JPH11228674A - Production of phenylene group-containing copolymer, and film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer excellent in heat resistance, low dielectric property, processability, transparency, adhesiveness, etc., by copolymerizing a specific phenylene group-containing compound with a specific compound in the presence of a specific catalyst system. SOLUTION: This method for producing a phenylene group-containing copolymer comprises copolymerizing (A) 50-95 mol.% phenylene group-containing compound of formula I X is a divalent organic group; R<1> to R<8> are each H, a halogen, a (halogenated)alkyl, an aryl, etc.; R<9> to R<10> are each OSO2 Z [Z is a (halogenated)alkyl or an aryl]} [e.g. 2,2-bis(4-methyisuifonyloxyphenyl) hexafluoropropane] with (B) 50-5 mol.% compound of formula II [R<11> to R<14> are each H, a halogen, a (halogenated)alkyl, OH or monovalent reactive organic group (precursor) and one or more groups among these groups are OH or a monovalent reactive organic group (precursor); R<15> to R<16> are each a halogen or OSO2 Z] (e.g. 2,4-dichlorobenzyl alcohol) in the presence of (C) a catalyst system containing a transition metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a phenylene group-containing compound having excellent heat resistance, low dielectric properties, workability, transparency and adhesion, and having excellent solvent resistance by being cured by mixing a crosslinking agent. The present invention relates to a method for producing a copolymer.

[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, the circuit resistance and the capacitance between the wirings (hereinafter, also referred to as “parasitic resistance” and “parasitic capacitance”, respectively) increase, which not only increases the power consumption, but also increases the delay time. This is a major factor in lowering the signal speed. 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 at the time of manufacturing a mounting board 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. This polyphenylene is excellent in heat resistance, but is inferior in the solubility in an organic solvent. Therefore, it is common to introduce a side chain. As such polyphenylene, for example, USP 52140
44, WO96 / 28491, EP629217 and the like. These polymers basically have a polyparaphenylene structure and partially copolymerize a flexible monomer, but are soluble only in a specific organic solvent and have poor processability. Further, many side chains are polar groups or alkyl groups, and thus do not sufficiently satisfy heat resistance and low dielectric properties. Further, these polymers are mainly produced from aromatic dichloro compounds such as paradichlorobenzene derivatives as raw materials. If an attempt is made to introduce a fluoroalkyl group or an aryl group into a side chain in order to produce a heat-resistant, low-dielectric material from such an aromatic dichloro compound, the synthesis becomes complicated, and a monomer cannot be stably obtained, There is an inconvenience that the degree of polymerization is not sufficiently increased due to steric hindrance of the chain. As described above, polyphenylene that sufficiently satisfies heat resistance, low dielectric properties, and workability and that can be manufactured by an inexpensive process has not been found so far.

[0004]

SUMMARY OF THE INVENTION The present invention provides a phenylene group-containing compound having a bent group introduced into the main chain, a hydroxyl group,
By using another compound that has a hydroxyalkyl group or a carboxyl group and can be copolymerized with it, it has excellent heat resistance, low dielectric properties, workability, transparency and adhesion, and is cured by mixing a crosslinking agent. It is intended to obtain a resin having excellent solvent resistance by using it.

[0005]

According to the present invention, there is provided a phenylene group-containing compound represented by the following general formula (I) (hereinafter also referred to as "compound (I)") of 50 to 95 mol%; ) (Hereinafter also referred to as “compound (II)”) in an amount of 50 to 5 mol% (provided that (I) + (II) = 1)
[00mol%] in the presence of a catalyst system containing a transition metal compound, and a film-forming material comprising the polymer obtained by this method. Is provided.

[0006]

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[Wherein X is a divalent organic group, R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group or an aryl group, R ^{9 to} R ¹⁰ Is —OSO ₂ Z (where Z represents an alkyl group, a halogenated alkyl group or an aryl group)
R ^{11 to} R ¹⁴ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxyl group, a monovalent reactive organic group or a precursor thereof, and at least one of them. One is a hydroxyl group, a monovalent reactive organic group or a precursor thereof, and R ^{15 to} R ¹⁶ are a halogen atom or a group represented by —OSO ₂ Z (where Z is the same as described above). is there. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a phenylene group-containing compound represented by the above general formula (I) in which a bending group is introduced into the main chain, and the above general formula (II) having at least a hydroxyl group copolymerizable therewith. ), In the presence of a catalyst system containing a transition metal compound, by copolymerization in a polymerization solvent, heat resistance, low dielectric properties, processability, transparency, excellent adhesion, organic This is for producing a phenylene group-containing copolymer that is soluble in a solvent. Here, X in the compound represented by the general formula (I) is a divalent organic group, preferably -CY.
A group represented by Y'- (where Y to Y 'are the same or different and represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group, a halogenated alkyl group and an aryl group), or It is a fluorenylene group. Among Y to Y 'of -CYY'- in the compound (I), the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an i-
Propyl group and the like, as the halogenated alkyl group, trifluoromethyl group, pentafluoroethyl group and the like,
As the aryl group, a phenyl group, a biphenyl group,
Examples include a tolyl group and a pentafluorophenyl group.

Further, among R ^{1 to} R ^{8 in} the general formula (I), a fluorine atom or the like is used as a halogen atom, a methyl group or an ethyl group is used as an alkyl group, and a halogenated alkyl group is used as a halogenated alkyl group. , A trifluoromethyl group, a pentafluoroethyl group and the like, an allyl group includes a propenyl group and the like, and an aryl group includes a phenyl group and a pentafluorophenyl group. Furthermore, R ⁹ ~
R ¹⁰ is a group represented by —OSO ₂ Z (where Z represents an alkyl group, a halogenated alkyl group, or an aryl group). Constituting the Z in the above -OSO ₂ Z, methyl as the alkyl group group, and ethyl group, and a trifluoromethyl group as a halogenated alkyl group, the aryl group phenyl, p- tolyl group, p -Fluorophenyl group and the like.

Specific examples of the phenylene group-containing compound represented by the general formula (I) 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, 9,9- Screw (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 and the like.

Specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane and bis (4-trifluoro Methylsulfonyloxyphenyl) 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-trifluoromethylsulfur) 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) and the like.

Further, specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane and bis (4-phenylsulfonyl). Loxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyl) Roxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene , 9,9-bis (4-phenylsulfonyloxy-3-methyl) Phenyl) fluorene, 9,9
-Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyl) Roxy
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, etc. Is mentioned.

Further, specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (p-tolylsulfonyloxyphenyl) hexafluoropropane and bis (p-tolylsulfonyl). Loxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyl) Roxy
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) trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like can be mentioned.

In the present invention, the phenylene group-containing compound represented by the general formula (I) may be copolymerized using at least two kinds. Preferred combinations include 2, 2
-Bis (4-methylsulfonyloxyphenyl) hexafluoropropane / 9,9-bis (4-methylsulfonyloxyphenyl) fluorene, 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane / bis (4-methylsulfonyloxyphenyl) diphenylpropane, 9,9-bis (4-methylsulfonyloxyphenyl) fluorene / bis (4-methylsulfonyloxyphenyl) diphenylpropane, 2,2-bis (4-methyl Sulfonyloxy-3-propenylphenyl) propane / 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) propane / 2 , 2-bis (4-methylsulfonyloxyphenyl) Propane, 2,2-bis (4-methylsulfonyl b hydroxyphenyl) hexafluoropropane /
2,2-bis (4-methylsulfonyloxyphenyl)
And propane.

The other copolymerizable compound used in the present invention is preferably at least one of the compounds represented by the above general formula (II). In the above general formula (II), R
^{11 to} R ¹⁴ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxyl group, a monovalent reactive organic group or a precursor thereof, and at least one of them is a hydroxyl group, Is a reactive organic group of a valence or a precursor thereof. Examples of the monovalent reactive organic group include a hydroxyalkyl group and a carboxyl group, and the precursor indicates a group in which the reactive organic group is protected or an alkoxycarbonyloxy group, as described later. In the compound represented by the general formula (II), when two adjacent substituents are carboxyl groups, the compound may have a structure in which two carboxyl groups are dehydrated and closed. Here, a halogen atom is a fluorine atom, an alkyl group is a methyl group, an ethyl group, a propyl group, etc., a halogenated alkyl group is a trifluoromethyl group, a hexafluoroethyl group, and a hydroxyalkyl group is a hydroxymethyl group, a hydroxyalkyl group. Examples of the alkoxycarbonyloxy group such as an ethyl group include a methoxycarbonyloxy group and an ethoxycarbonyloxy group. In addition, the above general formula (I
In the formula (I), R ^{15 to} R ¹⁶ represent a halogen atom or —SO ₂ Z
It is a group represented by a group. Here, examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
The —SO ₂ Z group is the same as in the general formula (I).

Here, specific examples of the compound (II) include 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-butoxycarbonyloxyphenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-
Dibromobenzoic acid, 2,5-dibromobenzoic acid, 3,5
-Dibromobenzoic acid, methyl 2,4-dichlorobenzoate, methyl 2,5-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 2,4-dibromobenzoate,
Methyl 2,5-dibromobenzoate, methyl 3,5-dibromobenzoate, t-butyl 2,4-dichlorobenzoate, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, etc. Is mentioned. Compound (II) is
One type may be used alone, or two or more types may be used in combination.

The compound (I) and the compound (II) are used in an amount of 50 to 95 mol%, preferably 60 to 95 mol%, of the compound (I).
To 90 mol%, 50 to 5 mol% of compound (II), preferably 40 to 10 mol% [(I) + (II) = 10
0 mol%]. When the amount of the compound (I) is less than 50 mol% (the amount of the compound (II) exceeds 50 mol%), sufficient low dielectric properties and heat resistance cannot be obtained. ) Is less than 5 mol%], but sufficient solvent resistance cannot be obtained even when the composition is cured by mixing with a crosslinking agent. When it is in the above range, a copolymer having excellent solubility and adhesion and having a high molecular weight can be obtained.

The catalyst used for producing the phenylene group-containing copolymer of the present invention is a catalyst system containing a transition metal compound. The catalyst system includes a transition metal salt and a ligand, or a coordination compound. A transition metal salt to which a coordinator is coordinated and a reducing agent are essential components, and a “salt” may be added to increase the polymerization rate. Here, as the transition metal salt, 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 and iron bromide And iron compounds such as iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel compounds such as 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. 2'-bipyridine is preferred.

Further, examples of the transition metal salt to which a ligand is coordinated in advance include, for example, nickel chloride 2-triphenylphosphine, nickel bromide 2-triphenylphosphine, nickel iodide 2-triphenylphosphine, and nickel nitrate 2-triphenylphosphine. Phenylphosphine, 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, with preference given to nickel chloride2triphenylphosphine and nickel chloride 2,2'bipyridine.

The catalyst used for producing the phenylene group-containing copolymer of the present invention is a catalyst system containing a transition metal compound. The catalyst system includes a transition metal salt and a ligand, or a coordinator. A transition metal (salt) to which a ligand is coordinated and a reducing agent are essential components, and a “salt” may be added in order to increase the polymerization rate. Here, as the transition metal salt, 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 and iron bromide And iron compounds such as 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. 2 '
-Bipyridine is preferred. The above-mentioned ligands may be used alone.
Alternatively, two or more kinds can be used in combination.

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

Examples of the reducing agent that can be used in the catalyst system of the present invention include iron, zinc, manganese, aluminum, magnesium, sodium, and calcium, and zinc and manganese are preferred. These reducing agents can be used after being activated by contact with an acid or an organic acid. The “salt” that can be used in the catalyst system of the present invention includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium fluoride, potassium chloride, and bromide. Potassium compounds such as potassium, potassium iodide, and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate; and sodium bromide, iodine Sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

The proportion of each component used in the catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is 1 mol per 1 mol of the total amount of the compound (I) and the compound (II). Usually, 0.0001 to 10 mol, preferably 0.0
1 to 0.5 mol. If the amount is less than 0.0001 mol, the polymerization reaction does not sufficiently proceed.
There is a problem that the molecular weight decreases. In the catalyst system,
When a transition metal salt and a ligand are used, the use ratio of the ligand is usually 0.1 to 1 with respect to 1 mol of the transition metal salt.
00 mol, preferably 1 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 proportion of the reducing agent used in the catalyst system is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the total amount of the compound (I) and the compound (II). If the amount is less than 0.1 mol, the polymerization does not proceed sufficiently, while
If it exceeds 100 moles, there is a problem that purification of the obtained copolymer becomes difficult. Further, when a “salt” is used in the catalyst system, the use ratio is usually 0.001 to 1 mol of the total amount of the compound (I) and the compound (II).
To 100 mol, preferably 0.01 to 1 mol.
If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, while if it exceeds 100 mol, there is a problem that it is difficult to purify the obtained copolymer.

Examples of the polymerization solvent which 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,
-Methyl-2-pyrrolidone is preferred. These polymerization solvents are preferably used after being sufficiently dried. The concentration of the compound (I) and the compound (II) in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 40% by weight.
% By weight. The polymerization temperature when polymerizing the copolymer of the present invention is usually 0 to 200 ° C, preferably 50 to 8 ° C.
0 ° C. The polymerization time is usually 0.5 to 100.
Hours, preferably 1 to 40 hours.

An example of a model reaction formula for obtaining a phenylene group-containing copolymer using the above compounds (I) and (II) is as follows. The phenylene group-containing copolymer obtained by the copolymerization of the present invention may be a random copolymer or a block copolymer. Here, in order to obtain a random copolymer, there is a method in which the compound (I) and the compound (II) are present in the polymerization system immediately before, immediately after or immediately after the start of the polymerization. Also,
In order to obtain a block copolymer, compound (I) and compound (II) are each polymerized in the presence of a catalyst system containing a transition metal compound in advance, and then the reaction mixture is mixed.
A method of polymerizing, or a method of purifying the reaction solution once and polymerizing again in the presence of a catalyst system containing a transition metal compound, or the above compound (I) and compound (II),
A method in which polymerization is carried out in advance in the presence of a catalyst system containing a transition metal compound in advance, and another copolymerization component is added in the middle to carry out polymerization.

[0026]

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In the present invention, the compound (II)
May have its hydroxyl group and carboxyl group protected. Here, in order to protect the hydroxyl group, dicarbonate -t-
A method of reacting butyl in the presence of a base such as triethylamine, a method of acetylation by reacting with a carboxylic acid derivative such as acetic acid or acetyl chloride, and a method of protecting a carboxyl group by reacting an acid in an alcohol. Thus, a method of esterification and the like can be mentioned. In the present invention, when the hydroxyl group or carboxyl group of compound (II) is protected as described above, the obtained copolymer is dissolved in an appropriate solvent, and an acid such as p-toluenesulfonic acid is added and heated. The protected group can be returned to a hydroxyl group or a carboxyl group by a method or a method of adding an alkali such as potassium tert-butoxide, sodium methoxide and heating, and then washing with an acid.

According to the present invention, a phenylene group-containing copolymer comprising a structural unit represented by the following general formula (III) is obtained, and in particular, a repeating structure represented by the following general formula (IV) or (V) Copolymers having units are preferred. The phenylene group-containing copolymer having the repeating structural units represented by the general formulas (III) to (V) is particularly excellent in low dielectric properties, heat resistance, organic solvent solubility, and economic efficiency.

[0029]

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[In the above general formulas (III) to (V), R ^{1 to} R
⁸ is the same as in the general formula (I), R ^{11 to} R ¹⁴ are the same as in the general formula (II), and one of R ^{17 to} R ¹⁸ is a hydroxyl group, a carboxyl group, or a —CH ₂ OH group And the other is a hydrogen atom, m / n (molar ratio) = 95 to 50/5
~ 50. ]

The phenylene group-containing copolymer obtained according to the present invention has a weight average molecular weight in terms of polystyrene of 1,000.
0 to 1,000,000, preferably 1,500 to 20
It is 0000. If it is less than 1,000, the coating properties and strength are insufficient, while if it exceeds 1,000,000, the solubility becomes insufficient.

The phenylene group-containing copolymer of the present invention has a structure of 900 to 675 c
m ^-1 , 1,300 to 1,000 cm ^-1 , 1,500 to
1,400Cm ^-1, confirmed by the absorption of 3,100～3,000Cm ^-1, these composition ratio can be determined by elemental analysis. Further, the structure can be confirmed from a peak at 6.0 to 8.5 ppm by a nuclear magnetic resonance spectrum.

The phenylene group-containing copolymer having the structural unit represented by the above general formula (III) is suitable as a film-forming material, for example, an interlayer insulating material, a protective film, a low refractive material, an optical waveguide material, It can be used for applications such as an antireflection film, a sealing material, a liquid crystal alignment film, a printed circuit board material, and a gas permeable film, and is particularly suitable for an insulating material and an optical material.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In Examples,% and parts are by weight unless otherwise specified. Various measurement items in the examples were obtained as follows.

The weight average molecular weight (Mw ) was determined by gel permeation chromatography (GPC) in terms of polystyrene. ¹ H-NMR analysis 90% N, N-dimethylformamide-d7
Measured in MHz. IR analysis Measured by KBr method. 5% weight loss temperature (Td5 ) The temperature was measured by a TG method in a nitrogen atmosphere at a heating rate of 10 ° C./min. Glass transition temperature Measured at a heating rate of 20 ° C./min by the DSC method.

Relative dielectric constant (ε ) The obtained copolymer is dissolved in a solvent such as cyclohexane, propylene glycol-1-monomethyl ether-2-acetate, and then applied to a SUS substrate by spin coating, followed by firing. As a result, a coating film of the copolymer was obtained. Next, a gold electrode is formed by mask evaporation,
The sample was used for measuring the relative dielectric constant. The capacitance of this sample was measured with an LCR meter, and the relative dielectric constant was determined from the following equation. ε = C · d / ε ₀ · S Here, ε is a relative permittivity, C is a capacitance, ε ₀ is a permittivity in a vacuum, and S is an upper electrode area. Adhesion test A sample obtained by applying a sample to a predetermined substrate is subjected to JIS K5
According to the 400 crosscut tape method, the number of crosscuts after tape peeling was counted. A sample obtained by applying a sample to a solvent-resistant glass substrate was immersed in a predetermined solvent for 1 hour, and the appearance was observed. ○: No change △: Peeling, swelling ×: Dissolution

Example 1 Internal volume 500 equipped with an argon gas inlet tube and a thermometer
7.5 g of sodium iodide in a 3-ml three-necked flask,
1.3 g of anhydrous nickel chloride, triphenylphosphine 1
5.7 g, zinc powder activated in acetic acid 45.8 g, 2,
2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane (hereinafter also referred to as “AFMs”) 3
9.4 g (80 mmol) and 3.54 g (20 mmol) of 2,4-dichlorobenzyl alcohol were added, and after drying for 24 hours under vacuum, 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 reacting as it is at 70 ° C. for 20 hours, the reaction solution was reduced to 36%
The mixture was poured into a mixture of 50 ml of hydrochloric acid and 2,000 ml of methanol, and the precipitate was collected. The obtained precipitate was added to and suspended in chloroform, extracted with a 2N aqueous hydrochloric acid solution, and then the chloroform layer was poured into methanol, and the precipitate was collected to obtain a dry white powdery polymer. The analysis and evaluation results of the obtained polymer are shown in Tables 1 and 2.

Examples 2-6 Example 1 was repeated except that the monomers were charged according to the composition shown in Table 1.
A polymer was obtained in the same manner as described above. The analysis and evaluation results of the obtained polymer are shown in Tables 1 and 2.

Example 7 Example 1 was repeated except that the monomers were charged according to the composition shown in Table 1.
A polymer having a protecting group was obtained in the same manner as described above. Next, 10.9 g of potassium-t-butoxide and 100 ml of dimethyl sulfoxide were added to an eggplant-shaped flask equipped with a stirrer to form a uniform solution. To this solution, 10 g of the polymer obtained above was added, and the mixture was stirred at 80 ° C. for 4 hours. This reaction solution was mixed with 250 ml of 0.5 N hydrochloric acid and 500 ml of methanol.
And the precipitate was collected. The obtained precipitate was dissolved in 100 ml of chloroform, and the solution was diluted with 2N hydrochloric acid.
After washing once with pure water and then reprecipitating with methanol, a white powder of a polymer having a carboxyl group was obtained. Table 1 shows the analysis and evaluation results of the obtained polymer.
It is shown in FIG.

Examples 8 to 9 Polymers having a protective group were obtained in the same manner as in Example 1 except that the monomers were charged in the compositions shown in Table 1. Then
10 g of this polymer was poured into a 300 m
l of the eggplant-shaped flask, 0.5 g of p-toluenesulfonic acid monohydrate and 220 g of toluene were added.
The mixture was stirred at 20 ° C for 3 hours. The reaction solution was concentrated to about 50 ml and reprecipitated with methanol to obtain a white powder of a polymer having a hydroxyl group. The analysis and evaluation results of the obtained polymer are shown in Tables 1 and 2.

[0041]

[Table 1]

In Table 1, the abbreviations of the monomers are as follows. AFMs; 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane o-CBzA; 2,4-dichlorobenzyl alcohol m-CBzA; 3,5-dichlorobenzyl alcohol p-CPhAA; 3,6-dichloro Phthalic anhydride m-CBMe; methyl 3,5-dichlorobenzoate CPh-t-Boc; 3,5-dichloro-t-butoxycarbonyloxybenzene PFMs; bis (methylsulfonyloxyphenyl) trifluoromethylphenylmethane

[0043]

[Table 2]

Test Examples 1 to 5 Polymethylolated melamine (Cymel 300, manufactured by Mitsui Cytec Co., Ltd.) was used for 100 parts of the polymer obtained in the examples.
Was mixed in the composition shown in Table 3, and 1 part of 1-glycidyloxy-3-trimethoxysilylpropylene was used as a solvent, and propylene glycol-1-monomethyl ether was used as a solvent.
300 parts of 2-acetate was added to obtain a thermosetting resin composition. This resin composition was spin-coated on a predetermined substrate, and baked at 80 ° C. and 120 ° C. for 2 minutes each and at 230 ° C. for 30 minutes to evaluate a thin film obtained. Table 3 shows the results.

[0045]

[Table 3]

*) The solvents used in the solvent resistance test are as follows. NMP; 1-methyl-pyrrolidone DMSO; dimethyl sulfoxide PGMEA; propylene glycol-1-monomethyl ether-2-acetate

Test Example 6 The polymer obtained in Example 4 was dissolved in cyclohexanone to form a solution having a solid concentration of 10%.
After adding 10 parts of di-n-butoxybis (ethylacetoacetate) zirconium and reacting at 23 ° C. for 20 minutes, 100 parts of methyltrimethoxysilane, 2 parts of di-n-butoxybis (ethylacetoacetate) zirconium and ion-exchanged water 14 parts were added, and the mixture was further reacted at 60 ° C. for 4 hours. Subsequently, 5 parts of acetylacetone was added, and
The mixture was reacted at 0 ° C. for 1 hour to prepare a thermosetting resin composition having a solid content of 15%. This resin composition is spin-coated on a predetermined substrate, and the mixture is heated at 80 and 120 ° C. for 2 minutes each for 3 minutes.
The thin film obtained by baking at 00 ° C. for 60 minutes was evaluated. Table 4 shows the results.

Test Example 7 A thin film was obtained in the same manner as in Test Example 6, except that the polymer obtained in Example 7 was used instead of the polymer obtained in Example 4. Table 4 shows the results.

Test Example 8 To 10 g of the polymer obtained in Example 8, 40 g of cyclohexanone was added to prepare a varnish (solution A). On the other hand, after uniformly mixing 13 g of methyltrimethoxysilane and 66 g of cyclohexanone, tetrabutoxyzirconium 2
2 g and 6.5 g of ethyl acetoacetate were stirred at 60 ° C. for 3 hours to obtain an ethyl zirconium tributoxyacetoacetate solution (solution B). 2.6 g of ion-exchanged water was added to 1.16 g of this solution B, and the mixture was stirred at room temperature to form a homogeneous solution, followed by stirring at 60 ° C. for 3 hours. Solution A was added to this solution, and the mixture was stirred at 60 ° C. for 2 hours, and then concentrated under reduced pressure to obtain a thermosetting resin composition having a solid content of 21.5%. This resin composition is spin-coated on a predetermined substrate,
The thin films obtained by baking at 80 and 120 ° C. for 2 minutes each and at 300 ° C. for 60 minutes were evaluated.
Table 4 shows the results.

[0050]

[Table 4]

[0051]

The phenylene group-containing copolymer obtained according to the present invention has excellent heat resistance, low dielectric properties, transparency and adhesion, and is soluble in an organic solvent, so that it is easy to process and has a high electronic conductivity. It can be very suitably used for a wide range of applications as a material or an optical material.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of Example 1.

FIG. 2 is an IR spectrum of Example 1.

FIG. 3 is a ¹ H-NMR spectrum of Example 2.

FIG. 4 is an IR spectrum of Example 2.

FIG. 5 is a ¹ H-NMR spectrum of Example 3.

FIG. 6 is an IR spectrum of Example 3.

FIG. 7 is a ¹ H-NMR spectrum of Example 4.

FIG. 8 is an IR spectrum of Example 4.

9 is a ¹ H-NMR spectrum of Example 7. FIG.

FIG. 10 is an IR spectrum of Example 7.

FIG. 11 is a ¹ H-NMR spectrum of Example 8.

FIG. 12 is an IR spectrum of Example 8.

FIG. 13 is a ¹ H-NMR spectrum of Example 9.

14 is an IR spectrum of Example 9. FIG.

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[Procedure amendment]

[Submission date] March 26, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Method for producing phenylene group-containing copolymer and film-forming material

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd.

Claims (5)

[Claims] 1. A phenylene group-containing compound represented by the following general formula (I): 50 to 95 mol%;
A method for producing a phenylene group-containing copolymer, comprising copolymerizing 50 to 5 mol% of the compound represented by the formula (I) in the presence of a catalyst system containing a transition metal compound. Embedded image Embedded image [Wherein X is a divalent organic group, R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group or an aryl group, R ^{9 to} R ¹⁰
Is a group represented by —OSO ₂ Z (where Z represents an alkyl group, a halogenated alkyl group or an aryl group);
R ^{11 to} R ¹⁴ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxyl group, a monovalent reactive organic group or a precursor thereof, and at least one of them is a hydroxyl group, A reactive organic group or a precursor thereof, wherein R ^{15 to} R ¹⁶ are a halogen atom or-
It is a group represented by OSO ₂ Z (where Z is the same as above). ] 2. In the general formula (I), X is -CYY'- (where Y to Y 'are the same or different, and at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogenated alkyl group and an aryl group) 2. The method for producing a phenylene group-containing copolymer according to claim 1, wherein the phenylene group-containing copolymer is a group represented by the following formula: 3. The method for producing a phenylene group-containing copolymer according to claim 1, wherein the monovalent reactive organic group represented by R ^{11 to} R ^{14 in} the general formula (I) is a hydroxyalkyl group or a carboxyl group. 4. A film-forming material comprising a polymer having a structural unit represented by the following general formula (III). Embedded image [Wherein R ^{1 to} R ¹⁴ are the same as above, m / n (molar ratio) =
95 to 50/5 to 50. ] 5. X in the general formula (III) is -CYY'- (where Y to Y 'are the same or different, and at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogenated alkyl group and an aryl group) The film forming material according to claim 4, which is a group represented by one of the following groups: or a fluorenylene group.