JPH0717835B2 - Photosensitive heat-resistant resin composition - Google Patents

Description

The present invention relates to a novel and useful photosensitive heat-resistant resin composition. More specifically, the present invention comprises a specific ladder-type polysiloxane, a specific silanol compound, and ammonium dichromate, respectively, as essential components, and particularly, excellent adhesion, The present invention relates to a heat resistant resin composition having photosensitivity.

The object of the present invention is to provide the ladder-type polysiloxane having a high heat resistance, which is particularly suitable for use as a photosensitive coating solution for forming a coating film, and to a substrate. And to provide a resin composition capable of giving a coating film having extremely good adhesion.

The ladder-type polysiloxane referred to here refers to a high heat-resistant material having a thermal decomposition initiation temperature of 400 to 700 ° C. in a nitrogen atmosphere, and as such, because it is easy to form a coating film, As a heat-resistant interlayer insulating film for ICs and LSIs, and as an α-ray blocking protective film for memories, in addition to being colorless and transparent, it forms a coating film on transparent electrode substrates and glass substrates of liquid crystal assemblies. As a material, various heat resistant materials, or use as a functional material can be considered, but the photosensitive heat resistant resin composition of the present invention is intended for a wide range of applications as described above because of its excellent properties. .

[Conventional technology]

Heretofore, as a method for preparing this type of photosensitive ladder-type polysiloxane resin composition, 1) a method of reacting an alkoxysilane having a (meth) acryl group with a terminal hydroxyl group of the ladder-type polysiloxane, 2 ) A method of reacting a ladder type polysiloxane with an aromatic azide compound and / or an aromatic sulfonyl azide compound (JP-A-58-96654), or 3) a method of mixing ammonium bichromate with the ladder type polysiloxane ( Methods such as JP-A-58-185658) have been proposed.

However, in the case of the above methods 2) and 3), when the terminal cage type is used as the ladder type polysiloxane, the adhesion between the pattern obtained after the photoreaction and the substrate is poor. However, when a terminal hydroxyl group type is used as the ladder-type polysiloxane, the adhesion of the pattern obtained after photoreaction is improved, but there is a drawback that cracks easily occur when exposed to high temperature. On the other hand, in the case of the above method 1), the manufacturing method itself is very complicated, and the pattern obtained after the photoreaction is inferior in heat resistance.

[Problems to be solved by the invention]

As described above, the conventional ladder-type polysiloxane resin composition having photosensitivity is inferior in heat resistance and substrate adhesion, which is a major drawback or difficulty.

However, the present inventors have earnestly studied for the purpose of providing a novel photosensitive heat-resistant resin composition, which is excellent not only in heat resistance but also in particular in adhesiveness. I went.

[Means for solving problems]

Therefore, as a result of intensive studies, the inventors of the present invention have solved the various drawbacks of the prior art as described above.
A composition comprising a specific ladder-type polysiloxane having a terminal cage type and / or a terminal hydroxyl group type, a specific silanol compound, and ammonium dichromate has photosensitivity, and in particular, at a high temperature. It was found that even underneath, cracks did not occur, and in addition to having extremely good adhesion to the base material, solvent resistance, etc., it also provided a colorless and transparent coating film. Thus, the present invention has been completed here.

That is, the present invention, as an essential component, the general formula [Wherein R ³ and R ⁴ in the formula each represent a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and n is 4,000 or less. It shall be an integer. ] A terminal cage type ladder type polysiloxane represented by
Or general formula [Wherein R ³ and R ⁴ in the formula each represent a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and m is 4,000 or less. It shall be an integer. ] A terminal hydroxyl group type ladder polysiloxane (A) represented by
And R ¹ SiX ₃ [wherein R ¹ is an alkyl group, aryl group, alkenyl group or alkynyl group represented by C _{1 to} C ₁₈ , and X is
It represents an alkoxyl group represented by C _{1 to} C ₄ or a halogen atom. Hydrolysis products of the compounds represented by] the general formula Si (OR ²⁾ ₄ [however, R ² in the formula denote the C ₁ -C ₄ becomes an alkyl group. ] A silanol compound (B) typified by a hydrolysis product of the compound represented by and / or a mixture thereof, and ammonium dichromate (C) are contained, and the ladder-type poly [(A) + (B)] :( C) of both components of the siloxane (A) and the silanol compound (B) and the ammonium dichromate (C)
Is in the range of 9.800: 0.200 to 9.999: 0.001, that is, [(A) + (B)] :( C) is [(A) + (B )]:
It is intended to provide a highly heat-resistant photosensitive heat-resistant resin composition having a mixing weight ratio of (C) within the range of 9.999: 0.001, which is particularly excellent in adhesiveness. The present invention is intended to provide a resin composition which itself has photosensitivity and is highly heat resistant, which is useful as a coating liquid composition having extremely good adhesion.

Here, the above-mentioned terminal cage type ladder-type polysiloxane is synthesized by the method described in, for example, Japanese Patent Publication No. 40-15989. That is, the synthetic method is represented by the general formula R ⁵ SiCl ₃ [V] [wherein R ⁵ represents a monovalent hydrocarbon group. ] The intermediate compound obtained by hydrolyzing trichlorosilane represented by is to further have a high molecular weight in the presence of an alkali catalyst such as potassium hydroxide,
In this way, the desired end cage type ladder type polysiloxane can be easily obtained.

On the other hand, the above-mentioned terminal hydroxyl group type ladder polysiloxane is disclosed, for example, in JP-A-53-88099 and JP-B-58-5.
It is synthesized by the method described in Japanese Patent No. 0567. That is, of the synthesis methods, the former method is
In the presence of an amine, trichlorosilane R ⁵ SiCl _{2 represented} by the general formula [V] above is hydrolyzed in an ether-ketone mixed solvent, while the latter method is described above. This trichlorosilane represented by the general formula [V] is first hydrolyzed, and then the intermediate thus obtained is further used with carbodiimides
That is, by hydrolyzing it, it becomes a polymer.

It is obtained in this way. The compound of the above terminal ladder type or terminal hydroxyl group type both ladder type polysiloxane (A) is the same as those of the above formula [III] or [IV], in which R ³ and R ⁴ are the same. There are various compounds such as substituted or unsubstituted monovalent hydrocarbon groups which may be different from each other. Typical examples of the monovalent hydrocarbon group include a methyl group or an ethyl group. An alkyl group such as, an alkenyl group such as a vinyl group,
Examples include an alkynyl group such as an ethynyl group, an aryl group such as a phenyl group or a substituted phenyl group, that is, an aromatic hydrocarbon group, and a halogen-substituted product of each of these hydrocarbon groups.

The weight average molecular weight of the ladder-type polysiloxane (A) is appropriately in the range of 1 × 10 ³ to 1 × 10 ^{6 in} terms of polystyrene.

Further, the silanol compound (B) described above refers to, for example, a compound represented by the general formula R ¹ SiX ₃ [I] [wherein R ¹ represents an alkyl group, an aryl group, an alkenyl group or an alkynyl group represented by C _{1 to} C ₁₈ , Also, X is
It represents an alkoxyl group represented by C _{1 to} C ₄ or a halogen atom. ] And / or the general formula Si (OR ² ) ₄ [II] [wherein R ^{2 in} the formula represents an alkyl group of C _{1 to} C _4] . A hydrolyzate of a silane compound represented by the formula [1], which has a molecular weight in the range of being soluble in a solvent, is preferred as the silanol compound (B). ] A compound in which R ¹ directly bonded to a silicon atom (Si) in the formula is an alkyl group of C _{1 to} C ₄ , and particularly preferred is a compound in which R ¹ is a methyl group. .

The silanol compound (B) is, for example, the above-mentioned R ¹ Si.
It can be easily obtained by hydrolyzing each silane compound of X ₃ or Si (OR ² ) ₄ in an organic solvent in the presence of an acid or a base.

The mixing ratio of the ladder-type polysiloxane (A) and the silanol compound (B) should be appropriately determined according to the purpose and application.

That is, when the proportion of the silanol compound (B) is large, for example, when used as a coating liquid composition, the adhesion between the coating film and the substrate increases, but the heat resistance deteriorates. On the contrary, when the ratio of the compound (B) is small, the heat resistance is good, but the adhesion between the coating film and the substrate is inevitably deteriorated.

Therefore, the mixing ratio of both components of the ladder-type polysiloxane (A) and the compound (B) should be determined in consideration of such a balance between both properties of adhesion and heat resistance. From the viewpoint of coating film physical properties, a particularly preferable mixing ratio of the component (A) to the component (B) is appropriately within the range of 8: 2 to 3: 7 by weight.

On the other hand, the mixing weight ratio of both resin components (A) and (B) and ammonium dichromate (C) is 9.800:
The suitable range is 0.200 to 9.999: 0.001.

The reason for this is that when the mixing ratio of the component (C), which is ammonium dichromate, exceeds 0.200, it becomes difficult to obtain the heat resistance and adhesion that are the original characteristics of the coating, and conversely, when it is less than 0.001, sufficient photosensitivity is achieved. This is because it becomes difficult to obtain the above, which is a disadvantage.

Then, the reason why the photosensitivity is realized by the ammonium dichromate is considered as follows.

That is, this dichromate ion is decomposed by light irradiation to become an active ion Cr ³⁺ , and such Cr ³⁺ exhibits a catalytic action, and the terminal groups of the terminal hydroxyl group-type ladder-type polysiloxane or silanol compounds are It is considered that the condensation irradiation through the silanol groups of, and further through the respective terminal groups proceeds, and thus the crosslinking reaction is caused to insolubilize the light-irradiated portion.

In addition to the above-mentioned essential components constituting the photosensitive heat-resistant resin composition of the present invention, as the solvent used in preparing the composition of the present invention, the above-mentioned terminal cage type ladder-type polysiloxane and / or terminal is used. Any one may be used as long as it dissolves various ladder-type polysiloxanes (A), which are hydroxyl-type ladder-type polysiloxanes, silanol compounds (B), and various essential components, such as ammonium dichromate (C). Examples of the solvent include known solvents such as alcohols, esters, ketones, ethers and aromatic hydrocarbons, and the solvent component may be used alone or in combination of two or more.

Next, in applying the photosensitive heat-resistant resin composition of the present invention, a method for forming a coating film and a method for exposing the coating film to light when used as a coating liquid composition will be briefly described.

First, the terminal cage type ladder-type polysiloxane and / or the terminal hydroxyl group-type ladder-type polysiloxane and the silanol compound are dissolved in a suitable solvent to obtain a so-called resin solution.

Next, ammonium dichromate previously dissolved in a small amount of water is further diluted with alcohol or the like, and this is added to the above resin solution to obtain a photosensitive and heat resistant resin composition.

Then, the composition of the present invention thus obtained is applied to a substrate such as a glass plate by a spinner or a brush, and then dried to obtain a desired coating film.

Further, a mask is attached to this coating film to expose it. The exposed coating film is treated with a developer such as xylene or toluene,
Next, heat treatment or alkali treatment is performed, and then heat treatment is further performed to further promote insolubilization, and thus, further,
The coating pattern becomes strong.

As described above, the composition of the present invention has heat resistance, good adhesion to a substrate such as glass or metal, and can easily obtain a negative pattern having good solvent resistance. Is to have.

Therefore, the photosensitive heat-resistant resin composition of the present invention is
As a heat-resistant insulating film for electronic devices such as a heat-resistant interlayer insulating film, and when a coating film is formed from the composition of the present invention, a colorless transparent film is applied to a glass substrate. It is used for a wide variety of purposes, for example, as a coating film forming material on a transparent electrode substrate of a liquid crystal assembly, and as a surface protecting coating film forming material for solar system equipment and equipment.

Although the composition of the present invention has photosensitivity by itself, when it is desired to further improve the photosensitivity, the composition such as benzoin methyl ether, benzophenone, diphenyl sulfide or methylene blue is added. It does not prevent addition of a compound of a kind called a sensitizer or a luminescent dye to the composition of the present invention.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, all parts and% are based on weight unless otherwise specified.

Example 1 ▲ ▼ has a phenyl group of 5.5 × 10 ⁵ and has a terminal cage type ladder-type polysiloxane [hereinafter, referred to as polysiloxane (A-
Abbreviated as 1). ] Part, and ▲ ▼ becomes 2,000,
A silanol compound that is a hydrolysis product of methyltriethoxysilane [hereinafter, abbreviated as silanol compound (B-1). ], And a 10% aqueous solution of ammonium dichromate was prepared in advance, and 0.25 parts of the solution obtained by diluting this 10 times with ethanol was mixed with 11 parts of tetrahydrofuran. The desired resin composition was obtained.

This composition is then applied to a glass substrate using a spinner.
It was spin-coated at 3,000 rpm and dried at room temperature for 30 minutes. Thereafter, the coating film thus obtained was exposed for 60 seconds by a high pressure mercury lamp. After exposure, develop with toluene, then develop the pattern with 1,8-diazabicyclo-
[5,4,0] -7-Undecene (hereinafter abbreviated as DBU)
It was immersed in a 1% toluene solution of and then dried at room temperature. Then, it was heated at 120 ° C. for 1 hour to be completely cured to obtain a desired pattern.

The pattern obtained here had excellent adhesion to the glass substrate, good solvent resistance, and was colorless and transparent.
Also, even if exposed to high temperature conditions of 300 ° C for 1 hour,
No change was observed in its adhesiveness and transparency.

Example 2 (2) is a terminal hydroxyl group ladder type polysiloxane having a methyl group and a phenyl group of 1 × 10 ⁴ [hereinafter abbreviated as polysiloxane (A-2). ] Part of, ▲
The hydrolysis product of tetraethoxysilane having a ▼ of 1,000 [hereinafter, abbreviated as silanol compound (B-2). ]
Of 0.3%, and 0.25 part of a solution obtained by diluting a previously prepared 10% aqueous solution of ammonium dichromate 10 times with ethanol, tetrahydrofuran / n-butanol =
5 parts of a mixed solvent of 1/1 (volume ratio) was mixed to obtain a photosensitive resin composition.

Then, this composition was spun on a glass substrate with a 3,000r
It was spin coated under conditions of pm, dried at room temperature for 30 minutes and then exposed with a high pressure mercury lamp for 50 seconds.

After exposure, it was developed with a mixed solvent of toluene / xylene = 1/1 (volume ratio), and the development pattern thus obtained was 2
% Toluene / xylene with triethanolamine =
It was immersed in a 1/1 (volume ratio) mixed solvent and then dried at room temperature.

Then, it was heated at 150 ° C. for 1 hour to obtain a completely cured target pattern.

The pattern obtained here had excellent adhesion to a glass substrate, good solvent resistance, and was colorless and transparent.
Also, even if it is placed under high temperature conditions of 300 ° C for 1 hour,
No change was observed in such adhesion and transparency.

Examples 3 to 5 The intended photosensitive resin composition was obtained in the same manner as in Example 1 except that the composition ratio was changed as shown in Table 1, and then the intended pattern was obtained. .

The table below summarizes the performance evaluations for each pattern.

Comparative Example 1 A solution obtained by diluting 1 part of phenyl group-containing cage polysiloxane having a phenyl group of 5.5 × 10 ^{5 and} a 10% aqueous solution of ammonium dichromate with ethanol 10 times.
15 parts and 11 parts of tetrahydrofuran were mixed to obtain a photosensitive resin composition for comparison.

Then, this composition was spun on a glass substrate with a 3,000r
It was spin coated under the condition of pm, dried at room temperature for 30 minutes, and then exposed with a high pressure mercury lamp for 90 seconds.

After that, it was developed with toluene to obtain a desired pattern, and subsequently heated at 100 ° C. for 30 minutes.

When the pattern thus obtained was placed under a high temperature condition of 300 ° C. for 1 hour, a small crack was included in the pattern, and the adhesion between the glass substrate and this pattern was poor.

Comparative Example 2 A solution prepared by diluting 1 part of a terminal hydroxyl group type ladder polysiloxane containing 1 × 10 ⁴ methyl groups and ethyl groups and a 10% ammonium dichromate aqueous solution with ethanol 10 times. Was mixed with 2.5 parts of a mixed solvent of xylene / n-butanol = 1/1 (volume ratio) to obtain a photosensitive composition for comparison.

Next, this composition was post-treated in the same manner as in Comparative Example 1 except that the exposure condition with a high-pressure mercury lamp was changed to 60 seconds and xylene was used as a developing solution, and the temperature was 300 ° C. It was obtained as a pattern with small cracks all over when it was placed under a high temperature condition of 1 hour.

[Effects of the Invention] As is clear from the results shown in Table 1, it is known that the photosensitive heat-resistant resin composition of the present invention has excellent adhesion and is colorless and transparent.

Claims (1)

[Claims] 1. A compound represented by the general formula [Wherein R ³ and R ⁴ in the formula each represent a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and n is 4,000 or less. It shall be an integer. ] A terminal cage type ladder type polysiloxane represented by
Or general formula [Wherein R ³ and R ⁴ in the formula each represent a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and m is 4,000 or less. It shall be an integer. ] A terminal hydroxyl group type ladder polysiloxane (A) represented by
And R ¹ SiX ₃ [wherein R ¹ is an alkyl group, aryl group, alkenyl group or alkynyl group represented by C _{1 to} C ₁₈ , and X is
It represents an alkoxyl group represented by C _{1 to} C ₄ or a halogen atom. Hydrolysis products of the compounds represented by] the general formula Si (OR ²⁾ ₄ [however, R ² in the formula denote the C ₁ -C ₄ becomes an alkyl group. ] A silanol compound (B) represented by a hydrolysis product of the compound represented by and / or a mixture thereof and ammonium dichromate (C) are contained, and the ladder-type poly [(A) + (B)] :( C) of both components of the siloxane (A) and the silanol compound (B) and the ammonium dichromate (C)
A photosensitive heat-resistant resin composition, characterized in that the mixed weight ratio thereof is from 9.800: 0.200 to 9.999: 0.001.