JPS62259245A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To avert the long-period use of member-fixing jigs in the stage of thermal curing and cold curing and to prevent the deformation of a substrate by sealing by incorporating an epoxy resin, photodecomposable org. silicon compd. and composite catalyst consisting of a metallic complex into an adhesive agent for sealing. CONSTITUTION:This medium has a fitting hole 2 in the central part of a disk- shaped substrate 1 and is formed with a recording layer 3 to one face of the transparent substrates 1. The substrate 1 are so disposed by a concentrically disposed inside spacer 4 and outside spacer 5 that the recording disposed inside space 4 and outside spacer 5 that the recording layers 3 are positioned to the inside. The substrates 1 are stuck to each other by using an adhesive agent 7 via the spacers so as to form a space 6 between the substrates, by which the information recording medium 8 is constituted. The photodecomposable org. silicon compd. and the composite catalyst consisting of the metallic complex and used as a photopolymn. initiator for the epoxy resin in the adhesive agent 7. The silicon compd. is decomposed by UV rays to form silanol. An epoxy compd. is started by the effect of the silanol and the metallic complex.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a sealed disc-shaped information recording medium in which a recording layer is provided on the surface of a disc-shaped substrate and information is recorded and reproduced optically.

[Prior art]

Conventionally, when manufacturing an optical information recording medium by sealing two disc-shaped substrates using a strip, adhesive using an epoxy adhesive was used as a method for bonding the substrate and the strip. measures have been adopted. Conventional epoxy adhesives reduced the reflectance of the disc recording material! It can be said to be an excellent adhesive in that it does not have any negative effects such as lowering the +8/N ratio. However, since the epoxy adhesive is heat-curable, the substrate may be deformed when heated, and it takes a long time to harden, resulting in poor productivity as it requires a jig to fix the parts during that time. . Therefore, in order to avoid these drawbacks, ultraviolet curable resins containing radical polymerization type photoinitiators have been newly used as sealing adhesives. Although the ultraviolet curable resin does not have the above-mentioned drawbacks of epoxy adhesives, it may reduce the reflectance of the recording member of the disk due to uncured portions of the sealing adhesive that protrude, or cause S/S/
New problems such as lowering the N ratio have arisen.

〔the purpose〕

The present invention has been made in view of the above problems, and its objectives are to avoid long-term use of component fixing jigs during heat curing and room temperature curing (improve productivity), and to prevent deformation of substrates due to sealing. It's about prevention. Another object of the present invention is to provide a sealed optical information recording medium in which the recording material is not adversely affected by uncured protruding portions of the sealing adhesive.

〔composition〕

The above object can be achieved by using an adhesive containing an epoxy resin, a photodegradable organosilicon compound, and a metal complex composite catalyst as a sealing adhesive in an optical information recording medium.

That is, according to the present invention, a pair of substrates having a recording layer on one side of at least one of two disc-shaped substrates are placed facing each other with the recording layer on the inside, and are bonded with or without a space between them. An optical information recording medium is provided which has a sealing structure bonded by an adhesive, and further includes an epoxy resin, a photodegradable organosilicon compound, and a metal complex composite catalyst.

The "epoxy resin" in the present invention refers to a compound having two or more epoxy groups in one molecule, and can be broadly classified as follows.

(a) Bisphenol A-epichlorohydrin type (abbreviated as shrimp bisuya) (n = 0 to 16) (1)) Novolac type ^ (C) Compound that is an epoxy compound with an alicyclic structure (d) Long chain Aliphatic type (e) Brominated epoxy resin Resin made from brominated bisphenol A (f) Glycidyl ester (g) Heterocyclic type This includes hydantoin type and TGIC type Hydantoin type Representative of the above epoxy resins Examples selected from commercially available products are as follows.

Araldite AY101, AZ102, AY103, A
Y105, AW106, AV121N%AV121B,
AV123B%AV129, AW134, AW156
)1. AV136N, AW1201, AV138, A
Ylol, AY105, ATl, AZ15 :GY2
50.260.6071.6099: ECN128
0; CY2O3,8011,192,350,36
2 (manufactured by Ciba Gaiki Co., Ltd.); Rekunn Bond 1001A, 1002A, 1004A
(The above is ■Tetsunura); Dana: L-LE EX-810, 811, 851, 830
,832,841.861.911.941.920.
921.931.211.212, 221.721: Dayna Call EX-313, 314, 321, 411, 4
21,512,521,611,612,614,61
4B, 622 (above, ■manufactured by Nagase Sangyo): Epicote 152.828.1001 (above, ■manufactured by Shell):
ERL 4221 (manufactured by Union Carbide).

The above epoxy resins may be used alone or in combination of two or more.

In particular, examples of epoxy compounds having an alicyclic structure include:
Celloxide 2021.2000.3000, EHPE
-slso-1 (manufactured by Daicel Chemical Industries, Ltd.); ER
L 4206.4289.4299.4254 (Union Carbide #): Araldite CY 1
77.179 (manufactured by Teva Gaiki Co., Ltd.), vinylcyclohexene epoxide, vinylcyclohexene epoxide, and the like.

In addition, when performing sealing adhesive work using these epoxy compounds having an alicyclic structure, if the viscosity is too low, it will flow by itself and the workability will be poor, so the viscosity of this compound should be at least 300 mPa8 ( 25°C) or higher, preferably 500 mPa5 (25°C) or higher. In addition, in sealing and adhering optical information recording media, vapor generated from the adhesive used must not have a negative effect on the recording layer, so the boiling point of an epoxy compound having an alicyclic structure is at least 101 KPa (-760 mmH).
g) Examples of particularly preferable compounds from these points of view are listed below.

Celloxide 2021 ERL 4289 El, 4299 In addition, the above epoxy compounds having an alicyclic structure may be used alone or in a mixture of 28 or more, or epoxy compounds having no alicyclic structure (e.g. Epicote 828
It may also be used in combination with an Epibis type epoxy resin such as that manufactured by Ciel Corporation.

The photodegradable organosilicon compound and metal complex composite catalyst of the present invention is used as a photopolymerization initiator for epoxy resins. Photodegradable organosilicon compounds are stable in the dark, but quickly decompose when exposed to ultraviolet light, producing silanols. Next, polymerization of the epoxy compound starts due to the action of this silanol and the metal complex.

As the photodegradable organosilicon compound, for example, silyl oxide, 0-nitropenzylsilyl ether, alkoxysilane, silyl ketone, etc. can be used.

Examples of silyl peroxides include (h)) (2-naphthyl) silyl-1-butyl peroxide, (12) U phenyl (1-naphthyl) silyl-1-butyl peroxide, (15) ) (4- chlorophenyl)silyl-
Butyl peroxide, (14) diphenyl-2-methylphenylsilyl-
1-Butyl ruoxide, (+5) di(1-naphthyl)silyl di(t-butyl is ruoxide, (16) ), 9 phenylsilyl-1-butyl peroxide, (17) diphenylsilane di(t,-butyl peroxide, and so on.

Examples of 0-nitropenlylsilyl ethers include (Is) (0-nitrobenzyloxy)triphenylsilane, (+9) bis(0-nitrobenzyloxy)diphenylsilane, (110) tris(4-chlorophenyl)- (0-
nitrobenzyloxy)silane, etc.

Examples of alkoxysilanes include (111) diphenyldimethoxysilane, (112
) Diphenyljethoxysilane, (115) Diphenyldiisopropoxinrane, (114) Diphenyldiacetoxysilane, (115) U-phenyldiphenoxysilane, (114) )! j phenylmethoxysilane, (117) triphenylethoxysilane, (11B) diphenylvinylethoxysilane, (119) ) 9 phenylhydroxysilane.

and so on.

Examples of silyl ketones include (12G)) liphenylsilylphenyl ketone.

Furthermore, examples of metal complexes include the following compounds.

(01)) Tris(β-diketonato)aluminums such as (C2) tris(ethylacetoacetonato)aluminum; (C5)) tris(ethoxyacetylacetonato)aluminum such as tris(ethoxyacetylacetonato)aluminum; (β-ketoesterato)aluminums; (C4) Tris(ortho-carbonylphenolado)aluminums of tris(salicylaldehydato)aluminato: (05)) Aluminum with N, O-chelates such as tris(oxynato)aluminum Complex: (Cs)
) Lis(acetylacetonato)chromium (07)
) Lis(acetylacetonato) cobalt (CB)
) Squirrel (acetylacetonato)iron (C9) ) Squirrel (
acetylacetonato) rhodium (C10) bis(acetylacetonato)zinc (C11) bis(acetylacetonato)copper (012) bis(acetylacetonato)nickel (C1s) tetra(acetylacetonato)zirconium (014) bis( acetylacetonato)tin chloride (C1s) bis(acetylacetonato)molybdenum oxide.

The ratio of the epoxy resin, photodegradable organosilicon compound, and metal complex composite catalyst contained in the sealing adhesive in the present invention is α1 to 100 parts by weight of the photodegradable organosilicon compound to 100 parts by weight of the epoxy resin. 20 parts by weight preferably 0
．． 5 to 10 heavy coverings, and metal complex composite catalyst has 0.0
The amount is 5 to 10 parts by weight, preferably 01 to 5 parts by weight.

Note that a photosensitizer such as benzophenone, amine, benzoin ether, etc. can be added to the photodegradable organosilicon compound and metal complex composite catalyst in the present invention to increase the photodecomposition of the organosilicon compound, Furthermore, the activity of the composite catalyst can be increased by adding zeolite, porous silica, titanium oxide, etc.

Next, the structure of the encapsulated information recording medium of the present invention will be explained based on the drawings.

The disk-shaped substrate 1.1 is made of a transparent plastic plate, for example, and has a fitting hole 2 in its center, and a recording layer 3 is formed on at least one side of the substrate 1.1. The recording layer 3 is arranged inside these substrates 1.1 through an inner spacer 4 and an outer spacer 5 which are arranged concentrically, and the spacers are arranged so that a space 6 is formed between each substrate 1.1. An information recording medium 8 is constructed by pasting them together using an adhesive 7. Note that when the adhesive is cured by light, a certain temperature is required, so it is necessary to take measures to prevent the heat generated in the adhesive portion by light irradiation during photocuring from escaping by conduction. For the recording layer 5, any material known as a recording material for recording media can be used without being limited to a specific material. There are thin films of organic dyes such as merocyanine dyes and merocyanine dyes. In addition to the above configuration example, although not shown, the recording layer 3 can also be formed on both sides of the substrate 1.1.

〔Example〕

Next, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Tetrahydrofurfuryl acrylate 10 I
Benzoin isobutyl ether 2I isopropyl alcohol 50 I toluene
A mixture of 101 or more was stirred and mixed, and the diameter was 200 m and the thickness was t.
It was applied by dipping onto two polymethyl methacrylate disks (No. 2), dried for 15 minutes, and then irradiated with ultraviolet rays from a high-pressure mercury lamp (2FF) for 15 seconds from a distance of 20 (:II).Separately, benzoin isobutyl ether 3I was dropped onto a stamper (N1). After that, the plates obtained earlier were stacked and pressed together and irradiated with ultraviolet rays from a 2KW high-pressure mercury lamp for 30 seconds from a distance of 201 cm.By peeling off, the stamper mold was clearly transferred to the acrylic plate. Cyanine dye NK125 (Japanese photosensitive dye 3! α7 weight - 2,
Prepare a 2'-dichloroethane solution, and add PA-1006 (manufactured by Mitsui Toatsu Fine) to it at a weight ratio of 15% to the dye.
A recording layer with a thickness of 600X was formed by coating and drying a solution containing the following: The following surface treatment was carried out using ultrasonic cleaning using tetrahydrofuran solvent for about 40 seconds, and then ultrasonic cleaning was performed using isopropyl alcohol for semiconductors. As shown in the figure, they were bonded together and sealed with an adhesive through inner and outer spacers made of polymethyl methacrylate having a thickness of 1 mm, which had been surface-treated by Freon drying. As the adhesive, one having the structure shown in -F was used.

Rixon Bond 1001A @ 100 parts by weight (epoxy resin) Silicon compound) Tris(acetylacetonato)alpha5I minium (metal complex composite catalyst) As the ultraviolet light source, a high-pressure mercury lamp (UVL- manufactured by Ushio Inc.)
2000-08), irradiation distance 10α, irradiation time 6
It was cured under irradiation conditions of 0 seconds.

Comparing the sealing disk prepared in this way with a sample sealed using a conventional ultraviolet curable adhesive, it was found that there was no bleeding into the dye due to the uncured parts that protruded when the adhesive was applied, and therefore the reflectance and S Regarding the C ratio, almost no difference was observed compared to the sample sealed using thermal polymerization type RIXON BOND 1004A/13 (manufactured by Chitsun).

In this way, RIXON BOND 1004A, which has no adverse effect on the recording material, could be cured by photopolymerization, and the productivity in the adhesive sealing process was significantly improved.

Examples 2 to 5 Optical information recording media were produced in exactly the same manner as in Example 1, except that the adhesive having the composition shown in the table below was used, and the same results as in Example 1 were obtained. Ta.

Example 6 Two recording media produced in the same manner as in Example 1 were bonded together and sealed using an adhesive having the following composition.

Cero Nakaside 2021 100 parts by weight silicon compound) The ultraviolet light source is a high-pressure mercury lamp (Ushio Inc. Ura tJVL)
-2000-08L was used for curing under irradiation conditions of irradiation distance of 101 and irradiation time of 60 seconds.

Comparing the sealing disk produced in this way with a sample sealed using a conventional ultraviolet curable adhesive, it was found that even the protruding areas during application were completely cured, and there was no bleeding into the dye, so the reflectance was 8/8. Regarding the N ratio, almost no difference was observed compared to the sample sealed using thermally polymerized Rixon Bond 10041VT3 (manufactured by Chisso).

Example 7 Polycarbonate substrate 2 with a diameter of 2001 mm and a thickness of 1 mm
cyanine dye NK 2421 on each substrate.
(Nippon Kanko Shiki) 2.0 parts by weight of 1.2-dichloroethane containing 1% by weight, 78 parts by weight of methanol, 3 parts by weight of isopropyl alcohol, and 0.5 parts by weight of n-butanol.
A solution consisting of parts by weight was prepared, and HC099 (Hodogaya Chemical H) α15 amount was added to this solution, applied as a bath liquid, dried, and a thickness of 600X was recorded! - was formed to produce each recording medium. The two recording media were pasted and sealed with an adhesive as shown in the figure with a spacer having a thickness of 111 m interposed therebetween. ERL 4299 using adhesive with the following composition
80 heavy ffi part epicoat 8
28 20 parts by weight (0-nitrobenzyloxy) tri 51 phenylsilantris (salicylaldehydade)
UVL-2000-O8), irradiation distance 105! ,
It was cured with an irradiation time of 120 seconds. Comparing the sealing disk prepared in this way with a sample sealed using a conventional UV-curable adhesive, it was found that even the protruding areas when the adhesive was applied were completely cured, and there was no bleeding into the dye. Therefore, in terms of reflectance and SA ratio, almost no difference was observed between the two samples compared to the sample sealed using thermally polymerized Rixon Bond 10041v'B (manufactured by Chisso).

〔effect〕

According to the present invention, the influence of the sealing adhesive on the recording material is significantly reduced, and since the adhesive is cured by photopolymerization, unlike thermal polymerization, productivity is significantly improved. As a result, deformation of the substrate during sealing can be prevented, and an increase in adhesive force and durability of the adhesive force in a high temperature and humid environment can be achieved.

[Brief explanation of drawings]

The figure is a sectional view showing an example of an encapsulated information recording medium according to the present invention. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Fitting hole, 3... Recording layer, 4...
... Inner spacer, 5... Outer spacer, 6... Space, 7... Adhesive, 8... Information recording medium. Patent applicant Rico Co., Ltd. - 2 others

Claims (1)

[Claims] A seal in which a pair of substrates having a recording layer on one side of at least one of two disc-shaped substrates are placed facing each other with the recording layer on the inside and bonded together with an adhesive with or without a space between them. 1. An optical information recording medium, wherein the adhesive further contains an epoxy resin, a photodegradable organosilicon compound, and a metal complex composite catalyst.