JP3016401B2 - (Meth) acrylate derivative, resin composition containing the same, and coating agent for optical disk - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel (meth) acrylate derivative, a resin composition containing the same, a material for an optical disk, and a cured product thereof.

[0002]

2. Description of the Related Art At present, an ultraviolet-curable overcoating agent is used as a protective coating agent for consumer compact disk recording media. On the other hand, at present, a writable and erasable optical disk is being developed, and a protective coating agent for an optical disk and a hard coating agent for preventing damage are also being developed.

[0003]

A recording medium for an optical disk is susceptible to moisture and heat shock, and a cured product excellent in moisture resistance, heat shock resistance, hardness and the like as a protective coating agent is required. . Conventionally used protective coating agents for compact disks have insufficient moisture resistance and are not suitable for use as protective coating agents or hard coating agents for optical disks.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have assiduously studied and developed a novel epoxy (meth) acrylate, and by using this, the curing speed is high, The present invention has been completed by successfully providing a resin composition suitable for an optical disc material having excellent adhesion to a substrate, high hardness of a cured product, and excellent moisture resistance.

That is, the present invention provides: A (meth) acrylate derivative represented by the formula (1),

[0006]

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(Wherein R is H or CH ₃ , provided that the acryloyloxy group and the hydroxy group are bonded to the 3- or 4-position of the cyclohexane ring). 5 to 65% by weight of the (meth) acrylate (A) derivative according to claim 1, a compound (B) having one or more ethylenically unsaturated groups in a molecule, and a photopolymerization initiator (C) as an optional component. A resin composition characterized in that: (However, component (B) is 100 to 900 parts by weight when component (A) is 100 parts by weight, and component (C) is component (A) +
(The component (B) is contained in an amount of 0 to 10 parts by weight based on 100 parts by weight of the total amount of the component.) The (meth) acrylate derivative (A) according to claim 1, a compound (B) having at least one ethylenically unsaturated group in a molecule, and a photopolymerization initiator (C) as an optional component.
An optical disc coating agent comprising: 4. A cured product of the resin composition according to claim 2. 5. A cured product of the coating agent for an optical disc according to claim 3.

The (meth) acrylate derivative (A) of the present invention has the formula (2)

[0009]

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(Wherein R is H or CH ₃ ) and can be obtained by reacting (meth) acrylic acid with a compound represented by the formula: The compound represented by the formula (2) can be easily obtained from the market. For example, AETHB manufactured by Daicel Chemical Industries, Ltd.

[0011]

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And METHB

[0013]

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And so on. In the reaction of the compound represented by the formula (2) with acrylic acid or methacrylic acid, the compound represented by the formula (2)
The use ratio of (meth) acrylic acid to 1 chemical equivalent of the epoxy group of the compound represented by the formula is preferably 0.5 to 1.5 chemical equivalents, and particularly preferably 0.9 to 1.0 chemical equivalent. The reaction temperature is preferably from 70 to 130 ° C, particularly preferably from 80 to 100 ° C. The reaction can be promoted using a catalyst. Examples of such a catalyst include known catalysts such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, and triphenylstibine. The amount of the catalyst is preferably 0.05 to 10% by weight based on the weight of the raw material. Particularly preferably, 0.1 to 5% by weight is used. The reaction time is preferably 5 to 48 hours.

Next, specific examples of the compound (B) having one or more ethylenically unsaturated groups in the molecule used in the present invention include neopentyl glycol di (meth) acrylate, Pentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, acryloyl morpholine, carbitol (meth) acrylate, tricyclodecane (meth)
Acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A),
Epoxy (meth) acrylic acid ester (for example, a reaction product of epoxy resin such as bisphenol type epoxy resin and novolak type epoxy resin with (meth) acrylic acid.) Urethane (meth) acrylate (for example, polyether polyol, polyester polyol, Polyols such as polycarbonate polyol, polycaprolactone polyol, ethylene glycol and 1,6-hexanediol, organic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate, and 2-hydroxyethyl (meth)
It can be obtained by reacting with a hydroxy group-containing (meth) acrylate such as acrylate or 2-hydroxypropyl (meth) acrylate. ) And the like. Particularly preferred are neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate, tricyclodecane acrylate, carbitol acrylate, tetrahydrofurfuryl acrylate, and the like. Is mentioned.

The amount of the compound (B) having one or more ethylenically unsaturated groups in the molecule is represented by the formula (1) in a resin composition or a material for an optical disk (hereinafter simply referred to as a composition). Epoxy (meth) acrylate (A)
When used as parts by weight, 50 to 2000 parts by weight is preferable,
Particularly preferably, the amount is 100 to 900 parts by weight.

As the photopolymerization initiator (C) used as an optional component, any known photopolymerization initiator can be used, but one having good storage stability after compounding is desirable. Examples of such a photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, benzyldimethylketal, 2-hydroxy-2-methylpropiophenone, benzophenone, 2,4-diethylthioxanthone, isopropylthioxanthone, and p-dimethylamino Examples include acetophenone, p-dimethylaminobenzaldehyde, and ethyl p-dimethylaminobenzoate. Such photopolymerization initiators can be used alone or in combination of two or more. Preferred photopolymerization initiators (C) include, for example, 1-hydroxycyclohexylphenyl ketone, benzophenone, p-dimethylaminoacetophenone, and the like. Photopolymerization initiator (C)
Is preferably 0 to 10% by weight, particularly preferably 1 to 8% by weight, based on 100 parts by weight of the total of (A) component + (B) component in the composition. The composition of the present invention comprises:
It can be prepared by mixing and dissolving the components (A), (B) and (C) (optional components). or,
The composition of the present invention achieves its intended purpose sufficiently with only the component materials (A), (B) and (C) (optional components). Materials such as a silane coupling agent, a polymerization inhibitor and a leveling agent can be added as long as they are not changed. Examples of the sila coupling agent include γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.
Examples of the polymerization inhibitor include methoquinone, benzoquinone, methylhydroquinone and the like. Examples of the leveling agent include Modaflow (manufactured by Monsanto), Fluorad (manufactured by 3M), and the like.

The cured product of the composition of the present invention can be obtained as a cured product by ultraviolet irradiation or electron beam irradiation according to a conventional method. In the case of electron beam irradiation, it is not necessary to mix a photopolymerization initiator. Curing of the composition of the present invention by irradiation with ultraviolet light can be performed by a conventional method. For example, ultraviolet irradiation may be performed using a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. The composition of the present invention is particularly useful as a protective coating agent for a recording film of an optical disk having a plastic substrate as a substrate, or as a hard coating agent for an optical disk, but may also be used as a metal, plastic, rubber, paper, wood, and ceramic. It can also be used for paints and the like. The coating agent for an optical disk of the present invention is particularly a protective coating agent for a recording film of an optical disk,
It is also useful as a hard coat agent for optical disks. The protective film for the recording film of the optical disk using the coating agent for an optical disk of the present invention is formed by applying a coating agent for an optical disk on the recording film of the optical disk by, for example, a spin coating method and irradiating with ultraviolet rays to cure the coating. This forms a protective film. When a coating agent for an optical disk is applied on a recording film of an optical disk, the thickness is usually preferably about 1 to 50 μm. In these methods, the curing of the coating agent for an optical disk may be performed by electron beam irradiation instead of ultraviolet irradiation.

[0019]

The present invention will be described below in more detail with reference to examples. Parts in Examples are parts by weight. Example of (meth) acrylate derivative (A) Example 1 Compound of the above formula (3) (manufactured by Daicel Chemical Industries, Ltd .;
ETHB) 193 parts, acrylic acid 68.4 parts, methoquinone 0.1 part, triphenylstibine 1.3 parts were charged,
The reaction was carried out until the acid value (mg / KOH / g) became 1.0 or less while maintaining the liquid temperature at 95 to 100 ° C. to obtain an acrylate derivative. This has the following properties. Viscosity (25 ° C.) 90 poise Acid value (mg / KOH / g) 0.5 The result of nuclear magnetic resonance (NMR) measurement of the obtained product is shown below. No. ppm No. ppm 1 166.203 5 79.397 2 165.554 6 77.708 3 130.727 7 77.188 4 128.388 8 75.109 No. ppm No. ppm 9 73.030 17 31.576 10 72.250 18 30.667 11 70.561 19 28.588 12 68.092 20 27.548 13 67.053 21 24.429 14 66.663 22 23.650 15 35.345 23 22.740 16 31.836 24 0.000 In the above measurement, tetramethylsilane was used as the reference substance and tetramethylsilane as the solvent. And a proton decoupling method using deuterated chloroform.

Example 2 Compound of the above formula (4) (manufactured by Daicel Chemical Industries, Ltd.
ETHB) 193 parts, acrylic acid 81.8 parts, methoquinone 0.1 part, triphenylstibine 1.4 parts,
The reaction was performed until the acid value (mgKOH / g) became 1.0 or less while maintaining the liquid temperature at 95 to 100 ° C., to obtain a methacrylate derivative. This has the following properties. Viscosity (25 ° C) 100 Whised acid value (mgKOH / g) 0.7 NMR measurement result ppm No. ppm 1 168.932 8 125.529 2 167.502 9 79.528 3 165.683 10 77.318 4 136.445 11 75.239 5 131.507 12 73.160 6 130.988 13 72.510 7 128.778 14 70.561 No. ppm No. ppm 15 68.682 22 27.678 16 67.312 23 24.560 17 66.793 24 23.780 18 35.475 25 23.000 19 31.707 26 18.322 20 30.797 27 0.000 21 28.718

Examples of resin compositions Example 3 30 parts of the acrylate derivative obtained in Example 1, 55 parts of tricyclodecane dimethylol diacrylate, 15 parts of tetrahydrofurfuryl acrylate, 5 parts of benzophenone and N, N-dimethylamino Two parts of acetophenone were mixed to prepare an ultraviolet-curable resin composition (material for an optical disk). The above-mentioned UV-curable resin composition is applied on a recording film of an optical disk having a recording film formed on a polycarbonate substrate by a spin coater, and irradiated with a high-pressure mercury lamp (2KW, manufactured by Nippon Battery Co., Ltd.), and the composition is irradiated. Cured. 90% RH at 60 ° C.
And a humidity resistance test was performed. As a result, no abnormality was found in the recording film even after 1000 hours.

Example 4 40 parts of the methacrylate derivative obtained in Example 2, 40 parts of tricyclodecane acrylate, 20 parts of neopentyl glycol diacrylate, 5 parts of benzophenone and N,
Two parts of N-dimethylaminoacetone phenone were mixed to prepare an ultraviolet-curable resin composition (material for an optical disk). Using this, an optical disk coated with protection was obtained in the same manner as in Example 3. As a result of the same moisture resistance test as in Example 3, no abnormality was found even after 1000 hours.

Example 5 20 parts of the acrylate derivative obtained in Example 1, neopentyl glycol diacrylate hydroxypivalate 30
Parts, trimethylolpropane triacrylate 20 parts,
30 parts of tricyclodecane acrylate and 5 parts of Irgacure 184 (a photopolymerization initiator manufactured by Ciba-Geigy) are mixed, and an ultraviolet-curable resin composition (material for an optical disk)
Was prepared. Using this, an optical disk coated with protection was obtained in the same manner as in Example 3. As a result of the same moisture resistance test as in Example 3, no abnormality was found even after 1000 hours.

Example 6 An electron beam-curable resin composition (material for an optical disk) was prepared in the same manner as in Example 3 except that benzophenone and N, N-dimethylaminoacetophenone were excluded. did. In the same manner as in Example 3, the above-mentioned electron beam-curable resin composition was applied on a recording film of an optical disk with a spin coater, and the electron beam (test machine, 1
(75 keV) to cure the composition. When the optical disk coated with the protection was left in a state of 90% RH at 60 ° C. and subjected to a moisture resistance test, there was no abnormality in the recording film even after 1000 hours.

[0025]

The cured product obtained by curing the resin composition containing the (meth) acrylate derivative of the present invention is excellent in moisture resistance, durability, and adhesiveness, and particularly, a protective coating agent for a recording film of an optical disk. Useful as

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI G11B 7/24 534 G11B 7/24 534D (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 69/54 C08F 220 / 20,220 / 28 C08F 20 / 20,20 / 28 C09D 4/00 -4/06 C08F 290/06 G11B 7/24 534 CA (STN)

Claims (5)

(57) [Claims] 1. A (meth) acrylate derivative represented by the following formula (1). Embedded image (Wherein, R is H or CH _3. However, acryloyloxy group and hydroxy group is attached to the 3- or 4-position of the cyclohexane ring) 2. The (meth) acrylate (A) according to claim 1, a compound (B) having at least one ethylenically unsaturated group in a molecule, and a photopolymerization initiator (C) as an optional component.
A resin composition comprising: (However,
Component (B) is 10 when component (A) is 100 parts by weight.
0 to 900 parts by weight, (C) component is (A) component + (B)
0 to 10 parts by weight based on 100 parts by weight of the total amount of the components) 3. A composition comprising the (meth) acrylate derivative (A) according to claim 1, a compound (B) having one or more ethylenically unsaturated groups in a molecule, and a photopolymerization initiator (C) as an optional component. A coating agent for optical discs, characterized in that: 4. A cured product of the resin composition according to claim 2. 5. A cured product of the coating agent for an optical disk according to claim 3.