JP2001055490A - Phenylene group-bearing (co)polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject phenylene group-bearing polymer composition that can form coating layer of high uniformity and is suitable as a raw material for protecting film or insulating film in liquid crystal display by using a specific (co)polymer and a surfactant. SOLUTION: The objective (co)polymer composition includes (A) 100 pts.wt. of a phenylene group-bearing (co)polymer of the formula X is -CQQ'- [Q and Q' are each a (halogenated) alkyl, H, a halogen, an aryl], fluorenylene; R1-R20 are each H, a halogen, a monovalent organic group; l is 5-100 (mole) %; m and n are each 0-95 mole % where l+m+n=100%}, (B) 0.001-1 pt.wt. per 100 pts.wt. of the component A, of a surfactant and, when necessary (C) a solvent. As a component A, are cited a silicone surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, but the silicone surfactant is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a phenylene group-containing (co) polymer composition. More specifically, LS
I, system LSI, DRAM, SDRAM, RDRA
Low dielectric interlayer insulating films for semiconductor devices such as M and D-RDRAMs; protective films such as surface coat films for semiconductor devices; low dielectric interlayer insulating films for multilayer wiring substrates; protective films and insulating films for liquid crystal display devices. The present invention relates to a phenylene group-containing (co) polymer composition having excellent uniformity when formed into a coating film, which is suitable as a raw material such as.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) have become highly integrated, multifunctional, and high-performance, reflecting the progress of fine processing technology. As a result, circuit resistance and capacitance between wirings (hereinafter, sometimes referred to as “parasitic resistance” and “parasitic capacitance”, respectively) are increased, which not only increases power consumption but also increases delay time. This is a major factor in reducing the signal speed of the device. Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to cover the periphery of the wiring with an interlayer insulating film to reduce the parasitic capacitance and respond to the speeding up of the device. I have.

However, the interlayer insulating film needs to have excellent heat resistance that can withstand post-processes such as a thin film forming process, chip connection, and pinning at the time of manufacturing a mounting substrate. Polyimide is widely known as the organic material having high heat resistance, however, since it contains a highly polar imide group, no satisfactory material is obtained in terms of low dielectric property and low water absorption.

On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. Polyphenylene is excellent in heat resistance, but is poor in organic solvent solubility.In general, side chains are generally introduced.However, by introducing side chains, heat resistance is reduced or production of raw materials is complicated. There were problems such as becoming.

Conventional polyphenylenes include, for example, US Pat. No. 5,214,044 and International Application WO 96/2.
No. 8441, EP-A-629217 and the like. These polymers basically have a polyparaphenylene structure and partially copolymerize a flexible monomer.

However, these polymers are soluble only in specific organic solvents and have poor processability. In addition, since many of the side chains are polar groups or alkyl groups, heat resistance,
Insufficient low dielectric properties (US Pat. No. 52
No. 14044, EP-A-629217.
), And many steps were required for the synthesis of raw materials (International application WO96 / 28491 has a heat-resistant and low-dielectric structure, but the synthesis of monomers was complicated).

[0007] Further, these polymers are mainly produced from aromatic dichloro compounds such as paradichlorobenzene as raw materials, but such aromatic dichloro compounds are complicated to synthesize and cannot stably secure monomers. It was not favorable in point.

Furthermore, conventional polyparaphenylenes have insufficient transparency and cannot be used for optical applications.

The present inventors have conducted various studies on such problems of the conventional polyphenylene, and as a result, have found that polyphenylene which can sufficiently satisfy heat resistance, low dielectric properties and workability, and which can be manufactured by an inexpensive process. (For example, Japanese Patent Application Nos. 10-29068, 10-29070 and 10-273522).

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has been made in addition to the above proposals.
I, system LSI, DRAM, SDRAM, RDRA
Low dielectric interlayer insulating films for semiconductor devices such as M and D-RDRAMs; protective films such as surface coat films for semiconductor devices; low dielectric interlayer insulating films for multilayer wiring substrates; protective films and insulating films for liquid crystal display devices. It is an object of the present invention to provide a phenylene group-containing (co) polymer composition having excellent uniformity when formed into a coating film, which is suitable as a raw material such as.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by forming a composition containing a specific phenylene group-containing (co) polymer and a surfactant, The inventors have found that the above object can be achieved and completed the present invention. That is, the present invention provides the following phenylene group-containing (co) polymer composition.

[1] A phenylene group-containing (co) polymer composition comprising a phenylene group-containing (co) polymer represented by the following formula (1) and a surfactant.

[0013]

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[In the formula (1), X is -CQQ'- (where 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. group shown in the illustrated), and is at least one selected from the group consisting of fluorenylene group, R ¹ ~
R ²⁰ may be the same or different and represents a hydrogen atom, a halogen atom, or a monovalent organic group, 1 is 5 to 100 mol%, m is 0 to 95 mol%, and n is 0 to 95 mol% ( l +
m + n = 100 mol%). ]

[2] l in the above formula (1) is 50 to 9
The phenylene group-containing (co) polymer composition according to the above [1], wherein 5 mol% and m are 5 to 50 mol%.

[3] The mixing ratio of the surfactant is 100 parts by weight of the phenylene group-containing (co) polymer.
The phenylene group-containing (co) polymer composition according to the above [1] or [2], which is 0.001 to 1 part by weight.

[4] The phenylene group-containing (co) polymer composition according to any one of [1] to [3], wherein the surfactant is a silicone-based surfactant.

[5] The above [1] to [10] further containing a solvent.
The phenylene group-containing (co) polymer composition according to any one of [4].

As described above, the phenylene group-containing (co) polymer composition of the present invention can be used as a coating composition by forming a composition containing a specific phenylene group-containing copolymer and a surfactant. Uniformity can be improved.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The phenylene group-containing (co) polymer composition of the present invention comprises the phenylene group-containing (co)
It is characterized by containing a polymer and a surfactant.

Hereinafter, the phenylene group-containing (co) polymer composition of the present invention will be described more specifically for each component. 1. Phenylene group-containing (co) polymer The phenylene group-containing (co) polymer used in the present invention is:
Although shown in the above equation (1), the equation (1) is shown below again for convenience of explanation.

[0022]

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In the formula (1), X is -CQQ'- (where 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. group shown in the illustrated), and is at least one selected from the group consisting of fluorenylene group, R ¹ ~
R ²⁰ may be the same or different and represents a hydrogen atom, a halogen atom, or a monovalent organic group, 1 is 5 to 100 mol%, preferably 50 to 95 mol%, and m is 0 to 95 mol% , Preferably 5 to 50 mol%, n is 0 to 95 mol%, preferably 0 to 50 mol%, (l + m + n = 10
0 mol%). ]

The repeating unit is preferably connected to X and O at the para position.

Such a phenylene group-containing (co) polymer can be produced, for example, by polymerizing a monomer containing a compound represented by the following formula (2) in the presence of a catalyst system containing a transition metal compound. .

[0026]

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In the formula (2), X is -CQQ'- (where 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. group shown in the illustrated), and is at least one selected from the group consisting of fluorenylene group, R ¹ ~
R ⁸ may be the same or different and represents a hydrogen atom, a halogen atom or a monovalent organic group, and Z represents an alkyl group, a halogenated alkyl group or an aryl group. ]

In Q and Q 'constituting X in the above formula (2), the halogenated alkyl group is a trifluoromethyl group, a pentafluoroethyl group or the like, and the alkyl group is a methyl group, an ethyl group or the like. Examples of the halogen atom include a fluorine atom, and examples of the aryl group include a phenyl group, a biphenyl group, a tolyl group, and a pentafluorophenyl group.

In R ^{1 to} R ⁸ in the formula (2), a halogen atom is a fluorine atom, a monovalent organic group is an alkyl group, a methyl group, an ethyl group, etc. Examples of the alkyl group include a trifluoromethyl group and a pentafluoroethyl group, examples of the allyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group.

In the formula (2), Z constituting —OSO ₂ Z is a methyl group, an ethyl group, or the like as an alkyl group, a halogenated alkyl group, a trifluoromethyl group, or an aryl group as a halogenated alkyl group. Phenyl group, p-tolyl group, p-fluorophenyl group and the like.

X in the above formula (2) is preferably a divalent group shown below.

[0032]

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[0033]

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[0034]

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[0035]

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Of these, a fluorenylene group is more preferred.

Specific examples of the compound (monomer) represented by the formula (2) include 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-methyl) Phenyl) 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-propenyl) Phenyl) propane, 2,2-bis (4-phenylsulfonyloxyphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (4-phenylsulfur Phonyloxy-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-dimethyl) Phenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluoro) Phenyl) 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-trifluoromethylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfone) Phonyloxy-3-phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy)
3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-triphenylmethane) Fluoromethylsulfonyloxy-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-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane Bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) 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-phenylsulfonyloxy-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-phenylsulfonyloxy) Phenyl) Tan, bis (4-phenylsulfonyl b carboxymethyl-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) hexafluoro Propane, screw (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) hexa Fluoropropane, 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-dimethylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy) 3,5-difluorophenyl) 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 can be mentioned.

In the present invention, two or more compounds represented by the above formula (2) may be copolymerized.

The compound represented by the formula (2) can be synthesized, for example, by the following production method. That is, a bisphenol compound (for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane) and a base of 2 equivalents or more of the bisphenol compound are dissolved 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 form a suspension. The obtained suspension is reprecipitated in 3 to 20 times the volume 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 bisphenol compound (for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane) is added to an aqueous solution of sodium hydroxide 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, if necessary, a phase transfer catalyst such as acetyltrimethylammonium chloride is added thereto, followed by vigorous stirring. 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 formula (2) may be copolymerized with at least one compound selected from the group consisting of the compounds represented by the following formulas (3) to (6). Good.

[0043]

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[In the formula (3), R ^{9 to} R ¹⁶ may be the same or different and each represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ³¹ represents —OSO ₂ Z (here, Z Represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom. ]

Of R ^{9 to} R ¹⁶ , 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. As the Z constituting a -OSO 2 _Z, examples of the alkyl group, methyl group, ethyl group and the like, halogenated alkyl group, a trifluoromethyl group, aryl group, a phenyl group, p- tolyl group, p- Examples thereof include a fluorophenyl group.

The compound represented by the formula (3) includes, for example, 4,4'-dichlorodiphenyl ether, 4,4 '
-Dibromodiphenyl ether, 4,4'-diiododiphenyl ether, 3,3'-dichlorodiphenyl ether, 3,3'-dibromodiphenyl ether, 3,
3′-diiododiphenyl ether, 3,4′-dichlorodiphenyl ether, 3,4′-dibromodiphenyl ether, 3,4′-diiododiphenyl ether,
4,4'-dimethylsulfonyloxyphenyl ether, 4,4'-ditrifluoromethylsulfonyloxyphenyl ether and the like can be mentioned.

The compounds represented by the formula (3) can be used alone or in combination of two or more.

[0048]

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[In the formula (4), R ^{17 to} R ²⁰ may be the same or different and each represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ³² represents —OSO ₂ Z (here, Z Represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom. ]

In the above formula (4), halogen atoms constituting R ^{17 to} R ²⁰ include a fluorine atom, and monovalent organic groups include a hydroxyl group, a carboxyl group, an allyl group, and an alkoxycarbonyloxy group. be able to. R ¹⁷ ~
At least one group of R ²⁰ is preferably a reactive group or a precursor thereof, from the viewpoint of improving the adhesion of the obtained polymer.

When two adjacent groups out of R ^{17 to} R ²⁰ are carboxyl groups, the two carboxyl groups may react with each other to form an acid anhydride.

In the present invention, the precursor of the reactive group is
A group in which a reactive group is protected with a protecting group, which means that the protecting group can be dissociated and returned to the reactive group later.

As a method for protecting the reactive group, in the case of a hydroxyl group, a method for protecting by reacting tert-butyl dicarbonate in the presence of a base such as triethylamine, or a method for protecting a carboxylic acid organic compound such as acetic acid or acetyl chloride. May be acetylated by a conventional method to form a protecting group. In the case of a carboxyl group, there is a method in which an acid is reacted in an alcohol to esterify and protect the carboxyl group.

Z constituting --OSO ₂ Z is, for example, a methyl group or an ethyl group as an alkyl group, a trifluoromethyl group or the like as a halogenated alkyl group, a phenyl group or a p-tolyl group as an aryl group. , P-fluorophenyl group and the like.

Specific examples of the compound represented by the formula (4) include, for example, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-
Dibromotoluene, 2,5-diiodotoluene, 2,5
-Dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene,
2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5 6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodo-2,3,5
6-tetrafluorobenzene, 2,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, methyl 2,5-dichlorobenzoate, methyl 2,5-dibromobenzoate, 2,5
-T-butyl-dichlorobenzoate, t-butyl 2,5-dibromobenzoate, 3,6-dichlorophthalic anhydride and the like, and preferably p-dichlorobenzene and p-dimethylsulfonyloxy. Benzene, 2,5-
Dichlorotoluene, 2,5-dichlorobenzotrifluoride, 2,5-dichlorobenzophenone, 2,5-dichlorophenoxybenzene and the like.

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

[0057]

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[In the formula (5), R ^{17 to} R ²⁰ may be the same or different and each represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ³³ represents —OSO ₂ Z (here, Z Represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom. ]

In R ^{17 to} R ²⁰ in the formula (5), the halogen atom includes a fluorine atom, and the monovalent organic group includes a hydroxyl group, a carboxyl group, an allyl group, and an alkoxycarbonyloxy group. be able to. R ¹⁷
At least one of the radicals to R ^20, it is a reactive group or a precursor thereof are preferred from the viewpoint for better adhesion of the resulting polymer.

When two adjacent groups out of R ^{17 to} R ²⁰ are carboxyl groups, the two carboxyl groups may react with each other to form an acid anhydride.

Z in -OSO ₂ Z is a methyl group or an ethyl group as an alkyl group, a trifluoromethyl group or the like as a halogenated alkyl group, a phenyl group, a p-tolyl group as an aryl group, Examples thereof include a p-fluorophenyl group.

Examples of the compound represented by the formula (5) include m-dichlorobenzene, m-dibromobenzene,
-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-diiodotoluene, 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-butoxycarbonyl Loxyphenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2 Methyl 4,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,
Methyl 5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate,
T-butyl 3,5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, t-butyl 3,5-dibromobenzoate and the like, preferably m-dichlorobenzene, , 4-dichlorotoluene, 3,5-
Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene and the like.

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

[0064]

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[In the formula (6), R ^{17 to} R ²⁰ may be the same or different and each represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ³⁴ represents —OSO ₂ Z (here, Z Represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom. ]

In the formula (6), the halogen atom constituting R ^{17 to} R ²⁰ is a fluorine atom, and the monovalent organic group is a hydroxyl group, a carboxyl group, an allyl group, an alkoxycarbonyloxy group or the like. be able to. R ¹⁷ ~
At least one group of R ²⁰ is preferably a reactive group or a precursor thereof, from the viewpoint of improving the adhesion of the obtained polymer.

When two adjacent groups out of R ^{17 to} R ²⁰ are carboxyl groups, the two carboxyl groups may react with each other to form an acid anhydride.

Z in -OSO ₂ Z is, for example, a methyl group or an ethyl group as an alkyl group; a trifluoromethyl group or the like as a halogenated alkyl group; a phenyl group, a p-tolyl group as an aryl group; Examples thereof include a p-fluorophenyl group.

Examples of the compound represented by the formula (6) include, for example, o-dichlorobenzene, o-dibromobenzene, o-dibromobenzene,
-Diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3 2,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene,
3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,4-diiodobenzotrifluoride, 1,2-dibromo-3,4,5
6-tetrafluorobenzene, 4,5-dichlorophthalic anhydride and the like can be mentioned.

The compounds represented by the above formula (6) can be used alone or in combination of two or more.

In the present invention, when the compound represented by the above formula (2) and the compound represented by the above formula (3) are copolymerized, the compounding ratio is usually from 5 to 99 of the compound represented by the above formula (2).
Mol%, preferably 50 to 95 mol%, 1 to 95 mol% of the compound represented by the formula (3), preferably 5 to 50 mol%
It is.

In the present invention, when the compound represented by the formula (2) and the compound represented by the formula (4) are copolymerized, the compounding ratio is usually from 5 to 99 of the compound represented by the formula (2).
Mol%, preferably 50 to 95 mol%, of the above formula (4)
Is 1 to 95 mol%, preferably 5 to 50 mol%.

In the present invention, when the compound represented by the above formula (2) and the compound represented by the above formula (5) are copolymerized, the compounding ratio is usually from 5 to 99 of the compound represented by the above formula (2).
Mol%, preferably 50 to 95 mol%, of the above formula (5)
Is 1 to 95 mol%, preferably 5 to 50 mol%.

In the present invention, when the compound represented by the formula (2) and the compound represented by the formula (6) are copolymerized, the compounding ratio is usually from 5 to 99 of the compound represented by the formula (2).
Mol%, preferably 50 to 95 mol%, of the above formula (6)
Is 1 to 95 mol%, preferably 5 to 50 mol%.

The catalyst used for producing the phenylene group-containing polymer used in the present invention is preferably a catalyst system containing a transition metal compound. Examples of the catalyst system include the following catalyst systems. 1) a catalyst system comprising a transition metal salt and a ligand; 2) a catalyst system comprising a transition metal (salt) to which a ligand is coordinated; 3) a reducing agent is added to the catalyst system of 1) or 2). And a catalyst system to which a "salt" is added, if necessary, 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 compounds such as palladium chloride, palladium bromide and palladium iodide; Examples thereof include iron compounds such as iron bromide and iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Among them, nickel chloride and nickel bromide are preferable.

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

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 among them, nickel chloride 2 triphenylphosphine and nickel chloride 2,2 ′ bipyridine are preferable.

The reducing agent that can be added in such a catalyst system includes, for example, iron, zinc, manganese,
Aluminum, magnesium, sodium, calcium and the like can be mentioned, and among them, zinc and manganese are preferable. These reducing agents can be used after being activated by contact with an acid or an organic acid.

The "salt" which can be added as required in such a catalyst system includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate and the like. Potassium compounds such as potassium, potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate; Among them, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferable.

The use ratio of each component in such a catalyst system is as follows. In the case of the catalyst systems shown in the above 1) and 2), the transition metal salt or the transition metal (salt) to which the ligand is coordinated is used in the ratio of the compound (A) or the compound (B).
And usually 1 mol per 1 mol of the compound (C).
The amount is from 01 to 10 mol, preferably from 0.01 to 0.5 mol. If the amount is less than 0.0001 mol, the polymerization reaction does not proceed sufficiently, while if it exceeds 10 mol, the molecular weight may be reduced.

In the case of the catalyst systems described in 1) and 2) above, the ligand is used in an amount of usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. . If it is less than 0.1 mol, the catalytic activity becomes insufficient, while if it exceeds 100 mol, there is a problem that the molecular weight decreases.

In the case of the catalyst system shown in 3), the reducing agent is used in an amount of usually 0.1 to 100 with respect to 1 mol of the total amount of the compound (A), the compound (B) and the compound (C). Mol, preferably 1 to 10 mol. If it is less than 0.1 mol, the polymerization does not proceed sufficiently, and if it exceeds 100 mol,
Purification of the resulting polymer may be difficult.

Further, in the case of the catalyst system shown in the above 3), when a “salt” is further added to this catalyst system, the proportion of the compound (A), compound (B) and compound (C) Is usually from 0.001 to 100 per mol of the total amount of
Mole, preferably 0.01 to 1 mole. 0.001
When the amount is less than mol, the effect of increasing the polymerization rate is insufficient, and when it exceeds 100 mol, purification of the obtained polymer may be difficult.

The polymerization solvent used in the present invention is not particularly restricted but includes, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, γ -Butyrolactone, γ-butyrolactam and the like, 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 concentration of the compound of the formula (2) or the compound of the formula (2) and the compound of the formulas (3) to (6) in the polymerization solvent is usually 1 to 100% by weight, preferably Is 5 to 40% by weight.

The polymerization temperature for polymerizing the (co) polymer used in the present invention is usually 0 to 200 ° C., preferably 50 to 80 ° C. The polymerization time is usually
It is 0.5 to 100 hours, preferably 1 to 40 hours.

2. Surfactant The surfactant used in the present invention is not particularly limited. For example, a silicone surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, Fluorinated surfactants and the like can be mentioned.

The silicone-based surfactant is not particularly limited, and examples thereof include a dimethylpolysiloxane-polyoxyalkylene copolymer represented by the following formula (7).

[0090]

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[In the formula (7), R ³⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, u is an integer of 1 to 20, and v and w are each independently an integer of 5 to 50. is there. ]

The nonionic surfactant is not particularly restricted but includes, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; sorbitan fatty acid esters; fatty acid-modified polyoxyethylenes; Examples thereof include an ethylene-polyoxypropylene block copolymer.

The fluorosurfactant is not particularly restricted but includes, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-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-hexa) Fluoropentyl)
Ether, octapropylene glycol di (1,1,
2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8, 9, 9, 1
0,10-decafluorododecane, 1,1,2,2,3
Examples thereof include compounds made of a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain and side chain sites such as 3-hexafluorodecane. Among them, silicone surfactants are preferable because they have excellent film-forming properties and do not generate metal corrosive gas.

Commercially available silicone surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH7PA, SH21PA, and SH21PA.
28PA, SH30PA, ST94PA (all manufactured by Dow Corning Toray Silicone) and the like. Commercially available nonionic surfactants include (meth)
Acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. Commercially available fluorine-based surfactants include BM-1000,
BM-1100 (above, manufactured by BM Chemie), MegaFac F142D, F172, F173, F
183 (above, manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, 303, and 352 (manufactured by Shin-Akita Chemical Co., Ltd.), Florado FC-430, and FC-431
(Manufactured by Sumitomo 3M Limited), 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.), DISPE
RBYK (manufactured by BYK Japan KK), Solsperse (manufactured by Zeneca Corporation) and the like can be mentioned. These surfactants can be used alone or in combination of two or more.

The mixing ratio of the surfactant used in the present invention is preferably 0.001 to 1 part by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the phenylene group-containing (co) polymer.
0.1 parts by weight is more preferred. When the amount is 0.001 to 1 part by weight, the coatability is further improved.

An additive can be added to the phenylene group-containing (co) polymer composition used in the present invention, if necessary. Examples of the additive include a silane coupling agent, a cross-linking agent such as a methylolated melamine, and a triazene compound.

3. Film formation of phenylene group-containing (co) polymer composition The phenylene group-containing (co) polymer composition of the present invention has a LS
I, system LSI, DRAM, SDRAM, RDRA
Low dielectric interlayer insulating films for semiconductor devices such as M and D-RDRAMs; protective films such as surface coat films for semiconductor devices; low dielectric interlayer insulating films for multilayer wiring substrates; protective films and insulating films for liquid crystal display devices. It is suitably used as a raw material for the above. In this case, a method for forming the phenylene group-containing (co) polymer composition into a film is not particularly limited. For example, a phenylene group-containing (co) polymer composition is dissolved in a solvent and cast on a substrate. Alternatively, there may be mentioned a method of removing the solvent by firing after applying by spin coating.

The thickness of the phenylene group-containing (co) polymer composition film is usually 0.1 to 10 μm.

The solvent for dissolving the phenylene group-containing (co) polymer composition includes, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, and the like.
N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate , Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate,
Propylene glycol ethyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl amyl ketone, 4-hydroxy-4-methyl-2-pentanone,
Ethyl 2-hydroxypropionate, 2-hydroxy-
Methyl 2-methylpropionate, 2-hydroxy-2-
Ethyl methyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate ,Ethyl acetate,
Butyl acetate, methyl lactate, ethyl lactate, chloroform,
Methylene chloride and the like can be mentioned, and preferably, cyclohexanone, N, N-dimethylacetamide, 1-
Methyl-2-pyrrolidone, γ-butyrolactone, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and methyl amyl ketone.

The concentration of the phenylene group-containing (co) polymer composition dissolved in the solvent is 1 to 60% by weight, preferably 5 to 40% by weight. When the amount is less than 1% by weight, a coating film having a sufficient thickness cannot be obtained, and when it exceeds 60% by weight, the film does not flow sufficiently and a uniform coating film may not be obtained.

Examples of applications of the film (coating film) obtained by forming the phenylene group-containing (co) polymer composition of the present invention include an interlayer insulating material, a protective film, a low refractive material, a high refractive material, Examples include an optical waveguide material, an antireflection film, a sealing material, a liquid crystal alignment film, a printed circuit board material, a gas permeable film, and the like. It is suitable.

[0102]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples.

Synthesis of phenylene group-containing copolymer (Synthesis Example 1) 7.5 g of sodium iodide, 1.3 g of anhydrous nickel chloride, and 500 g of a three-necked flask equipped with an argon gas inlet tube and a thermometer were used. 15.7 g of triphenylphosphine, 45.8 g of zinc powder activated with acetic acid, 30.4 g of 9,9-bis (4-methylsulfonyloxyphenyl) fluorene, bis (4-methylsulfonyloxyphenyl) ether 13 After adding 0.7 g and drying under vacuum for 24 hours, the inside of the three-necked flask was filled with argon gas. Subsequently, 150 ml of dry N, N-dimethylacetamide was added, and the mixture was stirred at 70 ° C. under a stream of argon, whereby the reaction solution turned brown.
After allowing the reaction to proceed at 70 ° C. for 20 hours,
The mixture was poured into a mixed solution of 500 ml of 6% hydrochloric acid and 200 ml of methanol to collect a precipitate. The obtained precipitate was added to and suspended in chloroform, and extracted with a 2N aqueous hydrochloric acid solution. Then, the chloroform layer was poured into methanol, and the precipitate was collected and dried to obtain a white powder polymer (P1). The molecular weight of the obtained copolymer (P1) was 7,500.

(Synthesis Example 2) In the synthesis example 1, the 9,9-
The charged amounts of bis (4-methylsulfonyloxyphenyl) fluorene and bis (4-methylsulfonyloxyphenyl) ether were 35.5 g and 10.3, respectively.
A copolymer (P2) was obtained in the same manner as in Synthesis Example 1 except that g was changed to g. The molecular weight of the obtained copolymer (P2) was 7,900.

(Synthesis Example 3) In Synthesis Example 1, the 9,9-
The charged amounts of bis (4-methylsulfonyloxyphenyl) fluorene and bis (4-methylsulfonyloxyphenyl) ether were 40.5 g and 6.80, respectively.
A copolymer (P3) was obtained in the same manner as in Synthesis Example 1 except that g was changed to g. The molecular weight of the obtained copolymer (P3) was 8,800.

Table 1 summarizes the above synthesis examples. In addition, the molecular weight measured the weight average molecular weight (Mw) in polystyrene conversion by gel permeation chromatography (GPC) measurement.

[0107]

[Table 1]

Preparation of Composition and Film Formation (Example 1) Copolymer (P1) 10 obtained in Synthesis Example 1
To 0 part, 0.02 part of an organosiloxane polymer (trade name: KP341 manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in cyclohexanone to form a varnish having a solid content of 12% by weight, and spin-coated on an 8-inch silicon wafer by spin coating. And baked at 80 ° C. for 2 minutes and 200 ° C. for 2 minutes to obtain a coating film having a thickness of 1.0 μm. Dielectric constant of the obtained coating film,
Table 2 shows the evaluation of the elastic modulus and the uniformity of the coating film.

(Example 2) In Example 1, Synthesis Example 1
In the same manner as in Example 1 except that the copolymer (P2) obtained in Synthesis Example 2 was used instead of the copolymer (P1) obtained in Step 1. Table 2 shows the evaluation of the obtained coating film for the dielectric constant, elastic modulus, and coating film uniformity.

(Example 3) In Example 1, Synthesis Example 1
In the same manner as in Example 1 except that the copolymer (P2) obtained in Synthesis Example 3 was used instead of the copolymer (P1) obtained in Step 1. Table 2 shows the evaluation of the obtained coating film for the dielectric constant, elastic modulus, and coating film uniformity.

(Comparative Example 1) In Example 1, the organosiloxane polymer (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
Same as Example 1 except that KP341) was not added. Table 2 shows the evaluation of the obtained coating film for the dielectric constant, elastic modulus, and coating film uniformity.

The evaluation was performed by the following measuring method. (1) Dielectric constant An aluminum electrode pattern was formed on the obtained coating film by a vapor deposition method to prepare a dielectric constant measurement sample. This sample was manufactured under the conditions of a frequency of 100 kHz and a room temperature, HP1 manufactured by Yokogawa Hewlett-Packard Co., Ltd.
6451B electrode and HP4284A precision LCR
The dielectric constant of the coating film prepared by the CV method was measured using a meter. (2) Elastic Modulus The obtained coating film was measured by a continuous stiffness measuring method using a nano indenter XP (manufactured by Nano Instruments). (3) Uniformity of coating film To evaluate the uniformity of coating film (in-plane uniformity of film thickness), the obtained film was measured by using an optical film thickness meter (Rudolph Techno).
Logies, SpectraLaser200)
Was used to measure 50 points in the coating film plane. 3 of the obtained film thickness
σ was calculated and evaluated according to the following criteria. ：: 3σ of coating film is less than 100 nm ×: 3σ of coating film is 100 nm or more

[0113]

[Table 2]

[0114]

As described above, according to the present invention, an LSI, a system LSI, a DRAM, an SDRAM,
Low dielectric interlayer insulating films for semiconductor devices such as RDRAMs and D-RDRAMs; protective films such as surface coat films for semiconductor devices; low dielectric interlayer insulating films for multilayer wiring boards; protective films and insulating prevention films for liquid crystal display devices. It is possible to provide a phenylene group-containing (co) polymer composition which is suitable as a raw material and has excellent uniformity when formed into a coating film.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation F-term (reference) 4J002 CE001 CH022 CH052 CP182 EB066 ED046 EH046 EV256 FD312 FD316 GQ01 GQ05 HA05

Claims (5)

[Claims] 1. A phenylene group-containing (co) polymer composition comprising a phenylene group-containing (co) polymer represented by the following formula (1) and a surfactant. Embedded image [In the formula (1), X represents -CQQ '-(where Q, Q'
Is at least one selected from the group consisting of even or different, halogenated alkyl group, an alkyl group, a hydrogen atom, a group shown in a halogen atom or an aryl group) and a fluorenylene group, in the same, R ¹ ~ R ²⁰ may be the same or different and include a hydrogen atom, a halogen atom,
Or a monovalent organic group, 1 is 5 to 100 mol%, m is 0 to 95 mol%, n is 0 to 95 mol% (l + m + n = 1
00 mol%). ] 2. The phenylene group-containing (co) polymer composition according to claim 1, wherein 1 in the formula (1) is 50 to 95 mol% and m is 5 to 50 mol%. 3. The mixing ratio of the surfactant is 0.0 to 100 parts by weight of the phenylene group-containing (co) polymer.
The phenylene group-containing (co) polymer composition according to claim 1, wherein the amount is from 0.01 to 1 part by weight. 4. The phenylene group-containing (co) polymer composition according to claim 1, wherein said surfactant is a silicone surfactant. 5. The phenylene group-containing (co) polymer composition according to claim 1, further comprising a solvent.