JP2000351835A - Process for treating phenylene-containg copolymer and treated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenylene-containing (co)polymer film improved in mechanical strengths and solvent resistance by irradiating a phenylene-containing (co)polymer film formed on a substrate with electron beams. SOLUTION: A solvent-solution containing 1-60 wt.% phenylene-contining (co)polymer of the formula is applied to a substrate to form a 0.1-10 μm thick phenylene-containing (co)polymer film thereon. This film is irradiated with electron beams. In the formula, X is at least one group selected from -CQ'- and fluoreylene; Q and Q' are each a (halo)alkyl, H, a halogen or an aryl; R1 to R20 are each H, a halogen or a monovalent organic group; Y is -CO-, -COO-, -CONH-, or -SO2-; 1 is 5-100 mol%; m is 0-95 mol%; n is 0-95 mol%; 1+m+n=100 mol%; and t is 0 or 1. The irradiation with electron beams is carried out under conditions including an atmosphere of nitrogen or argon or a vacuum, a temperature of 20-450 deg.C, an energy of 1-30 keV, and a dose of 0.01-20 mC/cm2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating a phenylene group-containing (co) polymer. More specifically, an LSI, a system LSI, a DRA capable of improving mechanical strength and solvent resistance of a phenylene group-containing copolymer film.
Interlayer insulating films for semiconductor devices such as M, SDRAM, RDRAM, and D-RDRAM; protective films such as surface coat films for semiconductor devices; interlayer insulating films for multilayer wiring substrates; The present invention relates to a method for treating a phenylene group-containing (co) polymer suitably used for production and a treated membrane.

[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 during chip manufacturing and chip connection and pinning.

[0003] Polyimide is widely known as the organic material having high heat resistance. However, since it contains a highly polar imide group, no satisfactory material has been 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 raw material synthesis (International application WO96 / 28491 has a heat-resistant, low-dielectric structure but complicated monomer synthesis).

[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 unfavorable 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]

However, the above-mentioned Japanese Patent Application Nos. 10-29068 and 10-29070,
Also in the method proposed in Japanese Patent Application No. 10-273522, the mechanical strength and solvent resistance of the resulting polyphenylene film when formed into a film were not always satisfactory. The present invention has been made in view of the above problems, and provides a method for treating a phenylene group-containing copolymer capable of improving mechanical strength and solvent resistance of a phenylene group-containing copolymer film. Aim.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have achieved the above object by irradiating a specific phenylene group-containing (co) polymer film with an electron beam. The inventors have found that the present invention can be performed, and have completed the present invention. That is, the present invention provides the following method for treating a phenylene group-containing copolymer.

[1] A phenylene group-containing (co) polymer represented by the following formula (1) is formed on a substrate, and the obtained phenylene group-containing (co) polymer film is irradiated with an electron beam. For treating a phenylene group-containing (co) polymer.

[0013]

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[In the formula (1), X is -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) And at least one member selected from the group consisting of a fluorenylene group, wherein R ^{1 to} R ²⁰ are the same or different and represent a hydrogen atom, a halogen atom, or a monovalent organic group; -COO-, -CONH
At least one selected from the group consisting of — and —SO ₂ — groups, 1 is 5 to 100 mol%, m is 0 to 95 mol%, and n is 0 to 95 mol% (1 + m + n = 100 mol%) , T is 0 or 1. ]

[2] l in the above formula (1) is 50 to 1
The method for treating a phenylene group-containing copolymer according to the above [1], which is 00 mol%.

[3] The method for treating a phenylene group-containing (co) polymer according to [1] or [2], wherein the phenylene group-containing (co) polymer film has a thickness of 0.1 to 10 μm. .

[4] The phenylene group-containing (co) polymer film is coated with 20 to 45
0 ° C. temperature, 1-30 keV energy, and 0.0
The method for treating a phenylene group-containing (co) polymer according to any one of the above [1] to [3], wherein an electron beam is irradiated at an electron dose of 1 to ²⁰ mC / cm ² .

[5] A film processed by the method according to any one of [1] to [4].

[0019]

According to the method for treating a phenylene group-containing (co) polymer of the present invention, a cross-link is formed by irradiating a specific phenylene group-containing copolymer film with an electron beam, as described above. And the solvent resistance can be improved.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. In the method for treating a phenylene group-containing (co) polymer of the present invention, a phenylene group-containing (co) polymer represented by the following formula (1) is formed on a substrate, and the obtained phenylene group-containing (co) polymer is obtained. The film is irradiated with an electron beam under specific conditions.

Hereinafter, each component will be described more specifically. 1. Phenylene group-containing (co) polymer The phenylene group-containing (co) polymer used in the present invention is:
This is shown in the following equation (1).

[0022]

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[In the formula (1), X represents -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, alkyl group, hydrogen atom, halogen atom or aryl group) And at least one member selected from the group consisting of a fluorenylene group, wherein R ^{1 to} R ²⁰ are the same or different and represent a hydrogen atom, a halogen atom, or a monovalent organic group; -COO-, -CONH
At least one selected from the group consisting of — and —SO ₂ — groups, 1 is 5 to 100 mol%, m is 0 to 95 mol%, and n is 0 to 95 mol% (1 + m + n = 100 mol%) It is. ]

[0024] Among these, X is hexafluoroisopropylidene group, a fluorenyl group,> CPh ₂ groups are preferred.

1 is 5 to 100 mol%, and m is 0 to 9
5 mol%, n is preferably 0 to 95 mol%, more preferably 1 is 50 to 100 mol%, m is 0 to 50 mol%, and n is 0 to 50 mol%.

The repeating unit is preferably connected to X and Y 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. .

[0028]

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[In the formula (2), X is -CQQ'- (where Q and Q 'are the same or different and each represents a halogenated alkyl group, alkyl group, hydrogen atom, halogen atom or aryl group) And at least one member selected from the group consisting of fluorenylene groups, wherein R ^{1 to} R ⁸ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, or an aryl group. , Z represents an alkyl group, a halogenated alkyl group or an aryl group. ]

Among Q and Q 'in the formula (2), the halogenated alkyl group is a trifluoromethyl group, a pentafluoroethyl group or the like, and the aryl group is a phenyl group, a biphenyl group, a tolyl group, Examples thereof include a pentafluorophenyl group.

In R ^{1 to} R ^{8 in} the above formula (2), a fluorine atom or the like is used as the halogen atom, a methyl or ethyl group is used as the alkyl group, and a trialkyl is used as the halogenated alkyl group. Examples of the allyl group such as a fluoromethyl group and a pentafluoroethyl group include a propenyl group and the like, and examples of the aryl group include a phenyl group and a pentafluorophenyl group.

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

As X in the above formula (2), the following groups are preferred.

[0034]

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[0035]

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[0036]

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[0037]

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Of these, a fluorenylene group is more preferred.

Specific examples of the phenylene group-containing polymer having a repeating structural unit represented by the above formula (2) include 2,2
-Bis (4-methylsulfonyloxyphenyl) hexafluoropropane, bis (4-methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-methylsulfonyl) Roxy-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-phenylsulfonyloxy-3) -Propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane, 2,
2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxyphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methyl) Phenyl) 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 Tolyl sulfonyl Russia carboxy -
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 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 two or more equivalents of a base of a 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.
And sulfonic acid chloride (anhydride) (for example,
Methanesulfonic acid chloride) is added dropwise over 5 to 60 minutes under a dry nitrogen stream while maintaining the temperature at 15 ° C. or lower. 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 dissolved in 2 equivalents of an aqueous alkali solution such as an aqueous sodium hydroxide 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, the compound represented by the formula (2) and at least one selected from the compounds represented by the following formulas (3) to (5) may be copolymerized.

[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 ³⁴ represents a halogen atom or a group represented by —OSO ₂ Z. (Z represents an alkyl group, a halogenated alkyl group or an aryl group), and Y represents -CO-, -COO-, -CO
At least one selected from the group consisting of NH— and —SO ₂ — groups, and t is 0 or 1. ]

The compound represented by the formula (3) 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.

[0046]

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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 ³¹ represents a halogen atom or a group represented by —OSO ₂ Z. (Z is an alkyl group, a halogenated alkyl group or an aryl group). In R ^{17 to} R ²⁰ in the formula (4), the halogen atom may be a fluorine atom, and the monovalent organic group may be a hydroxyl group, a carboxyl group, an allyl group, an alkoxycarbonyloxy group, or the like. it can. R ^{17 to} R
^It is preferable that at least one of the groups ²⁰ is 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 of protecting a reactive group, in the case of a carboxyl group, there is a method of protecting the reactive group by esterification by reacting with an acid in an alcohol.

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.

[0052]

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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 ³² represents a halogen atom or a group represented by —OSO ₂ Z. (Z is an alkyl group, a halogenated alkyl group or an aryl group). Here, as the halogen atom of R ^{17 to} R ²⁰ , the monovalent organic group, and the alkyl group, halogenated alkyl group and aryl group of R ³² , those similar to the aforementioned general formula (4) can be exemplified. .

Also in the above formula (5), R ^{17 to} R ²⁰
It is preferable to use at least one of them as a reactive group or a precursor thereof from the viewpoint of increasing the adhesion of the polymer.

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.

In addition to the compounds represented by the formula (3) or (4), for example, 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-dimethylsulfonyloxybenzene, 3,4 -Dimethylsulfonyloxybenzene, 3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,
4-diiodobenzotrifluoride, 1,2-dibromo-3,4,5,6-tetrafluorobenzene, 4,5
-Can be copolymerized with dichlorophthalic anhydride or the like.

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

In the present invention, when the compound represented by the formula (2) and the compound represented by the formula (4) are copolymerized, the proportion of the compound represented by the formula (2) is usually 5 to 99 mol%, Preferably, it is 50 to 95 mol%, 1 to 95 mol%, preferably 1 to 50 mol% of the compound represented by the formula (4).

In the present invention, when the compound represented by the formula (2) and the compound represented by the formula (5) are copolymerized, the proportion of the compound represented by the formula (2) is usually 5 to 99 mol%, Preferably, it is 50 to 95 mol%, 1 to 95 mol%, preferably 1 to 50 mol% of the compound represented by the formula (5).
It is.

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. As the catalyst system, a transition metal salt and a ligand, or a The transition metal (salt) to which the ligand is coordinated and the 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 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. 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 chloride2triphenylphosphine and nickel chloride2,2'bipyridine are preferable.

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

Examples of the “salt” usable in such a catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium fluoride, and potassium chloride. Potassium bromide, potassium iodide, potassium compounds such as potassium sulfate, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, ammonium compounds such as tetraethylammonium sulfate and the like, Preferred are sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide.

The proportion of each component used in such a catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is a compound represented by the above formula (2) or a compound represented by the above formula (2).
Is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, per 1 mol of the total amount of the compound represented by the formula (3) to the compound represented by the formula (3) to (5). If the amount is less than 0.0001 mol, the polymerization reaction does not proceed sufficiently, while
If it exceeds 0 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, while if it exceeds 100 mol, there is a problem that the molecular weight decreases.

The ratio of the reducing agent used in the catalyst system is 1% of the total amount of the compound represented by the formula (2) or the compound represented by the formula (2) and the compounds represented by the formulas (3) to (5).
Usually, 0.1 to 100 moles, preferably 1 mole,
10 to 10 mol. If the amount is less than 0.1 mol, the polymerization does not proceed sufficiently. If the amount exceeds 100 mol, purification of the obtained polymer may be difficult.

Further, when a “salt” is used in the catalyst system,
The use ratio thereof is usually 0.001 to 100 with respect to 1 mol of the compound represented by the formula (2) or the compound represented by the formula (2) and the compound represented by the formulas (3) to (5). Mole, preferably 0.01 to 1 mole. If it is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, and if it exceeds 100 mol, it may be difficult to purify the obtained polymer.

Examples of the polymerization solvent which can be used 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 concentration of the compound of the formula (2) or the compound of the formula (2) and the compounds of the formulas (3) to (5) in the polymerization solvent is usually from 1 to 100% by weight, preferably from 1 to 100% by weight. Is 5 to 40% by weight.

The polymerization temperature when polymerizing the polymer of the present invention is usually 0 to 200 ° C., preferably 50 to 80 ° C.
It is. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

2. Film formation of phenylene group-containing (co) polymer In the present invention, the method for forming the phenylene group-containing (co) polymer is not particularly limited, but usually, the phenylene group-containing (co) polymer is dissolved in a solvent. And cast it on the 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 film is usually 0.1 to 10 μm.

Examples of the solvent for dissolving the phenylene group-containing (co) polymer include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, 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 dissolved in the solvent is 1 to 60% by weight, preferably 5 to 40% by weight. If it is less than 1% by weight,
When a coating film having a sufficient thickness cannot be obtained and exceeds 60% by weight,
It may not be cast sufficiently and a uniform coating film may not be obtained.

Additives can be added to the phenylene group-containing (co) polymer used in the present invention, if necessary. Examples of the additives include silane coupling agents,
Crosslinking agents such as methylolated melamine and triazene compounds can be mentioned.

3. Irradiation with Electron Beam The method for irradiating the phenylene group-containing (co) polymer film with an electron beam used in the present invention is not particularly limited, but is preferably performed, for example, under the following conditions. Atmosphere: nitrogen, argon, or vacuum (especially, vacuum is more preferable.) Temperature: 20 to 450 ° C. (100 to 425 ° C. is more preferable.) Energy: 1 to 30 keV (1 to 20 keV is more preferable.) Electron dose: 0 .01 to 20 mC / cm ² (1 to 15
mC / cm ² is more preferred. )

When the treatment is performed in a nitrogen, argon, or vacuum atmosphere, the film is not oxidized, and sufficient heat resistance and low dielectric properties can be obtained. When the temperature is from 20 to 450 ° C., crosslinking proceeds sufficiently and decomposition hardly occurs. Energy is 1
When it is in the range of ３０30 keV, crosslinking easily proceeds. When the electron dose is in the range of 0.01 to 20 mC / cm ² , crosslinking proceeds sufficiently and decomposition of the polymer hardly occurs.

Examples of uses of the phenylene group-containing copolymers represented by the formulas (1) and (10) after the electron beam irradiation treatment obtained in the present invention include, for example, interlayer insulating materials, protective films, and low refractive materials. , A high-refractive material, an optical waveguide material, an antireflection film, a sealing material, a liquid crystal alignment film, a printed circuit board material, a gas permeable film, etc., and are particularly suitable for an insulating material and an optical material.

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-neck 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, 2,2-bis (4
After addition of 20.3 g of -methylsulfonyloxyphenyl) diphenylmethane and drying under vacuum for 24 hours, the inside of the three-necked flask was filled with argon gas. Continued
When 150 ml of dry N, N-dimethylacetamide was added and the mixture was stirred at 70 ° C. under an argon stream, the reaction solution turned brown. After allowing the reaction to proceed at 70 ° C. for 20 hours, 500 ml of 36% hydrochloric acid and methanol 2
The mixture was poured into a 00 ml mixture, and the precipitate was collected. 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 acetone, and the precipitate was recovered and dried to obtain a white powder polymer.

Synthesis Example 2 20.3 g of 2,2-bis (4-methylsulfonyloxyphenyl) diphenylmethane
In place of 2,4-dichlorophenoxybenzene 9.
Synthesis was performed in the same manner as in Synthesis Example 1 except that 6 g was added.

(Examples 1 and 2) The polymer obtained in Synthesis Example 1 (Example 1) and the polymer obtained in Synthesis Example 2 (Example 2) were dissolved in cyclohexanone, and the solid content concentration was 20%.
Was applied to an 8-inch silicon wafer by spin coating, and baked at 80 ° C. for 2 minutes and at 160 ° C. for 30 minutes to obtain a coating film having a thickness of 1.0 μm. This substrate was subjected to 5 mC at 350 ° C. and 8 eV under vacuum using an electron beam irradiation apparatus.
/ Cm ² of electron beam. Evaluation of the coating film after electron beam irradiation was performed by the following method. Table 1 shows the results.

Evaluation method Dielectric constant An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a dielectric constant measurement sample. This sample was sampled at a frequency of 100 kHz using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.
The dielectric constant of this coating film was measured by the V method.

The modulus of elasticity of the obtained film was measured by a continuous rigidity measuring method using a nano indenter XP (manufactured by Nano Instruments).

Solvent Resistance The substrate on which the coating film was formed was immersed in N-methyl-2-pyrrolidone at 90 ° C. for 1 hour, and the residual film ratio was evaluated by the following equation. (Residual film ratio) = (Film thickness after immersion) / (Film thickness before immersion) × 1
00 (%)

Comparative Example 1 The procedure of Example 1 was repeated, except that the method shown in Table 1 was used. Table 1 shows the results.

[0089]

[Table 1]

[0090]

As described above, according to the present invention, there is provided a method for treating a phenylene group-containing (co) polymer which can improve the mechanical strength and solvent resistance of a phenylene group-containing copolymer film. Can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA04 AA69 AE19 AF02 AF14 AG14 AH12 BA02 BB02 BC01 BC12 4F073 AA13 AA32 BA32 BA34 CA42 HA03 HA04 HA05 HA11 4J032 CA04 CA22 CB01 CB04 CB05 CC01 CC02 CD02 CD07 CE03 CE02 CE

Claims (5)

[Claims] A phenylene group-containing (co) polymer represented by the following formula (1) is formed on a substrate, and the obtained phenylene group-containing (co) polymer film is irradiated with an electron beam. For treating phenylene group-containing (co) polymers. Embedded image [In the formula (1), X represents -CQQ '-(where Q, Q'
Are the same or different and represent at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom and an aryl group), and a fluorenylene group, and R ^{1 to} R ²⁰ are the same. or different, represent a hydrogen atom, a halogen atom, or a monovalent organic group, Y, -CO -, - COO -, - CONH-, and -SO ₂ - is at least one selected from the group consisting of group , L is 5 to 100 mol%, m is 0 to 95 mol%, n
Is 0 to 95 mol% (l + m + n = 100 mol%), and t is 0 or 1. ] 2. The method for treating a phenylene group-containing copolymer according to claim 1, wherein 1 in the formula (1) is 50 to 100 mol%. 3. The method for treating a phenylene group-containing (co) polymer according to claim 1, wherein the thickness of the phenylene group-containing (co) polymer film is 0.1 to 10 μm. 4. The phenylene group-containing (co) polymer film,
Temperature of 20 to 450 ° C., energy of 1 to 30 keV, and 0.01 to 2 in an atmosphere of nitrogen, argon or vacuum
The method for treating a phenylene group-containing (co) polymer according to claim 1, wherein the electron beam is irradiated at an electron dose of 0 mC / cm ² . 5. A film processed by the method according to claim 1.