JPS61250056A - Photosensitive heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide a composition capable of giving highly heat-and solvent- resistant photosensitive colorless clear coating films of extremely high adherability to base, comprising ladder type polysiloxane, silanol compound, ammonium dichromate. CONSTITUTION:The objective composition comprising (A) a ladder type polysiloxane, (B) a silanol compound, i.e., a hydrolyzate from compound of formula R<1>SiX2 (R<1> is 1-18C alkyl, aryl, alkenyl or alkynyl; X is 1-4C alkoxyl or halogen), another hydrolyzate from compound of formula SiCOR<2>)4 (R<2> is 1-4C akyl), or a mixture thereof, and (C) ammonium dichromate. The weight ratio (A)/(B) is 8/2-3/7, that of (A+B)/(C) being 9.800/9.999-0.200/0.001.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a new and useful photosensitive heat-resistant resin composition, and more particularly, it relates to a ladder-type polysiloxane, a silanol compound, and ammonium dichromate. The present invention relates to a heat-resistant resin composition having particularly excellent adhesion and photosensitivity, comprising as an essential component a ladder-type polysiloxane particularly for forming a coating film. High durability suitable for use as a photosensitive coating solution.

It is an object of the present invention to provide a resin composition that has heat properties and provides a coating film with extremely good adhesion to a substrate.

The ladder-type polysiloxane referred to here is a highly heat-resistant material with a thermal decomposition initiation temperature of 400 to 700°C in a nitrogen atmosphere, and it is easy to form a coating film. In addition to being used as a heat-resistant interlayer insulating film for ICs and LSIs, and as an α-ray blocking protective film for memo IJ-,
Since it is colorless and transparent, it can be used as a coating film for transparent electrode substrates and glass substrates of liquid crystal assemblies, as various heat-resistant materials, or as functional materials. Because of their excellent properties, heat-resistant resin compositions can be used in a wide range of applications as described above.

[Prior art and problems to be solved by the invention]
Conventionally, the method for producing a ladder-type polysiloxane resin composition having this kind of photosensitivity is as follows: 1) A method of reacting an alkoxysilane having a (meth)acrylic group with the terminal hydroxyl group of a ladder-type polysiloxane;
2) A method in which a ladder type polysiloxane is reacted with an aromatic azide compound and/or an aromatic sulfonyl azide compound (JP-A-58-96654), or 5) A method in which ammonium dichromate is mixed into a ladder type polysiloxane. (Methods such as Japanese Unexamined Patent Publication No. 185658/1983 have been proposed.

However, in the case of methods 2) and 3) above, when an end-cage type polysiloxane is used as the ladder type polysiloxane, there is a drawback that the adhesion between the pattern obtained after photoreaction and the substrate is poor. Next, when using a polysiloxane with a terminal hydroxyl group as a ladder type polysiloxane, the adhesion of the pattern obtained after photoreaction is improved, but it has the disadvantage of being prone to cracking when exposed to high temperatures. On the other hand, in the case of method 1), the manufacturing method itself is very complicated, and furthermore, the pattern obtained after photoreaction has the disadvantage of poor heat resistance.

[Means for solving problems]

However, as a result of intensive studies by the present inventors to solve the various drawbacks of the prior art as described above, we found that a ladder-type polysiloxane having a terminal cage type and/or a terminal hydroxyl group type, a specific silanol compound, and further dichromium The composition consisting of ammonium acid not only has photosensitivity, but also does not generate cracks even at high temperatures and has extremely good adhesion to the substrate.
The present invention was completed by discovering that a colorless and transparent coating film with good solvent resistance could be provided.

That is, the present invention uses, as essential components, (A) a terminal cage type ladder type polysiloxane represented by the general formula and/or a terminal hydroxyl group type ladder type polysiloxane represented by the general formula;
B) A silanol compound and (C) Ammonium dichromate, the present invention provides a photosensitive heat-resistant resin composition that has particularly excellent adhesion and is highly heat-resistant. .

Here, the above-mentioned terminal cage type ladder type polysiloxane is synthesized, for example, by a method as disclosed in Japanese Patent Publication No. 15989/1989. That is, in this synthesis method, an intermediate compound obtained by hydrolyzing trichlorosilane represented by the general formula % [ ] is further made to 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 type polysiloxane is synthesized, for example, by the method shown in Japanese Patent Application Laid-Open No. 53-88099 and Japanese Patent Publication No. 58-50567. That is, among such synthetic methods,
The former method involves hydrolyzing the trichlorosilane R'5i (J) represented by the above general formula [v] in the presence of an amine in an ether/ketone mixed solvent; on the other hand, the latter method The method involves first hydrolyzing the trichlorosilane represented by the above general formula [v], and then dehydrating and condensing the thus obtained intermediate using a carbodiimide to increase the molecular weight.

The above-mentioned terminal cage type or terminal hydroxyl group type both ladder type polysiloxane (A) obtained in this way has the above-mentioned [acceptable] or ["I%'1 formula, where ash and R4 are respectively Compounds are substituted or unsubstituted monovalent hydrocarbon groups that may be the same or different, and typical examples of such -valent hydrocarbon groups include methyl or ethyl groups. an alkyl group such as a vinyl group, an alkenyl group such as a vinyl group, an alkynyl group such as an ethynyl group, an aryl group such as a phenyl group or a substituted phenyl group, an aromatic hydrocarbon group, and furthermore, a nitrogen group of each of these hydrocarbon groups. There are substitution products, etc.

The weight average molecular weight of the ladder type polysilosan (A) is 1X10' to 1X10' in terms of polystyrene.
It is appropriate to fall within the following range.

In addition, the above-mentioned silanol compound 'IMB) is, for example, a hydrolysis product of a silane compound represented by the general formula %[) and a hydrolysis product of a silane compound represented by the general formula %[). Among the silanol compounds (mB), preferred are the silanol compounds (mB) that have a molecule t within a range that is soluble in a solvent. These are compounds in which R1 is an alkyl group of C1 to C4, and particularly preferred are compounds in which R1 is a methyl group.

The silanol compound mB) is, for example, the above-mentioned R'
SiX.

or st (oa''), each silane compound can be easily obtained by hydrolysis in an all-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) described above should be appropriately determined depending on the purpose and use.

That is, when the proportion of the silanol compound B) increases, for example, when it is used as a coating composition.

Although the adhesion between the coating film and the substrate increases, the heat resistance deteriorates.On the other hand, if the ratio of mB) decreases, although the heat resistance improves, the coating film inevitably deteriorates. Adhesion to the substrate becomes poor.

Therefore, these ladder type polysilo Φ suns (A
) and the compound 4MB) should be determined. Furthermore, from the viewpoint of 11rM physical properties, a particularly preferable mixing ratio of Seishu N to Seishu B) is 8 in terms of heavy electric ratio. :24 to 6:7 is suitable.

On the other hand, the mixing weight ratio of both resin components Seishu A) and (B) and ammonium dichromate (C) is 9.80.
A suitable range is 0:9.999 to 0.200:0.001.

The reason for this is ammonium dichromate (when the mixing ratio of the Q component exceeds 0.200, the heat resistance and adhesion, which are the inherent characteristics of the film, cannot be obtained, and on the other hand, when it is less than 1001, it is insufficient). It becomes difficult to obtain photosensitivity,
This is because it causes inconvenience.

The reason why the ammonium dichromate exhibits photosensitivity is thought to be as follows.

That is, this dichromate ion is decomposed by light irradiation to become active ion Cr8+, and these Cr)+
exhibits a catalytic effect, and the terminal groups of the terminal hydro-group-type ladder-type polysiloxane are the same or the silanol groups of the silanol compound.

Furthermore, it is thought that condensation polymerization proceeds between the respective terminal groups, thereby causing a crosslinking reaction, thereby completely rendering the light-irradiated portion indestructible.

In addition to the above-mentioned essential components constituting the photosensitive heat-resistant resin composition of the present invention, the solvent used in preparing the composition of the present invention includes the above-mentioned terminal cage type ladder type polysiloxane and/or terminal Hydroxyl group type ladder type polysiloxane (A), silanol compound mB) and dichromated ammonium (C
Any solvent may be used as long as it dissolves one essential component.Of these, only one type of solvent component may be used, or 21 or more of them may be used in combination.

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

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

Next, ammonium dichromate, which has been previously dissolved in a small amount of water, is further diluted with alcohol or the like, and then added to the above-mentioned resin solution to form a photosensitive and highly heat-resistant resin composition.

Thereafter, the composition of the present invention thus obtained is applied to a substrate such as a glass plate using a spinner or C11 hair, and then dried to form the desired coating film.

Furthermore, a mask is attached to this coating film and it is exposed to light. After exposure, the coating film is treated with a liquid solution such as xylene or toluene.
Next, heat treatment or alkali treatment followed by heat treatment further promotes insolubilization, thus further improving
The coating pattern becomes strong.

In this way, it is said that the composition of the present invention has heat resistance, good adhesion to substrates such as glass and metal, and can easily produce negative patterns with good solvent resistance. It has characteristics.

For this purpose, the photosensitive heat-resistant resin composition of the present invention
Electronics, such as heat-resistant interlayer insulation films such as SI
It can be used as a heat-resistant insulating film for devices, and when a coating film is formed from the composition of the present invention, it can be used for coating glass substrates from where it provides a colorless, 3-bright Wx, or as a transparent electrode base for liquid crystal assemblies. It can be used in a wide variety of applications, including as coatings on materials, and as coatings on solar system equipment and equipment.

The composition of the present invention has photosensitivity by itself, but in order to further improve the photosensitivity, a sensitizer such as benzoin methyl ether, benzophenone, diphenyl sulfide or methylene blue or There is nothing to prevent the addition and blending of a type of compound called a photosensitive dye into the composition of the present invention.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.
゜All bases are based on weight.

Example 1 A terminal cage type ladder type polysiloxane having a phenyl group with i; of 5.5 x 10'' [hereinafter referred to as polysiloxane (A
-1). ] and a silanol compound (hereinafter abbreviated as silanol compound (B-1)) which is a hydrolysis product of methyltriethoxysilane and has a Mw of 2.000. ], 0.5 parts of a 10% aqueous solution of ammonium dichromate was prepared in advance, diluted 10 times with ethanol, 0.25 parts of the solution obtained, and further 11 parts of tetrahydrofuran. The desired resin composition was obtained by mixing the following.

Next, this composition was spin-coated onto a glass substrate using a spinner at 5,000 rpm, and the composition was coated at 300 rpm at room temperature.
Let dry for a minute. Thereafter, the thus obtained coating was exposed for 60 seconds to a high-pressure mercury lamp. After exposure, the film is developed with toluene, and then the developed pattern is 1,8-diazabicyclo-[5,4,O]-7-undecene C, hereinafter abbreviated as DRU. ) in a 1% toluene solution and then dried at room temperature. Thereafter, it was heated to 120° C. for 1 hour to completely cure it and obtain the desired pattern.

The pattern obtained here has excellent adhesion to the glass substrate, good solvent resistance, colorimetric transparency, and even when exposed to high temperature conditions such as 300°C for 1 hour,
No change could be expected in both adhesion and transparency.

Example 2 A terminal hydroxyl group type ladder type box with a methyl group and a phenyl group where i is lX10'! 1 siloxane [hereinafter abbreviated as polysiloxane (A-2). ] and Mw is t
ooo, a hydrolysis product of tetraethoxysilane [
Hereinafter, it will be abbreviated as silanol compound (B-2). ] no n
, 3 parts of Q, 25 parts of a solution obtained by diluting a 10% aqueous solution of ammonium dichromate prepared in advance with ethanol 10 times, and tetrahydrofuran/n-
A photosensitive resin composition was obtained by mixing with 5 parts of a mixed solvent of butanol=1/1 (volume ratio).

Next, this composition was applied onto a glass substrate using a spinner.
The coating was spin-coated at 0 rpm, dried at room temperature for 30 minutes, and then exposed to a high-pressure water lamp for 50 seconds.

After exposure, it is developed with a mixed solvent of toluene/xylene = 1/1' (volume ratio), and the developed pattern thus obtained is mixed with 2% triethanolamine? The sample was immersed in a mixed solvent containing 1/1 (volume ratio) luene/xylene, and then dried at room temperature.

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

The pattern obtained here has excellent adhesion to the glass substrate, good solvent resistance, and is colorless and transparent.
Also. Even when placed under high temperature conditions of 300° C. for 1 hour, no change was observed in the adhesion and transparency.

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

The performance of the 7fL+5'a pattern is all evaluated in the same table.

Comparative Example 1 1 part of a phenyl group-containing end-cage polysiloxane having a maximum size of 5.5×10′, 0.15 part of a solution obtained by diluting a 10% aqueous solution of ammonium dichromate 10 times with ethanol, and A comparative photosensitive resin composition was obtained by mixing 11 parts of tetrahydrofuran.

Next, this composition was applied onto a 3.0-tone glass substrate using a spinner.
The coating was spin-coated under conditions of 0 Orpm, dried at room temperature for 30 minutes, and then exposed to a high-pressure mercury lamp for 90 seconds.

Thereafter, it was developed with toluene to obtain the desired pattern, and subsequently heated to 100° C. for 30 minutes.

When the thus obtained pattern was heated at a high temperature of 300° C. for 1 hour, small cracks were formed in the pattern, and the adhesion between the glass substrate and this pattern was poor.

Comparative Example 2 A 10% aqueous solution of 1 part 1 dichromium 51 ammonium of a terminal hydroxyl group-type ladder type polysiloxane containing a methyl group and an ethyl group where 4 is l 25 parts of xylene/n-butanol = 1/1 (volume ratio) mixed solvent.
A comparative photosensitive composition was obtained by mixing 5 parts.

Next, this composition was subjected to post-treatment in the same manner as in Comparative Example 1, except that the mist light conditions using a high-pressure mercury lamp were changed to a 6-part scale, and the developing solution was changed to use a Φ cylinder. , when placed under high temperature conditions of 300° C. for 1 hour, a pattern containing small glue racks was obtained throughout.

〔Effect of the invention〕

As is clear from the results in Table 1, the photosensitive heat-resistant W composition of the present invention has excellent % adhesion and is colorless and transparent.

Claims (1)

[Claims] 1. A photosensitive heat-resistant resin composition with particularly excellent adhesion, comprising (A) a ladder-type polysiloxane, (B) a silanol compound, and (C) ammonium dichromate as essential components. thing. 2. The above-mentioned silanol compound (B) has the general formula R^1
SiX_3 [I] [However, R^1 in the formula represents an alkyl group, aryl group, alkenyl group, or alkynyl group of C_1 to C_1_6, and X represents an alkoxyl group of C_1 to C_4 or a halogen atom. ] The composition according to claim 1, which is a hydrolysis product of a compound represented by: 3. The silanol compound (B) described above has the general formula Si (
OR^2)_4 [II] [However, R^2 in the formula represents an alkyl group of C_1 to C_4. ] The composition according to claim 1, which is a hydrolysis product of a compound represented by: 4. The above-mentioned silanol compound (B) has the general formula R^1
SiIX_3[I] [However, R^1 in the formula represents an alkyl group, aryl group, alkenyl group, or alkynyl group of C_1 to C_1_8, and X represents an alkoxy group of C_1 to C_4 or a halogen atom. ] A hydrolysis product of a compound represented by the general formula Si(O
R^2)_4 [II] [However, R^2 in the formula represents an alkyl group of C_1 to C_4. ] A composition according to claims, characterized in that it is a mixture of a compound represented by the above with a hydrolysis product.