JP2009007568A - Resin composition curable with active energy ray - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition curable with active energy ray, having good curing property and excellent release property from a die (particularly, from a mold) and giving a cured product excellent in scratch resistance, rigidity and adhesiveness to a substrate. <P>SOLUTION: The resin composition curable with active energy ray comprises an epoxy (meth)acrylate (A) produced from an epoxide (a1) and a (meth)acrylic acid, a (meth)acrylate (B) excluding (A), a photopolymerization initiator (C), and release property imparting agent(D), wherein the agent (D) comprises a salt of a phosphoric acid ester (d1) and a tertiary amine (d2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition that gives a cured product excellent in releasability from a mold (particularly a mold).

Conventionally, prism lenses used for liquid crystal displays, and optical lenses such as Fresnel lenses and lenticular lenses used for projection TVs are generally manufactured by injection molding or hot press molding of thermoplastic resin. . In these manufacturing methods, since a long time is required for heating and cooling at the time of manufacturing, productivity is low, and due to thermal contraction of the optical lens, there is a problem that the reproducibility of the fine structure is poor and warps. . In order to solve these problems, a method in which an ultraviolet curable resin composition is poured into a mold in which a transparent resin base material is set on the inner surface of a mold and is cured by irradiating with ultraviolet rays.
In recent years, with high-definition displays, optical lenses have also been required to have high-definition. Therefore, a lens with a sharp tip and a fine apex angle of 60 to 70 ° and a pitch of several tens of μm. Need to form. However, since the lens is easily damaged by scratches or the like, the prevention thereof has been studied. A method of introducing a rigid structure such as a bisphenol skeleton (see, for example, Patent Document 1) or the addition of a fluorine compound or the like can cause slippage on the surface. There have been proposed a method for imparting the property to make it difficult to be damaged (for example, see Patent Document 2), a method for further providing a hard coat layer on the lens (for example, see Patent Document 3), and the like.

JP-A-11-240926 JP 2005-272700 A JP 11-326607 A

However, these methods have problems in that the releasability from the mold is poor, cracking and breakage occur frequently, and the yield decreases.
An object of the present invention is an active energy ray curable mold which has a good curability, an excellent releasability from a mold (particularly a mold), and gives a cured product excellent in scratch resistance, rigidity and adhesion to a substrate. The object is to provide a resin composition.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to epoxy (meth) acrylate (A) formed from epoxide (a1) and (meth) acrylic acid, (meth) acrylate (B) excluding (A), photopolymerization initiator (C). And a mold release property-imparting agent (D), wherein (D) is a salt of a phosphate ester (d1) and a tertiary amine (d2).

The active energy ray-curable resin composition of the present invention has the following effects.
(1) It is excellent in curability, and the obtained cured product is excellent in releasability from a mold (particularly a mold).
(2) The cured product is excellent in adhesion to the substrate, excellent in scratch resistance and rigidity.

Epoxy (meth) acrylate (A) in the present invention is epoxide (a1) and (meth).
It is formed from acrylic acid.
In (a1), the following polyvalent (divalent to hexavalent or higher) phenol or alkylene oxide thereof [carbon number (hereinafter abbreviated as C) 2 to 4. Hereinafter, abbreviated as AO. same as below. Poly (divalent to hexavalent or higher) glycidyl ether of adduct, poly (divalent to hexavalent or higher) alcohol or poly (divalent to hexavalent or higher) glycidyl ether of AO adduct thereof Is included.

(1) Diglycidyl ether of dihydric phenol C6-30 dihydric phenol such as monocyclic phenol (catechol, resorcinol etc.) and polycyclic phenol [condensed polycyclic phenol (dihydroxynaphthalene etc.), bisphenol compound (bisphenol A and- F, etc.), halogenated bisphenol compounds (dichloro- and tetrachlorobisphenol A etc.), biphenyl compounds (tetramethylbiphenyl etc.) etc.] diglycidyl ether, di-obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin. (2) Polyglycidyl ethers of trivalent to hexavalent or higher polyhydric phenols such as glycidyl ethers, etc. Polyglycidyl ethers of trihydric to hexavalent or higher polyhydric phenols of C6 or higher and Mn 5,000 or lower, for example Di- and triglycidyl ethers of trivalent phenols [pyrogallol, dihydroxynaphthylcresol, tris (hydroxyphenyl) methane, etc.], tetra-, tri and diglycidyl ethers of tetravalent phenols [tetrakis (4-hydroxyphenyl) ethane, etc.], Polyglycidyl ethers of hexavalent or higher polyhydric phenols [phenol or cresol novolak resin (Mn 200 to 5,000), polyhydric phenol obtained by condensation reaction of resorcin and acetone (Mn 400 to 5,000), etc.], etc.

(3) Diglycidyl ether of dihydric alcohol C2-30 dihydric alcohol such as aliphatic dihydric alcohol [ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol (hereinafter referred to as EG, respectively) PG, BD, HD, etc.), decanediol, etc.], alicyclic divalent alcohols [cyclopentanediol, cyclohexanediol, norbornanediol, isobornyldiol, adamantanediol, cyclopentadienyldiol, cyclohexanedimethanol, di Cyclopentadienedimethanol, etc.], diglycidyl ethers of aromatic alcohols containing dihydric alcohols [xylylenediol, diethanolbenzene, etc.] (4) polyglycidyl ethers of trihydric to hexahydric or higher polyhydric alcohols C6 or higher Polyglycidyl ethers of trihydric to hexahydric or higher polyhydric alcohols having Mn of 5,000 or less, such as trimethylolpropane (hereinafter abbreviated as TMP), glycerin (hereinafter abbreviated as GR), pentaerythritol (hereinafter abbreviated as PE) and Polyglycidyl ether of di PE, etc.

(5) Polyglycidyl ethers of polyvalent (divalent to hexavalent or higher) alcohols or polyvalent (divalent to hexavalent or higher) phenols AO adducts as exemplified in the above (1) to (4) Polyglycidyl ethers of compounds obtained by adding AO to polyhydric alcohols, polyhydric alcohols, and mixtures thereof.
Examples of AO include ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 2,3-, 1,3- and isobutylene. Examples thereof include oxide, tetrahydrofuran (hereinafter abbreviated as THF), and a mixture thereof. Of these, EO is preferable from the viewpoint of adhesion between the cured product and the substrate, which will be described later.
The number of moles of AO added to the polyhydric phenol or polyhydric alcohol is preferably 1 to 20 moles, more preferably 2 to 15 moles, particularly preferably from the viewpoint of the adhesion between the cured product and the substrate and the rigidity of the cured product. Is 2 to 10 moles. As an additional format when AOs are different, either random and / or block may be used.

The molecular weight of (A) is preferably 150 or more and Mn 3,000 or less, more preferably 180 or more and Mn 1,500 or less, from the viewpoint of the adhesion between the cured product and the substrate and the rigidity of the cured product.
The number of hydroxyl groups in (A) is usually 2 to 6 or more, preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 from the viewpoint of adhesion between the cured product and the substrate and an industrial viewpoint. ~ 3.
The number of (meth) acryloyl groups in (A) is usually 2 to 6 or more, preferably 2 to 6, more preferably 2 to 4, from the viewpoint of curability of the resin composition of the present invention and an industrial viewpoint. Especially preferably, it is 2-3.

  (B) in the present invention is a (meth) acrylate excluding the above (A), and (B) includes the following (B1), (B2) and a mixture thereof.

(B1) One (meth) acryloyl group-containing monomer C4-18, such as aliphatic (meth) acrylate [methyl-, ethyl-, octyl- and 2-ethylhexyl (meth) acrylate, etc.], alicyclic ring-containing (meth) Acrylate [cyclohexyl (meth) acrylate, etc.], aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc.], heterocyclic compound [tetrahydrofurfuryl (meth) acrylate, (meth) acryloyl Morpholine, etc.], [alkyl (C1-20)] (meth) acrylate of phenol (C6-30) AO 1-10 mol adduct [eg (meth) acrylate of phenol PO8 mol adduct, EO 8 mol adduct of nonylphenol (Meth) acrylate etc.], average And mono (meth) acrylates of the AO adducts of the exemplified polyhydric (divalent to hexavalent or higher) alcohols and the polyhydric alcohol and / or polyvalent (divalent to hexavalent or higher) phenols.

(B2) 2 to 6 or more (meth) acryloyl group-containing monomers (B2-1) 2 (meth) acryloyl group-containing monomers C8 to 30 such as aliphatic di (meth) acrylate [EG di ( Meth) acrylate, 1,6-HD di (meth) acrylate, etc.], alicyclic di (meth) acrylate [dimethylolcyclotridecane diacrylate, etc.] and bisphenol (C13 or more and Mn400 or less) AO2 to 10 mol adduct Di (meth) acrylates [2 mol of EO of bisphenol A, di (meth) acrylates of PO4 mol adducts of bisphenol A, -F, and -S, etc.], and the above exemplified polyvalent (divalent to hexavalent or More) alcohol, and the polyhydric alcohol and / or polyvalent (divalent to hexavalent or higher) pheno AO adduct di (meth) acrylate

(B2-2) 3 to 6 or more (meth) acryloyl group-containing monomers Poly (meth) acrylates of polyvalent (trivalent to hexavalent or higher) alcohols (C3 to 40), such as TMP tri ( (Meth) acrylate, GR tri (meth) acrylate, tri (meth) acrylate of TMP-PO3 molar adduct, tri (meth) acrylate of TMP-EO3 molar adduct, PE tri- and PE-tetra (meth) acrylate, PE Tri- and tetra (meth) acrylates of EO4 molar adducts, and tri-, tetra-, penta- and hexa (meth) acrylates of diPE

  Of the above (B1), (B2), and a mixture thereof, a mixture of (B1) and (B2) is preferable from the viewpoints of adhesion of the cured product to the substrate and mold release properties. In the case of a mixture of (B1) and (B2), the weight ratio [(B1) / (B2)] is preferably 25/75 to 90/10 from the same viewpoint.

  The molecular weight of (B) is preferably 100 (more preferably 150) or more and Mn 1,000 (more preferably 800) or less from the viewpoint of the curability of the resin composition of the present invention and the adhesion of the cured product to the substrate. It is.

As the photopolymerization initiator (C) in the present invention, C8 or more and Mn 1,000 or less, such as hydroxybenzoyl (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin) Alkyl ethers), benzoylformate (methylbenzoylformate, etc.), thioxanthone (isopropylthioxanthone, etc.), benzophenone (benzophenone, etc.), phosphate ester (1,3,5-trimethylbenzoyldiphenylphosphine oxide, etc.), ketal (benzyl) Dimethyl ketal).
Among (C), from the viewpoint of suppressing the coloration of the cured product, hydroxybenzoyl and phosphate are preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl are more preferable. Ketones and 1,3,5-trimethylbenzoyldiphenylphosphine oxide.

  The mold releasability imparting agent (D) in the present invention contains a salt composed of a phosphate ester (d1) and a tertiary amine (d2).

The phosphate ester (d1) includes those represented by the following general formula (1) and mixtures of different types thereof.

_{^{(R 1) n -P (=}} O) - (OH) m (1)

In the formula, R ¹ is a C1-20 or higher alkoxy group, a residue obtained by removing an active hydrogen of AO1 to 30 mol adduct of C1-20 or higher alcohol, or [alkyl (C1-20)] phenol. Residue excluding active hydrogen of AO1-30 mol adduct of (C6-30); m and n are integers of 1 or 2 satisfying m + n = 3.
As AO, EO is preferable from the viewpoints of storage stability of the composition, adhesion to the substrate, and the like.

  Specific examples of (d1) include dodecanol phosphate mono- and / or diester, tridecanol phosphate mono- and / or diester, tetradecanol phosphate mono- and / or diester, stearyl alcohol phosphate mono -And / or diester, phosphoric mono- and / or diester of dodecanol EO 2 mol or PO2 mol adduct, phosphoric mono- and / or diester of tetradecanol EO 2 mol or PO2 mol of triester EO2 mol or PO2 mol adduct Phosphate mono- and / or diester of adduct, stearyl alcohol EO 10 mol adduct phosphate mono- and / or diester, dodecanol EO 10 mol adduct phosphate mono- and / or diester, tridecano Examples include phosphoric acid mono- and / or diester of EO 10 mol adduct, phosphoric acid mono- and / or diester of tetradecanol EO 10 mol adduct, and phosphoric acid mono- and / or diester of stearyl alcohol EO 10 mol adduct. It is done.

Among these, from the viewpoint of imparting mold releasability (D) and industrial viewpoint, phosphoric acid mono- and / or diester of dodecanol, mono- and / or diester of stearyl alcohol, and 10 mol of stearyl alcohol EO are added. Phosphoric acid mono- and / or diesters, and tridecanol EO 10 mol adduct phosphoric acid mono- and / or diesters, more preferably a monoester / diester mixture having a monoester / diester molar ratio of 1/1. is there.

  As tertiary amine (d2), C3 or more and Mn 1,500 or less, for example, C3-30 aliphatic tertiary amine, aliphatic primary amine (C1-30) AO 2-30 mol adduct, and aliphatic 2 AO 1-30 mol adduct of a primary amine (C2-30), a tertiary alkanolamine (C6-12), an AO 1-30 mol adduct of a primary alkanolamine (C2-12), and mixtures thereof. Can be mentioned.

Examples of the aliphatic tertiary amine include triethylamine, tributylamine, lauryldimethylamine, and dimethylstearylamine.
Examples of the aliphatic primary amine AO adduct include butylamine EO 4 mol adduct and PO 10 mol adduct, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct and PO15 mol adduct.
Examples of AO adducts of aliphatic secondary amines include EO 4 mol adduct and PO 10 mol adduct of diethylamine, EO 4 mol adduct and PO 10 mol adduct of dibutylamine, EO 10 mol adduct of laurylmethylamine, and methylstearylamine. EO 10 mol adduct, PO 10 mol adduct and the like can be mentioned.
Examples of the tertiary alkanolamine include triethanolamine and tripropanolamine.
As the AO adduct of primary to tertiary alkanolamines, ethanolamine EO4 mol adduct, butanolamine PO4 mol adduct, hexanolamine EO4 mol adduct, dodecanolamine EO4 mol adduct, dodecanolamine PO10 mol adduct, Examples include diethanolamine EO2 mol adduct, dibutanolamine PO2 mol adduct, dihexanolamine EO2 mol adduct, dibutanolamine PO10 mol adduct, triethanolamine EO3 mol adduct, triethanolamine PO12 mol adduct, and the like.
Among the above (d2), from the viewpoint of imparting mold releasability of (D), preferred are aliphatic tertiary amines and AO adducts of aliphatic primary amines, and more preferred are dimethylstearylamine and stearylamine. EO 10 molar adduct.

The equivalent ratio (d1 / d2) of (d1) and (d2) in the neutralization reaction between (d1) and (d2) is not particularly limited, but the storage stability of the composition and the mold release property of the cured product From this viewpoint, it is preferably 0.5 / 1 to 3/1, more preferably 0.8 / 1 to 2/1.
(D) includes a salt produced by a neutralization reaction between (d1) and (d2), and unreacted (d1) and / or (d2). The content of the salt in (D) is preferably 65 to 100%, more preferably 80 to 100% from the viewpoints of storage stability and mold releasability of the composition.
In the method of containing (D) in the composition of the present invention, (1) (d1) and (d2) are reacted in advance and then mixed with other components, and (2) (d1) and ( Included is a method of separately mixing d2) with other ingredients. Among these methods, the method (1) is preferable from the viewpoint of the storage stability of the composition.

Specific examples of the salt consisting of (d1) and (d2) include salts of dodecanol phosphate mono- and / or diester-dimethylstearylamine, tridecanol phosphate mono- and / or diester-dimethylstearylamine, Tetradecanol phosphate mono- and / or diester-dimethylstearylamine salt, stearyl alcohol phosphate mono- and / or diester-dimethylstearylamine salt, tetradecanol EO 10 mol or PO4 mol adduct phosphoric acid Mono- and / or diester-lauryldimethylamine salt, tetradecanol EO 10 mol or PO5 mol adduct phosphoric acid mono- and / or diester-dimethylstearylamine salt, lauryl alcohol EO 2 mol or PO2 Phosphoric acid mono- and / or diester-laurylamine EO 10 mol or PO5 mol adduct salt, tetradecanol EO2 mol or PO2 mol adduct phosphoric acid mono- and / or diester-stearylamine EO10 Mole or PO5 mole adduct salts and stearyl alcohol EO 10 moles or PO5 mole adduct phosphate mono- and / or diester-stearylamine EO 10 moles or PO4 mole adduct salts.

  Among these, from the viewpoint of imparting mold releasability and industrial viewpoint, the salt of dodecanol phosphate mono- and / or diester-dimethylstearylamine, the stearyl alcohol phosphate mono- and / or diester-dimethylstearylamine are preferred. And salts of stearyl alcohol EO 10 mol adduct phosphoric acid mono- and / or diester-stearyl amine EO 10 mol adduct, more preferably monoester / phosphoric acid ester (d1) having a molar ratio of 1/1 Each salt is a mixture of diesters.

The proportion (%) of each component based on the total weight of (A) to (D) is preferably from 5 to 70, more preferably from 20 to (A) from the viewpoint of rigidity of the cured product and adhesion to the substrate. 55, particularly preferably 25-45;
(B) is preferably 25 to 90, more preferably 45 to 80, particularly preferably 55 to 75 from the viewpoint of scratch resistance of the cured product and adhesion to the substrate.
(C) is preferably 0.1 to 20, more preferably 0.3 to 10, particularly preferably 0.5 to 5 from the viewpoint of curability and coloring suppression.
(D) is preferably 0.01 to 5, more preferably 0.03 to 3, particularly preferably 0.05, from the viewpoint of imparting mold releasability and adhesion to the substrate and increasing the refractive index of the cured product. ~ 1.

If necessary, the composition of the present invention may further contain various additives (E) used for paints and inks as long as the effects of the present invention are not impaired. (E) includes inorganic fine particles (E1), organic pigments (E2), dispersants (E3), antifoaming agents (E4), leveling agents (E5), silane coupling agents (E6), thixotropic agents ( (Thickener) (E7), slip agent (E8), antioxidant (E9) and ultraviolet absorber (E10).
The total amount of (E) used is usually 60% or less, preferably 0.005 to 50%, based on the total weight of the composition of the present invention.

  Examples of the inorganic fine particles (E1) include alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused product of alumina and silica, alumina surface coated with silica, etc.)], zirconia , Metal carbide (tungsten carbide, titanium carbide, silicon carbide, boron carbide, etc.), diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (finely divided silicic acid, hydrous silicic acid, diatom, Colloidal silica, etc.), silicates (fine powdered magnesium silicate, aluminosilicate, sodium aluminosilicate, calcium silicate, talc, soapstone, stearite, etc.), carbonates (settling (active, dry, heavy or light) ) Calcium carbonate Magnesium carbonate, etc.], clay (kaolin clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acidic clay, etc.), sulfate [aluminum sulfate (sulfate band, satin white, etc.), barium sulfate ( Barite powder, precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (stone koji) (anhydrous koji, hemihydrate koji, etc.)], lead white, mica powder, zinc white, titanium oxide, activated calcium fluoride , Cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, and microballoon.

Of these, alumina, silica, silicate, carbonate, sulfate, and titanium oxide are preferable from the viewpoint of scratch resistance and composition of the cured product, and coloring suppression of the cured product, and silica, precipitated carbonic acid are more preferable. Calcium, barium sulfate and titanium oxide.
(E1) may be used in combination of two or more, or may be a composite of two or more (for example, titanium oxide fused to silica). The shape of (E1) is not particularly limited, and may be any of an indefinite shape, a spherical shape, a hollow shape, a porous shape, a petal shape, an aggregated shape, and a granular shape, for example.
The volume average particle diameter of (E1) is usually 0.01 to 1 μm.
The amount of (E1) used is usually 50% or less based on the total weight of the composition of the present invention, preferably from 1 to 30%, more preferably from 3 to 25, from the viewpoint of the addition effect and the flexibility of the cured product. %.

Examples of the organic pigment (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, indanthrone blue, quinacridone red, dioxazine violet, etc. (3) dyed lake basic dyes (Victoria Pure Blue BO lake, etc.), (4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc. (E2) is used based on the total weight of the composition. Usually less than 50% And preferably 5-40% of a flexible point of view of the cured product, more preferably 10-30%.

  Examples of the dispersant (E3) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight of 100 or more and less than Mn 2,000)] and inorganic dispersants.

  Examples of the polymer dispersant include naphthalene sulfonate [alkali metal (Na and K) salt, ammonium salt, etc.] formalin condensate, polystyrene sulfonate, polyacrylate, poly (2-4) carboxylic acid Polymer (maleic acid / glycerin / monoallyl ether copolymer, etc.) salts, carboxymethyl cellulose (Mn 1,000 to 10,000), polyvinyl alcohol (Mn 1,000 to 100,000) and the like can be mentioned.

The following are mentioned as a low molecular weight dispersing agent.
(1) A polyoxyalkylene type aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and AO 1-30 mol adduct of aliphatic (C4-30) amide N-, i-, sec- and t-butanol, octanol, dodecanol and the like as the aliphatic alcohol; phenol, methylphenol and nonylphenol as the (alkyl) phenol; laurylamine and methylstearyl as the aliphatic amine Examples of the aliphatic amides include stearic acid amides.
(2) Polyhydric alcohol type Monoester compound (3) of C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (divalent-6 hexavalent or higher) alcohol (eg GR, PE, sorbitol and sorbitan) ) Carboxylate type C4-30 fatty acid (same as above) alkali metal (same as above) salt (4) sulfate ester type C4-30 fatty alcohol (same as above) and aliphatic alcohol AO1-30 Mole adduct sulfate alkali metal (same as above) salt etc.

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonic acid alkali metal salt (same as above) (6) Phosphate ester type C4-30 aliphatic alcohol (same as above) ) And mono- or diphosphate esters of aliphatic alcohol AO 1-30 mol adducts [alkali metal (same as above) salts, quaternary ammonium salts, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid (same as above) monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyl) Inorganic acid (same as above) salts of laurylmethylammonium, dimethyldistearylammonium and the like.

Examples of the inorganic dispersant include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphoric acid ester, dialkyl phosphoric acid ester and the like).
The amount of (E3) used is usually 10% or less based on the total weight of the composition of the present invention, and preferably 0.05 to 5% from the viewpoint of the effect of addition and the scratch resistance of the cured product.

As the antifoaming agent (E4), lower alcohol (C1-6) (methanol, butanol, etc.), higher alcohol (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acid (C10-20) (oleic acid) , Stearic acid, etc.), higher fatty acid esters (C11-30) (glycerin monolaurate), phosphate esters (tributyl phosphate, tetradecanol EO 2 mol adduct phosphate ester, etc.), metal soap (calcium stearate, stearic acid) Aluminum), polyether [polyethylene glycol (hereinafter abbreviated as PEG) (Mn200 to 10,000), polypropylene glycol (hereinafter abbreviated as PPG) (Mn200 to 10,000), etc.], silicone (dimethylsilicone oil, alkyl) Modified silico N'oiru, fluorosilicone oils, etc.) and mineral oil (silica powder those dispersed in mineral oil) and the like.
The amount of (E4) used is usually 3% or less based on the total weight of the composition of the present invention, and preferably 0.01 to 2% from the viewpoint of the effect of addition and the scratch resistance of the cured product.

As the leveling agent (E5), PEG type nonionic surfactant (nonylphenol EO 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct, etc.), polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester) Sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorosurfactants (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oil [poly Ether-modified silicone oil, (meth) acrylate-modified silicone oil, etc.].
The amount of (E5) used is usually 3% or less based on the total weight of the composition of the present invention, preferably 0.1 to 2% from the viewpoint of the effect of addition and scratch resistance of the cured product.

Examples of the silane coupling agent (E6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminofuropyltrimethoxysilane, etc.), ureido group-containing silane. Coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacrylic) Loxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agents (γ- Isocyanate-propyltriethoxysilane, etc.), polymer-type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-amino Propyltrimethoxysilane hydrochloride, etc.].
The amount of (E6) used is usually 10% or less based on the total weight of the composition of the present invention, and preferably 0.5 to 7% from the viewpoint of the effect of addition and scratch resistance of the cured product.

Thixotropy imparting agent (thickener) (E7) includes inorganic thixotropic imparting agents [bentonite, organically treated bentonite (surface wax coating treated bentonite, etc.) and ultrafine surface treated calcium carbonate (colloidal calcium carbonate, etc.)] and Examples include organic thixotropic property-imparting agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc.).
The amount of (E7) used is usually 20% or less based on the total weight of the composition of the present invention, preferably 0.5 to 10% from the viewpoint of the effect of addition and the flexibility of the cured product.

Examples of slip agents (E8) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax. And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (E8) used is usually 5% or less based on the total weight of the composition of the present invention, and preferably 0.01 to 2% from the viewpoint of the effect of addition and the scratch resistance of the cured product.

Antioxidants (E9) include hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The use amount of (E9) is usually 3% or less based on the total weight of the composition of the present invention, and preferably 0.005 to 2% from the viewpoint of the effect of addition and the scratch resistance of the cured product.

Examples of the ultraviolet absorber (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-triazin-2-yl) -5-[(hexyl) oxy] -phenol]
Benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone) and oxalic acid anilide compound (such as 2-ethoxy-2′-ethyloxalic acid bisanilide).
The amount of (E10) used is usually 3% or less based on the total weight of the composition of the present invention, preferably 0.005 to 2% from the viewpoint of the addition effect and curability, and the scratch resistance of the cured product. .

  When the additives are the same and overlap between (E1) to (E10) above, the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

If necessary, the composition of the present invention can further contain a thermosetting catalyst (F1) and a photoacid generator (F2) as long as the effects of the present invention are not impaired.
Examples of (F1) include peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). Of these, peroxides are preferable from the viewpoint of stability and reactivity of the composition, and t-butyl peroxybenzoate and methyl ethyl ketone peroxide are more preferable.

  When the composition of the present invention contains (F1), it can be cured by heat in addition to the active energy ray described later, and a cured product excellent in chemical resistance and scratch resistance can be obtained. Curing by heat is usually heat-treated in an oven at 50 to 200 ° C. for 1 minute to 20 hours, preferably 80 to 150 ° C. for 10 minutes to 10 hours.

  The amount of (F1) used is usually 20% or less, preferably 0.1 to 10%, based on the total weight of (A) and (B) of the composition of the present invention.

Examples of (F2) include C8 or more and Mn 1,000 or less, for example, sulfonium salts, iodonium salts, phosphonium salts, pyridinium salts, and iron-arene complexes.
Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) -phenyl] sulfide bishexafluorophosphate, and bis [4- (diphenylsulfonio) -phenyl] sulfide bishexafluoroantimonate. 4-di (p-toluyl) sulfonio-4-t-butylphenylcarbonyl-diphenylsulfide hexafluorophosphate, 4-di (p-toluyl) sulfonio-4-t-butylphenylcarbonyl-diphenylsulfide hexafluoroantimonate, 7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone hexafluorophosphate, 7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone hexafur Roanchimoneto, and JP-A 7-61964, JP-A No. 8-165290, JP-U.S. Patent No. 4,231,951, and aromatic sulfonium salts described in U.S. Patent No. 4,256,828 Pat like.
Examples of the iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, and JP-A-6-184170 and US Pat. No. 4,256,828. Aromatic iodonium salts described in the above.
Examples of the phosphonium salt include tetraphenylphosphonium hexafluorophosphate, tetraphenylphosphonium hexafluoroantimonate, and aromatic phosphonium salts described in JP-A-6-157624.
Moreover, as a pyridinium salt which is a cationic polymerization initiator, the pyridinium salt described in patent gazette 2519480, Unexamined-Japanese-Patent No. 5-222112 etc. is mentioned, for example.
Of these (F2), a sulfonium salt is preferred from the viewpoint of storage stability.

  The amount of (F2) used is usually 20% or less, preferably 0.1 to 10%, based on the total weight of (A) and (B) of the composition of the present invention.

  The composition of the present invention can be prepared by mixing (1) (A) to (D) and, if necessary, (E) and (F) at once, or (2) (A) to (D) at once. If necessary, (E) and (F) can be added to the mixture and mixed. Among these, the method (1) is preferable from the viewpoint of production.

  The composition of the present invention is diluted with a solvent as necessary in order to adjust the viscosity suitable for coating when coating a mold (mold, resin mold, etc.) in the case of molding. It can be a paint. The amount of the solvent used is usually 2,000% or less based on the weight of the composition, and preferably 10 to 500% from the viewpoints of productivity and coatability. Moreover, the viscosity of a coating material is the temperature at the time of use (usually 5-60 degreeC), and is 5-500,000 mPa * s normally, Preferably it is 50-10,000 mPa * s from a viewpoint of coating property.

The dilution solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic ring-containing hydrocarbons (C7-10, such as toluene, xylene and ethylbenzene), esters or ether esters (C4-10, such as ethyl acetate, butyl acetate and methoxybutyl acetate), ethers (C4-10, Eg diethyl ether, THF, EG monoethyl ether, EG monobutyl ether, PG monomethyl ether and DEG monoethyl ether), ketones (C3-10, eg acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and Cyclohexanone), alcohols (C1-10, such as methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and benzyl alcohol) , Amides (C3-6, such as dimethylformamide, dimethylacetamide, N- methylpyrrolidone), sulfoxides (C2-4, such as dimethyl sulfoxide), water, and combinations of two or more mixed solvents thereof.
Of these solvents, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferable, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferable from the viewpoint of handleability.

The composition of the present invention is diluted with a solvent if necessary, applied to at least a part of at least one side of the substrate, dried if necessary, and then cured by irradiation with active energy rays described later. It is also possible to obtain a coating having a cured product (coating film) on at least a part of the front surface and / or back surface.
In the coating, a commonly used apparatus such as a coating machine [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 is usually 0.5 to 300 μm as the film thickness after drying and curing, and the preferable upper limit from the viewpoint of drying property and curability is 250 μm, and the preferable lower limit from the viewpoint of scratch resistance, solvent resistance, and contamination resistance. Is 1 μm.

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

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

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

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

  The composition of the present invention is usually cured by active energy rays (ultraviolet rays, electron beams, X-rays, infrared rays, visible rays, etc.), but if necessary, the thermosetting catalyst (F1) is cured by heat. It can also be made. For example, in the production of a molded body, from the viewpoint of productivity, a method of coating the composition of the present invention on a mold surface, first curing the active energy rays to a level that allows the mold to be released, and then completely curing with heat Can be adopted.

  The rigidity of the cured product of the present invention is represented by a tensile elastic modulus (tensile speed: 50 mm / min, unit: MPa), preferably 1,500 to 4,500 from the viewpoint of scratch resistance and adhesion to a substrate. More preferably, it is 2,000-4,000. This rigidity can be adjusted to the said preferable range by increasing / decreasing content of (A) in a composition.

  The refractive index of the cured product of the present invention is preferably 1.500 to 1.580, more preferably 1.530 to 1.570, from the viewpoint of ease of application to an optical member and synthesis. The refractive index can be adjusted by increasing or decreasing the benzene skeleton content derived from (A) and (B) in the cured product. The benzene skeleton content is represented by the ratio BZ (%) of carbon constituting the benzene skeleton based on the total weight of (A) and (B), and BZ (%) for the cured product to have a refractive index in the above preferred range is , Preferably 15-50, more preferably 18-45.

  The composition of the present invention can also be used as a coating agent for a substrate, and the resulting coating can be used as an optical member, an electric / electronic member, or the like. Although it does not specifically limit as a base material applied, For example, paper, a plastics, glass, and a metal are mentioned. Specifically, paper (for example, thin paper, inter-paper reinforced paper, titanium paper, latex-impregnated paper and base paper for gypsum board), plastic (plastic (vinyl chloride, polyester, polypropylene, polymethyl methacrylate, etc.) film, plastic (polymethyl) Methacrylate, polycarbonate, methyl methacrylate / styrene copolymer, etc.) plate, etc.], glass plate, copper plate, iron plate and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following, parts indicate parts by weight, and% indicates% by weight.

Examples 1-11, Comparative Examples 1-2
It compounded according to the composition of Table 1, and obtained the resin composition (Examples 1-11, Comparative Examples 1-2). The blending components in the table are as follows. In addition, each component for mold release property imparting agents was mixed in a predetermined amount in advance to form a salt, and then mixed with other components.
Monomer (A-1): Diacrylate monomer of bisphenol A diglycidyl ether (A-2): Diacrylate monomer of propylene glycol diglycidyl ether (A-3): Diacrylate of polyethylene glycol diglycidyl ether
(Mn 1,500)
Monomer (A-4): Dimethacrylate monomer of bisphenol A diglycidyl ether (B-1): Isobornyl acrylate monomer (B-2): Phenoxyethyl acrylate monomer (B-3): EO4 molar adduct of bisphenol A Diacrylate monomer (B-4): DPE pentaacrylate / hexaacrylate = weight ratio 60 /
40 monomer mixture (B-5): EG dimethacrylate photopolymerization initiator (C-1): 1-hydroxycyclohexyl phenyl ketone [trade name “I
Ruga 184 ", manufactured by Ciba Specialty Chemicals Co., Ltd.]
Mold release agent component (d1-1): Dodecanol phosphate ester (monoester)
/ Diester = molar ratio 1/1)
Component for mold releasability (d1-2): phosphate ester of stearyl alcohol (mono
Ester / diester = molar ratio 1/1)
Component for mold releasability (d1-3): Stearyl alcohol EO 10 mol adduct
Acid ester (monoester / diester = molar ratio 1/1)
Component for mold releasability imparting agent (d2-1): Component for dimethyl stearylamine mold releasability imparting agent (d2-2): 10 mol adduct of stearylamine EO

The following items were evaluated for the resin composition and its cured product. The results are shown in Table 2. 1. Viscosity The composition was placed in a glass container (50 ml) having a height of 7 cm and a diameter of 30 mm, and the viscosity at 25 ° C. was measured using a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.].

2. Elastic modulus (i) Cured product preparation method Glass plate [trade name “GLASS PLATE”, manufactured by AS ONE Co., Ltd., vertical 200 mm × width 200 mm × thickness 5 mm, and so on. ] The sample was filled in a frame of a spacer frame (thickness 10 μm, width 50 mm) set in the peripheral part of], a glass plate was further stacked thereon, and air was pushed out by being sandwiched between nip rollers. Thereafter, ultraviolet rays of 1,000 mJ / cm @ 2 were irradiated using an ultraviolet irradiation device. Thereafter, the glass plate was removed to obtain a cured product. This was cut out into a dumbbell shape and used as a test piece.
(Ii) Evaluation of elastic modulus Using an autograph [manufactured by Shimadzu Corporation], the tensile elastic modulus was measured at a test speed of 50 mm / min (unit: MPa).

3. Scratch resistance (i) Hardened product preparation method A sample is filled in a frame of a spacer frame (thickness 10 μm, width 10 mm) set on the periphery of a glass plate, and further a PET film substrate [trade name “A -4300 ", manufactured by Toyobo Co., Ltd., vertical 200 mm × width 200 mm × thickness 0.1 mm], and was sandwiched between nip rollers to extrude air. Thereafter, ultraviolet rays of 1,000 mJ / cm ² were irradiated from the PET film side using an ultraviolet irradiation device. Thereafter, the glass plate was removed to obtain a molded body with a PET film having a cured product (film) on one side.
(Ii) Scratch resistance evaluation The surface of the cured film was rubbed 10 times using a surface fastener [trade name “Majikurosu”, model number 1K2L, manufactured by Shinwa Co., Ltd.], and the total light transmittance was measured according to JIS K-7361-1. The haze was measured using an apparatus (unit:%). A smaller haze value indicates better scratch resistance.

4). Mold releasability and adhesion to substrate Using a dispenser for a mold (vertical 50 cm, width 50 cm, mold temperature 35 ° C.) whose temperature was adjusted to 35 ° C. and chrome plating was applied to the inner surface in advance. Coating was performed so that the thickness was 50 to 150 μm. Next, a 2 mm thick (vertical 50 cm × width 50 cm) transparent base material [trade name “Sumipex HT”, manufactured by Sumitomo Chemical Co., Ltd.] made of a methyl methacrylate copolymer is applied to the mold. Pressure lamination was performed so that air did not enter from above. Further, the composition was cured by irradiating 1,000 mJ / cm ² of ultraviolet rays from above the substrate using an ultraviolet irradiation device. The releasability from the mold of the molded body with a substrate (film) and the adhesion to the substrate were evaluated by the following methods.

(1) Mold releasability (difficulty of mold release from mold)
The mold releasability when the cured product with a substrate (film) (substrate coating) was slowly peeled off from the mold was evaluated from the following viewpoints.

○ Easy to release × Difficult to release, deformation of film at release

(2) Adhesion with substrate [Adhesion between cured product (film) and substrate]
Create a grid (10x10) by cutting a 1mm width with a knife on the surface of the cured product (film) of the cured product (film) with a substrate, and paste cellophane adhesive tape on the grid 90 The number of cured products (films) peeled from the substrate was evaluated.

表２中、比較例１の、型離型性を除く項目の評価用試験片の作成に当っては金型に予め外部離型剤［商品名「ダイフリー」、ダイキン工業(株)製］を塗布した。それ以外の試験片作成時は、型に外部離型剤は塗布しなかった。

In Table 2, an external mold release agent [trade name “Daifree”, manufactured by Daikin Industries, Ltd.] is preliminarily applied to the mold when preparing a test piece for evaluation of items of Comparative Example 1 excluding mold release properties. Was applied. During the preparation of other test pieces, no external release agent was applied to the mold.

  A cured product obtained by curing the composition of the present invention is excellent in scratch resistance, rigidity, and adhesion to a substrate, and has good releasability from a mold (particularly a mold). It is widely used for optical lenses and the like that require refining, and is extremely useful.

Claims (6)

Epoxy (meth) acrylate (A) formed from epoxide (a1) and (meth) acrylic acid, (meth) acrylate (B) excluding (A), photopolymerization initiator (C) and mold release An active energy ray-curable resin composition comprising an agent (D), wherein (D) comprises a salt of a phosphate ester (d1) and a tertiary amine (d2). Based on the total weight of (A) to (D), (A) is 5 to 70%, (B) is 25 to 90%, (C) is 0.1 to 20%, and (D) is 0.01. The composition of claim 1 which is -5%. A coating agent comprising the composition according to claim 1 or 2. A cured product obtained by curing the composition according to claim 1. An optical member or an electric / electronic member comprising the cured product according to claim 4. The composition according to claim 1 or 2 is coated on a mold surface, a transparent base material is pressure-laminated on the coated material, and cured by irradiation with active energy rays from the base material. A method for producing a molded body, which comprises releasing the mold.