JPH09241385A - Fluorinated polysilane copolymer, silicon polymer composition and production of cross-linked fluorinated siloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorinated polysilane copolymer for producing a cross- linked fluorinated siloxane having a low permittivity and a high Tg by combining specific aromatic silane structural units with fluorinated aromatic silane structural units. SOLUTION: This copolymer comprises structural units represented by formula I (wherein A<1> r is an aromatic group) and structural units represented by at least one of formulae II-V (wherein A<2> r is a fluorinated aromatic group; and R<1> is a fluorinated hydrocarbon group) and contains 10-90% structural units of formula I. An organosilicon compound film composed primarily of the above copolymer is formed on a substrate and exposed to a light in a given wavelength range. After the exposure, the film is heat-treated and then developed by removing unexposed parts by dissolving the same in an organic solvent to give a cross-linked fluorinated siloxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing polysilane and a silicon polymer composition for producing a fluorine-containing siloxane crosslinked body which can be used in electronic devices such as semiconductor devices and liquid crystal display elements, and a fluorine-containing siloxane crosslinked body. Manufacturing method.

[0002]

2. Description of the Related Art In the manufacture of a semiconductor device, a liquid crystal display device, etc., an insulating film is usually formed on the surface of a semiconductor element, a liquid crystal display device, wiring, etc. to ensure insulation from other regions. There is. The insulating film for covering the wiring is formed by, for example, a method of depositing a silicon compound by CVD, applying organosilica sol or the like, and then heating and drying.

In some cases, it is required to pattern the insulating film formed on the wiring to form the contact hole, but the insulating film formed by such a method cannot be easily patterned. . That is, a resist pattern is formed on the formed insulating film,
After patterning the insulating film using this resist pattern as an etching mask, the resist pattern must be removed. Since the process is complicated as described above, the insulating film pattern cannot be obtained at low cost.

On the other hand, a technique has been proposed in which the photosensitivity of polysilane is used to form a pattern of polysilane and then the pattern is heated and insulated to simplify the process. That is, since polysilane has a property that its molecular weight is reduced by exposing it to ultraviolet rays, it is possible to form a polysilane film and selectively expose it to a polar solvent such as alcohol or ketone. A pattern is formed by selectively dissolving and developing.
Subsequently, if necessary, the pattern is irradiated with ultraviolet rays, and then heated and dried to polysiloxane siloxane to obtain an insulating film pattern.

However, since the pattern here is composed of one-dimensional siloxane obtained by heating and drying polysilane, there is a problem in reliability such as heat resistance when used as an insulating film. .

More recently, low-dielectric-constant insulating films have attracted particular attention as passivation films and interlayer insulating films, but conventional low-dielectric-constant materials such as fluororesins have glass transition temperatures (Tg). It was low and none of these applications could perform well. In addition, conventional fluorine-containing resins generally have insufficient adhesion to the substrate due to the volatility of fluorine, and improvements have been demanded.

[0007]

As described above, a material for producing an insulating film having a low dielectric constant and a high Tg has not yet been obtained, and moreover, such an insulating film can be patterned easily and accurately. No method of manufacturing has been found.

Therefore, the present invention has a low dielectric constant and a high T.
An object of the present invention is to provide a fluorine-containing polysilane copolymer for producing a fluorine-containing siloxane cross-linked product having g.

Further, according to the present invention, the fluorine-containing siloxane crosslinked product having such a low dielectric constant and high Tg can be manufactured by patterning with high accuracy without complicated steps as necessary. It is an object of the present invention to provide a method for producing a crosslinked fluorine-containing siloxane.

Further, the present invention has a low dielectric constant and a high Tg.
The present invention provides a silicon polymer composition for producing a crosslinked fluorine-containing siloxane having:

[0011]

In order to solve the above problems, the first invention is selected from the structural unit represented by the following general formula (1) and the following general formulas (2) to (4). Provided is a fluorine-containing polysilane copolymer comprising a structural unit represented by at least one kind.

[0012]

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In the above general formula, Ar ¹ is an aromatic group,
It may be substituted with a substituent containing no fluorine, Ar
² is a fluorine-substituted aromatic group, and R ¹ is a fluorine-substituted hydrocarbon group.

The second invention is a film forming step of forming an organic silicon compound film mainly composed of a fluorine-containing polysilane composed of a polymer represented by the following general formula (5) on a substrate,
A method for producing a crosslinked fluorine-containing siloxane, which comprises a three-dimensional process of heating and drying the organic silicon compound film.

[0015]

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In the above general formula, Ar ¹ is an aromatic group,
It may be substituted with a substituent containing no fluorine, Ar
² is a fluorine-substituted aromatic group, and R ¹ is a fluorine-substituted hydrocarbon group. Further, n, m, l and k are m + l +
It is an integer that satisfies the relations of k> 0 and n + 1> 0.

Further, a third invention is a silicon polymer represented by any of the following general formulas (6) and (8) to (10), and a polymerizable fluorine compound represented by the following general formula (7). There is provided a silicon polymer composition containing:

[0018]

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In the above formula, Ar ³ is a substituted or unsubstituted aromatic group, R ⁵ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R ⁶ is —OR ⁵ ′ (R ^{5 ′} is a hydrogen atom) Or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted hydrocarbon group. n represents the degree of polymerization.

[0020]

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In the above general formula (6), R ³ is a hydrogen atom or a methyl group, R ⁴ is a fluorine-substituted alkyl group, and A is a single bond or an ester bond.

Here, in the composition of the third invention,
A silicon polymer represented by the general formula (9), and (1
When the silicon polymer represented by 0) is used, a compound that generates an acid upon exposure or heating (hereinafter referred to as an acid generation catalyst) and a compound that generates a radical upon exposure or heating (hereinafter referred to as a radical generation catalyst) At least one of the compounds). Further, such an acid-generating catalyst and a radical-generating catalyst have a silicon polymer represented by the above general formula (6) from the viewpoint of accelerating the crosslinking of the silicon polymer and the polymerization of the polymerizable fluorine compound during the production of the fluorine-containing siloxane crosslinked product. It is also preferable to add the compound represented by the formula or the compound represented by the general formula (8). Note that the exposure here means ultraviolet rays, deep
The irradiation with light such as UV light is not particularly limited, and any acid or radical may be generated by irradiation with actinic radiation such as electron beam (EB), X-ray, or ion beam.

The present invention will be described in detail below.

In the fluorine-containing polysilane of the first invention, Ar ^{1 in} the general formula (1) is, for example,
Examples thereof include a phenyl group, a naphthyl group, an anthranyl group, and a phenethyl group. These aromatic groups are alkyl groups having 1 to 12 carbon atoms, halogen atoms other than fluorine,
It may be substituted with an organic group such as an alkoxy group, a nitro group, an amino group, a hydroxyl group, and a cyano group.

The proportion of the structural unit represented by the general formula (1) is from 10 to 90 in all the structural units constituting the copolymer.
It is preferably set to%. If it is less than 10%,
The adhesiveness between the obtained crosslinked fluorosiloxane and the substrate tends to decrease, while when it exceeds 90%, the dielectric constant does not decrease so much.

As R ¹ in the general formulas (2) and (3), a fluorine-containing alkyl group represented by CH ₂ C (R ³ ) H-A-R ⁴ is preferable. Here, R ³ , R ⁴ , and A are the same as those in the above general formula (7). Examples of Ar ² in the general formulas (3) and (4) include those in which a fluorine-containing alkyl group is introduced into the aromatic group exemplified as Ar ¹ as described above. At this time, the fluorine-containing alkyl group is preferably introduced at a position where there is little steric hindrance.

The fluorine-containing polysilane copolymer of the present invention is
For example, reduction polymerization of dichlorosilane corresponding to the structural unit represented by the general formula (1) and the structural unit represented by at least one selected from the general formulas (2) to (4), or A homopolymer having a structural unit represented by the formula (1) and a polymerizable fluorine-containing compound CH
It can be easily synthesized by adding ₂ = CR ³ -A-R ⁴ to introduce a fluorine-containing alkyl group.

Here, Ar ¹ SiH ₃ is subjected to a dehydrogenation reaction or electrolytic polymerization in the presence of a titanium or zirconium catalyst, and then a fluorine-containing alkyl group is introduced into the obtained polymer having a Si—H bond. The method is particularly suitable without contamination with metallic sodium.

An example of the method for synthesizing the fluorine-containing polysilane copolymer of the present invention will be described below.

First, in a measuring flask in which argon was replaced,
Zirconocene dichloride and diethyl ether are received and stirred. Then, the eggplant flask is cooled to about −78 to 0 ° C. and, for example, an ether solution of methyllithium is added.
Add dropwise over 5-10 minutes. Here, the concentration of methyllithium is preferably about 1 to 2 mol / liter. Further, the mixture is stirred for 30 to 90 minutes, the solvent is removed by an evaporator, and the zirconocene dimethyl is isolated by sublimation.

Next, a predetermined amount of zirconocene dimethyl was placed in a three-necked flask which had been purged with argon, and then a predetermined amount of phenylsilane was dropped therein by a dropping funnel. After reacting for 20 to 60 minutes, it is heated to 40 to 80 ° C., reacted for 2 to 8 hours, and reprecipitated with methanol 3 to 5 times to obtain a polyphenylsilane represented by the following general formula (a-1). Is obtained.

[0032]

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In the above formula, n represents the degree of polymerization.

The polyphenylsilane obtained here is
The average molecular weight is preferably about 700 to 1,000,000.

Next, the obtained polyphenylsilane, azobisisobutyronitrile (AIBN) and the polymerizable fluorine-containing compound represented by the following general formula (b-1) were placed in a round-bottomed flask, and the round-bottomed flask was filled with the liquid. Cool with nitrogen and degas with a vacuum pump. Here, the compounding amount of the polymerizable fluorine-containing compound is 5 to 9 with respect to the structural unit of polyphenylsilane.
It is preferably set within the range of 5 mol%. This is because when the compounding amount of the polymerizable fluorine-containing compound is out of this range, the structural unit represented by the general formula (1) as described above is 10 to 90% of the total structural units, and the fluorine-containing polysilane copolymerization weight is This is because it becomes difficult to obtain a coalescence.

[0036]

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In the above formula, n is an integer.

The mixture is then refluxed for 2-6 hours,
By concentrating with an evaporator and reprecipitating with methanol, a fluorinated polysilane copolymer represented by the following general formula (c-1) can be obtained.

[0039]

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In the above formula, m and k represent the degree of polymerization.

Alternatively, the fluorine-containing polysilane copolymer of the present invention can be synthesized as follows.

First, the following general formula (d
-1) in a diethyl ether solution of a fluorine-containing compound, at a temperature of -78 to -20 ° C, a predetermined amount of t-BuLi (t-
Bu is a t-butyl group), and the solution is added dropwise to 30 to 12
Incubate for 0 minutes.

[0043]

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In the above formula, n is an integer.

Thereafter, the solution is returned to room temperature, the reaction mixture is placed in a dropping funnel, and the solution is dropped into an eggplant flask containing a predetermined amount of tetrachlorosilane under an argon atmosphere. Further, the reaction is carried out for 0.5 to 2 hours, and the following general formula (e
The compound represented by -1) is obtained.

[0046]

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This compound is dissolved in a solvent such as ether,
Introduce LiAlH into an eggplant flask under argon atmosphere.
₄ Add ether solution. After reacting at room temperature for 0.5 to 2 hours, the mixture is refluxed for 1 to 4 hours, concentrated and distilled to obtain a compound represented by the following general formula (f-1).

[0048]

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Further, zirconocene dimethyl is stored in a three-necked flask which has been purged with argon. Here, the compound represented by the general formula (f-1) and phenylsilane are mixed and added dropwise with a dropping funnel. After reacting for 20 to 60 minutes, it is heated to 40 to 80 ° C. and reacted for 2 to 8 hours, and reprecipitated with methanol to give a fluorine-containing polysilane copolymer represented by the following general formula (g-1). can get.

[0050]

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In the above formula, m and k represent the degree of polymerization.

The molecular weight of the fluorine-containing polysilane copolymer of the present invention is preferably 700 to 1,000,000, more preferably 5,000 to 20,000. Molecular weight is 7
If it is less than 00, the durability of the formed film may be lowered, while if it is more than 1,000,000, the solubility of the fluorine-containing polysilane in the solvent may be lowered to make film formation difficult.

Examples of the fluorine-containing polysilane copolymer of the present invention will be given below.

[0054]

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[0055]

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[0056]

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[0057]

[Chemical 21]

[0058]

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[0059]

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[0060]

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[0061]

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The fluorine-containing polysilane copolymer of the first invention comprises a structural unit having no hydrogen and an aromatic group having a hydrogen atom directly bonded to a silicon atom in its side chain and a silicon atom in its side chain. And a structural unit having a bonded fluorine-containing substituent.

When a film containing such a fluorine-containing polysilane copolymer is formed and subjected to heat treatment to produce a fluorine-containing crosslinked product, hydrogen atoms contribute to three-dimensional crosslinkage, resulting in a film of the obtained film. Increases durability and mechanical strength. Meanwhile,
The presence of fluorine atoms can ensure a low dielectric constant. Moreover, at this time, since the structural unit containing no fluorine and the structural unit containing fluorine cause phase separation, the region composed of the structural unit containing fluorine is
Maintains high adhesion between the fluorine-containing siloxane crosslinked product and the substrate. Therefore, the fluorine-containing siloxane crosslinked product produced using the fluorine-containing polysilane copolymer of the first invention has a low dielectric constant, a high glass transition temperature (Tg), and an excellent adhesion to the substrate. Is also excellent,
It is most suitable as a passivation film and an interlayer insulating film.

Next, the method for producing the fluorine-containing siloxane crosslinked product of the second invention will be described in detail.

In the method of the second invention, the fluorinated polysilane represented by the above general formula (5) can be used. This fluorinated polysilane is obtained by combining the structural units represented by the above general formulas (1) to (4). The minimum element here is at least one structural unit selected from the general formulas (1) and (4) and at least one structural unit selected from the general formulas (2) and (3). Copolymer; or a homopolymer of the structural unit represented by the general formula (4).

The fluorine-containing polysilane used in the second invention preferably satisfies the following conditions. That is, in all structural units, general formulas (2) to (4)
The total amount of structural units represented by is 10% or more,
And the structural unit represented by the general formula (1) and the general formula (4)
The total amount with the structural unit represented by is 5% or more.

When the total amount of the structural units represented by the general formulas (2) to (4) is less than 10%, a sufficient amount of fluorine atoms do not exist, so that the dielectric constant may not be lowered so much. On the other hand, if the total amount of the general formulas (1) and (4) is less than 5%, high-density three-dimensional crosslinking cannot be achieved.
A crosslinked product having good Tg, hardness and mechanical strength cannot be obtained. This is explained as follows.

That is, the structural units represented by the general formulas (1) and (4) have a hydrogen atom directly bonded to a silicon atom in their side chain, and are mainly heated or irradiated with ultraviolet rays to generate After the Si-Si bond of the chain is broken, oxygen and moisture in the air are taken in to generate a silanol-type hydroxyl group, and this hydrogen atom in the side chain is also changed to a silanol-type hydroxyl group. Therefore, since three silanolic hydroxyl groups are generated for each silicon atom, a silicon-based matrix having a three-dimensional structure of Si—O—Si bond, which is an oxide thereof, is formed, and in this matrix, four silanol groups are formed. One of the bonds of the book is bonded to the aromatic group, and the remaining three are used for the Si-O-Si bond. That is, a silicon atom having one Si-C bond is Si-
It is possible to form a silicon-based matrix having a three-dimensional structure with O—Si bonds, and the durability and mechanical strength of the obtained fluorine-containing siloxane crosslinked product are enhanced. At this time, when the silicon-based matrix is formed by the silicon atom having one Si—C bond, the reason why the durability and mechanical strength of the fluorine-containing siloxane crosslinked product are increased is that two or more Si—C bonds are present. In a silicon atom having
A three-dimensional structure of —O—Si bond cannot be obtained, and the silicon atom does not have a Si—C bond, and all four bonds are Si.
This is because when it is used for a —O—Si bond, the flexibility of the silicon-based matrix formed is reduced.

For this reason, in the fluorine-containing polysilane used in the method of the second invention, the total amount of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (4). Is preferably 5% or more,
It is more preferably 25% or more, still more preferably 5%.
0% or more.

Further, also in the second invention, from the viewpoint of obtaining a fluorine-containing siloxane crosslinked product having particularly high Tg and excellent adhesion to a substrate, the structural unit represented by the general formula (1) and the general formula ( At least 1 selected from 2) to (4)
It is preferable to use the fluorine-containing polysilane copolymer of the first invention containing a structural unit represented by a seed.

The molecular weight of the fluorine-containing polysilane used here is the same as in the case of the copolymer of the first invention.
700 to 1,000,000, and further 5,000 to
20,000 is preferred. If the molecular weight is less than 7,000, the durability of the formed film may be lowered, while if it exceeds 1,000,000, the solvent solubility of the fluorine-containing polysilane is lowered and film formation becomes difficult.

Specifically, in addition to the above-mentioned fluorine-containing polysilane copolymer of the first invention, the following fluorine-containing polysilane can be mentioned.

[0073]

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In the formula, n and m represent the degree of polymerization.

In the manufacturing method of the second invention, first,
After preparing a solution containing the fluorine-containing polysilane represented by the above general formula (5) and applying it on a predetermined substrate, 5
It is dried at a temperature of about 0 to 150 ° C. to volatilize the solvent,
An organosilicon compound film mainly containing fluorinated polysilane is formed. At this time, as the solvent for the fluorinated polysilane, toluene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl acetate cellosolve, butyrolactone, butyl lactic acid, or the like can be used, and a solution containing 1 to 50 wt% of the fluorinated polysilane is prepared and necessary. Accordingly, after filtering with a filter of about 0.1 μm, spin coating may be performed on the substrate. The film thickness of the organosilicon compound film formed on the substrate can be appropriately selected, and can be, for example, about 0.1 to 5 μm.

In the second invention, as the substrate, a transparent substrate made of translucent glass or resin, a semiconductor substrate having wiring formed on its surface, a glass substrate having the wiring formed thereon, or the like can be used.

The heat treatment of the formed organosilicon compound film is preferably carried out at a temperature of 100 to 600 ° C. When the heat treatment temperature is lower than 100 ° C., sufficient oxidation is not performed, and it becomes difficult to perform three-dimensionalization sufficiently. On the other hand, if the heat treatment temperature exceeds 600 ° C., the volume shrinkage becomes too large, and the formed fluorine-containing siloxane crosslinked product may be cracked. A more preferable heat treatment temperature is 200 to 500 ° C.

It is preferable that after the solution containing the fluorine-containing polysilane is applied on the substrate to form a film, the whole surface is exposed to ultraviolet rays before the film is heat-treated. In this exposure process, the wavelength of ultraviolet rays is 150 to 400.
It may be about nm, but it is particularly preferable to irradiate with ultraviolet rays having a wavelength of 200 to 300 nm. The irradiation dose is
It is preferably set to about 10 mJ to 10 J, and more preferably about 100 mJ to 3 J.

By performing the whole surface exposure in this way,
Polysilane in the film is decomposed to generate a silanol bond (Si-OH) having high acidity. By heating the organosilicon compound film after such exposure, a siloxane bond (Si-O-Si) having a high cross-linking density is entirely formed.
Are quickly formed. Therefore, it is possible to perform heat treatment at a lower temperature than in the case where the exposure step is not performed, and it is possible to easily form a siloxane crosslinked body having high adhesion to the substrate and good heat resistance.

Further, in the method for producing a fluorine-containing siloxane crosslinked product according to the second aspect of the invention, after the film-formed organosilicon compound film is selectively exposed, it is developed to form a patterned fluorine-containing siloxane crosslinked product. It is also possible to get a body. The methods for obtaining the positive pattern and the negative pattern will be described in detail below.

To obtain a positive type pattern, first, the organic silicon compound film is selectively exposed to light and then developed with an alkaline aqueous solution to selectively dissolve and remove the exposed area.

The pattern exposure can be performed under the same conditions as described above. That is, the wavelength of ultraviolet rays is 150 to 40
It may be about 0 nm, but it is particularly preferable to irradiate with ultraviolet rays having a wavelength of 200 to 300 nm. The irradiation dose is preferably set to about 10 mJ to 10 J, and more preferably about 100 mJ to 3 J.

As the alkaline aqueous solution, for example,
Organic alkalis such as tetramethylammonium hydroxide and choline; inorganic alkalis such as KOH and NaOH can be used. The organic silicon compound film after development is appropriately washed with pure water.

The organosilicon compound film after development is subjected to overall surface exposure as necessary, and then subjected to heat treatment at a temperature of 100 to 600 ° C., preferably 200 to 500 ° C. to form a patterned fluorine-containing siloxane. A crosslinked product is obtained.

The entire surface exposure can be performed under the same conditions as the pattern exposure described above.

In the formation of the positive type pattern as described above, by selectively exposing the organosilicon compound film, the polysilane in the film is decomposed and the silanol group (Si) having a high acidity (Si) in the exposed area is decomposed. -OH) is selectively formed. By developing with an alkaline aqueous solution after such exposure, the exposed portion of the organosilicon compound film is selectively dissolved and removed to form a positive pattern. Then, the organosilicon compound film pattern is exposed on the entire surface if necessary, so that the silanol group (S
i-OH) is formed, and heat treatment is performed thereafter to form a siloxane bond (S
i-O-Si) is formed. Therefore, it is possible to easily form a highly precise pattern made of a glass matrix and having high adhesion to the substrate and good heat resistance.

On the other hand, in the case of obtaining a negative type pattern, first, the organosilicon compound film is selectively exposed to light, heat-treated, and then developed with an organic solvent to selectively dissolve and remove the unexposed portion.

The pattern exposure can be performed under the same conditions as described above. That is, the wavelength of ultraviolet rays is 150 to 40
It may be about 0 nm, but it is particularly preferable to irradiate with ultraviolet rays having a wavelength of 200 to 300 nm. The irradiation dose is preferably set to about 10 mJ to 10 J, and more preferably about 100 mJ to 3 J.

The heat treatment before development is preferably carried out at a temperature of 100 to 150 ° C., although it depends on the heating time. If the temperature is lower than 100 ° C., the cross-linking in the exposed area where the silanol hydroxyl group is generated may be insufficient.
If the temperature exceeds ℃, the crosslinking of the silicon polymer may proceed even in the unexposed area, and in any case, it becomes difficult to pattern the organosilicon compound film with high accuracy.

As the organic solvent, for example, an aromatic solvent such as toluene or xylene, or methanol,
Examples thereof include alcohol solvents such as ethanol, ketone solvents such as acetone and methyl ethyl ketone, and polar solvents such as ketone solvents such as methyl acetate, ethyl acetate and butyl acetate.

The developed organic silicon compound film has a thickness of 100 to
By subjecting to a heat treatment at a temperature of 600 ° C., preferably 200 to 500 ° C., a patterned fluorine-containing siloxane crosslinked product can be obtained.

In the formation of the negative type pattern as described above, by selectively exposing the organic silicon compound film to light, polysilane in the film is decomposed to select silanol-containing hydroxyl groups (Si-OH) in the exposed area. To generate. After such exposure, a relatively low temperature (for example, 100 to 150) is used.
The silanol-containing hydroxyl group (Si-OH) is selectively crosslinked by heat treatment at (° C). As a result, a siloxane bond (Si-O-Si) having a crosslink density that is insoluble in the solvent
Are formed in the exposed portion, and selective solubility appears between the exposed portion and the unexposed portion. Then, by developing with an organic solvent, the unexposed portion is selectively dissolved and removed to form a negative pattern. After that, the patterned organosilicon compound film is heat-treated at a relatively high temperature (for example, 200 to 500 ° C.), so that a siloxane bond (Si—O—Si) having a high crosslink density is generated throughout. Therefore,
A highly precise pattern composed of a vitrified silicon-based matrix and having high adhesion to a substrate and good heat resistance can be easily formed.

The shape of the obtained pattern is superior to the negative type pattern, but the positive type pattern has an advantage that an alkaline aqueous solution which has little influence on the environment can be used.

By using the second invention, Si--O
It is possible to produce a fluorine-containing siloxane crosslinked product which is composed of a vitrified silicon-based matrix having a three-dimensional structure of —Si bond and which contains a fluorine component as a hydrocarbon residue in the three-dimensional structure. In this fluorine-containing siloxane crosslinked product, even if the fluorine component is present uniformly,
Alternatively, the fluorine component may cause phase separation with the silicon-based matrix. However, in order to improve the adhesion with the substrate while maintaining a higher Tg, it is preferable that the structure has a micro phase separation structure unless the surface irregularities become remarkable. In order to cause such phase separation, The use of the fluorine-containing polysilane copolymer according to the invention is advantageous.

Next, the silicon polymer composition of the third invention will be described in detail.

In the silicon polymer composition of the third invention, the silanol hydroxyl groups formed by heating or exposure react with each other to crosslink the silicon polymer, resulting in the first and second inventions. A vitrified silicon-based matrix is obtained in the same manner as in. The molecular weight of the silicon polymer here is not particularly limited, but as in the case of the fluorine-containing polysilane copolymer of the first invention, the molecular weight is 700 to 1,000,000, and further 5,000.
~ 20,000 is preferred. If the molecular weight is less than 700, the durability of the formed film may be lowered, while if it exceeds 1,000,000, the solvent solubility of the silicon polymer is lowered and film formation becomes difficult.

Ar in the general formulas (6) and (10)
Specific examples of ³ include a phenyl group, a naphthyl group, an anthranyl group, and a phenethyl group. The aromatic group Ar ³ is, for example, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkoxy group. It may be substituted with an organic group such as a nitro group, an amino group, a hydroxyl group, and a cyano group.

R ⁵ in the above general formulas (8) and (9) is not particularly limited as long as it is a hydrogen atom or a hydrocarbon group, but the crosslinking of the silicon polymer is difficult to proceed at room temperature and the silicon polymer is heated at the time of heating. The 1-substituted ethyl group is preferable in that the crosslinking of 1 proceeds rapidly. In particular,
For example, t-butyl group, isopropyl group, 1,1-phenylmethylethyl group, 1-methoxyethyl group, 1,1-
Methyl methoxyethyl group, 1-ethoxyethyl group, 1,
Examples thereof include 1-methylethoxyethyl group, 1,1-diphenylethyl group, 1,1-dimethylpropyl group, 1-ethoxypropyl group, and 1,1-methylethoxypropyl group.

Specific examples of R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group and pentyl group. , N-hexyl group, cyclohexyl group,
Phenyl group, naphthyl group, anthranyl group, phenethyl group, t-butoxy group, isopropoxy group, 1,1-phenylmethylethoxy group, 1-methoxyethoxy group, 1,
1-methylmethoxyethoxy group, 1-ethoxyethoxy group, 1,1-methylethoxyethoxy group, 1,1-diphenylethoxy group, 1,1-dimethylpropoxy group, 1
Examples thereof include an -ethoxypropoxy group and a 1,1-methylethoxypropoxy group. However, 1
Silicon atom having Si-C bonds is Si-O-Si
In order to obtain a fluorine-containing siloxane crosslinked product which is composed of a silicon-based matrix having a three-dimensional structure with a bond and has particularly excellent durability and mechanical strength, R ⁶ is a substituted or unsubstituted hydrocarbon group. Is preferred. Further, from the viewpoint of increasing the Tg of the fluorine-containing siloxane crosslinked product, R ⁶ is more preferably a substituted or unsubstituted aromatic group.

Specific examples of the silicon polymer used in the third invention are shown below.

[0101]

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[0102]

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[0103]

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Further, the polymerizable fluorine compound is not particularly limited as long as it is represented by the general formula (7), and examples thereof include the compounds shown below.

[0105]

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[0106]

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[0107]

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[0108]

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The compounding amount of this polymerizable fluorine compound is not particularly limited, but it is
0.01 to 10 parts by weight is preferred. If the compounding amount of the polymerizable fluorine compound is less than 0.01 part by weight, properties such as low dielectric constant and low water absorption may be deteriorated.
If it exceeds the weight part, problems such as a decrease in Tg and film formability may occur.

Examples of the compound that generates an acid upon exposure or heating (hereinafter referred to as an acid generation catalyst) used in the third invention include, for example, onium salts, halogen-containing compounds, quinonediazide compounds, sulfone compounds, sulfonic acid compounds, And a compound such as a nitrobenzyl compound which generates an acid upon exposure to light and a compound which generates an acid upon heating represented by the following general formula.

[0111]

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In the above general formula, R ⁴⁰ represents a substituted or unsubstituted alkyl group or aryl group.

Further, as the compound which generates an acid upon exposure, the compounds more specifically exemplified below can be used.

Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, and the like, and a compound represented by the following formula (11) is preferable.

[0115]

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Here, R ⁴¹ , R ⁴² and R ^{43, which} may be the same or different, are a hydrogen atom, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. X is SbF ₆ , AsF
₆ , PF ₆ , BF ₄ , CF ₃ CO ₂ , ClO ₄ , CF ₃
It is selected from SO ₃ and the compounds shown below.

[0117]

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In the above formula, R ⁴⁴ is a hydrogen atom, an amino group,
Anilino group, C1-4 alkyl group or C1
Is an alkoxy group of 4 to 4, and R ⁴⁵ and R ^{46 each} have 1 carbon atom.
R ⁴⁷ is a hydrogen atom, an amino group, an anilino group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Furthermore, equations (12) and (1
The compound represented by 3) can also be used.

[0120]

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In the above formulas (12) and (13), R ⁴¹ ,
The definitions of R ⁴² , R ⁴³ and X are the same as in the above formula (11).

Examples of the halogen-containing compound include a halogen alkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like, and the compounds represented by the following formulas (14) and (15) are preferable. .

[0123]

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In the above formula (14), R ⁴⁸ is a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group.

[0125]

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In the above formula (15), R ⁴⁹ , R ⁵⁰ , and R
¹¹ may be the same or different, and each is a hydrogen atom,
It is a halogen atom, a methyl group, a methoxy group or a hydroxyl group.

Examples of the quinonediazide compound include:
Examples thereof include a diazobenzoquinone compound and a diazonaphthoquinone compound, and preferably the following formula (1
6) and (17).

[0128]

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Further, compounds represented by the following formulas (18) and (19) can be used.

[0130]

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In the above formula (18), R ¹² is —CH ₂ —, —
_{C (CH 3) 2 -,} - C (= O) -, or -SO ₂ -
And q and r are 1 ≦ (q + r) ≦ 6, 1 ≦ q ≦
It is an integer that satisfies the relationship of 6.

[0132]

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In the above formula (19), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is —CH ₂ — or —C (CH ₃ ) ₂
-, - C (= O) -, or -SO ₂ - and is, s and t are integers satisfying the relation of 1 ≦ (s + t) ≦ 6,1 ≦ s ≦ 6.

Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone and the like, and a compound represented by the following formula (20) is preferable.

[0135]

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In the above formula (20), Y is —C (═O) — or —SO ₂ —, R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different and have 1 to 4 carbon atoms. Is an alkyl or halogen atom, and n is an integer of 0 to 3.

Examples of the nitrobenzyl compound include:
Examples thereof include a nitrobenzyl sulfonate compound and a dinitrobenzyl sulfonate compound, and a compound represented by the following formula (21) is preferable.

[0138]

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Here, R ¹⁹ is an alkyl group having 1 to 4 carbon atoms, R ²⁰ is a hydrogen atom or a methyl group, and R ²¹
Is a group selected from the group shown below, and n is an integer of 1 to 3.

[0140]

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Here, R ²² is a hydrogen atom or a methyl group, R ²³ and R ²⁴ may be the same or different and are an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3. Is.

Examples of the sulfonic acid compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, and imino sulfonate, and the following formulas (22) to (2) can be mentioned.
The compound represented by 4) is preferable.

[0143]

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In the above formula (22), R ²⁵ and R ²⁶ may be the same or different and each represents a hydrogen atom or a carbon number of 1 to 4
R ²⁷ and R ^{28, which} may be the same or different, are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0145]

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Here, R ²⁹ is a hydrogen atom or a carbon number of 1 to
A 4 alkyl, R ³⁰ and R ^31, which may be the same or different, an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 4 carbon atoms, or R ³⁰ and R
³¹ and may be bonded to each other to form a ring with the nitrogen atom to which they are bonded.

[0147]

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Here, Z is a fluorine atom or a chlorine atom.

Of the above-mentioned compounds, onium salts and quinonediazide compounds are particularly preferable.

The content of these acid generating catalysts may be 0.01 to 50 mol%, and further 0.1 to 5 mol% based on the structural unit of the silicon polymer. If the blending amount is less than 0.01 mol%, a sufficient amount of acid cannot be generated, while if it exceeds 50 mol%,
The state of the coating film may deteriorate.

In the silicon polymer composition of the third invention, the compounds that generate radicals by exposure or heating (hereinafter referred to as radical generating catalysts) include carbonyl compounds, peroxides, azobis compounds, sulfur compounds, and halogens. A compound or the like can be used. Specifically, t-butyl peroxide, benzoyl peroxide, and lauroyl peroxide, azobisisobutyronitrile,
Azobis-2,4-dimethylvaleronitrile, and azobiscyclohexanecarbonitrile, benzoin, benzoin alkyl ether, benzoin allyl ether, benzoin alkylaryl thioether benzyl alalkyl ketal, phenyl-glyoxal alkyl acetal, benzyl oxime, thioxanthone, tetramethyl Examples thereof include thiuram, tetraethylthiuram disulfide, and organic halides represented by the following chemical formula.

[0152]

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[0153]

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In the formula, P is --O--, --CH _2- , --CHQ
-, -S-, or -C (= O)-, Q is a chlorine atom, a bromine atom or an iodine atom, V is a hydrogen atom or a substituted or unsubstituted alkyl group, and W is the same or different. Further, each represents a substituted or unsubstituted alkyl group, aryl group, heteroaryl group, alkoxyl group, amine group or vinyl group.

Among these, t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, and azobiscyclohexanecarbonitrile. Compounds and azobis compounds are preferable because they generate radicals by both exposure and heating.

The content of the radical generating catalyst may be 0.01 to 50 mol%, and further 0.1 to 30 mol% based on the structural unit of the silicon polymer. If the blending amount is less than 0.01 mol%, a sufficient amount of radicals cannot be generated, while if it exceeds 50 mol%, the state of the coating film may deteriorate.

The silicon polymer composition of the third invention is prepared by dissolving the above-mentioned silicon polymer, polymerizable fluorine compound, and optionally an acid-generating catalyst or a radical-generating catalyst, in an appropriate organic solvent. Is prepared. Here, as the organic solvent that can be used, specifically, toluene, xylene, dimethylformamide, methyl cellosolve, o-dichlorobenzene, chloroform,
Ethanol, i-propyl alcohol, cyclopentanone, cyclohexanone, ethyl cellosolve acetate,
Acetone, methyl ethyl ketone, ethyl acetate, butyl acetate and the like are exemplified, and these can be used alone or in the form of a mixture.

When the silicon polymer composition of the third invention is used, an organosilicon compound film is formed on the substrate according to the method of the second invention described above, and after the entire surface is exposed, if necessary. The heat treatment may be performed under the same conditions as in the second aspect of the invention to produce a fluorine-containing siloxane crosslinked product having good Tg, hardness, mechanical strength and the like.

That is, in the silicon polymer composition of the third invention, the acid or radical generated at this time serves as an initiator of the polymerization reaction of the polymerizable fluorine compound, and the silicon polymer is crosslinked to form a vitrified silicon-based matrix. Thus, the polymerizable fluorine compound also has a high molecular weight. Therefore, a fluorine-containing siloxane crosslinked product having a low dielectric constant and a high Tg can be obtained, while the low molecular weight compound that may lower Tg is hardly contained in the crosslinked product.

When the silicon polymer is the polysilane represented by the above general formula (6) or (8), the Si—Si bond of the polysilane is cleaved by exposure or heating to generate radicals. Therefore, as described above, the acid generation catalyst and the radical generation catalyst can be made unnecessary. Moreover, since the reaction between the radical generated by the cleavage of the Si-Si bond and the polymerizable fluorine compound proceeds in parallel with the polymerization of the polymerizable fluorine compound, the high molecular weight fluorine component is converted into Si-O-Si. It is possible to chemically bond with a silicon-based matrix having a three-dimensional bond structure, and it is possible to obtain a fluorine-containing siloxane crosslinked product having a higher Tg.

The silicon polymer composition of the third invention comprises a silicon polymer represented by the above-mentioned general formula (9) or (10), a polymerizable fluorine compound, and an acid which can be obtained by exposing only to light exposure or heating. Alternatively, when it is composed of a compound that generates a radical, the entire surface exposure before the heat treatment is indispensable for generating an acid or a radical. However, the wavelength of light is determined according to the light absorption band of the acid generating catalyst or the radical generating catalyst, and the wavelength of 150 to 400 n is used.
It is not particularly limited to the ultraviolet ray of m.

When the silicon polymer is the polysilane represented by the general formula (6) or the general formula (8), it is necessary to perform the exposure prior to the heat treatment by using Si--Si.
It is preferable in that it promotes cleavage of the bond,
Light with a wavelength of 0 to 400 nm, preferably 200 to 300 nm can be used. The irradiation amount is in the range of 10 mJ to 10 J, preferably 100 mJ to 3 J.

Further, in the silicon polymer composition of the third invention, when the silicon polymer is represented by the above general formula (6), an organic silicon compound film is formed on the substrate and selectively exposed. It is possible to form a positive pattern by dissolving and removing the exposed portion with an alkaline aqueous solution after performing. Such a positive type pattern can be formed using the same alkaline aqueous solution as the developing solution under the same conditions as those described in the second invention.

That is, in the polysilane represented by the general formula (6), when the polysilane is irradiated with ultraviolet rays, the S of the polysilane is reduced.
After the i-Si bond is cleaved, oxygen and water in the air are taken in to form silanol-containing hydroxyl groups,
The hydrogen atom in the side chain also changes to a silanol group hydroxyl group. Therefore, more silanol hydroxyl groups are produced than in ordinary polysilane. Moreover, in this polysilane, since the aromatic group directly bonded to the silicon atom in the side chain and the hydrogen atom are present, when the silanol-containing hydroxyl group is formed as described above, the electron-withdrawing aromatic group has an acidity of And the steric hindrance of the aromatic group stabilizes the silanol bond. Therefore, it becomes possible to selectively dissolve and remove only the exposed portion with the alkaline aqueous solution, and a positive pattern is obtained.

Therefore, after development with an alkaline aqueous solution,
By irradiating with ultraviolet rays again as necessary and reheating, a fluorine-containing siloxane crosslinked product having a high crosslinking density and a higher Tg can be obtained.

On the other hand, the negative pattern can be formed by using any silicon polymer composition. Here, under the same conditions as described in the second invention,
It can be formed using the same organic solvent as a developing solution.

However, for this purpose, when the silicon polymer is a polysiloxane represented by the general formula (9) or the general formula (10), an acid generating catalyst or a radical generating catalyst, particularly an acid or It is necessary to add a compound that generates a radical. That is, in a silicon polymer composition obtained by blending a compound that generates an acid or a radical upon exposure to such a polysiloxane, the acid or radical generated in the exposed portion is a side chain alkoxy group of the polysiloxane or a silanol of a hydrogen atom. A siloxane bond (Si—O—Si) having a crosslink density that is insoluble in the solvent is formed in the subsequent heat treatment by promoting the conversion into a hydroxyl group.

On the other hand, when the silicon polymer is polysilane represented by the general formula (6), a siloxane bond (Si-O-Si) is formed in the exposed portion based on the reaction as described in the second invention. The three-dimensional structure of is selectively formed,
Also in the case where the silicon polymer is polysilane represented by the general formula (8), the radicals generated by the cleavage of the Si-Si bond in the exposed portion promote the conversion of the alkoxy group of the side chain into the silanol group hydroxyl group, and the exposed portion Then, the three-dimensional structure of the siloxane bond (Si-O-Si) is selectively formed. Therefore, in either case, the unexposed portion can be selectively dissolved and removed with an organic solvent to form a negative pattern, and subsequent heat drying can be performed under the same conditions as in the above-mentioned second invention. Good.

In the silicon polymer composition of the third invention, the polymerization reaction of the polymerizable fluorine compound or the photolysis of the polymerizable fluorine compound and polysilane was caused in the presence of the acid or radical generated by exposure. Since the reaction with radicals can proceed even at room temperature, it is possible to form a negative pattern without performing heat treatment at a relatively low temperature after pattern exposure.

As described above, by using the silicon polymer composition of the third invention, it is possible to produce a fluorine-containing siloxane crosslinked product containing a high molecular weight fluorine component in the silicon-based matrix. In this fluorine-containing siloxane crosslinked product, even if the fluorine component is present uniformly,
Alternatively, the fluorine component and the silicon-based matrix may undergo phase separation. In addition, in order to improve the adhesion to the substrate while maintaining a higher Tg, it is preferable that the structure has a micro phase separation structure unless the surface irregularities become remarkable.

[0171]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example I In this example, a fluorine-containing siloxane crosslinked product was produced using fluorine-containing polysilane.

(Fluorine-containing polysilane copolymer (c-2)
First, polyphenylsilane was synthesized as follows.

Zirconocene dichloride 10.462 g (0.0
7 mol) and 250 ml of diethyl ether were added and stirred. Then, the eggplant flask was cooled to −20 ° C. and 100 mL of a methyllithium ether solution (1.4 mol / l) was added.
ml was added dropwise over 5 minutes. Then, the mixture was stirred for 45 minutes, the solvent was removed by an evaporator, and zirconocene dimethyl was isolated by sublimation.

Further, a mechanical stirrer and a condenser were attached to a 500 ml three-necked flask which had been purged with argon, and 2.9 g of zirconocene dimethyl was contained. 62.39 g of phenylsilane was added dropwise thereto with a dropping funnel. After reacting for 30 minutes, heat to 40 ° C and
After reacting for a time and reprecipitating three times with methanol,
The polyphenylsilane represented by the following formula (a-2) is 54
g were obtained. When the molecular weight was measured by GPC, the average molecular weight was about 1,000.

[0176]

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Subsequently, 1 g (9.4 mol) of polyphenylsilane and 0.1 parts of AIBN were placed in a 50 ml volumetric flask.
6 g (0.98 mol) and a fluorine-containing compound represented by the following formula (b-2) were charged, the volumetric flask was cooled with liquid nitrogen, and degassed with a vacuum pump. Then, the mixture was refluxed for 4 hours, concentrated with an evaporator, and reprecipitated with methanol to obtain a fluorine-containing polysilane copolymer represented by the following formula (c-2).

[0178]

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[0179]

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The fluorine-containing polysilane copolymer had the following properties.

[0181] ^{IR: Si-C 810cm -1,} 1250cm -1 CH 2 -CH 2 2850cm -1 CF 2 -CF 2 1300cm -1 Si-Ph 1430cm -1 Si-H 2110cm -1 1 H-NMR: 3~ 5 ppm, 6.5 to 8 ppm (Synthesis of Fluorine-Containing Polysilane Copolymer (g-2)) First, in an argon atmosphere, a solution of 1 mol of a fluorine-containing compound represented by the following formula (d-2) in diethyl ether was added to -90.
A 2-fold molar amount of a t-butyllithium solution was added dropwise at 0 ° C, and the reaction was performed for 30 minutes.

[0182]

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Thereafter, the temperature was returned to room temperature over 30 minutes. The salt-removed reaction mixture was housed in a dropping funnel and added dropwise to an eggplant flask containing 1 mol of tetrachlorosilane under an argon atmosphere. After reacting for 1 hour, a compound represented by the following formula (e-2) was obtained by distillation.

[0184]

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This compound was dissolved in ether, introduced into an eggplant flask under an argon atmosphere, and a LiAlH ₄ ether solution was added. After reacting at room temperature for 1 hour, the mixture was refluxed for 2 hours and distilled to obtain a compound represented by the following formula (f-2).

[0186]

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Then, a mechanical stirrer and a condenser were attached to a 500 ml, three-necked flask which had been replaced with argon, and zirconocene dimethyl was put therein. 88.105 g of compound (f-2) and phenylsilane 54.1
1 g was mixed and added dropwise with a dropping funnel. After reacting for 30 minutes, the mixture was heated to 40 ° C., reacted for 5 hours, and reprecipitated 3 times with methanol to obtain 85.3 g of a fluorine-containing polysilane copolymer represented by the following formula (g-2). GP
When the molecular weight was measured by C, the weight average molecular weight was about 2000.

[0188]

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The fluorine-containing polysilane copolymer had the following properties.

[0190] ^{IR: Si-Ph 1430cm -1 Si} -H 2110cm -1 1 H-NMR: 3.5~5.4ppm, 6.5~7pp
m (Example I-1) The compound (FF-1) was used as the fluorine-containing polysilane copolymer, and a fluorine-containing siloxane crosslinked product was produced using this toluene solution.

In the compound (FF-1) used here, n = 70 and m = 30 and the molecular weight was about 4,50.
0.

First, this fluorine-containing polysilane copolymer 1
A toluene solution in which 5 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

A mask for a color filter is placed on the obtained organosilicon compound film, and 1 J of ultraviolet rays are emitted from a low pressure mercury lamp.
/ Cm ² irradiation and then immersing in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 60 seconds, the exposed portion was dissolved and a pattern having a line width of 10.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 3.0 and did not soften even when heated to 150 ° C.

Example I-2 A line width of 10.0 μm was obtained in the same manner as in Example (I-1) except that the compound (FF-2) was used as the fluorine-containing polysilane copolymer. A patterned fluorine-containing siloxane crosslinked product was produced.

In the compound (FF-2) used here, n = 60 and m = 40 and the molecular weight was about 5,000.
0.

The obtained coating film had a dielectric constant of 2.8 and did not soften even when heated to 150 ° C.

Example I-3 A compound (FF-7) was used as the fluorine-containing polysilane copolymer, and a fluorine-containing siloxane crosslinked product was produced using this toluene solution.

In the compound (FF-7) used here, n = 50 and m = 50 and the molecular weight was about 5,000.
0.

First, this fluorine-containing polysilane copolymer 1
A toluene solution in which 5 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

A mask for a color filter is placed on the obtained organosilicon compound film, and 1 J of ultraviolet rays are emitted from a low pressure mercury lamp.
/ Cm ² irradiation, after heating for 5 minutes at 100 ℃, immersed in toluene for 60 seconds, the unexposed area was dissolved,
A pattern having a line width of 10.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, further at 130 ° C. for 10 minutes, and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.5 and did not soften even when heated to 150 ° C.

(Example I-4) A pattern having a line width of 10.0 μm was formed in the same manner as in the above-mentioned Example (I-3) except that the compound (FF-3) was used as the fluorine-containing polysilane copolymer. The crosslinked fluorine-containing siloxane was produced.

In the compound (FF-3) used here, n = 30 and m = 70 and the molecular weight was about 5,50.
0.

The obtained coating film had a dielectric constant of 2.5, and the film did not soften even when heated to 150 ° C.

Example I-5 The compound (FF-27) was used as the fluorine-containing polysilane copolymer, and this toluene solution was used to produce a fluorine-containing siloxane crosslinked product.

In the compound (FF-27) used here, n = 30, m = 20, l = 20, k = 30, the molecular weight was about 5,500, and the trifluoromethyl group was introduced at the position of introduction. It is the meta position of the benzene ring.

First, this fluorine-containing polysilane copolymer 1
A toluene solution in which 5 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

A mask was placed on the obtained organosilicon compound film, and ultraviolet rays were irradiated from a low-pressure mercury lamp at 700 mJ / cm ² and then dipped in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 40 seconds. Then, a pattern having a line width of 7.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, further at 130 ° C. for 10 minutes, and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.7 and did not soften even when heated to 150 ° C.

Example I-6 A compound (FF-24) was used as the fluorine-containing polysilane copolymer, and this toluene solution was used to produce a fluorine-containing siloxane crosslinked product.

In the compound (FF-24) used here, n = 50, m = 30 and l = 20, the molecular weight was about 5,000, and the trifluoromethyl group was introduced at the meta position of the benzene ring. Rank.

First, this fluorine-containing polysilane copolymer 1
A toluene solution in which 5 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

A mask was placed on the obtained organosilicon compound film, and after irradiating ultraviolet rays from a low-pressure mercury lamp at 1 J / cm ² , the film was heated at 100 ° C. for 5 minutes and immersed in toluene for 60 seconds. Dissolve, line width 10.0 μm
Pattern was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.5 and did not soften even when heated to 150 ° C.

Example I-7 A compound (FF-31) shown below having a molecular weight of about 4,000 as a fluorine-containing polysilane.
A toluene solution prepared by dissolving 15 g of toluene in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

[0221]

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A mask was overlaid on the obtained organosilicon compound film, irradiated with ultraviolet rays of 500 mJ / cm ² from a low pressure mercury lamp, and then immersed in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 30 seconds. Then, a pattern having a line width of 5.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.7 and did not soften even when heated to 150 ° C.

Further, after the coating film was cured at 400 ° C., an adhesion test was conducted by a substrate test. As a result, 70/100 of the formed film remained on the substrate even after the test.

Example I-8 Fluorine-containing polysilane copolymer represented by the following formula (FF-32) (molecular weight 4,000)
A toluene solution in which 15 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

[0227]

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A mask was overlaid on the obtained organosilicon compound film, and ultraviolet rays of 500 mJ / cm ^{2 were} irradiated from a low-pressure mercury lamp, followed by immersion in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 30 seconds. Then, a pattern having a line width of 5.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.9 and did not soften even when heated to 150 ° C.

Further, after the coating film was cured at 400 ° C., an adhesion test was conducted by the same basic test as in the above-mentioned (Example I-7).
0/100 remained on the substrate. From the results of this Example and the results of (Example I-7) described above, the amount of the structural unit containing no fluorine and the structural unit having the fluorine-containing substituent was determined by using the fluorine-containing polysilane as the copolymer structure. It can be seen that a fluorine-containing siloxane crosslinked product exhibiting even more excellent adhesion can be obtained from a homopolymer composed of only structural units having a fluorine-containing substituent.

Example I-9 Fluorine-containing polysilane copolymer represented by the following formula (FF-33) (molecular weight: 5,0001
A toluene solution in which 5 g of toluene was dissolved in 70 g of toluene was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2 μm.

[0233]

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A mask for a color filter is placed on the obtained organosilicon compound film, and 1 J of ultraviolet rays are emitted from a low pressure mercury lamp.
/ Cm ² irradiation and then immersing in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 120 seconds, the exposed portion was dissolved and a pattern having a line width of 15.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.7 and did not soften even when heated to 150 ° C.

Comparative Example I-1 A toluene solution prepared by dissolving 15 g of methylphenylpolysilane (molecular weight 9,000) in 70 g of toluene was applied on a glass substrate by spin coating and then dried to give a film thickness of about 2 μm. An organosilicon compound film was formed.

A mask was placed on the obtained organosilicon compound film, and ultraviolet rays were applied at 1 J / cm ² from a low pressure mercury lamp.
It was immersed in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 120 seconds, but no pattern could be formed.

(Comparative Example I-2) A toluene solution prepared by dissolving 15 g of methylphenylpolysilane (molecular weight 9,000) in 70 g of toluene was applied on a glass substrate by spin coating and then dried to give a film thickness of about 2 μm. An organosilicon compound film was formed.

[0240] A mask was placed on the obtained organosilicon compound film, which was irradiated with 1 J / cm ^{2 of} ultraviolet rays from a low-pressure mercury lamp, heated at 100 ° C for 5 minutes, and immersed in toluene for 60 seconds. Dissolve, line width 10.0 μm
Pattern was formed.

The obtained coating film had a dielectric constant of 4.5, and the film softened when heated to 150 ° C.

From the above results, it is understood that a fluorine-containing siloxane crosslinked product having a low dielectric constant and a high Tg is formed by using the production method of the present invention. Particularly when the fluorine-containing polysilane copolymer of the present invention is used,
A fluorine-containing siloxane crosslinked product having further improved adhesion to a substrate can be obtained.

Example II In this example, a fluorine-containing siloxane crosslinked product was produced using a silicon polymer composition.

First, the acid generation catalyst used in this example is shown below.

[0245]

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Example II-1 15 g of a compound (E-1) having a molecular weight of about 1,000 as a silicon polymer and 15 g of a compound (F-2) as a polymerizable fluorine compound were dissolved in 70 g of toluene. A toluene solution is applied on a glass substrate by spin coating and then dried to give a film thickness of about 2 μm.
The organic silicon compound film of was formed.

A mask for a color filter was placed on the obtained organosilicon compound film, and ultraviolet rays of 1 J /
After the irradiation with cm ² , the film was immersed in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 60 seconds, and then the exposed portion was dissolved and a pattern having a line width of 10.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.8 and did not soften even when heated to 150 ° C.

Example II-2 15 g of the compound (E-1) having a molecular weight of about 1,000 as a silicon polymer and 15 g of the compound (F-7) as a polymerizable fluorine-containing compound were dissolved in 70 g of toluene. The toluene solution was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a film thickness of about 2 μm.

A mask for a color filter was placed on the obtained organosilicon compound film, and ultraviolet rays of 1 J /
After the irradiation with cm ² , the film was immersed in a 2.38 wt% tetraethylammonium hydroxide aqueous solution for 60 seconds, and then the exposed portion was dissolved and a pattern having a line width of 10.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 3.1 and did not soften even when heated to 150 ° C.

Example II-3 15 g of the compound (E-1) having a molecular weight of about 1,000 as a silicon polymer and 15 g of the compound (F-10) as a polymerizable fluorine compound were dissolved in 70 g of toluene. This toluene solution was applied on a glass substrate by spin coating and then dried to give a film thickness of about 2 μm.
m organic silicon compound film was formed.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A pattern of 0.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.7 and did not soften even when heated to 150 ° C.

Example II-4 15 g of a compound (E-12) having a molecular weight of about 1,000 as a silicon polymer and 15 g of a compound (F-8) as a polymerizable fluorine-containing compound.
Was dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2.2 μm.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A 5.0 μm pattern was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.9 and did not soften even when heated to 150 ° C.

Example II-5 15 g of a compound (E-10) having a molecular weight of about 5,000 as a silicon polymer and 15 g of a compound (F-8) as a polymerizable fluorine-containing compound.
Was dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2.5 μm.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low-pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A pattern of 0.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, further at 130 ° C. for 10 minutes, and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.8, and the film did not soften even when heated to 150 ° C.

Example II-6 15 g of a compound (E-12) having a molecular weight of about 1,000 as a silicon polymer, 15 g of a compound (F-8) as a polymerizable fluorine-containing compound, and a compound as an acid generating catalyst. 0.6 g of (P-1) was dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to give a film thickness of about 2 μm.
The organic silicon compound film of was formed.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A pattern of 0.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, and further at 130 ° C. for 10 minutes and 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.9 and did not soften even when heated to 150 ° C.

Example II-7 15 g of a compound (E-17) having a molecular weight of about 20,000 as a silicon polymer, 15 g of a compound (F-8) as a polymerizable fluorine-containing compound, and azo as a radical generating catalyst. 0.57 g of bisisobutyronitrile was dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2.2 μm.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low-pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A 5.0 μm pattern was formed.

When this substrate was heated at 100 ° C. for 10 minutes, further at 130 ° C. for 10 minutes, and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.9 and did not soften even when heated to 150 ° C.

(Example II-8) 15 g of a compound (E-17) having a molecular weight of about 20,000 as a silicon polymer, 15 g of a compound (F-8) as a polymerizable fluorine-containing compound, and a compound as an acid generating catalyst ( P-1) 0.6 g and 0.57 g of azobisisobutyronitrile as a radical generating catalyst were dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to form a film. An organosilicon compound film having a thickness of about 2 μm was formed.

A mask for a color filter was placed on the obtained organosilicon compound film, and 1 J / ul of ultraviolet light was emitted from a low-pressure mercury lamp.
After irradiating with cm ^2, it was heated at 100 ° C for 5 minutes and immersed in toluene for 1 minute.
A pattern of 0.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, further heated at 130 ° C. for 10 minutes and then at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.9 and did not soften even when heated to 150 ° C.

Example II-9 15 g of a compound (E-13) having a molecular weight of about 20,000 as a silicon polymer, 15 g of a compound (F-8) as a polymerizable fluorine-containing compound, and a compound as an acid generating catalyst ( P-1) 0.6 g and 0.57 g of azobisisobutyronitrile as a radical generating catalyst were dissolved in 70 g of toluene, and this toluene solution was applied onto a glass substrate by spin coating and then dried to form a film. An organosilicon compound film having a thickness of about 2 μm was formed.

A mask for a color filter was placed on the obtained organosilicon compound film, and a 0.5 V ultraviolet ray was emitted from a low pressure mercury lamp.
After irradiation with J / cm ² , after heating at 100 ° C. for 5 minutes and immersing in toluene for 1 minute, the unexposed portion was dissolved and a pattern having a line width of 10.0 μm was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.8 and did not soften even when heated to 150 ° C.

Example II-10 15 g of a compound (E-24) having a molecular weight of about 20,000 as a silicon polymer, 15 g of a compound (F-8) as a polymerizable fluorine-containing compound,
Further, 1.0 g of the compound (P-1) as an acid generation catalyst was dissolved in 70 g of toluene, and the toluene solution was applied onto a substrate by spin coating and then dried to form an organosilicon compound film having a thickness of 2 μm. .

A mask was overlaid on the obtained organosilicon compound film, which was then irradiated with ultraviolet rays from a low-pressure mercury lamp at 1 J / cm ² and then dipped in methyl ethyl ketone for 60 seconds. A pattern was formed.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed.

The obtained coating film had a dielectric constant of 2.7 and did not soften even when heated to 150 ° C.

Example II-11 15 g of a compound (E-27) having a molecular weight of about 18,000 as a silicon polymer, 15 g of a compound (F-6) as a polymerizable fluorine-containing compound,
Further, 0.5 g of benzoyl peroxide as a radical generating catalyst was dissolved in 70 g of toluene, and this toluene solution was applied onto a substrate by spin coating and then dried to form an organosilicon compound film having a thickness of 2 μm. In addition, in the compound (E-27) used here, the introduction position of the trifluoromethyl group is the meta position of the benzene ring.

A mask was placed on the obtained organosilicon compound film, which was irradiated with ultraviolet rays from a low-pressure mercury lamp at 1 J / cm ² and then heated at 100 ° C. for 5 minutes and immersed in toluene for 1 minute. A pattern having a line width of 10.0 μm was formed by melting.

When this substrate was heated at 100 ° C. for 10 minutes, then at 130 ° C. for 10 minutes and at 150 ° C. for 30 minutes, a tough coating film was formed. The dielectric constant of this film was measured and found to be 2.8.

The coating film did not soften even when heated to 150 ° C.

(Comparative Example II-1) 15 g of a compound (E-13) having a molecular weight of about 20,000 as a silicon polymer and a compound (F-8) 15 as a polymerizable fluorine-containing compound.
g was dissolved in 70 g of toluene, and this toluene solution was applied on a glass substrate by spin coating and then dried to form an organosilicon compound film having a thickness of about 2.2 μm.

A mask for a color filter was placed on the obtained organosilicon compound film, and a low pressure mercury lamp was used to apply ultraviolet rays of 0.5.
After irradiation with J / cm ² , after heating at 100 ° C. for 5 minutes and immersing in toluene for 1 minute, all were dissolved and a pattern could not be formed.

Separately from this, an ultraviolet ray of 0.5 J / cm ^{2 was applied} to the entire surface of this organic silicon compound film from a low pressure mercury lamp.
After irradiating, the substrate was heated at 100 ° C. for 10 minutes, further at 130 ° C. for 10 minutes, and at 150 ° C. for 30 minutes.

From the above results, it is understood that the silicon polymer composition of the present invention containing the silicon polymer and the polymerizable fluorine-containing compound forms a fluorine-containing siloxane crosslinked product having a low dielectric constant and a high Tg.

[0294]

As described in detail above, according to the present invention,
Provided are a fluorine-containing polysilane and a silicon polymer composition capable of producing a fluorine-containing siloxane crosslinked product having a low dielectric constant and a high Tg. Further, according to the present invention, there is provided a method for producing a fluorine-containing siloxane crosslinked product having the above-mentioned excellent properties.

The fluorine-containing siloxane crosslinked product produced according to the present invention is useful as a passivation film or an interlayer insulating film of a semiconductor device, and its industrial value is great.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Rikako Kani 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Incorporated Toshiba Research and Development Center

Claims (9)

[Claims] 1. A structural unit represented by the following general formula (1) and a structural unit represented by at least one selected from the following general formulas (2) to (4). Fluorine-containing polysilane copolymer. Embedded image (In the above general formula, Ar ¹ is an aromatic group, which may be substituted with a substituent containing no fluorine, Ar ² is a fluorine-substituted aromatic group, and R ¹ is a fluorine-substituted hydrocarbon group. .) 2. A film forming step of forming an organosilicon compound film mainly composed of a fluorine-containing polysilane represented by the following general formula (5) on a substrate, and a three-dimensional step of heating and drying the organosilicon compound film. A method for producing a crosslinked fluorine-containing siloxane, comprising: Embedded image (In the above general formula, Ar ¹ is an aromatic group, which may be substituted with a substituent containing no fluorine, Ar ² is a fluorine-substituted aromatic group, and R ¹ is a fluorine-substituted hydrocarbon group. Further, n, m, l and k are integers that satisfy the relations of m + l + k> 0 and n + l> 0.) 3. An exposure step of irradiating a predetermined region of the organosilicon compound film with ultraviolet rays prior to heating and drying the organosilicon compound film, and an exposed portion of the organosilicon compound film after the exposure with an alkaline aqueous solution. The method for producing a crosslinked fluorine-containing siloxane according to claim 2, comprising a developing step of dissolving and removing. 4. The method for producing a fluorine-containing siloxane crosslinked product according to claim 2, further comprising a whole surface exposure step of irradiating the organic silicon compound film with ultraviolet rays before heating and drying the organic silicon compound film. . 5. An exposure step of irradiating a predetermined region of the organosilicon compound film with ultraviolet light before heating and drying the organosilicon compound film, a heat treatment step of heating the exposed organosilicon compound film, and the heat treatment. The method for producing a crosslinked fluorine-containing siloxane according to claim 2, further comprising a developing step of dissolving and removing an unexposed portion of the organic silicon compound film afterwards with an organic solvent. 6. A silicon polymer composition comprising a silicon polymer represented by the following general formula (6) and a polymerizable fluorine-containing compound represented by the following general formula (7). Embedded image (In the above general formula, Ar ³ is a substituted or unsubstituted aromatic group, R ³ is a hydrogen atom or a methyl group, R ⁴ is a fluorine-substituted alkyl group, and A represents a single bond or an ester bond. Also, n represents the degree of polymerization.) 7. A silicon polymer composition comprising a silicon polymer represented by the following general formula (8) and a polymerizable fluorine-containing compound represented by the following general formula (7). Embedded image (In the above general formula, R ³ is a hydrogen atom or a methyl group, R ⁴ is a fluorine-substituted alkyl group, A represents a single bond or an ester bond, and R ⁵ is a hydrogen atom or a substituted or unsubstituted group. hydrocarbon group, R ⁶ is -OR ⁵ '(R
^5'is a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted hydrocarbon group. n represents the degree of polymerization. ) 8. A silicon polymer represented by the following general formula (9), a polymerizable fluorine-containing compound represented by the following general formula (7), a compound which generates an acid by exposure or heating, and a compound by exposure or heating. A silicon polymer composition, which comprises at least one compound which generates a radical. Embedded image (In the above general formula, R ³ is a hydrogen atom or a methyl group, R ⁴ is a fluorine-substituted alkyl group, A represents a single bond or an ester bond, and R ⁵ is a hydrogen atom or a substituted or unsubstituted group. hydrocarbon group, R ⁶ is -OR ⁵ '(R
^5'is a hydrogen atom or a substituted or unsubstituted hydrocarbon group), or a substituted or unsubstituted hydrocarbon group. n represents the degree of polymerization. ) 9. A silicon polymer represented by the following general formula (10), a polymerizable fluorine-containing compound represented by the following general formula (7), a compound which generates an acid by exposure or heating, and a compound by exposure or heating. A silicon polymer composition, which comprises at least one compound which generates a radical. [Chemical 6] (In the above general formula, Ar ³ is a substituted or unsubstituted aromatic group, R ³ is a hydrogen atom or a methyl group, R ⁴ is a fluorine-substituted alkyl group, and A represents a single bond or an ester bond. . N represents the degree of polymerization.)