JPS62129957A - Optical infomration recording medium - Google Patents

Abstract

PURPOSE:To shorten the time for using fixing jigs during curing, to prevent the deformation by sealing and to avert the adverse influence of an adhesive agent bleeding part by sticking substrates by using an adhesive agent contg. an epoxy resin and cation polymn. type photopolymn. initiator. CONSTITUTION:The substrates 1, 1 on one side of which recording layers 3 are formed are disposed via an inside spacer 4 and an outside spacer 5 to position the layers 3 on the inside. The substrates 1, 1 are then stuck by using the adhesive agent 7 via the spacers 4, 5 to form a space 6 therebetween, by which an information recording medium 8 is constituted. The epoxy resin and cation polymn. type photopolymn. initiator are incorporated into the adhesive agent 7. The long-term use of the jig for fixing the members during curing of the adhesive agent 7 is thus eliminated, by which the deformation of the substrates 1, 1 by sealing is prevented. The adverse influence of the uncuring of the adhesive agent 7 bleeding part on the recording material is thereby prevented.

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 producing an optical information recording medium by sealing two disc-shaped substrates using a spacer, an adhesive method using an epoxy adhesive was adopted as a method of bonding the substrate and spacer together. It has been. Conventional epoxy adhesives can be said to be excellent adhesives in that they do not have adverse effects such as lowering the reflectance of the recording material of the disk or lowering the S/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 protruding from the adhesive, and may reduce the S/N ratio.
New problems such as lowering the 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. 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 is achieved by photocuring the epoxy resin using a υ cationic polymerization type photoinitiator, which is different from the conventional method of curing the epoxy resin by thermal polymerization. here"
"Light" means electromagnetic waves such as X-rays, ultraviolet rays, visible light, and infrared rays.

That is, according to the present invention, a pair of disk-shaped substrates each having a recording layer on at least one side are placed facing each other with the core recording layer on the inside, and an adhesive is applied with or without a space therebetween. An optical information recording medium is provided which has a sealing structure in which the adhesive is bonded together and further includes the adhesive at least an epoxy resin and a cationic polymerizable photoinitiator.

The epoxy resin used as the main component of the sealing adhesive in the present invention is a compound having two or more epoxy groups in one molecule, and can be broadly classified into the following types.

(C) Alicyclic epoxy Cd) Long chain aliphatic type -CH-0-CH2-CH-CH2 (e) Brominated epoxy resin Resin made from brominated bisphenol A (f) Glycidyl ester type (g) Complex Cyclic systems include the hydantoin and 'I'GIC systems.

Hydantoin type CH2-CH-CH2 ■ TGIC type A5/L as a representative example of the epoxy resin in the present invention
/ Daito AY 101, AZ102, Ayt03,
AYlas, AW106, AV121N, A
V121B, input V123B % input v12
9, AW134, AW136H, AW136N, AW
1201, AV138, AYIol, AY103,
ATl, AZ15; GY250.6099; E
C'N1280: CY175, C'Y2O3:80
11: CY192: C150, CY362 (
That's all CIBA-GEIGY! ! ) ; LIXON BOND IQO2A, LIXON B
OND 1004A (made by Chisso); Daynacol EX-810, 811, 851, 850,
862,841,861,911,941,920,9
21,961,211, 212.221.721; f
'Ina: I-/L/EX-313, 314, 321,
421, 512, 521 (Nagase Kasei Kogyo), etc. Note that the above epoxy resins may be used alone or in combination.

Further, examples of the cationic polymerization type photoinitiator to be included in the epoxy resin of the present invention include diazonium salts and onium compounds. A typical example of diazonium salt is 2+
5-'j Butoxy 4-morpholinobenzenediazonium tetrachloroborate, 2,5-jethoxy-4-
(4-ethoxyphenyl)benzenediazonium tetrafluoroborate, 1-chloro-5-methoxy-4-N,
N-dibenzylaminobenzenediazonium tetrafluoroborate% 2+5-9methoxy-4-N, N'methylbenzoylobenzenediazonium tetrafluoroborate, and the like.

Further, examples of onium compounds include sulfonium salts and derivatives thereof, iodonium salts and derivatives thereof, and the like represented by the following structural formulas.

16 Sulfonium salt 1-1 triarylsulfonium salt H3 In the above structural formula, A is A31F6% 5bF6'', p
Indicates p, 5″ or BFX salt.

1-2 dialkylphenacylsulfonium salt 0"...)
○＠↓・O2-108F-1-3',; Alkyl-4
-Hydroxyphenylsulfonium salt 2 Diaryliodonium salt (I56) Bunkosha ○H (Engineering 57) o-I'@-◎ O2 Here, all salts contain As F6%sbF;, pF; or BFi.

These photopolymerization initiators are used in a range of 0.1 to 20 parts by weight per 100 parts by weight of the epoxy resin, but the preferred range is CL2 to 5 layered lid, and the weighted portion is the above-mentioned cationic polymerization type photoinitiator. Most of them have absorption wavelengths in the ultraviolet region, and many cannot effectively utilize wavelengths in the near-ultraviolet and visible regions emitted by high-pressure mercury lamps and the like.

Therefore, in order to effectively utilize wavelengths in the near-ultraviolet and visible regions,
It is preferable that the adhesive used in the present invention contains a photosensitizer.

Examples of photosensitizers include anthracene, perylene, phenothiazine, 1,2-benzanthracene, coronene, pyrene, tetracene, benzyl dimethyl ketal, and carbonyl compounds containing hydrogen donors such as benzophenone, acetophenone, and thioxanthone.

These photosensitizers are used at the wavelength that is most desired among the wavelengths emitted by the light source, for example, 366 nm when using a high-pressure mercury lamp.
The amount should be such that the sensitizer is well absorbed by the m-wavelength and can reach deep into the adhesive.

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

The disk-shaped substrates 1, 1 are made of, for example, a transparent plastic plate, and have a fitting hole 2 in the center thereof, and a recording layer 3 is formed on at least one surface of these substrates 1, 1. The inner spacer 4 and the outer spacer 5, in which these substrates 1 and 1 are arranged concentrically, are connected to the recording layer 3 through the spacer 5.
The information recording medium 8 is constructed by arranging the substrates 1 and 1 on the inside and pasting them together using an adhesive 7 via a spacer so that a space 6 is formed between the substrates 1 and 1. It has become. As the recording layer 6, any material known as a recording material for recording media can be used without being limited to a specific material, and typical examples thereof include T+3. Thin films of metals such as At, thin films of organic dyes such as polymethine dyes (eg, cyanine dyes, merocyanine dyes), etc. In addition to the above configuration example, although not shown, the recording layer 6 may be formed on both sides of the substrate 1.

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

Example 1 Jetoxyphenylfuropane 10 1 Tetrahydrofurfuryl acrylate 10 1 Benzoin isobutyl ether 21 Isopropyl alcohol 50 l Toluene
10 A mixture of 1 or more was mixed with stirring, applied by dipping onto two polymethyl methacrylate disks with a diameter of 200 mm and a thickness of 1.2 M, dried for 15 minutes, and then irradiated with ultraviolet rays from a high-pressure mercury lamp of 2 KW for 15 seconds from a distance of 20 crlL. did. Separately, add 3 parts by weight of benzoin isobutyl ether to N1
After applying the drops to the stamper, stack the plates obtained earlier and press them against each other, and apply ultraviolet rays from a high-pressure mercury lamp 2xw from a distance of 20α for 30 minutes.
Irradiated for seconds. By peeling it off, the Stannozo mold was clearly transferred to the acrylic plate. 0.7% by weight of cyanine dye NK125 (Japanese photosensitive dye M) was applied to the side of each of the above two acrylic plates to which the Stan J mold was transferred.
, 2'-dichloroethane solution was prepared, and a solution to which PAi[l[16 (manufactured by Mitsui Toatsu Fine Co., Ltd.]) was added at a weight ratio of 15% to the dye was applied and dried to form a recording layer with a thickness of 6aaX. After the surface treatment, the following surface treatment was performed: ultrasonic cleaning using tetrahydro7 run solvent for about 40 seconds, then ultrasonic cleaning with inpropyl alcohol for semiconductors, and drying with a thickness of 1M.
The inner and outer circumferences of the polymethyl methacrylate fissures were bonded and sealed with an adhesive as shown in the figure, via sabers. The adhesive used is Rixon Bond 1004A [f
[manufactured by ll chitsun] 1 ooit part to triphenylsulfonium hexafluoroantimonate 2.

Anthracene α2I was used. A high-pressure mercury lamp (Ushio Inc. U) was used as the ultraviolet light source.
VL-200o-os), irradiation distance 10CJr
It was cured under the irradiation conditions of L% irradiation time of 60 seconds.

Comparing the soil disc 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 was Regarding the S/N ratio, there was almost no difference between the sample and the sample sealed using thermally polymerized Rekunn Bond 1004A/B (manufactured by Chitsun).

In addition, regarding adhesive strength, thermal polymerization type Rixon Bond 10
It was approximately 1.5 times larger than that of 04A/B, and further increased to 2 and 2.5 times as the days passed, and the durability of the adhesive force under high temperature and high humidity conditions was also increased. .

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.

Example 2 In the above Example 1, an adhesive having a composition of 100]j parts of hexanecarboxylate, 11 parts of diphenyliodonium fluoroarsenate, 0.11 parts of phenothiazine was used as the adhesive, and NK2883 (Nippon Kanko Shokuryo) was used as the dye. A sealing disk was prepared in exactly the same manner as in Example 1.

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 /N ratio: thermal polymerization type Rixon Bond 1004A/B (made by Chitsun)
There was almost no difference observed between the sample and the sample sealed using .

In addition, regarding adhesive strength, thermal polymerization type Rekunnbond 10
The adhesive strength increased by about 1.5 times compared to that of 04A/8, and further increased to more than double as the days passed, and the durability of the adhesive force under high temperature and high humidity conditions was also increased.

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.

Example 3 Sealing was carried out in exactly the same manner as in Example 1, except that in Example 1, an adhesive having a composition of Boxylate 100 weight 1 part hexafluoroarsenate dimethyl 7-enacylsulfonium 1.51 Coronene 0.157 was used. A stopping disc was made.

Comparing the sealing disk produced in this way with a sample sealed using a conventional ultraviolet curable adhesive, first of all, there is no bleeding into the dye due to the uncured parts that protrude when the adhesive is applied, and therefore the reflectance and S/ Regarding the N ratio, use thermal polymerization type RIXON BOND 1004A/B [Made by Chitsun]
There was almost no difference observed between the sample and the sample sealed using .

In addition, regarding adhesive strength, thermal polymerization type Rixon Bond 10
The adhesive force increased by about 1.5 times compared to 04A/B, and further increased to 2.2 times as the days passed, and the durability of the adhesive force under high temperature and high humidity conditions was also increased.

In this way, Rekun'n Bond 1 has no adverse effect on recording materials.
004A could be cured by photopolymerization, and the productivity in the adhesive sealing process was significantly improved.

Example 4 In the above Example 2, Rixon Bond 1002A (manufactured by Chisso) 100 was used as the adhesive.
! A sealing disk was prepared in exactly the same manner as in Example 2 except that a composition consisting of dimethyl-4-hydroxynaphthylsulfonium tetrafluoroborate 4I was used.

Comparing the soil disc prepared in this way with a sample sealed using a conventional ultraviolet curable adhesive, first of all, there is no bleeding into the dye due to the uncured parts that protrude when the adhesive is applied, and therefore the reflectance is For the S/N ratio, thermal polymerization type Rixon Bond 1004A/B [Made by Chisso]
There was almost no difference observed between the sample and the sample sealed using .

In addition, regarding adhesive strength, thermal polymerization type Rekunnbond 10
It was approximately 1.5 times larger than that of 04A/B, and further increased to 2 and 2.5 times as the days passed, and the durability of the adhesive force under high temperature and high humidity conditions was also increased. .

In this way, Rekun'n Bond 1 has no adverse effect on recording materials.
004A could be cured by gold photopolymerization, and the productivity in the adhesive sealing process was significantly improved.

Example 5 A sealing disk was produced in exactly the same manner as in Example 1 except that 100 parts by weight of Araldye AYlol (manufactured by Ciba Geigy) was used as the adhesive.

Comparing the sealing disk produced 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 there was no reflection. In terms of rate and S/N ratio, there was almost no difference between the sample and the sample sealed using thermally polymerized RIXON BOND 1004A/B (manufactured by Chitsun).

In addition, regarding adhesive strength, thermal polymerization type Rixon Bond 10
The adhesive strength increased by about 1.5 times compared to that of 04A/B, and further increased by more than 1.8 times as the days passed, and the durability of the adhesive force under high temperature and high humidity conditions was also increased.

In this way, Rixon Bond I has no adverse effect on recording materials.
D04A could be cured by photopolymerization, and the productivity in the adhesive sealing process was significantly improved.

〔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, which is different from 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... Sickle layer, 4...
... Inner space is -S, 5... Outer space is -S, 6... Space, 7... Adhesive, 8... Information recording medium. Patent applicant Rico Co., Ltd. - 2 others

Claims (1)

[Claims] A sealing structure in which a pair of two disk-shaped substrates, at least one of which has a recording layer, are placed facing each other with the recording layer on the inside and bonded together with an adhesive with or without a space in between. An optical information recording medium, further comprising: an epoxy resin and a cationic polymerizable photoinitiator.