JP2010006760A - New condensate of acetylene compound, polycondensate, composition comprising the same and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric or oligomeric material that can be thermoset highly densely to exhibit enhanced mechanical strength. <P>SOLUTION: The condensate or the polycondensate is obtained by causing at least two of compounds represented by general formula (1) to react with each other making use of G as a reactive group. In general formula (1), A<SB>0</SB>-A<SB>4</SB>are each a single bond, or a hydrocarbon or heterocyclic linking group; Ar is an aromatic or heteroaromatic ring linking group; X<SB>0</SB>-X<SB>4</SB>are each a single bond or a bivalent linking group; R<SP>1</SP>is a hydrogen atom, a hydrocarbon group, a heterocyclic group or an alkylsilyl group; G is -NHR<SP>2</SP>or -COOQ; R<SP>2</SP>is a hydrogen atom or a hydrocarbon group; Q is a hydrogen atom, a hydrocarbon group, a metal element forming a salt, or an organoammonium; a<SB>1</SB>, m, n<SB>1</SB>and n<SB>2</SB>are each an integer of 1-5; and b<SB>1</SB>-b<SB>3</SB>are each an integer of at least 0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is useful as a raw material for liquid crystal materials, nonlinear optical materials, electronic materials, adhesive materials, sliding agent materials, photographic additives, gas separation membrane materials and other functional materials, and pharmaceutical and agrochemical intermediates. And a novel acetylene compound condensate having three or more acetylene groups in the molecule, a polycondensate, a composition containing them, and a cured product thereof.

Compounds having an ethynyl group are useful as raw materials for functional materials such as intermediates for medicines and agricultural chemicals, liquid crystals, and electronic materials, and in recent years, various functions utilizing the carbon-carbon triple bond structure present in the molecule. It is attracting attention as a research object related to sexual materials. For example, it is used as a terminal sealing material that imparts heat resistance and oxidation resistance to thermosetting properties to polyimide oligomers (for example, Patent Document 1 and Non-Patent Documents 1 to 3). Patent Document 5 describes a reactive monomer having an acetylene group at its terminal.

In the field of electronic materials, for example, when used in semiconductor applications, there is a demand for a crosslinking temperature that is high and low deformation due to moisture absorption, but what has been known so far has not been able to demonstrate sufficient performance. .
US Pat. No. 5,567,800 JP 2005-320417 A JP 2001-056469 A JP 2005-272352 A WO 2006/137369 “Polymer”, 1994, Vol. 35, p. 4874-4880 “Polymer”, 1994, Vol. 35, p. 4857-4864 “Functional Materials”, 2000, Vol. 20, No. 12, p. 33-40

  An object of the present invention is to provide a novel acetylene compound condensate, a polycondensate, a composition containing them, and a cured product thereof having three or more acetylene groups in a molecule that can be thermally cured at high density. To do.

As a result of diligent research in view of the above circumstances, the present inventors have found a novel acetylene compound having 3 or more acetylene groups in the molecule, and further, (poly) amine or (poly) carboxylic acid and dicarboxylic acid having an acetylene group. When synthesizing a polymer compound by dehydration condensation with an acid or diamine, an acetylene present in the molecule is obtained by reacting an amine or carboxylic acid having two or more acetylene groups in the molecule as a terminal blocking agent. The inventors have found a polymer with an increased amount of groups and have arrived at the present invention. That is, the above-mentioned subject of the present invention was specifically achieved by the following means.

<1> A condensate or polycondensate obtained by reacting at least two compounds represented by the following general formula (1) with G as a reactive group.

General formula (1)

(In the general formula (1), A ₀ , A ₁ , A ₂ , A ₃ and A ₄ each independently represents a single bond, a hydrocarbon group or a heterocyclic linking group. Ar represents an aromatic ring or a heteroaromatic ring. X ₀ , X ₁ , X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a single bond or a divalent linking group, and R ¹ represents a hydrogen atom, a hydrocarbon group, or a heterocyclic ring. Group represents an alkylsilyl group, G represents —NHR ² , or —COOQ, R ² represents a hydrogen atom or a hydrocarbon group, Q represents a metal atom that can form a hydrogen atom, a hydrocarbon group, or a salt, or Represents organic ammonium, a ₁ , m, n ₁ and n ₂ each independently represents an integer of 1 to 5. b ₁ , b ₂ and b ₃ each independently represents an integer of 0 or more.)
<2>
In the general formula (1), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group, a heterocyclic group, or an alkylsilyl group, The condensate or polycondensate according to <1>.
<3>
2. The condensate or polycondensate according to claim 1, wherein the two compounds are represented by the general formula (1), wherein one G is —NHR ² and the other G is —COOQ.
<4>
In the general formula (1), Ar, A ₀ and A ₄ are benzene ring groups or phthalimide ring groups which may have a substituent, and b ₁ , b ₂ and b ₃ are 0, The condensate or polycondensate according to <1>.

<5>
One of the compounds represented by the general formula (1) is G = —COOQ and m is 1, and the other is G = —NH ₂ and m is 2. Condensate.
<6>
One of the compounds represented by the general formula (1) is G = —COOQ and m is 2, and the other is G = —NH ₂ and m is 1. Condensate.
<7>
The polycondensation product according to <5> or <6>, wherein Ar, A ₀ and A ₄ in the general formula are unsubstituted.
<8>
In the above general formula, X ₀ and X ₄ are selected from the group consisting of a single bond, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —CO—. The polycondensate according to <7>, which is selected.

<9>
A compound residue in which G = —NH ₂ and m is 2 in the general formula (1) as a part of the diamine compound in the main chain of the polymer comprising any of polybenzimidazole, polybenzoxazole, polyamide, polyester, and polyimide The polycondensate according to <1>, further comprising a compound residue in which m is 1 in the general formula (1).
<10>
A compound residue in which m is 2 in the general formula (1) G = —COOQ as a part of the dicarboxylic acid compound on the main chain of the polymer composed of polybenzimidazole, polybenzoxazole, polyamide, polyester, or polyimide. The polycondensation product according to <1>, wherein the polycondensation product contains a compound residue in which m is 1 in the general formula (1).
<11>
The composition containing the condensate or polycondensate in any one of said <1>-<10> at least.
<12>
Hardened | cured material formed by hardening | curing the composition as described in said <11>.

According to the present invention, a compound having three or more acetylene groups in a molecule useful as a crosslinking agent can be provided. In addition, a polymer having a plurality of acetylene groups at the ends of the polymer and also having acetylene groups in the side chains can be obtained. Compositions cured using these compounds can have higher crosslink densities.

The present invention is described in detail below. One embodiment of the present invention is a condensate or polycondensate obtained by reacting at least two compounds represented by the following general formula (1) with G as a reactive group.
General formula (1)

(In the general formula (1), A ₀ , A ₁ , A ₂ , A ₃ and A ₄ each independently represents a single bond, a hydrocarbon group or a heterocyclic linking group. Ar represents an aromatic ring or a heteroaromatic ring. In the case where each of A ₀ , A ₁ , A ₂ , A ₃ , and A ₄ is a single bond, X ₀ , X ₁ , X ₂ , X ₃ , and X ₄ also represent a single bond, respectively. .
In general formula (1), A ₀ represents a single bond or a {(n ₁ + l) or (n ₁ + n ₂ ) or (n ₁ + n ₂ + m)}-valent hydrocarbon group or heterocyclic group. A ₁ and A ₃ each independently represents a single bond, a divalent hydrocarbon group or a heterocyclic ring. A ₂ represents a single bond or a {divalent or (n ₂ +1) or (n ₂ + m + 1)} hydrocarbon group or heterocyclic ring.
A ₄ represents a single bond or a (m + 1) -valent hydrocarbon group or heterocyclic group. Ar represents a {(a ₁ +1) or (a ₁ + n ₂ ) or (a ₁ + n ₂ + m)}-valent aromatic ring group or heteroaromatic ring group. X ₀ , X ₁ , X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a single bond or a divalent linking group. R ¹ represents a hydrogen atom, a hydrocarbon group, a heterocyclic group or an alkylsilyl group. G represents —NHR ² or —COOQ. R ² represents a hydrogen atom or a hydrocarbon group. Q represents a hydrogen atom, a hydrocarbon group, or a metal element or organic ammonium capable of forming a salt. _{a 1, m, n 1,} n 2 are each independently an integer of 1-5. b ₁ , b ₂ and b ₃ each independently represents an integer of 0 or more. )

Each hydrocarbon group or heterocyclic group in A ₀ , A ₁ , A ₂ , A ₃ may be unsubstituted or substituted at any position. Examples of the unsubstituted hydrocarbon group include a linear or branched aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic ring group having 6 to 20 carbon atoms. Examples of the linear or branched aliphatic group include an alkyl group (for example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, etc.), Alkenylene groups (eg, propenyl, butenyl, etc.), and alicyclic groups include cycloalkyl groups (eg, cyclopentyl, cyclohexyl, menthyl, etc.), cycloalkenyl groups (eg, cyclohexenyl, etc.), alicyclic polycyclic groups ( For example, bornyl, norbornyl, norbornenyl, decalinyl, adamantyl, diamantyl, triamantyl, bisadamantyl, etc.), spiro ring (eg, spiro [3.4] octane, spiro [4.4] nonane, spiro [5.5] undecane, etc.) Is mentioned. Examples of the aromatic ring of the aromatic ring group include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like.

  Examples of the unsubstituted heterocycle of the heterocyclic group include unsubstituted heteroaromatic rings and unsubstituted heteroalicyclic compounds. Examples of the unsubstituted heteroaromatic ring include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, oxazole, thiazole, imidazole, pyrimidine, triazine, indole, chromene, chroman, quinoline, purine, benzimidazole, benzoxazole, benzo Examples include thiazole, dibenzofuran, phthalimide, thiophthalimide, quinoxaline, and carbazole. Examples of the unsubstituted heteroalicyclic compound include oxetane, thietane, azetidine, oxolane, thiolane, pyrroline, pyrrolidine, pyrazoline, imidazoline, thiazoline, pyran, oxane, thiane, piperidine, morpholine, coumaran, chroman, pyrrolidone and the like. It is done.

  Examples of the optionally substituted hydrocarbon group or the optionally substituted heterocyclic group include the halogenated hydrocarbon group exemplified above and the unsubstituted heterocyclic group, for example, a halogen atom. Atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, sulfonyl group, amide group, C1-C20 alkoxy group (for example, methoxy, butoxy, dodecyloxy), C1-C1 20 acyl groups (for example, acetyl, propionyl, butyroyl, isobutyroyl, benzoyl, cinnamoyl, etc.), C1-20 acyloxy groups (for example, acetyloxy, propionyloxy, butyroyloxy, isobutyroyloxy, benzoyloxy, cinnamoyloxy) Etc.), an acylamino group having 1 to 20 carbon atoms (for example, acetyla Carbon, N-methylacetylamino, propionylamino, benzoylamino, etc.), carbon atoms having a structure substituted at any position with an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl, etc.), hydroxyl group, silyl group, etc. Examples thereof include a hydrogen group and a heterocyclic group.

Among these, as A ₀ , A ₁ , A ₂ , A ₃ , an alkyl group, a cycloalkyl group, an alicyclic polycyclic group, respectively, from the viewpoint of obtaining a high tensile elastic modulus and a high glass transition point, etc. Or an aromatic ring group such as benzene, naphthalene, biphenyl, benzimidazole, benzoxazole, benzothiazole, phthalimide, and the like, an alkyl group, cyclohexyl, norbornyl, adamantyl, or an aromatic ring group of benzene, benzimidazole, benzoxazole, phthalimide In view of availability of raw materials and ease of production, aromatic ring groups such as benzene, benzimidazole, and phthalimide are particularly preferable.

A ₄ represents a single bond, a (m + 1) -valent hydrocarbon group, or a heterocyclic group. When A ₄ is a single bond, X ₄ also represents a single bond. A ₄ may be unsubstituted or substituted at any position, and the unsubstituted hydrocarbon group may be a linear or branched aliphatic group having 1 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms. And an aromatic ring group having 6 to 20 carbon atoms. Examples of the linear or branched aliphatic group include an alkyl group (for example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, etc.), Alkenylene groups (eg, propenyl, butenyl, etc.), and alicyclic groups include cycloalkyl groups (eg, cyclopentyl, cyclohexyl, menthyl, etc.), cycloalkenyl groups (eg, cyclohexenyl, etc.), alicyclic polycyclic groups ( For example, a group such as bornyl, norbornyl, norbornenyl, decalinyl, adamantyl, diamantyl, triamantyl, bisadamantyl, etc., spiro ring (eg spiro [3.4] octane, spiro [4.4] nonane, spiro [5.5] undecane, etc. ) And the like. Examples of the aromatic ring of the aromatic ring group of A ₄ include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like.

A ₄ may be an (m + 1) -valent unsubstituted or optionally substituted heterocyclic group. Examples of the heterocyclic ring of the unsubstituted heterocyclic group include a heteroaromatic ring and a heteroalicyclic compound. Heteroaromatic rings include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, oxazole, thiazole, imidazole, pyrimidine, triazine, indole, chromene, chroman, quinoline, purine, benzimidazole, benzoxazole, benzothiazole, dibenzofuran, phthalimide , Thiophthalimide, quinoxaline, carbazole and the like. Examples of the heteroalicyclic compound include oxetane, thietane, azetidine, oxolane, thiolane, pyrroline, pyrrolidine, pyrazoline, imidazoline, thiazoline, pyran, oxane, thiane, piperidine, morpholine, coumaran, chroman, pyrrolidone and the like.

  The optionally substituted hydrocarbon group or optionally substituted heterocyclic group is, for example, a halogen atom (for example, fluorine) with respect to the unsubstituted hydrocarbon group or unsubstituted heterocyclic group. Atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, sulfonyl group, amide group, alkoxy group having 1 to 20 carbon atoms (for example, methoxy, butoxy, dodecyloxy), acyl group having 1 to 20 carbon atoms. (For example, acetyl, propionyl, butyroyl, isobutyroyl, benzoyl, cinnamoyl, etc.), C1-C20 acyloxy groups (for example, acetyloxy, propionyloxy, butyroyloxy, isobutyroyloxy, benzoyloxy, cinnamoyloxy, etc.), carbon A number 1 to 20 acylamino group (for example, acetylamino, N-methyl) Acetylamino, propionylamino, benzoylamino, etc.), C6-C20 aryl groups (eg phenyl, naphthyl etc.), hydroxyl groups, silyl groups, etc., hydrocarbon groups having a structure substituted at any position, or hetero A cyclic group is mentioned.

Among these, from the viewpoint of obtaining a high tensile elastic modulus and a high glass transition point, A ₄ includes a single bond, an (m + 1) -valent alkyl group, a cycloalkyl, an alicyclic polycyclic group, benzene, or naphthalene. An aromatic ring group such as biphenyl, benzimidazole, and phthalimide is preferable, and a single bond is particularly preferable from the viewpoint of availability of raw materials and ease of production.

Ar represents a {(a ₁ +1) or (a ₁ + n ₂ ) or (a ₁ + n ₂ + m)}-valent aromatic ring or heteroaromatic linking group. Ar may be unsubstituted or substituted at any position. Examples of the unsubstituted aromatic ring include benzene, indene, indane, naphthalene, fluorene, anthracene, biphenyl, and tetralin, and examples of the unsubstituted heteroaromatic ring include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, oxazole, thiazole, Examples include imidazole, pyrimidine, triazine, indole, chromene, chromane, quinoline, purine, benzimidazole, benzoxazole, benzothiazole, dibenzofuran, phthalimide, thiophthalimide, quinoxaline, carbazole and the like.

  Among these, from the viewpoint that high tensile elastic modulus and high heat resistance (glass transition point) can be obtained, as the aromatic ring of the Ar linking group, benzene, indene, indane, naphthalene, and biphenyl are heteroaromatics of the Ar linking group. As the ring, pyridine, pyrimidine, triazine, indole, quinoline, purine, benzimidazole, benzoxazole, benzothiazole, phthalimide, quinoxaline, carbazole and the like are preferable. As the aromatic ring, benzene, biphenyl, naphthalene is used as the heteroaromatic ring. Is more preferably pyridine, triazine, indole, quinoline, benzimidazole, benzoxazole, or phthalimide. Benzene, benzimidazole, and phthalimide are particularly preferable from the viewpoint of availability of raw materials and ease of production.

  The aromatic ring or heteroaromatic ring of the Ar linking group may be substituted with other substituents. Examples of the substituent include halogen atoms (—F, —Br, —Cl, —I), alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyls. Dithio group, aryldithio group, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, Ν-alkylcarbamoyloxy group, N-arylcarbamoyloxy Group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkyl Acylamino group, N-aryl acyl Mino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido Group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group N ′, N′-dialkyl-N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-ary -N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino Group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, acyloxy group, alkoxycarbonyl group, arylcarbonyl group, arylcarbonyloxy group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfo Group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diaryl Sulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N- Diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, dialkylphosphono group, diarylphosphono group, alkylarylphosphono group, monoalkylphosphono group, monoarylphosphono group, dialkylphosphonooxy Group, diarylphosphonooxy group , Alkylarylphosphonooxy group, monoalkylphosphonooxy group, monoarylphosphonooxy group, morpholino group, cyano group and nitro group.

  Specific examples of the alkyl group in these substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t -Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned. Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphona Include a phenyl group. Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of G1 in the acyl group (G1CO-) include hydrogen and the above alkyl groups and aryl groups. Examples of the aralkyl group include those in which the above aryl group is substituted on the above alkyl group.

  Of these substituents, halogen atoms (-F, -Br, -Cl), alkyl groups, aryl groups, aralkyl groups, alkenyl groups, alkoxy groups are preferred from the viewpoint of availability of raw materials and ease of production. Aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, acyl group, alkoxycarbonyl group, arylcarbonyl group, Arylcarbonyloxy group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfonate group, sulfamoyl group, N -Alkylsulfamo Le group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group and a cyano group.

  Of these substituents, more preferred are a halogen atom (—F, —Cl), an alkyl group (methyl group, trifluoromethyl group, ethyl group, trifluoroethyl group, propyl group, butyl group, isopropyl group, t -Butyl group), aryl group (phenyl group, tolyl group, mesityl group, cumenyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group), aralkyl group (benzyl group, phenethyl group) Group), alkoxy group (methoxy group, ethoxy group, isopropoxy group), aryloxy group (phenoxy group), acyloxy group (acetoxy group, propionyloxy group), acetyl group, acetoxy group, benzoyl group, benzoyloxy group, acylamino group (Acetylamino group).

Among these, from the viewpoint of availability of raw materials and ease of production, Ar may be a {(a ₁ +1) or (a ₁ + n ₂ ) or (a ₁ + n ₂ + m)}-valent halogen atom, carbon number 1-8 alkyl group, cycloalkyl group, alkoxy group, acyloxy group, acylamino group, aryl group having 6 to 10 carbon atoms, aryloxy group, aralkyl group, aralkyloxy group, hydroxy group, substituted with cyano group, or Preferred are unsubstituted benzene, biphenyl, naphthalene, pyridine, triazine, benzimidazole, benzoxazole, phthalimide, indole, quinoline groups, (a ₁ +1) valent chloro atom, C 1-6 alkyl group, alkoxy group , Acyloxy group, aryloxy group having 6 to 10 carbon atoms, aralkyl group, hydroxy group, cyano group Substituted or unsubstituted benzene, biphenyl, pyridine, triazine, benzimidazole, benzoxazole, the group of phthalimide more preferably, further, _{(a 1 +1) or _(a 1 + _{n 2)} or _(a 1 + _{n 2} + M)}-valent alkyl group having 1 to 4 carbon atoms, alkoxy group, acyloxy group, aryloxy group having 6 to 10 carbon atoms, aralkyl group, cyano group-substituted or unsubstituted benzene, biphenyl, benzimidazole, More preferred are phthalimide groups. In particular, {(a ₁ +1) or (a ₁ + n ₂ ) or (a ₁ + n ₂ + m)}-valent unsubstituted benzene, biphenyl, benzimidazole, and phthalimide groups are preferable.

X ₀ represents a single bond or a divalent linking group, but its structure is not particularly limited. For example, X ₀ is specifically an alkylene having 1 to 20 carbon atoms (for example, methylene, ethylene, propylene, 2,2-propylene, 1,1,1,3,3,3 hexafluoro-2,2- Propylene, butylene, 2,2-dimethylpropylene, octylene, dodecylene, etc.), alkenylene having 1 to 20 carbon atoms (eg, ethylenylene, propenylene, butyleneylene, hexenylene, dodecenylene, etc.), -OCO-, -COO-, -NRCO- , —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR—, —OCSO—, —SO—, —SO ₂ —, —O—, One or more selected from the group consisting of -S-, -NR-, -CO-, -CS-, and a single bond are used in combination. It is possible.

Among them, since high tensile elastic modulus and high heat resistance (glass transition temperature) can be obtained, X ₀ is a single bond, alkylene having 1 to 8 carbon atoms, —OCO—, —COO—, —NRCO—, —CONR—. , —NRCOO—, —OCONR—, and —NRCONR— are more preferable, and —OCO—, —COO—, —NRCO—, and —CONR— are particularly preferable.

X ₁ , X ₂ , X ₃ and X ₄ each represent a single bond or a divalent linking group, but the structure is not particularly limited. For example, specifically, alkylene having 1 to 20 carbon atoms (for example, methylene, ethylene, propylene, 2,2-propylene, 1,1,1,3,3,3 hexafluoro-2,2-propylene, butylene, 2,2-dimethylpropylene, octylene, dodecylene, etc.), alkenylene having 1 to 20 carbon atoms (for example, ethylenylene, propenylene, butyleneylene, hexenylene, dodecenylene, etc.), -OCO-, -COO-, -NRCO-, -CONR- , —NRCOO—, —OCONR—, —NRCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR—, —OCSO—, —SO—, —SO ₂ —, —O—, —S—, One or two or more selected from the group consisting of -NR-, -CO-, -CS-, and a single bond can be used in combination. . Among these, since high tensile elastic modulus and high heat resistance (glass transition temperature) can be obtained, X ₁ , X ₂ , X ₃ and X ₄ are each a single bond, —OCO—, —COO—, —NRCO—, — CONR-, -NRCOO-, -OCONR-, and -NRCONR- are more preferable, and a single bond is particularly preferable.

R ¹ represents a monovalent hydrogen atom, a hydrocarbon group, a heterocyclic group or an alkylsilyl group. The hydrocarbon group and heterocyclic group may be substituted at any position. As an unsubstituted hydrocarbon group, a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an alicyclic polycyclic group having 6 to 20 carbon atoms, carbon An aromatic ring group of several 6-20 etc. are mentioned. Examples of the unsubstituted aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, and hexadecyl. , Cycloalkyl groups such as cyclopentyl, cyclohexyl and menthyl, alicyclic polycyclic groups such as bornyl, norbornyl, norbornenyl, decalinyl, adamantyl, diamantyl, triamantyl, bisadamantyl, spiro [3.4] octane, spiro [4.4 ] Spiro ring groups such as nonane and spiro [5.5] undecane. Examples of the unsubstituted aromatic ring group include groups such as benzene, naphthalene, fluorene, anthracene, indene, indane, and biphenyl.
Examples of the unsubstituted heterocyclic group include a heteroaromatic ring group and a heteroalicyclic group. Examples of the heteroaromatic ring of the heteroaromatic ring group include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, oxazole, thiazole, imidazole, pyrimidine, triazine, indole, chromene, chroman, quinoline, purine, benzimidazole, benzothiazole, Examples include dibenzofuran, phthalimide, thiophthalimide, quinoxaline, and carbazole. Examples of the heteroalicyclic ring of the heteroalicyclic group include oxetane, thietane, azetidine, oxolane, thiolane, pyrroline, pyrrolidine, pyrazoline, imidazoline, thiazoline, pyran, oxane, thiane, piperidine, morpholine, coumaran, chroman, and pyrrolidone. It is done.

  Examples of the optionally substituted hydrocarbon group and the optionally substituted heterocyclic group include the above-mentioned unsubstituted hydrocarbon group or unsubstituted heterocyclic group, a halogen atom (for example, a fluorine atom, Chlorine atom, bromine atom, iodine atom), cyano group, nitro group, sulfonyl group, amide group, alkoxy group having 1 to 20 carbon atoms (for example, methoxy, butoxy, dodecyloxy), acyloxy group having 1 to 20 carbon atoms (for example, Acetyloxy, propionyloxy, pentylcarbonyloxy, undecylcarbonyloxy, etc.), C1-C20 acylamino groups (eg, acetylamino, N-methylacetylamino, propionylamino, etc.), aryl groups (eg, phenyl, naphthyl) , Hydrocarbons having a structure in which hydroxyl group, silyl group, etc. are substituted at any position , Or a heterocyclic group. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, diisopropylmethylsilyl and the like.

Among these, as R ¹ , since the solvent solubility of the condensate and polycondensate of the present invention is excellent and thermosetting becomes easy, a hydrogen atom, an optionally substituted aliphatic hydrocarbon group Or an alkylsilyl group, a hydrogen atom, an unsubstituted or optionally substituted alkyl group or a cycloalkyl group is more preferable, and from the viewpoint of availability of raw materials and ease of production, a hydrogen atom is particularly preferable. preferable.

G represents —NHR ² or —COOQ. R ² and R each represent a hydrogen atom, an unsubstituted or optionally substituted cyclic or non-cyclic hydrocarbon group. As the unsubstituted hydrocarbon group, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, etc.), a cycloalkyl group (for example, cyclopentyl, cyclohexyl, cycloheptyl, etc.), Examples include cycloalkylene groups (for example, cyclohexenyl and the like), aromatic ring groups (for example, groups such as benzene, naphthalene, and fluorene), and alicyclic polycyclic groups (for example, bornyl, norbornyl, decalinyl, adamantyl, and diamantyl).

  Examples of the optionally substituted cyclic or acyclic hydrocarbon group include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a cyano group with respect to the unsubstituted hydrocarbon group exemplified above. , A nitro group, a sulfonyl group, an amide group, an alkoxy group having 1 to 20 carbon atoms (for example, methoxy, butoxy, dodecyloxy), an aryl group (for example, phenyl, naphthyl), a hydroxyl group, a silyl group and the like are substituted at any position. And hydrocarbon groups having the above structure.

  Q represents a hydrogen atom, a cyclic or acyclic hydrocarbon group, a metal element capable of forming a salt or organic ammonium, and the cyclic or acyclic hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl). , Isopropyl, butyl, octyl, hexadecyl, etc.), phenyl group, naphthyl group and the like, and examples of the metal element capable of forming a metal salt include monovalent alkali metals such as lithium, sodium and potassium. Moreover, polyvalent metals, such as alkaline-earth metals, such as magnesium, calcium, and strontium, are also mentioned. In the case of a polyvalent metal, the case where the compound of the general formula (1) and the polyvalent metal form a salt other than 1: 1 such as 2: 1 or 3: 1 is included. Moreover, you may form the complex salt of the compound of the said General formula (1), a polyvalent metal, and other acids (For example, weak acids, such as an acetic acid and hydrogencarbonate, etc.).

  Organic ammonium includes primary ammonium such as ammonium, methylammonium, ethylammonium and butylammonium, secondary ammonium such as dimethylammonium, methylethylammonium, diethylammonium, dipropylammonium, dibutylammonium, morpholinium, pyrrolinium and piperidinium, dimethylethanol Ammonium, trimethylammonium, triethylammonium, N-methylmorpholinium, N-ethylmorpholinium, N-methylpyrrolinium, N-butylpyrrolinium, N-methylpiperidinium, N-ethylpiperidinium, N-butylpiperidinium, N, N-dimethylanilinium, N, N-diethylanilinium, pyridinium, quinolinium, isoquinolinium , Tertiary ammonium such as picolinium, lutidinium, 1,5-diazabicyclo- [4,3,0] -5-nonenium, 1,8-diazabicyclo- [5,4,0] -7-undecenium, tetraethylammonium, tetra Tetraalkylammonium such as butylammonium, tetraoctylammonium, dodecyltrimethylammonium tributylmethylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyltriamylammonium, benzylethyldibutylammonium, phenethyltriethylammonium, phenethyltributylammonium, Aralkyltrialkylammonium compounds such as phenethylbutyldiethylammonium, diethylpyrrolium Dibutylpyrrolium, dihexylpyrrolium, methylbenzylpyrrolium, diethylpyrrolidinium, dibutylpyrrolidinium, dihexylpyrrolidinium, ethylbenzylpyrrolidinium, diethylpiperidinium, dibutylpiperidinium, dihexylpiperidinium, methyl Benzylpiperidinium, diethylindolinium, dibutylindolinium, dihexylindolinium, ethylbenzylindolinium, diethylmorpholinium, dibutylmorpholinium, dihexylmorpholinium, methylbenzylmorpholinium, diethylthiazinium, dibutylthia Dinium, dihexylthiazinium, ethylbenzylthiazinium, butylpyridinium, hexylpyridinium, octylpyridinium, laurylpyridinium Um, benzylpyridinium, tetramethylpiperazinium, tetraethylpiperazinium, dimethyldibutylpiperazinium, dimethyldihexylpiperazinium, dimethyldibenzylpiperazinium, tetramethylimidazolidinium, tetraethylimidazolidinium, dimethyldibutylimidazolidi And cyclic oniums such as nium, dimethyldihexylimidazolidinium and dimethyldibenzylimidazolidinium, and tetraarylammoniums such as tetraphenylammonium. Moreover, the onium compound etc. which are described in Unexamined-Japanese-Patent No. 2004-226794, 2004-233854, etc. can also be mentioned. Q is preferably a hydrogen atom, sodium, potassium, an alkyl group having 1 to 12 carbon atoms (for example, methyl, butyl, octyl, dodecyl, etc.), more preferably a hydrogen atom, sodium, or a methyl group.

_{a 1, m, n 1,} n 2 are each independently an integer of 1-5. Among these, a ₁ , m, n ₁ , and n ₂ are each preferably 1 to 3 from the viewpoint of availability of raw materials and ease of production, and a ₁ , m, n ₁ , and n ₂ are each 1 or 2 Particularly, a ₁ and m are each preferably 1 or 2, and n ₁ and n ₂ are preferably 1.

b ₁ , b ₂ , and b ₃ each independently represent an integer of 0 or more, but 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of production, and 0 to 2 are more preferable, and 0 to 2 are preferable. 1 is more preferable, and 0 is particularly preferable.

About the compound represented by the general formula (1),
In the present invention, a method for producing a novel acetylene compound is generally used when X _{0 to} X ₄ represent —O—, —NR—, —S—, —SO—, —SO ₂ —, —CO—, or —CS—. The method is not particularly limited as long as it is a method for synthesizing a simple ether bond, thioether bond, or substituted amine. For example, “Chemical Reviews”, 1951, 49, 273-412 and the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds (III)” (published by Maruzen Co., Ltd.), 1699 To 1875, edited by The Chemical Society of Japan, "Experimental Chemistry Course 4th Edition Volume 21 Organic Synthesis II" (published by Maruzen Co., Ltd.), pages 149 to 353, and the like.

In the present invention, X _{0 to} X ₄ are —OCO—, —NRCO—, —OCS—, —NRCS—, —NRCONR′—, —NRCOO—, —OCONR—, —OCOO—, —NRCSNR′— or —OCSO—. A method for producing a novel acetylene compound representing a group includes a compound having one amino group having a carboxylic acid group, a carboxylic acid ester group, a carbamic acid ester group, a thiocarboxylic acid group, and a thiocarboxylic acid ester group having a corresponding structure, and a molecule It can be produced by a method in which a compound having one or more ethynyl groups having an amino group, a hydroxyl group, or a thiol group is subjected to a condensation reaction.

  Specific examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereby.

When a condensate is obtained by reacting at least two kinds of the compound represented by the general formula (1), a compound in which the — (G) m group is —NHR ² and a — (G) m group are represented by — (COOQ) ) Method of condensing ₂ or -COOQ compound, or-(G) m group is-(NHR ² ) ₂ in general formula (1) and-(G) m group is -COOQ compound The method of condensing is preferable.
In addition, two compounds of the general formula (1) in which the — (G) m group is —NHR ² are di-, tri-, or tetracarboxylic acids described below or their anhydride compounds, diisocyanates, dithioisocyanates, or A method of condensing via an aldehyde compound, or the-(G) m group in the general formula (1) is -COOQ, and a di, tri, or tetraamino compound, or a di, tri, or tetra described below. A method of condensing via an all compound is also preferably used.
More specifically, there are a method in which the compound represented by the general formula (1) is directly reacted and a method in which one of the compounds to be reacted is changed to a more active intermediate and then the other compound is reacted. To do. These will be described in order.

1) Description of the method of directly reacting the compound represented by the general formula (1) When reacting the compound represented by the general formula (1), a catalyst is added to the reaction system as necessary. It is possible to carry out the reaction in the presence of a catalyst. Specifically, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid and phosphoric acid, organic acids such as p-toluenesulfonic acid and camphor-10-sulfonic acid, acidic ion exchange resins such as amberlite and amberlist, etc. Alternatively, the reaction may be performed by a method using a condensing agent such as diacid carbodiimide or 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide.

  As a solvent that can be used for the reaction, as long as it does not cause problems in process operation, does not disturb the progress of the reaction, and does not adversely affect the reaction by decomposition in the amidation, esterification, or thioesterification process of the present invention. Although there is no particular limitation, for example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), Ureido solvents (eg tetramethylurea), ether solvents (eg dioxane, cyclopentylmethyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), halogen solvents (For example, tetrachloroethane, chlorobenze ), Pyridine-based solvents (e.g. pyridine, .gamma.-picoline, 2,6-lutidine), ester solvents (e.g. ethyl acetate, butyl acetate), and nitrile-based solvents (e.g., acetonitrile) is used alone or in combination. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

  The reaction temperature is preferably in the range of −30 ° C. to 300 ° C., more preferably 0 ° C. to 200 ° C., further preferably 20 ° C. to 150 ° C. The reaction time varies depending on the amount charged and the reaction temperature, but is preferably in the range of 0.5 to 12 hours, more preferably in the range of 0.5 to 6 hours. The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture reduces the reaction rate, it is preferably reduced as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.

  Examples of the method for isolating the acetylene compound of the present invention from the reaction mixture include separation and purification methods such as chromatography, crystallization or recrystallization after extraction with an organic solvent. When the acetylene compound is precipitated by cooling the solvent extracted with the organic solvent, the acetylene compound can be isolated by ordinary solid-liquid separation. Alternatively, it is also possible to crystallize the acetylene compound from a suitable solvent system and isolate it by solid-liquid separation.

Organic solvents for extracting acetylene compounds include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether and methoxybenzene, ester solvents such as ethyl acetate and n-butyl acetate, and fats such as hexane, heptane and cyclohexane. Aromatic hydrocarbon solvents such as toluene and xylene, halogen solvents such as chloroform and methylene chloride, etc. from the viewpoint of mass production suitability, safety, availability, etc. on an industrial scale To ester solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (may be any of o-form, m-form, p-form, or a mixture of these in any proportion), mesitylene, ethylbenzene, isopropylbenzene. (Cumene), chlorobenzene, hexane, heptane, ethyl acetate, n-butyl acetate, etc., among which toluene, xylene, ethylbenzene, hexane, heptane, ethyl acetate, n-butyl acetate are more preferable, and toluene, hexane Further preferred solvents are heptane and ethyl acetate. The above solvents may be used alone or in combination of two or more.

As an organic solvent which crystallizes an acetylene compound, the mixed system of the organic solvent demonstrated above and another organic solvent is mentioned, for example. Other organic solvents to be mixed include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether and methoxybenzene, nitrile solvents such as acetonitrile, aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane, toluene An aromatic hydrocarbon solvent such as xylene, and an alcohol solvent such as 2-propanol and t-butanol, are ester based from the viewpoints of suitability for mass production on an industrial scale, safety, availability, etc. Solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and water are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (which may be o-isomer, m-isomer, p-isomer, or a mixture of these in any proportion), 2-propanol, t- Butanol, mesitylene, ethylbenzene, isopropylbenzene (cumene), hexane, heptane, acetonitrile, propionitrile, diisopropyl ether, methyl-t-butyl ether, methoxybenzene are more preferable, toluene, acetonitrile, diisopropyl ether, methyl-t-butyl ether, water Is more preferable. The above solvents may be used alone or in combination of two or more.

2) Explanation of a method of reacting the other compound after changing one of the compounds to be reacted to a more active intermediate

The compound to be converted into an active intermediate may be either a compound in which — (G) m group is —NHR ^{2 and} a compound in which — (G) m group is — (COOQ) ₂ or —COOQ. From the viewpoint of properties, the method of activating the — (COOQ) ₂ or —COOQ compound is more preferable.

As a method of activation, a method of synthesizing by replacing-(COOQ) ₂ or -COOQ group with-(COL) ₂ or -COL is preferable.
As an activator, when L is chlorine, chlorine, thionyl chloride, oxalyl chloride, phosphorus pentachloride, N-chlorosuccinimide, carbon tetrachloride, etc., when L is bromine, bromine, N -Bromosuccinimide, carbon tetrabromide, etc., when L is a sulfonyl derivative, methanesulfonyl chloride, -p-toluenesulfonyl, etc., when it is an acid anhydride, methyl chlorocarbonate, ethyl chlorocarbonate, chloro And alkyl chlorocarbonates such as isopropyl carbonate.
Among these, the method using thionyl chloride, oxalyl chloride, and methanesulfonyl chloride is preferable. The activator can be added to the reaction system from the start of the reaction, but a method of dropping it into the reaction system is more preferable.

When substituting — (COOQ) ₂ or —COOQ group with — (COL) ₂ or —COL, a base may be added to the reaction system as necessary. The base that can be used is not particularly limited, and both organic bases and inorganic bases can be used.
The amount of the activator used when synthesizing by replacing-(COOQ) ₂ or -COOQ group with-(COL) ₂ or -COL is that the desired compound is obtained in high yield and used. From the viewpoint that the unreacted amount of the activator is small, the range of 0.5 to 20 times mol is preferable, more preferably 0.8 to 3.0 times mol, and still more preferably 0.9 to 2. 2 moles.

  The solvent that can be used for the reaction is not particularly limited as long as it does not cause problems in the process operation, does not disturb the progress of the reaction, and does not adversely influence the reaction in the halogenation, acid anhydride formation, and sulfonyl derivatization steps of the present invention. Although not limited, for example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), ureido Solvent (for example, tetramethylurea), ether solvent (for example, dioxane, cyclopentylmethyl ether), ketone solvent (for example, acetone, cyclohexanone), hydrocarbon solvent (for example, toluene, xylene, n-decane), halogen solvent ( For example, tetrachloroethane, chlorobenzene , Pyridine-based solvents (e.g. pyridine, .gamma.-picoline, 2,6-lutidine), ester solvents (e.g. ethyl acetate, butyl acetate), and nitrile-based solvents (e.g., acetonitrile) is used alone or in combination. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

The reaction temperature is preferably in the range of -30 ° C to 50 ° C, more preferably -20 ° C to 30 ° C, still more preferably -10 ° C to 20 ° C. The reaction time varies depending on the amount charged and the reaction temperature, but is preferably in the range of 0.5 to 12 hours, more preferably in the range of 0.5 to 6 hours. The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture leads to decomposition of the compound of G =-(COL) ₂ or -COL, it is preferable to reduce it as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.
Although the active intermediate synthesized by the above method can be taken out, it may be generated in the reaction system and used as it is for the reaction with the compound represented by the following -NHR ² compound.

Next, the reaction between a compound of G =-(COL) ₂ or -COL and a compound represented by G = -NHR ² will be described.
The amount of the compound represented by the compound of G = —NHR ² relative to the compound of G = — (COL) ₂ or —COL is such that the target compound can be obtained in a high yield and each used as a raw material. The range of 0.1 to 10-fold mol is preferred, more preferably 0.7 to 3.0-fold mol, and even more preferably 0.8 to 2.2, because of the advantage that the amount of unreacted compounds is low. Double mole.

In addition, the method for adding the compound represented by G = —NHR ² is not particularly limited, but a method of adding dropwise may be preferable because the addition may generate heat.
As the solvent usable in the reaction, G = - _(COL) if used as it is ₂ or -COL compounds without isolating the G = - you used to synthesize _{(COL) 2} or -COL compound solvent Can be used as is. G = — (COL) ₂ or a solvent in the case where a compound of —COL is once isolated and newly charged, does not cause problems in process operation, does not disturb the progress of the reaction, and amidation of the present invention. There is no particular limitation as long as it does not adversely affect the reaction by decomposing in the esterification or thioesterification step. For example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone) , Sulfone solvents (eg sulfolane) sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethyl urea), ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), carbonization A hydrogen-based solvent (for example, toluene, xylene, n-decane), Halogen-based solvents (for example, tetrachloroethane, chlorobenzene), pyridine-based solvents (for example, pyridine, γ-picoline, 2,6-lutidine), ester-based solvents (for example, ethyl acetate, butyl acetate), and nitrile-based solvents (for example, acetonitrile) Use alone or in combination. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

The reaction temperature is preferably in the range of -30 ° C to 100 ° C, more preferably -10 ° C to 80 ° C, still more preferably 0 ° C to 50 ° C. The reaction time varies depending on the charged amount and the reaction temperature, but is preferably in the range of 0.1 to 12 hours, and more preferably in the range of 0.5 to 6 hours. The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture leads to decomposition of the compound of G =-(COL) ₂ or -COL, it is preferable to reduce it as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.
The conditions for taking out the acetylene compound after completion of the reaction are the same as those for taking out the acetylene compound after completion of the reaction described in 1).

In the present invention, when X represents —O—, —NR—, —S—, —SO—, —SO ₂ —, —CO—, or —CS—, the method for producing a novel acetylene compound is a general ether. Any method for synthesizing a bond, a thioether bond, and a substituted amine is not particularly limited. For example, “Chemical Reviews”, 1951, 49, 273-412 and the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds (III)” (published by Maruzen Co., Ltd.), 1699 To 1875, edited by The Chemical Society of Japan, "Experimental Chemistry Course 4th Edition Volume 21 Organic Synthesis II" (published by Maruzen Co., Ltd.), pages 149 to 353, and the like.

  Specific examples of condensates obtained by reacting at least two compounds represented by the general formula (1) of the present invention with G as a reactive group are shown below, but the present invention is limited thereby. is not.

Examples of the polycondensate obtained by reacting at least two compounds represented by the general formula (1) of the present invention with G as a reactive group include polyamine, polyimide, polyisoimide, polyesterimide, polyetherimide, and polyamide. Examples include imide, polyamic acid, polyamic acid ester, polyamide, polythioamide, polyurethane, polyurea, polyazomethine, polyoxazole, polyimidazole, etc., preferably polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, polyamic acid , Polyamide acid ester, polyamide, and more preferably polyimide, polyisoimide, polyester imide, polyether imide, polyamide imide, and polyamic acid.
The polycondensate may be a single or block copolycondensate. The backbone skeleton may be aromatic or aliphatic, and may contain silicone, fluorene, or the like in the main chain or side chain, but is preferably aromatic.

  As the polymer containing the acetylene compound as a structural unit, at least two kinds of the compound represented by the general formula (1), and a —COOH group, a —COOR ′ group, a —CSOH group, a —COSH group, A compound having two of -CSH, -NCO, or -NSO, an acid anhydride, a substituted or unsubstituted hydrocarbon compound (amine compound) having two or more amino groups in the molecule, and / or Or it can adjust by making a polyol compound react with an aldehyde compound as needed.

Examples of the compound having any one of -CHO group, -COOH group, -COOR 'group, -CSOH group, -COSH group, -CSSH group, -NCO group and -NSO group in the molecule include dialdehydes ( For example, terephthalaldehyde, isophthalaldehyde, phthalaldehyde, 4-methylphthalaldehyde, 4-methylisophthalaldehyde, 2,5-dimethylterephthalaldehyde, 1,4-cyclohexanedialdehyde, 2-fluoro-1,4-benzenedialdehyde, 3-methoxy-1,4-benzenedialdehyde, 1,6-hexanedialdehyde, 4,4′-dialdehydebiphenyl, 2,2-bis (4-aldehydephenyl) propane, 1,3-diacetylbenzene, 1 , 4-diacetylcyclohexane), dicarboxylic acids (eg terephthalate) , Isophthalic acid, phthalic acid, 4-methylphthalic acid, 4-methylisophthalic acid, 2,5-dimethylterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 2-fluoro-1,4-benzenedicarboxylic acid, 3-methoxy- 1,4-benzenedicarboxylic acid, 1,6-hexanedicarboxylic acid, 4,4′-dicarboxybiphenyl, 2,2-bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) sulfone, 4,4 '-Dicarboxybenzophenone, 4,4'-dicarboxybiphenyl ether, 3,3'-dicarboxybiphenyl, 2,2-bis (3-carboxyphenyl) propane, bis (3-carboxyphenyl) sulfone, 3,3 '-Dicarboxybenzophenone, 4,4'-dicarboxy-3,3'-dimethylbiphenyl ether 4,4′-dicarboxy-3,3′-dimethylbiphenyl, 2,2-bis (4-carboxy-3-methylphenyl) propane, bis (4-carboxy-3-methylphenyl) sulfone, 4,4 '-Dicarboxy-3,3'-dimethylbenzophenone, 4,4'-dicarboxy-3,3'-dichlorobiphenyl, 2,2-bis (4-carboxy-3-chlorophenyl) propane, bis (4 -Carboxy-3-chlorophenyl) sulfone, 4,4'-dicarboxy-3,3'-dichlorobenzophenone, malonic acid, ethylmalonic acid, maleic acid, succinic acid, 2,2-dimethylsuccinic acid, 2, 3-dimethyl succinic acid, adipic acid, azelaic acid, sebacic acid, lutidine acid, dipicolinic acid, etc.), diesters (for example, dimethyl isophthalate, diisophthalate) Chill, dimethyl terephthalate, dimethyl phthalate, dimethyl 4-methylphthalate, dimethyl 4-methylisophthalate, dimethyl 2,5-dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, diethyl 1,4-cyclohexanedicarboxylate, Dimethyl 2-fluoro-1,4-benzenedicarboxylate, dimethyl 3-methoxy-1,4-benzenedicarboxylate, dimethyl 1,6-hexanedicarboxylate, 4,4′-dimethoxycarbonylbiphenyl, 2,2-bis ( 4-methoxycarbonylphenyl) propane, 2,2-bis (4-ethoxycarbonylphenyl) propane, bis (4-methoxycarbonylphenyl) sulfone, 4,4′-dimethoxycarbonylbenzophenone, 4,4′-dimethoxycarbonylbiphenyl ether 3,3′-dimethoxycarbonylbiphenyl, 2,2-bis (3-methoxycarbonylphenyl) propane, bis (3-methoxycarbonylphenyl) sulfone, 3,3′-dimethoxycarbonylbenzophenone, 4,4′-dimethoxycarbonyl -3,3'-dimethylbiphenyl ether, 4,4'-dimethoxycarbonyl-3,3'-dimethylbiphenyl, 2,2-bis (4-methoxycarbonyl-3-methylphenyl) propane, bis (4-methoxycarbonyl) -3-methylphenyl) sulfone, 4,4′-dimethoxycarbonyl-3,3′-dimethylbenzophenone, 4,4′-dimethoxycarbonyl-3,3′-dichlorobiphenyl, 2,2-bis (4-methoxy) Carbonyl-3-chlorophenyl) propane, bis (4-methoxycarbonyl) 3-chlorophenyl) sulfone, 4,4′-dimethoxycarbonyl-3,3′-dichlorobenzophenone, dimethyl malonate, diethyl malonate, dimethyl ethyl malonate, dimethyl maleate, dimethyl succinate, diethyl succinate, 2 , 2-dimethyl succinate, dimethyl 2,3-dimethyl succinate, dimethyl adipate, diethyl adipate, dimethyl azelate, dimethyl sebacate, dimethyl lutizate, dimethyl dipicolinate, etc.)
Dithiocarboxylic acids (for example, hexanedithio-s-acid, hexanedithiodicarboxylic acid), diisocyanates (for example, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane dicyanate), dithioisocyanates (for example, 1, 4-phenylene dithioisocyanate, 1,3-phenylene dithioisocyanate, 1,4-cyclohexyl diisothiocyanate, 5-methyl-1,3-phenylene dithioisocyanate and the like. These can be used alone or in combination of two or more.

  The amine compound that can be used in the polymer of the present invention is not particularly limited, but a diamine compound is desirable from the viewpoint of obtaining a high tensile elastic modulus and high heat resistance (glass transition temperature). Specifically, the following diamine compounds are exemplified. p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,4-diamino-2-methylbenzene, 1,3-diamino-4-methyl-benzene, 1,3-diamino-4-chloro-benzene, 1,3-diamino-4-acetylamino-benzene, 1,3-bisaminoethyl-benzene, hexamethylenediamine,

3,3′-diaminobiphenyl, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino-3,3′-dichlorobiphenyl, 2, 2′-difluoro-4, 4 ′ -Diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-5,5'-diaminobiphenyl, 3,3'-difluoro-5,5'-diaminobiphenyl, 2 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro -5,5'-diaminobiphenyl, 2,2'-dibromo-4,4'-diaminobiphenyl, 3,3'-dibromo-4 , 4'-diaminobiphenyl, 2,2'-dibromo-5,5'-diaminobiphenyl, 3,3'-dibromo-5,5'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4 , 4'-diamine biphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -5,5'-diaminobiphenyl, 3,3 '-Bis (trifluoromethyl) -5,5'-diaminobiphenyl, 2,2'-bis (trichloromethyl) -4,4'-diaminebiphenyl, 3,3'-bis (trichloromethyl) -4,4 '-Diaminobiphenyl, 2,2'-bis (trichloromethyl) -5,5'-diaminobiphenyl, 3, 3'-bis (trichloromethyl) -5,5'-diaminobiphenyl, 2,2'-bis (tribromomethyl) -4,4'-diaminebiphenyl, 3,3'-bis (tribromomethyl) -4 , 4'-diaminobiphenyl, 2,2'-bis (tribromomethyl) -5,5'-diaminobiphenyl, 3,3'-bis (tribromomethyl) -5,5'-diaminobiphenyl, 3,3 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3'-dimethylbiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfi 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis (4-amino-3-methylphenyl) sulfone, bis (4-amino-3-chloro) Phenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (5-fluoro-4-aminophenyl) sulfone, bis (5-fluoro-3-aminophenyl) sulfone, bis ( 5-chloro-4-aminophenyl) sulfone, bis (5-chloro-3-aminophenyl) sulfone, bis (5-bromo-4-aminophenyl) sulfone, bis (5-bromo-3-aminophenyl) sulfone, Bis (5-trifluoromethyl-4-aminophen Sulfone, bis (5-trifluoromethyl-3-aminophenyl) sulfone, bis (5-trichloromethyl-4-aminophenyl) sulfone, bis (5-trichloromethyl-3-aminophenyl) sulfone, bis (5 -Tribromomo-4-aminophenyl) sulfone, bis (5-tribromomethyl-3-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone 4,4′-diamino-3,3′-dimethylbenzophenone, 4,4′-diamino-3,3′-dichlorobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-Aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-methylphenyl) Propane, 2,2-bis (4-amino-3-chlorophenyl) propane,

1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) ) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethyl Benzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4- Amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) ) Benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine,

  4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-amino Phenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro-4-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro-3-aminophenoxy) phenyl] sulfone, bis [ 4- (5-Chloro-4-aminophenoxy) Nyl] sulfone, bis [4- (5-chloro-3-aminophenoxy) phenyl] sulfone, bis [4- (5-bromo-4-aminophenoxy) phenyl] sulfone, bis [4- (5-bromo-3 -Aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-3-aminophenoxy) phenyl] sulfone, bis [ 4- (5-trichloromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trichloromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5-tribromomethyl-4-amino Phenoxy) phenyl] sulfone, bis [4- (5- Ribromomethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl ] Methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3- Aminophenoxy) phenyl] -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane,

  1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) Benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3- Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [ 4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene,

4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [ 4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′- Diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone,
6,6'-bis (3-aminophenoxy) 3,3,3, '3,'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) 3,3,3 , '3,'-tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, diaminopolysiloxane, and the like can be used alone or in combination of two or more.

  The amine compounds exemplified above can be used alone or in combination as appropriate. In the amine compound, a part or all of the hydrogen atoms on the aromatic ring of the amine compound are substituted with a substituent selected from a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Diamine may be used. For the purpose of introducing branching, a part of the amine compound may be replaced with a triamine compound or a tetraamine compound. Specific examples of such triamine compounds include, for example, pararose aniline.

  Although it does not specifically limit as an acid anhydride which can be used for the polycondensate of this invention, For example, the following are mentioned. Pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3-chloropyromellitic dianhydride, 3-bromopyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3 -Trichloromethylpyromellitic dianhydride, 3-Tribromomethylpyromellitic dianhydride, 3, 6-Difluoropyromellitic dianhydride, 3, 6-Dichloropyromellitic dianhydride, 3, 6- Dibromopyromellitic dianhydride, 3,6-bistrifluoromethylpyromellitic dianhydride, 3,6-bistrichloromethylpyromellitic dianhydride, 3,6-bistribromomethylpyromellitic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylte Lacarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (2,3-dicarboxyl Phenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride Bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) -1, 1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) ) Biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 9, 9-bi (3,4-Dicarboxyphenyl) fluorenic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride, 4,4'-biphenylenebis (trimerit Acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride), p-methylphenylenebis (trimellitic acid monoester acid anhydride), p- (2,3-dimethylphenylene) bis (Trimellitic acid monoester acid anhydride) 1,4-naphthalenebis (trimellitic acid monoester acid anhydride) 2,6-naphthalenebis (trimellitic acid monoester acid anhydride) 2,2,2-bis [ 4- (trimellitic acid monoester anhydride) phenyl] propane, 2,2-bis [4 (Trimellitic acid monoester anhydride) phenyl] hexafluoropropane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,1,3,3-tetramethyldisiloxane dianhydride, 1- (2 , 3-Dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,1,3,3-tetramethyldisiloxane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic acid dianhydride.

  The acid anhydrides exemplified above can be used alone or in combination as appropriate. In addition, any of the above tetracarboxylic dianhydrides may be selected from a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group, with some or all of the hydrogen atoms on the aromatic ring. It can also be used after being substituted with a substituent. Further, part of the acid anhydride may be replaced with hexacarboxylic dianhydrides and octacarboxylic dianhydrides.

  The polyol compound that can be used in the case of using a polyol for the polymer of the present invention is not particularly limited, and specific examples thereof include the following. For example, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) sulfone, 4 , 4′-dihydroxybenzophenone, 4,4′-dihydroxybiphenyl ether, 3,3′-dihydroxybiphenyl, 2,2-bis (3-hydroxyphenyl) propane, bis (3-hydroxyphenyl) sulfone, 3,3 ′ -Dihydroxybenzophenone, 4,4'-dihydroxy-3,3'-dimethylbiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, bis (4-hydroxy-3-methylphenyl) sulfone, 4,4 -Dihydroxy-3,3'-dimethylbenzophenone, 4,4'-dihydroxy-3,3'-dichlorobiphenyl, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-amino- 3-chlorophenyl) sulfone, 4,4′-diamino-3,3′-dichlorobenzophenone, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxy-2-methylbenzene, 1, 3-dihydroxy-4-methyl-benzene, 1,3-dihydroxy-4-chloro-benzene, 1,3-dihydroxy-4-acetoxy-benzene, 1,3-bishydroxyethyl-benzene, ethylene glycol, diethylene glycol, propylene Glycol, dipropylene glycol, butane polyol, hexane polio Le, cyclohexane polyol, 1,6-bis hydroxymethyl cyclohexane, but neopentyl glycol, but is not limited thereto. These can be used alone or in combination of two or more.

  Although it does not specifically limit as an aldehyde compound which can be used when using an aldehyde compound for the polymer of this invention, Specifically, the following are mentioned, for example. Examples include formaldehyde, acetaldehyde, trioxane, propionaldehyde, and benzaldehyde. These can be used alone or in combination of two or more. Among these, formaldehyde and acetaldehyde are preferable. The polymer of the present invention can also contain dicarboxylic acids, diesters, diureas, diisocyanates and the like as other structural units.

Although it does not restrict | limit especially as a manufacturing method of the polymer of this invention, The polymer of this invention can be prepared by using the said acetylene compound and said monomer or monomer mixture. For example, as a method for producing a polyimide polymer according to the present invention, a method of ring-closing and imidizing after passing through a polyamic acid, a method of passing through a polyisoimide, a part of which is imidized and further passing through a polyamic acid However, there is no particular limitation on the production of the polyimide polymer included in the present invention. A method in which an acid anhydride is dispersed in an organic solvent in which an amine compound such as diamine is dissolved, and is completely dissolved and polymerized by stirring. After the acid anhydride is dissolved and / or dispersed in an organic solvent, the amine is dissolved. Known polymerization methods such as a method of polymerizing using a compound and a method of polymerizing by reacting a mixture of an acid anhydride and an amine compound in an organic solvent can be used.
In imidization, water is generated by cyclization of polyamic acid, and this water can be azeotroped with benzene, toluene, xylene, tetralin, etc. and removed from the reaction system to promote imidization. Preferably, if a dehydrating agent such as an aliphatic acid anhydride such as acetic anhydride or an aromatic acid anhydride is used, the imidization reaction easily proceeds.

  In addition, if necessary, a polycondensation accelerator can be added to the reaction system to complete the reaction quickly. Examples of such polycondensation accelerators include basic polycondensation accelerators and acidic polycondensation accelerators. Both can be used together. Examples of the basic polycondensation accelerator include N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, and triethylamine. , Tributylamine, tripentylamine, N-methylmorpholine, diazabicycloundecene, diazabicyclononene and the like. Examples of acidic polycondensation accelerators include benzoic acid, o-hydroxybenzoic acid, m- Hydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, phosphoric acid, p-phenolsulfonic acid, p-toluenesulfonic acid, crotonic acid, etc. Can be mentioned.

The polycondensation accelerator is used in an amount of 1 to 50 mol%, preferably 5 to 35 mol%, based on the diamine or diamine component. By using these polycondensation accelerators, the reaction temperature is lowered. Since it can be set, not only side reactions caused by heating, which is often caused by coloring, can be prevented, but the reaction time can be greatly shortened, which is economical.
The polymerization temperature of the polyamic acid is preferably 60 ° C. or lower, and more preferably 40 ° C. or lower because the reaction is efficient and the viscosity of the polyamic acid is likely to increase.

  Examples of the solvent that can be used in the production of the polymer include ureas such as tetramethylurea, N, N-dimethylethylurea, sulfoxides or sulfones such as dimethyl sulfoxide, diphenylsulfone, and tetramethylsulfone, N, Such as N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N′-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyllactone, hexamethylphosphoric triamide Amide or aprotic solvent of phosphorylamide, alkyl halides such as chloroform and methylene chloride, aromatic hydrocarbons such as benzene and toluene, phenols such as phenol and cresol, dimethyl ether, diethyl ether, p- Crezo Ethers such as methyl ether, and the like. Usually, these solvents are used alone, but two or more kinds may be used in appropriate combination as required. Of these, amides such as DMF, DMAc, and NMP are preferably used.

  Another aspect of the present invention is a composition comprising a polymer containing at least one acetylene compound of the acetylene compound represented by the general formula (1) as a structural unit. Examples of the composition used include a polymer solution, a mixture of the polymer solution and particles such as filler, a mixture of polymer solid and filler particles, and the polymer solution immersed in fibers. And the like. From the viewpoint of easy curing, a polymer solution is preferred.

  The solvent used for the polymer solution is not particularly limited. For example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) are used. ) Sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethyl urea), ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, Xylene, n-decane), halogen solvents (eg, tetrachloroethane, chlorobenzene, methylene chloride, chloroform), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg, ethyl acetate, acetic acid) The Le), and nitrile-based solvents (e.g., acetonitrile) is used alone or in combination. Of these, from the viewpoint of good solubility of the polymer, preferably an amide solvent, a sulfone solvent, a sulfoxide solvent, a ureido solvent, an ether solvent, a halogen solvent, a pyridine solvent, and a nitrile solvent. More preferred are amide solvents, ether solvents, halogen solvents, and nitrile solvents, and more preferred are amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

  Specific examples of polycondensates obtained by reacting at least two compounds represented by the general formula (1) of the present invention with G as a reactive group are shown below, but the present invention is limited thereby. It is not a thing.

  Another aspect of the present invention is a composition comprising a condensate and / or a polycondensate obtained by reacting at least two compounds represented by the general formula (1) with G as a reactive group. is there. The composition includes at least a polymer containing at least one acetylene compound as a constituent unit of any one of the acetylene compounds represented by the general formula (1) to the general formula (3). Yes, liquid crystal materials, nonlinear optical materials, electronic materials (for example, semiconductor protective films, flexible printed circuit boards, etc.), adhesive materials, and sliding agents, where the composition is used as a final product or an intermediate product thereof Depending on the application and purpose of various industries, such as functional materials such as materials, photographic additives, gas separation membrane materials, and raw materials for medical and agrochemical intermediates, etc. They can be selected and added together.

<Other additives>
Examples of other additives include a polymerizable compound, a resin, a crosslinkable resin, a solvent, a polymerization initiator, a colorant, a polymerization inhibitor, a filler, a silane coupling agent, and a release agent.

  The polymerizable compound is, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Other examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, JP-A-2- Those having an aromatic skeleton described in 226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule described in JP-A No. 2004-252201, wherein a vinyl monomer containing a hydroxyl group is added to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418, and further described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. And addition polymerizable compounds having an amino structure or a sulfide structure in the molecule.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used. In addition, polymerizable compounds described in JP-A-2004-252201, JP-A-2007-138105, JP-A-2007-177177, and the like can also be used.

  In addition, Shinzo Yamashita, “Cross-linking agent handbook” (1981 Taiseisha); Kato Kiyomi ed., “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Radtech study group, "UV and EB curing technology application and market", p. 79, (1989, CMC); Eiichiro Takiyama, "Polyester resin handbook", (1988, Nikkan Kogyo Shimbun), etc. And known radically polymerizable or crosslinkable monomers, oligomers and polymers can be used.

  Examples of the polymerizable compound include those described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, and the like. There are known photocurable polymerizable compound materials used in the photopolymerizable compositions that are used, and these can also be applied to the composition of the present invention as appropriate.

  Aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; allyl esters such as allyl acetate; halogens such as vinylidene chloride and vinyl chloride Containing monomers; vinyl cyanides such as (meth) acrylonitrile; high-boiling olefins;

  Examples of the resin added as necessary include alkyd resins, polyester resins, polyether resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, polyolefin resins, polyurea resins, Melamine resin, epoxy resin, nylon resin, polyimide resin, polystyrene resin, polyacetal resin, polybutyral resin, polyketal resin, novolac resin, resol resin, silicone resin, cellulose-modified resin, waxes, etc. should be added as appropriate Can do.

  A cross-linking agent may be added to the composition of the present invention in order to adjust its curability and curing speed. The cross-linking agent is not particularly limited as long as it can be thermally cross-linked, photo-cross-linked, UV-cross-linked, electron beam cross-linked, etc., and can be cured by a cross-linking reaction. Melamine compound, guanamine compound, glycoluril compound or urea compound, methylol group and alkoxy substituted with at least one substituent selected from narate, polyimide precursor, epoxy resin, methylol group and alkoxymethyl group and acyloxymethyl group Examples thereof include a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a methyl group and an acyloxymethyl group, and a polyfunctional epoxy resin is particularly preferable.

  The epoxy resin can be used without any particular limitation as long as it has an epoxy group and has crosslinkability. Examples of these compounds include bisphenol-A-diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester, N, N -Divalent glycidyl group-containing low molecular weight compounds such as diglycidyl aniline, as well as trivalent glycidyl group represented by trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc. Low molecular weight compounds, as well as tetravalent glycidyl groups such as pentaerythritol tetraglycidyl ether and tetramethylol bisphenol-A-tetraglycidyl ether Molecular compounds, as well as polymolecular glycidyl group-containing low molecular compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol Glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct and the like.

  Examples of commercially available products include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (all manufactured by Japan Epoxy Resin); Epicoat 806, Epicoat 4004 (all manufactured by Japan Epoxy Resin), and Epicron 830CRP. Bisphenol F type epoxy resin such as Dainippon Ink Co .; Bisphenol S type epoxy resin such as Epicron EXA1514 (Dainippon Ink Co.); 2,2′-diallyl such as RE-810NM (Nippon Kayaku Co., Ltd.) Bisphenol A type epoxy resin; Hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by Dainippon Ink &Co.); Propylene oxide-added bisphenol A type epoxy resin such as EP-4000S (manufactured by Asahi Denka); EX-201 (Nagaseke) Resorcinol type epoxy resin such as Tex Co .; Biphenyl type epoxy resin such as Epicoat YX-4000H (Japan Epoxy Resin Co.); Sulfide type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.); YSLV-80DE (Toto) Ether type epoxy resins such as Kasei); dicyclopentadiene type epoxy resins such as EP-4088S (Asahi Denka); naphthalene type epoxy such as Epicron HP4032, Epicron EXA-4700 (both manufactured by Dainippon Ink and Co.) Resin; Phenol novolak type epoxy resin such as Epicron N-770 (manufactured by Dainippon Ink Co., Ltd.); Orthocresol novolak type epoxy resin such as Epicron N-670-EXP-S (manufactured by Dainippon Ink and Co., Ltd.); Epicron HP7200 (Dai Nippon) Ink Co.) Clopentadiene novolac type epoxy resin; biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.); Glycidylamine type epoxy resins such as Epicron 430 (Dainippon Ink Co., Ltd.), TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.); ZX-1542 (Toto Kasei Co., Ltd.), Epicron 726 (Dainippon Ink Co., Ltd.) Alkyl polyol type epoxy resins such as Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 (manufactured by Nagase ChemteX Corp.); YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (Daicel Chemical) Rubber-modified epoxy resin such as Glycidyl ester compounds such as Nacoal EX-147 (manufactured by Nagase ChemteX); Bisphenol A type episulfide resins such as Epicoat YL-7000 (manufactured by Japan Epoxy Resin); Others YDC-1312, YSLV-80XY, YSLV-90CR (any) Are also manufactured by Toto Kasei Co., Ltd.), XAC4151 (produced by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all produced by Japan Epoxy Resin Co., Ltd.), EXA-7120 (produced by Dainippon Ink), TEPIC (produced by Nissan Chemical Co., Ltd.), etc. Is done.

The blending amount of the epoxy resin is not particularly limited, and is appropriately adjusted according to the type and blending amount with the (meth) acrylate such as the epoxy (meth) acrylate described above according to the purpose of use.

<Thermosetting agent>
The composition of the present invention may further contain a thermosetting agent for the purpose of accelerating thermosetting of an epoxy resin or the like. The said thermosetting agent is for making the unsaturated bond in an curable resin, an epoxy group, etc. react and bridge | crosslink by heating, and has a role which improves the adhesiveness and moisture resistance of the hardened | cured material after hardening. The thermosetting agent is not particularly limited, but contains an amine and / or thiol group having excellent low-temperature reactivity when cured at a relatively low curing temperature of, for example, 100 to 150 ° C. using the composition of the present invention. It is preferable to do.

  Examples of the thermosetting agent containing the amine and / or thiol group include organic acid dihydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and adipic acid dihydrazide; dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl- s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2-imidazoline-2-thiol, 2-2'-thiodiethanethiol, various amines Addition products such as the epoxy resin. These may be used alone or in combination of two or more.

  In the composition of this invention, you may add a solvent as needed. The solvent is not particularly limited as long as it does not hinder the progress of the reaction such as when the composition is cured and does not adversely affect the storage stability of the composition of the present invention. For example, an amide solvent (for example, N , N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (eg sulfolane) sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethylurea), ether solvents (Eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), halogen solvents (eg tetrachloroethane, chlorobenzene), pyridine solvents (eg Pyridine, γ-picoline, 2,6-l Jin), ester solvents (e.g. ethyl acetate, butyl acetate), and nitrile-based solvent (e.g., acetonitrile) is used alone or in combination. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more. The amount of the solvent added to the composition of the present invention is selected according to the application field and the properties required for the field, but generally 0 to 90% by weight, preferably Is 0 to 80% by mass, more preferably 0 to 70% by mass, and it may be preferable not to use a solvent.

In addition, a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator may be added to the composition of the present invention for the purpose of accelerating the polymerization of the polymerizable compound or accelerating the reaction of the crosslinking agent.
Examples of the photopolymerization initiator include a photoinitiator described in Japanese Patent Application Laid-Open No. 2004-252201, a peroxide compound described in US Pat. No. 4,950,581, and US Pat. No. 4,9. Aromatic sulfonium, phosphonium or iodonium salts, or cyclopentadienyl-arene-metal complexes as described in 5 0, 5 8 1, eg described in EP 7 8 0, 7 2 9 And oxime sulfonic acid esters, pyridinium and (iso) quinolinium salts as described in European Patent Nos. 4 9 7, 5 3 1 and 4 4 1, 2 232 and the like. In addition, G. Buhr, R. Dam me elandc. Lind lie, Pol ly m. M at er. S c i. Eng. 61, 2 6 9 (1 9 8 9), and other halomethyltriazines, such as those described in European Patent No. 0 2 2 7 8 8; US Pat. Nos. 4, 3 7 1, 6 0 6 and A halomethyl oxazole photoinitiator, as described in US Pat. No. 4,3 7 1, 60 7; A. 1, 2-disulfone as described in Bartmanmann, Synthesis 5,490 (199.3); hexaarylbisimidazole, and hexaarylbisimidazole / Co-initiator systems (eg 2-mercaptobenzthiazole, ferrocenium compounds) or titanocene (eg bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyrylphenyl) o-chlorohexa in combination with titanium It is also possible to use a mixture with phenyl-bisimidazole. A photosensitizer may be used in combination. Examples of the photosensitizer include amines such as triethanolamine and 4-dimethylaminoethyl benzoate, benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof. And coumarin derivatives.

  Examples of the thermal polymerization initiator include azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), triazene, diazosulfide, pentaazadiene, and organic peroxides (for example, Hydroperoxide, peroxycarbonate, tert-butyl hydroperoxide) and the like. As the thermal polymerization initiator, it is particularly preferable to use an organic peroxide that does not generate bubbles. Organic peroxides that are used for general purposes can be used, and examples thereof include various peroxides such as peroxydicarbonate, peroxyester, peroxyketal, ketone peroxide, and hydroperoxide. Such organic peroxides may be used alone or in combination of two or more, and may be diluted with a solvent or adsorbed on a powder. The polymerization initiator is preferably used in an amount of 0.01 to 10% by mass based on the total amount of the composition. The ratio is 0. If it is less than 01% by mass, curing during heating tends to be insufficient, and if it exceeds 10% by mass, the curing reaction may be affected, which may be undesirable.

  The composition of the present invention may be appropriately added with known and commonly used additives such as a polymerization inhibitor, a chain transfer agent, a UV absorber and a stabilizer for the purpose of suppressing undesirable reactions during storage. You can also. Examples of the polymerization inhibitor include hydroquinone, hydroquinone derivatives, p-methoxyphenol, and sterically hindered phenols such as 2,6-di-tert-butyl-p-cresol. In order to increase the stability during storage in a dark place, for example, a copper compound (for example, naphthenic acid, stearic acid or copper octoate), a phosphorus compound (for example, triphenylphosphine, tributylphosphine, phosphorous acid) Triethyl acid, triphenyl phosphite or tribenzyl phosphite), quaternary ammonium compounds (for example, tetramethylammonium chloride or trimethylbenzylammonium chloride), hydroxylamine derivatives (for example, N-diethylhydroxylamine) Good. Examples of the chain transfer agent include mercaptans, amines, and benzothiazoles.

  In addition, a small amount of light stabilizer can be added, and examples of the light stabilizer include U V absorbers (for example, those of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type). . These compounds can be used alone or in the form of a mixture in the presence or absence of a sterically hindered amine. Examples of the U V absorber and light stabilizer include 2- (2′-hydroxyphenyl) benzotriazole, 2-hydroxybenzophenone, esters of substituted or unsubstituted benzoic acid, acrylates, sterically hindered amines, oxalamides, 2 -(2-Hydroxyphenyl) -1,3,5-triazine, phosphite, phosphonate and the like.

  In the composition of the present invention, a known and commonly used silane coupling agent, flow modifier, and adhesion promoter can be mixed as other components in order to improve adhesiveness. Specific examples of such a silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane (KA-10.03, Shin-Etsu Chemical), 2 -(3,4 epoxy cyclohexyl) ethyltrimethoxysilane (KBM-303, Shin-Etsu Chemical), p-styryltrimethoxysilane (KBM-14403, Shin-Etsu Chemical), 3-methacryloxypropylmethyl Dimethoxysilane (KBM-5502, Shin-Etsu Chemical), 3-acryloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical), 3-aminopropyltriethoxysilane, 3-aminopropyltri Methoxysilane (KBM-90.3, Shin-Etsu Chemical), N- (2 Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

<Filler>
Moreover, you may add a filler (filler) to the composition of this invention according to the objectives, such as adjustment of viscosity, storage stability, rigidity and viscoelasticity of hardened | cured material, and adjustment of a bulk density and an expansion coefficient. The filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, aluminum oxide (alumina), magnesium hydroxide, aluminum hydroxide, calcium carbonate, carbonic acid Magnesium, barium sulfate, magnesium sulfate, gypsum, calcium silicate, aluminum silicate, zirconium silicate, potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, US Pat. No. 5, 0 1 Copolymers obtained by copolymerizing inorganic fillers such as glass microspheres or micronized glass fibers described in 3, 7 6 8 specification, or polymethyl methacrylate, polystyrene and monomers copolymerizable therewith , Polyester fine particles, polyurea Down particles, known organic fillers such as rubber particles, and the like.

<Colorant>
In addition, a colorant such as a dye or a pigment may be added to the composition of the present invention from the viewpoints of texture, visibility, and design. As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, triarylmethane, carbonium, anthraquinone, naphthoquinone, quinoneimine, azomethine, azo, metal complex azo, benzylidene, oxonol, cyanine, phenothiazine, xanthene, phthalocyanine , Benzopyran-based, indigo-based, methine-based, azine-based, oxazine-based, thiazine-based, anthrapyridone-based, squarylium-based, pyrylium salt-based, and metal thiolate complex dyes.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Further, as another preferred example of the dye, there can be mentioned a near infrared absorbing dye described in US Pat. No. 4,756,993.
Also, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, U.S. Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 Dyes disclosed in JP-A Nos. 6-194828 and 2004-252201 can also be used.
Many dyes may cause a decrease in the sensitivity of the polymerization system, and it is particularly preferable to use a pigment as the colorant.

  Examples of pigments added as necessary in the present invention include commercially available pigments and Color Index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association, published in 1977), “Latest Pigment Applied Technology”. (CMC Publishing, published in 1986), "Printing Ink Technology" published by CMC, published in 1984), JP 2004-252201, JP 2007-138105, JP 2007-177177, and the like. Available pigments.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle diameter of the pigment is 0.01 μm or more, the stability of the dispersion in the image recording layer coating solution increases, and when it is 10 μm or less, the uniformity of the image recording layer is improved.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  In addition, a known additive can be added to the composition of the present invention as necessary. For example, surfactants and matting agents, for example, European Patent No. 4 38, 1 23, British Patent No. 2, 1 80, 3 58, and Japanese Patent Laid-Open No. 6-68, 3 09 Promoters and co-initiators such as thiols, thioethers, disulfides, phosphonium salts, phosphine oxides or phosphines described in the publication, auto-oxidants, optical brighteners, wetting agents, smoothing aids, dispersants, anti-aggregation agents, Antifoaming agent, leveling agent, ion trapping agent, ion exchange agent such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc. These plasticizers and other additives may be further used.

  The additives listed above are preferably selected according to the field of application and the properties required for that field. The above-mentioned additives are commonly used in the art, and therefore, it is preferable to add an amount commonly used in each application as the additive amount.

    Another aspect of the present invention is a composition comprising a condensate and / or a polycondensate obtained by reacting at least two compounds represented by the general formula (1) with G as a reactive group. It is a cured product obtained by curing. Examples of the method for obtaining the cured product include those obtained by heating and drying the composition of the present invention or a solution thereof, or those obtained by melting and solidifying the powder of the composition of the present invention. It is not something.

  The composition of the present invention has excellent storage stability without causing polymerization during storage, and starts polymerization efficiently by applying energy such as heat, light, ultraviolet rays, electron beams, etc., depending on the crosslinking group or polymerizable group. Then, the polymerizable compound is efficiently polymerized in a short time, or a cured resin is obtained by crosslinking and curing the crosslinking group bonded to the side chain, main chain, or terminal of the polymer or compound of the present invention, It becomes insoluble in organic solvents and improves solvent resistance, chemical resistance, heat resistance, mechanical strength, and the like. Therefore, when it is soluble in an organic solvent, it can be applied to various moldings by various molding means as various matrix resins, and is highly versatile. In addition, it can exhibit high solvent resistance, chemical resistance, and mechanical strength, is utilized as an excellent resin material, and is suitable as a mechanical member, electrical resistor, or the like. Therefore, the composition of the present invention can be used as a printing ink (eg, screen printing ink, offset, flexographic ink), as a transparent finish (eg, white or colored finish on wood or metal), as a powder coating (especially paper, wood, etc.). , Coating materials for metals or plastics), such as architecture, object marking and road marking, photoreproduction techniques, holographic recording materials, image recording techniques, or production of printing masters, sun curable coatings for the production of screen printing masks As a dental filling composition, as an adhesive, as a pressure sensitive adhesive, as a laminating resin, as a liquid and film etching resist, solder resist, electroplating resist or permanent resist, for printed circuit boards and electronic circuits As a photoconstitutive dielectric For various display applications, for the formation of structures in the manufacturing process of plasma display panels and electroluminescent display devices, for the manufacture of color filters (for example, U.S. Pat. Nos. 5,853,44,6, European Patent Nos. 8 63 3 and 53 4, Japanese Patent Laid-Open Nos. 9-2 4 4 2 30, 1 0 6 2 9 8 0, 8 -1 7 1 8 6 3, US Patent No. No. 5, 8440, 465, European Patent No. 855, 731, Japanese Patent Laid-Open No. 5-27 1 576, Japanese Patent Laid-Open No. 5-674 45 For color switches), optical switches, optical gratings (interference gratings), optical circuit manufacturing, mass curing (UV curing with transparent molds), or stereolithography techniques for manufacturing three-dimensional articles ( For example, U.S. Pat. No. 4,57.55,33.0 Composite materials (for example, styrenic polyesters containing at least glass fibers and / or other fibers and other auxiliaries) for the production of other thick layer compositions of electronic components and integrated circuits It can be used as a resist for coating or sealing, or as an optical fiber, or as an optical lens (eg, a coating for manufacturing contact lenses, Fresnel lenses). The photosensitive composition of the present invention can also be suitably used for the production of medical devices, auxiliary tools and implants. Furthermore, it is also suitably used for the production of gels having thermotropic properties, as described in German Patent Nos. 19, 7 0 0, 0 6 4 and European Patent Nos. 6 7 8, 5 3 4. be able to.

  In addition, by molding and curing after molding, very high solvent resistance, chemical resistance and mechanical strength can be exhibited, and it is utilized as an excellent resin material. Among them, materials for electric resistors and moisture-proof coating materials, for example, Japanese Patent Application Laid-Open Nos. 2006-225481, 2006-176548, 2006-169398, 2005-194370, and 2005 are disclosed. Particularly suitable as a sliding material described in JP-A-0336158. For example, it can be used for a carbon resin binder resin, a semiconductor moisture-proof coating material, and the like. In order to use it as a resistor for a variable resistor, for example, a resistor paste is prepared by mixing with carbon and then fired.

  In the present invention, it is preferable that the crosslinked structure is formed by heating. In the case where the energy application is performed by heating, as the heating means, for example, an oven using a heater, a hot plate, heating by photothermal conversion using infrared rays or visible light, or the like can be used. Moreover, although heat processing changes with kinds of hardened | cured material formed, it is performed by heating at 50 to 500 degreeC for about 0.1 second to 60 minutes.

In the case where the energy application is performed by light irradiation, as the light irradiation means, for example, light sources from ultraviolet to visible regions such as mercury lamps, metal halide lamps, and Xe lamps from low pressure to ultrahigh pressure can be used. .
Moreover, as a shape of the hardened | cured material obtained by this method, although there exist a film | membrane, a pellet, a fibrous thing, and other various molded products, it is not limited to these.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The acetylene compounds used as starting materials in these experiments were synthesized based on the synthesis methods described in Japanese Patent Application No. 2007-242585, Japanese Patent Application No. 2007-256372, and Japanese Patent Application No. 2007-256373, respectively, Japanese Patent Application No. 2007-256501.
The obtained compound was subjected to measurement of various spectra of H-NMR and MS for property evaluation. The measurement conditions for each characteristic were as follows.
<Test method>

(1) Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR): Measured at a resonance frequency of 400 MHz using AV400M manufactured by BRUKER. As a measurement solvent, deuterated dimethyl sulfoxide DMSO-d ₆ which is a deuterated solvent was used.
(2) Mass spectrometry (MS): Measured by ESI method using APIQSTAR Pulsar i manufactured by Applied Biosystems.

<Synthesis Example 1> Synthesis of Compound (1) -1 To a 1000 ml three-necked flask, 10 g (65.7 mmol) of 3,5-diaminobenzoic acid, 150 ml of t-butanol and 150 ml of 1N NaOH aqueous solution were added and stirred to confirm dissolution. . While cooling with ice, 29.4 g (134.7 mmol) of di-t-butyl dicarbonate was added dropwise and stirred. After confirming the disappearance of the raw materials by HPLC, 300 ml of toluene was added, and hydrochloric acid was added for neutralization and liquid separation was performed. After 200 ml of water was added for liquid separation, 6.7 g (65.7 mmol) of triethylamine was added to the oil layer, and the mixture was stirred under a nitrogen atmosphere. To this reaction solution, 7.5 g (65.7 mmol) of methanesulfonyl chloride was added dropwise under ice cooling, and the mixture was stirred for 30 minutes under ice cooling. To this reaction solution, a solution prepared by mixing 7.7 g (65.7 mmol) of 3-ethynylaniline and 6.7 g (65.7 mmol) of triethylamine in 10 ml of toluene was dropped. After confirming disappearance of the raw material by HPLC, 200 ml of water was added to separate the layers. To the obtained toluene layer, 22.1 g (230 mmol) of methanesulfonic acid was stirred at room temperature. After confirming disappearance of the raw material by HPLC, the solution was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained organic layer was concentrated by an evaporator to obtain (1) -17.74 g (yield 47%).

<Synthesis Example 2> Synthesis of Compound (1) -18 Synthesis was performed in the same manner as in Synthesis Example 1 to obtain (1) -18. The yield was 33%.

<Synthesis Example 3> Synthesis of Compound (1) -30 To a 1000 ml three-necked flask, 12.95 g (65.7 mmol) of 2,4-diaminophenol dihydrochloric acid, 150 ml of t-butanol and 150 ml of 1N NaOH aqueous solution were added and stirred. And dissolution was confirmed. While cooling with ice, 29.4 g (134.7 mmol) of di-t-butyl dicarbonate was added dropwise and stirred. After confirming the disappearance of the raw materials by HPLC, 300 ml of toluene was added, and hydrochloric acid was added for neutralization and liquid separation was performed. After 200 ml of water was added for liquid separation, 10.29 g (65.7 mmol) of phenyl chlorocarbonate and 15.59 g (197.1 mmol) of pyridine were added to the oil layer under ice cooling, and the mixture was stirred at room temperature. After confirming disappearance of the raw materials by HPLC, 7.76 g (65.7 mmol) of 3-ethynylphenol and 7.31 g (72.27 mmol) of triethylamine were added and reacted at 80 ° C. for 5 hours. To the obtained toluene layer, 22.1 g (230 mmol) of methanesulfonic acid was stirred at room temperature. After confirming disappearance of the raw material by HPLC, the solution was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained organic layer was concentrated and then added to water to precipitate a solid. (1) -308.54g was obtained (yield 32%).

<Synthesis Example 4> Synthesis of Compound (1) -34 Compound (1) -34 was synthesized in the same manner as Synthesis Example 1. The yield was 28%.

<Synthesis Example 5> Synthesis of compound (1) -54 10 g (51.0 mmol) of 4,5-diaminophthalic acid, 150 ml of t-butanol, and 150 ml of 1N NaOH aqueous solution were added and stirred to confirm dissolution. While cooling with ice, 29.4 g (134.7 mmol) of di-t-butyl dicarbonate was added dropwise and stirred. After confirming disappearance of the raw material by HPLC, 300 ml of toluene was added, hydrochloric acid was added to precipitate a solid, and the solid was taken out by filtration. The solid thus taken out was dissolved in 100 ml of N-methyl-2-pyrrolidone, and 5.97 g (51.0 mmol) of 4-ethynylaniline, 12.1 g (153 mmol) of pyridine and 30 g of acetic anhydride were added and heated to reflux for 12 hours to precipitate a solid Was removed by filtration. Acetonitrile and 22.1 g (230 mmol) of methanesulfonic acid were added to the obtained solid and stirred at room temperature. After confirming disappearance of the raw material by HPLC, the solution was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained organic layer was concentrated with an evaporator and then added to water to precipitate a solid. The obtained solid was filtered to obtain (1) -545.93 g (yield 42%).

Synthesis Example 6 Synthesis of Compound (1) -62 4-fluoro-3,5-diaminobenzoic acid 10 g (58.8 mmol) was dissolved in N-methyl-2-pyrrolidone 100 ml, and triethylamine 5.95 g (58.8 mmol). Were put in order and stirred. Under ice cooling, 6.7 g (58.8 mmol) of methanesulfonyl chloride was added dropwise, and the mixture was stirred for 30 minutes under ice cooling. To this reaction solution, a solution prepared by mixing 6.87 g (58.8 mmol) of 3-ethynylaniline and 5.95 g (58.8 mmol) of triethylamine in 5 ml of acetonitrile was added dropwise. After confirming disappearance of the raw material by HPLC, 250 ml of water and 250 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. 80 ml of methanol was added to the total amount of the obtained solid, and the mixture was heated to reflux with stirring. After confirming complete dissolution, the mixture was ice-cooled for 2 hours, and the obtained crystals were filtered to obtain (1) -625.6 g (20.8 mmol) (yield 35.4%).

<Synthesis Example 7> Synthesis of (1) -26 (1) -26 was synthesized in the same procedure as in Synthesis Example 3. The yield was 27%.

<Synthesis Example 8> Synthesis of (2) -1 In a 1000 ml three-necked flask, 18.5 g (65.7 mmol) of 5- (t-butylcarboxy) aminoisophthalic acid, 200 g of N-methyl-2-pyrrolidone, under a nitrogen stream, 13.4 g (131.4 mmol) of triethylamine was added and stirred. To this reaction solution, 15 g (131.4 mmol) of methanesulfonyl chloride was added dropwise under ice cooling, and the mixture was stirred for 30 minutes under ice cooling. To this reaction solution, a solution prepared by mixing 15.4 g (131.4 mmol) of 3-ethynylaniline and 13.4 g (131.4 mmol) of triethylamine in 30 ml of N-methyl-2-pyrrolidone was added dropwise. After confirming disappearance of the raw material by HPLC, 300 ml of toluene and 200 ml of water were added to separate the layers. To the obtained toluene layer, 22.1 g (230 mmol) of methanesulfonic acid was added and stirred at room temperature. After confirming disappearance of the raw material by HPLC, the solution was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained organic layer was concentrated by an evaporator to obtain (2) -18.47 g (yield 34%).

<Synthesis Example 9> Synthesis of (2) -2 (2) -2 was synthesized in the same procedure as in Synthesis Example 8. The yield was 43%.
<Synthesis Example 10> Synthesis of (2) -9 (2) -9 was synthesized in the same procedure as in Synthesis Example 8. The yield was 25%.

<Synthesis Example 11> Synthesis of (2) -15 2,4-dibromoaniline 5 g (19.9 mmol) and 3-ethynylphenol 2.58 g (21.8 mmol) were dissolved in 20 ml of N-methylpyrrolidone, and potassium-t- 6.73 g (60 mmol) of butoxide was added and stirred at 190 ° C. for 6 hours. 50 ml of ethyl acetate and 50 ml of a 5 wt% multilayer aqueous solution were sequentially added to the obtained reaction solution for liquid separation, and the resulting oil layer was concentrated to obtain a crude product. The obtained crude product was recrystallized from methanol to obtain 2.0 g of (2) -15 (yield 30.9%).

<Synthesis Example 12> Synthesis of (2) -13 Synthesis was performed in the same manner as in Synthesis Example 11 to obtain (2) -13. The yield was 25%.
<Synthesis Example 13> Synthesis of (2) -14 Synthesis was performed in the same procedure as in Synthesis Example 11 to obtain (2) -14. The yield was 37%.
<Synthesis Example 14> Synthesis of (2) -17 Synthesis was performed in the same procedure as in Synthesis Example 11 to obtain (2) -17. The yield was 11%.
<Synthesis Example 15> Synthesis of (2) -27 Synthesis was performed in the same procedure as in Synthesis Example 8 to obtain (2) -27. The yield was 31%.
<Synthesis Example 16> Synthesis of (2) -49 Compound (2) -49 was obtained by synthesis in the same procedure as in Synthesis Example 8. The yield was 46%.

<Synthesis Example 17> Synthesis of (3) -3 In a 2000 mL three-necked flask, 52 g of dimethyl 5-aminoisophthalate, 600 mL of tetrahydrofuran, and 21 g of pyridine were added and stirred for 15 minutes. While continuing stirring in the 2000 mL three-necked flask, 41 g of phenyl chlorocarbonate diluted with 100 mL of tetrahydrofuran was added dropwise using a dropping funnel over 10 minutes, and stirring was continued for 3 hours at room temperature.
Subsequently, 30 g of 3-ethynyl-5-methylaniline was dropped over 10 minutes using a dropping funnel. Subsequently, 76 g of triethylamine diluted with 100 mL of tetrahydrofuran was added dropwise over 10 minutes using a dropping funnel, and the mixture was heated to reflux for 4 hours.
After returning to room temperature, an aqueous sodium hydroxide solution prepared by adding 25 g of sodium hydroxide from 200 mL of ion-exchanged water was added dropwise using a dropping funnel over 10 minutes, heated to 40 ° C., and stirring was continued for 2 hours. The mixture was ice-cooled until the internal temperature became 10 ° C. or lower, and 160 mL of 3M hydrochloric acid was added dropwise using a dropping funnel over 10 minutes, and stirring was continued for 30 minutes while continuing ice cooling.
The above reaction solution was transferred to a 5000 mL separatory funnel, and the ethyl acetate phase was extracted with 2500 mL of ethyl acetate and 800 mL of ion-exchanged water, and concentrated under reduced pressure using a rotary evaporator and dissolved in 200 mL of tetrahydrofuran. 49.2g of target exemplary compound (3) -3 was obtained by dripping over 30 minutes to the 2000 mL three necked flask containing acetonitrile, and filtering the obtained crystal | crystallization. (Yield 58%).

<Synthesis Example 18> Synthesis of (3) -6 Compound (3) -6 was obtained by synthesis in the same procedure as in Synthesis Example 15. The yield was 65%.
<Synthesis Example 19> Synthesis of (3) -8 Synthesis was performed in the same manner as in Synthesis Example 15 to obtain Compound (3) -8. The yield was 53%.

<Synthesis Example 20> Synthesis of (3) -43 5-aminoisophthalic acid 10 g (55 mmol) and 4-ethynylbenzoic anhydride 9.5 g (55 mmol) were dissolved in NMP 50 ml, pyridine 13 g (165 mmol) was added, and 90 ° C. For 5 hours. The reaction solution was cooled and then slowly added to an aqueous hydrochloric acid solution, and the resulting solid was removed by filtration. After drying, 10.1 g of (3) -43 was obtained. (Yield 55%).

<Synthesis Example 21> Synthesis of (4) -1 61 g of 3,5-diaminobenzoic acid and 600 mL of N-methyl-2-pyrrolidone were placed in a 2000 mL three-necked flask and stirred for 15 minutes. While continuing stirring in the 2000 mL three-necked flask, 143 g of phenyl chlorocarbonate was added dropwise using a dropping funnel over 10 minutes, and stirring was continued for 30 minutes at room temperature.
The above reaction solution was transferred to a 5000 mL separatory funnel, and the ethyl acetate phase was extracted with 2500 mL of ethyl acetate and 800 mL of ion-exchanged water, and concentrated to dryness under reduced pressure using a rotary evaporator, and 600 mL of N-methyl-2-pyrrolidone. And transferred to a 2000 mL 3-neck flask.
Subsequently, 60 g of 3-ethynylaniline was added dropwise over 10 minutes using a dropping funnel. Subsequently, 153 g of triethylamine was dropped over 10 minutes using a dropping funnel, and the mixture was heated to reflux for 4 hours.
The above reaction solution was transferred to a 5000 mL separatory funnel, and the ethyl acetate phase was extracted with 2500 mL of ethyl acetate and 800 mL of ion-exchanged water, and concentrated under reduced pressure using a rotary evaporator and dissolved in 200 mL of tetrahydrofuran. Ethyl acetate was added, 100 mL of hexane was further added dropwise over 30 minutes, and the resulting crystals were filtered to obtain 81 g of the target exemplified compound (4) -1. (Yield 46%).

<Synthesis Example 22> Synthesis of (4) -5 Compound (4) -5 was obtained in the same procedure as in Synthesis Example 21. The yield was 42%.
<Synthesis Example 23> Synthesis of (4) -20 Compound (4) -20 was obtained in the same procedure as in Synthesis Example 21. The yield was 34%.
<Synthesis Example 24> Synthesis of (4) -22 Compound (4) -22 was obtained in the same procedure as in Synthesis Example 21. The yield was 31%.
<Synthesis Example 25> Synthesis of (4) -26 Compound (4) -26 was obtained in the same procedure as in Synthesis Example 21. The yield was 21%.

Synthesis Example 26 Synthesis of (4) -33 3,5-Dibromobenzoic acid 5 g (17.9 mmol) and 3-ethynylphenol 4.23 g (35.8 mmol) were dissolved in N-methylpyrrolidone 20 ml, and potassium-t -Butoxide 10.1 g (90 mmol) was added, and it stirred at 190 degreeC for 6 hours. 50 ml of ethyl acetate and 50 ml of a 5 wt% multilayer aqueous solution were sequentially added to the obtained reaction solution for liquid separation, and the resulting oil layer was concentrated to obtain a crude product.
The obtained crude product was recrystallized from methanol to obtain 1.50 g of (4) -33 (yield 23.6%).

<Synthesis Example 27> Synthesis of (4) -40 8.37 g (55 mmol) of 3,5-diaminobenzoic acid and 19.0 g (110 mmol) of 4-ethynylbenzoic anhydride were dissolved in 80 ml of NMP, and 26 g (329 mmol) of pyridine. And reacted at 90 ° C. for 5 hours. The reaction solution was cooled and then slowly added to an aqueous hydrochloric acid solution, and the resulting solid was removed by filtration. After drying, 12.1 g of (4) -40 was obtained. (Yield 48%)
<Synthesis Example 28> Synthesis of (4) -47 Compound (4) -47 was obtained in the same procedure as in Synthesis Example 26. The yield was 53%.

<Example 1>
The following compound (5) -1 is synthesized.

  In a 100 ml three-necked flask, 4.38 g (10 mmol) of compound (4) -1, 20 ml of acetonitrile, and 1.01 g (10 mmol) of triethylamine were sequentially added and stirred under a nitrogen stream. Under ice cooling, 1.15 g (10 mmol) of methanesulfonyl chloride was added dropwise and stirred for 30 minutes. A solution prepared by mixing 3.90 g (10 mmol) of compound (2) -1 and 1.15 g (10 mmol) of triethylamine in 10 ml of acetonitrile was added dropwise to the reaction solution. After confirming disappearance of the raw materials by HPLC, 100 ml of water and 100 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The obtained concentrate was purified by column chromatography to obtain 5.76 g of a brown solid (yield 72%).

The physical properties of the obtained compound were as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 3H), 8.90 (s, 4H), 8.38 (s, 2H), 8.27 (s, 1H), 8 .24 (s, 1H), 7.87 (s, 2H), 7.81 (s, 4H), 7.62 (d, 4H), 7.29 (t, 4H), 7.14 (d, 4H), 4.10 (s, 4H)
MS: M ⁺ = 799.25

<Example 2>

The following compound (5) -2 is synthesized.

In Example 1, Example (1) was used except that 10 mmol of Compound (4) -5 was used instead of Compound (4) -1 and 10 mmol of Compound (2) -2 was used instead of Compound (2) -1. Similarly, compound (5) -2 was synthesized. The yield was 6.53 g (81.6%). The physical properties of the obtained compound were as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 3H), 8.90 (s, 4H), 8.38 (s, 2H), 8.27 (s, 1H), 8 .24 (s, 1H), 7.87 (s, 2H), 7.61 (d, 8H), 7.40 (s, 8H), 3.06 (s, 4H)
MS: M ⁺ = 799.25

<Example 3>
The following compound (6) -1 is synthesized.

  In a 100 ml three-necked flask, 8.76 g (20 mmol) of compound (4) -1, 40 ml of acetonitrile, and 2.01 g (20 mmol) of triethylamine were added and stirred under a nitrogen stream. Under ice cooling, 2.30 g (20 mmol) of methanesulfonyl chloride was added dropwise and stirred for 30 minutes (solution 1).

  Under a nitrogen stream, Compound (1) -12.70 g (10 mmol), acetonitrile 40 ml and triethylamine 1.15 g (10 mmol) were added to a 200 ml three-necked flask and dissolved by stirring. Solution 1 prepared on ice was added dropwise. After confirming disappearance of the raw material by HPLC, 150 ml of water and 150 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The resulting concentrate was produced by column chromatography to obtain 6.91 g of a brown solid (yield 63%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 3H), 8.90 (s, 8H), 8.27 (s, 3H), 7.87 (s, 6H), 7 .81 (s, 5H), 7.62 (d, 5H), 7.29 (t, 5H), 7.14 (d, 5H), 4.10 (s, 5H)
MS: M ⁺ = 1091.35

<Example 4> Synthesis of (6) -30

Compound (6) -30 was synthesized in the same manner as in Example 3 except that 10 mmol of Compound (4) -25 was used instead of Compound (4) -1. The physical properties of the obtained compound were as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 3H), 8.90 (s, 8H), 8.27 (s, 3H), 7.87 (s, 6H), 7 .78 (s, 4H), 7.62 (d, 1H), 7.29 (t, 1H), 7.14 (d, 5H), 6.92 (d, 4H), 4.10 (s, 1H), 3.06 (s, 4H)
MS: M ⁺ = 1163.38

Example 5 Synthesis of (6) -6

Example 3 is the same as Example 3 except that 10 mmol of compound (4) -5 was used instead of compound (4) -1 and 10 mmol of compound (1) -18 was used instead of compound (1) -1. In the same manner, Compound (4) was synthesized. The physical properties of the obtained compound were as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 3H), 8.90 (s, 8H), 8.27 (s, 3H), 7.87 (s, 6H), 7 .81 (s, 1H) 7.62 (d, 1H), 7.61 (d, 8H), 7.40 (d, 8H), 7.29 (t, 1H), 7.16 (d, 1H) ), 3.06 (s, 4H), 1.60 (m, 5H), 1.10 (m, 5H)
MS: M ⁺ = 1173.43

Example 6 Synthesis of Compound (7) -8

Under a nitrogen stream, 3.24 g (10 mmol) of Compound (3) -6, 40 ml of dimethylacetamide and 2.53 g (22 mmol) of triethylamine were added to a 100 ml three-necked flask and dissolved by stirring. To this solution, 2.38 g (20 mmol) of thionyl chloride was added dropwise under ice cooling while keeping the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred for 30 minutes with ice cooling.
In a 200 ml three-necked flask, 6.5 g (20 mmol) of (2) -17 and 50 ml of dimethylacetamide were added and dissolved by stirring under a nitrogen atmosphere. Solution 1 prepared under ice cooling was added dropwise to this solution. After confirming disappearance of the raw material by HPLC, 150 ml of water and 150 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The resulting concentrate was produced by column chromatography to obtain 2.91 g of a brown solid (yield 31%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 2H), 8.90 (s, 2H), 8.38 (s, 2H), 8.24 (s, 1H), 7 .61 (d, 2H) 7.40 (d, 2H), 7.27 (d, 4H), 7.19 (d, 4H), 7.14 (d, 4H), 7.08 (s, 4H) ), 3.06 (s, 5H)
MS: M ⁺ = 938.27

<Example 7> Synthesis of (7) -11

In Example 6, compound (2) -14 was used in the same molar amount instead of compound (2) -17, and compound (3) -8 was used in the same molar amount instead of compound (3) -6. Compound (4) was synthesized in the same manner as Example 6. Yield 2.87 g (22% yield). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 2H), 8.90 (s, 2H), 8.38 (s, 3H), 8.24 (s, 1H), 7 .61 (d, 2H) 7.40 (d, 2H), 7.27 (s, 4H), 7.19 (t, 4H), 7.14 (d, 4H), 6.90 (d, 4H) ), 6.39 (s, 1H), 2.48 (q, 1H), 1.70 (q, 2H), 1.49 (m, 2H), 1.46 (m, 1H), 1.45 (Q, 2H), 1.43 (m, 1H), 1.39 (m, 2H), 0.08 (s, 36H)
MS: M ^<+> = 1308.51

<Example 8> Synthesis of (7) -20

In Example 6, compound (2) -48 was used in the same molar amount instead of compound (2) -17, and compound (3) -43 was used in the same molar amount instead of compound (3) -6. Compound (7) -20 was synthesized in the same manner as Example 3. Yield 2.59 g (28% yield). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 2H), 8.58 (s, 2H), 8.43 (s, 4H), 8.29 (s, 1H), 8 .24 (s, 1H), 8.10 (d, 1H), 8.06 (s, 2H) 7.85 (d, 1H), 3.06 (s, 1H), 2.51 (s, 4H) ), 1.67 (s, 24H)
MS: M ⁺ = 925.28

Example 9 Synthesis of (7) -18

In Example 6, compound (2) -13 was used in the same molar amount instead of compound (2) -17, and compound (3) -3 was used in the same molar amount instead of compound (3) -6. Compound (7) -18 was synthesized in the same manner as Example 1. Yield 2.13 g (17% yield). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 2H), 8.90 (s, 2H), 8.38 (s, 2H), 8.24 (s, 1H), 7 .62 (s, 1H), 7.42 (s, 1H), 7.31 (s, 4H), 7.27 (s, 4H), 7.07 (s, 4H), 7.02 (s, 4H), 6.39 (s, 2H), 3.06 (s, 5H), 2.35 (s, 3H)
MS: M ^<+> = 1263.93

<Example 10> Synthesis of (5) -20

Example 1 is the same as Example 1 except that 10 mmol of compound (4) -40 was used instead of compound (4) -1 and 10 mmol of compound (2) -9 was used instead of compound (2) -1. The compound was synthesized in the same manner. The yield of the obtained compound was 5.10 g (yield 62.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.25 (s, 3H), 9.20 (s, 1H), 8.29 (s, 2H), 8.27 (s, 1H), 8 .10 (d, 2H), 8.07 (s, 2H), 7.92 (s, 1H), 7.85 (d, 2H), 7.61 (d, 4H), 7.40 (d, 4H), 3.06 (s, 5H)
MS: M ^<+> = 821.19

Example 11 Synthesis of (5) -22

In Example 1, 20 mmol of compound (4) -40 was used instead of compound (4) -1, and 20 mmol of compound (2) -17 was used instead of compound (2) -1. The compound was synthesized in the same manner. The yield of the obtained compound was 5.59 g (yield 73.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 1H), 9.77 (s, 2H), 8.29 (d, 2H), 8.27 (s, 1H), 8 .10 (d, 2H), 8.07 (s, 2H), 7.85 (d, 2H), 6.98 (t, 2H), 6.76 (d, 2H), 6.62 (s, 2H), 6.20 (s, 2H), 5.40 (s, 1H), 3.06 (s, 4H)
MS: M ⁺ = 765.20

<Example 12> Synthesis of (5) -16

Example 11 is the same as Example 11 except that 20 mmol of compound (2) -15 was used instead of compound (2) -17 and 20 mmol of compound (4) -20 was used instead of compound (4) -40. The compound was synthesized in the same manner. The yield of the obtained compound was 2.93 g (yield 34.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 1H), 8.90 (s, 4H), 8.27 (s, 1H), 8.23 (d, 1H), 7 .81 (s, 2H), 7.29 (t, 2H), 7.19 (t, 2H), 7.16 (d, 2H), 7.14 (d, 2H), 7.08 (s, 2H), 6.90 (d, 2H), 6.62 (d, 1H), 6.56 (s, 1H), 5.45 (s, 2H), 3.06 (s, 2H), 1. 47 (s, 12H)
MS: M ⁺ = 861.32.

Example 13 Synthesis of (5) -18

Example 11 is the same as Example 1 except that 20 mmol of compound (2) -27 was used instead of compound (2) -17 and 20 mmol of compound (4) -26 was used instead of compound (4) -40. The compound was synthesized in the same manner. The yield of the obtained compound was 4.71 g (yield 48.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 3H), 8.90 (s, 4H), 8.27 (s, 1H), 8.12 (d, 2H), 7 .87 (s, 2H), 7.61 (d, 4H), 7.40 (d, 4H), 7.36 (s, 1H), 7.14 (d, 2H), 6.98 (t, 2H), 3.06 (s, 2H), 0.08 (s, 18H)
MS: M ^<+> = 979.31

<Example 14> Synthesis of (6) -4

In a 100 ml three-necked flask, 8.76 g (20 mmol) of Compound (4) -1, 30 ml of N, N-dimethylacetamide, and 2.21 g (21 mmol) of triethylamine were sequentially added and stirred. Under cooling with ice, 2.30 g (21 mmol) of methanesulfonyl chloride was added dropwise and stirred for 30 minutes.
A solution prepared by mixing 2.68 g (10 mmol) of compound (1) -30 and 1.15 g (10 mmol) of triethylamine in 20 ml of N, N-dimethylacetamide was dropped into a 200 ml three-necked flask under a nitrogen stream. After confirming disappearance of the raw materials by HPLC, 100 ml of water and 100 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The obtained concentrate was purified by column chromatography to obtain 6.10 g of a brown solid (yield 55%).

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 1H), 8.90 (s, 6H), 8.27 (s, 1H), 7.87 (s, 2H), 7 .81 (s, 4H), 7.62 (d, 4H), 7.35 (d, 1H), 7.29 (t, 4H), 7.23 (t, 2H), 7.20 (t, 2H), 7.14 (d, 4H), 7.05 (d, 1H), 7.03 (d, 1H), 4.08 (s, 4H), 3.06 (s, 1H)
MS: M ⁺ = 1108.33

Example 15 Synthesis of (6) -28

In Example 14, Example 1 was used except that Compound (1) -54 was used instead of Compound (1) -30 and Compound (4) -22 was used in an equimolar amount instead of Compound (4) -1. The compound was synthesized in the same manner as above. The yield of the obtained compound was 3.92 g (yield 35.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 2H), 8.90 (s, 8H), 8.49 (s, 2H), 8.31 (s, 2H), 7 .87 (d, 2H), 7.81 (s, 2H), 7.80 (d, 2H), 7.62 (d, 2H), 7.40 (d, 2H), 7.29 (t, 4H), 7.14 (d, 4H), 4.08 (s, 4H), 3.06 (s, 1H)
MS: M ^<+> = 1177.33

Example 16 Synthesis of (6) -22

In Example 14, it implemented except having used compound (1) -54 equimolar amount instead of compound (1) -30, and having used compound (4) -33 equimolar amount instead of compound (4) -1. The compound was synthesized in the same manner as in Example 14. The yield of the obtained compound was 4.24 g (yield 45.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 3H), 8.05 (s, 2H), 7.81 (s, 1H), 7.62 (d, 1H), 7 .29 (t, 1H), 7.19 (t, 4H), 7.14 (d, 5H), 7.08 (s, 4H), 6.90 (s, 6H), 4.08 (s, 1H), 3.06 (s, 4H)
MS: M ⁺ = 941.25

<Example 17> Synthesis of (6) -18

In Example 14, Example 1 was used except that Compound (1) -34 was used instead of Compound (1) -30 and Compound (4) -5 was used instead of Compound (4) -1. The compound was synthesized in the same manner as above. The yield of the obtained compound was 3.60 g (yield 32.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 3H), 8.90 (s, 8H), 8.27 (s, 3H), 7.87 (s, 6H), 7 .69 (s, 1H), 7.61 (d, 8H), 7.51 (d, 1H), 7.40 (d, 8H), 6.72 (d, 1H), 3.73 (s, 3H), 3.06 (s, 5H)
MS: M ⁺ = 1121.36

Example 18 Synthesis of (6) -29

In Example 14, Example 14 was used except that Compound (1) -26 was used instead of Compound (1) -30 and Compound (4) -47 was used instead of Compound (4) -1. The compound was synthesized in the same manner as above. The yield of the obtained compound was 3.57 g (yield 24.1%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): 10.25 (s, 2H), 8.29 (s, 4H), 8.27 (s, 2H), 8.10 (d, 4H), 7 .85 (d, 4H), 7.59 (d, 1H), 7.43 (s, 1H), 7.23 (t, 2H), 7.20 (t, 1H), 7.05 (d, 1H), 6.79 (d, 2H), 3.06 (s, 1H), 2.48 (q, 4H), 1.70 (m, 8H), 1.49 (m, 8H), 1. 46 (m, 8H), 1.45 (m, 8H), 1.39 (m, 8H)
MS: M ⁺ = 1480.52.

<Synthesis of polycondensation polymer>
Example 19 Synthesis of (8) -1

  In a 200 mL three-necked flask substituted with an inert gas, 0.023 mol of 3,3′-diaminodiphenylmethane, 0.004 mol of compound (1) -1 and 0.0004 mol of (2) -2 were taken, and N— Add 110 mL of methyl-2-pyrrolidone and dissolve. While stirring this reaction solution at 15 ° C., isophthaloyl chloride was added and stirred at room temperature for 2 hours to obtain a polyamide solution. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The obtained polyamide film was measured for a 5% mass reduction temperature and a coefficient of humidity expansion. The results are shown in Table 1.

<Measurement conditions>
-5% weight loss temperature TG / DTA was measured and calculated, and 2 mg of the synthesized polymer was contained in the measurement cell of EXSTAR6000 manufactured by Seiko Instruments Inc., and the flow rate was 30 ° C to 550 ° C under N ₂ flow rate of 200 ml / min. TG / DTA measurement was performed by heating at a heating rate of 10 ° C./min.
・ Humidity expansion coefficient:
A sample obtained by cutting a 5 mm × 30 mm wide film into a length of 30 mm was used. The measurement device is a self-made device incorporating a laser scanning micrometer manufactured by Keyence Corporation. The sample is set and a device with a load of 1 N is placed in a chamber controlled under a constant environment of 30 ° C., and the humidity is 10 The change in film width was measured while changing from% RH to 80% RH, and the humidity expansion coefficient was determined by the following equation.
<Humidity expansion coefficient> = ((change in film width) / (initial film width)) / (change in humidity)

Example 20 Synthesis of (8) -2

A polyamide solution was obtained in the same manner as in Example 19 except that 0.004 mmol of the compound (4) -1 was used instead of the compound (2) -1. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed on the 5% mass loss temperature and humidity expansion coefficient of the obtained polyamide film. The results are shown in Table 1.

<Example 21> Synthesis of (8) -3

In a 200 mL three-necked flask substituted with an inert gas, 0.023 mol of 4,4′-diaminodiphenyl ether and 0.004 mol of each of the compounds (1) -1 and (2) -1 were taken, and N-methyl-2 -Add 110 mL of pyrrolidone and dissolve. While stirring this reaction solution at 15 ° C., 0.023 mol of pyromellitic anhydride was added, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.05 mol of acetic anhydride and 0.005 mol of pyridine were added and stirred at room temperature for 1 hour, then heated to 60 ° C. and stirred for 3 hours to obtain a polyimide solution.
The obtained solution was dropped into 300 mL of acetonitrile, and the resulting precipitate was filtered and dried to obtain (8) -3 powder. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone to obtain a polyimide solution having (8) -3 at both ends. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as Example 19 was performed about the 5% mass reduction | decrease temperature and humidity expansion coefficient of the obtained polyimide film. The results are shown in Table 1.

<Examples 22, 23, and 24> Synthesis of (8) -5, 6, and 7 (8) -5, 6, and 7 were synthesized in the same manner as in Example 21.

<Example 25> Synthesis of Exemplified Compound (8) -8 To a three-necked flask was added 120 g of polyphosphoric acid, 22.5 g of 3,3 ′, 4,4′-tetraaminobiphenyl, and (1) -13 g. Then, 16.6 g of isophthalic acid was added and heated to 200 ° C., and stirring was continued for 12 hours. Further, 10 g of polyphosphoric acid and 2.3 g of Exemplified Compound (2) -1 were added, and stirring was continued for 12 hours.
The obtained reaction solution was put into a beaker containing 500 mL of ion-exchanged water, and the obtained target product solid was washed with an aqueous sodium hydrogen carbonate solution, then ion-exchanged water and methanol, and then filtered to obtain an average molecular weight of about 30000 (8) -8 was obtained. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as Example 19 was performed about the 5% mass reduction | decrease temperature and humidity expansion coefficient of the obtained polybenzimidazole film. The results are shown in Table 1.

Example 26 Synthesis of Exemplified Compound (8) -10 3,3′-diamino-4,4′-dihydroxybiphenyl 22 instead of 22.5 g of 3,3 ′, 4,4′-tetraaminobiphenyl Example 25 is the same as Example 25 except that 7g was used. The measured values of the obtained polybenzoxazole film are shown in Table 1.

Example 27 Synthesis of Exemplified Compound (8) -12

  Hydroquinone, (3) -1, (2) -1, and pyridine were placed in a 100 ml three-necked flask under a nitrogen atmosphere, and 20 ml of NMP was added and dissolved. While maintaining the internal temperature at 15 ° C. or lower, terephthaloyl chloride was added to this solution. After the temperature was raised to 80 ° C. and reacted for 12 hours, the reaction solution was reprecipitated with water and filtered to take out the desired product. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed on the 5% mass loss temperature and the coefficient of humidity expansion of the obtained polyester film. The results are shown in Table 1.

Example 28 Synthesis of Exemplified Compound (8) -13 0.023 mol of phenylenediamine and 0.004 mol of (1) -1 are placed in a 300 ml three-necked flask sufficiently substituted with an inert gas. 1,3-phenylene diisocyanate (0.023 mol) is dissolved in 30 ml of NMP and added dropwise to the flask while stirring the solution. After making it react at 130 degreeC for 3 hours, the solution was obtained, this was dropped in water, and the produced | generated polymer was precipitated and dried, and (8) -13 was obtained. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed for the 5% mass loss temperature and the humidity expansion coefficient of the obtained polyurethane film. The results are shown in Table 1.

<Comparative Example 1>
Synthesis of the following compound (A ′)

The above compound was synthesized according to Patent Document WO2006 / 137369. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed on the 5% mass reduction temperature and humidity expansion coefficient of the obtained polyurethane film. The results are shown in Table 1.

Comparative Example 2 Synthesis of the following Compound (B ′) Compound (B ′) was synthesized according to the following method.

(B ')

A 100 ml four-necked flask was charged with 3.0 g (11.9 mmol) of (1) -1 and 20 g of NMP and dissolved in a nitrogen stream. 4-Ethynylphthalic anhydride (4.11 g, 23.9 mmol) was added in portions and stirred at room temperature for 4 hours to synthesize an amic acid solution. Subsequently, 0.19 g (2.39 mmol) of pyridine and 7.32 g (71.6 mmol) of acetic anhydride were added dropwise. The mixture was stirred at room temperature for several hours, and the precipitated crystals were filtered and dried to obtain 5.01 g of Compound B ′ (yield 75%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 8.29 (s, 2H), 8.27 (s, 1H), 8.10 (d, 2H), 8 .07 (s, 2H), 7.85 (d, 2H), 7.81 (s, 1H), 7.62 (d, 1H), 7.29 (t, 1H), 7.14 (d, 1H), 4.08 (s, 1H), 3.06 (s, 2H)
MS: M ⁺ = 559.12

10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed on the 5% mass reduction temperature and humidity expansion coefficient of the obtained polyurethane film. The results are shown in Table 1.

<Comparative Example 3>
Synthesis of the following compound (C ′)

In a 100 mL four-necked flask, 4.5 g (11.9 mmol) of (1) -1 and 20 g of NMP were charged and dissolved under a nitrogen stream. 4-Ethynylphthalic anhydride (2.05 g, 11.9 mmol) was added in portions and reacted at room temperature for 4 hours to synthesize an amic acid solution. Subsequently, 0.95 g (1.19 mmol) of pyridine and 3.66 g (35.8 mmol) of acetic anhydride were added dropwise. The mixture was stirred at room temperature for 5 hours, and the precipitated crystals were filtered and dried to obtain 4.44 g (yield 70%) of compound (C ′).
10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone. The solution was applied onto a quartz glass plate using a blade, dried, and heat-cured at 300 ° C. The same measurement as in Example 19 was performed for the 5% mass loss temperature and the humidity expansion coefficient of the obtained polyurethane film. The results are shown in Table 1.

<Comparative example 4>
Synthesis of the following compounds

In Example 21, an imide oligomer was isolated in the same manner as in Example 21 except that (2) -1 was changed to 3-ethynylbenzene. The obtained powder was formed into a film in the same manner as in Example 21, and the physical properties were measured. The results are shown in Table 1.

<Comparative Example 5>
Synthesis of the following compounds

In Example 21, an imide oligomer was isolated in the same manner as in Example 21 except that (2) -1 was changed to 4-ethynylphthalic anhydride. The obtained powder was formed into a film in the same manner as in Example 21, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 6 Synthesis of the following compound

In Example 21, an imide oligomer was isolated in the same manner as in Example 21 except that (1) -1 was not used. The obtained powder was formed into a film in the same manner as in Example 21, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 7 Synthesis of the following compound

In Example 21, an imide oligomer was isolated in the same manner as in Example 21 except that (2) -1 was not used. The obtained powder was formed into a film in the same manner as in Example 21, and the physical properties were measured. The results are shown in Table 1.

<Comparative Example 8>

A polyamic acid solution was obtained in the same manner as in Example 20 except that (2) -1 was changed to 3-ethynylbenzene in Example 20. The obtained solution was formed into a film in the same manner as in Example 20, and the physical properties were measured. The results are shown in Table 1.

<Comparative Example 9>

In Example 25, polybenzimidazole was isolated in the same manner as in Example 25 except that (2) -1 was changed to 3-ethynylbenzaldehyde. The obtained powder was formed into a film in the same manner as in Example 25, and the physical properties were measured. The results are shown in Table 1.

<Comparative Example 10>

In Example 26, polybenzoxador was isolated in the same manner as in Example 26 except that (2) -1 was changed to 3-ethynylbenzaldehyde. The obtained powder was formed into a film in the same manner as in Example 26 and measured for physical properties. The results are shown in Table 1.

<Performance evaluation>
About the film obtained by the Example and Comparative Examples 4-7, the 5% mass reduction | decrease temperature and the humidity expansion coefficient were measured. The results are shown in Table 1.

  As is apparent from Table 1 above, the film prepared from the compound obtained according to the present invention has a higher 5% mass loss temperature and a smaller humidity expansion coefficient than the film prepared from the conventionally known compound. I understand that.

<Example 29>
<Create film of polycondensed compound>
2 g of the acetylene compound obtained in Example 1 was dissolved in 20 g of N-methyl-2-pyrrolidone. 2 g of the obtained solution was added to 10 g of U varnish (manufactured by Ube Industries), and this was applied as a coating solution on a quartz glass plate using a blade, dried, and subjected to thermosetting treatment at 300 ° C. The obtained film was measured for a 5% mass reduction temperature and a coefficient of humidity expansion. The results are shown in Table 2.

<Examples 30 to 40>
In Example 29, a film was produced in the same manner as in Example 29 except that each of the acetylene compounds synthesized in Examples 2 to 14 was used. The obtained film was measured for a 5% mass reduction temperature and a coefficient of humidity expansion. The results are shown in Table 2.

<Comparative Examples 11-13>
In Example 29, a film was produced in the same manner as in Example 21 except that the acetylene compound obtained in Comparative Examples 1 to 3 was used instead of the acetylene compound obtained in Example 1. The obtained film was measured for a 5% mass reduction temperature and a coefficient of humidity expansion. The results are shown in Table 2.

As is apparent from Table 2 above, the film prepared from the compound obtained by the present invention has a higher 5% mass loss temperature and a smaller wet thermal expansion coefficient than the film prepared from the conventionally known compound. I can see that

<Examples 41 and 42>
A composition in which the following silane coupling agent was added to the polyimide solution obtained in Example 21 was prepared and applied onto glass and dried in the same manner as in Example 21.
About the obtained film, the adhesiveness test with glass was measured and the result was put together in Table 3.
Adhesion test: The surface of the film was scratched with a cutter according to JIS K-5400 to make 100 squares of 1 mm square, and cellophane adhesive tape (Sekisui Chemical, # 252, 25 mm width, SP adhesive strength: 750 gf / 25 mm) Width) was adhered. One end of this tape is kept at a right angle to the surface of the substrate, and represents the number of base meshes that have been peeled off instantaneously. The state in which all 100 bases are peeled is 0, and the state in which all 100 bases are not peeled is 100.

<Comparative Examples 14-16>
In Example 41, a composition was prepared in the same manner as in Example 41 using the compounds synthesized in Comparative Examples 4, 6, and 7 instead of the compound obtained in Example 21, and applied onto glass. Dried.
About the obtained film, the adhesiveness test with glass was implemented, and the result was put together in Table 3.

As can be seen from Table 3 above, it can be seen that the composition prepared from the compound obtained according to the present invention has higher adhesion than the compositions prepared from conventionally known compounds and is superior.

  The acetylene compound provided by the present invention can provide a new thermosetting polymer or oligomer capable of improving the mechanical strength.

Claims (12)

A condensate or polycondensate obtained by reacting at least two compounds represented by the following general formula (1) with G as a reactive group.
General formula (1)

(In the general formula (1), A ₀ , A ₁ , A ₂ , A ₃ and A ₄ each independently represents a single bond, a hydrocarbon group or a heterocyclic linking group. Ar represents an aromatic ring or a heteroaromatic ring. X ₀ , X ₁ , X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a single bond or a divalent linking group, and R ¹ represents a hydrogen atom, a hydrocarbon group, or a heterocyclic ring. A group or an alkylsilyl group, G represents —NHR ² , or —COOQ, R ² represents a hydrogen atom or a hydrocarbon group, Q represents a metal element that can form a hydrogen atom, a hydrocarbon group, or a salt, or Represents organic ammonium, a ₁ , m, n ₁ and n ₂ each independently represents an integer of 1 to 5. b ₁ , b ₂ and b ₃ each independently represents an integer of 0 or more.) 2. The condensate or polycondensate according to claim 1, wherein in the general formula (1), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group, a heterocyclic group, or an alkylsilyl group. 2. The condensate or polycondensate according to claim 1, wherein the two compounds are represented by the general formula (1), wherein one G is —NHR ² and the other G is —COOQ. In the general formula (1), Ar, A ₀ and A ₄ are benzene ring groups or phthalimide ring groups which may have a substituent, and b ₁ , b ₂ and b ₃ are 0, The condensate or polycondensate according to claim 1. 5. The condensation according to claim 4, wherein one of the compounds represented by the general formula (1) is G = —COOQ and m is 1, and the other is G = —NH ₂ and m is 2. object. 5. The condensation according to claim 4, wherein one of the compounds represented by the general formula (1) is G = —COOQ and m is 2, and the other is G = —NH ₂ and m is 1. object. The condensate according to claim 5 or 6, wherein Ar, A ₀ , and A ₄ in the general formula are unsubstituted. In the above general formula, X ₀ and X ₄ are selected from the group consisting of a single bond, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —CO—. The condensate according to claim 7, which is selected. A compound residue in which G = —NH ₂ and m is 2 in the general formula (1) as a part of the diamine compound in the main chain of the polymer comprising any of polybenzimidazole, polybenzoxazole, polyamide, polyester, and polyimide The polycondensate according to claim 1, further comprising a compound residue having m at 1 in the general formula (1). A compound residue in which m is 2 in the general formula (1) G = —COOQ as a part of the dicarboxylic acid compound on the main chain of the polymer composed of polybenzimidazole, polybenzoxazole, polyamide, polyester, or polyimide. 2. The polycondensate according to claim 1, wherein the polycondensate comprises a compound residue having m at 1 in the general formula (1).   A composition comprising at least the condensate or polycondensate according to any one of claims 1 to 10.   A cured product obtained by curing the composition according to claim 11.