JP2001002901A - Phenylene group-containing (co)polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in coating properties at the time of forming a film and suitable as a raw material for layer insulating films for semiconductor elements, layer insulating films, etc., for multilayered wiring substrates by including a specific phenylene group-containing (co)polymer and a surfactant. SOLUTION: This composition is obtained by including (A) a phenylene group- containing (co)polymer represented by the formula X is CQQ' [Q and Q' are each a (halogenated)alkyl, H, a halogen or an aryl] or fluorenylene; 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% and (l+m+n) is 100 mol%; and (t) is 0 or 1) and (B) a surfactant in an amount of 0.001-1 pt.wt., preferably 0.01-0.1 pt.wt. based on 100 pts.wt. of the component A and, as necessary, (C) a solvent. A silicone-based surfactant is preferably used as the component B.

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
Suitable as a raw material such as an interlayer insulating film for semiconductor devices such as M and D-RDRAM; a protective film such as a surface coat film of a semiconductor device; an interlayer insulating film of a multilayer wiring substrate; And a phenylene group-containing (co) polymer composition having excellent coatability during film formation.

[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-described problems, and has been made in consideration of an LSI, a system LSI, and a DR.
Interlayer insulating films for semiconductor devices such as AM, SDRAM, RDRAM, and D-RDRAM; protective films such as surface coat films for semiconductor devices; interlayer insulating films for multilayer wiring boards; protective films and insulating films for liquid crystal display devices; An object of the present invention is to provide a phenylene group-containing (co) polymer composition which is suitable as a raw material and has excellent coatability during film formation.

[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 making a specific phenylene group-containing (co) polymer film and a surfactant-containing composition, 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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[X is -CQQ '-(where Q, Q'
Are the same or different, and are a halogenated alkyl group, an alkyl
Group, hydrogen atom, halogen atom or aryl group)
Selected from the group consisting of:
At least one kind of R¹~ R ²⁰Are the same or different
Represents a hydrogen atom, a halogen atom, or a monovalent organic group.
And Y is -CO-, -COO-, -CONH-, and
-SO₂At least one member selected from the group consisting of
1 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] l in the above formula (1) is 50 to 1
The phenylene group-containing (co) polymer composition according to the above [1], which is 00 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].

The phenylene group-containing (co) polymer composition of the present invention, as described above, is formed into a composition containing a specific phenylene group-containing copolymer and a surfactant, so that the coating property during film formation is improved. 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 is a phenylene group-containing (co) polymer represented by the following formula (1).
It is characterized by containing a polymer and a surfactant.

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%) And t is 0 or 1. ]

[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) phenyl Methane, 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-trifluoromethylsulfone) Phonyloxy-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-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-phenylsulfur Phonyloxy-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-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-tolylsulfate) Phonyloxy-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-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)
Examples thereof include trifluoromethylphenylmethane and bis (p-tolylsulfonyloxyphenyl) phenylmethane.

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 a base of two 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. In addition, 4
-A catalyst such as 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 converted to a sodium hydroxide aqueous solution or the like.
Dissolve in an equivalent amount of an alkaline aqueous solution. On the other hand, sulfonic acid chloride (anhydride) (for example, methanesulfonic acid chloride) is dissolved in an organic solvent such as toluene and chloroform. Then, 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.

[0045]

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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 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-, -CON.
H-, and -SO ₂ - is at least one selected from the group consisting of groups, t is 0 or 1. ]

The compound represented by the above 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.

[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 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 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. It is preferable that at least one of R ^{17 to} R 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 for protecting the reactive group, in the case of a carboxyl group, there is a method of protecting the carboxyl group by esterification by reacting with an acid in alcohol.

Specific examples of the compound represented by the above 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.

[0055]

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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 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, a halogen atom of R ^{17 to} R ²⁰ ,
Examples of the monovalent organic group and the alkyl group, halogenated alkyl group, and aryl group represented by R ³³ include the same groups as those in Formula (4).

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.

The compound represented by the above formula (5) includes, for example, 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 from 50 to 95 mol%, from 1 to 95 mol%, preferably from 5 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 5 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, 50 to 95 mol%, 1 to 95 mol% of the compound represented by the formula (5), preferably 5 to 50 mol%
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; iron chloride; 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, 1,3-bis (diphenylphosphino) propane and the like. 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 is 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, 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 the compound represented by the formula (2) or the compound represented by the 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 1 mol, per mol of the transition metal salt. 10 to 10 mol. 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.

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, and if it exceeds 100 mol, the purification of the obtained polymer may be difficult.

Further, when a “salt” is used in the catalyst system,
The 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. When the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, and when the amount exceeds 100 mol, it may be difficult to purify the obtained polymer.

Examples of the polymerization solvent that can be used in the present invention include 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 for 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. 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 (6).

[0079]

Embedded image

[In the formula (6), R ³⁴ 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, 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, per 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 comprises LS
I, system LSI, DRAM, SDRAM, RDRA
Suitable as a raw material for an interlayer insulating film for a semiconductor element such as an M or D-RDRAM; a protective film such as a surface coat film for a semiconductor element; an interlayer insulating film for a multilayer wiring board; Used. In this case, the method for forming the phenylene group-containing (co) polymer composition into a film is not particularly limited.
After dissolving the polymer composition in a solvent, applying the composition on a substrate by casting or spin coating, and then removing the solvent by baking.

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

Examples of the solvent for dissolving the phenylene group-containing (co) polymer composition 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 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 uses of the 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, an optical waveguide material, Examples thereof include an antireflection film, a sealing material, a liquid crystal alignment film, a printed circuit board material, and a gas permeable film, 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-necked flask equipped with an argon gas inlet and a thermometer. 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.

Preparation of Composition and Film Formation (Example 1) 100 parts of the polymer obtained in Synthesis Example 1 was dissolved in 0.02 parts of organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) in cyclohexanone. A varnish having a solid concentration of 12% by weight was applied to an 8-inch silicon wafer by a spin coating method.
And baked at 160 ° C. for 30 minutes to obtain a coating film having a thickness of 1.0 μm. Table 1 shows the evaluation results of the obtained coating films. The evaluation was based on the following method.

Evaluation Method (Coating Uniformity) In order to evaluate coating uniformity (in-plane uniformity of film thickness), the obtained film was measured with an optical film thickness meter (Rudolph).
SpectraLa, manufactured by Technologies
(Ser200) was used to measure 50 points in the coating film surface. 3σ of the obtained film thickness was calculated and evaluated according to the following criteria. ○: 3σ of the coating film was less than 100 nm ×: 3σ of the coating film was 100 nm or more (dielectric constant) An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for dielectric constant measurement. This sample at a frequency of 100 kHz,
Yokogawa-Hewlett-Packard Co., Ltd., HP1645
The dielectric constant of the coating film was measured by a CV method using a 1B electrode and an HP4284A precision LCR meter. . (Elastic Modulus) The obtained film was measured by a continuous stiffness measuring method using a Nanoindenter XP (manufactured by Nano Instruments).

(Comparative Example 1) In parts by weight, an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Was performed in the same manner as in Example 1, except that was not added.
Table 1 shows the evaluation results of the obtained coating films.

[0096]

[Table 1]

As described above, according to the present invention, an LSI, a system LSI, a DRAM, an SDRAM,
Suitable as a raw material such as an interlayer insulating film for semiconductor devices such as RDRAM and D-RDRAM; a protective film such as a surface coat film of a semiconductor device; an interlayer insulating film of a multilayer wiring board; In addition, it is possible to provide a phenylene group-containing (co) polymer composition having excellent coatability during film formation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 83:04) (72) Inventor Kohei Goto 11-24, Tsukiji 2-chome, Chuo-ku, Tokyo JSR Corporation F term (reference) 4D077 AA01 AB06 BA07 BA15 DD56X DD56Y DE02X 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'
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 phenylene group-containing (co) polymer composition according to claim 1, wherein 1 in the formula (1) is 50 to 100 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.