JPH07331173A - Coating composition for formation of optical material and optical material - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. capable of forming a coating film excellent in high-temp. and high-moisture resistance, toughness, coatability, evenness, uniformity of refractive index by blending a siloxane polymer with a specific metal alkoxide and/or a metal chelate compd. derived from the metal alkoxide. CONSTITUTION:A silioxane polymer obtd. by hydrolysis and RxSi(OR')4-x(wherein R and R' are each H, alkyl, aryl, alkenyl, or a substd. deriv. thereof; and x is an integer of 0 to 3) is blended with a metal alkoxide of the formula: MOOR'')m (wherein M is titanium, zirconium, or aluminum; R'' is H, alkyl, aryl, alkenyl, or a substd. deriv. thereof; and m is the valence of the metal atom M) and/or a metal chelate compd. derived from the metal alkoxide. The mixing proportion is such that 100 pts.wt. siloxane polymer is blended with 0.1-20 pts.wt. metal alkoxide and/or metal chelate compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material for forming an optical material containing a siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane, a metal alkoxide and / or a metal chelate compound derived from the metal alkoxide. The present invention relates to a liquid composition, and more specifically, to a coating liquid composition for forming an optical material capable of obtaining a coating film excellent in high temperature and high humidity resistance, toughness, coatability, and flatness. In particular, the present invention relates to a coating composition for forming an optical material such as an optical waveguide or an optical filter used in a system utilizing optical communication or light.

[0002]

2. Description of the Related Art An optical communication system has been attracting attention as a means for increasing the transmission speed of a conventional telecommunication system, and a material compatible with light has been required as a component material thereof. A wide range of properties such as transparency, heat resistance, adhesion, solvent resistance, chemical resistance, high temperature and high humidity resistance, and uniform refractive index are required for optical component materials.

From the viewpoint of heat resistance, a thermosetting coating liquid composition for forming such an optical material is disclosed in Japanese Patent Application Laid-Open No. Hei 4-
As shown in Japanese Patent No. 157402, a siloxane polymer has been proposed.

A coating liquid composition containing a siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane is disclosed in JP-A-63-241076,
It is widely known as disclosed in JP-A-3-126612 and JP-A-3-188179. But,
The obtained coating does not have resistance to high temperature and high humidity, that is, when it is stored in a high temperature and high humidity environment for a long period of time, pinhole-like defects and microcracks occur in the coating, and the coating peels from the substrate. Had a point.

A coating liquid composition containing a polymer obtained by subjecting an alkoxysilane and another metal alkoxide or its chelate compound as a raw material to hydrolysis and condensation is also disclosed in JP-A-3-20377 and JP-A-3-20377. It is known as disclosed in Japanese Patent Publication No. 279210, etc., but it has problems that production is difficult and filterability is poor because the reactivity of alkoxysilane and other metal alkoxide is very different.

[0006]

An object of the present invention is to obtain a coating film having excellent resistance to high temperature and high humidity, excellent toughness, coating property, flatness, and uniform refractive index, and to provide a manufacturing method. It is to provide a simple coating composition for forming an optical material.

[0007]

The object of the present invention is as follows.
This is achieved by a coating liquid composition for forming an optical material, which contains the following component (A) and component (B). (A) The following general formula (1) R _X Si (OR ') _4-X (1) (wherein R and R'may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, Or a substituent thereof, and X is 0 to
It is an integer of 3. ) A siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane represented by (B) The following general formula (2) M (OR ″) _m (2) (where M is a metal atom of titanium, zirconium, or aluminum. R ″ may be the same or different and each is hydrogen. , An alkyl group, an aryl group, an alkenyl group, and a substitution product thereof.
Means the valence of the metal atom M. And a metal chelate compound derived from the metal alkoxide.

The inventors of the present invention have used visible light as an optical material.
Since the transparency in the near-infrared region is excellent, attention was paid to a coating liquid composition composed of a siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane. However, as described above, an optical material obtained by applying a coating composition containing a conventional siloxane polymer and forming a film has poor resistance to high temperature and high humidity. Then, the inventors of the present invention examined the cause of this defect and found that the main cause was the low degree of curing of the optical material. Then, as a result of intensive studies by the present inventors, by adding a metal alkoxide or a metal chelate compound derived from the metal alkoxide to a siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane, We have found an optical material that can be sufficiently cured even at a curing temperature of ℃ or less.

On the other hand, as a similar composition using an alkoxysilane and another metal alkoxide as a raw material, a composition containing a polymer obtained by cohydrolyzing and further condensing an alkoxysilane and another metal alkoxide as a raw material. Things are known. However, in this composition, it is very difficult to co-hydrolyze the alkoxysilane and other metal alkoxides because they have very different hydrolysis reactivity, and it is difficult to co-hydrolyze them. In addition to problems such as poor filterability,
Even if a coating solution is obtained, there are many problems such as poor storage stability, lack of toughness, poor coatability, poor flatness, and lack of uniformity in refractive index of the obtained coating film. On the other hand, according to the method of the present invention, only an alkoxysilane having low hydrolysis reactivity is first hydrolyzed and condensed, and then another metal alkoxide or a metal chelate compound derived from the metal alkoxide is added. Therefore, it can be easily manufactured without these problems.

Therefore, the inventors have found that a coating film having excellent resistance to high temperature and high humidity can be obtained, and that a coating liquid composition for forming an optical material having a simple manufacturing method can be obtained, and thus the present invention has been achieved.

The structure of the present invention will be described below in order.

Component (A): a siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane.

The siloxane polymer used in the present invention is made to have a high molecular weight by causing the alkoxysilane to react with water to hydrolyze, and further to partially dehydrate and condense by heating or standing at room temperature.

The alkoxysilane used in the present invention is represented by the following general formula (1). R _X Si (OR ') _4-X (1) (wherein R and R'may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substitution product thereof. , X is 0
It is an integer of 3. )

R is, for example, hydrogen; an alkyl group such as a methyl group, an ethyl group, an n-propyl group or an i-propyl group; an aryl group such as a phenyl group; an alkenyl group such as a vinyl group; β- (3,4 -Epoxycyclohexyl) ethyl group, γ-methacryloxypropyl group, γ-glycidoxypropyl group, γ-chloropropyl group, γ-mercaptopropyl group, γ-aminopropyl group, N-phenyl-
γ-aminopropyl group, N-β (aminoethyl) γ-
Aminopropyl group, trifluoromethyl group, 3, 3, 3
-Substituted alkyl groups such as trifluoropropyl group and the like can be mentioned. Of these, one kind may be used, or two or more kinds may be used in combination. With this choice,
It is possible to adjust the properties of the resulting coating. In particular, from the viewpoint of improving the toughness of the coating, it is desirable that R has a reactive group except an alkoxy group. For example, vinyl group, γ-methacryloxypropyl group, γ-
It is a glycidoxypropyl group. By using these, not only the siloxane skeleton but also the skeleton formed by cross-linking by these reactive groups is formed in the obtained coating film, and the toughness of the film is improved.

R'is, for example, hydrogen; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples thereof include alkyl groups such as sec-butyl group and t-butyl group; aryl groups such as phenyl group; substituted alkyl groups such as acetyl group and β-methoxyethoxy group.

Specific examples of these alkoxysilanes include tetrahydroxysilane, tetramethoxysilane,
Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane can be mentioned. Alkoxysilane may be used alone, or two or more.

The hydrolysis and condensation reactions of these alkoxysilanes may be carried out in the absence of solvent, but they are usually carried out in an organic solvent. For example, alcohols such as methanol, ethanol, propanol, butanol and 3-methyl-3-methoxybutanol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether,
Ethers such as diethyl ether; ketones such as methyl isobutyl ketone and diisobutyl ketone; amides such as dimethylformamide and dimethylacetamide;
Ethyl acetate, ethyl cellosolve acetate, 3-
Acetates such as methyl-3-methoxybutylacetate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane, as well as N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethyl sulfoxide. .

In the present invention, the solvent of the coating liquid finally obtained can be used also without removing the solvent. Therefore, from the viewpoint of improving the coating property of the obtained coating liquid,
It is preferable to use a liquid having a boiling point of 100 to 300 ° C.

Although the amount of the solvent can be arbitrarily selected, it is preferably used in the range of 0.1 to 10.0 parts by weight with respect to 1 part by weight of the alkoxysilane.

The water used for the hydrolysis and partial condensation reaction is preferably ion-exchanged water, and the amount thereof is preferably in the range of 1 to 4 times mol relative to 1 mol of alkoxysilane.

Further, a catalyst can be used if necessary for carrying out the hydrolysis and condensation reactions. The catalyst used is hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid,
Acid catalysts such as phosphoric acid, boric acid, p-toluenesulfonic acid, ion exchange resins, triethylamine, diethylamine,
Examples thereof include basic catalysts such as triethanolamine, diethanolamine, sodium hydroxide and potassium hydroxide, and acid catalysts are preferable from the viewpoint of improving the toughness of the resulting coating.

The amount of the catalyst is preferably 0.001 to 0.1 part by weight based on 1 part by weight of alkoxysilane. If it exceeds 0.1 part by weight, the storage stability and flatness of the coating solution are impaired. On the other hand, when the amount is less than 0.001 part by weight, only a polymer having a low degree of polymerization is obtained and the coating property is impaired.

The reaction temperature for hydrolysis and partial condensation is usually selected in the range from the freezing point to the boiling point, but the reaction can be carried out at a temperature above the boiling point while distilling off the low boiling point alcohol and water by-produced. It is preferable in terms of coating properties and storage stability.

The metal alkoxide of component (B) or the metal chelate compound derived from the metal alkoxide is added to component (A) for the purpose of lowering the curing temperature of the protective film, which is a feature of the present invention. It is an ingredient.

The metal alkoxide used in the present invention is represented by the following general formula (2). M (OR ″) _m (2) (M is a metal atom of titanium, zirconium, or aluminum. R ″ may be the same or different and each is hydrogen, an alkyl group, an aryl group, an alkenyl group, and Represents a substitution product thereof, and m means the valence of the metal atom M.)

M is a metal atom of titanium, zirconium, or aluminum. Boron, magnesium, etc. are not practical for low-temperature curing because they have a reactivity similar to that of silicon alkoxide, or are extremely high in reactivity and are not practical. Titanium, zirconium,
Only when using an aluminum alkoxide compound,
The effect of lowering the curing temperature of the coating, which is a feature of the present invention, was observed, and a coating excellent in high-temperature and high-humidity resistance could be obtained, and it was found to be suitable as an optical material. Moreover,
Of the titanium, zirconium, and aluminum, when zirconium is used, it is very effective to improve the toughness of the coating film, so that it is particularly preferable to use zirconium alkoxide or a chelate compound of zirconium alkoxide. Further, when titanium is used, it is very effective in adjusting the refractive index of the coating film. Therefore, when it is necessary to adjust the refractive index of the optical material, titanium alkoxide or a chelate compound of titanium alkoxide is used. It is preferable to use. R ″ is, for example, hydrogen; methyl group, ethyl group, n-propyl group, i-propyl group,
Examples thereof include alkyl groups such as n-butyl group, sec-butyl group and t-butyl group; aryl groups such as phenyl group; substituted alkyl groups such as acetyl group and β-methoxyethoxy group.

Specific examples thereof include tetraisopropoxytitanium, tetranormalbutoxytitanium, tetraisopropoxyzirconium, tetranormalbutoxyzirconium, triisopropoxyaluminum, and trinormalbutoxyaluminum.

The metal chelate compound used in the present invention is a metal chelate compound derived from the metal alkoxide represented by the general formula (2).

Further, the metal chelate compound is easily obtained by reacting a metal alkoxide with a chelating agent, and a compound represented by the following general formula (3) is preferable.

[Chemical 1] (However, M is a metal atom of titanium, zirconium, or aluminum. R ″ may be the same or different, and each of hydrogen, an alkyl group, an aryl group, an alkenyl group, and their substitution products, and R ₁ is They may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group or a substitution product thereof, m is the valence of the metal atom M, and n is a number from 0 to m. Yes.)

Examples of the chelating agent include β-diketones such as acetylacetone, benzoylacetone and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

Since the metal alkoxide reacts with various stoichiometric amounts of chelating agents to form the corresponding metal chelate compounds, the amount of chelating agent used is 1
Ingredient (A) in the range of 0.1 to 10 moles relative to moles.
It is preferable to determine according to the reactivity of. That is, when the reactivity of the component (A) is low, a metal alkoxide or a low-coordination metal chelate compound can be used, but when the reactivity of the component (A) is high, the hydrolysis stability is higher. It is preferable to use a metal compound having a high coordination and a high coordination.

It is preferable to use a reaction solvent which is azeotropic with the produced alcohol and which has been dehydrated. For example, methanol, ethanol, propanol,
Alcohols such as butanol and 3-methyl-3-methoxybutanol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether and diethyl ether; methyl isobutyl ketone , Ketones such as diisobutyl ketone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, ethyl cellosolve acetate and 3-methyl-3-methoxybutyl acetate; aromatics such as toluene, xylene, hexane and cyclohexane Alternatively, in addition to aliphatic hydrocarbons, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, etc. may be mentioned. Door can be. The amount of the solvent can be arbitrarily selected, but with respect to 1 weight of the metal alkoxide,
It is preferably used in the range of 1 to 50.0 weight.

The reaction temperature is usually selected from the freezing point to the boiling point.

The reaction atmosphere is preferably a nitrogen atmosphere.

In the coating composition for forming an optical material of the present invention, the siloxane polymer of the component (A) and the metal alkoxide of the component (B), or the metal chelate compound derived from the metal alkoxide, are each usually Organic solvent,
Preferably, an organic solvent having a boiling point of 100 ° C. or higher is used as a solvent in a solution state. As the solvent, the reaction solvent used when synthesizing the siloxane polymer in the component (A) and the reaction solvent used when synthesizing the metal chelate compound in the component (B) can be used as they are. Further, if necessary, after the reaction, it is possible to carry out solvent substitution for the purpose of improving the coating property, and to add or remove the solvent for adjusting the concentration. As the solvent at this time, the above-mentioned solvents that can be used for the synthesis of the siloxane polymer or the metal chelate compound can be used alone or in combination of two or more kinds.

The coating liquid composition for forming an optical material of the present invention is prepared by uniformly mixing the solution of the siloxane polymer of the component (A) and the solution of the metal alkoxide or the metal chelate compound of the component (B). can get.

The mixing ratio is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the siloxane polymer.

As a mixing method, after mixing at room temperature,
It is preferable to leave it for about 1 hour to 1 day or to carry out heating at a temperature below the boiling point for several hours.

Further, a film curing agent, a viscosity modifier, a surfactant, a stabilizer, a coloring agent, a vitreous forming agent and the like are added to the coating liquid composition for forming an optical material of the present invention, if necessary. can do.

Next, a method for producing an optical member using an optical material from the optical material coating composition of the present invention will be described.

The coating composition for forming an optical material of the present invention is formed on a substrate to be formed, for example, a glass plate, by a known method such as spin coating, dipping coating, spray coating, screen coating, screen printing and offset printing. Apply and dry. Dry in the range of 50-150 ℃
The film thickness after drying is 0 to 30 minutes, and is 1 to 20 μm.
Is preferred.

After drying, if necessary, using an exposure device such as PLA, 50 to 2000 mJ / cm ² (365 nm)
Exposing the entire surface.

Pattern formation can also be carried out by exposing through a desired mask when the coating liquid composition contains a compound capable of generating an acid or a base by light. When forming a pattern, it is preferable to perform heating (post-exposure bake) after exposure. By performing the post-exposure bake, the high molecular weight of the exposed area progresses from the unexposed area due to the action of the acid or basic compound generated by the exposure, the difference in solubility of the developer with the unexposed area widens, and the resolution contrast increases. The effect of improvement is obtained. Post-exposure bake is preferably performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes.

Next, development is performed. As the developing solution, an organic solvent, an alkaline aqueous solution or the like can be used.
Specific examples thereof include organic solvents such as isopropanol and propylene glycol monomethyl ether; alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution and sodium carbonate aqueous solution. As for the developing method, it is preferable to immerse in these developing solutions for 10 seconds to 10 minutes.

After the development, the film can be rinsed with water or a general organic solvent and dried, and if necessary, the patterned film can be further exposed to the whole surface.

After that, the film is cured by heating. Heat curing
It is preferably carried out in the range of 200 to 500 ° C. for 10 minutes to 3 hours.

After drying or heat curing, it is also possible to expose with a light source having an appropriate wavelength through a desired mask. By this step, a difference in refractive index is generated between the exposed portion and the unexposed portion, and it is possible to properly use the core member and the clad member of the optical waveguide, for example.

The film thickness after heat curing is appropriately 1 to 20 μm, though it depends on the type and structure of the applied optical member.
Furthermore, 2-10 micrometers is preferable. This film thickness can be adjusted by the coating method.

Further, CMP (Chemical Mechanical Polishing) is carried out for the purpose of flattening the film thus obtained and enhancing the adhesion thereof.
Treatment, plasma treatment, etc. are also possible.

The optical member is formed as described above.

In the present invention, the optical material is used for an optical member, and the optical member means any member used for an optical signal transmission system. For example, in an optical waveguide, a core part having a high refractive index is covered with a clad part having a low refractive index, and an optical signal propagates while being totally reflected in the core part. It can be used as a member. The optical filter is used by being sandwiched between optical fibers in order to block light having a wavelength other than communication light, and the optical material of the present invention can be used as a substrate of this optical filter.

The coating film obtained from the coating composition for forming an optical material of the present invention includes, in addition to optical materials, a color filter protective film, a semiconductor element protective film, an interlayer insulating film, a planarizing film, a waveguide forming material, It can be used as a material for phase shifters and as a protective film for various electronic components.

[0054]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Example 1 Component (A) 10 mol of methyltrimethoxysilane and 10 mol of phenyltrimethoxysilane were used as 3-methyl-alkoxysilane.
It was dissolved in 4 kg of 3-methoxybutanol, and an aqueous phosphoric acid solution (60 mol of water, 0.17 mol of phosphoric acid) was added thereto while stirring. The obtained solution was heated in an oil bath at 100 ° C., and a reaction was carried out for 2 hours while distilling low-boiling substances. Then, the mixture was further heated in an oil bath at 130 ° C., and a reaction was carried out for 2 hours while distilling out low-boiling substances. The resulting solution was treated with 3-methyl-3-methoxybutanol,
The concentration was adjusted to 30%. (Hereinafter, the concentration indicates the solid content concentration) Component (B) 1 mol of tetrabutoxyzirconium is added to 3-methyl-3-
It was dissolved in 1500 g of methoxybutanol, and 5 mol of ethyl acetoacetate was added thereto with stirring. The resulting solution was reacted at room temperature for 1 hour with stirring. (concentration:
4.7%) Next, 650 g of the component (A) and 50 g of the component (B) were mixed and stirred at room temperature for 2 hours to obtain a uniform solution, and further 3-methyl-3-methoxybutanol was used. The solid content concentration was adjusted to 25% to obtain a coating liquid for forming an optical material.

No problems such as gelation, precipitation, and poor filterability were found in the obtained coating liquid.

The obtained coating solution was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 2 Component (A) Methyltrimethoxysilane (7 mol), dimethyldimethoxysilane (3 mol) and phenyltrimethoxysilane (2 mol) of alkoxysilane were dissolved in propylene glycol monomethyl ether (1.5 kg). Water 33
Mol, acetic acid 0.1 mol) was added with stirring. The obtained solution was heated in an oil bath at 100 ° C., and a reaction was carried out for 2 hours while distilling low-boiling substances. Then 13 more
The mixture was heated in an oil bath at 0 ° C., and the reaction was carried out for 2 hours while distilling out low-boiling substances. The resulting solution is 3-methyl-3
-Methoxybutyl acetate was used to adjust the concentration to 30%.

Next, 500 g of the component (A) and 100 g of the component (B) of Example 1 were mixed and stirred at room temperature for 2 hours to give a uniform solution, and further 3-methyl-3-methoxybutanol acetate. Was used to adjust the solid content concentration to 25% to obtain a coating liquid for forming an optical material.

The obtained coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 4H in the pencil hardness test.

Example 3 Component (A) 1 mol of methyltrimethoxysilane, 1 mol of phenyltrimethoxysilane, and 2 mol of γ-methacryloxypropyltriethoxysilane of alkoxysilane were dissolved in 1 kg of propylene glycol monomethyl ether. An aqueous phosphoric acid solution (20 mol of water, 0.03 mol of phosphoric acid) was added with stirring. The obtained solution was heated in an oil bath at 100 ° C., and a reaction was carried out for 2 hours while distilling low-boiling substances. Then, the mixture was further heated in an oil bath at 130 ° C., and a reaction was carried out for 2 hours while distilling out low-boiling substances. The obtained solution was adjusted to a concentration of 30% using propylene glycol monomethyl ether.

Next, 500 g of the component (A) and 5 g of the component (B) of Example 1 were mixed and stirred at room temperature for 2 hours to give a uniform solution, and further 3-methyl-3-methoxybutanol was added. Then, the solid content concentration was adjusted to 25% to obtain a coating liquid for forming an optical material.

No problems such as gelation, precipitation, and poor filterability were found in the obtained coating liquid.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 4 Component (A) 1 mol of methyltrimethoxysilane, 1 mol of phenyltrimethoxysilane, and 1 mol of vinyltriethoxysilane were dissolved in 1000 g of 3-methyl-3-methoxybutanol. An aqueous phosphoric acid solution (9 mol of water, 0.06 mol of phosphoric acid) was added with stirring. The obtained solution was heated in an oil bath at 100 ° C., and a reaction was carried out for 2 hours while distilling low-boiling substances. Then one more
The mixture was heated in an oil bath at 30 ° C., and a reaction was carried out for 2 hours while distilling out low boiling substances. The resulting solution is 3-methyl-3
-Methoxybutyl acetate was used to adjust the concentration to 30%. Next, 300 g of the component (A) and 100 g of the component (B) of Example 1 were mixed and stirred at room temperature for 2 hours,
A uniform solution was prepared, and further 3-methyl-3-methoxybutanol was used to adjust the solid content concentration to 25% to obtain a coating liquid for forming an optical material.

The obtained coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 5 In Example 1, a coating solution for forming an optical material was prepared by using a solution of tetra-normal-butylzirconium in 3-methyl-3-methoxybutanol (concentration: 4.7%) as the component (B). Obtained.

No problems such as gelation, precipitation, and poor filterability were found in the obtained coating liquid.

The coating solution thus obtained was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 6 In Example 2, a coating solution for forming an optical material was prepared by using a solution of tetra-normal-butylzirconium in 3-methyl-3-methoxybutanol (concentration: 4.7%) as the component (B). Obtained.

The obtained coating liquid did not show any problems such as gelation, precipitate formation, and poor filterability.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 4H in the pencil hardness test.

Example 7 In Example 3, a coating solution for forming an optical material was prepared by using a solution of tetra-normal-butylzirconium in 3-methyl-3-methoxybutanol (concentration: 4.7%) as the component (B). Obtained.

The resulting coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 8 In Example 4, a coating solution for forming an optical material was prepared by using a solution of tetra-normal-butylzirconium in 3-methyl-3-methoxybutanol (concentration: 4.7%) as the component (B). Obtained.

No problems such as gelation, precipitate formation, and poor filterability were found in the obtained coating liquid.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 5H in the pencil hardness test.

Example 9 A coating liquid for forming an optical material was obtained by using the following components as the component (B) in Example 1.

Component (B) 1 mol of tetraisopropoxy titanium is added to 3-methyl-3-
It was dissolved in 1500 g of methoxybutanol, and 5 mol of acetylacetone was added thereto with stirring. The resulting solution was reacted at room temperature for 1 hour with stirring. (concentration:
3.5%) The obtained coating liquid did not have any problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 2H in the pencil hardness test.

Example 10 A coating liquid for forming an optical material was obtained by using the component (B) of Example 9 as the component (B) in Example 2.

The coating liquid thus obtained had no problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was H in the pencil hardness test.

Example 11 A coating liquid for forming an optical material was obtained by using the component (B) of Example 9 as the component (B) in Example 3.

The coating liquid thus obtained had no problems such as gelation, precipitation, and poor filterability.

The obtained coating solution was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 2H in the pencil hardness test.

Example 12 Using the component (B) of Example 9 as the component (B) in Example 4, a coating liquid for forming an optical material was obtained.

The obtained coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 2H in the pencil hardness test.

Example 13 A coating liquid for forming an optical material was obtained by using the following components as the component (B) in Example 1.

Component (B) 1 mol of trisisopropoxyaluminum and 1 part of toluene
It was dissolved in 000 g and 4 mol of ethyl acetoacetate was added thereto with stirring. The resulting solution was reacted at room temperature for 1 hour with stirring. (Concentration: 3.0%) In the obtained coating liquid, there were no problems such as gelation, precipitation, and poor filterability.

The obtained coating liquid was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 3H in the pencil hardness test.

Example 14 In Example 2, the component (B) of Example 13 was used as the component (B) to obtain a coating liquid for forming an optical material.

No problems such as gelation, precipitation, and poor filterability were found in the obtained coating liquid.

The obtained coating liquid was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 2H in the pencil hardness test.

Example 15 Using the component (B) of Example 13 as the component (B) in Example 3, a coating liquid for forming an optical material was obtained.

The obtained coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating solution was applied onto a glass plate with a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after being left in a high temperature and high humidity atmosphere.

The toughness was 3H in the pencil hardness test.

Example 16 A coating liquid for forming an optical material was obtained by using the component (B) of Example 13 as the component (B) in Example 4.

The obtained coating liquid did not show any problems such as gelation, precipitation, and poor filterability.

The obtained coating solution was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to give a film thickness of 2
The presence or absence of defects is checked by μm, and then this coating is applied at 120 ° C.
It was left for 1 day in a high temperature and high humidity atmosphere of 100% RH and examined for deterioration.

As a result, problems such as pinhole-like defects, microcracks, and peeling did not occur before and after standing in a high temperature and high humidity atmosphere.

The toughness was 3H in the pencil hardness test.

Comparative Example 1 A coating solution containing only the component (A) used in Example 1 was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to check for defects with a film thickness of 2 μm. Then, this coating was left to stand in a high temperature and high humidity atmosphere of 120 ° C. and 100% RH for 1 day, and examined for deterioration.

As a result, although no problems such as pinhole-like defects, microcracks, and peeling occurred before leaving in a high-temperature and high-humidity atmosphere, pinhole-like defects and microcracks, after leaving in a high-temperature and high-humidity atmosphere, Problems such as peeling occurred.

Further, the toughness was H in the pencil hardness test.

Comparative Example 2 A coating solution containing only the component (A) used in Example 2 was applied onto a glass plate using a spin coater and cured at 280 ° C. for 1 hour to determine whether there was a defect at a film thickness of 2 μm. Then, this coating was left to stand in a high temperature and high humidity atmosphere of 120 ° C. and 100% RH for 1 day, and examined for deterioration.

As a result, although no problems such as pinhole-like defects, microcracks, and peeling occurred before leaving in a high-temperature and high-humidity atmosphere, pinhole-like defects and microcracks, after leaving in a high-temperature and high-humidity atmosphere, Problems such as peeling occurred.

The toughness was B in the pencil hardness test.

Comparative Example 3 A glass plate was coated with a coating solution containing only the component (A) used in Example 3 using a spin coater and cured at 280 ° C. for 1 hour to determine whether there was a defect at a film thickness of 2 μm. Then, this coating was left to stand in a high temperature and high humidity atmosphere of 120 ° C. and 100% RH for 1 day, and examined for deterioration.

As a result, although no problems such as pinhole-like defects, microcracks, and peeling occurred before leaving in a high-temperature and high-humidity atmosphere, pinhole-like defects and microcracks, after leaving in a high-temperature and high-humidity atmosphere, Problems such as peeling occurred.

The toughness was 2H in the pencil hardness test.

Comparative Example 4 A glass plate was coated with a coating solution containing only the component (A) used in Example 4 using a spin coater, and the coating was cured at 280 ° C. for 1 hour. Then, this coating was left to stand in a high temperature and high humidity atmosphere of 120 ° C. and 100% RH for 1 day, and examined for deterioration.

As a result, although no problems such as pinhole-like defects, microcracks, and peeling occurred before leaving in a high-temperature and high-humidity atmosphere, pinhole-like defects and microcracks, after leaving in a high-temperature and high-humidity atmosphere, Problems such as peeling occurred.

The toughness was 2H in the pencil hardness test.

Comparative Example 5 10 mol of methyltrimethoxysilane, 10 mol of phenyltrimethoxysilane and 0.1 mol of tetrabutoxyzirconium were dissolved in 4 kg of 3-methyl-3-methoxybutanol, and an aqueous phosphoric acid solution was added thereto. (60 mol of water, 0.17 mol of phosphoric acid) was added with stirring. The obtained solution was heated in an oil bath at 100 ° C., and a reaction was carried out for 2 hours while distilling low-boiling substances. afterwards,
Further, the mixture was heated in an oil bath at 130 ° C., and a reaction was carried out for 2 hours while distilling out low-boiling substances. The obtained solution was adjusted to have a concentration of 25% using 3-methyl-3-methoxybutanol to obtain a coating liquid for forming an optical material.

However, the obtained coating liquid could not be filtered with a 0.5 μm filter, and could not be applied onto a glass plate.

Comparative Example 6 A coating liquid for forming an optical material was obtained by using the following components as the component (B) in Example 1.

Component (B) 1 mol of triisopropoxyborone was dissolved in 1500 g of 3-methyl-3-methoxybutanol, and 4 mol of acetylacetone was added thereto with stirring. The resulting solution was reacted at room temperature for 1 hour with stirring. (concentration:
1.7%) The obtained coating liquid was applied onto a glass plate using a spin coater, cured at 280 ° C. for 1 hour, and checked for defects at a film thickness of 2 μm. 100% RH
It was left for 1 day in a high temperature and high humidity atmosphere and examined for deterioration.

As a result, although no problems such as pinhole-like defects, microcracks, and peeling occurred before leaving in a high-temperature and high-humidity atmosphere, pinhole-like defects and microcracks, after leaving in a high-temperature and high-humidity atmosphere, Problems such as peeling occurred.

Example 17 An optical waveguide was prepared using the following coating solution.

Solution A: Coating solution for forming buffer layer and clad layer The coating solution shown in Example 1 was prepared to have a solid content concentration of 30%.

Solution B: Core Layer-Forming Coating Solution The coating solution shown in Example 9 was prepared to a solid concentration of 30%.

Solution A was applied onto a glass plate using a spin coater and cured at 250 ° C. for 1 hour to form a buffer layer having a thickness of 10 μm. Further, the solution B was applied onto the buffer layer using a spin coater and cured at 250 ° C. for 1 hour to form a core layer having a thickness of 5 μm. Next, a photoresist pattern is formed in a desired shape on the core layer by a known method, and the core layer is subjected to R
It was etched by IE (reactive ion etching). After removing the mask, the solution A was applied again using a spin coater and cured at 250 ° C. for 1 hour to form a clad layer having a film thickness of 10 μm, thereby forming an embedded optical waveguide.

No defects such as cracks were found in the obtained optical waveguide, and the propagation loss of light having a wavelength of 1.55 μm was measured to show a good low loss property of -10 dB / m. In addition, heat resistance test by heating at 400 ℃, 50
The characteristics did not change even by the humidity resistance test of leaving it under high humidity of 85 ° C. and 85% RH for 1000 hours.

Comparative Example 7 An optical waveguide was prepared in the same manner as in Example 17, using the following coating liquid.

Liquid A: Coating liquid for forming buffer layer and clad layer The coating liquid shown in Comparative Example 1 prepared to have a solid content concentration of 30% was used.

Solution B: Core Layer-Forming Coating Solution The coating solution shown in Comparative Example 2 was prepared to have a solid content concentration of 30%.

No defects such as cracks were found in the obtained optical waveguide, and when the propagation loss of light having a wavelength of 1.55 μm was measured, a good low loss property of -10 dB / m was exhibited. However, in the heat resistance test by heating at 400 ° C, no change in properties was observed, but at 50 ° C, 85% R
According to the humidity resistance test of leaving it under high humidity of H for 1000 hours, the propagation loss of 1.55 μm wavelength light is ~ 200 d.
B / m greatly decreased.

Example 18 The coating solution prepared in Example 2 having a solid content concentration of 30% was applied onto a silicon wafer (temporary substrate) by using a spin coater and cured at 300 ° C. for 1 hour. Film thickness 10
A μm substrate layer was formed. TiO ₂ and S on this substrate layer
multi-layer film of iO ₂ was laminated. Then, it was peeled from the temporary substrate and cut into a predetermined size to obtain an optical filter.

The obtained optical filter has a wavelength of 9 μm for 1.3 μm and 1.55 μm wavelength light used for optical communication.
It showed a transmittance of 9% or more and satisfied the characteristics as an optical filter.

[0165]

The coating composition for forming an optical material of the present invention comprises:
A coating film excellent in high temperature and high humidity resistance, toughness, coatability, flatness, and uniform refractive index can be obtained, and the manufacturing method is simple.

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Claims (8)

[Claims] 1. A coating liquid composition for forming an optical material, which comprises the following components (A) and (B). (A) The following general formula (1) R _X Si (OR ') _4-X (1) (wherein R and R'may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, Or a substituent thereof, and X is 0 to
It is an integer of 3. ) A siloxane polymer obtained by hydrolyzing and condensing an alkoxysilane represented by (B) The following general formula (2) M (OR ″) _m (2) (where M is a metal atom of titanium, zirconium, or aluminum. R ″ may be the same or different and each is hydrogen. , An alkyl group, an aryl group, an alkenyl group, and a substitution product thereof.
Means the valence of the metal atom M. And a metal chelate compound derived from the metal alkoxide. 2. The coating liquid composition for forming an optical material according to claim 1, wherein the metal alkoxide is zirconium alkoxide. 3. The alkoxysilane has a reactive group excluding an alkoxy group.
The coating liquid composition for forming an optical material as described above. 4. The optical material formation according to claim 3, wherein the reactive group is at least one selected from a vinyl group, a γ-methacryloxypropyl group and a γ-glycidoxypropyl group. Coating composition for use. 5. When the alkoxysilane is hydrolyzed and condensed, a part or all of the solvent has a boiling point of 100 to 100.
The coating liquid composition for forming an optical material according to claim 1, wherein a liquid at 300 ° C. is used. 6. The coating composition for forming an optical material according to claim 1, wherein the reaction is allowed to proceed while distilling alcohol and water which are by-products when the alkoxysilane is hydrolyzed and condensed. . 7. The coating composition for forming an optical material according to claim 1, wherein an acid catalyst is used when the alkoxysilane is hydrolyzed and condensed. 8. An optical material obtained by curing the coating liquid composition for forming an optical material according to any one of claims 1 to 7.