JP2010031240A - Active energy ray-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition which gives a cured product having a good curability, excellent releasability from the molds, scratch resistance, rigidity, transparency, and contact with PET by solving such problems that present urethane(meth)acrylate compositions have a poor releasability from molds, are heavily liable to crack or break, and cause low yields, and show a lowered contact with a PET base resin, even though it is released from the molds. <P>SOLUTION: The active energy ray-curable resin composition includes (A) a bifunctional (meth)acrylate having a fluorene structure in the molecule, (B) a bifunctional urethane(meth)acrylate containing an aromatic ring in the molecule, (C) an aromatic ring-containing monofunctional (meth)acrylate, and (D) a mold-releasing agent. Its cured product is also described. <P>COPYRIGHT: (C)2010,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 provides a cured product having excellent releasability from a mold and excellent adhesion to PET.

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, a long time is required for heating and cooling at the time of manufacturing, so the productivity is low, and the reproducibility of the fine structure is poor and warps due to the thermal contraction of the optical lens. . 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. A method (for example, see Patent Document 2) for imparting the property to make it difficult to be damaged has been proposed.

Japanese Patent Laid-Open No. 11-240926 JP 2005-272700 A

However, these methods have problems in that the releasability from the mold is poor, cracking and breakage occur frequently, and the yield decreases. In addition, although the mold is released from the mold, there is a problem that the adhesiveness with the base resin PET is lowered.
The object of the present invention is to provide a cured product which has two properties that are difficult to achieve both mold releasability and PET adhesion, and also satisfies general properties of curability, scratch resistance, rigidity, and transparency. The object is to provide an active energy ray-curable 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 a bifunctional (meth) acrylate (A) having a fluorene skeleton in the molecule, a bifunctional urethane (meth) acrylate (B) containing an aromatic ring in the molecule, and an aromatic ring-containing monofunctional (meth). An acrylate (C) and a mold releasability imparting agent (D) are contained, and the mold releasability imparting agent (D) is a mixture of a phosphate ester (D1) and a tertiary amine (D2). An active energy ray-curable resin composition, and a cured product thereof.

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 the mold.
(2) The cured product is excellent in adhesion to the substrate, excellent in scratch resistance and rigidity.

The present invention is described in detail below.
The active energy ray-curable resin composition of the present invention comprises a bifunctional (meth) acrylate (A) having a fluorene skeleton in the molecule, a bifunctional urethane (meth) acrylate (B) containing an aromatic ring in the molecule, an aromatic A mold releasability imparting agent (D) comprising a ring-containing monofunctional (meth) acrylate (C) and a mixture of a phosphate ester (D1) and a tertiary amine (D2) is an essential component.

The fluorene skeleton-containing bifunctional (meth) acrylate (A) of the first component in the present invention has a chemical structure particularly if it has a fluorene skeleton in the molecule and two (meth) acryloyl groups. Is not limited.
A preferred structure is a monomer represented by the following general formula (1).

In the formula, R ¹ and R ² are each independently a hydrogen atom or CH ₃ . Preferably both R ¹ and R ² are hydrogen atoms.
R ³ and R ⁴ are independently O (CH ₂ ) ₂ , OCH (CH ₃ ) CH ₂ , OCH (CH ₂ CH ₃ ) CH ₂ , O (CH ₂ ) ₃ or O (CH ₂ ) _4. It is represented by Particularly preferably, R ³ and R ⁴ are both O (CH ₂ ) ₂ .

  The content of (A) in the present invention is usually 10 to 60%, preferably 15 to 50%, based on the total weight of (A), (B) and (C). If the content of (A) is less than 10%, the refractive index becomes low, and the original performance of the cured resin product cannot be exhibited. On the other hand, if it exceeds 60%, the resin itself becomes very hard, and cracks may occur when it is released from the mold.

  The bifunctional urethane (meth) acrylate (B) containing an aromatic ring in the molecule of the second component in the present invention is a urethane containing one or more aromatic rings and two (meth) acryloyl groups in the molecule. Although it will not specifically limit if it is a compound, The aromatic ring containing urethane (meth) acrylate formed from the urethanation reaction of the urethane prepolymer (B ') which has an isocyanate group, and a hydroxyl-containing (meth) acrylate (c) is preferable.

  The urethane prepolymer (B ′) having an isocyanate group is obtained by reacting the polyol (a) with the polyisocyanate (b), and the OH / NCO equivalent ratio in the reaction of (a) and (b) is , Usually 0.45 to 0.90, preferably 0.50 to 0.85.

The polyol (a) used as a raw material for the urethane prepolymer (B ′) includes a polyvalent polyol (a1) containing an aromatic ring, a polyvalent polyol (a2) not containing an aromatic ring, and two or more of these A mixture is included.
Examples of the polyhydric alcohol (a1) containing an aromatic ring include the following divalent polyol (a11) and trivalent or higher polyol (a12).

(A11) a dihydric alcohol having an aromatic ring (C8-20 or more; hereinafter, carbon number is abbreviated as C); an araliphatic dihydric alcohol [for example, xylylene glycol, bis (hydroxyethyl) Benzene etc.], C6-18 dihydric phenol [monocyclic dihydric phenol (eg hydroquinone, catechol, resorcinol, urushiol etc.), polycyclic divalent phenol {eg bisphenol (bisphenol A, F, C, B, AD and S, dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane etc.)}, and condensed polycyclic dihydric phenol {dihydroxynaphthalene (eg 1,5-dihydroxynaphthalene), binaphthol etc.}], polyether diol [Alkyl of the above dihydric alcohol or the above dihydric phenol Oxide (hereinafter abbreviated as AO) adduct (number average molecular weight (hereinafter abbreviated as Mn) is 150 to 20,000), polyester diol [(Mn 200 to 20,000), for example, the above dihydric alcohol or the above poly Ether diol and dicarboxylic acid {aliphatic dicarboxylic acid (C4 to C30 such as succinic acid, adipic acid, maleic acid, fumaric acid), aromatic (aliphatic) dicarboxylic acid (C8 to 30 such as isophthalic acid, terephthalic acid, phthalic acid Anhydride, xylylene dicarboxylic acid)}, polycarbonate (Mn 500 to 10,000), polyester diol, AO 1 to 300 mol adduct of polycarbonate, and the like.

  As the trihydric to octahydric or higher polyhydric alcohol (a12) having an aromatic ring, a trihydric to octahydric or higher polyhydric phenol, for example, a monocyclic polyhydric phenol (pyrogallol, phloroglucinol, etc.), And aldehyde or ketone (formaldehyde, glutaraldehyde, glyoxal, acetone, etc.) low condensate (eg phenol or cresol novolak resin, intermediate of resole, phenol) of monovalent or divalent phenol (phenol, cresol, xylenol, resorcinol, etc.) And polyphenols obtained by the condensation reaction of glyoxal or glutaraldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone), polyether polyols [multivalent to the above trivalent to octavalent or more AO adducts of phenol (Mn 200 to 20,000), etc.], polyester polyols [(Mn 370 to 20,000), such as the above polyether polyols and dicarboxylic acids {aliphatic dicarboxylic acids (C4 to C30, such as succinic acid, adipine) Acid, maleic acid, fumaric acid), aromatic (aliphatic) dicarboxylic acids (C8-30, such as isophthalic acid, terephthalic acid, phthalic anhydride, xylylene dicarboxylic acid)}, and polyester polyols thereof AO1 to 300 mol adducts and the like.

  Examples of the polyvalent polyol (a2) not containing an aromatic ring include the following divalent polyol (a21) not containing an aromatic ring and trivalent or higher polyol (a22) not containing an aromatic ring.

  Dihydric alcohol (a21) not containing an aromatic ring (C2-20 or higher); C2-12 aliphatic dihydric alcohol [eg (di) alkylene glycol [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter EG, DEG, PG, DPG, BD, respectively) , HD, NPG and MPD), dodecanediol, etc.], dihydric alcohols having a C6-10 alicyclic skeleton [1,3- and 1,4-cyclohexanediol, cyclohexanedimethanol, etc.], poly Ether diol [AO adduct of the above dihydric alcohol (Mn 150 to 0,000), polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn 400-10,000), etc.], polyester diol {Mn 200-20,000, for example, the above dihydric alcohol or the above polyether diol and dicarboxylic acid [fatty Group dicarboxylic acids [C4 to C30, such as succinic acid, adipic acid, maleic acid, fumaric acid] and the like.

  Trivalent to octavalent or higher polyhydric alcohols (a22) (C3-20 or higher) containing no aromatic ring, such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylol Propane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter abbreviated as GR, TMP, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and others Polyglycerin etc.], saccharides and derivatives thereof [sucrose, glucose, fructose, mannose, lactose, glucoside (methyl glucoside etc.) etc.], polyether polyol [AO adduct of the above polyhydric alcohol (Mn1) 0 to 20,000), polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn400 to 10,000), etc.], polyester polyol [(Mn300 to 20,000), for example, the above polyhydric alcohol or the above polyether polyol Condensates of aliphatic dicarboxylic acids (C4-C30 such as succinic acid, adipic acid, maleic acid, fumaric acid)], polycaprolactones with Mn of 200 to 10,000, polyisoprene polyols and hydrogenated polyisoprene polyols, and polyesters thereof AO1-300 mol adducts of polyol, polycaprolactone, polyisoprene polyol and hydrogenated polyisoprene polyol are included.

  Of the polyol (a) used as the raw material of the urethane prepolymer (B ′), (a11) and (a12) are preferable from the viewpoint of the high refractive index of the cured product of the present invention described later.

  The polyisocyanate (b) to be reacted with the polyol (a) in the urethane prepolymer (B ′) in the present invention includes the following (b1) to (b5) and a mixture of two or more thereof.

(B1): Aromatic polyisocyanate diisocyanate of C6-20 (excluding the number of carbon atoms in the NCO group; the same shall apply hereinafter) (hereinafter, diisocyanate is abbreviated as DI).
1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4,4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'- Diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and tri- or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate) and 4,4 ', 4 "-triphenylmethane triisocyanate

(B2): C2-18 aliphatic polyisocyanate DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2, 2 , 4- and / or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) Fumarate, bis (2-isocyanatoethyl) carbonate and trimethylhexamethylene diisocyanate (TMDI); -Isocyanate Tomethyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate (phosgenates of the reaction product of lysine and alkanolamine, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexanoate)

(B3): C4-45 alicyclic polyisocyanate
DI, for example isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexyl Silene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); PI (triisocyanate, etc.), such as bicycloheptane triisocyanate

(B4): C8-15 araliphatic polyisocyanate m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI)
(B5): Nurateated product of (b1) to (b4) above

  Of these polyisocyanates (b), (b1), (b4) and (b5) are preferable from the viewpoint of the high refractive index of the cured product of the present invention described later.

  The OH / NCO equivalent ratio in the reaction of the polyol (a) and the polyisocyanate (b) is 0.45 to 0.80, preferably 0.50 to 0.75, and more preferably 0.55 to 0.70. If the amount ratio is less than 0.45, the shrinkage rate at the time of curing is increased and the adhesion to the substrate described later is deteriorated.

  The urethane prepolymer (B ′) having an isocyanate group obtained by the reaction of the above (a) and (b) is further reacted with a hydroxyl group-containing (meth) acrylate (c) to form an aromatic ring as an essential component of the present invention. A bifunctional urethane (meth) acrylate (B) having the following can be obtained.

The hydroxyl group-containing (meth) acrylate (c) includes the following (c1) to (c6) and a mixture of two or more thereof.
(C1): AO adduct of (meth) acrylic acid [Mn 116 to 5,000]
(Meth) acrylic acid-2-hydroxyethyl, -2-hydroxypropyl, -2-hydroxybutyl, and AO adducts thereof (Mn 160 to 5,000), etc.

(C2): ε-caprolactone adduct of (a11) (Mn 230 to 5,000)
(Meth) acrylic acid-2-hydroxyethyl-ε-caprolactone 2-mole adduct, etc. (c3): mono (meth) acrylate diol of diol (Mn300 to 5,000) [Mn300 to 5,000, which will be described later (a16) Other than the polyols constituting the above, such as polycarbonate diol, polyether diol, polyester diol] mono (meth) acrylate

(C4): Reaction product of epoxide and hydroxy (meth) acrylic acid 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-biphenoxy-2-hydroxyprop (meth) acrylate, etc.

(C5): Reaction product of (meth) acrylic acid and a tri- or higher functional polyol (Mn 92 to 5,000) and an AO 1 to 100 mol adduct thereof Glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and Di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate, ditrimethylolpropane mono-, di- and tri (meth) acrylate, dipentaerythritol mono-, di-, tri-, tetra- and Penta (meth) acrylates and their AO adducts (addition mole number 1 to 100), etc.

(C6): reaction product of (meth) acrylic acid and at least one polyol (Mn 300 to 5,000) selected from the group consisting of butadiene polyol, isoprene polyol, hydrogenated butadiene polyol and hydrogenated isoprene polyol

  Of these hydroxyl group-containing (meth) acrylates (c), (c2) and (c3) are preferred from the viewpoint of reactivity with the polyisocyanate component (b), and (a1) is more preferred. is there.

The content (% by weight) of the aromatic ring in (B) is usually 35 to 50%, preferably 38 to 45%, from the viewpoint of increasing the refractive index of the cured product and light resistance.
When the aromatic ring content is less than 35%, it is difficult to increase the refractive index of the cured product, and when it exceeds 50%, the light resistance of the cured product is deteriorated.

Here, the aromatic ring means only the carbon constituting the benzene ring or its condensed ring (naphthalene ring, phenanthrene ring, etc.). The aromatic ring may be derived from (a) or from (b). The aromatic ring content can be measured by ¹ H and ¹³ C-NMR (nuclear magnetic resonance spectrum) or IR (infrared absorption spectrum) analysis.
For example, when the aromatic ring content is determined by ¹ H-NMR, an internal standard substance is added, and the integrated value of the 1H peak derived from the internal standard substance and the 1H peak derived from the phenyl group in (B) ( The number of moles of the phenyl group in (B) is determined from the ratio of the integral value of 7 ppm to about 8 ppm, and the phenyl group content can be determined by multiplying by the molecular weight.

The benzene ring in (B) in the present invention may be contained in any part of the polyol (a), the polyisocyanate (b), or the hydroxyl group-containing (meth) acrylate (c).
For example, (a11) a dihydric alcohol having an aromatic ring and (b1) C6-20 aromatic diisocyanate are preferred.

  In the production of (B), a urethanization catalyst may be used. Urethane catalysts include metal compounds (organic bismuth compounds, organic tin compounds, organic titanium compounds, etc.) and quaternary ammonium salts.

  The amount of the urethanization catalyst used is usually 1% or less based on the weight of (B), preferably 0.001 to 0.5%, more preferably 0.05 to 0.00 from the viewpoint of reactivity and transparency. 2%.

  The conditions for the urethanization reaction of (a) and (b) are not particularly limited. For example, (a) and (b) are mixed, and usually from 40 to 100 ° C., from the viewpoint of reactivity and stability of the mixture. Preferably (B) can be manufactured by making it react at 60-95 degreeC for 2 to 20 hours. Further, if necessary, the reaction may be carried out by diluting with a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.).

  The amount of the solvent used is usually 5,000% or less based on the total weight of (a) and (b), the lower limit is from the viewpoint of handleability of the mixture, and the upper limit is preferably from 10 to 1, from the viewpoint of reaction rate. 000%.

  The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be judged, for example, by measuring the NCO% and hydroxyl value of the reaction system.

 The content of (B) in the present invention is usually 10 to 50%, preferably 15 to 45%, based on the total weight of (A), (B) and (C). If the content of (B) is less than 10%, the resin itself becomes very brittle and the strength may deteriorate. Moreover, when it exceeds 50%, adhesiveness with a base material will deteriorate and it may peel easily.

The monofunctional (meth) acrylate (C) having an aromatic ring as the third essential component in the present invention is not particularly limited in its chemical structure as long as it has an aromatic ring in the molecule.
A preferred structure is a monomer represented by the following general formula (2).

In the formula, R ⁵ is represented by a hydrogen atom or CH ₃ , and preferably a hydrogen atom.
X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, COOH or COOCH ₂ CH ₂ OH, and preferably a hydrogen atom.
Y is represented by an aromatic ring.
Z is an alkylene group having 1 to 20 carbon atoms, a polyoxyalkylene group [(CH ₂ CH ₂ O) _n (n is 2 to 20), [CH ₂ CH (CH ₃ ) O] _n (n is 2 to 20). , [CH ₂ CH (OH) CH ₂ ]] or [CH ₂ C (CH ₃ ) ₂ CH ₂ OCO], particularly preferably CH ₂ CH ₂ O.

  Specific examples of the monofunctional (meth) acrylate (C) having an aromatic ring in the present invention are shown below. The following compounds may be used alone or a mixture thereof

(C1): (Meth) acrylate of phenol (C6-30) AO 1-30 mol adduct For example, phenoxyethyl (meth) acrylate, (meth) acrylate of phenol EO2 mol adduct, PO3 mol adduct of phenol (Meth) acrylate and the like.

(C2): (Meth) acrylate of AO1-30 mol adduct of [alkyl (C1-20)] phenol (C6-30) For example, (meth) acrylate of EO1 mol adduct of nonylphenol.

(C3): Aromatic carboxylic acid modified (meth) acrylate For example, monohydroxyethyl phthalate (meth) acrylate, monohydroxyethyl (meth) acrylate 2-hydroxypropyl phthalate, monohydroxyethyl 2-hydroxyethyl phthalate ( (Meth) acrylate, neopentyl glycol (meth) acrylic acid benzoate, and the like.

(C4): Aromatic epoxy acrylate For example, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

(C5): Other aromatic ring-containing monofunctional (meth) acrylates For example, benzyl (meth) acrylate and the like.

Of the above (C1) to (C5), benzyl (meth) acrylate is preferred from the viewpoint of adhesion to the resin and the refractive index of the cured product, and phenoxyethyl (meth) acrylate is more preferred.
Among (C1) to (C5), those having an active hydrogen atom are added after completion of the urethanization reaction, and those having no active hydrogen atom are added at any stage during and / or after the urethanization reaction. Good.

Based on the total weight of (A), (B) and (C) in the present invention, the content of the aromatic ring-containing monofunctional (meth) acrylate (C) is usually 30% to 70%, preferably 40% to 65. %, More preferably 50% to 60%.
When the content of (C) is less than 30%, the adhesion to the substrate may be deteriorated and easily peeled off. If it exceeds 65%, the resin itself becomes very brittle and the strength may deteriorate.

  The mold releasability imparting agent (D), which is the fourth essential component in the present invention, is usually a mixture comprising a phosphate ester (D1) and a tertiary amine (D2).

  As the phosphoric ester (D1) constituting the mold releasability-imparting agent (D), primary or secondary alkyl (C1-20 or higher) phosphoric ester, or primary or secondary A phosphate ester of an AO 1-30 mol adduct of alcohol (C1-20 or higher).

The tertiary amine (D2) constituting the mold releasability-imparting agent (D) includes C4-30 tertiary aliphatic amine, primary or secondary aliphatic (C4-30) amine AO ( C2-4) 1-30 mol adducts, etc. are mentioned.
Examples of the aliphatic amine include triethylamine, tributylamine, lauryldimethylamine, and dimethylstearylamine.

  As the AO (C2-4) 1-30 mol adduct of aliphatic (C4-30) amine, EO 4 mol adduct of butylamine, 10 EO mol adduct of butylamine, EO 10 mol adduct of laurylamine, EO10 of stearylamine Mol adduct, stearylamine EO 15 mol adduct, diethylamine EO4 mol adduct, diethylamine EO 10 mol adduct, dibutylamine EO4 mol adduct, dibutylamine EO 10 mol adduct, laurylmethylamine EO 10 mol adduct And EO 15 mol adduct of methylstearylamine.

  Conventional mold releasability-imparting agents include, for example, fluorosurfactants such as perfluoroalkyl EO 1 to 50 mole adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines, and polyether-modified silicone oils. And silicone-based surfactants such as (meth) acrylate-modified silicone oils are known, but when these are applied as the mold releasability imparting agent (D) of the present invention, the releasability from the mold is Although it is excellent, there is a problem that adhesion with PET as a base resin cannot be ensured.

Based on the total weight of (A), (B) and (C) in the present invention, the content of the mold releasability imparting agent (D) is usually 300 ppm to 2,000 ppm, preferably 500 ppm to 1,500 ppm. More preferably, it is 700 ppm to 1,200 ppm.
When the content of (D) is less than 300 ppm, the releasability from the mold is extremely deteriorated, and the resin may stick to the mold without being peeled off. Moreover, when it exceeds 2,000 ppm, it will bleed out and adhesiveness with a base material may deteriorate.

The weight ratio of (D1) / (D2) in the mold releasability imparting agent (D) is usually 0.75 to 1.75, preferably 0.85 to 1.50, particularly preferably 1. 0.01 to 1.30.
If it is less than 0.75, the storage stability of the composition tends to deteriorate, and if it exceeds 1.75, the mold releasability tends to deteriorate.

The composition of the present invention can contain a photopolymerization initiator (E) as necessary as long as the effects of the present invention are not impaired. Those added with a photopolymerization initiator can be cured by heat and / or ultraviolet rays in addition to the electron beam. In the case of curing by ultraviolet rays, the irradiation amount of ultraviolet rays is usually 10 to 10,000 mJ / cm ² .

  Examples of the photopolymerization initiator (E) include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate compounds (methyl) Benzoylformate, etc.), thioxanthone compounds (isopropylthioxanthone, etc.), benzophenones (benzophenone, etc.), phosphate ester compounds (1,3,5-trimethylbenzoyldiphenylphosphine oxide, etc.), benzyldimethyl ketal, and the like. Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of preventing coloring of the cured product. is there.

  The amount of (E) used is usually 20% or less, preferably 0.1 to 10%, respectively, based on the total weight of the composition of the present invention. More preferably, it is 1 to 5%.

If necessary, the composition of the present invention may further contain various additives (F) used for paints and inks as long as the effects of the present invention are not impaired.
(F) includes an antioxidant (F1) and an ultraviolet absorber (F2).
The total amount of (F) used is usually 60% or less, preferably 0.005 to 50%, based on the total weight of the composition of the present invention.

Antioxidants (F1) 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 amount of (F1) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

Examples of the ultraviolet absorber (F2) 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), An oxalic acid anilide compound (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) is mentioned.
The amount of (F2) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

  When the additive is the same and overlaps between (F1) and (F2) 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.

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

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic 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, such as Diethyl ether, tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG and monoethyl ether of EEG), 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). Call), an amide (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 preferred, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferred.

The curable resin 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 an active energy ray to be described later. Thus, a coating having a cured product on at least a part of the front surface and / or the back surface of the substrate can be obtained.
For 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 curing and drying, and the preferable upper limit is 250 μm from the viewpoint of drying properties and curability, and the preferable lower limit is 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 drying time is usually 10 minutes or less, and preferably 1 to 5 minutes from the viewpoint of physical properties and productivity of the cured film.

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

When the active energy ray-curable resin composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses (for example, model number “VPS / I600” manufactured by Fusion UV Systems Co., Ltd.), xenon lamp as a light source, high pressure Mercury lamps, metal halide lamps, and the like can be used. The dose of the ultraviolet radiation is typically 10~10,000mJ / cm ^2, preferably from a flexible viewpoint of curability and cured product of the composition (cured film) is 100~5,000mJ / cm ^2.

  When the active energy ray-curable resin 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 amount of electron beam is usually 0.5 to 20 Mrad, and the preferable lower limit from the viewpoint of the curability of the composition is 1 Mrad, the flexibility of the cured product, and avoiding damage to the cured product (coating film) or the substrate From the viewpoint, a preferable upper limit is 15 Mrad.

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

The refractive index of the cured product of the present invention is usually 1.570 to 1.585, preferably 1.580 to 1.585, from the viewpoint of application to an optical member and shrinkage during curing.
The refractive index can be increased by increasing the proportion of (A) in the composition or increasing the content of aromatic rings in the cured product.

  The composition of the present invention can be used as a substrate coating agent, adhesive, sealing material and 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 film (film of vinyl chloride, polyester, polypropylene, polymethyl methacrylate, etc.), plastic plate (Plates of polymethyl methacrylate, polycarbonate and methyl methacrylate / styrene copolymer, etc.)], glass plates, copper plates, iron plates and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this. In the following, “parts” means “parts by weight” and “%” means “weight%” unless otherwise specified.
Production Example In a reaction vessel equipped with a stirrer, a condenser and a thermometer, a PO2 molar adduct of bisphenol A [trade name: New Pole BP-2P, manufactured by Sanyo Chemical Industries, Ltd., the same applies below] 288.4 parts, 181 parts of xylylene diisocyanate [trade name: Takenate 500, manufactured by the same, hereinafter the same] and bismuth tri (2-ethylhexanoate) (2-ethylhexanoic acid 50% solution) (hereinafter the same) as urethanization catalyst Charge 2 parts, react at 80 ° C. for 6 hours, then add 2-hydroxyethyl acrylate [trade name: Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd., the same applies below] and react at 80 ° C. for 3 hours to make urethane acrylate (B-1) was obtained. (NCO content: 0.1%)

Examples 1-3, Comparative Examples 1-3
According to the blending composition of Table 1, mixing and stirring were performed with a disperser, and the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained. In each of the examples and comparative examples, the components were mixed together and uniformly mixed to prepare a composition.
In addition, the compounding component in a table | surface is as follows.

(A-1): 9,9′-bis (4-hydroxyethyl) fluorene EO-modified diacrylate (C-1): phenoxyethyl acrylate (D-1): phosphate ester of tridecanol [monoester: diester = 1 : 1 (molar ratio)]
(D-2): Dimethylalkyl (C14-C18) amine (trade name: Farmin DM8680 manufactured by Kao Corporation)
(D′-1): Dimethyl silicone (E-1): 1-hydroxycyclohexyl phenyl ketone [“Irgacure 184”,
Ciba Specialty Chemicals Co., Ltd.]
(F-1): 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole

  The resin composition was evaluated for refractive index, mold releasability, resin adhesion, and resin adhesion after wet heat treatment. The results are shown in Table 1.

(1) Refractive index The resin composition is sandwiched between two PET films [trade name: Lumirror S, manufactured by Toray Industries, Inc.] so that the composition becomes about 5 μm, and an ultraviolet irradiation device [trade name: VPS / I600] , Made by Fusion UV Systems Co., Ltd., and the same below] was irradiated with 1000 mJ / cm ² of ultraviolet light and cured to obtain a coating.
The PET film was removed from this coating, and the refractive index of the obtained cured film was measured using a refractometer [trade name: Abbe refractometer 4T, manufactured by Atago Co., Ltd.] in an environment of 25 ° C.

(2) Evaluation method of mold releasability and resin adhesion To a mold (vertical 50 cm, width 50 cm, mold temperature 35 ° C.) in which the temperature of the resin composition is adjusted to 35 ° C. and chrome plating is applied to the surface in advance. It applied so that it might become thickness of 50-150 micrometers using a dispenser. Next, a PET film [trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness 100 μm] was pressure-laminated so that air would not enter from above the resin coated on the mold.
Furthermore, 1000 mJ / cm < ² > of ultraviolet rays were irradiated from above the base resin using an ultraviolet irradiation device to cure the composition to obtain a coating.

The releasability of the coating resin from the mold and the adhesion between the cured coating resin and the base resin were evaluated by the following methods.
(2-1) Mold releasability (difficulty of mold release from mold)
The releasability when the coating was slowly peeled off from the mold was evaluated from the following viewpoints.
<Rewrite the objective criteria a little more. If Yoshida-kun does, it will be judged as ○, but if Mr. Inoue who is unfamiliar with it may judge it as ×. If it is difficult to understand, I will consult you. >
○: There is no catch on the mold, and no cracks occur in the cured product (film). X: One or more catches occur on the mold, or a crack occurs in the cured product (film).

(2-2) Resin adhesion (adhesion between cured product and base resin)
After leaving still for 24 hours in an environment of 23 ° C. and 50% RH, a 1 mm wide cut is made with a knife on the surface of the cured product (film) side of the coating to create a grid (10 × 10). A cellophane adhesive tape was applied on the grid and peeled by 90 degrees, and the peeled state of the cured product (film) from the base material was visually observed and evaluated.
○: 90% or more area of the cured product remains on the base material Δ: Area of the cured product 10 to 90% remains on the base material ×: The area of the cured product remaining on the base material is 10% or less

(3) Resin adhesion after wet heat treatment (Adhesion between cured product and base resin after wet heat treatment)
The coating was allowed to stand for 72 hours at 60 ° C. and 90% RH using a constant temperature and humidity machine. Then, it was left still for 24 hours in an environment of 23 ° C. and 50% RH.
Evaluation was performed using the same operations and criteria as in (2-2) above.

From the results of Table 1, the cured product (film) obtained by curing the active energy ray-curable resin composition of the present invention has a high refractive index while maintaining releasability from the mold, It can be seen that the adhesiveness is excellent, and the adhesiveness degradation with the base resin after the wet heat treatment is extremely small.
On the other hand, in Comparative Example 1, since the essential component (C) having a strong anchoring effect on the base resin is lacking, the resin adhesion deteriorates. In Comparative Example 2, since (D), which is an essential component for mold releasability, is lacking, the releasability from the mold deteriorates. In Comparative Example 3, since a silicone-based release agent having low compatibility with the resin is used as the release agent instead of the release agent (D) of the present invention, the release property from the mold is excellent. It can be seen that bleed-out easily occurs at the interface with the base resin, and the adhesiveness deteriorates.

  The cured product obtained by curing the composition of the present invention has a high refractive index and excellent resin adhesion. Therefore, optical members (plastic lenses, prisms, optical fibers, etc.), electrical / electronic members (flexible printed wiring board solders) Resists, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, etc.), and widely used as coating agents for paper, plastics and the like.

Claims (9)

  A bifunctional (meth) acrylate (A) having a fluorene skeleton in the molecule, a bifunctional urethane (meth) acrylate (B) containing an aromatic ring in the molecule, an aromatic ring-containing monofunctional (meth) acrylate (C), and The mold releasability imparting agent (D) is contained as an essential component, and the mold releasability imparting agent (D) is composed of a mixture of a phosphate ester (D1) and a tertiary amine (D2). An active energy ray-curable resin composition.   The active energy ray-curable resin composition according to claim 1, comprising 300 ppm to 2000 ppm of the mold releasability imparting agent (D) based on the total weight of (A), (B) and (C).   The active energy ray according to claim 1, comprising 30 to 70% of the aromatic ring-containing monofunctional (meth) acrylate (C) based on the total weight of (A), (B) and (C). A curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the fluorene skeleton-containing (meth) acrylate (A) is a monomer represented by the following formula (1).

Wherein R ¹ and R ² are each independently H or CH ₃ ; R ³ and R ⁴ are each independently O (CH ₂ ) ₂ , OCH (CH ₃ ) CH ₂ , OCH (CH ₂ CH ₃ ) Represents a divalent group of CH ₂ , O (CH ₂ ) ₃ or O (CH ₂ ) ₄ . ]   The urethane (meth) acrylate (B) is a urethane prepolymer (B ′) having an isocyanate group obtained by reacting the polyol (a) and the polyisocyanate (b), a hydroxyl group-containing (meth) acrylate (c), The active energy ray-curable resin composition according to any one of claims 1 to 4, which is an aromatic ring-containing urethane (meth) acrylate formed from the urethanization reaction. The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the aromatic ring-containing monofunctional (meth) acrylate (C) is represented by the following formula (2).

[Wherein R ⁵ represents a hydrogen atom or CH ₃ . X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, COOH or COOCH ₂ CH ₂ OH. Y represents an aromatic ring. Z is an alkyl group having 1 to 20 carbon atoms, a polyoxyalkyl group [(CH ₂ CH ₂ O) _n (n is 2 to 20), [CH ₂ CH (CH ₃ ) O] _n (n is 2 to 20). , [CH ₂ CH (OH) CH ₂ ]] or [CH ₂ C (CH ₃ ) ₂ CH ₂ OCO]. ]   The weight ratio (D1) / (D2) of the phosphate ester (D1) to the tertiary amine (D2) in the mold release agent (D) is 0.75 to 1.75. An active energy ray-curable resin composition according to any one of the above.   The active energy ray-curable resin composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator. The active energy ray-curable resin composition according to any one of claims 1 to 8 is applied to at least a part of at least one surface of a base material and irradiated with active energy rays to be cured, and the refractive index thereof is 1.570. Resin hardened | cured material which is -1.585.