JP2010077192A - Resin composition, cured article using the same, flexible copper-clad laminate plate, and flexible printed board - Google Patents

Abstract

An object of the present invention is to provide a resin composition having heat resistance and bending resistance. Moreover, it is providing the hardened | cured material using this resin composition, the flexible copper clad laminated board using this resin composition, and a flexible printed circuit board.
A resin composition comprising an ethynyl group-containing compound having the following general formula (3) as a structural unit and an epoxy compound:

(In General Formula (3), A ₀ represents a (l + m) -valent hydrocarbon group. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom. A ₁ is a single bond. Or R ₁ represents a hydrogen atom or a hydrocarbon group, Ar represents an (a + 1) -valent aryl group or aromatic heterocyclic group, and X ₀ and X ₁ are independently of each other. Represents a divalent linking group, a, l, m, and n each independently represents an integer of 1 to 5, except when m and n are both 1.
[Selection figure] None

Description

  The present invention relates to a novel resin composition. In particular, it relates to a cured product, a flexible copper-clad laminate and a flexible printed board using the resin composition.

  Epoxy resin compositions are mainly used for electronic materials such as semiconductors and devices such as IC and LSI, and printed boards, and are used in various electronic and electrical devices. In recent years, the market trend of electronic devices has been reduced in size, weight and performance, and in order to respond to this trend, the integration of semiconductor elements and pattern wiring has been increasing year by year.

  When these semiconductor elements are encapsulated or when a conventional epoxy resin composition is applied to a printed circuit board material, it must be rapidly placed in a high-temperature environment of 260 ° C. or higher in a solder dipping or solder reflow process during surface mounting. As a result, shrinkage occurs in the cured product of the resin composition, or moisture absorbed in the cured product explosively evaporates, and the stress causes cracks in the semiconductor device or on the semiconductor element, the lead frame, and the inner lead. There is a problem that peeling occurs at the interface between the plated portion and the cured product of the epoxy resin composition, and the electrical reliability is remarkably lowered. In order to cope with the thermal stress at the time of mounting, a method of improving the strength of the cured product of the resin composition by using a low-viscosity resin component and highly filling it with an inorganic filler has been made. The flexibility was impaired, and the bending resistance tended to be inferior.

  In addition, as a resin component, a technique of reducing water absorption of a cured product by using a crystalline epoxy compound such as biphenyl type epoxy or a dicyclopentadiene-modified phenol type epoxy compound has been used. However, an epoxy resin composition using these epoxy resins has a glass transition temperature of a cured product lower than that of the conventional one, and is inferior in reliability in a high temperature and high humidity environment. In particular, a solder described in JIS C6471 In the heat resistance test, there was a problem that blistering and peeling were likely to occur in a solder heat resistance test exceeding 260 ° C.

In order to solve such a problem, a technique for blending an epoxy resin with a thermosetting imide resin has been proposed (see, for example, Patent Documents 1 and 2). However, although these proposed resin compositions are excellent in solder heat resistance, they have low adhesive strength with copper foil and base film, and when used as an adhesive around a flexible printed circuit board, the durability is inferior. There existed a subject that peeling will arise between copper foils in a flexibility test.
JP 2000-239488 A JP 2005-281428 A

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a thermosetting resin composition having high solder heat resistance and bending resistance, which is suitable for use as a flexible substrate. And

As a result of intensive studies in view of the above circumstances, the present inventors have found that the above-described problems of the present invention can be solved by the following means.
<1> A resin composition containing an epoxy compound and a compound having an ethynyl group having the following general formula (3) as a structural unit:

(In General Formula (3), A ₀ represents a (l + m) -valent hydrocarbon group. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom. A ₁ is a single bond. Or R ₁ represents a hydrogen atom or a hydrocarbon group, Ar represents an (a + 1) -valent aryl group or aromatic heterocyclic group, and X ₀ and X ₁ are independently of each other. Represents a divalent linking group, a, l, m, and n each independently represents an integer of 1 to 5, except when m and n are both 1.
<2> The resin composition according to <1>, wherein the compound having an ethynyl group is a compound represented by the following general formula (1):

(In general formula (1), A represents a tetrafunctional hydrocarbon group. B represents a linking group derived from general formula (3). R ₂ and R ₃ are hydrocarbon groups, and Represents a group represented by the following general formula (2), k is an integer of 1 or more);

(In General Formula (2), R ₁ , Ar, and a have the same meanings as in General Formula (3)).
<3> The resin composition according to <1> or <2>, wherein the compound having an ethynyl group has a molecular weight of 100,000 or less.
<4> A cured product obtained by heat-treating the compound having an ethynyl group on a copper foil, followed by heat treatment at 100 ° C to 400 ° C.
<5> A flexible copper-clad laminate in which the resin composition according to any one of <1> to <3> and a copper foil are laminated.
<6> A flexible printed board obtained by processing the flexible copper-clad laminate of <5>.

The resin composition of the present invention has thermosetting properties, high adhesive strength with a copper foil or a base film, and excellent solder heat resistance. Furthermore, it is rich in flexibility and has high strength against physical deformation of bending such as a bending resistance test.
The flexible copper-clad laminate to which the resin composition of the present invention is applied has a sufficiently strong adhesion strength with a copper foil or a base film, and a flexible printed board using this flexible copper-clad laminate is a solder during reflow soldering. It has good heat resistance and excellent bending resistance.

Hereinafter, the present invention will be described in more detail.
[Compound having ethynyl group]
The compound having an ethynyl group (—C≡C—) used in the resin composition of the present invention will be described in detail.
The compound having an ethynyl group (—C≡C—) of the present invention is a compound having the following general formula (3) as a structural unit.

In general formula (3), A ₀ represents a (l + m) -valent hydrocarbon group. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom. A ₁ represents a single bond or a divalent hydrocarbon group. R ₁ represents a hydrogen atom or a hydrocarbon group. Ar represents an (a + 1) -valent aryl group or an aromatic heterocyclic group. X ₀ and X ₁ each independently represent a divalent linking group. a, l, m, and n each independently represents an integer of 1 to 5. However, the case where m and n are both 1 is excluded.

  Preferably, the compound having the ethynyl group is a compound represented by the following general formula (1).

In general formula (1), A represents a tetrafunctional hydrocarbon group. B represents a linking group derived from the general formula (3). R ₂ and R ₃ are hydrocarbon groups, at least one of which represents a group represented by the following general formula (2). k is an integer of 1 or more.

In general formula (2), R ₁ , Ar, and a have the same meaning as in general formula (3).

  Preferably, the molecular weight of the compound having an ethynyl group is 100,000 or less.

R ₂ and R ₃ are aliphatic or aromatic hydrocarbon groups, at least one of which is a group represented by the general formula (2). When the group is not a group represented by the general formula (2), the structure is not particularly limited, but an aromatic group such as an alkyl group, an alkenyl group, a phenyl group or a naphthyl group, and these Those substituted with halogen or other hydrocarbon groups can be used.

The hydrocarbon group represented by A is a tetrafunctional hydrocarbon group, which may be unsubstituted or optionally substituted, and may be cyclic or acyclic.
Hereinafter, the tetrafunctional hydrocarbon group will be described. In the present invention, in order to clarify the explanation and facilitate understanding, the hydrocarbon group name is shown as the name of the compound. The position of the tetrafunctional bond may be any position and is not particularly limited. Specific examples include benzene, naphthalene, biphenyl, diphenyl ether, benzophenone, diphenylsulfone, diphenylmethane, 2,2'-diphenylpropane, aromatic diesters, cyclohexane, cyclopentane, cyclobutane, and their halogens and hydrocarbons. Various derivatives substituted with a group can be used, and specific monomers (tetracarboxylic acid anhydrides) that can be used in the present invention will be described later.

k is an integer of 1 or more, preferably 2 or more, more preferably an integer of 3 or more.
a is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2.

  B is a linking group derived from a structural unit represented by the following general formula (3).

In general formula (3), A ₀ represents a (l + m) -valent hydrocarbon group. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom. A ₁ represents a single bond or a divalent hydrocarbon group. Ar, R ₁ and a are as defined in general formula (2). X ₀ and X ₁ each independently represent a divalent linking group. l, m, and n each independently represent an integer of 1 or more and 5 or less. However, the case where m and n are both 1 is excluded.

The (l + m) -valent hydrocarbon group represented by A ₀ may be unsubstituted or further substituted, and may be cyclic or acyclic. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom.
Next, it will be described in detail represented by (l + m) valent hydrocarbon group A _0, for convenience of description, names hydrocarbon group with monovalent group name. Further, in the case of higher order, the corresponding higher order group is shown based on each monovalent group.
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 (for example, propenyl, butenyl, etc.) include alicyclic groups such as cycloalkyl groups (for example, cyclopentyl, cyclohexyl, menthyl, etc.), cycloalkenyl groups (for example, cyclohexenyl), and alicyclic polycyclic groups. (For example, bornyl, norbornyl, decalinyl, adamantyl, diamantyl and the like).
Examples of the aromatic ring include benzene, naphthalene, fluorene, anthracene, indene, indane, and biphenyl.

  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 acylamino group having 1 to 20 carbon atoms (for example, acetylamino, N-methylacetylamino, propionylamino) And a hydrocarbon group having a structure substituted at an arbitrary position with an aryl group having 6 to 20 carbon atoms (for example, phenyl, naphthyl, etc.), a hydroxyl group, a silyl group, and the like.

Among these, as A ₀ , (l + m) -valent alkyl group, cycloalkyl, alicyclic polycyclic group, benzene, naphthalene, and biphenyl are preferable from the viewpoint of obtaining a high tensile elastic modulus and a high glass transition point. (L + m) -valent alkyl group, cyclohexyl, norbornyl, adamantyl and benzene are more preferable, and benzene is particularly preferable from the viewpoint of availability of raw materials and ease of production.

A ₁ represents a (n + 1) -valent unsubstituted or optionally substituted cyclic or non-cyclic hydrocarbon group, a single bond.
Next, the (n + 1) -valent hydrocarbon group represented by A ₁ will be described in detail. For convenience of description, the hydrocarbon group name is indicated by the name of a monovalent group. Further, in the case of higher order, the corresponding higher order group is shown based on each monovalent group.
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, decalinyl, adamantyl, diamantyl, etc.) can be mentioned. Examples of the aromatic ring include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like.

  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 acylamino group having 1 to 20 carbon atoms (for example, acetylamino, N-methylacetylamino, propionylamino) And a hydrocarbon group having a structure substituted at an arbitrary position with an aryl group having 6 to 20 carbon atoms (for example, phenyl, naphthyl, etc.), a hydroxyl group, a silyl group, and the like.

Among these, high tensile modulus, in view of the high glass transition temperature can be obtained, as the A _1, (n + ₁₎ valent alkyl group, a cycloalkyl, an alicyclic polycyclic group, a benzene, naphthalene, biphenyl are preferred In view of availability of raw materials and ease of production, a single bond is particularly preferable.

Ar represents an (a + 1) -valent optionally substituted aromatic group or heterocyclic group.
Next, it will be described in detail represented by (a + 1) -valent hydrocarbon group in A _r, for convenience of description, names hydrocarbon group with monovalent group name. Further, in the case of higher order, the corresponding higher order group is shown based on each monovalent group.
Examples of aromatic rings include benzene, indene, indane, naphthalene, biphenyl, and tetralin. , Benzimidazole, benzothiazole, quinoxaline, carbazole and the like.

  Among these, benzene, indene, indane, naphthalene, and biphenyl are used as aromatic rings, and pyridine, pyrimidine, and triazine are used as heterocycles from the viewpoint of obtaining high tensile modulus and high heat resistance (glass transition point). , Indole, quinoline, purine, benzimidazole, benzothiazole, quinoxaline, carbazole and the like are preferable, benzene, biphenyl, or naphthalene is preferable as the aromatic ring, and pyridine, triazine, indole, or quinoline is more preferable as the heterocycle . In view of availability of raw materials and ease of production, benzene is particularly preferable.

  The aromatic ring or heterocycle 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-alkylureate 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′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N— Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group 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, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, dialkylphosphono group, A diarylphosphono group, Alkylaryl phosphono group, monoalkyl phosphono group, monoaryl phosphono group, dialkyl phosphonooxy group, diaryl phosphonooxy group, alkylaryl phosphonooxy group, monoalkyl phosphonooxy group, monoaryl phosphonooxy 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, and phosphate Natofeniru group, and the like can be mentioned. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group. 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, and acylamino Group (acetylamino group).

  Among these, from the viewpoint of availability of raw materials and ease of production, as Ar, (a + 1) valent halogen atom, C 1-8 alkyl group, cycloalkyl group, alkoxy group, acyloxy group, acylamino group Preferred are aryl groups having 6 to 10 carbon atoms, aryloxy groups, aralkyl groups, aralkyloxy groups, hydroxy groups, cyano groups, or unsubstituted benzene, biphenyl, naphthalene, pyridine, triazine, indole, or quinoline. A + 1-valent chloro atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an acyloxy group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group, a hydroxy group, a cyano group, or an unsubstituted benzene, Biphenyl, pyridine, or triazine is more preferable. Alkyl group, an alkoxy group, an acyloxy group, an aryloxy group having 6 to 10 carbon atoms, substituted with an aralkyl group, or a cyano group, or an unsubstituted benzene, biphenyl is more preferable. In particular, (a + 1) -valent unsubstituted benzene and biphenyl are preferable.

X ₀ represents a divalent linking group, but its structure is not particularly limited. For example, specifically, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR—, One or more selected from the group consisting of —OCSO—, —SO—, —SO ₂ —, —O—, —S—, —NR—, —CO—, —CS—, and a single bond. Can be used in combination. Among them, since a high tensile elastic modulus and high heat resistance (glass transition temperature) can be obtained, X ₁ is a single bond, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—. Or -NRCONR- is more preferable, and -OCO-, -COO-, -NRCO-, or -CONR- is particularly preferable.

X ₁ represents a divalent linking group, but its structure is not particularly limited. For example, specifically, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, —NRCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR—, One or more selected from the group consisting of —OCSO—, —SO—, —SO ₂ —, —O—, —S—, —NR—, —CO—, —CS—, and a single bond. Can be used in combination. Among them, since a high tensile elastic modulus and high heat resistance (glass transition temperature) can be obtained, X ₁ is a single bond, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—. Or -NRCONR- is more preferable, and a single bond is particularly preferable.

R ¹ represents a hydrogen atom, an unsubstituted or an optionally substituted cyclic hydrocarbon group or an acyclic hydrocarbon group, and the solvent solubility of a polymer containing an acetylene compound as a structural unit is excellent, In view of ease of thermosetting, a hydrogen atom, an unsubstituted or optionally substituted cyclic aliphatic hydrocarbon group or an acyclic aliphatic hydrocarbon group is preferable. From the viewpoint of ease, a hydrogen atom is particularly preferable.

  Aromatic rings include benzene, indene, indane, naphthalene, biphenyl, tetralin, and heterocycles include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, oxazole, thiazole, imidazole, pyrimidine, triazine, indole, quinoline, purine , Benzimidazole, benzothiazole, quinoxaline, carbazole and the like.

  As an unsubstituted cyclic or acyclic aliphatic hydrocarbon group, a linear or branched aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an alicyclic group having 6 to 20 carbon atoms. A polycyclic group is mentioned. 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, or hexadecyl). ), Alkenylene groups (eg, propenyl, butenyl, etc.), etc., and alicyclic groups such as cycloalkyl groups (eg, cyclopentyl, cyclohexyl, menthyl, etc.), cycloalkenyl groups (eg, cyclohexenyl, etc.), etc. Examples of the formula polycyclic group include bornyl, norbornyl, decalinyl, adamantyl, and diamantyl.

  Examples of the optionally substituted cyclic or acyclic aliphatic hydrocarbon group include the above-mentioned unsubstituted cyclic or acyclic aliphatic hydrocarbon group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Or 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.), an acylamino group having 1 to 20 carbon atoms (eg, acetylamino, N-methylacetylamino, or propionylamino), an aryl group (eg, phenyl, naphthyl), a hydroxyl group, Hydrocarbon groups with a structure in which silyl groups are substituted at any position It is below.

l, m, and n each independently represent an integer of 1 or more. However, since it becomes difficult to incorporate into the target polymer, the case where both m and n are 1 is excluded. When l and m are each 2 or more, a plurality of R ¹ , Ar, X ₀ , X ₁ , and A ₁ may be the same or different from each other.

  From the viewpoint of obtaining a high tensile elastic modulus and high heat resistance (glass transition temperature), a, l, m, and n are each independently preferably 1-4 and (l + m) is preferably 3 or more, and a, l, m, and n are each independently preferably 1 to 3, and (l + m) is preferably 3 or more. In particular, from the viewpoint of availability of raw materials and ease of production, a, l, m, and n are each independently 1-2, and (l + m) = 3 is preferable.

  The monomer unit represented by the general formula (3) is preferably contained in an amount of 1 to 100% of the linking group B present in the imide compound having the ethynyl group. From the viewpoint of improving chemical resistance, 20% to 100% is more preferable.

  Specific examples of the compound represented by the general formula (3) are shown below, but the present invention is not limited thereto.

The compound having an ethynyl group in the present invention may be a monomer such as the compound described in the previous section, or may be a polymer. The polymer may be an addition polymer or a condensate.
The basic skeleton of the polymer may be either aromatic or aliphatic, and may contain silicone, fluorene, etc. in the main chain or side chain, but is preferably aromatic.

  The polymer having an ethynyl group in the present invention is not particularly limited except that the ethynyl group is an essential component, but preferably a monomer having an ethynyl group represented by the general formula (3) and a molecule -COOH group, -COOR 'group, -CSOH group, -COSH group, -CSH group, -NCO group, -NCO group, a compound having two of -NSO groups, an acid anhydride, and an amino group in the molecule It can be prepared by reacting with two or more substituted or unsubstituted hydrocarbon compounds (amine compounds), acid anhydrides, polyol compounds, and, if necessary, aldehyde compounds.

  As a compound containing an ethynyl group constituting the present invention, in addition to the monomer represented by the general formula (3), another monomer containing an ethynyl group may be introduced as a structural unit as necessary. Is possible. As such a monomer, an acid anhydride containing an ethynyl group or an amine compound containing an ethynyl group can be used. By using these monomers, it is possible to introduce an ethynyl group at the end of a compound structure containing an ethynyl group.

  Examples of acid anhydrides containing such an ethynyl group include 4-ethynyl phthalic anhydride, 3-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 3-phenylethynyl phthalic anhydride, and ethynylnaphthalenedicarboxylic acid anhydride. , Phenylethynylnaphthalenedicarboxylic anhydride, ethynylanthracene dicarboxylic anhydride, phenylethynylanthracene dicarboxylic anhydride, 4-naphthylethynyl phthalic anhydride, 3-naphthylethynyl phthalic anhydride, naphthylethynylnaphthalenedicarboxylic anhydride, naphthylethynyl Anthracene dicarboxylic anhydride, 4-anthracenyl ethynyl phthalic anhydride, 3-anthracenyl ethynyl phthalic anhydride, anthracenyl ethynyl naphthalene dicarboxylic anhydride, anthracenyl ethynyl anthracene Include such dicarboxylic anhydride, hydrogen atoms on these aromatic, alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, may be substituted with a halogen atom. In consideration of availability, 4-phenylethynyl phthalic anhydride and 4-ethynyl phthalic anhydride are preferably used. These may be used alone or in combination of two or more.

  Examples of amine compounds containing such an ethynyl group include 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, 4-phenylethynylaniline, 3-naphthylethynylaniline, 4-naphthylethynylaniline, 3 -Anthracenyl ethynyl aniline, 4-anthracenyl ethynyl aniline, etc. are mentioned, and the hydrogen atom on the aromatic is substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, or a halogen atom. May be. In view of availability, it is desirable to use 3-aminophenylacetylene, 4-aminophenylacetylene, 3-phenylethynylaniline, and 4-phenylethynylaniline. These may be used alone or in combination of two or more.

[Compound having any two of -CHO group, -COOH group, -COOR 'group, -CSOH group, -COSH group, -CSSH group, -NCO group, -NSO group in the molecule]
The compound which has either -CHO group, -COOH group, -COOR 'group, -CSOH group, -COSH group, -CSSH group, -NCO group, -NSO group in the molecule | numerator which concerns on the composition of this invention As 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, , 3-diacetylbenzene, 1,4-diacetylcyclohexane, etc.), dicarboxylic acid (For example, terephthalic acid, 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′-dimethyl Rubiphenyl 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),

Diesters (for example, isophthalic acid methyl ester, terephthalic acid dimethyl ester), dithiocarboxylic acids (for example, hexanedithio-s-acid, hexanedithiodicarboxylic acid), dicarbamates (for example, N-fe xy), thiocarbamine sun diesters (For example) diisocyanates (for example tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate), dithioisocyanates (for example 1,4-phenylene dithioisocyanate, 1,3-phenylene dithioisocyanate, 1,4-cyclohexyl diisothiocyanate, 5-methyl-1,3-phenylenedithioisocyanate) or the like can be used alone or in combination of two or more.

  Although the amine compound which can be used for the synthesis | combination of the polymer which has an ethynyl group in this invention is not specifically limited, A diamine compound is desirable from a viewpoint that a high tensile elasticity modulus and high heat resistance (glass transition temperature) are obtained. 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'-dichloro-4,4'- Aminobiphenyl, 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′-diaminebiphenyl, 3,3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2, 2′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 2,2′-bis (trichloro) Methyl) -4,4'-diamine, 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 sulfide, 3,3'-diaminodiphenyl sulfone, 3,4 -Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis (4-amino-3-methylphenyl) sulfone, bis (4-amino-3-chlorophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (5-fluoro-4aminophenyl) 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-aminophenyl) sulfone, Bis (5-trifluoromethyl-3-aminophenyl) sulfone, bis (5-trichloro) Methyl-4-aminophenyl) sulfone, bis (5-trichloromethyl-3-aminophenyl) sulfone, bis (5-tribromomethyl-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-minophenyl) -1,1,1,3,3,3-hexafluoroapropane, 2,2-di (4-aminophenyl) -1,1,1,3 , 3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -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-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene Zen, 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-aminophenoxy) 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) phenyl] 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 Hong, bis [4- (5-trifluoromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5-trichloro Methyl-4-aminophenoxy) phenyl] sulfone,

Bis [4- (5-trichloromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5-tribromomethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-tribromomethyl- 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] -1,1,1,3,3,3-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-amino Phenoxy) -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) benzene Zoyl] 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, '-te Tramethyl-1,1′-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-amino) Propyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, diaminopolysiloxane and the like can be used alone or in combination of two or more.

In the amine compound exemplified above, 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. It may be a substituted diamine. 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 synthesis | combination of the polymer which has an ethynyl group in 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′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3 3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (2,3-carboxyphenyl) 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) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, , 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-bis (3,4-dicarboxyphenyl) fluoric acid dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric acid dianhydride, 4,4′-biphenylenebis (Trimellitic acid monoester 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) Product), 1,4-naphthalene bis (trimellitic acid monoester anhydride), 2,6-naphthalene bis (trimellitic acid monoester anhydride), 2,2-bis [4- (trimellitic acid mono) Ester 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- Carboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 1- (2,3-dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,3 3-tetramethyldisiloxane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8- Naphthalenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and the like can be used alone or in combination of two or more.

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, a part of the acid anhydride may be replaced with hexacarboxylic dianhydrides and octacarboxylic dianhydrides.

  The polyol compound that can be used when a polyol is used for the synthesis of the polymer having an ethynyl group in the present invention is not particularly limited, but 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, and 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 compound containing the ethynyl group which comprises this invention, Specifically, the following are mentioned. 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 compound containing an ethynyl group constituting the present invention may contain dicarboxylic acids, diesters, diureas, or diisocyanates as other structural units.

<Polymerization method>
The method for producing a polymer having an ethynyl group in the present invention is not particularly limited, and the monomer having an ethynyl group explained in the previous section and a monomer or a monomer mixture such as the above diamine or acid anhydride, Can be used.

For example, as a method of producing a polymer having an ethynyl group in the present invention, a method of ring-closing and imidizing after passing through a polyamic acid, a method of passing through a polyisoimide, and further passing through a polyamic acid after imidizing a part thereof However, there is no particular limitation on the production of a compound containing an ethynyl group 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, and crotonic acid Etc.

The polycondensation accelerator is used in an amount of 1 mol% to 50 mol%, preferably 5 mol% to 35 mol%, based on the diamine or diamine component. By using these polycondensation accelerators, Since the reaction temperature can be set low, not only the side reaction due to heating, which is often caused by coloring, can be prevented, but also 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.

<Polymerization solvent>
Examples of the solvent that can be used for the production of the compound containing an ethynyl group constituting the present invention include ureas such as tetramethylurea and N, N-dimethylethylurea, dimethyl sulfoxide, diphenylsulfone, and tetramethylsulfone. Such sulfoxides or sulfones, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N′-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyllactone Amides such as hexamethylphosphoric triamide, aprotic solvents such as phosphorylamides, 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, etc. ethers such as p- cresol methyl ether. 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.

The molecular weight of the compound having an ethynyl group used in the present invention is preferably 100,000 or less for the purpose of optimizing the solution viscosity. More preferably, they are 500 or more and 80,000 or less, More preferably, they are 1000 or more and 50,000 or less.
When the molecular weight exceeds 100,000, the solution viscosity of the compound having an ethynyl group is increased, and it is difficult to form a thin film.
When the molecular weight is less than 500, the mechanical strength of the resulting polymer is lowered and weak against external impacts and the like, which is not preferable.

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

(Epoxy compound)
The epoxy compound used in the present invention is a compound having at least one epoxy group in the molecule, and unsaturated glycidyl esters represented by the following general formulas (I), (II) and (III): Unsaturated epoxy compounds such as unsaturated glycidyl ethers, epoxy alkenes, and p-glycidyl styrenes.

  In the general formulas (I), (II), and (III), R represents a C2-C18 hydrocarbon group having an ethylenically unsaturated bond, and R 'is a hydrogen atom or a methyl group.

  Specifically, N-glycidyl phthalimide, N-glycidyl tetrahydrophthalimide, phenyl glycidyl ether, p-butylphenyl glycidyl ether, styrene oxide, neohexene oxide are exemplified as an epoxy compound having one epoxy group in the molecule, Moreover, as an epoxy compound which has two or more epoxy groups in a molecule | numerator, diepoxide of both terminal olefins, such as 1,2,3,4-diepoxybutane and 1,2,7,8-diepoxyoctane, ethylene Diglycidyl ether of glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polytetramethylene glycol, triglycidyl ether of trimethylolpropane, pentaerythris Polyglycidyl ethers of polyols such as tetraglycidyl ether of toll, hydroquinone diglycidyl ether, resorcin diglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1 , 3-bis (N, N-diglycidylaminomethyl) cyclohexane and other polyglycidyl amines, diglycidyl phthalate, diglycidyl hexahydrophthalate and other glycidyl esters, glycidyl acrylate and glycidyl methacrylate and other acrylic monomers. And epoxy compounds. Also, epoxy resins such as bisphenol A type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin can be used. As such bisphenol A type epoxy resin, Epicoat 827 (trade name, Yuka Shell Epoxy Co., Ltd., epoxy equivalent 180-190), Epicoat 1001 (Japan Epoxy Resin Co., Ltd., epoxy equivalent 450-500), Epicoat 1010 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 3000-5000), and as a phenol novolac type epoxy resin, Epicoat 152 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 172-179) is cresol. Examples of the novolak type epoxy resin include Epicoat 180S65 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 205-220), and these are used alone or in combination of two or more.

  The epoxy equivalent of the epoxy compound is preferably 10,000 or less, and more preferably 1,000 or less, because higher chemical resistance, heat discoloration improving effect, and silver generation improving effect can be obtained.

[Curing agent]
In the resin composition of the present invention, a curing agent can be blended for the purpose of promoting the curing of the epoxy compound. The curing agent that can be used can be used without particular limitation as long as it can be used for curing the above epoxy compound. For example, an aliphatic amine curing agent, an alicyclic amine curing agent, Aromatic amine curing agents, acid anhydride curing agents, dicyandiamide, boron trifluoride amine complex salts, imidazole compounds and the like can be mentioned. These may be used alone or in combination of two or more. Specific examples of curing agents that can be used include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 1 -Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4- Illustrative are imidazole curing agents such as diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-S-triazine, and these can be used alone or in combination of two or more.

  Although the compounding quantity of the hardening | curing agent based on this invention can be defined according to the compounding quantity of an epoxy compound, it is preferable to mix | blend in the ratio of 0.1-50 mass parts with respect to 100 mass parts of epoxy resins, for example.

[solvent]
Although it does not specifically limit as another structural component which comprises the resin composition of this invention, A solvent, organic or inorganic particle | grains, organic or inorganic fiber, another organic or inorganic polymer, etc. are mentioned. From the viewpoint of easy handling and curing such as coating and coating, a solvent is preferable. Thus, a preferred embodiment of the composition of the present invention is a solution.

  Solvents that can be used in the solution that is a preferred embodiment are not particularly limited, and examples thereof include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone. Solvent (eg sulfolane) sulfoxide solvent (eg dimethyl sulfoxide), ureido solvent (eg tetramethyl urea), ether solvent (eg dioxane, cyclopentyl methyl ether), ketone solvent (eg acetone, cyclohexanone, methyl ethyl ketone), carbonization Hydrogen-based solvents (for example, toluene, xylene, n-decane), halogen-based solvents (for example, tetrachloroethane, chlorobenzene, methylene chloride, chloroform), pyridine-based solvents (for example, pyridine, γ-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, 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.

[Composition ratio]
The mixing ratio of the imide compound having an ethynyl group and the epoxy compound in the binder resin is not particularly limited, but the imide compound / epoxy compound having an ethynyl group from the viewpoint of heat resistance, chemical resistance, and low dielectric constant. Is a mass ratio of 5/95 to 95/5, more preferably 10/90 to 90/10. More preferably, it is 20 / 80-80 / 20.
In general, the binder resin is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass in the resin composition. Is preferred.

  When the composition ratio is in the above range, a low dielectric constant resin composition having heat resistance and chemical resistance can be obtained. Moreover, when the composition ratio is not within the above range, the resin composition has a reduced physical property such as heat resistance, chemical resistance, or low dielectric constant.

[Auxiliary]
In addition to the binder resin and the solvent, a filler, an antioxidant, a UV absorber, a dye, a pigment, an antistatic agent, a flame retardant, and the like may be blended in the resin composition of the present invention. Further, other polymers can be used in combination as long as the performance is not impaired.
The amount added is usually about 5% to 95% by weight based on the resin composition, but preferably about 10% to 90% by weight. More preferably, it is desirable to blend approximately 20% by mass to 80% by mass.

  The viscosity of the resin composition is not particularly limited, but considering workability such as coating, the viscosity at 30 ° C. measured with a cone plate viscometer is preferably 1000 mPa · s to 5000 mPa · s. . Since this viscosity depends on the molecular weight of the binder resin, it is preferable to adjust the slurry viscosity within the above range by appropriately adjusting the amount of the solvent according to the molecular weight of the resin used.

[Heat-treated cured product]
A cured product can be formed by heat-treating the resin composition of the present invention at 100 ° C to 400 ° C.
The resin composition of the present invention can be cured by causing a crosslinking reaction by heat treatment. The compound having an ethynyl group according to the present invention undergoes an addition reaction between ethynyl groups, and is cured by a ring-opening reaction between epoxy groups when the epoxy compound is contained in the resin composition of the present invention.

<Curing conditions for forming a cured product>
The conditions necessary for curing the resin composition of the present invention are not particularly limited, but a method of adding electromagnetic waves such as ultraviolet rays and visible light, electron beams, heat, radicals, acids, bases, and the like can be used. Particularly, a curing reaction by heat is preferable from the viewpoint of not using an additive and excellent reaction efficiency.

  When performing the curing reaction by heat, the preferable temperature condition is preferably 100 ° C. to 400 ° C., more preferably 150 ° C. to 350 ° C., because the reaction efficiency is high and the obtained cured product has excellent mechanical properties. More preferably, it is 200 degreeC-300 degreeC. If the treatment temperature at the time of curing is less than 100 ° C., the curing reaction becomes insufficient, and if it exceeds 400 ° C., the resin composition tends to be thermally decomposed, which is not preferable.

  Since the cured product obtained by the present invention has a crosslinked structure, it is excellent in mechanical properties and thermal properties, and is also excellent in chemical stability such as solvent resistance.

[Flexible copper-clad laminate]
A flexible copper-clad laminate can be formed by laminating the resin composition of the present invention and a copper foil.
The flexible copper-clad laminate of the present invention is provided with an adhesive layer made of the resin composition according to the present invention on one side or both sides of a polymer film, and copper is attached to one side or both sides of the polymer film via the adhesive layer. It is formed by laminating foil. By using the polymer film and the adhesive layer, it is possible to obtain a flexible copper-clad laminate having excellent mechanical strength, heat resistance, workability, and adhesiveness, and particularly excellent solder heat resistance. be able to.

<Polymer film>
Next, the polymer film that can be used for the flexible copper-clad laminate of the present invention will be described. In the flexible copper-clad laminate of the present invention, since the polymer film forms an insulating layer together with the adhesive layer, it is necessary to prevent the insulating layer from becoming extremely thin and to realize a uniform insulating layer thickness.

  As the polymer film that can be used for the rexible copper-clad laminate of the present invention, a material excellent in dimensional stability, heat resistance and mechanical properties is preferable. For example, polyolefin such as polyethylene, polypropylene, polybutene; polyester such as ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, ethylene-2,6-naphthalate; and nylon-6, nylon-11, aromatic Polyamide, polyamideimide resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyketone resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, fluororesin, polyarylate resin, liquid crystal polymer resin, polyphenylene ether resin, polyimide Examples thereof include a resin film.

  Here, the polymer film preferably has a tensile elastic modulus of 5 GPa or more, and more preferably 6 GPa or more, in order to impart sufficient rigidity to the flexible copper-clad laminate of the present invention.

  For the formation of small diameter via holes, the thickness of the polymer film is preferably 50 μm or less, more preferably 35 μm or less, and even more preferably 25 μm or less. Preferably it is 1 micrometer or more, More preferably, it is 2 micrometers or more. A polymer film that is not so thick and ensures sufficient electrical insulation is desirable.

Furthermore, since thermal stability is required when processing a flexible copper-clad laminate, dimensional stability is desired for the polymer film. Therefore, a polymer film having a linear expansion coefficient of 2.0 × 10 ⁻⁵ / ° C. or less, more preferably 1.5 × 10 ⁻⁵ / ° C. or less, and further preferably 1.0 × 10 ⁻⁵ / ° C. or less. desirable. Furthermore, a polymer film having a low water absorption rate is desirable so as not to cause defects such as blistering due to heat during processing. The water absorption rate of the polymer film measured according to ASTM-D570 depends on the thickness even in the same composition, but the water absorption rate of the film having a thickness of 25 μm is preferably 1.5% or less, more preferably 1.2%. A polymer film having the following composition is desirable.

  A polyimide film is mentioned as a film satisfying the above-mentioned various characteristics. A polyimide film is obtained from the polyamic acid polymer solution which is the precursor. This polyamic acid polymer solution can be produced by a method commonly used by those skilled in the art. That is, one or more tetracarboxylic dianhydride components and one or more diamine components are used in substantially equimolar amounts and polymerized in an organic polar solvent to obtain a polyamic acid polymer solution.

  Typical tetracarboxylic dianhydride components used in the production of polyimide films include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4 ′ -Oxydiphthalic anhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4′-hexafluoroisopropylide Diphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid mono Ester anhydride), and aromatic tetracarboxylic dianhydrides such as p-phenylenediphthalic anhydride.

Among these tetracarboxylic dianhydrides, for obtaining a polyimide film having a tensile modulus of 5 GPa or more, a linear expansion coefficient of 2.0 × 10 ⁻⁵ / ° C. or less, and a water absorption of 1.5% or less. When a preferable combination is exemplified, as the tetracarboxylic dianhydride, 0 to 80 mol% of pyromellitic dianhydride and 100 to 20 mol% of p-phenylenebis (trimellitic acid monoester anhydride) may be used. Can be mentioned.

  In addition, the combination of the tetracarboxylic dianhydride described here shows only one specific example for obtaining a polyimide film suitable for the polymer film constituting the flexible copper-clad laminate of the present invention. It is possible to adjust the characteristics of the polyimide film by changing the combination of tetracarboxylic dianhydride to be used and the use ratio, not limited to these combinations.

  On the other hand, as the diamine component, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) Phenyl) sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenyl Sulfone, 9,9-bis (4-aminophenyl) fluorene, bisaminophen Xyloketone, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,3-phenylenebis (1-methylethylidene)) bisaniline, metaphenylenediamine, paraphenylene Aromatic diamines such as diamine, 4,4'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, or other fats Group diamines can be mentioned.

Among these diamine components, a preferable combination for obtaining a polyimide film having a tensile elastic modulus of 5 GPa or more, a linear expansion coefficient of 2.0 × 10 ⁻⁵ / ° C. or less, and a water absorption of 1.5% or less is exemplified. Then, the case where 20-80 mol% of a diamine component and 80-20 mol% of 4,4'-diaminodiphenyl ether are used for paraphenylenediamine and / or 4,4'-diaminobenzanilide is mentioned.

  In addition, the combination of the diamine component described here shows one specific example for obtaining the polyimide film suitable for the polymer film which comprises the flexible copper clad laminated board of this invention. It is possible to adjust the characteristics of the polyimide film by changing the combination of diamine components to be used and the ratio of use without being limited to these combinations.

  When a polyimide film is used as the polymer film constituting the flexible copper-clad laminate of the present invention, the number average molecular weight of the precursor polyamic acid is preferably 10,000 to 1,000,000. If the average molecular weight is less than 10,000, the resulting film may become brittle. On the other hand, when the number average molecular weight exceeds 1,000,000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, becomes too high and handling may be difficult.

  It is also possible to form a composite polyimide film by adding various organic additives, inorganic fillers, or various reinforcing materials to polyamic acid.

  Examples of the organic polar solvent used for the formation reaction of the polyamic acid copolymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; Phenol, o-, m-, or p -Phenol solvents such as cresol, xylenol, halogenated phenol, catechol; or hexamethylphosphoramide, γ-butyrolactone, and the like. These are preferably used alone or as a mixture. Furthermore, aromatic hydrocarbons such as xylene and toluene may be partially mixed in the solvent.

  Further, it is desirable from the viewpoint of handling that the polyamic acid copolymer is dissolved in the organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 30% by weight.

  In order to obtain a polyimide film from this polyamic acid copolymer solution, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent may be used, but the polyimide film produced by the chemical method is used. This is preferable because it has excellent mechanical properties such as elongation and tensile strength.

  The example about preparation of the polyimide film by a chemical method is demonstrated below. A solution obtained by adding a stoichiometric or higher amount of a dehydrating agent and a catalytic amount of a tertiary amine to the polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. Drying at a temperature of ℃ or less for about 5 minutes to 90 minutes gives a self-supporting polyamic acid film. Next, this is peeled off from the support and the end is fixed. Thereafter, it is imidized by gradually heating to about 100 ° C. to 500 ° C., and after cooling, fixing of the end portion is released to obtain a polyimide film. Examples of the dehydrating agent herein include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline.

In addition, the polymer film can be subjected to various surface treatments for the purpose of improving the adhesion with the adhesive layer.
For example, a method of forming a metal oxide adhesive layer on the surface of the polymer film by sputtering, plasma ion implantation, or the like on the surface of the polymer film using a metal oxide such as Cr, Ni, Ti, or Mo, a thermosetting resin , Methods of applying various organic substances such as thermoplastic resins, organic monomers and coupling agents as primers, methods of surface treatment with metal hydroxide, organic alkali, etc., methods of plasma treatment, corona treatment, methods of grafting the surface For example, a method of performing a surface treatment in the production stage of the polymer film can be used. The polymer film surface may be treated alone or in various combinations. Moreover, the said surface treatment method can be utilized also for improving adhesiveness with the contact bonding layer of the other surface side.

<Copper foil>
Although there is no restriction | limiting in particular in the copper foil used for the rexible copper clad laminated board of this invention, The thickness of copper foil is 12 micrometers or less in order to produce a pinch pitch circuit pattern, More preferably, it is 10 micrometers or less, More preferably, it is 5 micrometers or less. is there. A copper foil provided with a peeling carrier can also be used. In that case, the carrier for peeling is not particularly limited, and polyester foil such as polyethylene terephthalate, polycarbonate, release paper, and metal foil such as copper foil, aluminum foil, 42 alloy foil can be used. When using copper foil like this, it is preferable to use copper foil also for the carrier for peeling. Although there is no restriction | limiting in particular in the thickness of the carrier for peeling, Preferably they are 1 micrometer-100 micrometers, More preferably, they are 5 micrometers-50 micrometers.

<Method for producing flexible copper-clad laminate>
Hereinafter, the manufacturing method of a flexible copper clad laminated board is shown.
First, the resin composition of the present invention comprising an ethynyl group-containing compound and an epoxy resin is dissolved in a solvent to obtain a resin solution, which is then applied to the surface of the polymer film and dried to obtain a bonding sheet. Or after casting the resin solution obtained as mentioned above on a support body and removing a solvent to make a sheet, it can be bonded to a polymer film to obtain a bonding sheet. Next, the flexible copper-clad laminate of the present invention can be obtained by laminating a copper foil on both surfaces of the bonding sheet by a method such as pressing or roll heating. It is preferable to manufacture by a roll-to-roll system at the point which can manufacture a flexible copper clad laminated board efficiently.

  Moreover, it is also possible to use a protective film for the purpose of protecting the surface of the flexible copper-clad laminate of the present invention.

  The above-mentioned method for producing a flexible copper-clad laminate is an example, and any method within the range that can be carried out by those skilled in the art is possible.

  As described above, the flexible copper-clad laminate of the present invention has been described, but the present invention is not limited thereto, and various improvements, modifications, and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention. Needless to say, the present invention can be implemented in a modified form.

[Flexible printed circuit board]
The flexible printed board of the present invention is obtained by processing the copper-clad laminate. And this flexible printed circuit board forms a desired circuit pattern by etching in copper foil, and it becomes a flexible printed wiring board used for electrical connection of an electronic device or the like.

  Since the flexible printed circuit board of the present invention has high heat resistance, it is difficult to cause deformation in the solder bath and trouble of peeling between the copper and the resin, and has excellent bending resistance defined by JIS C5016, etc. It is suitable for a sliding mobile phone. In particular, by using the compound having an ethynyl group according to the present invention, it has been possible to use it in a region where it has not been achieved. In other words, when the heat resistance of the resin used is increased, the flex resistance of the flexible printed circuit board tends to decrease. On the contrary, when a soft resin is selected to improve the flex resistance, the heat resistance is increased. There was a tendency for the sex to decline.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

First, a synthesis example of a compound having an ethynyl group will be described.
Synthesis Example 1 Preparation of Compound 1 Containing Ethynyl Group In a 200 mL three-necked flask equipped with a stirrer, 0.018 mol of bis (4-aminophenyl) ether and N- (3′-ethynylphenyl) -3.5 -0.005 mol of diaminobenzamide (compound (1) -1), 0.004 mol of 3-ethynylaniline, and 110 mL of N-methyl-2-pyrrolidone were added, and the flask was dissolved while purging with nitrogen. While stirring at 23 ° C., 0.025 mol of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride was added as a solid to the mixture, and polymerization of polyamic acid started. The stirring was continued for 2 hours to complete the polymerization.
Thereafter, 0.05 mol of acetic anhydride and 0.005 mol of pyridine were added while stirring, and the mixture was stirred at room temperature for 1 hour and further at 60 ° C. for 3 hours to obtain a target solution of Compound 1 containing an ethynyl group. The weight average molecular weight measured by GPC was 7,400. Moreover, when the monomer unit represented by General formula (3) was computed, it was confirmed that 25% is contained in the compound.

Synthesis Example 2 Preparation of Compound 2 Containing Ethynyl Group In a 200 mL three-necked flask equipped with a stirrer, 0.018 mol of bis (4-aminophenyl) ether, 0.005 mol of m-phenylenediamine, 3-ethynylaniline Of 0.004 mol and N-methyl-2-pyrrolidone (110 mL) were added, and the inside of the flask was dissolved while purging with nitrogen. While stirring at 23 ° C., 0.025 mol of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride was added as a solid to the mixture, and polymerization of polyamic acid started. The stirring was continued for 2 hours to complete the polymerization.
Thereafter, 0.05 mol of acetic anhydride and 0.005 mol of pyridine were added while stirring, and the mixture was stirred at room temperature for 1 hour and further at 60 ° C. for 3 hours to obtain a target solution of Compound 2 containing an ethynyl group. The weight average molecular weight measured by GPC was 7,800.

Synthesis Example 3 Preparation of Imide Compound 3 Containing No Ethynyl Group In a 200 mL three-necked flask with a stirrer, 0.018 mol of bis (4-aminophenyl) ether, 0.004 mol of aniline, N-methyl-2- Pyrrolidone (110 mL) was added, and the flask was dissolved while purging with nitrogen. While stirring at 23 ° C., 0.025 mol of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride was added as a solid to the mixture, and polymerization of polyamic acid started. The stirring was continued for 2 hours to complete the polymerization.
Thereafter, 0.05 mol of acetic anhydride and 0.005 mol of pyridine were added with stirring, and the mixture was stirred at room temperature for 1 hour and further at 60 ° C. for 3 hours to obtain a target solution of imide compound 3 containing no ethynyl group. The weight average molecular weight measured by GPC was 7,200.

Synthesis Example 4 Preparation of Compound 4 Containing Ethynyl Group In the example described in Synthesis Example 1, N- (3′-ethynylphenyl) -3,5-diaminobenzamide (Compound (1) -1), 3-ethynyl Other than changing the amino compound to bis [4- (4-aminophenoxy) phenyl] sulfone and the acid anhydride to diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, leaving the aniline as it is. Was similarly polymerized and imidized, and the weight average molecular weight measured by GPC was 8,100. Moreover, when the monomer unit represented by General formula (3) was computed, it was confirmed that 25% is contained in the compound.

  The following epoxy compounds were prepared.

1) Epoxy compound 1: bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “Epicoat 837”)
2) Epoxy compound 2: Tetrabromobisphenol A type epoxy resin (“Epicoat 5050” manufactured by Japan Epoxy Resin Co., Ltd.)
3) Epoxy compound 3: Brominated phenol novolac type epoxy resin (“BREN-S” manufactured by Nippon Kayaku Co., Ltd.)
4) Epoxy compound 4: Cresol novolac type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “Epicoat 180S65”)

[Example 1]
(Preparation of resin composition)
60 parts of Compound 1 having an ethynyl group prepared in Synthesis Example 1, 40 parts of an epoxy compound (50/50 mixture by mass ratio of Epoxy Compound 1 and Epoxy Compound 2), and an imidazole compound (2HPZ-CN) as a curing catalyst 0.6 parts of Shikoku Kasei Kogyo Co., Ltd.) and a solvent N-methyl-2-pyrrolidone (NMP) were mixed at a ratio of solid content of 15% by mass to prepare a resin composition.

[Examples 2 to 7]
As in Example 1, 100 parts in total of the compound having an ethynyl group (shown in Table 1) and an epoxy compound (shown in Table 1), and an imidazole compound (2HPZ-CN, manufactured by Shikoku Chemicals Co., Ltd.) as a curing catalyst ) 0.6 part was blended with the composition shown in Table 1 and dissolved in NMP to prepare a resin composition having a solid content of 20% by mass.

[Comparative Examples 1-3]
Comparative Example 1: In Example 1, a resin composition containing only the compound 1 having an ethynyl group was prepared except for the epoxy compound.
Comparative Example 2: A resin composition containing only an epoxy compound was prepared in Example 1 except for a compound having an ethynyl group.
Comparative Example 3: A resin composition was prepared in Example 1 using the imide compound 3 having no ethynyl group instead of the compound 1 having an ethynyl group.

(Manufacture of flexible copper-clad laminates)
(1) Film production The resin composition (solution) obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was applied to a polyimide film (Kapton 50H, manufactured by Toray Du Pont Co., Ltd., 12.5 μm thickness) as a bar coater. The base film side adhesive layer was formed by coating at a thickness of 10 μm after removing the solvent and drying in an oven at 150 ° C. for 15 minutes. Next, a copper foil (rolled copper foil, manufactured by Nikko Metal Co., Ltd., M surface roughness Rz = 1.4 μm, 18 μm thickness) is heat-laminated at a roll temperature of 300 ° C. on the base film side adhesive layer, and flexible A copper clad laminate was obtained.

(2) Evaluation item <Peel strength>
A test piece of a flexible printed circuit board is prepared according to JIS C6471, and the peel strength between the copper foil and the resin is measured using a strograph manufactured by Toyo Seiki Co., Ltd. under conditions of 50 mm / min and a peeling angle of 90 °. It was measured.
<Solder heat resistance>
In accordance with JIS C6471, the test piece is floated with the film surface facing upward in a solder bath set at 5 seconds, 260 ° C., 280 ° C., and 300 ° C. The state of swells (bubbles) and peeling was confirmed according to the following criteria.
○: Deformation is not seen at all △: Deformation such as undulation is seen, but there is no blister (bubble) or peeling ×: Duff (bubble) or peeling is seen

<Flexibility>
A test piece of a flexible printed circuit board is prepared in accordance with JIS C5016, and a durability test is performed under the conditions of a bending speed of 175 times / minute, a curvature radius of 0.38 mm, and a load of 500 g. Was counted (rounded to the nearest hundred).

  The obtained results are shown in Table 1.

  From the results in Table 1, the flexible copper-clad laminate using the compositions of the present invention of Examples 1 to 7 and the flexible printed circuit board using the same are both peel strength and solder heat resistance at 260 ° C to 300 ° C. And the bending resistance is good.

  The flexible copper-clad laminate using the composition containing no epoxy compound of Comparative Example 1 and the flexible printed circuit board using the same were excellent in soldering heat resistance but inferior in bending resistance.

  The composition containing no compound having an ethynyl group in Comparative Example 2 was excellent in flex resistance but poor in solder heat resistance at 300 ° C.

  The flexible copper-clad laminate using the imide compound that does not contain the structure of the general formula (3) and the flexible printed board using the same of Comparative Example 3 were inferior in bending resistance.

  The flexible copper-clad laminate using the imide compound containing no ethynyl group and the flexible printed circuit board using the same of Comparative Example 4 were inferior in bending resistance.

Claims (6)

Resin composition containing an ethynyl group-containing compound having the following general formula (3) as a structural unit and an epoxy compound:

(In General Formula (3), A ₀ represents a (l + m) -valent hydrocarbon group. However, A ₀ does not include the case where three or more aromatic rings are directly connected from the same carbon atom. A ₁ is a single bond. Or R ₁ represents a hydrogen atom or a hydrocarbon group, Ar represents an (a + 1) -valent aryl group or aromatic heterocyclic group, and X ₀ and X ₁ are independently of each other. Represents a divalent linking group, a, l, m, and n each independently represents an integer of 1 to 5, except when m and n are both 1. The resin composition according to claim 1, wherein the compound having an ethynyl group is a compound represented by the following general formula (1):

(In the formula (1), A is .B representing a tetrafunctional hydrocarbon radical .R ₂ and R ₃ represents a linking group derived from the formula (3) is a hydrocarbon group, at least one Represents a group represented by the following general formula (2), k is an integer of 1 or more);

(In the general formula (2), R ₁ , Ar, and a have the same meanings as in the general formula (3)).   The resin composition according to claim 1 or 2, wherein the compound having an ethynyl group has a molecular weight of 100,000 or less.   The hardened | cured material heat-processed at 100 to 400 degreeC after apply | coating the compound which has the said ethynyl group on copper foil.   The flexible copper clad laminated board which laminated | stacked the resin composition and copper foil of any one of Claims 1-3.   A flexible printed circuit board obtained by processing the flexible copper-clad laminate according to claim 5.