JPS63210118A - Optical disc material - Google Patents

Abstract

PURPOSE:To make it possible to form an optical disc material high in a curing rate by ultraviolet and excellent in mold release, hot-water resistance, heat shock resistance, hardness, etc., by mixing a polycarbonate di(meth)acrylate and/or polyurethane di(meth)acrylate with a specified compound. CONSTITUTION:This optical disc material comprises a polycarbonate di(meth) acrylate (A) and/or polyurethane di(meth)acrylate (B), a compound (C) of formula I (wherein R1 is H or CH3, and R2 is CH3 or C2H5) and a photosensitizer (D) as an optional component. The mixing ratio among said components is preferably such that (A+B) is 5-40wt.%, (C) is 60-95wt.%, and (D) is 0-10wt.% based on the optical disc material (composition).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a base material that is cured by ultraviolet rays and is useful as a groove material for optical disk recording media that records and reproduces optical signals at high speed and high density. The present invention relates to a material for optical disks that has excellent adhesive properties, good mold peeling properties, hot water resistance, and hardness.

(Prior Art) Polycarbonate resin and methyl methacrylate resin are currently used as materials for consumer discs. Further, a material for the disk made of monomers such as 2,2-bis(A-(meth)acryloyloxyphenyl)propane and styrene has also been proposed. Industrial optical discs are
Due to quality requirements such as long-term reliability, disks are being developed using inorganic glass as a base material, and at the same time, groove materials for glass base materials are also being developed.

- (Problem to be solved by the invention) Since long-term reliability is required for industrial optical disks, the properties of the groove material include peeling resistance, hot water resistance, heat shock resistance, high hardness, and transparency. Excellent quality is required.

Conventionally, many compositions have been known as ultraviolet curable resin compositions, but the reality is that no composition has been found to date that fully satisfies the above characteristics. JP-A-59-71317 proposes a photocurable adhesive composition for optical disks using glass as a base material. This composition is mainly composed of mono(meth)acrylate having an OH group in the molecule, such as 2-ethyl-2-hydroxyethyl(meth)acrylate. It is unsuitable due to insufficient hot water resistance and hardness.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have conducted extensive research, and have found that hardening is rapid with ultraviolet rays, mold peelability, hot water resistance,
We have succeeded in providing an optical disk material with excellent heat shock resistance and hardness. That is, the present invention relates to polycarbonate di(meth)acrylate (5) or/and polyurethane di(meth)acrylate (B) and general formula (1).
) or C2H. ) Photosensitizer (
(to)). Polycarbonate di(meth) used in the present invention
The acrylate can be obtained by esterifying polycarbonate diol and (meth)acrylic acid. Polycarbonate diol can be produced, for example, as follows. i.e. carbonate derivatives, for example diaryl carbonates such as diphenyl carbonate, bis-chlorophenyl carbonate, dinaphthyl carbonate, phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate, 2-tolyl-4-tolyl-carbonate, dimethyl carbonate, diethyl carbonate; Dialkyl carbonates and diols, such as 1,6-hexanediol, neopentyl glycol, 1,4-butanediol,
1,8-octanediol, 1,6-bis-(hydroxymethyl)-cyclohexane, 2-methylpropanediol, dipropylene glycol, diethylene glycol or the above diol compounds and oxalic acid, malonic acid, succinic acid, adipic acid, azelain It can be obtained by transesterification with a polyester diol, which is a reaction product of an acid, a dicarboxylic acid such as hexahydrophthalic acid, or a reaction product of ε-caprolactone or β-methyl-δ-valerolactone. The polycarbonate diol thus obtained is a polycarbonate diol having two or more carbonate structures in the molecule, and can be easily obtained from the market. For example, Desmophen 2020E (manufactured by Bayer ■, average molecular weight 2000)
), DN-980 (manufactured by Nippon Polyurethane ■, average molecular weight 2000), DN-981 (manufactured by Nippon Polyurethane ■, average molecular weight 2000),
average molecular weight 1ooo), DN-982 (manufactured by Nippon Polyurethane ■, average molecular weight 2000), DN-983 (manufactured by Nippon Polyurethane ■, average molecular weight 1000), Plaxel C
D-210 (manufactured by Daicel Chemical Industries, Ltd., average molecular weight 100
0) etc.

The polyurethane di(meth)acrylate (B) used in the present invention includes polyols such as polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, ethylene glycol, propylene glycol, and 1,6-hexanediol. , neopentyl glycol, diethylene glycol,
Polyhydric alcohols such as dipropylene glycol, polyhydric alcohols and polybasic acids such as cono-phosphoric acid, adipic acid,
Polyester polyols obtained from azelaic acid, phthalic acid, hexahydrophthalic anhydride, reaction products of the polyhydric alcohol and ε-caprolactone, reaction products of the polyhydric alcohol, polybasic acid, and ε-caprolactone, and polycarbonate polyols such as A polycarbonate polyol obtained by the reaction of 1,6-6-hexanediol and diphenyl carbonate, and an organic polyisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4 ′-Diisocyanate etc. and hydroxy(
Obtained by reaction with meth)acrylate compounds.

Examples of hydroxy (meth)acrylate compounds include:
Hydroxyethyl (meth)acrylate, hydroxypropyl (methacrylate, ε-caprolactone-β
- Hydroxyel (meth)acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1, FM ~ 1.FA
-2 etc.). Among these polyurethane poly(meth)acrylates, particularly preferred polyols include polytetramethylene glycol, polycarbonate diol, and organic cyanate.
Examples of isophorone diisocyanate and hydroxy (meth)acrylate compounds include polyurethane diacrylates obtained using hydroxyethyl acrylate, hydroxyethyl acrylate, and the like.

Compound (C) represented by general formula CI) can be easily obtained from the market. For example, Nippon Kayaku ■KAYARAD R-604 is represented by the formula:

As the photosensitizer CDI, any known photosensitizer can be used, but one with good storage stability after blending is desirable. Examples of such photosensitizers include benzoin ethyl ether, penzoin butyl ether natonopensoin alkyl ether, acetophenone such as 2+2-jetoxyacetophenone, and 4'-phenoxy-2,2-dichloroacetophenone; Propiophenone series such as 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketone, and 2-ethylanthraquinone , anthraquinones such as 2-chloroanthraquinone, 2-chlorothioxanthone, 2.4-
Examples include thioxanthone photosensitizers such as dimethylthioxanthone. Particularly preferred are 1-
Examples include hydroxycyclohexylphenyl ketone. These photosensitizers can be used alone or in combination of two or more at any desired level.

In the present invention, either or both of the active ingredient and the active ingredient (B) are used, and the amount of the active ingredient (B) is preferably 5 to 40% by weight of the optical disc material (composition). Particularly preferably 10 to 30% by weight. (C)
The amount of the component is preferably 60-95% by weight, particularly preferably 70-90% by weight of the optical disc material (composition). (To) The amount of the component is the optical disk material (composition)
It is preferably 0 to 10% by weight, particularly preferably 1 to 5% by weight. The material for optical discs of the present invention includes
Alternatively, (B), (C), and (D) (optional ingredients) alone are sufficient to achieve the desired purpose, but in order to further improve performance, silane may be added without changing the original properties. Materials such as coupling agents, polymerization inhibitors, and leveling agents may also be added. As the silane coupling agent, r-methacryloxypropyltrimethoxysilane, γ
-(2-aminoethyl)aminopropyltrimethoxysilane, r-mercaptoglobiltrimethoxysilane, and the like. Examples of the polymerization inhibitor include methoquinone, methyl hydroquinone, and benzoquinone. or,
As a leveling agent, Modern Rho (manufactured by Monsando)
, Fluorad (manufactured by 3M), and the like. The amount of the silane coupling agent, polymerization inhibitor, and leveling agent used is preferably in the range of 0 to 3% by weight of the composition. Curing of the optical disc material of the present invention by irradiation with 1e-UV rays can be carried out by a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp, a xenon lamp, or the like.

The material for optical discs of the present invention can be used particularly as a groove material for optical discs using inorganic glass as a substrate (a resin composition for forming grooves on an inorganic glass substrate), and as a protective coating agent for recording films of optical discs. It is useful as Formation of grooves on a glass substrate using the optical disc material of the present invention is as follows:
Apply optical disc material (groove material) onto the stamper (mold) using a spin code method, etc., place a glass substrate/plate on the coated surface to prevent air from entering, and irradiate ultraviolet rays through the glass substrate. By curing the groove material and then releasing the stamper from the glass substrate, grooves are formed on the glass substrate. When applying the groove material on the stamper, it is preferable that the thickness thereof is usually about 10 to 100 microns.

A metal (e.g., Gd, Tb, Te, Ge1AllP
it Pb, Sb, 'ri, Ag+ Ss, T
An alloy of aO2, Fe, etc.) is deposited by a conventional method to form a recording film. Thereafter, an optical disc material (protective coating agent for optical discs) is preferably applied to a thickness of 1 to 5 μm on the snobbery vine film (recording film) by a spin-coding method, etc., and the protective coating agent is applied by irradiating ultraviolet rays. When cured, a protective film is formed.

In these methods, the optical disc material may be cured by electron beam irradiation instead of ultraviolet irradiation.

(Example) The present invention will be specifically explained below using examples. Note that parts in the examples are parts by weight.

Example 1 Polyurethane diacrylate (reacted with 2 moles of polytetramethylene glycol (molecular weight 1000) and 3 moles of inphorone diisocyanate, and then reacted with 2 moles of 2-hydroxyethyl acrylate) (B)
20 parts, Formula 0%) (080 parts, Irgacure 184 [manufactured by Chinoku/Geigy ■, photosensitizer] (1-hydroxycyclohexycyclohexylphenyl ketone) (D) 3 parts were mixed and exposed to ultraviolet light. A curable resin composition a (material for optical disc) was prepared.The test results are shown in Table 1.

Example 2 Polyurethane diacrylate [1 mole of polycarbonate diol (manufactured by Sumitomo Bayer ■, Deskami 2020E, molecular weight 2000) was reacted with 2 moles of isophorone diisocyanate, and then reacted with 2 moles of 2-hydroxyethyl acrylate] (E 10 parts, Example 1
KAYARAD R-604 (manufactured by Nippon Kayaku ■) used in
(C) and 3 parts of Irgacure 184 (D) were mixed to prepare an ultraviolet curable resin composition (material for optical disc). The test results are listed in Table ■.

Example 3 Polycarbonate diacrylate [Polycarbonate diol (manufactured by Nippon Polyurethane ■, DN-981,1,6
- Polycarbonate diol containing hexanediol as a diol component, molecular weight 100) obtained by esterification reaction of acrylic acid. ) (A) 30 parts, Example I
KAYARAD R-604 (manufactured by Nippon Kayaku ■) used in
(70 parts of C1' and 3 parts of Irgacure 184 (to) were mixed to prepare ultraviolet curable resin composition C, (material for optical disc). The test results are listed in Table 1.

Example 4゜Polycarbonate diacrylate [Polycarbonate diol (manufactured by Nippon Polyurethane ■, DN-980,1,6
- Polycarbonate diol containing hexanediol as a diol component, molecular weight 2000) obtained by esterification reaction of acrylic acid. ) (A) 10 parts, polyurethane diacrylate [polytetramethylene glycol (
(B) 10 parts,
KAYARADR-604 [manufactured by Nippon Kayaku ■] used in Example 1 (C) 80 parts, IRGAKIA-184 (D)
Three parts were mixed to prepare ultraviolet curable resin composition d (material for optical disc).

The test results are listed in Table I.

Comparative Example 1 70 parts of 1-ethyl-2-hydroxyethyl acrylate, 2,2-bis(A-acryloylpolyoxyethyleneoxyphenyl)prono(Nippon Kayaku ■, KAYA
RAD, R-551) 30 copies, Irgacure 18
4.3 parts were mixed to prepare an ultraviolet curable resin composition e. The test results are listed in Table I.

Test method I type peeling: Apply isopropyl alcohol containing 1% by weight of α-methacryloxypropyltrimethoxysilane to a clean soda glass plate, heat at 100°C for 30 minutes,
The silane was subjected to baking treatment. Each prepared resin composition (arb, c, d, li) was applied onto a stamper (mold, nickel plate), a silane-treated glass plate was placed on the applied surface to prevent air bubbles, and a high-pressure mercury lamp (Toshiba Company-made, 2KW)
The composition was cured by irradiating it from the glass surface.

Then, separate the stamper and glass plate.

The stamper and glass plate are easily separated.
・・It takes a lot of strength from the priest to separate the stamper and the glass plate・
・・・・・・△When the stamper and the glass plate are separated, the glass breaks ・・・・・・・・・×Hot water resistance: The glass substrate with the grooves created in the mold peeling test was heated to 100°C. Test the hot water resistance by soaking it in water for 1 hour.

There was nothing wrong with the board...
・・・・・・○The resin layer forming the grooves is slightly whitened...
・・・・・・・・・・・・・△〃 Partially peels off・・・・・・・・・× Heat shock resistance: The glass substrate with grooves prepared in the mold peeling test was Soak in liquid nitrogen for 5 minutes.

There was no abnormality at all on the board...
・・・・○ Slight cracks occur in the resin layer forming the grooves ・・・・・・・・・・ Cracks occur in △〃 Some parts peel off ・・・・・・× Hardness (ShoreD): Applicable The composition was applied to a thickness of 2 mm on a nickel plate and cured in N2 gas with a high-pressure mercury lamp.
The hardness of this was determined to be constant at 17 using a 5hore D hardness meter.

(Effects of the Invention) The material for optical disks of the present invention has good mold peelability of the cured product obtained by curing, excellent hot water resistance and heat shock resistance, high hardness, and excellent transparency. It is particularly useful as a material for optical discs such as a groove material for optical discs or a protective coating agent for optical discs.

Claims (1)

[Claims] Polycarbonate di(meth)acrylate (A) or/
and polyurethane di(meth)acrylate (B) and the compound (C) of the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, R_1 is H or CH_3, and R_2 is C
H_3 or C_2H_5. ) A material for an optical disc, characterized in that it contains a photosensitizer (D) as an optional component.