WO2012081216A1 - Ultraviolet-curable resin composition, cured product and optical disk - Google Patents

Abstract

An ultraviolet-curable resin composition which comprises (A) a triazole derivative represented by formula (1) or (2) [wherein Rm is a hydrogen atom or C_1-3 alkyl; R₁ is C_1-3 alkylene; R₂ and R₃ are each independently a hydrogen atom, an optionally substituted C_1-20 aliphatic group, or phenyl; and X is a nitrogen atom or a sulfur atom], (meth)acrylate compounds (for example, (B) a (meth)acrylate monomer and (C) a urethane (meth)acrylate and/or an epoxy (meth)acrylate), and (D) a photopolymerization initiator. The resin composition is suitable as an ultraviolet-curable resin composition for an optical disk which has a reflecting film, particularly a reflecting film made of either silver or a silver alloy. The resin composition does not cause bleed-out and exhibits excellent curability. Further, an optical disk having a layer made of a cured product of the resin composition exhibits high durability, heat resistance and light resistance.

Description

UV curable resin composition, cured product and optical disc

The present invention relates to a novel ultraviolet curable resin composition containing a triazole derivative, a cured product thereof, and an optical disc having a layer made of the cured product. The resin composition is suitable for forming an adhesive layer or cover layer for an optical disc having a reflective film made of silver or a silver alloy, and an optical disc having a cured product layer of the resin composition is excellent in durability.

In recent years, the capacity of optical discs has been increasing, and Blu-ray Discs (hereinafter referred to as BD) using a blue-violet light source as a higher density and larger capacity disc than DVD (Digital Versatile Disc) are products. It is becoming. BD uses a lens with a numerical aperture (NA) of about 0.85 to form a fine laser spot by Blu-ray, record information, and reproduce by Blu-ray. BD is a large-capacity medium of about 25 Gbytes for single-sided single-layer recording and about 50 Gbytes for single-sided dual-layer recording, about 5 times that of DVD.

A BD is a disc on which a recording layer is formed on a transparent or opaque plastic substrate and a light transmission layer of about 0.1 mm is laminated on the recording layer, and recording / reproduction is performed through the light transmission layer. . In the BD as well as the DVD, the recording layer usually includes a reflective film, and a relatively inexpensive silver or silver alloy is mainly used for the reflective film.

However, since silver or a silver alloy is easily oxidized, there is a problem in that the reflective film of silver or a silver alloy changes in a high temperature and high humidity environment, and reading errors increase.
As means for solving this problem, Patent Document 1 proposes an ultraviolet curable CD-R protective coat resin characterized by containing an alkylene thiol compound and Patent Document 2 containing an alkyl thioether compound.

In general, the protective coating layer for CD-R is as thin as about 10 μm and is less affected by stress after curing. Therefore, even if the resin system has a high crosslinking density and good heat resistance, the warpage of the substrate is within the standard range. It is easy to fit in. On the other hand, adhesive layers such as DVDs with a relatively large thickness, especially light-transmitting layers such as Blu-ray discs with a greater thickness, have a large substrate warping when a resin with high heat resistance and high crosslink density is used. Therefore, it is difficult to increase the crosslink density of the resin and increase the heat resistance of the resin itself.
Therefore, with alkylene thiol compounds and alkyl thioether compounds premised on use for conventional protective coating resins for CD-R, silver or silver alloy reflection in light-transmitting layers such as DVDs and Blu-ray discs The effect of preventing the deterioration of the film is not sufficiently obtained.
At present, there are various additives on the market. In view of the above situation, there is a need for an additive having characteristics that prevent deterioration of the silver alloy reflective film.
However, in general, when the additive is used in combination with an ultraviolet curable resin composition, examples of causing problems such as poor curability of the resin composition or poor compatibility with the resin composition and bleeding out. There are many. Therefore, there is a demand for an additive that performs the intended function without adversely affecting the resin composition. As such a resin composition containing such an additive, Patent Document 4 discloses an ultraviolet curable resin composition containing a thiophenol compound, which describes an example of use in a light transmission layer of a BD-ROM. In addition, it has achieved the effect of preventing alteration of the silver alloy reflective film. However, at present, development of a resin composition having a more excellent effect is desired.
As for the triazole derivative used in the present invention, a functional oil such as biodiesel oil is used as a kind of additive for reducing adverse effects from heat, light, oxygen and metals such as iron or copper, etc. An example in which a triazole-based compound including benzene is used as a metal deactivating agent is found (Patent Document 3). However, there is no example in which the triazole-based compound is used in a photocurable resin composition.

Japanese Patent No. 3861589 Japanese Patent No. 4016669 Japanese translation of PCT publication 2010-511667 WO2009 / 144926 pamphlet

The ultraviolet curable resin composition containing a thiophenol compound described in Patent Document 4 can impart excellent durability to an optical disc when used in an optical disc having a reflective film made of silver or a silver alloy. An object of the present invention is to develop an ultraviolet curable resin composition having an excellent effect equivalent to or higher than that and an optical disk having a cured product layer of the resin composition.
That is, the present invention protects the reflective film itself made of silver or a silver alloy, prevents its alteration, has good compatibility with the ultraviolet curable resin composition, and does not bleed out. Finding an excellent additive that does not adversely affect physical properties such as curability of the composition, and an ultraviolet curable resin composition containing the additive and having excellent curability, and silver or silver When a cured layer of the resin composition is formed on a reflective film of an optical disk having a reflective film made of an alloy, the effect of the BD on the warping of the optical disk during curing is small, and the protective function of the reflective film It is an object of the present invention to provide an ultraviolet curable resin composition that is excellent in durability and can impart durability such as high heat resistance and light resistance to an optical disc, and to provide an optical disc having a cured product layer of the resin composition. .

（式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基、フェニル基、Ｘは窒素原子または硫黄原子を表す）、
式（２）

 （式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基またはフェニル基、Ｘは窒素原子または硫黄原子を表す）。 As a result of intensive studies to solve the above problems, the inventors of the present invention have a good compatibility with the (meth) acrylic compound used in the present invention for the triazole compound represented by the formula (1) or (2), Even if cured, it does not bleed out, and the ultraviolet curable resin composition of the present invention containing the triazole compound is applied onto a reflective film of an optical disc having a reflective film made of silver or a silver alloy, It has been found that an optical disc having a cured film obtained has excellent durability such as moisture and heat resistance and light resistance even when cured, and the present invention has been completed.
That is, the present invention relates to the following inventions.
1. UV curing for optical discs having a reflective film made of silver or a silver alloy, containing a triazole derivative (A) represented by the following formula (1) or (2), a (meth) acrylate compound and a photopolymerization initiator (D) Mold resin composition,
Formula (1)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms, a phenyl group, X represents a nitrogen atom or a sulfur atom),
Formula (2)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, and X represents a nitrogen atom or a sulfur atom).

（式中、Ｒ_２１及びＲ_３１は、それぞれ独立に、炭素数１～３のアルキル基、フェニル基で置換された炭素数１～３のアルキル基、分岐鎖を有する炭素数７～９のアルキル基又はフェニル基を表す。）
５．　トリアゾール誘導体（Ａ）が、１－（ジ－（２－エチルヘキシル）アミノメチル）トリアゾール、１－（ジ－（フェニルメチル）アミノメチル）トリアゾール又は１－（ジ－（エチル）アミノメチル）トリアゾールである上記２または３に記載の光ディスク用紫外線硬化型樹脂組成物。 2. The (meth) acrylate compound is a (meth) acrylate monomer (B) and a (meth) acrylate oligomer (C), and R ₂ and R ₃ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group. 2. The ultraviolet curable resin composition for optical discs according to 1 above, which is a substituted alkyl group having 1 to 10 carbon atoms or a phenyl group.
3. X is a nitrogen atom, and R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or a branched chain having 6 to 10 carbon atoms. 3. The ultraviolet curable resin composition for optical disks according to 2 above, which is an alkyl group.
4). The ultraviolet curable resin composition for optical disks according to 2 or 3 above, wherein the triazole derivative (A) is a triazole derivative represented by the formula (3):
Formula (3)

(Wherein R ₂₁ and R ₃₁ each independently represents an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 7 to 9 carbon atoms having a branched chain) Represents a group or a phenyl group.)
5. The triazole derivative (A) is 1- (di- (2-ethylhexyl) aminomethyl) triazole, 1- (di- (phenylmethyl) aminomethyl) triazole or 1- (di- (ethyl) aminomethyl) triazole 4. The ultraviolet curable resin composition for optical disks according to 2 or 3 above.

6). 4. The ultraviolet curable resin composition for optical disks according to 2 or 3 above, wherein the triazole derivative (A) is 1- (di- (2-ethylhexyl) aminomethyl) triazole.
7. 7. The ultraviolet curable resin composition for optical disks according to any one of 2 to 6 above, which contains the triazole derivative (A) in an amount of 0.001 to 5% by weight based on the total amount of the composition.
8). The optical disk ultraviolet ray according to any one of claims 2 to 7, wherein the component (C) is one or both of epoxy (meth) acrylate (C-1) and urethane (meth) acrylate (C-2). A curable resin composition.
9. The (meth) acrylate monomer (B) is dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, At least one selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide-modified bisphenol A type di (meth) acrylate 9. The ultraviolet curable resin composition for optical disks according to any one of 2 to 8 above.

（式中、Ｒ_２１及びＲ_３１は、それぞれ独立に、炭素数１～３のアルキル基、フェニル基で置換された炭素数１～３のアルキル基、分岐鎖を有する炭素数７～９のアルキル基又はフェニル基を表す）、
（メタ）アクリレートモノマー（Ｂ）が、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、及びエチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレートからなる群から選ばれる少なくとも１種である上記２～９の何れか一項に記載の光ディスク用紫外線硬化型樹脂組成物。
１１．　更に、リン酸（メタ）アクリレート（Ｅ）を含む上記２～１０の何れか一項に記載の光ディスク用紫外線硬化型樹脂組成物。
１２．　光重合開始剤（Ｄ）として、オリゴ［２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン又は［２－ヒドロキシ－２－メチル－１－｛４－（１－メチルビニル）フェニル｝プロパノン］の２量体の、少なくとも、いずれか１種を含有する上記２～１０の何れか一項に記載の光ディスク用紫外線硬化型樹脂組成物。
１３．　更に、リン酸（メタ）アクリレート（Ｅ）を含み、光重合開始剤（Ｄ）として、オリゴ［２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン又は［２－ヒドロキシ－２－メチル－１－｛４－（１－メチルビニル）フェニル｝プロパノン］の２量体の、少なくとも、いずれか１種を含有する上記２～１０の何れか一項に記載の光ディスク用紫外線硬化型樹脂組成物。
１４．　上記２～１３に記載の光ディスク用紫外線硬化型樹脂組成物に活性エネルギー線を照射して得られる硬化物。 10. The triazole derivative (A) is a triazole derivative represented by the following formula (3),
Formula (3)

(Wherein R ₂₁ and R ₃₁ each independently represents an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 7 to 9 carbon atoms having a branched chain) Group or a phenyl group),
The (meth) acrylate monomer (B) is dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, At least one selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide-modified bisphenol A type di (meth) acrylate 10. The ultraviolet curable resin composition for optical discs according to any one of 2 to 9 above.
11. 11. The ultraviolet curable resin composition for optical disks according to any one of 2 to 10 above, further comprising phosphoric acid (meth) acrylate (E).
12 As the photopolymerization initiator (D), oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone or [2-hydroxy-2-methyl-1- {4- (1 11. The ultraviolet curable resin composition for optical disks according to any one of 2 to 10 above, which contains at least one of dimers of —methylvinyl) phenyl} propanone].
13. Further, it contains phosphoric acid (meth) acrylate (E) and, as a photopolymerization initiator (D), oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone or [2 The optical disk according to any one of 2 to 10 above, which contains at least one of the dimers of -hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] UV curable resin composition.
14 Hardened | cured material obtained by irradiating an active energy ray to the ultraviolet curable resin composition for optical discs of said 2-13.

（式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基またはフェニル基、Ｘは窒素原子または硫黄原子を表す）、
式（２）

（式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基またはフェニル基、Ｘは窒素原子または硫黄原子を表す）。
１７．　式（１）又は式（２）のＲ_ｍが水素原子、Ｘが窒素原子であり、Ｒ_２及びＲ_３がそれぞれ独立に、炭素数１～３のアルキル基、フェニル基で置換された炭素数１～３のアルキル基、又は分岐鎖を有する炭素数６～１０のアルキル基である上記１６に記載の紫外線硬化型樹脂組成物。 15. 14. An optical disk having a cured layer of the ultraviolet curable resin composition for optical disks according to any one of 2 to 13 above on a reflective film made of silver or a silver alloy.
16. An ultraviolet curable resin composition containing a triazole derivative (A) represented by the following formula (1) or (2), a (meth) acrylate compound and a photopolymerization initiator (D);
Formula (1)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, X represents a nitrogen atom or a sulfur atom),
Formula (2)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, and X represents a nitrogen atom or a sulfur atom).
17. In Formula (1) or Formula (2), R _m is a hydrogen atom, X is a nitrogen atom, and R ₂ and R ₃ are each independently a carbon number substituted with an alkyl group having 1 to 3 carbon atoms or a phenyl group. 17. The ultraviolet curable resin composition according to 16 above, which is an alkyl group having 1 to 3 alkyl groups or a branched alkyl group having 6 to 10 carbon atoms.

18. 0.005 to 5% of the triazole derivative (A) represented by the formula (1) or (2), 75% to 99% of the (meth) acrylate compound, and light, based on the total amount (weight ratio) of the composition 18. The ultraviolet curable resin composition as described in 16 or 17 above, containing 0.5 to 20% of a polymerization initiator (C).
19. (Meth) acrylate compound is (i) (meth) acrylate monomer (B) and (ii) one or both of epoxy (meth) acrylate (C-1) and urethane (meth) acrylate (C-2) ( 19. The ultraviolet curable resin composition according to any one of 16 to 18 above, which is C).
20. 20. The ultraviolet curable resin composition according to any one of the above 16 to 19, wherein the ultraviolet curable resin composition is for an optical disc having a reflective film made of silver or a silver alloy.
21. 20. A cured product of the ultraviolet curable resin composition according to any one of 16 to 19 above.
22. 20. An optical disc having a reflective film made of silver or a silver alloy having a cured product layer of the ultraviolet curable resin composition according to any one of 16 to 19 above.

The ultraviolet curable resin composition of the present invention is excellent in curability without bleeding out of the triazole derivative (A), and further cured on the reflective film of an optical disk using silver or a silver alloy as the reflective film. When a film is formed, there is little influence on the warp of the optical disk, and it is possible to obtain an optical disk having high light resistance and moist heat resistance and having excellent durability. In addition, the ultraviolet curable resin composition of the present invention is equivalent to the use of a protective coat having high light resistance and moist heat resistance without taking measures for improving the heat resistance such as increasing the crosslinking density of the resin. High durability can be obtained, and a highly reliable optical disk can be provided even under high temperature and high humidity.

The ultraviolet curable resin composition of the present invention (also referred to as the resin composition of the present invention) can be used for various applications and is suitable for a surface protective coating of silver or a silver alloy. In particular, since the resin composition of the present invention has excellent effects as described above, the resin composition of the present invention is used for an optical disc having a reflective film made of silver or a silver alloy, particularly for an optical disc formed directly on the reflective film, particularly a Blu-ray disc. Suitable for cover layer (light transmission layer).
The resin composition includes a triazole derivative (A) represented by the formula (1) or (2) (also referred to as a component (A)), a (meth) acrylate compound {preferably a (meth) acrylate monomer (B) (described later) (Also referred to as component (B)) and (meth) acrylate oligomer (C) (preferably one or both of epoxy (meth) acrylate and urethane (meth) acrylate (C)) (also referred to as component (C))) and A photopolymerization initiator (D) (also referred to as (D) component) is contained.

　式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基、フェニル基、Ｘは窒素原子または硫黄原子を表す。
式（２）

　式中、Ｒ_ｍは水素原子または炭素数１～３のアルキル基、Ｒ₁は炭素数１～３のアルキレン基、Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１～２０の脂肪族基、フェニル基、Ｘは窒素原子または硫黄原子を表す。 The triazole derivative (A) contained in the resin composition of the present invention is represented by the following general formula (1) or (2).

Formula (1)

In the formula, R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. A good aliphatic group having 1 to 20 carbon atoms, phenyl group, X represents a nitrogen atom or a sulfur atom.
Formula (2)

In the formula, R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. A good aliphatic group having 1 to 20 carbon atoms, phenyl group, X represents a nitrogen atom or a sulfur atom.

In the triazole derivative (A) used in the present invention, preferred groups in each symbol are as follows.
Examples of the aliphatic group having 1 to 20 carbon atoms which may have a substituent in R ₂ and R ₃ include a saturated or unsaturated aliphatic group which may have a substituent. The aliphatic group may be linear, branched or an aliphatic group containing a C5-C6 aliphatic ring group or a C5-C6 aliphatic ring. In addition, examples of the substituent on the aliphatic group include nitrogen atoms such as (i) phenyl group, (ii) morpholino group, pyrrolidino group, piperidino group or perhydroazepino group, and hetero atoms such as oxygen atoms. 5- to 6-membered heterocyclic groups containing 1 to 2 groups, (iii) hydroxy groups, (iv) C1-C6 alkoxy groups such as methoxy groups or butoxy groups, (v) C1-C6 alkylthio groups such as butylthio groups, etc. Can be mentioned. Preferred examples of the aliphatic group include an alkyl group having 1 to 10 carbon atoms (more preferably an alkyl group having 1 to 3 carbon atoms), an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or a branched chain. And an alkyl group having 6 to 10 carbon atoms having
R _m is preferably a hydrogen atom, and R ₁ is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group.
R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 6 to 10 carbon atoms having a branched chain. More preferably, both R ₂ and R ₃ are an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 6 to 10 carbon atoms having a branched chain. Most preferably, both are branched alkyl groups having 6 to 10 carbon atoms. Of the alkyl groups having 6 to 10 carbon atoms having a branched chain, alkyl groups having 7 to 9 carbon atoms having a branched chain are preferable.
X is preferably a nitrogen atom.

式中、Ｒ_２１及びＲ_３１はそれぞれ独立に、炭素数１～３のアルキル基、フェニル基で置換された炭素数１～３のアルキル基、分岐鎖を有する炭素数７～９のアルキル基又はフェニル基を表す。好ましくは、Ｒ_２１及びＲ_３１はそれぞれ独立に、炭素数１～３のアルキル基、フェニル基で置換された炭素数１～３のアルキル基又は分岐鎖を有する炭素数７～９のアルキル基である。
　さらに好ましくは、下記構造式（４）で表される化合物を挙げることができる。
式（４）

式中、Ｒ_２２及びＲ_３２はそれぞれ独立に、分岐鎖を有する炭素数７～９のアルキル基を表す。 As an example of a preferable compound of the triazole derivative (A), a compound represented by the following formula (3) can be given.
Formula (3)

In the formula, each of R ₂₁ and R ₃₁ independently represents an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, an alkyl group having 7 to 9 carbon atoms having a branched chain, or Represents a phenyl group. Preferably, R ₂₁ and R ₃₁ are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 7 to 9 carbon atoms having a branched chain. is there.
More preferably, the compound represented by following Structural formula (4) can be mentioned.
Formula (4)

In the formula, each of R ₂₂ and R ₃₂ independently represents a branched alkyl group having 7 to 9 carbon atoms.

Specific examples of the triazole derivative (A) represented by the formula (1) or (2) include the following compounds.
1- (or 4)-(dimethylaminomethyl) triazole, 1- (or 4)-(diethylaminomethyl) triazole, 1- (or 4)-(di-isopropylaminomethyl) triazole, 1- (or 4)- (Di-n-butylaminomethyl) triazole, 1- (or 4)-(di-n-hexylaminomethyl) triazole, 1- (or 4)-(di-isooctylaminomethyl) triazole, 1- (or 4)-(di- (2-ethylhexyl) aminomethyl) triazole, 1- (or 4)-(di-n-octylaminomethyl) triazole, 1- (or 4)-(di-n-decylaminomethyl) Triazole, 1- (or 4)-(di-n-dodecylaminomethyl) triazole, 1- (or 4)-(di-n-octadecylaminomethyl) tri Sol, 1- (or 4)-(di-n-eicosylaminomethyl) triazole, 1- (or 4)-[di- (prop-2′-enyl) aminomethyl] triazole, 1- (or 4) -[Di- (but-2'-enyl) aminomethyl] triazole, 1- (or 4)-[di- (eicose-2'-enyl) aminomethyl] triazole, 1- (or 4)-(di -Cyclohexylaminomethyl) triazole, 1- (or 4)-(di- (phenylmethyl) aminomethyl) triazole, 1- (or 4)-(di-phenylaminomethyl) triazole, 1- (or 4)-( 4′-morpholinomethyl) triazole, 1- (or 4)-(1′-pyrrolidinomethyl) triazole, 1- (or 4)-(1′-piperidinomethyl) triazole, 1- (or 4)-(1 ′ Perhydroazepinomethyl) triazole, 1- (or 4)-[(2 ′, 2 ″ -dihydroxyethyl) aminomethyl] triazole, 1- (or 4)-(dibutoxypropyl-aminomethyl) triazole, 1- (Or 4)-(dibutylthiopropyl-aminomethyl) triazole, 1- (or 4)-(di-butylaminopropyl-aminomethyl) triazole, N, N-bis- (1- or 4-triazolylmethyl) ) Laurylamine, N, N-bis- (1- or 4-triazolylmethyl) oleylamine, N, N-bis- (1- or 4-triazolylmethyl) ethanolamine and N, N, N ′, N′-tetra (1- or 4-triazolylmethyl) ethylenediamine, 1- (or 4)-(di- (2-propenyl) aminomethyl) triazole, -(Or 4)-(methyloctadecylaminomethyl) triazole, 1- (or 4)-(dioctylaminomethyl) triazole, 1- (or 4)-(di- (2,4,4-trimethylpentyl) aminomethyl ) Triazole, 1- (or 4)-(di- (2-methoxyethyl) aminomethyl) triazole and the like. Preferred compounds include 1- (di- (2-ethylhexyl) aminomethyl) triazole, 1- (di- (phenylmethyl) aminomethyl) triazole or 1- (di- (ethyl) aminomethyl) triazole. it can. You may use these individually or in mixture of 2 or more types.

From the viewpoint of obtaining excellent durability, light resistance, curability, and compatibility, the compound represented by the formula (3) is preferable. Specifically, 1- (di- (2-ethylhexyl) aminomethyl) triazole, 1- (di- (phenylmethyl) aminomethyl) triazole, 1- (di- (ethyl) aminomethyl) triazole, etc. should be used. Can do. As a more preferable compound, the compound represented by Formula (4) can be mentioned. Examples of the compound represented by the formula (4) include 1- (di- (2-ethylhexyl) aminomethyl) triazole.

Although the said triazole derivative (A) can be used without specifically limiting, specifically, IRGAMET ^RTM 30 etc. by Ciba Specialty Chemicals Co., Ltd. is mentioned.

The content of component (A) is usually 0.001 to 5% by weight, preferably 0.005 to 3% by weight, more preferably 0.01 to 2% by weight, based on the total amount of the resin composition of the present invention. More preferably, it is 0.02 to 1% by weight. In some cases, 0.03 to 0.5% by weight is preferable. In some cases, it may be 0.1 to 2% by weight. If the amount is too small, there is no effect, and if the amount is too large, durability and light resistance corresponding to the added amount are not improved, which is economically disadvantageous.

As the (meth) acrylate compound used in the present invention, at least any one of (meth) acrylate monomer (B), epoxy (meth) acrylate or urethane (meth) acrylate (C) described below and any (Meth) acrylate compounds, such as phosphoric acid (meth) acrylate (E) which are one of the additives, can be mentioned.
In the present invention, the (meth) acrylate monomer (B) is an epoxy (meth) acrylate or / and urethane (meth) acrylate (C) and (meth) acrylate (for example, phosphoric acid (for example) contained in any other additive. It means (meth) acrylate monomer excluding (meth) acrylate (E) and (meth) acrylate contained in hindered amine).
In the present invention, the expression “(meth) acrylate” means methacrylate or / and acrylate. The same expression with “(meta)” has the same meaning.
The content of the (meth) acrylate compound in the resin composition of the present invention is the remainder excluding the triazole derivative (A), the photopolymerization initiator (C), and any additive described later from the total amount of the resin composition. Usually, it is 70% by weight or more based on the total amount of the resin composition, for example, about 70 to 99% by weight, preferably 75 to 99% by weight, more preferably about 80 to 98% by weight, Preferably, it may be about 85 to 96% by weight, and in some cases, 90 to 96% by weight.
As the (meth) acrylate monomer (B) in the present invention, monofunctional (meth) acrylate, bifunctional (meth) acrylate or / and trifunctional or higher (meth) acrylate can be used. One of the preferable embodiments of the present invention is an embodiment in which monofunctional to trifunctional (meth) acrylate is used as the (meth) acrylate monomer (B), more preferably monofunctional or / and bifunctional (meth) acrylate. The mode which uses can be mentioned.

Here, the monofunctional (meth) acrylate that can be used is not particularly limited. For example, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxyditripropylene glycol (meth) acrylate, tri Cyclodecane (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadieneoxyethyl (meth) Acrylate, dicyclopentenyl acrylate (for example, Hitachi Chemical Co., Ltd. ^FANCRYL RTM FA-511A), dicyclopentenyl oxyethyl acrylate (e.g., Hitachi Chemical Co., Ltd. ^FANCRYL RTM FA-512A), dicyclopentenyloxy methacrylate ( For example, FANCYR ^RTM FA-512M manufactured by Hitachi Chemical Co., Ltd., dicyclopentanyl acrylate (for example, FANCRRY ^RTM FA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (for example, manufactured by Hitachi Chemical Co., Ltd.) FANCRYL ^RTM FA-513M), 1- adamantyl acrylate (for example, Adamantate ^RTM AA manufactured by Idemitsu Kosan Co., Ltd.), 2-methyl-2- Adamanchirua Relate (e.g., Idemitsu Kosan Co., Ltd. Adamantate ^RTM MA), 2- ethyl-2-adamantyl acrylate (for example, Idemitsu Kosan Co. Adamantate ^RTM EA), 1- adamantyl methacrylate (for example, manufactured by Idemitsu Kosan Co. Adamantate ^RTM AM ) And the like. The superscript “RTM” indicates a registered trademark.
Among the above monofunctional (meth) acrylates, from the viewpoint of improving light resistance, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, dicyclopentenyloxyethyl acrylate (dicyclohexane) Pentadieneoxyethyl acrylate) can be preferably used, and other preferable monofunctional (meth) acrylates include phenoxy polyethylene glycol (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. it can. The preferred compounds and other preferred monofunctional (meth) acrylates from the viewpoint of improving the light resistance listed here are hereinafter also referred to as Ba group (meth) acrylates.
Among the above, phenoxyethyl (meth) acrylate and / or dicyclopentenyloxyethyl acrylate can be preferably used.

As the bifunctional (meth) acrylate that can be used as the (meth) acrylate monomer (B), known ones can be used without any particular limitation.
Specifically, cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate (for example, KAYARAD manufactured by Nippon Kayaku Co., Ltd.) ^RTM R-684, tricyclodecane dimethylol diacrylate, etc.), dioxane glycol di (meth) acrylate (for example, KAYARAD ^RTM R-604, dioxane glycol diacrylate, manufactured by Nippon Kayaku Co., Ltd.), neopentyl glycol di (meta) ) Acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, alkylene oxide modified 1,6-hexanediol di (meth) acrylate, alkylene oxide modified Neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include ethylene oxide-modified bisphenol A type di (meth) acrylate.

Among these, polypropylene glycol di (meth) acrylate (the number of propylene glycol repeats is about 2 to 10, preferably about 2 to 5, more preferably 2 or 3), ethylene oxide modified bisphenol A Type di (meth) acrylate (preferred addition number of ethylene oxide is 2 to 15 mol) and / or 1,6-hexanediol di (meth) acrylate. The preferable bifunctional (meth) acrylate mentioned here is called Bb group (meth) acrylate.
Among the group Bb (meth) acrylates, more preferred compounds include polypropylene glycol diacrylate, ethylene oxide-modified bisphenol A diacrylate and / or 1,6-hexanediol diacrylate.
The use of 1,6-hexanediol di (meth) acrylate or / and polypropylene glycol di (meth) acrylate (preferred propylene glycol repeat number is 2 to 5) is more preferable in some cases.

As the tri- or higher functional (meth) acrylate that can be used as the (meth) acrylate monomer (B), known ones can be used without any particular limitation.
Specifically, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxy Polypropoxytri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, caprolactone modified tris [(meth) acryloyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, ethylene oxide modified trimethylolpropane Tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol polyethoxytetra ) Acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified Examples thereof include polyfunctional monomers such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

In the ultraviolet curable resin composition for an optical disk of the present invention, these components (B) can be used alone or in admixture of two or more at any ratio.
Preferred compounds of the component (B) include dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Group consisting of phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide-modified bisphenol A type di (meth) acrylate (group Bc (meth) acrylate At least one compound selected from (also referred to as). Among them, the number of repeating polyethylene glycols in the phenoxypolyethylene glycol (meth) acrylate is preferably about 2 to 10, more preferably about 2 to 5, and still more preferably 2 to 3.
The content of the (meth) acrylate monomer (B) is usually 30 to 98% by weight, preferably 40 to 80% by weight, particularly preferably 40 to 60% by weight, based on the total amount of the ultraviolet curable resin composition.
One preferred embodiment is a combined use of a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate, more preferably a combined use of a monofunctional (meth) acrylate and a bifunctional to trifunctional (meth) acrylate, and more preferably This is a combination of monofunctional (meth) acrylate and bifunctional (meth) acrylate. In the case of the combined use of a monofunctional (meth) acrylate and a bifunctional (meth) acrylate, at least one of the Ba group (meth) acrylates as a monofunctional (meth) acrylate and the Bb group ( A mode in which at least one (preferably 2 to 4) of meth) acrylate is used in combination is more preferable. In some cases, only a polyfunctional (meth) acrylate may be used.
When monofunctional (meth) acrylate and polyfunctional (meth) acrylate are used in combination, the ratio of the two is 1 to 10 parts by weight of polyfunctional (meth) acrylate, preferably 1. The amount is about 5 to 5 parts by weight, more preferably about 2 to 5 parts by weight.

When an example of a preferred combination of monofunctional (meth) acrylate and bifunctional (meth) acrylate is shown, the following embodiments can be exemplified.
(I) at least one selected from the group consisting of the monofunctional (meth) acrylates exemplified above as the monofunctional (meth) acrylate and at least one selected from the group consisting of the above exemplary compounds as the bifunctional (meth) acrylate. A mode in which two are used together.
(Ii) Monofunctional (meth) acrylates exemplified as preferred as monofunctional (meth) acrylates, specifically, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate and dicyclo The embodiment of (i) above, wherein at least one selected from the group consisting of pentenyloxyethyl acrylate is used.
(Iii) The embodiment of (i) or (ii) above, wherein phenoxyethyl (meth) acrylate or / and dicyclopentenyloxyethyl acrylate is used as the monofunctional (meth) acrylate.

(Iv) The embodiment according to any one of (i) to (iii) above, wherein dicyclopentenyloxyethyl acrylate is used as the monofunctional (meth) acrylate.
(V) The compound exemplified as a preferred bifunctional (meth) acrylate as the bifunctional (meth) acrylate, more specifically, polypropylene glycol di (meth) acrylate (the number of propylene glycol repeats is about 2 to 10, preferably About 2 to 5), ethylene oxide 2 to 15 moles modified bisphenol A type di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are used. The aspect according to any one of (iv).
(Vi) The embodiment according to any one of (i) to (iv) above, wherein at least two or more di (meth) acrylates are used as the bifunctional (meth) acrylate.
(Vii) Di (meth) acrylate is either (a) polypropylene glycol di (meth) acrylate (the number of propylene glycol is about 2 to 10) or ethylene oxide 2 to 15 mol modified bisphenol A type di (meth) acrylate Alternatively, the embodiment described in (vi) above, wherein both are used in combination with (b) 1,6-hexanediol di (meth) acrylate.
(Viii) The aspect according to any one of (i) to (vii) above, wherein the polypropylene glycol di (meth) acrylate is di- or tripropylene glycol di (meth) acrylate.
(Ix) Any one of the above (v) to (viii), wherein the ethylene oxide 2 to 15 mol modified bisphenol A type di (meth) acrylate is ethylene oxide 4 to 10 mol modified bisphenol A type di (meth) acrylate. Description aspect.
(X) 1 to 10 parts by weight, preferably 1.5 to 5 parts by weight, more preferably 2 to 5 parts by weight of bifunctional (meth) acrylate per 1 part by weight of monofunctional The aspect according to any one of (ix).

The (meth) acrylate oligomer (C) contained in the composition of the present invention is preferably urethane (meth) acrylate and / or epoxy (meth) acrylate, and has one or more (meth) acryloyl groups, preferably 1 to Two epoxy (meth) acrylates (C-1) or urethane (meth) acrylates (C-2) can be used. In some cases, the combined use of both is more preferred. The epoxy (meth) acrylate (C-1) or the urethane (meth) acrylate (C-2) is preferably epoxy di (meth) acrylate or urethane di (meth) acrylate.
The molecular weight of the component (C) is preferably 400 to 10,000, more preferably 600 to 10,000.

The epoxy (meth) acrylate (C-1) used in the present invention has a function of improving curability and improving the hardness and curing speed of the cured product.
Moreover, in this invention, as an epoxy (meth) acrylate, if it was obtained by making the epoxy compound (it is also glycidyl ether type epoxy hereafter) which has a glycidyl ether group, and (meth) acrylic acid react, Either can be used.
As the glycidyl ether type epoxy compound for obtaining an epoxy (meth) acrylate preferably used in the present invention, (i) glycidyl ether of bisphenol compound, for example, diglycidyl ether of bisphenol A or its alkylene oxide adduct, bisphenol F Or diglycidyl ether of the alkylene oxide adduct, hydrogenated bisphenol A or diglycidyl ether of the alkylene oxide adduct, hydrogenated bisphenol F or diglycidyl ether of the alkylene oxide adduct, and (ii) C2-C8 fat Glycidyl ethers of aliphatic glycols such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycol Jill ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol diglycidyl ether. These glycidyl ethers react with the generated glycidyl ether and glycol at the stage of synthesis of glycidyl ether to produce oligomers having about 2 to 20 molecules, preferably about 2 to 10 repeating units.

Among the above compounds, preferred compounds include glycidyl ethers of bisphenol compounds (bisphenol A or F, hydrogenated bisphenol A or F, or alkylene oxide adducts thereof). Examples of the alkylene oxide in the above-mentioned alkylene oxide adduct include C2-C4 alkylene oxide, and more preferably C2 or C3 alkylene oxide.
Among the glycidyl ethers of bisphenol compounds, glycidyl ethers of bisphenol A compounds (hereinafter also referred to as bisphenol A type epoxy compounds or bisphenol A compound glycidyl ethers) are preferable. Examples of the bisphenol A compound include bisphenol A, hydrogenated bisphenol A, or bisphenol A alkylene oxide adduct and hydrogenated bisphenol A alkylene oxide adduct. The alkylene in the alkylene oxide adduct is usually preferably C2-C4 alkylene, more preferably C2 or C3 alkylene. The added mole number is about 1 to 20, preferably about 1 to 15, and more preferably about 2 to 10.
Of the bisphenol A compound glycidyl ethers, bisphenol A diglycidyl ether is more preferred.

In the present invention, examples of preferable epoxy (meth) acrylate include epoxy (meth) acrylate obtained by adding (meth) acrylic acid to the above-mentioned preferable glycidyl ether. Specifically, an epoxy (meth) acrylate obtained by adding (meth) acrylic acid to a glycidyl ether of a bisphenol compound (more preferably a bisphenol A compound), that is, a bisphenol compound epoxy (meth) acrylate, more preferably Bisphenol A compound epoxy (meth) acrylate (hereinafter also referred to as bisphenol A type epoxy (meth) acrylate). More specifically, bisphenol compound diglycidyl ether di (meth) acrylate, more preferably bisphenol A compound diglycidyl ether di (meth) acrylate, and still more preferably bisphenol A diglycidyl ether di (meth) acrylate.
As described above, since the glycidyl ether used as the raw material is an oligomer, the resulting epoxy (meth) acrylate is also an oligomer.
In the present invention, the molecular weight of the epoxy (meth) acrylate (C-1) is preferably 500 to 10,000.
A preferred epoxy (meth) acrylate (C-1) is a bisphenol A type epoxy (meth) acrylate obtained by the reaction of a bisphenol A type epoxy compound and (meth) acrylic acid as described above, and more preferably Is bisphenol A diglycidyl ether di (meth) acrylate.
The reaction of these glycidyl ether type epoxy compounds and (meth) acrylic acid to obtain an epoxy (meth) acrylate can be usually carried out under the following conditions.

(1) (Meth) acrylic acid is reacted in an amount of 0.9 to 1.5 mol, more preferably 0.95 to 1.1 mol, per 1 equivalent of epoxy group of the glycidyl ether type epoxy compound. The reaction temperature is preferably 80 to 120 ° C., and the reaction time is about 10 to 35 hours. A catalyst can be used to accelerate the reaction. As the catalyst, a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acid catalyst include metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. Among these, an acidic catalyst is preferable, and a tin compound is more preferable. The addition amount is 50 to 1000 ppm with respect to the glycidyl ether type epoxidized product. In addition, a polymerization inhibitor (for example, paramethoxyphenol, methylhydroquinone, etc.) can be used to prevent polymerization during the reaction.

ウ レ タ ン Urethane (meth) acrylate used as the component (C-2) in the present invention has a function of improving the mechanical properties (warpage, distortion, etc.) of the optical disk using the ultraviolet curable resin composition for optical disk of the present invention. Urethane (meth) acrylate is obtained by reacting a polyhydric alcohol, an organic polyisocyanate, and a hydroxy (meth) acrylate compound.

Examples of the polyhydric alcohol include (i) a linear or cyclic aliphatic polyhydric alcohol having 2 to 4 hydroxyl groups and having 2 to 12 carbon atoms, such as neopentyl glycol, 3-methyl-1,5-pentane. A polyol having 3 to 4 hydroxyl groups such as diol, ethylene glycol, propylene glycol, 1,4-butanediol, alkylene glycol having a linear or branched chain such as 1,6-hexanediol, trimethylolpropane or pentaerythritol, Polyols having a cyclic structure such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, etc. (ii) polyhydric alcohols (aliphatic alcohols) and polybasic acids (for example, succinic acid, phthalate) Acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azela Polyester polyols obtained by reaction with acid, tetrahydrophthalic anhydride, etc.) (iii) caprolactone alcohol obtained by reaction of polyhydric alcohol (aliphatic alcohol) of (i) above with ε-caprolactone, (iv) Polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate) or (v) polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.) Etc. You may use these individually or in mixture of 2 or more types. It is preferable to use a polyether polyol in terms of productivity, cost, and versatility.
Here, it is preferable to use a polyether polyol from the viewpoint of improving the compatibility with other (meth) acrylates and from the viewpoint of durability.
As the polyether polyol (preferably polyether diol), for example, poly C2-C4 alkylene glycol or ethylene oxide-modified bisphenol A is preferable, and poly C2-C4 alkylene glycol is more preferable. Examples of the poly C2-C4 alkylene glycol include those having a molecular weight of about 100 to 10000, preferably about 300 to 5000, more preferably about 300 to 2000, and most preferably about 300 to 1500.

The organic polyisocyanate used for the synthesis of urethane (meth) acrylate can be used without any particular limitation.
It is preferable to use diisocyanate from the viewpoint of ensuring flexibility (viscosity that can be stirred) when the hydroxy (meth) acrylate compound is reacted. Examples of the diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl isocyanate, and the like. You may use these individually or in mixture of 2 or more types. Of these, isophorone diisocyanate is more preferred.

Examples of the hydroxy (meth) acrylate compound used for the synthesis of urethane (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylol cyclohexyl mono (meth) acrylate, Examples include hydroxycaprolactone (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Hydroxy C2-C10 aliphatic hydrocarbon (meth) acrylate is more preferred, and hydroxy C2-C4 alkyl (meth) acrylate is still more preferred.

The urethane (meth) acrylate synthesis reaction can be performed, for example, as follows. That is, an organic polyisocyanate is mixed per equivalent of hydroxyl group of a polyhydric alcohol so that the isocyanate group is preferably 1.1 to 2.0 equivalent, and reacted at room temperature to 100 ° C, preferably 50 ° C to 90 ° C. Synthesize urethane oligomers. Next, a hydroxy (meth) acrylate compound is mixed per equivalent of isocyanate group of the urethane oligomer so that the hydroxyl group is preferably 1 to 1.5 equivalent, and reacted at room temperature to 100 ° C, preferably 50 ° C to 90 ° C. Thus, the desired urethane (meth) acrylate can be obtained. A polymerization inhibitor for preventing gelation and a catalyst for accelerating the reaction can be used. As a preferable urethane (meth) acrylate, polyether urethane (meth) acrylate using a polyether polyol, preferably a polyether diol, as a polyhydric alcohol is preferable. A more preferable urethane (meth) acrylate is a urethane (meth) acrylate obtained by using each of the above-mentioned preferable raw material compounds.
The molecular weight of the urethane (meth) acrylate (C-2) is preferably 400 to 10,000, and more preferably 600 to 10,000.

In the ultraviolet curable resin composition for an optical disk of the present invention, the component (C) can be used alone or in combination of two or more at any ratio. From the viewpoint of balancing the flexibility and curability, the combined use of epoxy (meth) acrylate and urethane (meth) acrylate is preferred. On the other hand, it is preferable to use urethane (meth) acrylate alone from the viewpoint of suppressing warpage during curing and suppressing the influence of warpage in temperature change.
The ratio of both urethane (meth) acrylate (C-2) and epoxy (meth) acrylate (C-1) is not particularly limited. Usually, 0.1 to 20 parts by weight of epoxy (meth) acrylate (C-1), preferably 1 to 15 parts by weight, more preferably 1 part by weight of urethane (meth) acrylate (C-2). The ratio is 2 to 10 parts by weight.

The content of component (C) is usually 2 to 50% by weight, preferably 20 to 50% by weight, based on the total amount of the ultraviolet curable resin composition.
In the resin composition of this invention, these (B) component and (C) component can be used 1 type or in mixture of 2 or more types by arbitrary ratios.
In the resin composition of this invention, phosphoric acid (meth) acrylate (E) can be added as needed as one of the other additives. Phosphoric acid (meth) acrylate improves the adhesion between aluminum, silver or a silver alloy and the cured adhesive, but may corrode the metal film, and its amount used is limited.
The phosphoric acid (meth) acrylate that can be contained in the resin composition of the present invention is not particularly limited as long as it is a (meth) acrylate having a phosphate ester skeleton, such as a monoester, a diester, or a triester. Phenoxylated phosphoric acid (meth) acrylate, ethylene oxide modified butoxylated phosphoric acid (meth) acrylate, ethylene oxide modified octyloxylated phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) Examples thereof include acrylate and the like, and are available as PM-2 (ethylene oxide-modified phosphate dimethacrylate) manufactured by Nippon Kayaku Co., Ltd. In the present invention, ethylene oxide-modified phosphate dimethacrylate is preferably used. Phosphoric acid (meth) acrylate can be used alone or in combination of two or more. When phosphoric acid (meth) acrylate is contained in the resin composition of the present invention, its content is usually 0.005 to 5% by weight, preferably 0.05 to 3% by weight, based on the total amount of the resin composition. is there.

The photopolymerization initiator (D) contained in the resin composition of the present invention is not particularly limited. For example, 1-hydroxycyclohexyl phenyl ketone (Irgacure ^RTM 184; manufactured by Ciba Specialty Chemicals), 2-Hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer (KIP-150; ONE-Rifened; manufactured by Sybel Hegner, Japan), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-2-methyl-1-propan-1-one (Irgacure ^RTM 2959; manufactured by Ciba Specialty Chemicals), 2-hydroxy-1- {4- [4- (2-hydroxy- 2-Methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane- - one (Irgacure ^RTM 127; manufactured by Ciba Specialty Chemicals Corporation), 2,2-dimethoxy-2-phenylacetophenone (Irgacure ^RTM 651; manufactured by Ciba Specialty Chemicals Corporation), 2-hydroxy-2- Methyl-1-phenyl-propan-1-one (Darocur ^RTM 1173; manufactured by Ciba Specialty Chemicals), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one ( Irgacure ^RTM 907; manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone Isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, oligo [2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propanone, dimer of [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] (Esacure ^RTM ONE; manufactured by Nippon Siber Hegner), bis ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.
Among the components (D), a 2- to 10-mer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, preferably from the viewpoint of imparting excellent light resistance and durability, Is preferably a dimer to pentamer, specifically, a compound referred to as oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and / or [2 The use of a dimer of -hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] is preferred.

In the resin composition of the present invention, these (D) components can be used alone or in admixture of two or more. The content of the component (D) in the resin composition is usually 0.5 to 20% by weight, preferably 1 to 10% by weight.

Furthermore, as one of other additives, if necessary, amines that can serve as photopolymerization initiation assistants can be used in combination with the above photopolymerization initiator. Examples of amines that can be used include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester. The content of the amine and the like in the resin composition of the present invention is usually 0 to 5% by weight based on the total amount of the resin composition. When the photopolymerization initiation aid is used, 0.005 to 5% by weight, preferably 0.01 to 3% by weight.

The resin composition of the present invention may further contain other additives such as antioxidants, organic solvents, silane coupling agents, polymerization inhibitors, leveling agents, antistatic agents, surface lubricants, fluorescent enhancement agents as necessary. You may add additives, such as a whitening agent, a light stabilizer (for example, hindered amine compound etc.), and a filler.
Specific examples of hindered amine compounds include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2,6,6. -Pentamethyl-4-piperidyl (meth) acrylate (LA-82), 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, manufactured by Ciba Specialty Chemicals, CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 123, TINUVIN 123S, TINUVIN 144, TINUVIN 765, TINUVIN 477, TINUVIN 770DF, TINUVIN 111FDL, TINUVIN 783FDL, TINUVIN 791FB, TINUVIN XT850FF, TINUVIN XT855FF, etc.
The content of the additive in the resin composition of the present invention is usually 0 to 5% by weight with respect to the total amount of the resin composition, and when contained, 0.005 to 5% by weight, preferably 0.01 to 3%. % By weight.
In the resin composition of the present invention, the total content of other additives other than the components (A) to (D) is 0 to 20% by weight, preferably 0 to 10% by weight, based on the total amount of the resin composition. More preferably, it is 0 to 5% by weight.

Preferred embodiments of the resin composition of the present invention are as follows. In addition, unless otherwise indicated,% and a part are weight% or a weight part.
(I) As a triazole derivative of component (A), R _{m in} formula (1) is a hydrogen atom, R ₁ is an alkylene group having 1 to 3 carbon atoms (preferably methylene), X is a nitrogen atom, R ₂ and R ₃ Are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 6 to 10 carbon atoms having a branched chain, (meth) acrylate UV curable resin composition containing (meth) acrylate monomer (B), urethane (meth) acrylate or epoxy (meth) acrylate (C), and photopolymerization initiator (D) as a compound object.
(Ii) The content of the triazole derivative of the component (A) is 0.005 to 5%, the content of the (meth) acrylate monomer (B) is 30 to 98% by weight, and the component (C) The content of urethane (meth) acrylate or epoxy (meth) acrylate) is 2 to 50%, and the content of the photopolymerization initiator (D) is 0.5 to 20%. UV curable resin composition.
(Iii) The ultraviolet curable resin composition according to the above (ii), wherein the total amount of the (meth) acrylate compound (component (B) and component (C)) is 75 to 99%.
(Iv) The ultraviolet curable type according to any one of (i) to (iii), wherein the (meth) acrylate monomer (B) is at least one selected from the group consisting of the Ba group and the Bb group. Resin composition.
(V) The ultraviolet curable resin according to any one of (i) to (iv) above, wherein the (meth) acrylate monomer (B) is a combination of a monofunctional (meth) acrylate and a bifunctional (meth) acrylate. Composition.

(Vi) The ultraviolet curable resin composition according to any one of the above (i) to (v), wherein the (meth) acrylate monomer (B) is at least one selected from the group consisting of the Bc group. .
(Vii) The ultraviolet curable resin composition according to any one of (i) to (vi) above, wherein the component (C) is both urethane (meth) acrylate and epoxy (meth) acrylate.
(Viii) The ultraviolet curable resin composition according to any one of the above (i) to (vii), wherein the urethane (meth) acrylate is a polyetherurethane acrylate.
(Ix) The above (i) to (viii), wherein the epoxy (meth) acrylate is an epoxy (meth) acrylate obtained by adding (meth) acrylic acid to a glycidyl ether of a bisphenol compound (more preferably a bisphenol A compound). The ultraviolet curable resin composition as described in any one of these.
(X) The ratio of both urethane (meth) acrylate (C-2) and epoxy (meth) acrylate (C-1) is 1 part of urethane (meth) acrylate (C-2), and epoxy (meth) acrylate The ultraviolet curable resin composition according to (vii) above, wherein (C-1) is in a proportion of 0.1 to 20 parts, preferably 1 to 15 parts.

The optical disk adhesive resin composition of the present invention can be obtained by mixing and dissolving the above-mentioned components at room temperature to 80 ° C. If necessary, impurities may be removed by an operation such as filtration. In the adhesive resin composition of the present invention, it is preferable to appropriately adjust the blending ratio of the components so that the viscosity at 25 ° C. is in the range of 100 to 5000 mPa · s in view of applicability. Here, when used as a protective coating agent for optical disks, the viscosity at 25 ° C. is preferably in the range of 500 to 2000 mPa · s.

The resin composition of the present invention is suitable as a protective coating agent for optical disks. In particular, it can be suitably used as a coating agent for a light transmission layer on the laser incident side such as a Blu-ray disc or an adhesive for a bonded optical disc such as a DVD.
Specifically, the coated resin has a film thickness of 1 to 150 μm (preferably 90 to 110 μm when used as a light transmission layer coating agent on the laser incident side such as a Blu-ray disc), for example, The composition is applied onto the reflective film of the optical disk substrate by spin coating, 2P, roll coating, screen printing, or the like. In the case of a bonding type, after coating on at least one of the bonding sides of two optical disk substrates, preferably on a reflective film, and stacking the two optical disk substrates so as to be bonded on the coated surface Then, the adhesive layer is cured and bonded by irradiating ultraviolet rays to near ultraviolet rays (wavelength of 200 to 400 nm) from one side or both sides. In this case, since there is a reflection film on the bonding side of at least one of the two optical disk substrates, the resin composition of the present invention is usually applied and bonded onto the reflection film. As a result, the resulting optical disc has a structure in which both sides are protected by an optical disc substrate, and a reflective film and a cured product layer of the resin composition of the present invention are interposed between the two substrates. Become.
In addition, when the cured product layer of the resin composition of the present invention is a light-transmitting layer of a Blu-ray disc, the composition is applied on a reflective film formed on the recording surface of the substrate, and then ultraviolet to near from one side or both sides. Curing is performed by irradiating with ultraviolet rays (wavelength of 200 to 400 nm). In this case, the obtained Blu-ray disc has a structure in which one side of the disc is a substrate and the opposite side is a light-transmitting layer and is sandwiched between the two and has a reflective film formed on the recording surface. . In any of these cases, the cured product layer of the resin composition of the present invention exists in direct contact with the reflective film. The resin composition of the present invention can also be applied to BD-R or BD-RE. Moreover, you may provide a hard-coat layer etc. on said light transmissive layer as needed.
In producing the optical disc, the irradiation amount of ultraviolet rays to be irradiated to form a cured product layer of the resin composition of the present invention is preferably from about 50 ~ 1500mJ / cm ^2, particularly preferably, 100 ~ 1000mJ / cm ² of about It is. For curing by irradiation with ultraviolet to near ultraviolet rays, any light source may be used as long as it is a lamp that emits ultraviolet to near ultraviolet rays. For example, a low-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, (pulse) xenon lamp, or electrodeless lamp can be used.

As the optical disk substrate, a known substrate, that is, a substrate in which a translucent reflective film is formed using silicon, a silicon compound, silver, or a silver alloy can be used. In particular, the resin composition of the present invention is suitable for an optical disc in which a total reflection film or a semitransparent reflection film is formed of silver or a silver alloy.
An optical disk in which the present invention is particularly effective in durability and light resistance is an optical disk using a substrate having a translucent reflective film formed of silver or a silver alloy. The translucent reflective film can be obtained, for example, by forming a thin film of silver or an alloy thereof on the surface on the recording layer side of a substrate such as polycarbonate by a method such as sputtering or vapor deposition.
And, by forming a layer made of a cured product of the ultraviolet curable resin composition of the present invention on a layer in which another layer such as a recording layer is interposed directly on the reflective film of silver or a silver alloy of the production substrate The above effects can be obtained effectively. In particular, the above effect can be effectively exhibited by forming a layer made of the cured product of the ultraviolet curable resin composition of the present invention directly on a reflective film of silver or a silver alloy.

In the present invention, a cured film obtained by coating the composition on an optical disk substrate having a thickness of 1.1 mm obtained by irradiating two optical disk substrates by irradiating ultraviolet rays with the resin composition of the present invention. An optical disk in which a light transmission layer is formed by laminating a transparent film is also included. In particular, an optical disk substrate is a bonded optical disk, at least one of which is an optical disk substrate having a silver or silver alloy total reflection film or a semitransparent reflection film, and a Blu-ray disk having a silver or silver alloy total reflection film or a semitransparent reflection film In addition, an optical disk obtained by applying the resin composition of the present invention is preferable.
The optical disk is a DVD-ROM (DVD-5, DVD-10, DVD-9, DVD-14, DVD-18), DVD-R, DVD + R, DVD-RW, DVD + RW, DVD-RAM, DVD-R single-sided, double-layer It is used for the DVD + R single-sided double layer method, DVD-RW single-sided double layer method, DVD + R single-sided double layer method, HD DVD-ROM, HD DVD-R, BD-ROM, BD-R, BD-RE, and the like.
In particular, a Blu-ray disc in which a cured film of the resin composition of the present invention is present on a silver or silver alloy total reflection film of a Blu-ray disc such as a BD-ROM is preferable.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Examples A1, A2 and A3 and Comparative Example B1
(I) Preparation of UV-curable resin composition UV-curable resin compositions of Examples A1, A2 and A3 of the present invention having the compositions shown in Table 1 below and UV-curable resin composition of Comparative Example B1 for comparison The product was prepared by mixing and stirring the components so as to be uniform.
In Comparative Example B1, in the ultraviolet curable resin composition of Example A1, 3-ethyl-4-hydroxythiophenol (described in Patent Document 4) was used instead of containing 0.1% by weight of Additive 1. EHTP) (Additive 3) is added in an amount of 0.5 parts by weight.
(Ii) Creation of Blu-ray Disc The silver reflective film substrate is a 1.1 mm thick PC substrate on which pits for BD-ROM are formed, using a silver alloy GB-100 manufactured by Kobe Steel, Ltd., and sputtered to an average film thickness of 30 nm. Four disk substrates with a silver reflecting film were produced.
2. The substrate obtained in 1 above is placed on a spin table so that the surface of the silver reflecting film is on top, and a circular cap treatment is performed so as to cover the inner diameter of 11.5 mm, and then the present invention obtained in (i) above or 2.5 g of each of the comparative ultraviolet curable resin compositions was supplied onto the cap at the center of each substrate.
3. In accordance with the viscosity of the ultraviolet curable resin composition of the present invention or for comparison, spin coating was performed at a speed range of 1000 rpm to 1500 rpm for 4 seconds to 7 seconds, and each coating film thickness was 95 μm to 105 μm. Immediately after the end of spin coating, the xenon flash lamp was irradiated with two shots, and cured so that the fluidity of the surface disappeared.
4). The present invention has a light transmission layer by using a xenon flash lamp to irradiate the coating film with 8 shot ultraviolet rays at 80 J from the upper side of each substrate having the coating film obtained in 3 above to completely cure the coating film. A comparative Blu-ray disc (BD-ROM) was obtained.
In the Blu-ray discs of Examples A1, A2 and A3 of the present invention and the Blu-ray disc of Comparative Example B1, no added triazole derivative of formula (1) or EHTP bleed out was observed, and the curability was good. It was.
The disk of the present invention can be hard-coated on the resin surface. However, in the following evaluation, the durability of the light transmission layer itself is evaluated. went.

Evaluation Test Using the BD-ROM obtained above, the following (i) light resistance test and (ii) durability test were performed.
The state before and after the above test was evaluated by reflectance (R-8H), jitter value, electrical signal (RSER) of the optical disk, visual evaluation (reflection film appearance evaluation), and comprehensive evaluation.
R-8H, jitter, and RSER are one of electrical signals of the optical disk. The lower the value of R-8H, the more the data on the optical disc is degraded. Further, the greater the increase in the value of jitter, the more the optical disk data is degraded. The higher the RSER value, the more the optical disk data is degraded.
The reflectance (R-8H), jitter value, and RSER were measured using a Blu-ray Disc data signal measuring device ODU-1000 manufactured by Pulstec Industrial Co., Ltd.
(A) Evaluation of jitter The jitter was compared with the jitter value before the test and evaluated by how much the jitter value increased after the test.
(B) Evaluation of R-8H R-8H was evaluated by comparing with the R-8H value before the test and by how much the R-8H value after the test was reduced.
(C) Evaluation of RSER About evaluation of RSER, it evaluated by the RSER value after a test.
(D) Visual evaluation (reflection film appearance evaluation)
After the test, the state of the reflective film of the optical disk was visually observed. The observation results were evaluated according to the following criteria.
○: No change was observed in the state of the reflective film before and after the test.
X: Discoloration is observed in the reflective film after the test as compared to before the test.

(E) Comprehensive evaluation In the comprehensive evaluation, each of the evaluation of jitter, R-8H and RSER is performed based on the following ○ × criteria, and the above visual evaluation is combined. Is ○ when the evaluation is ○, and when any one of the evaluations is ×, the evaluation is ×.
○ Evaluation of reference jitter for × ○ Jitter value increase is less than 4.0.
X: Jitter value rise is 4.0 or more.
Evaluation of R-8H ○ ・ ・ ・ R-8H value decrease is less than 7.0.
X: R-8H value decreased by 7.0 or more.
Evaluation of RSER ○: RSER value less than 2.0E-04 (represents 2.0 × 10 ⁻⁴ ) × ・ ・ ・ RSER value 2.0E-04 (represents 2.0 × 10 ⁻⁴ ) or more.
Note that the RSER value 2.0E-04 represents 2.0 × 10 ⁻⁴ as described above, and the same applies to other values of the RSER value in Table 1.

(I) Light resistance test (fluorescent lamp test)
Each of the optical disk of the present invention and the optical disk of the comparative example is installed with a distance of about 10 cm from a fluorescent lamp having a color temperature of 6700 K so that the light transmission layer (cured resin layer) surface of the disk hits the fluorescent lamp. Left for hours.
The R-8H evaluation, the jitter evaluation, the RSER evaluation, the visual evaluation, and the comprehensive evaluation after the test were performed according to the above-mentioned criteria.
(Ii) Durability test (moisture and heat resistance test)
The durability test was allowed to stand for 250 hours in an environment of 80 ° C. and 85% RH.
The R-8H evaluation, the jitter evaluation, the RSER evaluation, the visual evaluation and the comprehensive evaluation after the test were performed according to the above-mentioned standards.

In addition, each component shown with the abbreviation in Table 1 is as follows.
EPA: epoxy acrylate (bisphenol A diglycidyl ether diacrylate),
UA-1: urethane acrylate (reactant having a molar ratio of 1: 2: 2 of three components of polytetramethylene glycol (molecular weight 850), isophorone diisocyanate, 2-hydroxyethyl acrylate).
BPE4A: Ethylene oxide 4 mol modified bisphenol A diacrylate, Daiichi Kogyo Seiyaku Co., Ltd. BPE-10: Ethylene oxide 10 mol modified bisphenol A diacrylate, Daiichi Kogyo Seiyaku Co., Ltd. DPGDA: Dipropylene glycol diacrylate TPGDA : Tripropylene glycol diacrylate HDDA: 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd.)
FA-512A: Dicyclopentadieneoxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)
PM-2: Ethylene oxide modified dimethacrylate phosphate (manufactured by Nippon Kayaku Co., Ltd.)
Irgacure ^RTM 184D: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals)
Esacure ^RTM ONE-Rifened: 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer (manufactured by Nippon Siebel Hegner)
LA-82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (hindered amine) (manufactured by Asahi Denka Co., Ltd.)
KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
EHTP: 3-ethyl-4-hydroxythiophenol (silver reflection film discoloration inhibitor)
Additive 1: 1- (Di- (2-ethylhexyl) aminomethyl) triazole (Ciba Specialty Chemicals Co., Ltd.) IRGAMET ^RTM 30
Additive 2: 1- (Di- (phenylmethyl) aminomethyl) triazole Additive 3: 1- (Di- (ethyl) aminomethyl) triazole

From the results shown in Table 1, the resin compositions for optical discs of Examples A1 to A3 containing the triazole derivative (A) used in the present invention have good electrical characteristics even in the light resistance and durability tests of Blu-ray Discs. was gotten. Comparative Example B1 which does not contain the compound represented by the formula (1) or (2) was poor in electric characteristics of light resistance or durability test.

Comparative Example B2 and Comparative Example B3
Additive 1 of Example A1 was replaced with 2-benzothiazoyl disulfide (additive 4) and 2- (4-morpholinyl-dithio) benzothiazole used in the resin composition as a metal antioxidant or rust inhibitor. A UV resin composition was prepared and a BD-ROM was prepared in the same manner as in Example A1, except that each of (Additive 5) was replaced.
A UV resin composition containing 0.1% by weight of 2-benzothiazoyl disulfide (Additive 4) and a BD-ROM obtained using the same were used as Comparative Example B2, and 2- (4-morpholinyl-dithio) benzo A UV resin composition containing 0.1% by weight of thiazole (Additive 5) and a BD-ROM obtained using the same are referred to as Comparative Example B3.
In the obtained BD-ROMs of Comparative Example B2 and Comparative Example B3, curing was performed in the same manner as in Example A1, but there were cured and uncured parts, and there was stickiness. It could not be used. Therefore, other evaluations were omitted.

Summary of Evaluation Optical disks having cured layers of the resin composition of the present invention containing the specific triazole derivative (Examples A1 to A3 of the present invention) include a conventionally known silver or silver alloy reflective film protective agent EHTP. Compared with the optical disk having the cured product layer of the resin composition (Comparative Example B1), the present invention is not different in the visual judgment of the silver reflecting film after the fluorescent lamp test (light resistance test), although both are not recognized. It can be seen that the optical disk of No. 1 is remarkably excellent in the reflectance (R8H) and RSER values after the fluorescent lamp test, and also excellent in the RSER value after the durability test. That is, in the optical disk of the present invention after the fluorescent lamp test, the decrease value of the reflectance (R8H) is as small as 2 to 5, and the RSER value is also very high from 9.4 × 10 ⁻⁵ to 1.5 × 10 ⁻⁴ . In contrast, in the comparative example, the decrease in reflectance (R8H) is as large as 15 and the value of RSER is as large as 6 × 10 ^{−3 in} the comparative example. Therefore, the optical disk of the present invention is remarkably superior in light resistance as compared with the optical disk of Comparative Example B1, and also excellent in wet heat durability.
Further, Comparative Example B2 or B3 containing additive 4 or 5 conventionally used as a metal antioxidant or rust prevention has a problem in the curability of the coating film (cover layer). In that respect, there was no problem.

The optical disk of the present invention and the resin composition of the present invention used therefor have excellent effects as described above, and a cured resin layer used directly on the reflective film of an optical disk having a silver or silver alloy reflective film. In particular, it is suitable for a light transmission layer of a Blu-ray disc and is very useful in industry.

Claims (22)

UV curing for optical discs having a reflective film made of silver or a silver alloy, containing a triazole derivative (A) represented by the following formula (1) or (2), a (meth) acrylate compound and a photopolymerization initiator (D) Mold resin composition,
Formula (1)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, and X represents a nitrogen atom or a sulfur atom)
Formula (2)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, and X represents a nitrogen atom or a sulfur atom.) The (meth) acrylate compound is a (meth) acrylate monomer (B) and a (meth) acrylate oligomer (C), and R ₂ and R ₃ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group. 2. The ultraviolet curable resin composition for optical disks according to claim 1, which is a substituted alkyl group having 1 to 10 carbon atoms or a phenyl group. X is a nitrogen atom, and R ₂ and R ₃ are an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl group having 6 to 10 carbon atoms having a branched chain. The ultraviolet curable resin composition for optical discs according to claim 2. The ultraviolet curable resin composition for an optical disk according to claim 3, wherein the triazole derivative (A) is a triazole derivative represented by the formula (3):
Formula (3)

(Wherein R ₂₁ and R ₃₁ are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl having a branched chain having 7 to 9 carbon atoms) Represents a group or a phenyl group.) The triazole derivative (A) is 1- (di- (2-ethylhexyl) aminomethyl) triazole, 1- (di- (phenylmethyl) aminomethyl) triazole or 1- (di- (ethyl) aminomethyl) triazole The ultraviolet curable resin composition for optical disks according to claim 4. The ultraviolet curable resin composition for optical disks according to claim 2, wherein the triazole derivative (A) is 1- (di- (2-ethylhexyl) aminomethyl) triazole. The ultraviolet curable resin composition for optical disks according to claim 2, comprising 0.001 to 5% by weight of the triazole derivative (A) based on the total amount of the composition. 3. The ultraviolet curable resin composition for optical disks according to claim 2, wherein the component (C) is one or both of epoxy (meth) acrylate (C-1) and urethane (meth) acrylate (C-2). The (meth) acrylate monomer (B) is dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, At least one selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide-modified bisphenol A type di (meth) acrylate The ultraviolet curable resin composition for optical discs according to claim 2. The triazole derivative (A) is a triazole derivative represented by the following formula (3),
Formula (3)

(Wherein R ₂₁ and R ₃₁ are each independently an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a phenyl group, or an alkyl having a branched chain having 7 to 9 carbon atoms) Group or phenyl group),
The (meth) acrylate monomer (B) is dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, At least one selected from the group consisting of phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide-modified bisphenol A type di (meth) acrylate Yes,
The ultraviolet curable resin composition for optical disks according to claim 2, wherein the component (C) is one or both of epoxy (meth) acrylate (C-1) and urethane (meth) acrylate (C-2). Furthermore, the ultraviolet curable resin composition for optical discs of Claim 2 containing phosphoric acid (meth) acrylate (E). As the photopolymerization initiator (D), at least oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone or [2-hydroxy-2-methyl-1- {4- The ultraviolet curable resin composition for an optical disk according to claim 2, comprising at least one of dimers of (1-methylvinyl) phenyl} propanone]. Further, it contains phosphoric acid (meth) acrylate (E), and at least oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone or photopolymerization initiator (D) or 11. The ultraviolet curable type for an optical disk according to claim 10, comprising at least one of dimers of [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone]. Resin composition. A cured product obtained by irradiating the ultraviolet curable resin composition for an optical disk according to claim 2 with active energy rays. An optical disc having a cured product layer of the ultraviolet curable resin composition for an optical disc according to claim 2, 10 or 13, on a reflective film made of silver or a silver alloy. An ultraviolet curable resin composition containing a triazole derivative (A) represented by the following formula (1) or (2), a (meth) acrylate compound and a photopolymerization initiator (D);
Formula (1)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms, a phenyl group, X represents a nitrogen atom or a sulfur atom),
Formula (2)

Wherein R _m is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkylene group having 1 to 3 carbon atoms, and R ₂ and R ₃ each independently have a hydrogen atom or a substituent. An aliphatic group having 1 to 20 carbon atoms or a phenyl group, and X represents a nitrogen atom or a sulfur atom). In Formula (1) or Formula (2), R _m is a hydrogen atom, X is a nitrogen atom, and R ₂ and R ₃ are each independently a carbon number substituted with an alkyl group having 1 to 3 carbon atoms or a phenyl group. The ultraviolet curable resin composition according to claim 16, which is an alkyl group having 1 to 3 alkyl groups or an alkyl group having 6 to 10 carbon atoms having a branched chain. 0.005 to 5% of the triazole derivative (A) represented by the formula (1) or (2), 75% to 99% of the (meth) acrylate compound, and light, based on the total amount (weight ratio) of the composition The ultraviolet curable resin composition according to claim 16, comprising 0.5 to 20% of a polymerization initiator (C). The (meth) acrylate compound is (i) (meth) acrylate monomer (B) and (ii) one or both of epoxy (meth) acrylate (C-1) and urethane (meth) acrylate (C-2) ( The ultraviolet curable resin composition according to any one of claims 16 to 18, which is C). The ultraviolet curable resin composition according to claim 19, wherein the ultraviolet curable resin composition is an ultraviolet curable resin composition for an optical disc having a reflective film made of silver or a silver alloy. A cured product of the ultraviolet curable resin composition according to claim 19. An optical disc having a reflective film made of silver or a silver alloy having a cured product layer of the ultraviolet curable resin composition according to claim 19.