JP2002038081A - Composition for forming film and material for forming insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a film excellent in heat resistance, low permittivity, crack resistance and adhesion properties to a substrate as an interlayer insulating film in a semiconductor element or the like. SOLUTION: The composition for forming a film comprises (A) both or either of an aromatic polyarylene and an aromatic polyarylene ether, (B) both or either of a silane coupling agent bearing a reactive group and a hydrolyzate condensate thereof and (C) an organic solvent. The material for forming an insulating film comprises this composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film-forming composition, and more particularly, to a material for an interlayer insulating film in a semiconductor device or the like, which is excellent in heat resistance, low dielectric property, crack resistance, and adhesion to a substrate. The present invention relates to a film-forming composition capable of forming a coating film.

[0002]

2. Description of the Related Art In recent years, in the application of electronic materials, circuit resistance and capacitance between wirings have been increased due to high integration, multifunctionality, and high performance. And the signal speed of the device is reduced, which is a major cause of crosstalk.
Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to reduce the parasitic capacitance and increase the speed of the device by covering the periphery of the wiring with a low dielectric interlayer insulating film. I'm trying to respond. In addition, in LCD-related applications, there is a demand for transparency in addition to low dielectric properties.

[0003] Polyimide is widely known as a heat-resistant organic material that meets this demand, but has a problem that it contains a highly polar imide group and thus has low dielectric properties, low water absorption, and is further colored. , Not satisfied.
On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. This polyphenylene is excellent in heat resistance, but is inferior in solubility in an organic solvent, so that a soluble group is generally introduced into a side chain. Examples of such polyphenylene include, for example, US Pat.
No. 14,044, International Application WO 96/28491
And European Patent Publication No. 629217. These polymers basically have a polyparaphenylene structure and partially copolymerize flexible monomers, but are only soluble in specific organic solvents, and have high viscosity solutions due to rigid molecules. There are problems, and the workability is not always satisfactory.

[0004] Further, imparting solvent resistance, physical heat resistance,
In order to improve mechanical properties, etc., crosslinking of polyphenylene-based polymers has also been studied. Conventionally, a crosslinking reaction utilizing acetylene bonds has been known. There is a limit in the reaction, and there is a problem in the versatility of processing that a special acetylene compound is used as a raw material and the curing temperature is high. In addition, introduction of an ether element into a polymer has been studied to enhance the processability and solubility of the polyarylene, but there is a problem in the heat resistance of the obtained polymer. As described above, at present, there are very few polymer technologies for imparting widely applicable curability by a simple process for improving heat resistance, low dielectric property, crack resistance, and adhesion to a substrate.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has excellent heat resistance, low dielectric properties, crack resistance, and adhesion to a substrate as an interlayer insulating film in a semiconductor device or the like. It is an object of the present invention to provide a composition for forming a film.

[0006]

The present invention provides (A) an aromatic polyarylene and / or an aromatic polyarylene ether, (B) a silane coupling agent having a reactive group, and a hydrolytic condensate thereof. And (C) a film-forming composition containing an organic solvent. Here, the component (A) is preferably a polymer having a repeating structural unit represented by the following formula (1) and / or a repeating structural unit represented by the following formula (2).

[0007]

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(R ^{7 to} R ¹¹ each independently represent a group having 1 carbon atom
To 20 hydrocarbon groups, cyano groups, nitro groups, 1 to 1 carbon atoms
20 alkoxyl groups, aryl groups, or halogen atoms, X is -CQQ'- (where Q and Q 'may be the same or different, and halogenated alkyl groups, alkyl groups, hydrogen atoms, halogen atoms, Atom or aryl group) and a fluorenylene group, wherein Y is -O-, -CO
-, - COO -, - CONH -, - S -, - SO 2 - and at least one selected from the group consisting of phenylene group, a is 0 or 1, b to f is 0-4 integer Wherein g is 5 to 100 mol%, h is 0 to 95 mol%, i is 0 to 95 mol% (g + h + i = 100 mol%), j is 0 to 100 mol%, and k is 0 to 100 mol%. %
(However, j + k = 100 mol%). 〕Also,
The component (A) preferably contains a hydrocarbon group having 1 to 20 carbon atoms in the polymer. On the other hand, as the silane coupling agent having a reactive group constituting the component (B),
An alkoxysilane compound containing a reactive double bond group and / or a triple bond group in the molecule, an acetoxysilane compound containing a reactive double bond group and / or a triple bond group in the molecule, At least one selected from the group consisting of an alkoxysilane compound containing a tolyl group in the molecule and an acetoxysilane compound containing a tolyl group in the molecule is preferable. The proportions of the components (A) and (B) are as follows.
The component (B) is 0.001 to 10 parts by weight based on 00 parts by weight. Further, the composition of the present invention, a radical generator,
At least one selected from the group consisting of a reactive double bond-containing compound and a reactive triple bond-containing compound may be contained. Next, the present invention relates to a material for forming an insulating film, comprising the above-described composition for forming a film.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Component (A) The component (A) of the present invention is an aromatic polyarylene and / or an aromatic polyarylene ether. As the component (A), a polymer having a repeating structural unit represented by the above formula (1) (hereinafter also referred to as “polymer (1)”) and a polymer having a repeating structural unit represented by the above formula (2) Polymer (hereinafter also referred to as “polymer (2)”),
Alternatively, a polymer having any one of the repeating structural units is preferable. The component (A) preferably contains a hydrocarbon group having 1 to 20 carbon atoms in the polymer from the viewpoint of improving the heat resistance of the coating film. The repeating structural unit of the polymer constituting the component (A) is preferably connected at the para-position to X because a high molecular weight polymer is obtained.

Polymer (1): The polymer (1) represented by the above formula (1) can be prepared, for example, by subjecting a monomer containing a compound represented by the following formula (3) to a catalyst system containing a transition metal compound. It can be produced by polymerization.

[0011]

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[In the formula (3), R ^{7 to} R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. The atom, X is -CQQ'- (where Q,
Q ′ may be the same or different and is at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group Yes, b ~
c represents an integer of 0 to 4, and Z represents an alkyl group, a halogenated alkyl group or an aryl group. ]

In Q and Q 'constituting X in the above formula (3), the alkyl group is a methyl group, an ethyl group, an i-
Propyl group, n-propyl group, butyl group, pentyl group,
Hexyl group and the like; halogenated alkyl groups such as trifluoromethyl group and pentafluoroethyl group; arylalkyl groups such as benzyl group and diphenylmethyl group; aryl groups such as phenyl group, biphenyl group, tolyl group, Examples thereof include a pentafluorophenyl group.

In the above formula (3), Z constituting --OSO ₂ Z is an alkyl group such as a methyl group or an ethyl group; and a halogenated alkyl group is a trifluoromethyl group or a pentafluoroethyl group. And the like; aryl groups include phenyl, biphenyl, p-tolyl,
Examples thereof include a p-pentafluorophenyl group.

X in the above formula (3) is
The divalent group shown in Chemical formula 11 is preferable. Of these,
Fluorenylene groups are more preferred.

[0016]

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Specific examples of the compound (monomer) represented by the above formula (3) include, for example, 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane and bis (4-methylsulfonyloxyphenyl) methane , Bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-methylsulfonyloxy-3)
-Methylphenyl) hexafluoropropane, 2,2-
Bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-
Methylsulfonyloxy-3,5-dimethylphenyl)
Hexafluoropropane, 2,2-bis (4-methylsulfonyloxyphenyl) propane, 2,2-bis (4
-Methylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3)
-Propenylphenyl) propane, 2,2-bis (4-
Methylsulfonyloxy-3,5-dimethylphenyl)
Propane, 2,2-bis (4-methylsulfonyloxy-3-fluorophenyl) propane, 2,2-bis (4
-Methylsulfonyloxy-3,5-difluorophenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxy-3- Propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxyphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (4-phenyl Sulfonyloxy-3-propenylphenyl) propane, 2,2-
Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy) Phenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis ( p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, bis (p-tolylsulfonyloxy-3-fluorophenyl) propane, bis (p-tolylsulfonyloxy-3,5-difluorophenyl) propane 9 , 9-bis (4-methylsulfonyloxyphenyl)
Fluorene, 9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ( 4-methylsulfonyloxy-3-propenylphenyl) fluorene, 9,
9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) Diphenylmethane, bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane,
Bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-methylsulfonyloxy-3-)
Fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl)
Fluorene, bis (4-methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxy-3-)
Methylphenyl) methane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4
-Methylsulfonyloxy-3-propenylphenyl)
Methane, bis (4-methylsulfonyloxyphenyl)
Trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenylmethane, 2,2-
Bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-
Trifluoromethylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3) -Propenylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) Fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9, 9-bis (4-trifluoromethylsulfonillo Ci-3-propenylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-) Fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-
Difluorophenyl) diphenylmethane, 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene , Bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) ) Methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-trifluoromethylsulfonyloxyphenyl) ), 2,2- Scan (4-phenylsulfonyl b hydroxyphenyl) hexafluoropropane, bis (4-phenylsulfonyl b hydroxyphenyl) methane, bis (4-phenylsulfonyl b hydroxyphenyl) diphenylmethane,
2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis ( 4-phenylsulfonyloxy-3,5-dimethylphenyl)
Hexafluoropropane, 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-phenylsulfur) Phonyloxy-3,5-dimethylphenyl) fluorene,
9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3) -Methylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3)
-Propenylphenyl) diphenylmethane, bis (4-
Phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl)
Fluorene, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxy-)
3-methylphenyl) methane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-phenylsulfonyloxy-3-propenylphenyl) methane, bis (4-phenylsulfonyloxyphenyl) ) Trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane 2,2-bis (p-tolylsulfonyloxyphenyl)
Hexafluoropropane, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy- 3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (p-tolylsulfonyloxyphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene, 9,9 -Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene,
9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethyl) Phenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-difluoro) Phenyl) diphenylmethane, 9,9-bis (p-tolylsulfonyloxy)
3-fluorophenyl) fluorene, 9,9-bis (p
-Tolylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxy-
3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane, bis (p-tolylsulfonyloxyphenyl) ) Trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like.

In the present invention, two or more compounds represented by the above formula (3) may be copolymerized.

The compound represented by the above formula (3) can be synthesized, for example, by the following production method. That is, a dihydroxy compound having two hydroxyl groups [eg, 2,2
-Bis (4-hydroxyphenyl) hexafluoropropane] and two or more equivalents of a dihydroxy compound in a solvent. At this time, pyridine or the like may be used as a solvent so that both the solvent and the base may be used.
If necessary, a catalyst such as 4-dimethylaminopyridine may be added.

Then, sulfonic acid chloride (anhydride) (for example, methanesulfonic acid chloride) is added to 15
The solution is added dropwise over 5 to 60 minutes under a stream of dry nitrogen while maintaining the temperature at not more than 0 ° C. Then, after stirring at that temperature for 0 to 60 minutes, the mixture is returned to room temperature and stirred for 0 to 24 hours to prepare a suspension. The obtained suspension is reprecipitated in 3 to 20 times the amount of ice water, the precipitate is recovered, and the operation such as recrystallization is repeated to obtain a bissulfonate compound as crystals.

Alternatively, first, a dihydroxy compound [for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane] is converted to a sodium hydroxide solution or the like.
Dissolve in an equivalent amount of an alkaline aqueous solution. On the other hand, sulfonic acid chloride (anhydride) (for example, methanesulfonic acid chloride) is dissolved in an organic solvent such as toluene and chloroform. Then, after a phase transfer catalyst such as acetyltrimethylammonium chloride is added to these, if necessary, the mixture is vigorously stirred. The desired bissulfonate compound can also be obtained by purifying the organic layer obtained by the reaction.

In the present invention, at least one compound represented by the above formula (3) and at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (5) may be copolymerized. Good.

[0023]

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[In the formula (4), R ^{9 to} R ¹⁰ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. The atoms R ^{12 to} R ¹³ represent —OSO ₂ Z (where Z represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and Y represents —O—, -CO-, -COO-, -CONH
-, - S -, - SO 2 - and at least one selected from the group consisting of phenylene group, a is 0 or 1,
de shows an integer of 0-4. ]

Of R ^{9 to} R ¹⁰ , a halogen atom is a fluorine atom, a monovalent organic group is an alkyl group such as a methyl group or an ethyl group, a halogenated alkyl group is a trifluoromethyl group, Examples of an allyl group such as a pentafluoroethyl group include a propenyl group and the like, and examples of an aryl group include a phenyl group and a pentafluorophenyl group. Examples of Z constituting —OSO ₂ Z include a methyl group and an ethyl group as an alkyl group, a trifluoromethyl group and the like as a halogenated alkyl group, a phenyl group, a p-tolyl group, and a p- Examples include a fluorophenyl group.

The compound represented by the above formula (4) includes, for example, 4,4'-dimethylsulfonyloxybiphenyl,
4,4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl, 4,4'-dibromobiphenyl,
4,4'-diiodobiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,
4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl, 4,4'-dimethylsulfonyloxy-
3,3 ', 5,5'-tetrafluorobiphenyl, 4,
4'-dibromooctafluorobiphenyl, 4,4-methylsulfonyloxyoctafluorobiphenyl, 3,
3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl, 4,4'-dichloro-2,2'-trifluoromethylbiphenyl, 4,4 '
-Dibromo-2,2'-trifluoromethylbiphenyl, 4,4'-diiodo-2,2'-trifluoromethylbiphenyl, bis (4-chlorophenyl) sulfone, 4,4'-dichlorobenzophenone, 2,4- Dichlorobenzophenone and the like can be mentioned.

The compounds represented by the above formula (4) can be used alone or in combination of two or more.

[0028]

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[0029] In the formula (5), R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom,, R ¹⁴
To R ¹⁵ are, -OSO ₂ Z (wherein, Z is an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, f is an integer of 0-4. ]

In R ¹¹ , a halogen atom is a fluorine atom, a monovalent organic group is an alkyl group such as a methyl group or an ethyl group, and a halogenated alkyl group is a trifluoromethyl group or a pentafluoroethyl group. Examples of the aryl group include a propenyl group and the like. Examples of the aryl group include a phenyl group and a pentafluorophenyl group. Z constituting —OSO ₂ Z
Examples thereof include an alkyl group such as a methyl group and an ethyl group, a halogenated alkyl group such as a trifluoromethyl group, and an aryl group such as a phenyl group, a p-tolyl group, and a p-fluorophenyl group.

The compound represented by the above formula (5) includes, for example, o-dichlorobenzene, o-dibromobenzene, o-dichlorobenzene,
-Diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3 , 4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene, m
-Dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiodotoluene, 3,5-dichloro Toluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2 2,6-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5
-Dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxy Phenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2, Methyl 4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,
Methyl 5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate,
Examples thereof include t-butyl 3,5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, and t-butyl 3,5-dibromobenzoate.
Dichlorobenzene, 2,4-dichlorotoluene, 3,5
-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene and the like.

The compounds represented by the above formula (5) can be used alone or in combination of two or more.

In the above formula (1), the proportion of the repeating structural unit in the polymer (1) is 5 to 100 mol%,
Is 0 to 95 mol%, i is 0 to 95 mol% (however, g +
h + i = 100 mol%).

The catalyst used for producing the polymer (1) used in the present invention is preferably a catalyst system containing a transition metal compound, and the catalyst system includes a transition metal salt and a ligand, or a coordination catalyst. A transition metal (salt) to which a ligand is coordinated and a reducing agent are essential components, and a “salt” may be added to increase the polymerization rate.

Here, the transition metal salt includes nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium chloride;
Examples thereof include palladium compounds such as palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferred.

Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, and 1,3-bis (diphenylphosphino) propane. Phenylphosphine and 2,2'-bipyridine are preferred. The ligand is
One type may be used alone, or two or more types may be used in combination.

Further, as the transition metal (salt) to which a ligand has been previously coordinated, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2 -Triphenylphosphine, nickel chloride 2,2 'bipyridine, nickel bromide 2,2' bipyridine, nickel iodide 2,2 'bipyridine, nickel nitrate 2,2' bipyridine, bis (1,5-cyclooctadiene) nickel , Tetrakis (triphenylphosphine)
Nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, and nickel chloride 2 triphenylphosphine and nickel chloride 2,2 ′ bipyridine are preferred.

Examples of the above-mentioned reducing agent which can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium and calcium, and zinc and manganese are preferred. These reducing agents can be used more activated by contact with an acid or an organic acid.

The "salt" which can be used in such a catalyst system includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, and the like.
Potassium compounds such as potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate can be given. But sodium bromide,
Preferred are sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide.

The use ratio of each component in such a catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is the compound of the above formula (3), (4) or (5) Usually, 0.0001 to 10 mol, based on 1 mol of the total amount of
Preferably it is 0.01-0.5 mol. 0.0001
If the amount is less than the mole, the polymerization reaction does not proceed sufficiently, while
If it exceeds 10 mol, the molecular weight may decrease.

When a transition metal salt and a ligand are used in such a catalyst system, the ligand is used in an amount of usually 0.1 to 100 mol, preferably 1 to 100 mol, per mol of the transition metal salt. 10 to 10 mol. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient.
There is a problem that the molecular weight decreases.

The proportion of the reducing agent used in the catalyst system is usually 0.1 to 100 mol, preferably 1 to 100 mol, per 1 mol of the total amount of the compounds of the above formulas (3), (4) and (5). 10 moles. If the amount is less than 0.1 mol, the polymerization does not proceed sufficiently. On the other hand, if it exceeds 100 mol, the purification of the obtained polymer may be difficult.

Further, when a “salt” is used in the catalyst system,
The proportion of the compound is usually 0.001 to 100 per 1 mol of the total amount of the compounds of the above formulas (3), (4) and (5).
Mole, preferably 0.01 to 1 mole. 0.001
If the amount is less than mol, the effect of increasing the polymerization rate is insufficient, while if it exceeds 100 mol, purification of the obtained polymer may be difficult.

Examples of the polymerization solvent usable in the present invention include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2
-Pyrrolidone, γ-butyrolactone, γ-butyrolactam, etc., and tetrahydrofuran, N,
N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone are preferred. These polymerization solvents are preferably used after being sufficiently dried.

The above formulas (3) and (4) in a polymerization solvent
The concentration of the total amount of the compound of (5) is usually 1 to 10
0% by weight, preferably 5 to 40% by weight.

The polymerization temperature at the time of polymerizing the above polymer is usually 0 to 200 ° C., preferably 50 to 80 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours. The weight average molecular weight of the polymer in terms of polystyrene is usually 1,000 to 1,000.
1,000,000.

Polymer (2): The polymer (2) represented by the above formula (2) is obtained by, for example, polymerizing a monomer containing a compound represented by the following formulas (6) to (8) in the presence of a catalyst system. It can be manufactured by doing.

[0048]

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[In the formula (6), R ^{7 to} R ⁸ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. The atom, X is -CQQ'- (where Q,
Q ′ may be the same or different and is at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group Yes, b ~
c represents an integer of 0 to 4, and R ^{16 to} R ¹⁷ represent at least one selected from the group consisting of a hydroxyl group, a halogen atom, and an —OM group (M is an alkali metal). ]

Specific examples of the compound (monomer) represented by the above formula (6) include, for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane (Hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane,
2-bis (4-hydroxy-3-propenylphenyl)
Hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3- Methylphenyl) propane, 2,2-bis (4-hydroxy-3-propenylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2
-Bis (4-hydroxy-3-fluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-difluorophenyl) propane, 2,2-bis (4-chlorophenyl) hexafluoropropane, bis (4 -Chlorophenyl) methane, bis (4-chlorophenyl) diphenylmethane, 2,2-bis (4-chloro-3-methylphenyl) hexafluoropropane, 2,2-bis (4-chloro-3-propenylphenyl) hexafluoropropane 2,2-bis (4-chloro-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-chlorophenyl) propane, 2,2-bis (4-chloro-
3-methylphenyl) propane, 2,2-bis (4-chloro-3-propenylphenyl) propane, 2,2-bis (4-chloro-3,5-dimethylphenyl) propane, 2,2-bis (4 -Chloro-3-fluorophenyl) propane, 2,2-bis (4-chloro-3,5-difluorophenyl) propane, 2,2-bis (4-chlorophenyl) hexafluoropropane, bis (4-bromophenyl) Methane, bis (4-bromophenyl) diphenylmethane, 2,2-bis (4-bromo-3-methylphenyl) hexafluoropropane, 2,2-bis (4
-Bromo-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-bromo-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4
-Bromophenyl) propane, 2,2-bis (4-bromo-3-methylphenyl) propane, 2,2-bis (4
-Bromo-3-propenylphenyl) propane, 2,2
-Bis (4-bromo-3,5-dimethylphenyl) propane, 2,2-bis (4-bromo-3-fluorophenyl) propane, 2,2-bis (4-bromo-3,5-difluorophenyl) Propane, bis (4-fluorophenyl) methane, bis (4-fluorophenyl) diphenylmethane, 2,2-bis (4-fluoro-3-methylphenyl) hexafluoropropane, 2,2-bis (4-
Fluoro-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-fluoro-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-fluorophenyl) propane, 2,2-bis (4
-Fluoro-3-methylphenyl) propane, 2,2-
Bis (4-fluoro-3-propenylphenyl) propane, 2,2-bis (4-fluoro-3,5-dimethylphenyl) propane, 2,2-bis (4-fluoro-3-
Fluorophenyl) propane and 2,2-bis (4-fluoro-3,5-difluorophenyl) propane. Among the above compounds, the compounds having a hydroxyl group may be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.

In the present invention, two or more compounds represented by the above formula (6) can be copolymerized.

[0052]

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[In the formula (7), R ^{9 to} R ¹⁰ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. And R ^{18 to} R ¹⁹ represent at least one selected from the group consisting of a hydroxyl group, a halogen atom, and an —OM group (M is an alkali metal), and Y represents —O—, —CO
-, - COO -, - CONH -, - S -, - SO 2 - and at least one selected from the group consisting of phenylene group, a is 0 or 1, d-e is 0-4 integer Is shown. ]

The compounds represented by the above formula (7) include, for example, 4,4'-dichlorobiphenyl, 4,4'-dibromobiphenyl, 4,4'-difluorobiphenyl,
4'-diiodobiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dipropenylbiphenyl, 4,4'-dihydroxy-3,3 '
-Dimethylbiphenyl, 4,4'-dihydroxy-3,
3'-diethylbiphenyl, 4,4'-dimethylhydroxy-3,3 ', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl,
4,4-dihydroxyoctafluorobiphenyl, 3,
3'-diallyl-4,4'-bis (4-hydroxy) biphenyl, 4,4'-dichloro-2,2'-trifluoromethylbiphenyl, 4,4'-dibromo-2,2'-
Trifluoromethylbiphenyl, 4,4'-diiodo-
2,2'-trifluoromethylbiphenyl, bis (4-
Chlorophenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (4-chlorophenyl) ether, bis (4-hydroxyphenyl) ether, 4,
4'-dichlorobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dichlorobenzophenone,
2,4-dihydroxybenzophenone and the like can be mentioned.

Among the above compounds, the compounds having a hydroxyl group may be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.

The compounds represented by the above formula (7) can be used alone or in combination of two or more.

[0057]

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[0058] In the formula (8), R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom,, R ²⁰
To R ²¹ are, -OSO ₂ Z (wherein, Z is an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, f is an integer of 0-4. ]

The compounds represented by the above formula (8) include, for example, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3
-Dihydroxytoluene, 2,5-dihydroxytoluene, 2,6-dihydroxytoluene, 3,4-dihydroxytoluene, 3,5-dihydroxytoluene, o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o- Dimethylsulfonyloxybenzene,
2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfone Phonyloxybenzene,
3,4-dimethylsulfonyloxybenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,
4-dichlorotoluene, 2,4-dibromotoluene,
2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodo Toluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride,
2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6 -Tetrafluorobenzene, 2,4-dichlorobenzyl alcohol,
3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxy Phenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid,
3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, methyl 2,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,5
-Methyl dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate, 3,
T-butyl 5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, t-butyl 3,5-dibromobenzoate
-Butyl and the like.

Among the above compounds, the compounds having a hydroxyl group may be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.

The compounds represented by the above formula (8) can be used alone or in combination of two or more.

The proportion of the repeating structural unit in the polymer represented by the above formula (2) is such that in the above formula (2), j is from 0 to 0.
100 mol%, k is 0 to 100 mol% (however, j + k
= 100 mol%).

As a method for synthesizing the polymer represented by the above formula (2), for example, the polymer is obtained by heating a dihydroxy compound having two hydroxyl groups and a dihalogenated compound in a solvent in the presence of an alkali metal compound. .

The dihydroxy compound and the dihalogenated compound are used in an amount of 45 to 55 mol%, preferably 48 to 52 mol%, and 55 to 45 mol%, preferably 52 to 48 mol%, of the dihydroxy compound. is there. When the use ratio of the dihydroxy compound is less than 45 mol% or more than 55 mol%, the molecular weight of the polymer hardly increases, and the coatability of the coating film may be poor.

The alkali metal compound used in this case includes, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, hydride Examples thereof include sodium, potassium hydride, lithium hydride, metal sodium, metal potassium, and metal lithium. These may be used alone or in combination of two or more.

The amount of the alkali metal compound to be used is generally 100 to 400 mol%, preferably 100 to 250 mol%, based on the dihydroxy compound.

In order to accelerate the reaction, copper metal, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, and sulfuric acid A co-catalyst such as cuprous copper, cupric sulfate, cuprous acetate, cupric acetate, cuprous formate, and cupric formate may be used. The amount of the cocatalyst to be used is generally 1 to 50 mol%, preferably 1 to 30 mol%, based on the dihydroxy compound.

Examples of the solvent used in the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (alkoxyl group has 1 to 4 carbon atoms), and trialkoxybenzene (alkoxyl group has 1 to 4 carbon atoms). , Diphenyl sulfone, dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide,
Diethylsulfone, diisopropylsulfone, tetrahydrofuran, tetrahydrothiophene, sulfolane, N
-Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone,
Dimethylformamide, dimethylacetamide and the like can be used. These may be used alone or in combination of two or more.

The reaction concentration when synthesizing the polymer represented by the formula (2) is 2 to 2 based on the weight of the monomer.
50% by weight and the reaction temperature is 50 to 250 ° C.
Further, in order to remove metal salts and unreacted monomers generated during the synthesis of the polymer, the reaction solution is filtered, or the reaction solution is reprecipitated with a solvent that is a poor solvent for the polymer or washed with an acidic or alkaline aqueous solution. Is preferred.

The weight average molecular weight of the polymer represented by the formula (2) obtained by the GPC method is usually 5
00 to 500,000, preferably 800 to 100,0
00.

Component (B) The film-forming composition of the present invention contains the components (A) and (B). The component (B) is a silane coupling agent having a reactive group and / or a hydrolytic condensate thereof. Here, (B) the silane coupling agent having a reactive group includes, for example, an alkoxysilane compound containing a reactive double bond group and / or a triple bond group in the molecule, and a reactive silane coupling agent in the molecule. An acetoxysilane compound containing a double bond group and / or a triple bond group, an alkoxysilane compound containing a tolyl group in the molecule, and at least one selected from the group consisting of an acetoxysilane compound containing a tolyl group in the molecule. One type is mentioned.

Specific examples of the silane coupling agent (B) having a reactive group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, and vinyltri-n-silane. Butoxysilane, vinyltri-i-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-t-butoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane,
Divinyl di-n-butoxy silane, divinyl di-i-butoxy silane, divinyl di-sec-butoxy silane,
Divinyldi-t-butoxysilane, trivinylmethoxysilane, trivinylethoxysilane, trivinyl-n-
Propoxysilane, trivinyl-i-propoxysilane, trivinyl-n-butoxysilane, trivinyl-i
-Butoxysilane, trivinyl-sec-butoxysilane, trivinyl-t-butoxysilane, vinyltris (2-methoxyethoxy) silane, divinylbis (2-
Methoxyethoxy) silane, trivinyl (2-methoxyethoxy) silane; vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, divinylmethylmethoxy Silane, divinylmethylethoxysilane, divinylethylmethoxysilane, divinylethylethoxysilane, divinylphenylmethoxysilane, divinylphenylethoxysilane; 1,3-divinyltetramethoxysiloxane, 1,3-divinyltetraethoxysiloxane, 1,3-divinyl -1,3-dimethyldimethoxysiloxane, 1,3-divinyl-1,
3-dimethyldiethoxysiloxane; vinyltriacetoxysilane, divinyldiacetoxysilane, trivinylacetoxysilane, vinylmethyldiacetoxysilane,
Vinylethyldiacetoxysilane, vinylphenyldiacetoxysilane, divinylmethylacetoxysilane, divinylethylacetoxysilane, divinylphenylacetoxysilane, 1,3-divinyltetraacetoxysiloxane, 1,3-divinyl-1,3-dimethyldiacetoxysiloxane ; (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) dimethylethoxysilane, N-3- (acryloxy-2-hydropropyl) -3-aminopropyltrimethoxysilane, N-3- (acryloxy) -2-hydropropyl)-
3-aminopropyltriethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) methyldiethoxysilane, (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) tri Ethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-
Allylamino) propyltriethoxysilane, allyldimethoxysilane, allyldiethoxysilane; ethynyltrimethoxysilane, ethynyltriethoxysilane, ethynyltri-n-propoxysilane, ethynyltri-i-
Propoxysilane, ethynyltri-n-butoxysilane, ethynyltri-i-butoxysilane, ethynyltri-sec-butoxysilane, ethynyltri-t-butoxysilane, diethynyldimethoxysilane, diethynylethoxysilane, diethynyl-n-propoxysilane, diethynyldi I-propoxysilane, diethynyldi-n-butoxysilane, diethynyldi-i-butoxysilane, diethynyldi-sec-butoxysilane, diethynyldi-t-butoxysilane, triethynylmethoxysilane, triethynylethoxysilane, triethynyl-
n-propoxysilane, triethynyl-i-propoxysilane, triethynyl-n-butoxysilane, triethynyl-i-butoxysilane, triethynyl-sec-butoxysilane, triethynyl-t-butoxysilane, ethynyltris (2-methoxyethoxy) silane, Diethynylbis (2-methoxyethoxy) silane, triethynyl (2-methoxyethoxy) silane; ethynylmethyldimethoxysilane, ethynylmethyldiethoxysilane, ethynylethyldimethoxysilane, ethynylethyldiethoxysilane, ethynylphenyldimethoxysilane, ethynylphenyldiethoxysilane , Diethynylmethylmethoxysilane, diethynylmethylethoxysilane, diethynylethylmethoxysilane, diethynylethylethoxysilane, diethini Phenylmethoxysilane, diethynylphenylethoxysilane; 1,3-diethynyltetramethoxysiloxane, 1,3-diethynyltetraethoxysiloxane, 1,3-diethynyl-1,3-dimethyldimethoxysiloxane, 1,3-diethynyl- 1,3-
Dimethyldiethoxysiloxane; ethynyltriacetoxysilane, diethynyldiacetoxysilane, triethynylacetoxysilane, ethynylmethyldiacetoxysilane, ethynylethyldiacetoxysilane, ethynylphenyldiacetoxysilane, diethynylmethylacetoxysilane, diethynylethylacetoxysilane , Diethynylphenylacetoxysilane, 1,3-diethynyltetraacetoxysiloxane, 1,3-diethynyl 1,3-
Dimethyldiacetoxysiloxane; (phenylethynyl) trimethoxysilane, (phenylethynyl) triethoxysilane, (phenylethynyl) tri-n-propoxysilane, (phenylethynyl) tri-i-propoxysilane, (phenylethynyl) tri-n -Butoxysilane, (phenylethynyl) tri-i-butoxysilane, (phenylethynyl) tri-sec-butoxysilane, (phenylethynyl) tri-t-butoxysilane,
Bis (phenylethynyl) dimethoxysilane, bis (phenylethynyl) diethoxysilane, bis (phenylethynyl) di-n-propoxysilane, bis (phenylethynyl) di-i-propoxysilane, bis (phenylethynyl) di-n- Butoxysilane, bis (phenylethynyl) di-i-butoxysilane, bis (phenylethynyl) di-sec-butoxysilane, bis (phenylethynyl) di-t-butoxysilane, tris (phenylethynyl) methoxysilane, tris (phenyl Ethynyl) ethoxysilane, tris (phenylethynyl) -n-propoxysilane, tris (phenylethynyl) -i-propoxysilane, tris (phenylethynyl) -n-butoxysilane, tris (phenylethynyl) -i-butoxysilane, tris Phenylethynyl)-sec-butoxysilane, tris (phenylethynyl)-t-butoxysilane, (phenylethynyl) tris (2-methoxyethoxy) silane, bis (phenylethynyl) bis (2
-Methoxyethoxy) silane, tris (phenylethynyl) (2-methoxyethoxy) silane; (phenylethynyl) methyldimethoxysilane, (phenylethynyl)
Methyldiethoxysilane, (phenylethynyl) ethyldimethoxysilane, (phenylethynylethyl) diethoxysilane, (phenylethynyl) phenyldimethoxysilane, (phenylethynyl) phenyldiethoxysilane, bis (phenylethynyl) methylmethoxysilane,
Bis (phenylethynyl) methylethoxysilane, bis (phenylethynyl) ethylmethoxysilane, bis (phenylethynyl) ethylethoxysilane, bis (phenylethynyl) phenylmethoxysilane, bis (phenylethynyl) phenylethoxysilane; 1,3-bis (Phenylethynyl) tetramethoxysiloxane, 1,3-
Bis (phenylethynyl) tetraethoxysiloxane,
1,3-bis (phenylethynyl) -1,3-dimethyldimethoxysiloxane, 1,3-bis (phenylethynyl) -1,3-dimethyldiethoxysiloxane; (phenylethynyl) triacetoxysilane, bis (phenylethynyl) Diacetoxysilane, tris (phenylethynyl) acetoxysilane, (phenylethynyl) methyldiacetoxysilane, (phenylethynyl) ethyldiacetoxysilane, (phenylethynyl) phenyldiacetoxysilane, bis (phenylethynyl) methylacetoxysilane, bis ( Phenylethynyl) ethylacetoxysilane, bis (phenylethynyl) phenylacetoxysilane, 1,3-bis (phenylethynyl) tetraacetoxysiloxane, 1,3-bis (phenylethynyl) -1,3-dimethyl Luzia Seto alkoxy siloxane, bis (trimethoxysilyl) acetylene, bis (triethoxysilyl) acetylene; p-tolyl trimethoxysilane, p- tolyl triethoxysilane, p- Torirutori -
n-propoxysilane, p-tolyltri-i-propoxysilane, m-tolyltrimethoxysilane, m-tolyltriethoxysilane, m-tolyltri-n-propoxysilane, m-tolyltri-i-propoxysilane; p-
Tolyl triacetoxy silane, m-tolyl triacetoxy silane and the like can be mentioned. Two or more of these (B) silane coupling agents having a reactive group may be used simultaneously.

As the component (B), in addition to the silane coupling agent having a reactive group as described above, a hydrolyzate of these silane coupling agents and / or a condensate thereof (hereinafter, these silane coupling agents are referred to as component (B)) May be collectively referred to as “hydrolysis condensate”).

In hydrolyzing and condensing at least one silane coupling agent selected from the group of the above-mentioned compounds, water of more than 0.5 mol and 150 mol or less per 1 mol of the compound may be used. It is particularly preferred to add more than 0.5 mol and 130 mol of water.

In producing the hydrolysis-condensation product serving as the component (B), a catalyst may be used when hydrolyzing and condensing at least one silane coupling agent selected from the group consisting of the above compounds. good. Examples of the catalyst that can be used at this time include a metal chelate compound, an acid catalyst, and an alkali catalyst.

Here, examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, and tri-i-propoxy mono (acetylacetonate). Titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (acetylacetonate) Nart) titanium, di-n-
Propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate)
Titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetyl) Acetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n
-Butoxy-tris (acetylacetonate) titanium,
Mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n- Propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t
-Butoxy bis (ethyl acetoacetate) titanium,
Monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelating compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy・ Mono (acetylacetonate) zirconium, tri-
n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonate) Nart) zirconium,
Tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxy.
Bis (acetylacetonate) zirconium, di-n-
Butoxy bis (acetylacetonate) zirconium, di-sec-butoxy bis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono -N-propoxy tris (acetylacetonate) zirconium, mono-i-propoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetyl) (Acetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium Tri -n- propoxy mono (ethylacetoacetate) zirconium, tri -i
-Propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-
Butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di- n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium , Mono-n
-Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-
sec-butoxy tris (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; Is a chelate compound of titanium or aluminum, particularly preferably a chelate compound of titanium. These metal chelate compounds may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and oxalic acid;
Acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid, Arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid,
Benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid And organic acids such as succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, a hydrolyzate of glutaric acid, a hydrolyzate of maleic anhydride, and a hydrolyzate of phthalic anhydride. And organic acids can be mentioned as more preferred examples. These compounds may be used alone or in combination of two or more.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
Picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, ammonia,
Methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine, decylamine,
N, N-dimethylamine, N, N-diethylamine,
N, N-dipropylamine, N, N-dibutylamine,
Trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and the like, and more preferably an organic amine Yes, ammonia, alkylamine and tetramethylammonium hydroxide are particularly preferred in view of the adhesion of the silica-based film to the substrate. One or two or more of these alkali catalysts may be used simultaneously.

The amount of the catalyst to be used is generally 0.000001 to 10 mol, preferably 0.000005 to 5 mol, per 1 mol of the total amount of the compounds. When the amount of the catalyst used is within the above range, there is little risk of precipitation of the component (B) and gelation during the reaction.

(B) The hydrolysis condensate is synthesized in at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents. it can. Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methyl Butanol,
sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol,
sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,
Ethylene glycol mono-2-ethyl butyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether,
Polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether; and the like. These alcohol solvents may be used alone or in combination.
More than one species may be used simultaneously.

Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl
n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-
Butyl ketone, methyl-n-hexyl ketone, di-i-
In addition to butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and fenchone, acetylacetone, 2,4-hexanedione, 2,4 -Heptanedione, 3,5-heptanedion, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2, 2,6,6-tetramethyl-3,5
Β-diketones such as -heptanedione and 1,1,1,5,5,5-hexafluoro-2,4-heptanedione. These ketone solvents may be used alone or in combination of two or more.

The amide solvents include formamide, N
-Methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
N-dimethylacetamide, N-ethylacetamide,
N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. Can be One or two or more of these amide solvents may be used simultaneously.

Examples of the ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ
Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, acetic acid 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate,
Cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-acetate
n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Methoxy triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, malonic acid Examples thereof include diethyl, dimethyl phthalate, and diethyl phthalate. These ester solvents are
One type or two or more types may be used simultaneously.

Examples of the aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, and N-methylpyrrole.
Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N −
Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1
H) -pyrimidinone and the like. These aprotic solvents may be used alone or in combination of two or more.

(B) Hydrolysis of silane coupling agent
For the condensation, for example, water or water diluted with the solvent is intermittently or continuously added to a solvent in which the compound is dissolved. At this time, the catalyst may be added to the solvent in advance, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually
It is 0-100 degreeC, Preferably it is 15-90 degreeC.

The weight-average molecular weight in terms of polystyrene of the hydrolyzed condensate of the silane coupling agent (B) thus obtained is usually from 300 to 100,000, preferably from 300 to 20,000.

The proportion of the components (A) and (B) in the composition is 0.001 to 10 parts by weight, preferably 0.005 parts by weight, per 100 parts by weight of the component (A).
８8 parts by weight. (B) The use ratio of the component is 0.001.
If the amount is less than 10 parts by weight, the adhesion of the coating film to the substrate may be impaired, while if it exceeds 10 parts by weight, the heat resistance of the coating film may be poor.

(C) Organic Solvent The film-forming composition of the present invention is obtained by dissolving or dispersing the components (A) and (B) in the organic solvent (C). Examples of the (C) organic solvent used in the present invention include n-pentane, i-pentane, n-hexane, i-hexane, and n-pentane.
Heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane,
Aliphatic hydrocarbon solvents such as methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i
Aromatic hydrocarbon solvents such as -butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-
Methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,
2-methylpentanol, sec-hexanol, 2-
Ethyl butanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol,
sec-octanol, n-nonyl alcohol, 2,6
-Dimethylheptanol-4, n-decanol, sec
-Undecyl alcohol, trimethyl nonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol,
Monoalcohol solvents such as methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol and cresol; ethylene glycol, 1,
2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1 ,
3, diethylene glycol, dipropylene glycol,
Triethylene glycol, tripropylene glycol,
Polyhydric alcohol solvents such as glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-
Butyl ketone, methyl-n-pentyl ketone, ethyl-
n-butyl ketone, methyl-n-hexyl ketone, di-
i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,
Ketone solvents such as 4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone and fenchone; ethyl ether, i-propyl ether, n
-Butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, Diethylene glycol mono-n-butyl Ether, diethylene glycol di -n- butyl ether, diethylene glycol mono -n
-Hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether solvents such as ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate,
γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate
Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate,
Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene acetate Glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-lactic acid n
Ester solvents such as -butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate;
N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N
Nitrogen-containing solvents such as -methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide,
Examples thereof include sulfur-containing solvents such as thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone.

These solvents can be used alone or in combination of two or more.

Other Additives The composition for forming a film obtained by the present invention further comprises colloidal silica, colloidal alumina, an organic polymer, a surfactant, a triazene compound, a radical generator, and a compound containing a reactive double bond. And a component such as a reactive triple bond-containing compound. The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle diameter of 5 to 30 mμ, preferably 10 to 20 mμ, and a solid concentration of 10 to 10 μm. It is about 40% by weight. As such colloidal silica,
Examples thereof include methanol silica sol and isopropanol silica sol, manufactured by Nissan Chemical Industries, Ltd .; Oscar, manufactured by Catalyst Chemicals, Inc. Examples of the colloidal alumina include alumina sol 5 manufactured by Nissan Chemical Industries, Ltd.
20, 100, 200; alumina clear sol, alumina sol 10, manufactured by Kawaken Fine Chemical Co., Ltd.
132 and the like. Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound,
Examples include dendrimers, polyimides, polyamic acids, polyamides, polyquinoxalines, polyoxadiazoles, fluoropolymers, compounds having a polyalkylene oxide structure, and the like.

Compound having a polyalkylene oxide structure
Compounds include polymethylene oxide structure, polyethylene
Len oxide structure, polypropylene oxide structure,
Polytetramethylene oxide structure, polybutylene oxide
And a side structure. Specifically,
Tylene alkyl ether, polyoxyethylene alkyl
Ether, polyoxyethylene alkylphenyl acrylate
Ter, polyoxyethylene sterol ether, polio
Xyethylene lanolin derivative, alkylphenol phor
Ethylene oxide derivative of marine condensate, polyoxyethylene
Polyoxypropylene block copolymer, polyoxy
Siethylene polyoxypropylene alkyl ether, etc.
Ether type compound, polyoxyethylene glycerin fat
Fatty acid ester, polyoxyethylene sorbitan fatty acid
Stele, polyoxyethylene sorbitol fatty acid esthetic
, Polyoxyethylene fatty acid alkanolamide sulfuric acid
Ether ester type compounds such as salts, polyethylene glycol
Chole fatty acid ester, ethylene glycol fatty acid ester
Ter, fatty acid monoglyceride, polyglycerin fatty acid ester
Stele, sorbitan fatty acid ester, propylene glyco
Fatty acid esters and sucrose fatty acid esters
Terester type compounds and the like can be mentioned. Poly
Oxytylene polyoxypropylene block copolymer
As the compound having the following block structure
No. -(X ') p- (Y') q--(X ') p- (Y') q- (X ') r- wherein X' is -CH_TwoCH_TwoA group represented by O-
Y 'is -CH_TwoCH (CH _Three) Represents a group represented by O-
And p is a number from 1 to 90, q is a number from 10 to 99, and r is a number from 0 to 90
Is shown. ]

Among them, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Ether-type compounds such as fatty acid esters can be mentioned as more preferable examples. These may be used alone or in combination of two or more.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the surfactant include a surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant, and preferably a fluorine-based surfactant and a silicone-based surfactant.

As the fluorine-based surfactant, for example,
1,1,2,2-tetrafluorooctyl (1,1,2,2
2-tetrafluoropropyl) ether, 1,1,2,2
-Tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,
2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3- Hexafluoropentyl)
Ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amido) propyl] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain such as perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1). Commercially available products are MegaFac F142D, F172, F173, and F173.
183 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC-430, FC-431
[Sumitomo 3M Ltd.], Asahi Guard AG71
0, Surflon S-382, SC-101, SC-
102, SC-103, SC-104, SC-1
05, SC-106 [manufactured by Asahi Glass Co., Ltd.], BM-10
00, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15
Examples include a fluorine-based surfactant commercially available under a name such as [NEOS CORPORATION]. Among them, the above MegaFac F172, BM-1000, BM-11
00, NBX-15 is particularly preferred.

Examples of the silicone-based surfactant include SH7PA, SH21PA, SH30PA, and ST9.
4PA (all manufactured by Dow Corning Toray Silicone Co., Ltd.) can be used. Among them, SH28PA and SH30PA are particularly preferable.

The amount of the surfactant to be used is 100% for the component (A).
It is usually 0.00001 to 1 part by weight based on part by weight. These may be used alone or in combination of two or more.

As the triazene compound, for example, 1,
2-bis (3,3-dimethyltriazenyl) benzene,
1,3-bis (3,3-dimethyltriazenyl) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis ( 3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3 ,
3-dimethyltriazenylphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)- 9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3- Phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl-4- (3,3 -Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl] Fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3
-Dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene and the like. These are 1
Species or two or more species may be used simultaneously.

Examples of the radical generator include, for example, isobutyryl peroxide, α, α'bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxide Oxydicarbonate,
1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2 -Ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, lauroyl par Oxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy ) Hexane, 1-cyclohexyl-
1-methylethyl peroxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, dibenzyl, 2,3-dimethyl-2,3-diphenylbutane, α, α′-dimethoxy-α, α′-diphenylbibenzyl, α, α′-diphenyl-α-methoxybibenzyl, α, α′-diphenyl-α, α′-dimethoxybibenzyl, α, α′-dimethoxy-α, α′-dimethylbibenzyl, α, α′- Dimethoxybibenzyl,
Examples thereof include 3,4-dimethyl-3,4-diphenyl-n-hexane and 2,2,3,3-tetraphenylsuccinic nitrile. These are one or two
More than one species may be used simultaneously.

Examples of the compound containing a reactive double bond include, for example, allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, α, .- diallyloxyalkanes, α ,. ―Diallyl alkenes, α, ・ ―
Diallyl alkenes, allylamine, diallylamine,
Allyl compounds such as triallylamine, N-allylphthalimide, N-allylpyromellitimide, N, N'-diallylurea, triallyl isocyanurate, 2,2'-diallylbisphenol A; styrene, divinylbenzene, trivinylbenzene, stilbene , Propenylbenzene, dipropenylbenzene, tripropenylbenzene, phenylvinylketone, methylstyrylketone,
α,.-divinyl alkanes, α, ...-divinyl alkenes, α, ...-divinyl alkynes, α, ...-divinyloxyalkanes, α, ...-divinyl alkenes, α,
.-Divinylalkynes, α, .- Diacryloxyalkanes, α, .- Diacrylalkenes, α, .- Diacrylalkenes, α, .- Dimethacryloxyalkanes, α, .- Dimethacryl Alkenes, α, -dimethacrylalkenes, bisacryloxybenzene,
Vinyl compounds such as trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide and N-vinylpyromellitimide; polyarylene ethers containing 2,2'-diallyl-4,4'-biphenol; Polyarylene containing 2,2'-diallyl-4,4'-biphenol and the like can be mentioned. These may be used alone or in combination of two or more.

As the reactive triple bond-containing compound, for example, ethynylbenzene, diethynylbenzene, triethynylbenzene, trantrimethylsilylethynylbenzene, trimethylsilylethynylbenzene, bis (trimethylsilylethynyl) benzene, tris (trimethylsilylethynyl) benzene, phenylethynyl benzene,
Bis (phenylethynyl) benzene, tris (phenylethynyl) benzene, bis (ethynylphenyl) ether, bis (trimethylsilylethynylphenyl) ether, bis (phenylethynylphenyl) ether, and the like can be given. These may be used alone or in combination of two or more.

The amount of at least one selected from the group consisting of the radical generator, the reactive double bond-containing compound and the reactive triple bond-containing compound is based on 100 parts by weight of the component (A) of the present invention. It is 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight. If less than 0.2 parts by weight,
In some cases, the heat resistance of the coating film is poor. On the other hand, when it exceeds 30 parts by weight, the coating uniformity of the coating film is poor. When the composition of the present invention contains at least one member selected from the group consisting of a radical generator, a reactive double bond-containing compound, and a reactive triple bond-containing compound, crosslinking improves the heat resistance of the coating film. Can be.

The total solid content of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted depending on the purpose of use. When the total solid content of the composition is 2 to 30
When it is% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent.

The composition of the present invention was applied to a silicon wafer, Si
When coating on a substrate such as an O ₂ wafer or a SiN wafer, a coating method such as spin coating, dipping, roll coating, or spraying is used.

In this case, a dry film thickness may be about 0.05 to 1.5 μm in a single coating, and about 0.1 to 3 μm in a double coating. it can. Thereafter, it can be formed by drying at normal temperature or by heating and drying at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used. Can be. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray.

The coating film (interlayer insulating film) thus obtained is excellent in heat resistance, low dielectric property, crack resistance, and adhesion to a substrate.
Interlayer insulating film for semiconductor devices such as AM, SDRAM, RDRAM, D-RDRAM, etching stopper film, C
MP stopper film, copper diffusion prevention film, protective film such as surface coating film of semiconductor element, intermediate layer and antireflection film in semiconductor manufacturing process using multilayer resist, interlayer insulation film of multilayer wiring board, for liquid crystal display element It is useful for applications such as protective films and insulating films.

[0107]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples are parts by weight and% by weight, respectively, unless otherwise specified. Further, the evaluation of the film-forming composition in the examples was measured as follows.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions. Sample: Prepared by dissolving 1 g of a polymer (hydrolysis condensate) in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1cc / min

A composition sample was applied on a silicon wafer having a relative dielectric constant of 8 inches by using a spin coating method.
The substrate was baked on a hot plate in a nitrogen atmosphere at 420 ° C. for 12 minutes. Aluminum was vapor-deposited on the obtained substrate to prepare a substrate for relative dielectric constant evaluation. The relative permittivity is HP1 manufactured by Yokogawa / Hewlett-Packard Co., Ltd.
6451B electrode and HP4284A Precision LC
It was calculated from the capacitance value at 10 kHz using an R meter.

2% Weight Loss Temperature (Td 2 ) A composition sample was applied on an 8-inch silicon wafer by using a spin coating method, and was applied on a hot plate at 100 ° C. for 1 hour.
The substrate was baked on a hot plate in a nitrogen atmosphere at 420 ° C. for 12 minutes. The coating film was peeled off from the substrate, and the measurement was carried out by a TG method in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min.

A sample of the composition was applied on a crack-resistant 8-inch silicon wafer by a spin coating method, and was placed on a hot plate at 100 ° C. for 1 hour.
The substrate was baked on a hot plate in a nitrogen atmosphere at 420 ° C. for 12 minutes. At this time, the final coating film thickness was 6 μm. The obtained substrate with a coating film was immersed in warm water at 60 ° C. for 2 hours, and the appearance of the coating film was observed with a 350,000 lux surface observation lamp, and evaluated according to the following criteria. ；: No crack is observed on the coating film surface. C: Cracks are observed on the coating film surface.

A sample of the composition was applied on an 8-inch silicon wafer having thermally oxidized SiO ₂ having a coating adhesion of 1,000 ° using a spin coating method, and was further heated at 100 ° C. for 1 minute on a hot plate for 4 minutes.
The substrate was baked on a hot plate in a nitrogen atmosphere at 20 ° C. for 12 minutes. After immersing this coated substrate in hot water at 60 ° C. for 2 hours, ten stud pins were fixed on the obtained substrate using epoxy resin, and dried at 150 ° C. for 1 hour. This stud pin was subjected to a pull-out test using the Sebastian method, and the adhesion was evaluated according to the following criteria. ○: No peeling at the interface of the stud pins 10 present both the silicon wafer and the coating film ×: peeling occurred wet heat resistance substrate at the interface between the silicon wafer and the coating film PCT (Pressure Cooker Te
(st) Using a device (manufactured by Hirayama Seisakusho, PC-242HS-A), a wet heat treatment was performed at 127 ° C., 100% RH, 2.5 atm for 1 hour, and the substrate surface was observed.

Synthesis Example 1 In a three-necked flask, 7.5 g of sodium iodide, 1.3 g of anhydrous nickel chloride, and 15.7 of triphenylphosphine were placed.
g, 19.6 g of zinc powder activated with acetic acid, and 16.7 g of 9,9-bis (methylsulfonyloxy) fluorene, and the mixture was dried under vacuum for 24 hours. Filled with gas. Next, 50 ml of dry N, N-dimethylacetamide, 50 ml of dry tetrahydrofuran, and 10.8 g of 2,4-dichlorotoluene were added, and the mixture was stirred at 70 ° C. under an argon stream, and the reaction solution turned brown. 7 as it is
After reacting at 0 ° C. for 20 hours, the reaction mixture was diluted with 36% hydrochloric acid 4
The mixture was poured into a mixture of 00 ml and 1600 ml of methanol to collect a precipitate. The obtained precipitate was added to and suspended in chloroform, extracted with a 2N aqueous hydrochloric acid solution, and then the chloroform layer was poured into methanol. The precipitate was collected and dried, and the precipitate having a weight average molecular weight of 10,300 was obtained. A white powdery polymer was obtained.

Synthesis Example 2 1 equipped with a nitrogen inlet tube, Dean Stark, and a cooling tube
26.48 g of 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-
(Hydro-3-methyloxyphenyl) fluorene 28.3
5 g, 45.60 g of anhydrous potassium carbonate, 500 mL of dimethylacetamide, and 150 mL of toluene were added, and the mixture was heated at 140 ° C. for 3 hours under a nitrogen atmosphere. After removing water and excess toluene generated during salt formation, the reaction solution was cooled to room temperature. Then, 4,4'-
32.73 g of difluorobenzophenone was added, and 16
The reaction was performed at 5 ° C. for 10 hours. After cooling, the reaction solution was
Reprecipitation was performed by throwing into 5 L of Cl-containing methanol. The precipitate was filtered, sufficiently washed with ion-exchanged water, and preliminarily dried in a vacuum oven. The precipitate was redissolved in tetrahydrofuran, the insoluble portion was removed, and the precipitate was reprecipitated in methanol. The polymer was purified by repeating this reprecipitation operation once more, and dried in a vacuum oven for 8 hours.
12 hours at 0 ° C., weight average molecular weight 150,000
A white powdery polymer was obtained.

Synthesis Example 3 In a quartz separable flask, 96.4 g of vinyltrimethoxysilane was dissolved in 362 g of cyclohexanone, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 38 g of ion-exchanged water in which 2.5 g of maleic anhydride was dissolved was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, a reaction solution was obtained. The weight-average molecular weight of the hydrolyzed condensate thus obtained was 1,300.

Synthesis Example 4 In a quartz separable flask, 96.4 g of ethynyltriacetoxysilane was dissolved in 362 g of cyclohexanone, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 38 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, a reaction solution was obtained. The weight-average molecular weight of the hydrolyzed condensate thus obtained was 900.

Synthesis Example 5 In a quartz separable flask, 96.4 g of p-tolyltrimethoxysilane was dissolved in 362 g of cyclohexanone, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Next, maleic anhydride 2.5
38 g of ion-exchanged water in which g was dissolved was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, a reaction solution was obtained. The weight-average molecular weight of the hydrolyzed condensate thus obtained was 1,150.

Synthesis Example 6 In a quartz separable flask, 96.4 g of p-tolyltrimethoxysilane was dissolved in 362 g of cyclohexanone, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 38 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, a reaction solution was obtained. The weight-average molecular weight of the hydrolyzed condensate thus obtained was 850.

Comparative Synthesis Example 1 In a separable quartz flask, 77.04 g of methyltrimethoxysilane and 24.05 g of tetramethoxysilane were used.
And 0.48 g of acetic acid were dissolved in 290 g of propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, 25 g of acetylacetone was added, the reaction was further performed for 30 minutes, and the reaction solution was cooled to room temperature. At 50 ° C., 149 g of a solution containing methanol and water was removed from the reaction solution by evaporation to obtain a reaction solution. The weight-average molecular weight of the hydrolyzed condensate thus obtained was 1,900.

Example 1 2 g of the polymer obtained in Synthesis Example 1 and 0.04 g of vinyltrimethoxysilane were dissolved in 18 g of cyclohexanone, and the solution was filtered through a filter made of polytetrafluoroethylene (Defon, Teflon) having a pore diameter of 0.2 μm. Was carried out to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by spin coating. When the relative dielectric constant of the coating film was measured, a coating film having a relative dielectric constant of 2.97 and a dielectric constant of 3 or less was obtained. When the 2% weight loss temperature of the coating film was measured, it was 4
It exhibited excellent heat resistance of 80 ° C. In addition, no cracks occurred even when the coating film was immersed in water, and no peeling from the silicon wafer occurred in the evaluation of adhesion.

Examples 2 to 6 Evaluations were made in the same manner as in Example 1 with the compositions shown in Table 1.

[0122]

[Table 1]

Example 8 A commercially available polyarylene ether solution [trade name: SiLK
I (manufactured by Dow Chemical Company)] The solution and the coating film were evaluated in the same manner as in Example 1 except that 0.04 g of vinyltrimethoxysilane was added to 100 g. When the relative dielectric constant of the coating film was measured, a coating film having a dielectric constant of 2.67 and a dielectric constant of 3 or less was obtained. When the 2% weight loss temperature of the coating film was measured, it showed excellent heat resistance of 510 ° C.
In addition, no cracks occurred even when the coating film was immersed in water, and no peeling from the silicon wafer occurred in the evaluation of adhesion.

Example 9 In Example 1, 1,3-bis (phenylethynyl)-was added to 100 g of a commercially available polyarylene ether solution [FLARE 2.0 (trade name, manufactured by Honeywell)].
The solution and the coating film were evaluated in the same manner as in Example 1 except that 0.04 g of 1,3-dimethyldiacetoxysiloxane was added. When the relative dielectric constant of the coating film was measured, a coating film having a relative dielectric constant of 2.87 and not more than 3 was obtained. When the 2% weight loss temperature of the coating film was measured, it showed excellent heat resistance of 473 ° C. In addition, no cracks occurred even when the coating film was immersed in water, and no peeling from the silicon wafer occurred in the evaluation of adhesion.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that only 2 g of the polymer obtained in Synthesis Example 1 was dissolved in 18 g of cyclohexanone. Although the coating film showed a relative dielectric constant of 2.97, the peeling of the interface between the seven stud pull pins and the silicon wafer was observed in the evaluation of the coating film adhesion.

Comparative Example 2 Evaluation was carried out in the same manner as in Example 1 except that only 2 g of the polymer obtained in Synthesis Example 2 was dissolved in 18 g of cyclohexanone. Although the coating film showed a relative dielectric constant of 2.98, peeling at the interface with the silicon wafer was observed in five stud pull pins in the evaluation of the coating film adhesion.

Comparative Example 3 A commercially available polyarylene ether solution [trade name: SiLK
I (manufactured by Dow Chemical Company)] was used, and the evaluation was performed in the same manner as in Example 1. Although the coating film showed a relative dielectric constant of 2.66, peeling of the interface between the two stud pull pins and the silicon wafer was observed in the evaluation of the coating film adhesion.

Comparative Example 4 Commercially available polyarylene ether solution [trade name: FLARE
2.0 (manufactured by Honeywell)] alone, and the evaluation was performed in the same manner as in Example 1. The coating film is 2.
A dielectric constant of 84 was shown, but peeling of the interface between the three stud pull pins and the silicon wafer was observed in the coating film adhesion evaluation.

Example 10 2 g of the polymer obtained in Synthesis Example 1, 0.2 g of the reaction solution,
18 g of cyclohexanone was mixed and filtered through a filter made of polytetrafluoroethylene (Teflon, DuPont) having a pore diameter of 0.2 μm to obtain a film-forming composition of the present invention. The obtained composition was applied on a silicon wafer by spin coating. The relative dielectric constant of the coating film was measured.
A coating film having a specific dielectric constant of 94 or less was obtained. PCT (Pr
Even if the coating film after the Essure Cooker Test was immersed in water, no crack was generated, and no peeling at the interface was observed in the evaluation of adhesion.

Examples 11 to 15 In the same manner as in Example 10, evaluations were made with the compositions shown in Table 2.

[0131]

[Table 2]

Example 16 Commercially available polyarylene ether solution SiLK I
The solution and the coating film were evaluated in the same manner as in Example 10, except that 0.4 g of the reaction solution was added to 100 g (manufactured by Dow Chemical Company). When the relative dielectric constant of the coating film was measured, a coating film having a relative dielectric constant of 2.68 and a dielectric constant of 3 or less was obtained. No cracks occurred when the coating film after PCT was immersed in water, and no peeling at the interface was observed in the evaluation of adhesion.

Example 17 The procedure of Example 10 was repeated, except that 0.4 g of the reaction solution was added to 100 g of a commercially available polyarylene ether solution [FLARE 2.0 (trade name, manufactured by Honeywell)]. The solution and the coating film were evaluated. When the relative dielectric constant of the coating film was measured, a coating film having a relative dielectric constant of 2.87 and not more than 3 was obtained. No cracks occurred when the coating film after PCT was immersed in water, and no peeling at the interface was observed in the evaluation of adhesion.

Comparative Example 5 Evaluation was performed in the same manner as in Example 10 except that the reaction solution obtained in Comparative Synthesis Example 1 was used. The dielectric constant of the coating film was 3.23, and a number of cracks occurred in the coating film in the evaluation of crack resistance.

[0135]

According to the present invention, (A) an aromatic polyarylene and / or an aromatic polyarylene ether, and (B) a silane coupling agent having a reactive group and a hydrolytic condensate thereof or any one thereof on the other hand,
And (C) a film-forming composition (material for an interlayer insulating film) having an excellent balance of heat resistance, low dielectric property, crack resistance, adhesion to a substrate, and the like by using a composition containing an organic solvent. It is possible to provide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 65/34 C08G 65/34 5F033 C09D 4/06 C09D 4/06 5F058 5/25 5/25 5G305 171 / 12 171/12 183/04 183/04 H01B 3/30 H01B 3/30 M N 3/42 3/42 G H01L 21/312 H01L 21/312 A 21/768 21/90 S (72) Inventor Kinji Yamada 2-11-24 Tsukiji, Chuo-ku, Tokyo F-term in JSR Co., Ltd. (reference) 4J005 AA23 BA00 BB02 4J011 AA05 BA04 BB01 CA02 CA08 CC07 PA83 PA90 PB28 PB40 PC02 4J026 AB19 AB23 AB46 AC18 BA04 BA05 BA06 BA07 BA27 BA28 BA BA32 BA44 BB01 DA02 DA19 DB02 DB04 DB06 DB15 FA05 GA06 4J032 CA03 CA04 CB01 CB03 CC01 CD02 CD08 CE03 CE22 CG06 4J038 DC011 DF051 DL032 DL112 FA012 FA042 FA092 FA112 FA162 GA01 GA02 GA09 GA10 GA12 GA13 JA02 JA05 JA19 JA20 JA21 JA26 JA33 JA56 JA66 JC33 KA02 KA06 MA06 NA14 NA21 PA19 PB09 PC02 5F033 RR21 SS22 XX12 XX17 XX24 5F058 AA10 AC10 AF04 AG01 AH02 5G305 AA07 AA13 AB10 AB16 AB12 AB10

Claims (7)

[Claims] 1. An aromatic polyarylene and / or an aromatic polyarylene ether, (B) a silane coupling agent having a reactive group and / or a hydrolytic condensate thereof, and (C) A composition for forming a film, comprising an organic solvent. 2. The polymer according to claim 1, wherein the component (A) is a polymer having a repeating structural unit represented by the following formula (1) and / or a repeating structural unit represented by the following formula (2). Item 7. The film-forming composition according to Item 1. Embedded image Embedded image (R ^{7 to} R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group, or a halogen atom, and X is —C
QQ'- (wherein Q and Q 'may be the same or different and each represents a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a fluorenylene group Y is -O-, -CO-, -COO.
-, - CONH -, - S -, - SO 2 - and at least one selected from the group consisting of phenylene group, a is 0 or 1, b to f represents an integer of 0 to 4, g Is 5
100 mol%, h is 0 to 95 mol%, i is 0 to 95 mol% (however, g + h + i = 100 mol%), j is 0 to 1
00 mol%, k is 0 to 100 mol% (provided that j + k =
100 mol%). ] 3. The composition according to claim 1, wherein the component (A) contains 1 to 2 carbon atoms in the polymer.
The film forming composition according to claim 1, which contains 0 hydrocarbon groups. 4. An alkoxysilane compound containing a reactive double bond group and / or a triple bond group in a molecule, wherein the silane coupling agent having a reactive group constituting the component (B) is a silane coupling agent. Acetoxysilane compounds containing a reactive double bond group and / or a triple bond group, an alkoxysilane compound containing a tolyl group in the molecule, and an acetoxysilane compound containing a tolyl group in the molecule. 2. The film-forming composition according to claim 1, which is at least one member selected from the group consisting of: 5. The use ratio of the component (A) and the component (B) is as follows:
0.001 component (B) per 100 parts by weight of component (A)
The composition for forming a film according to claim 1, wherein the amount is from 10 to 10 parts by weight. 6. The film for forming a film according to claim 1, further comprising at least one selected from the group consisting of a radical generator, a reactive double bond-containing compound and a reactive triple bond-containing compound. Composition. 7. A material for forming an insulating film, comprising the composition for forming a film according to any one of claims 1 to 6.