JPS63288784A - Substrate for optical recording and production thereof - Google Patents

Abstract

PURPOSE:To obtain a substrate for optical recording which comprises a resin base and has excellent solvent resistance and flexibility, by laminating the resin base with a film formed from a polymer and an organosilicon compound. CONSTITUTION:A resin base is laminated with a film formed from a polymer and an organosilicon compound. The polymer is preferably a polymer having a hydrogen-bondable functional group, and may be polyvinyl alcohol, polyvinyl pyridine or the like. The organosilicon compound is preferably a compound of the formula R<1>R<2>aSi(OR<3>)3-a and/or a hydrolyzate thereof. The organosilicon compound is used in an amount of 0.5-500 pts.wt. per 100 pts.wt. of the polymer. The film, comprising the polymer in addition to the organosilicon compound, has sufficient flexibility, and is hardly cracked by rapid temperature changes or shocks. A solvent to be used may be any one that does not attack the resin base, for example, an alcohol or water.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optical recording substrate that can be recorded and read by laser light, and a method for manufacturing the same.

[Prior Art] In recent years, optical recording media that use organic compounds for recording, whose recording layer can be formed by coating, have been actively investigated.

However, when conventional organic compounds are formed as a coating on a resin substrate, the resin substrate surface is attacked by the coating solvent, and the groups (guide grooves) necessary for focus servo and tracking servo disappear. There was fear.

Therefore, there have been proposals to solve the above problems by providing various coatings between the substrate and the recording layer.

For example, a proposal to use silicon oxide as a coating (Japanese Unexamined Patent Publication No. 6)
0-204395), a proposal using a coating film of a colloidal particle dispersion of a silicon condensate (JP-A-61-11294)
JP-A-61-35288, JP-A-61-573, proposals using heat-treated layers of organoalkoxysilane, organoalkoxysilane, and organosilicon.
Publication No. 89).

[Problems to be Solved by the Invention] However, the proposal in JP-A No. 60-204395 involves the problem that the film is usually formed by vapor deposition or sputtering, and the film thickness is thin and non-uniform, and the productivity is also poor. It had a point.

Furthermore, the proposal of JP-A-61-11294 had a problem in that the coating solvent penetrated between the colloid particles and soaked the substrate.

Also, JP-A-61-35288, JP-A-61-5
The proposal in Publication No. 7389 requires a considerably high temperature for heat treatment, making it difficult to apply to resin substrates, and has the drawback that the silicone layer formed after heat treatment has very poor flexibility and easily cracks. had.

The present invention aims to eliminate the drawbacks of the prior art, and aims to provide a resin-based optical recording substrate that has excellent solvent resistance and flexibility, and a method for manufacturing the same. .

Means for Solving Problem F] In order to achieve the above object, the present invention has the following configuration.

(1) An optical recording substrate comprising a resin substrate and a coating made of a polymer and an organosilicon compound laminated thereon.

(2) Aliphatic lower alcohol,
1. A method for producing an optical recording substrate, comprising coating a solution of a polymer and a silicon compound using at least one selected from cellosolves and water as a solvent. ” The polymer in the present invention refers to aliphatic lower alcohol,
Any polymer can be used as long as it is soluble in one or more mixed solvents selected from cellosolves and water, but polymers with hydrogen-bonding functional groups are particularly preferred, and specific examples include polyvinyl alcohol, polyvinylpyridine, polyvinylpyrrolidone, and hydroxyl. Examples include those selected from the group consisting of ethylcellulose, acetylcellulose, hydroxybutylcellulose, or copolymers thereof.

The organosilicon compound used in the present invention has the general formula % (in the formula, R1 is a group having 1 to 10 carbon atoms, R2 is an alkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group,
R3 is an alkyl group, an alkoxyalkyl group, or an acyl group having 1 to 8 carbon atoms. a is O or 1. ) and/or a hydrolyzate thereof, and specific examples include the following.

β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, γ-glycidoxypropylmethyldime 1
-xysilane, γ-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyljethoxysilane, T-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyljethoxysilane, β- Glycidoxypropylethyljethoxysilane, β-glycidoxyethylpropyldimethoxysilane, β-(3,4 epoxycyclohexyl)ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-
Chloropropyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-
Examples include methacryloxypropylmethyldimethoxysilane. In addition, these compounds may be used alone or in combination with 2
It is also possible to use a mixture of more than one species.

When using the above-mentioned organosilicon compound, it can be added as a component as it is, or it can be added after being hydrolyzed in advance. Further, for hydrolysis, a conventional method can be used, for example, a method of hydrolysis using an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, an alkali such as caustic soda, or only water.

In addition, for the purpose of improving the hardness of the film of the organosilicon compound, the general formula is AQ-Xo-Y3□ (where X is a lower alkoxy group, Y is MI C0CH, C0M2, and M3C0CR).
It is preferred to add an aluminum chelate compound represented by a ligand derived from a compound selected from the group consisting of 2COOM 4 (Ml, M2, M3 and M4 are lower alkyl groups, n is 0.1 or 2) .

Various types of aluminum chelate compounds can be used, but preferred examples from the viewpoint of catalytic activity, solubility in the composition, and stability are aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, and aluminum bisacetoacetate. Examples include acetate acetylatonate, aluminum di-n-butoxide monoethyl acetate, aluminum di-propoxide monomethyl acetoacetate, and mixtures of these compounds can also be used.

The coating of the present invention is typically formed from a composition of components used in the following proportions. In all of these, the organosilicon compound is used in a solid content range of 0.5 to 500 parts by weight per 100 parts by weight of the polymer. If the amount of the organosilicon compound is less than 0.5 parts by weight, the coating solvent will penetrate and attack the substrate during formation of the recording layer. 50 again
If the amount is more than 0 parts by weight, unevenness will occur in the coating, making it difficult to form a recording layer. More preferably, it is 10 to 400 parts by weight. Moreover, when using a chelate compound for aluminum, it is preferable to use it within the range of 0.05 to 30 parts by weight. If it is less than 0.05 parts by weight, solvent resistance and adhesion may be insufficient, and if it is more than 30 parts by weight, the transparency of the film may be insufficient. A more preferable range is 0.1 to 20 parts by weight.

In addition to the ingredients mentioned above, the coating of the present invention also contains additives,
It is also possible to contain various modifiers.

As additives, various surfactants can be used for the purpose of improving surface smoothness, and examples include silicone compounds, fluorine surfactants, and organic surfactants. As a rough modifier, ethyl silicate, n
-propyl silicate, 1-propyl silicate, n-
It is also possible to add tetrafunctional silane compounds such as butyl silicate, i-butyl silicate, t-butyl silicate.

Other modifiers that can be added include various epoxy resins, melamine resins, and amide resins.

The film thickness of the film of the present invention is usually 0.005 μm to 0.1 μm.
It is preferably applied in the μm range. If the diameter is less than 0.005 μm, sufficient solvent resistance tends to not be obtained;
．． If it is thicker than 1 μm, there is a great risk that the groups formed on the substrate will be buried, making it difficult to make the tracking signal thicker. Note that for a substrate without groups, a film thickness of up to 10 μm is preferably applied.

Since the coating of the present invention uses a polymer in addition to an organosilicon compound, it has sufficient flexibility and does not easily crack due to sudden temperature changes or impacts.

The solvent for dissolving the polymer, organosilicon compound, etc. used in the production method of the present invention may be any solvent that does not attack the resin substrate, and examples thereof include alcohols, cellosolves, dimethyl sulfoxide, water, etc. . These solvents can be used not only alone but also in combination of two or more. Further, as a coating method, it is possible to use known methods such as brush coating, dip coating, spin coating, flow coating, spray coating, roll coating, curtain 70-coating, and the like.

Substrates that can be used in the present invention are plastic substrates, such as acrylic substrates, polycarbonate substrates, and epoxy resin substrates, which are commonly used for optical recording media.

Furthermore, if the substrate surface is plasma-treated, the adhesion between the substrate surface and the coating will be improved, giving more favorable results.

[Example] The present invention will be explained below using specific examples.

Example 1 (1) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 236q of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, and the liquid temperature was maintained at 10'C. , while stirring with a magnetic stirrer. (1
54 CI of 1N hydrochloric acid aqueous solution was gradually added dropwise. After the dropwise addition was completed, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyl 1-rimethoxysilane.

(2) Preparation of coating solution After stirring and dissolving 12.50% of hydroxypropyl cellulose in 964.5CI of methanol, 21.70% of the γ-glycidoxypropyltrimethoxysilane hydrolyzate and 0.130% of aluminum acetylacetonate were added. ,
The mixture was thoroughly stirred and mixed to prepare a coating solution.

(3) Coating and curing Using the coating solution described above, spin code method (1St - 1500rpm / 10Sec
.

2nd-3ooorpm/20sec),
Heat curing was performed at 90°C for 4 hours.

(4) Test results The coated polycarbonate substrate was subjected to the following tests.

The results are shown in Table 1.

(2) Solvent Resistance Test Solvents dimethylformamide, 1,2-dichloroethaneethyl acetate, and pyridine were dropped onto the coating film, and it was visually observed whether the substrate dissolved or whitened.

◎Appearance Transparency, presence of uneven coating, etc. were examined with the naked eye.

Dye dissolution and diffusion test film on O substrate
2 (114,2,0 wt%, dissolved in 1,2-dichloroethane) on a recording medium using a spin code method, and the state of the substrate and the coating was visually observed.

Example 2 (1) Preparation of coating solution After stirring and dissolving 12.5 g of acetyl cellulose in 919.9 CI of ethylene glycol methyl ether, 65.1 q of the γ-glycidoxypropyltrimethoxysilane hydrolyzate of Example 1 was added. 2.50% of aluminum acetylacetonate was added and thoroughly stirred and mixed to prepare a coating solution.

(2) Coating and curing Using the coating solution described above, apply according to Example 1, and cure at 120°C.
Heat curing was performed for 1 hour.

(3) Test results Tests were conducted according to Example 1. The results are shown in Table @1.

Example 3 Everything was carried out in the same manner as in Example 1, except that the polycarbonate substrate of Example 1 was subjected to plasma treatment by the method shown below. The results are shown in Table 1.

Gas diM gas flow rate: 100 CC/min Output: 50 W Processing time: 5 minutes Example 4 All procedures were performed in the same manner as in Example 1 except that aluminum acetylacetonate was removed from the preparation of the coating solution in Example 1. Ta. The results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 25.0 CI of hydroxypropyl cellulose was stirred and dissolved in 975.0 CI of methanol to prepare coating liquid 15.

The results are shown in Table 1.

Comparative Example 2 A test was carried out on a polycarbonate substrate to which no film was applied. The results are shown in Table 1.

〔Effect of the invention〕

By using the optical recording substrate of the present invention, the resin substrate is not attacked by solvents, has excellent flexibility, and a recording layer can be formed without dye diffusion.

Further, the method for manufacturing an optical recording substrate of the present invention has excellent productivity because a film can be easily formed on the substrate by coating.

Claims (12)

[Claims] (1) An optical recording substrate characterized by being formed by laminating a coating made of a polymer and an organosilicon compound on a resin substrate. (2) The optical recording substrate according to claim (1), wherein the polymer is a polymer having a hydrogen-bonding functional group. (3) The polymer having a hydrogen-bonding functional group is one or more selected from polyvinyl alcohol, polyvinylpyridine, polyvinylpyrrolidone, hydroxyethylcellulose, acetylcellulose, methylcellulose, hydroxypropylcellulose, and hydroxybutylcellulose. An optical recording substrate according to claim (2). (4) The optical recording substrate according to claim (1), wherein the organosilicon compound is contained in a proportion of 0.5 to 500 parts by weight per 100 parts by weight of the polymer. (5) The organosilicon compound is a compound represented by the following general formula (A),
1) The optical recording substrate described in item 1). R^1R^2_aSi(OR^3)_3_-_a(A) (wherein, R^1 is an organic group having 1 to 10 carbon atoms, R^2 is,
R^3 is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, and R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group. a is 0 or 1. ) (6) The optical recording substrate according to claim (1), wherein the organosilicon compound is a hydrolyzate of a compound represented by the following general formula (A). R^1R^2_aSi(OR^3)_3_-_a(A) (wherein, R^1 is an organic group having 1 to 10 carbon atoms, R^2 is,
R^3 is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, and R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group. a is 0 or 1. ) (7) Production of an optical recording substrate characterized by coating a resin substrate with a solution of a polymer and an organosilicon compound using at least one selected from aliphatic lower alcohols, cellosolves, and water as a solvent. Method. (8) The method for producing an optical recording substrate according to claim (7), wherein the polymer is a polymer having a hydrogen-bonding functional group. (9) The polymer having a hydrogen-bonding functional group is one or more selected from polyvinyl alcohol, polyvinylpyridine, polyvinylpyrrolidone, hydroxyethylcellulose, acetylcellulose, methylcellulose, hydroxypropylcellulose, and hydroxybutylcellulose. A method for manufacturing an optical recording substrate according to claim (8). (10) The optical recording substrate according to claim (7), wherein the organosilicon compound is contained in a proportion of 0.5 to 500 parts by weight per 100 parts by weight of the polymer. Production method. (11) The method for producing an optical recording substrate according to claim (7), wherein the organosilicon compound is a compound represented by the following general formula (A). R^1R^2_aSi(OR^3)_3_-_a(A) (wherein, R^1 is an organic group having 1 to 10 carbon atoms, R^2 is,
R^3 is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, and R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group. a is 0 or 1. ) (12) The method for producing an optical recording substrate according to claim (7), wherein the organosilicon compound is a hydrolyzate of a compound represented by the following general formula (A). R^1R^2_aSi(OR^3)_3_-_a(A) (wherein, R^1 is an organic group having 1 to 10 carbon atoms, R^2 is,
R^3 is an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group, and R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group. a is 0 or 1. )