monolaurelate), phosphate esters (tributyl phosphate, tetradecanol EO2 molar adduct phosphate ester, etc.), metal soaps (calcium stearate, aluminum stearate, etc.), polyethers [polyethylene glycol (hereinafter abbreviated as PEG) (Mn200-10,000), polypropylene glycol (hereinafter abbreviated as PPG) (Mn200-10,000), etc.], silicones (dimethyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.), and mineral oil-based products (silica powder dispersed in mineral oil). The content (by weight) of (E4) is preferably 3% or less, and more preferably 0.01 to 2%, based on the total weight of the composition of the present invention.

[0058] Examples of leveling agents (E5) include PEG-type nonionic surfactants (nonylphenol EO 1-40 molar adduct, stearate EO 1-40 molar adduct, etc.), polyhydric alcohol-type nonionic surfactants (sorbitan palmitate monoester, sorbitan stearate monoester, sorbitan stearate triester, etc.), fluorinated surfactants (perfluoroalkyl EO 1-50 molar adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), and modified silicone oils [polyether-modified silicone oil, (meth)acrylate-modified silicone oil, etc.]. The content (by weight) of (E5) is preferably 3% or less, and more preferably 0.1 to 2%, based on the total weight of the composition of the present invention.

[0059] Examples of silane coupling agents (E6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, etc.), ureido group-containing silane coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris(β-methoxyethoxy)silane, etc.], and methacrylate group-containing silane coupling agents (γ-methacryloxypropyltrimeth Examples include xysilane, γ-methacryloxypropylmethyldimethoxysilane, epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agents (γ-isocyanatetopropyltriethoxysilane, etc.), polymer-type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), and cationic silane coupling agents [N-(N-benzyl-β-aminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.]. The content (by weight) of (E6) is preferably 10% or less, and more preferably 0.5 to 7%, based on the total weight of the composition of the present invention.

[0060] Examples of thixotropy-imparting agents (thickeners) (E7) include inorganic thixotropy-imparting agents [bentonite, organically treated bentonite (such as surface wax-coated bentonite), and ultrafine surface-treated calcium carbonate (such as colloidal calcium carbonate)] and organic thixotropy-imparting agents (such as hydrogenated castor oil wax, calcium stearate, aluminum oleate, and polymerized linseed oil). The content (by weight) of (E7) is preferably 20% or less, and more preferably 0.5 to 10%, based on the total weight of the composition of the present invention.

[0061] Examples of slip agents (E8) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylenebis-stearate amide and oleamide), metal soaps (such as calcium stearate and aluminum oleate), waxes [such as paraffin wax, polyolefin waxes (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)], and silicones (e.g., dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil). The content (by weight) of (E8) is preferably 5% or less, and more preferably 0.01 to 2%, based on the total weight of the composition of the present invention.

[0062] Examples of antioxidants (E9) include hindered phenol compounds [triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.). The content (by weight) of (E9) is preferably 3% or less, and more preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

[0063] Examples of UV absorbers (E10) include benzotriazole compounds [2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, etc.], triazine compounds [2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol], benzophenones (2-hydroxy-4-n-octyloxybenzophenone, etc.), and oxalate anilide compounds (2-ethoxy-2'-ethyloxalic acid bisanilide, etc.). The content (by weight) of (E10) is preferably 3% or less, and more preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

[0064] If the same additives overlap between (E1) and (E10) above, the amount used should not be adjusted according to the purpose of use, taking into consideration that the effects of other additives may also be obtained simultaneously, rather than using the amount that each additive provides to achieve its corresponding additive effect regardless of the effects of other additives.

[0065] The composition of the present invention may optionally contain a photopolymerization initiator (F) and / or a thermosetting catalyst (G), as long as it does not impair the effects of the present invention. Compositions containing (F) and / or (G) can be cured not only by electron beam but also by heat and / or ultraviolet light, yielding cured products with excellent chemical resistance and scratch resistance. When curing by heat, a temperature of 50 to 200°C is preferred, and more preferably, heating in an oven at 80 to 180°C for 1 minute to 20 hours is desirable. When curing by ultraviolet light, the irradiation dose of ultraviolet light is preferably 10 to 10,000 mJ / cm². 2 That is the case.

[0066] Examples of (F) include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, benzoin alkyl ether, etc.), benzoyl formate compounds (methylbenzoyl formate, etc.), thioxanthone compounds (isopropylthioxanthone, etc.), benzophenone (benzophenone, etc.), phosphine oxide compounds (1,3,5-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.), benzyldimethyl ketal, etc. Of these, phosphine oxide compounds are preferred from the viewpoint of preventing discoloration of the cured product and mold release properties, and more preferably 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethylphenylphosphine oxide.

[0067] Examples of (G) include peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile and azobisisovaleronitrile, etc.). Of these, t-butyl peroxybenzoate and methyl ethyl ketone peroxide are preferred from the viewpoint of compositional stability and reactivity.

[0068] The content (by weight) of (F) and (G) is preferably 20% or less, and more preferably 0.1 to 10%, respectively, based on the total weight of the composition of the present invention.

[0069] The composition of the present invention can be diluted with a solvent as needed to adjust the solution viscosity to a level suitable for coating during application. The solvent content (weight %) is preferably 2,000% or less, more preferably 10 to 500%, based on the weight of the composition. The solution viscosity of the coating is preferably 5 to 500,000 mPa·s, more preferably 50 to 10,000 mPa·s, at the temperature during use (preferably 5 to 60°C), from the viewpoint of stable coating.

[0070] The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, examples include aromatic hydrocarbons (C7-10, e.g., toluene, xylene, and ethylbenzene), esters or ether esters (C4-10, e.g., ethyl acetate, butyl acetate, and methoxybutyl acetate), ethers (C4-10, e.g., diethyl ether, tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG, and monoethyl ether of EG), ketones (C3-10, e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone), alcohols (C1-10, e.g., methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol), amides (C3-6, e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (C2-4, e.g., dimethyl sulfoxide), water, and mixtures of two or more of these solvents. Of these solvents, those preferred from the viewpoint of ease of handling are esters, ketones, and alcohols with a boiling point of 70 to 100°C, and more preferably ethyl acetate, methyl ethyl ketone, i-propanol, and mixtures thereof.

[0071] The composition of the present invention can be diluted with a solvent as necessary, applied to at least a portion of at least one side of a substrate, dried as necessary, and then cured by irradiation with active energy rays as described later to obtain a coating having a cured product on at least a portion of the surface and / or back surface of the substrate. In this coating process, commonly used devices such as coating machines [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used. The coating film thickness, as the film thickness after drying and curing, is preferably 0.5 to 300 μm. From the viewpoints of drying property and curability, the preferable upper limit is 250 μm, and from the viewpoints of scratch resistance, solvent resistance, and stain resistance, the preferable lower limit is 1 μm.

[0072] When the composition of the present invention is diluted with a solvent and used, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is preferably 10 to 200 °C. From the viewpoint of the smoothness and appearance of the coating film, the preferable upper limit is 150 °C, and from the viewpoint of the drying speed, the preferable lower limit is 30 °C.

[0073] The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible light rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and resin deterioration.

[0074] When the composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation devices [Eye Grandage [trade name, manufactured by Eye Graphic Co., Ltd.], metal halide lamp, etc.] can be used. The irradiation dose of ultraviolet rays is preferably 10 to 10,000 mJ / cm 2 and from the viewpoint of the curability of the composition, the preferable lower limit is 100 mJ / cm 2 and from the viewpoint of the flexibility of the cured product, the preferable upper limit is 5,000 mJ / cm 2 is.

[0075] When the composition of the present invention is cured by electron beam irradiation, various electron beam irradiation devices [for example, electron beam, manufactured by Iwasaki Electric Co., Ltd.] can be used. The irradiation dose of electron beam is preferably 0.5 to 20 Mrad. From the viewpoint of the curability of the composition, the preferable lower limit is 1 Mrad, and from the viewpoints of the flexibility of the cured product and avoiding damage to the cured product (coating film) or the substrate, the preferable upper limit is 15 Mrad.

[0076] The composition of the present invention is usually cured by active energy rays (ultraviolet rays, electron beams, X-rays, etc.), but if a thermosetting catalyst is included as necessary, it can be cured by heat.

[0077] The refractive index of the cured product of the present invention is preferably 1.540 to 1.580, and more preferably 1.550 to 1.570, from the viewpoint of application to optical components and ease of synthesis. The refractive index can be increased by increasing the benzene skeleton content in the cured product.

[0078] The cured product of the composition of the present invention can be used as an optical component or an electrical / electronic component, or as a coating agent for shaping materials of a substrate. The substrates to which it can be applied are not particularly limited, but examples include paper, plastic, glass, and metal. Specifically, examples include paper (e.g., tissue paper, inter-paper reinforced paper, titanium paper, latex-impregnated paper, and base paper for gypsum board), plastics [plastic films (films such as vinyl chloride, polyester, polypropylene, and polymethyl methacrylate), plastic sheets (sheets such as polymethyl methacrylate, polycarbonate, and methyl methacrylate / styrene copolymer), etc.], glass sheets, copper sheets, iron sheets, etc. [Examples]

[0079] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. In the following, "parts" refers to parts by weight.

[0080] <Manufacturing Example 1> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 1044 parts of bisphenol A PO2 molar adduct [product name: Newpol BP-2P, manufactured by Sanyo Chemical Industries, Ltd.], 752.8 parts of xylylene diisocyanate, and 0.1 parts of bismathtri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid, the same applies hereafter) "Nitto Chemical Co., Ltd., Neostan U-600" were charged as a urethane catalyst. The mixture was reacted at 80°C for 4 hours, and then 232.2 parts of 2-hydroxyethyl acrylate were added (NCO / OH equivalent ratio = 1 / 1), and the mixture was reacted at 80°C for 6 hours to obtain urethane acrylate (A-1).

[0081] <Manufacturing Example 2> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 1200 parts of 3-mol bisphenol A adduct [product name: Newpol BP-3P, manufactured by Sanyo Chemical Industries, Ltd.], 752.8 parts of xylylene diisocyanate, and 0.1 parts of bismathtri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid, the same applies hereafter) "Nitto Chemical Co., Ltd., Neostan U-600" were charged as a urethane catalyst. The mixture was reacted at 80°C for 4 hours, and then 232.2 parts of 2-hydroxyethyl acrylate were added (NCO / OH equivalent ratio = 1 / 1), and the mixture was reacted at 80°C for 6 hours to obtain urethane acrylate (A-2).

[0082] <Manufacturing Example 3> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 2000 parts of polytetraethylene glycol [product name: PTMG-1000, manufactured by Mitsubishi Chemical Corporation, Mn 1,000], 666.9 parts of isophorone diisocyanate, and 0.1 parts of bismuth tri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid, the same applies hereafter) "Nitto Kasei Co., Ltd., Neostan U-600" were charged as a urethane catalyst. The mixture was reacted at 80°C for 4 hours, after which 232.2 parts of 2-hydroxyethyl acrylate were added (NCO / OH equivalent ratio = 1 / 1), and the mixture was reacted at 80°C for 6 hours to obtain urethane acrylate (A-3).

[0083] <Manufacturing Example 4> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 348 parts of 2-molar bisphenol A adduct [product name: Newport BP-2P, manufactured by Sanyo Chemical Industries, Ltd.], 444.6 parts of isophorone diisocyanate, and 0.1 parts of bismathtri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid, the same applies hereafter) "Nitto Chemical Co., Ltd., Neostan U-600" were charged as a urethane catalyst. The mixture was reacted at 80°C for 4 hours, and then 232.2 parts of 2-hydroxyethyl acrylate were added (NCO / OH equivalent ratio = 1 / 1), and the mixture was reacted at 80°C for 6 hours to obtain urethane acrylate (A-4).

[0084] <Manufacturing Example 5> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 484 parts of a 2-mol adduct of bisphenol A glycidyl ether to acrylic acid [product name: Viscoat #540, manufactured by Osaka Organic Chemical Industry Co., Ltd.] and 169 parts of isophorone diisocyanate were charged, followed by 620 parts of phenoxyethyl acrylate, and the mixture was reacted at 85°C for 2 hours. Then, 0.2 parts of bismathtri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid, the same applies hereafter) "Nitto Kasei Co., Ltd., Neostan U-600" was charged as a urethane catalyst, and the mixture was reacted at 85°C for 2 hours to obtain a urethane acrylate-containing product (S-1).

[0085] <Examples 1-9, Comparative Examples 1-5> Urethane acrylate compositions (X-1 to X-9, ratios X-1 to X-5) were obtained by compounding according to Table 1. Furthermore, the solution viscosity (unit: mPa·s) was measured for the obtained urethane acrylate compositions (X-1 to X-9, ratios X-1 to X-5), and the double bond content (unit: mmol / g) and aromatic content (unit: mmol / g) were calculated. The results are shown in Table 1.

[0086] The ingredients listed in Table 1 are as follows: Monomer (B-1): Diacrylate of 4-mol EO adduct of bisphenol A [Product name: Neomer BA-641, manufactured by Sanyo Chemical Industries, Ltd., Mn512] Monomer (B-2): 2-Phenoxyethyl acrylate (Mn192) Monomer (B-3): Benzyl acrylate (Mn162) Monomer (B-4): Diacrylate (Mn898) of the EO10 molar adduct of 9,9-diphenoxyfluorene Phosphate ester (c1-1): Phosphate ester of tetradecanol EO10 molar adduct Phosphate esters (C1-2): Hexadecanol phosphate esters (a 1:1 molar mixture of monohexadecyl phosphate and dihexadecyl phosphate) Tertiary amine (c2-1): Stearylamine EO15 molar adduct Tertiary amine (C2-2): Dimethyltetradecylamine Antioxidant: Tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane Photopolymerization initiator: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[0087] [Table 1]

[0088] The above-mentioned urethane acrylate composition was used to measure refractive index, mold release properties, substrate adhesion, and moisture and heat resistance using the following test methods. The results are shown in Table 2.

[0089] <Refractive index> After forming a film of the composition in the gap between two glass plates separated by a 50μm thick spacer, the glass is irradiated from one side with an ultraviolet light (150mW / cm²). 2 The material was cured using an LED lamp (365 nm) to obtain a cured film. The refractive index of the film at 25°C was measured using an Abbe refractometer.

[0090] <Mold release properties, substrate adhesion, moisture and heat resistance> The composition was heated to 35°C and applied to a mold (50cm long, 50cm wide, mold temperature 35°C) that had been pre-plated with chrome on its inner surface, using a dispenser to a thickness of 100 μm. Next, a 100 μm thick (50cm long, 50cm wide) transparent film made of polyethylene terephthalate [product name: Cosmoshine A-4360, manufactured by Toyobo Co., Ltd.] was pressure-laminated onto the urethane acrylate composition applied to the mold, ensuring no air was trapped inside. Furthermore, the composition was cured by irradiating it with ultraviolet light from the top surface of the substrate using an ultraviolet irradiation device. The mold release properties, substrate adhesion, and humidity and heat resistance of the cured product (film) with the film attached were evaluated according to the following criteria. 1.Mold releasability The release properties of the film-coated cured product (film) when slowly peeled from the mold were evaluated from the following perspectives. ◎: There is no snagging, and the mold release is smooth and easy. ○: There is some resistance, but the film releases without deformation. △: Deformation of the film occurred during demolding. ×: Not all of the hardened material can be released from the mold, and some remains in the mold. 2. Adhesion to the substrate A grid pattern (10 x 10) was created by making 1 mm wide cuts on the surface of the cured material (film) with a knife. Cellophane adhesive tape was then applied to the grid pattern and peeled off at a 90-degree angle. The peeling state of the cured material (film) from the substrate was observed and evaluated. ◎: The squares on the Go board are not peeling off at all, and there is no peeling at the corners of the squares. ○: The squares on the Go board do not peel off, but partial peeling is visible at the corners of the squares. ×: One or more squares on the Go board are detached. 3. Moisture and heat resistance The cured material (film) was placed in a constant temperature and humidity chamber adjusted to 60°C and 95%RH, and its appearance was observed after 1000 hours. The cured material (film) after the humidity and heat resistance test was evaluated in the same manner as in 2. Adhesion to the substrate. ◎: The squares on the Go board are not peeling off at all, and there is no peeling at the corners of the squares. ○: The squares on the Go board do not peel off, but partial peeling is visible at the corners of the squares. ×: One or more squares on the Go board are detached.

[0091] [Table 2]

[0092] As can be seen from the results in Table 2, the cured product (film) obtained by curing the composition of the present invention has a high refractive index, is easy to release from the mold, has good adhesion to the substrate, and has good resistance to moisture and heat. [Industrial applicability]

[0093] The cured product (film) obtained by curing the urethane (meth)acrylate composition of the present invention exhibits excellent release properties from molds, high refractive index, good adhesion to substrates, and good resistance to moisture and heat. Therefore, it is widely used in optical components (plastic lenses, optical fibers, etc.), electrical and electronic components (anti-reflective films, anti-gray films), and various coating agents.

Claims

1. An active energy ray-curable urethane (meth)acrylate composition (X) comprising urethane (meth)acrylate (A), a monomer (B) having a chemical formula weight of 100 or more and a number average molecular weight of 1,000 or less that does not have a urethane bond, and a tertiary amine salt of a phosphate ester (C), wherein (C) consists of a salt of a phosphate ester (c1) and a tertiary amine (c2), and (c2) consists of a tertiary aliphatic amine or an alkylene oxide adduct of a primary or secondary aliphatic amine, and satisfying all of the following requirements (1) to (3). Requirements: (1) The viscosity of the solution at 25°C is 2,500 to 5,000 mPa·s. (2) The double bond content is 3.2 to 3.8 mmol / g based on the weight of (X) (3) Aromatic content is 4.2 to 5.0 mmol / g based on the weight of (X)

2. The composition according to claim 1, further comprising a thermosetting catalyst and / or a photopolymerization initiator in the composition.

3. A coating agent comprising the composition described in claim 1.

4. An optical component or an electrical / electronic component comprising a cured product obtained by curing the composition described in claim 1.

5. A method for producing a coating, characterized by applying the composition described in claim 1 to at least a portion of at least one side of a substrate and curing it by irradiation with active energy rays.

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