CN113462278A

CN113462278A - Varnish composition, method for producing polyimide resin, and additive

Info

Publication number: CN113462278A
Application number: CN202110344299.2A
Authority: CN
Inventors: 田所惠典; 菊地浩之; 西条秀树; 盐田大
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2020-03-31
Filing date: 2021-03-30
Publication date: 2021-10-01
Anticipated expiration: 2041-03-30
Also published as: JP7437997B2; JP2021161267A; KR20210122186A

Abstract

The present invention relates to a varnish composition, a method for producing a polyimide resin, and an additive. The present invention provides a varnish composition capable of forming a polyimide resin having improved physical properties such as thermal expansion coefficient, elongation at break, and tensile strength, a method for producing a polyimide resin using the varnish composition, and an additive suitable for use as a constituent of the varnish composition. A compound represented by the following formula (C1) is added as an amide compound (C) to a varnish composition for forming a polyimide resin containing a polyamic acid (a) and a solvent (S). In the formula (C1), R^c1Is an n-valent organic radical bonded to the carbonyl group via a carbon-carbon bond, R^c2Is hydrogenAn alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4. R^c1‑(‑CO‑NH‑R^c2)_n···(C1)。

Description

Varnish composition, method for producing polyimide resin, and additive

Technical Field

The present invention relates to a varnish composition, a method for producing a polyimide resin using the varnish composition, and an additive suitably blended in a varnish composition for forming a polyimide resin.

Background

Polyimide resins have excellent properties such as heat resistance, mechanical strength, insulation properties, and low dielectric constant. Therefore, polyimide resins are widely used as insulating materials and protective materials for electrical and electronic components such as electronic substrates of various devices, multilayer wiring boards, and the like.

Generally, a polyimide resin is formed by heat-treating a polyamic acid obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component in a polar organic solvent. Under such a background, polyimide products for electronic materials are often supplied in the form of a solution of a polyimide precursor such as polyamic acid. Specifically, in the production of an electric/electronic component, a solution of a polyimide precursor is supplied to a site where an insulating material or a protective material is to be formed by a method such as coating or injection, and then the solution of the polyimide precursor is subjected to a heat treatment to form the insulating material or the protective material.

The technology related to such polyimide resins has been intensively studied, and various resin compositions containing polyamic acid and the like have been disclosed (for example, see patent document 1 and the like).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-58918

Disclosure of Invention

Problems to be solved by the invention

However, the polyimide resins disclosed in patent document 1 and the like are required to have further improved physical properties such as thermal expansion coefficient, elongation at break, and tensile strength.

The present invention has been made in view of the above problems, and an object thereof is to provide a varnish composition capable of forming a polyimide resin having improved physical properties such as a thermal expansion coefficient, a breaking elongation, and a tensile strength, a method for producing a polyimide resin using the varnish composition, and an additive suitably used as a constituent component of the varnish composition.

Means for solving the problems

The present inventors have found that the above problems can be solved by blending an amide compound (C) having a specific structure with a varnish composition for forming a polyimide resin containing a polyamic acid (a) and a solvent (S), and have completed the present invention. More specifically, the present invention provides the following.

The invention of claim 1 is a varnish composition for forming a polyimide resin, comprising a polyamic acid (A), an amide compound (C), and a solvent (S),

the amide compound (C) is a compound represented by the following formula (C1):

R^c1-(-CO-NH-R^c2)_n···(C1)

(in the formula (C1), R^c1Is an n-valent organic radical bonded to the carbonyl group via a carbon-carbon bond, R^c2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4. ).

The 2 nd aspect of the present invention is a method for producing a polyimide resin, including the steps of:

a molding step of molding the varnish composition according to embodiment 1; and

and an imidization step of heating the molded varnish composition to imidize it.

The invention according to mode 3 is an additive for obtaining a varnish composition for forming a polyimide resin by blending a polyamic acid-containing liquid containing a polyamic acid (A) and a solvent (S),

The additive comprises an amide compound (C),

the amide compound (C) is a compound represented by the following formula (C1):

R^c1-(-CO-NH-R^c2)_n···(C1)

(in the formula (C1), R^c1Is an n-valent organic radical bonded to the carbonyl group via a carbon-carbon bond, R^c2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4. )

In the case of obtaining a polyimide resin by heating the varnish composition, at least one of a decrease in the coefficient of thermal expansion, an increase in the elongation at break, and an increase in the tensile strength is caused in the obtained polyimide resin, as compared with the case of obtaining a polyimide resin by heating a polyamic acid-containing liquid.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a varnish composition capable of forming a polyimide resin having improved physical properties such as a thermal expansion coefficient, elongation at break, and tensile strength, a method for producing a polyimide resin using the varnish composition, and an additive suitably used as a constituent component of the varnish composition.

Detailed Description

Varnish composition

The varnish composition includes a polyamic acid (A), an amide compound (C), and a solvent (S). The varnish composition is used to form a polyimide resin.

By including the amide compound (C) in the varnish composition, a polyimide resin having improved physical properties such as a thermal expansion coefficient, elongation at break, and tensile strength can be formed using the varnish composition. The amide compound (C) is described in detail later.

Here, the improvement of the thermal expansion coefficient means improvement of dimensional stability of the polyimide resin due to a reduction of the thermal expansion coefficient. The improvement in elongation at break means an increase in elongation at break. The improvement in tensile strength means an increase in tensile strength.

Hereinafter, essential or optional components of the varnish composition will be described.

< Polyamic acid (A) >

The varnish composition comprises polyamic acid (a). The polyamic acid (a) is a precursor polymer of a polyimide resin generated when the varnish composition is cured. The polyamic acid (a) is not particularly limited as long as it is a resin conventionally used as a precursor polymer in the production of a polyimide resin.

The polyamic acid (a) can be generally obtained by condensing monomer components including a tetracarboxylic dianhydride and a diamine compound.

The polyamic acid may have a structural unit represented by the following formula (a 1).

(in the formula (a1), A¹Is a 4-valent organic group having 6 to 50 carbon atoms, A²Is a 2-valent organic group. )

The tetracarboxylic dianhydride and the diamine compound used for producing the polyamic acid (a), and the method for producing the polyamic acid (a) will be described below.

[ tetracarboxylic dianhydride ]

The tetracarboxylic dianhydride which generates the structural unit represented by the formula (a1) is represented by the following formula (a 1-1).

The tetracarboxylic dianhydride represented by the formula (a1-1) can react with a diamine compound described later to form a polyamic acid (a) having a structural unit represented by the formula (a 1). The tetracarboxylic dianhydride may be used alone or in combination of two or more.

(in the formula (a1-1), A¹A 4-valent organic group having 6 to 50 carbon atoms. )

In the formula (a1-1), A¹A 4-valent organic group having 6 to 50 carbon atoms. The organic group is preferably a group containing a carbon atom, and more preferably a group containing a carbon atom and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, and a halogen atom. A. the¹In addition to the acid anhydride group represented by 2-CO-O-CO-in the formula (a1-1), it may have one or more substituents.

Preferred examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a fluoroalkoxy group having 1 to 6 carbon atoms. The compound represented by the formula (a1-1) may contain a carboxyl group or a carboxylate group in addition to an acid anhydride group.

When the substituent is a fluoroalkyl group or a fluoroalkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferable.

The same explanation as for the above substituents is also applicable to 1 or more substituents which the aromatic group described later may have on the aromatic ring.

In the formula (a1-1), A¹Is a 4-valent organic group, and has a lower limit of 6 carbon atoms and an upper limit of 50 carbon atoms.

Constitution A¹The number of carbon atoms of (b) is more preferably 8 or more, and still more preferably 12 or more. In addition, constitution A¹The number of carbon atoms of (b) is more preferably 40 or less, and still more preferably 30 or less. A. the¹The group may be an aliphatic group, an aromatic group, or a combination of these structures. A. the¹May contain a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. A. the¹When an oxygen atom, a nitrogen atom, or a sulfur atom is contained, the oxygen atom, the nitrogen atom, or the sulfur atom may be selected from the group consisting of a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N-, -CH-N-, -COO-, -O-, -CO-, -SO-, -SO₂Forms of the radicals-S, -S-and-S-are contained in A¹Among them, more preferably selected from-O-, -CO-, -SO-, -SO₂Forms of the radicals-S, -S-and-S-are contained in A ¹In (1).

The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as raw materials for synthesizing polyamic acid. The tetracarboxylic dianhydride may be an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride.

Examples of the aliphatic tetracarboxylic dianhydride include 2, 2-bis (3, 4-dicarboxy) propane dianhydride, bis (3, 4-dicarboxy) methane dianhydride, and the like. In addition, the aliphatic tetracarboxylic dianhydride may contain an alicyclic structure. The alicyclic structure may be polycyclic. Examples of the polycyclic alicyclic structure include bridged alicyclic structures such as bicyclo [2.2.1] heptane. For example, the bridged alicyclic structure may be fused with another bridged alicyclic structure and/or a non-bridged alicyclic structure, or the bridged alicyclic structure may be connected to another bridged alicyclic structure and/or a non-bridged alicyclic structure by spiro union. When an aliphatic tetracarboxylic dianhydride is used, a polyimide resin having excellent transparency tends to be easily obtained by using the varnish composition.

Further, the structure A in the formula (a1-1)¹The aliphatic group of (a) may be, for example, a tetravalent group represented by the following formula (a 2). When such a group is used, a polyimide resin having excellent transparency tends to be easily obtained.

In the formula (a2), a is preferably 5 or less, more preferably 3 or less, from the viewpoint of ease of purification of the starting compound. In addition, a is preferably 1 or more, and more preferably 2 or more, from the viewpoint of excellent chemical stability of the raw material compound capable of forming the structural unit represented by formula (a 1).

A in the formula (a2) is particularly preferably 2 or 3.

(in the formula (a2), R^a11、R^a12And R^a13Each independently represents 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorine atom, and a is an integer of 0 to 12 inclusive. )

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 3,3 ', 4, 4' -oxydiphthalic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, and 3,3 ', 4, 4' -diphenylsulfonetetracarboxylic acid dianhydride.

The aromatic tetracarboxylic dianhydride may be, for example, a compound represented by the following general formulae (a1-2) to (a 1-4).

In the above formulae (a1-2) and (a1-3), R^a1、R^a2And R^a3Each of which is any one of an aliphatic group which may be substituted with a halogen, an oxygen atom, a sulfur atom, and an aromatic group through which 1 or more divalent elements are interposed, or represents a divalent group composed of a combination thereof. R ^a2And R^a3May be the same or different.

Namely, R^a1、R^a2And R^a3May contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond or a halogen element (fluorine, chlorine, bromine, iodine). Examples of the compound represented by the formula (a1-2) include 2, 2-bis (3, 4-dicarboxyphenoxy) propane dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, and the like.

In the above formula (a1-4), R^a4、R^a5The substituent is any of an aliphatic group which may be substituted with a halogen, an aromatic group having 1 or more divalent elements interposed therebetween, and a halogen, or represents a monovalent substituent composed of a combination thereof. R^a4And R^a5Each may be the same or different. As the compound represented by the formula (a1-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride or the like can be used.

Examples of the tetracarboxylic dianhydride for obtaining the fluorine-containing polyimide having fluorine in the molecular structure include (trifluoromethyl) pyromellitic dianhydride, bis (heptafluoropropyl) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride, bis {3, 5-bis (trifluoromethyl) phenoxy } pyromellitic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 5,5 '-bis (trifluoromethyl) -3, 3', 4,4 '-tetracarboxylbiphenyl dianhydride, 2', 5,5 '-tetrakis (trifluoromethyl) -3, 3', 4,4 '-tetracarboxylbiphenyl dianhydride, 5, 5' -bis (trifluoromethyl) -3,3 ', 4, 4' -tetracarboxyldiphenyl ether dianhydride, 5,5 ' -bis (trifluoromethyl) -3,3 ', 4,4 ' -tetracarboxylic benzophenone dianhydride, bis { (trifluoromethyl) dicarboxyphenoxy } benzene dianhydride, bis { (trifluoromethyl) dicarboxyphenoxy } (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2-bis {4- (3, 4-dicarboxyphenoxy) phenyl } hexafluoropropane dianhydride, bis { (trifluoromethyl) dicarboxyphenoxy } biphenyl dianhydride, bis { (trifluoromethyl) dicarboxyphenoxy } bis (trifluoromethyl) biphenyl dianhydride, bis { (trifluoromethyl) dicarboxyphenoxy } diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl dianhydride, Difluoropyromellitic dianhydride, 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) octafluorobiphenyl dianhydride, and the like.

As the tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride is preferably used in view of heat resistance, transparency, and the like of the polyimide resin obtained.

It is also possible to use an acid chloride or an ester of a tetracarboxylic acid having the same basic skeleton as the above-mentioned compound.

The tetracarboxylic dianhydride may be used in combination with a dicarboxylic anhydride. When these carboxylic anhydrides are used in combination, the properties of the resulting imide ring-containing polymer such as a polyimide resin may be further improved. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and cis-4-cyclohexene-1, 2-dicarboxylic anhydride.

[ diamine Compound ]

As the diamine compound, a compound represented by the following formula (a3-1) can be typically used. The diamine compound may be used alone or in combination of two or more.

H₂N-A²-NH₂···(a3-1)

(in the formula (a3-1), A²Represents a 2-valent organic group. )

In the formula (a3-1), A²Is a 2-valent organic group. The organic group is preferably a group containing carbon atoms, more preferably a group containing 1 or more carbon atoms, and is selected from the group consisting of H, O, S, A group of 1 or more atoms selected from the group consisting of Se, N, B, P, and halogen atoms. A. the²In addition to having 2 amino groups in formula (a3-1), one or more substituents may be present.

Preferred examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluoroalkoxy group having 1 to 6 carbon atoms, or a hydroxyl group.

In the formula (a3-1), A represents²The lower limit of the number of carbon atoms of the organic group (2) is preferably 2, more preferably 6, and the upper limit thereof is preferably 50, more preferably 30.

A²The organic group may be an aliphatic group, but is preferably an organic group having 1 or more aromatic rings.

A²In the case of an organic group containing 1 or more aromatic rings, the organic group may be 1 aromatic group per se, or 2 or more aromatic groups may be bonded to each other via a bond between an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, or a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. As A²The bond containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom in the above group includes-CONH-, -NH-, -N-, -CH-N-, -COO-, -O-, -CO-, -SO-, -SO ₂-, -S-, and-S-S-, etc., preferably-O-, -CO-, -SO-, -SO₂-, -S-, and-S-S-.

A²The aromatic ring bonded to the amino group in (1) is preferably a benzene ring. A. the²When the ring bonded to the amino group in (b) is a condensed ring including 2 or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring.

In addition, A²The aromatic ring contained in (1) may be an aromatic heterocyclic ring.

A²In the case of an aromatic ring-containing organic group, the organic group is preferably represented by the following formula (21) to (E), from the viewpoint of heat resistance of the polyimide resin formed using the varnish composition(24) At least one of the groups represented.

(in formulae (21) to (24), R¹¹¹Represents 1 kind selected from the group consisting of hydrogen atom, fluorine atom, hydroxyl group, alkyl group with 1-4 carbon atoms and halogenated alkyl group with 1-4 carbon atoms. In the formula (24), Q represents a group selected from 9, 9' -fluorenylidene, or the formula: -C₆H₄-、-CONH-C₆H₄-NHCO-、-NHCO-C₆H₄-CONH-、-O-C₆H₄-CO-C₆H₄-O-、-OCO-C₆H₄-COO-、-OCO-C₆H₄-C₆H₄-COO-、-OCO-、-O-、-S-、-CO-、-CONH-、-SO₂-、-C(CF₃)₂-、-C(CH₃)₂-、-CH₂-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-O-C₆H₄-C(CF₃)₂-C₆H₄-O-、-O-C₆H₄-SO₂-C₆H₄-O-、-C(CH₃)₂-C₆H₄-C(CH₃)₂-、-O-C₁₀H₆-O-、-O-C₆H₄-C₆H₄-O-, and-O-C₆H₄1 member of the group consisting of-O-.

-C in the example of Q₆H₄Is phenylene, preferably m-phenylene, and p-phenylene, more preferably p-phenylene. In addition, -C₁₀H₆Is naphthalene diyl, preferably naphthalene-1, 2-diyl, naphthalene-1, 4-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl and naphthalene-2, 7-diyl, more preferably naphthalene-1, 4-diyl and naphthalene-2, 6-diyl. )

R in the formulae (21) to (24)¹¹¹From the viewpoint of heat resistance of the polyimide resin to be formed, a hydrogen atom, a hydroxyl group, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group is more preferable, and particularly preferableSelected from hydrogen atom, hydroxyl or trifluoromethyl.

In the formula (24), Q is preferably 9, 9' -fluorenylidene, -O-C₆H₄-O-、-C(CF₃)₂-、-O-、-C(CH₃)₂-、-CH₂-, or-O-C₆H₄-C(CH₃)₂-C₆H₄-O-, -CONH-, particularly preferably-O-C₆H₄-O-、-C(CF₃)₂-or-O-.

When an aromatic diamine is used as the diamine compound represented by the formula (a3-1), for example, the aromatic diamines shown below can be preferably used.

That is, examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2, 4-diaminotoluene, 4 '-diaminobiphenyl, 4' -diamino-2, 2 '-bis (trifluoromethyl) biphenyl, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 4' -diaminodiphenylmethane, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminobenzanilide, 3' -diaminobenzanilide, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 2, 4-diaminotoluene, 4 '-diaminodiphenyl, 4' -diaminodiphenyl sulfide, and the like, 1, 3-bis (3-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-methylphenyl) fluorene, and 4, 4' - [1, 4-phenylenebis (1-methylethyl-1, 1-diyl) ] diphenylamine, and the like. Among these, p-phenylenediamine, m-phenylenediamine, 2, 4-diaminotoluene, 4 '-diaminodiphenyl ether, and 4, 4' -diaminobenzanilide are preferable from the viewpoint of cost, availability, and the like.

In addition, as A²A silicon atom-containing group which may have a chain aliphatic group and/or an aromatic ring may be used. As such a silicon atom-containing group, typically, the following groups can be used.

In addition, from the viewpoint of further improving the mechanical properties of the polyimide resin obtained, a is taken as²A group represented by the following formula (Si-1) can also be preferably used.

(in the formula (Si-1), R¹¹²And R¹¹³Each independently a single bond or a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, or the like. R¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷Each independently is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a group containing an amino group having 20 carbon atoms, -O-R¹¹⁸A group of (R)¹¹⁸A hydrocarbon group having 1 to 20 carbon atoms), an organic group having 2 to 20 carbon atoms and containing 1 or more epoxy groups. The organic group containing an epoxy group is preferably a group containing a carbon atom and an epoxy group, and more preferably a group containing 1 or more atoms selected from the group consisting of H, S, Se, N, B, P, and a halogen atom. l is an integer of 3 to 50 inclusive. )

As R in the formula (Si-1)¹¹²And R¹¹³Among them, an alkylene group having 2 to 20 carbon atoms is preferable from the viewpoint of heat resistance and residual stress, and examples thereof include 1, 2-ethylene (dimethyl), 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, and 1, 6-hexylene.

As R in the formula (Si-1)¹¹²And R¹¹³The cycloalkylene group having 3 to 20 carbon atoms in (A) is heat-resistant and remainsFrom the viewpoint of stress, a cycloalkylene group having 3 to 10 carbon atoms is preferable, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptylene group.

As R in the formula (Si-1)¹¹²And R¹¹³Among them, the arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 6 to 20 carbon atoms from the viewpoint of heat resistance and residual stress, and examples thereof include a phenylene group and a naphthylene group.

As R in the formula (Si-1)¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷The alkyl group having 1 to 20 carbon atoms in (b) is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.

As R in the formula (Si-1)¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷The cycloalkyl group having 3 to 20 carbon atoms in (b) is preferably a cycloalkyl group having 3 to 10 carbon atoms in view of heat resistance and residual stress, and specifically includes a cyclopentyl group, a cyclohexyl group and the like.

As R in the formula (Si-1)¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷The aryl group having 6 to 20 carbon atoms in (b) is preferably an aryl group having 6 to 12 carbon atoms in view of heat resistance and residual stress, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

As R in the formula (Si-1)¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷Examples of the amino group-containing group having not more than 20 carbon atoms in (b) include an amino group, a substituted amino group (e.g., a bis (trialkylsilyl) amino group), and the like.

As R in the formula (Si-1)¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷In (1) -O-R¹¹⁸Examples of the group include methoxy, ethoxy, propoxy, isopropyloxy, butoxy, phenoxy, tolyloxy, naphthyloxy and propenyloxy (for example, a group represented byAllyloxy), cyclohexyloxy, and the like.

Wherein, as R¹¹⁴、R¹¹⁵、R¹¹⁶And R¹¹⁷Methyl, ethyl, propyl, phenyl are preferred.

The group represented by the formula (Si-1) can be introduced by reacting a silicon-containing compound having amino groups at both terminals with an acid anhydride. Specific examples of such a silicon-containing compound include amino-modified methylphenylsilicone at both ends (for example, X-22-1660B-3 (number average molecular weight: about 4,400) and X-22-9409 (number average molecular weight: about 1,300) manufactured BY shin-Etsu chemical Co., Ltd.), amino-modified dimethylsilicone at both ends (for example, X-22-161A (number average molecular weight: about 1,600), X-22-161B (number average molecular weight: about 3,000) and KF8012 (number average molecular weight: about 4,400) manufactured BY shin-Etsu chemical Co., Ltd.), BY16-835U (number average molecular weight: about 900) manufactured BY Donglie Corning, and Silaplane FM3311 (number average molecular weight: about 1000) manufactured BY JNC Co., Ltd.).

[ method for producing Polyamic acid (A) ]

The polyamic acid (a) having a structural unit represented by the formula (a1) is typically a polymer obtained by reacting a tetracarboxylic dianhydride represented by the formula (a1-1) with a diamine compound represented by the formula (a3-1) in a solvent, and may be a polymer obtained by using 1 or two or more kinds of each of the diamine compound and/or the tetracarboxylic dianhydride. For example, the diamine compound may be a polymer obtained by polycondensation of a mixture containing two or more kinds of tetracarboxylic dianhydrides. The polyamic acid (a) may be used alone or in combination of two or more.

The amount of the tetracarboxylic dianhydride and the diamine compound used in the synthesis of the polyamic acid (a) is not particularly limited, but the diamine compound is preferably used in an amount of 0.50 mol or more and 1.50 mol or less, more preferably 0.60 mol or more and 1.30 mol or less, and particularly preferably 0.70 mol or more and 1.20 mol or less, based on 1 mol of the tetracarboxylic dianhydride.

The weight average molecular weight of the obtained polyamic acid (a) may be appropriately set according to the use, and is, for example, 5000 or more, preferably 7500 or more, and more preferably 10000 or more. On the other hand, the weight average molecular weight of the obtained polyamic acid (a) is, for example, 100000 or less, preferably 80000 or less, and more preferably 75000 or less.

The weight average molecular weight can be adjusted to the above value by adjusting the reaction conditions such as the amount of tetracarboxylic dianhydride and diamine compound blended, the solvent, and the reaction temperature.

The reaction of the tetracarboxylic dianhydride with the diamine compound is usually carried out in an organic solvent. The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine compound is not particularly limited as long as it is an organic solvent which can dissolve the tetracarboxylic dianhydride and the diamine compound and does not react with the tetracarboxylic dianhydride and the diamine compound. The organic solvent may be used alone or in combination of 2 or more.

Examples of the organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine compound include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-methylcaprolactam, and N, N' -tetramethylurea; dimethyl sulfoxide; acetonitrile; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran.

Among these organic solvents, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-methylcaprolactam, and N, N' -tetramethylurea are preferable in view of the solubility of the polyamic acid (a) to be produced.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature of the tetracarboxylic dianhydride and the diamine compound is preferably-5 ℃ or more and 150 ℃ or less, more preferably 0 ℃ or more and 120 ℃ or less, and particularly preferably 0 ℃ or more and 70 ℃ or less. The reaction time of the tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, and is typically preferably 1 hour or more and 50 hours or less, more preferably 2 hours or more and 40 hours or less, and particularly preferably 5 hours or more and 30 hours or less.

By the above-described method, a solution containing polyamic acid (a) can be obtained.

The solution containing polyamic acid (a) obtained in the above manner may be used as it is for the preparation of a varnish composition, or at least a part of the solvent may be removed from the solution of polyamic acid (a) under reduced pressure at a low temperature to such an extent that the conversion of polyamic acid into polyimide resin does not occur, and the paste or solid of the obtained polyamic acid may be used for the preparation of a varnish composition.

The content of the polyamic acid (a) in the varnish composition may be appropriately determined in consideration of coatability of the varnish composition, solubility of the polyamic acid (a) in the solvent (S), and the like. Typically, the content of the polyamic acid (a) in the varnish composition is preferably 5% by mass or more and 45% by mass or less, more preferably 7% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 30% by mass or less, with respect to the mass of the varnish composition.

< amide Compound (C) >

The amide compound (C) is a compound represented by the following formula (C1):

R^c1-(-CO-NH-R^c2)_n···(C1)

By including the amide compound (C) in the varnish composition, a polyimide resin having improved physical properties such as a thermal expansion coefficient, elongation at break, and tensile strength can be formed using the varnish composition.

In addition, when the varnish composition contains the amide compound (C), the occurrence of cloudiness and gelation with time during storage of the varnish composition can be easily suppressed. Therefore, the amide compound (C) is particularly preferably blended in the varnish composition containing the polyamic acid (a) capable of forming a transparent polyimide resin.

In formula (C1), n is an integer of 1 or more and 4 or less, preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1. From the viewpoint of being excellent in the effect of reducing the thermal expansion coefficient and the effect of increasing the tensile strength with respect to the polyimide resin formed using the varnish composition, n is preferably 3 or 4. From the viewpoint of good solubility stability of the amide compound (C) in the varnish composition, n is preferably 1 or 2, more preferably 1.

In the formula (C1), R is not particularly limited in the range not impairing the object of the present invention^c1The number of carbon atoms of (a) is not particularly limited. Typically, R^c1The number of carbon atoms of (a) is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 10.

With respect to as R^c1The organic group of (2) is preferably a group containing a carbon atom. As R^c1The organic group (c) may contain carbon atoms and hydrogen atoms, and 1 or 2 or more kinds of hetero atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a boron atom, a phosphorus atom, a halogen atom, and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

R^c1When it is a monovalent group, as R^c1Preferable specific examples thereof include saturated aliphatic groups such as alkyl groups, cycloalkyl groups and polycycloalkyl groups, unsaturated aliphatic groups such as alkenyl groups, cycloalkenyl groups and polycycloalkenyl groups, aryl groups (aromatic hydrocarbon groups), heteroaryl groups (aromatic heterocyclic groups), arylalkyl groups, arylalkenyl groups, heteroarylalkyl groups, heteroarylalkenyl groups and the like.

It is not limited to R^c1In the case of a monovalent group, R is a monovalent group, because rapid decomposition, sublimation, volatilization, or the like of the amide compound (C) in the production of the polyimide resin can be easily suppressed ^c1Preferably, aryl or heteroaryl groups are included, more preferably aryl groups are included.

As R^c1The alkyl group and the alkenyl group of (a) may be substituted with one or more substituents selected from the group consisting of a halogen atom, a cyano group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aliphatic acyl group having 2 to 6 carbon atoms, and an amino group.

As R^c1The cycloalkyl group, the polycycloalkyl group, the cycloalkenyl group, the polycycloalkenyl group, the aryl group, and the heteroaryl group in (a) may be substituted with one or more substituents selected from the group consisting of a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aliphatic acyl group having 2 to 6 carbon atoms, and an amino group.

As R^c1In the arylalkyl group, arylalkenyl group, heteroarylalkyl group, and heteroarylalkenyl group of (a), the aryl group or heteroaryl group contained in these groups may be substituted with one or more substituents selected from the group consisting of a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aliphatic acyl group having 2 to 6 carbon atoms, and an amino group.

It is not limited to R ^c1In the case where the monovalent group is used, in the case where the polyimide resin is transparent, R is preferably R in view of easy formation of a polyimide resin having high transparency^c1Has no amino group and no hydroxyl group.

As R^c1Preferred examples of the saturated aliphatic group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; and polycyclic alkyl groups such as adamantyl, norbornyl, isobornyl, tricyclodecyl, and tetracyclododecyl groups.

As R^c1Preferable specific examples of the unsaturated aliphatic group include alkenyl groups such as vinyl, 1-methylvinyl, 1-propenyl, 2-propenyl (allyl), 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl and 9-decenyl; cyclopropenyl, cyclobutenyl, and the like, Cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, and cyclodecenyl; polycyclic alkenyl groups such as adamantyl, norbornenyl, isobornyl, tricyclodecenyl, and tetracyclododecenyl.

As R^c1Preferred specific examples of the aryl group (aromatic hydrocarbon group) include phenyl group, naphthalene-1-yl group, naphthalene-2-yl group, 1 ' -biphenyl-4-yl group, 1 ' -biphenyl-3-yl group and 1,1 ' -biphenyl-2-yl group.

As R^c1Preferred examples of the heteroaryl group (aromatic heterocyclic group) include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group.

As R^c1Preferred specific examples of the arylalkyl group include benzyl, phenethyl, naphthalen-1-ylmethyl, naphthalen-2-ylmethyl, naphthalen-1-ylethyl and naphthalen-2-ylethyl groups.

As R^c1Preferable specific examples of the arylalkenyl group include a 2-phenylvinyl group, a 2- (naphthalen-1-yl) vinyl group, and a 2- (naphthalen-2-yl) vinyl group.

As R^c1Preferred specific examples of heteroarylalkyl groups include 1H-imidazol-2-ylmethyl, 1H-imidazol-2-ylethyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl, pyridin-2-ylethyl, pyridin-3-ylethyl and pyridin-4-ylethyl.

As R^c1Preferable specific examples of the heteroarylalkenyl group include 2- (1H-imidazol-2-yl) 2- (pyridin-2-yl) vinyl, 2- (pyridin-3-yl) vinyl, and 2- (pyridin-4-yl) vinyl.

R^c1When it is a divalent group, as R^c1Specific preferred examples thereof include divalent saturated aliphatic groups such as alkanediyl, cycloalkanediyl and polycycloalkanediyl having 2 or more carbon atoms, divalent unsaturated aliphatic groups such as alkenediyl, cycloalkenediyl and polycycloalkanediyl, arylene and heteroarylene groups, and alkyl and aryl groups in alkylaromatic hydrocarbons each having 1 hydrogen atom removed therefromA group obtained by removing 1 hydrogen atom from each of an alkenyl group and an aryl group in an alkenyl aromatic hydrocarbon, a group obtained by removing 1 hydrogen atom from each of an alkyl group and a heteroaryl group in an alkylheteroaromatic hydrocarbon, a group obtained by removing 1 hydrogen atom from each of an alkenyl group and a heteroaryl group in an alkenylheteroaromatic hydrocarbon, a group obtained by removing 1 hydrogen atom from each of 2 alkyl groups in a dialkylaromatic hydrocarbon, and a group obtained by removing 1 hydrogen atom from each of 2 alkyl groups in a dialkylheteroaromatic hydrocarbon.

R^c1When it is a trivalent radical, as R ^c1As a preferred example of (A) include alkanetriyl and N- (-R)^c3-)₃The group represented, an aromatic hydrocarbon triyl group, and a heteroaromatic hydrocarbon triyl group. R^c3Is an alkylene group having 1 to 4 carbon atoms. As R^c3Ethane-1, 2-diyl and propane-1, 3-diyl are preferable.

R^c1When it is a tetravalent group, as R^c1As preferable specific examples thereof, there may be mentioned alkanetetrayl, (-R)^c4-)₂-N-(-R^c5-)-N-(-R^c4-)₂The group represented, an aromatic hydrocarbon tetrayl group, and a heteroaromatic hydrocarbon tetrayl group. R^c4And R^c5Each independently is an alkylene group having 1 to 4 carbon atoms. As R^c4And R^c5Ethane-1, 2-diyl and propane-1, 3-diyl are preferable.

In the formula (C1), R^c2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. With respect to as R^c2Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, and a n-hexyl group. Among these alkyl groups, methyl and ethyl groups are preferred, and ethyl groups are more preferred.

As R^c1Preferable examples of the amide compound (C) in the case of a monovalent saturated aliphatic hydrocarbon group include acetamide (acetamide), propionamide, butyramide (butyramide), isobutyramide, valeramide (n-valeramide), isovaleramide, pivaloamide, 2-methylbutyramide, n-caproamide, 2-methylvaleramide, 3-methylvaleramide, 4-methylvaleramide, 2, 2-dimethylbutanamide, n-heptanamide, n-octanoylamide, n-nonanamide, n-decanoamide, n-dodecanamide, n-tridecanamide, n-tetradecanamide, n-pentadecanamide, n-hexadecanamide, n-heptadecanoamide, n-octadecanamide, n-nonadecanoamide, n-eicosanamide, cyclopropanecarboxamide, cyclopentane carboxamide, cyclopropanecarboxamide, cycloheptane carboxamide, and cyclooctane carboxamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of an alkyl group substituted with a halogen atom, a cyano group, a hydroxyl group, an acetyl group or a methoxy group include chloroacetamide, dichloroacetamide, trichloroacetamide, bromoacetamide, dibromoacetamide, tribromoacetamide, fluoroacetamide, difluoroacetamide, trifluoroacetamide, cyanoacetamide, acetoacetamide, 3-chloropropanamide, 3-bromopropanamide, 3-fluoropropanamide, 3-methoxypropanamide, pentafluoropropanamide, heptafluorobutanamide and lactamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of a monovalent unsaturated aliphatic hydrocarbon group include unsaturated aliphatic carboxylic acids such as acrylamide, methacrylamide, crotonamide, and oleamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1As preferred examples of the amide compound (C) in the case of an aryl group, there may be mentioned benzamide, 4-methylbenzamide, 3-methylbenzamide, 2-methylbenzamide, 4-methoxybenzamide, 3-methoxybenzamide, 2-methoxybenzamide and 4-chlorobenzeneFormamide, 3-chlorobenzamide, 2-chlorobenzamide, 4-bromobenzamide, 3-bromobenzamide, 2-bromobenzamide, 4-fluorobenzamide, 3-fluorobenzamide, 2-fluorobenzamide, 4-hydroxybenzamide, 3-hydroxybenzamide, 2-hydroxybenzamide, 4-aminobenzamide, 3-aminobenzamide, 2-aminobenzamide, naphthalene-2-carboxamide, naphthalene-1-carboxamide, and 1, 1' -biphenyl-4-carboxamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of an arylalkyl group include phenylacetamide, 4-methylphenylacetamide, 3-methylphenylacetamide, 2, 5-dimethylphenylacetamide, 2,4, 6-trimethylphenylacetamide, 4-tert-butylphenyl acetamide, 4-hydroxyphenylacetamide, 3-hydroxyphenylacetamide, 2-hydroxyphenylacetamide, 4-methoxyphenylacetamide, 3-methoxyphenylacetamide, 2-methoxyphenylacetamide, 4-chlorophenylacetamide, 3-chlorophenylacetamide, 2-chlorophenylacetamide, 4-bromophenylacetamide, 3-bromophenylacetamide, 2-bromophenylacetamide, 4-fluorophenylacetamide, 3-bromophenylacetamide, 4-bromophenylacetamide, 3-bromophenylacetamide, and the like, 3-fluorophenylacetamide, 2-fluorophenylacetamide, 4-trifluoromethylphenylacetamide, 3-trifluoromethylphenylacetamide, 4-hydroxymethylphenylacetamide, 3-methoxyphenylacetamide, 4-aminophenylacetamide, 2-phenylpropionamide, 2-phenyl-n-butylamide, 2-phenylisobutyramide, naphthalen-1-ylacetamide, naphthalen-2-ylacetamide, and 1, 1' -biphenyl-4-ylacetamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of arylalkenyl include cinnamamide, 4-methylcinnamamide, 3-methylcinnamamide, 2, 5-dimethylcinnamamide, 2,4, 6-trimethylcinnamamideA cinnamide, 4-tert-butylcinnamide, 4-hydroxycinnamide, 3-hydroxycinnamide, 2-hydroxycinnamide, 4-methoxycinnamide, 3-methoxycinnamide, 2-methoxyphenyl acetamide, 4-chlorocinnamide, 3-chlorophenyl acetamide, 2-chlorocinnamide, 4-bromophenyl acetamide, 3-bromocinnamide, 2-bromocinnamide, 4-fluorocinnamide, 3-fluorocinnamide, 2-fluorocinnamide, 4-trifluoromethyl cinnamide, 3-trifluoromethyl cinnamide, 4-hydroxymethyl cinnamide, 3-methoxycinnamide, and 4-aminocinnamide. Also preferred as the amide compound (C) are those wherein the nitrogen atom in the amide group of these compounds is substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein the nitrogen atom in the amide group of these compounds is substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of a 2-valent organic group include malonamide, succinamide (succinamide), adipamide, sebacamide, dodecanedioic diamide, dichloromalonamide, dibromomalonamide, terephthalic acid diamide, isophthalic acid diamide, phthalic acid diamide, naphthalene-2, 6-dicarboxylic acid diamide, naphthalene-2, 7-dicarboxylic acid diamide, naphthalene-1, 4-dicarboxylic acid diamide, biphenyl-4, 4' -dicarboxylic acid diamide, 1, 4-phenylenediacetic acid diamide, 1, 3-phenylenediacetic acid diamide, and 1, 2-phenylenediacetic acid diamide. Also preferred as the amide compound (C) are those wherein 1 or 2 of the nitrogen atoms in the amide group of these compounds are substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein 1 or 2 of the nitrogen atoms in the amide group of these compounds are substituted with a methyl group.

As R^c1Preferable examples of the amide compound (C) in the case of a 3-valent organic group include 1,2, 3-propanetricarboxylic acid triamide, 3' -nitrilotris (propionamide), benzene-1, 2, 3-tricarboxylic acid triamide, benzene-1, 2, 4-tricarboxylic acid triamide, benzene-1, 3, 4-tricarboxylic acid triamide, and benzene-1, 3, 5-tricarboxylic acid triamide. Also preferred as the amide compound are substituted compounds wherein 1 to 3 nitrogen atoms in the amide group of these compounds are substituted with a C1-C6 alkyl groupThe compound (C) is more preferably a substituted compound in which 1 to 3 nitrogen atoms in the amide group of the compound are substituted with methyl groups, as the amide compound (C).

As R^c1Preferable examples of the amide compound (C) in the case of a 4-valent organic group include ethylenediaminetetraacetic acid tetraamide and naphthalene-1, 4,5, 8-tetracarboxylic acid tetraamide. Also preferred as the amide compound (C) are those wherein 1 to 4 of the nitrogen atoms in the amide group of these compounds are substituted with a C1-C6 alkyl group, and more preferred as the amide compound (C) is one wherein 1 to 4 of the nitrogen atoms in the amide group of these compounds are substituted with a methyl group.

Among the above-described amide compounds (C), preferred are acetamide, N-methylacetamide, N-ethylacetamide, benzamide, N-methylbenzamide, N-ethylbenzamide, phenylacetamide, N-methylphenylacetamide, N-ethylphenylacetamide, cinnamamide, N-methylcinnamamide, N-ethylcinnamamide, malonamide, N ' -dimethylmalonamide, N ' -diethylmalonamide, 3 ' -nitrilotris (propionamide), 3 ' -nitrilotris (N-methylpropionamide), and 3,3 ' -nitrilotris (N-ethylpropionamide).

The amount of the amide compound (C) used in the varnish composition is not particularly limited within a range not impairing the object of the present invention. The amount of the amide compound (C) used is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, and further preferably 5 parts by mass or more and 25 parts by mass or less, relative to the entire solid content of the varnish composition, from the viewpoints of preventing excessive sublimation and volatilization of the amide compound (C) during production of the polyimide resin and easily obtaining a desired effect of improving the physical properties of the polyimide resin.

In addition, in the case where the varnish composition contains the thermal alkali generator (B), the mass ratio ((B): (C)) of the thermal alkali generator (B) to the amide compound (C) is, for example, 100: 30-100: 500, more preferably 100: 100-100: 300. the thermal alkali generator (B) is preferably a compound represented by formula (B1), formula (B2), or formula (B4) described later, and more preferably a compound represented by formula (B4).

< solvent (S) >

The varnish composition contains a solvent (S). The varnish composition may be a paste containing a solid or a solution, and preferably a solution. The solvent (S) may be used alone or in combination of 2 or more.

The type of the solvent (S) is not particularly limited insofar as the object of the present invention is not impaired, and examples thereof include: glycol monoethers such as water, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monophenyl ether; glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether; glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl ether acetate, 2-ethoxybutyl acetate, 2-methoxybutyl acetate, 2-methoxypentyl acetate, 2-ethoxybutyl acetate, 3-methoxybutyl acetate, and 2-methoxybutyl acetate, Monoether monoacetates of glycols such as 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, and cyclohexanone; methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-propoxypropionate, propyl 3-methoxypropionate, isopropyl 3-methoxypropionate, ethyl ethoxyacetate, ethyl oxoacetate, methyl 2-hydroxy-3-methylbutyrate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl acetate, ethyl propionate, esters such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, and γ -butyrolactone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, benzyl methyl ether, benzyl ethyl ether, and tetrahydrofuran; aromatic compounds such as benzene, toluene, xylene, ethylbenzene, cresol, and chlorobenzene; aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol; glycols such as polyethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; glycerol; and so on.

In addition, a solvent used in the reaction of the tetracarboxylic dianhydride and the diamine compound described above can also be preferably used as the solvent (S).

The solvent (S) may contain a nitrogen-containing compound represented by the following formula (S1).

(in the formula (S1), R^S1And R^S2Each independently an alkyl group having 1 to 3 carbon atoms, R^S3Is a hydrogen atom, or a group represented by the following formula (S1-1) or the following formula (S1-2):

R^S4is a hydrogen atom or a hydroxyl group, R^S5And R^S6Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R^S7And R^S8Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R^S3When it is a group represented by the formula (S1-1), R^S2And R^S3May be bonded to each other to form a ring. )

R in the nitrogen-containing compound represented by the formula (S1)^S3Specific examples of the hydrogen atom or the group represented by the formula (S1-1) include N, N-dimethylformamide, N-dimethylacetamide, N, 2-trimethylpropionamide, N-ethyl-N, 2-dimethylpropionamide, N-diethyl-2-methylpropionamide, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, and N, N-diethyl-2-hydroxy-2-methylpropionamide.

R in the nitrogen-containing compound represented by the formula (S1)^S3Is a group represented by the formula (S1-1), and R ^S2And R^S3Specific examples of the ring formed by bonding to each other include N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

R in the nitrogen-containing compound represented by the formula (S1)^S3Specific examples of the group represented by the formula (S1-2) include N, N, N ', N' -tetramethylurea, N, N, N ', N' -tetraethylurea and the like.

Among the above examples of the nitrogen-containing compound represented by the formula (S1), particularly preferable examples thereof include N, N-dimethylformamide, N-dimethylacetamide, N, 2-trimethylpropionamide, and N, N' -tetramethylurea. Among these, N, N, 2-trimethylpropionamide and N, N, N ', N' -tetramethylurea are preferable. The boiling point under atmospheric pressure of N, N, 2-trimethylpropionamide is 175 ℃ and the boiling point under atmospheric pressure of N, N, N ', N' -tetramethylurea is 177 ℃. Thus, N, N, 2-trimethylpropionamide and N, N, N ', N' -tetramethylurea have a low boiling point in the organic solvent (S-I).

Therefore, when a varnish composition containing a solvent (S) containing at least one selected from N, 2-trimethylpropionamide and N, N' -tetramethylurea is used, the solvent (S) is less likely to remain in a polyimide resin produced by heating when the polyimide resin is formed, and the mechanical properties of the obtained polyimide resin are less likely to be deteriorated.

N, 2-trimethylpropionamide and N, N' -tetramethylurea are substances having low harmfulness, and are not specified as SVHC (High attention Substance) which is a Substance having a fear of harmfulness in REACH regulations of EU (european union), and are useful from this point of view.

The content of the solvent (S) in the varnish composition is not particularly limited within a range not impairing the object of the present invention. The content of the solvent (S) in the varnish composition is appropriately adjusted depending on the content of the solid content in the varnish composition. The solid content in the varnish composition is, for example, in the range of 5 mass% to 99.9 mass%, preferably 5 mass% to 70 mass%, and more preferably 10 mass% to 60 mass%.

< thermal alkali-producing agent (B) >

For the purpose of making the polyamide resin well generated from the polyamic acid (a) by firing, the varnish composition preferably contains a thermal alkali generator (B) that generates a basic nitrogen-containing heterocyclic compound by heating.

The basic nitrogen-containing heterocyclic compound generated by the thermal alkali generator (B) may be an alicyclic compound or an aromatic compound. When the basic nitrogen-containing heterocyclic compound is a compound in which 2 or more monocyclic rings are condensed, the 2 or more monocyclic rings may contain only an aliphatic ring, only an aromatic ring, or a combination of an aliphatic ring and an aromatic ring.

Examples of the basic nitrogen-containing heterocyclic compound generated by the thermal alkali-producing agent (B) include: nitrogen-containing 5-membered ring compounds such as pyrrolidine, pyrazolidine, imidazolidine, triazolidine, tetrazoline, pyrroline, pyrazoline, imidazoline, triazoline, tetrahydrozoline, pyrrole, pyrazole, imidazole, triazole, and tetrazole; nitrogen-containing 6-membered rings such as piperidine, piperazine, triazinane, pyridine, pyridazine, pyrimidine, and pyrazine; compounds in which these compounds are substituted with one or more substituents; these compounds are condensed with cyclopentane, cyclohexane, benzene, etc.

When the basic nitrogen-containing heterocyclic compound has a substituent on the nitrogen-containing heterocycle, the substituent is the same as R in the formula (B1) described later¹、R²And R³The same groups.

The basic nitrogen-containing heterocyclic compound generated as the component of the thermal alkali generator (B) is preferably an imidazole compound represented by the following formula (B1) in view of its excellent effect of promoting the formation of a polyimide resin from the polyamic acid (a):

(in the formula (B1), R¹、R²And R³Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group (sulfo group), a phosphino group, a phosphinyl group, a phosphonate group (phospho group), or an organic group. ).

As R¹、R²And R³The organic group in (1) is preferably a group containing a carbon atom, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. As R¹、R²And R³Examples of the organic group in (3) include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, or cyclic. The organic group is usually monovalent, but may be divalent or more in the case of forming a cyclic structure or the like.

Then R¹And R²These may be bonded to form a cyclic structure, or may further include a bond of a hetero atom. Examples of the cyclic structure include a heterocycloalkyl group, a heteroaryl group, and a condensed ring.

R¹、R²And R³The bond contained in the organic group (2) is not particularly limited as long as the effect of the present invention is not impaired. The organic group may contain a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, a silicon atom, or the like. Specific examples of the heteroatom-containing bond include an ether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a carbamate bond, an imino bond (-N-C (-R) -, -C (-NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, an azo bond, and the like.

As R¹、R²And R³The organic group (b) may have a heteroatom-containing bond, and from the viewpoint of heat resistance of the imidazole compound, an ether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N ═ C (-R) -, -C (═ NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, and a sulfonyl bond are preferable.

At R¹、R²And R³When the organic group(s) is a substituent other than a hydrocarbon group, R¹、R²And R³The present invention is not particularly limited as long as the effects of the present invention are not impaired. R¹、R²And R³Specific examples of (3) are, as described above, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate ester group, a phosphino group, a phosphinyl group, and a phosphonate ester group. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. The hydrocarbon group included in the substituent may be linear, branched, or cyclic.

As R¹、R²And R³The alkyl group having 1 to 12 carbon atoms, the aryl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, and the halogen atom are preferable, and the hydrogen atom is more preferable.

The thermal alkali generator (B) is not particularly limited as long as it is a compound capable of generating a basic nitrogen-containing heterocyclic compound by heating. Compounds (thermal alkali generators) that have been conventionally incorporated in various compositions and generate amines by the action of heat can be used as the thermal alkali generators (B) by replacing the skeleton derived from the amines generated upon heating with a skeleton derived from a desired basic nitrogen-containing heterocyclic compound.

Suitable examples of the thermal alkali-producing agent (B) include compounds represented by the following formula (B2):

(in the formula (B2), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b1And R^b2Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, R^b3、R^b4、R^b5、R^b6And R^b7Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, or an organic group, for R^b3、R^b4、R^b5、R^b6And R^b7Two or more of them may be bonded to form a cyclic structure, or may contain a bond of a hetero atom. ).

In the formula (B2), R¹、R²And R³And R as described for formula (B1)¹、R²And R³The same is true.

In the formula (B2), R^b1And R^b2Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group.

As R^b1And R^b2Examples of the organic group in (1) include those for R¹、R²And R³The radicals illustrated. To the organic groupTo said, with R¹、R²And R³In the same manner, the organic group may contain a hetero atom. The organic group may be linear, branched, or cyclic.

In the above, as R^b1And R^b2Each of which is independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms and having a cyano group, an alkyl group having 1 to 10 carbon atoms and having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group), an aryl group having 6 to 20 carbon atoms and substituted with an electron donating group and/or an electron withdrawing group, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having a carbon atom number of 1 to 10 carbon atoms and a heteroaryl group, A benzyl group or a cyano group substituted with an electron donating group and/or an electron withdrawing group. More preferably, R ^b1And R^b2Both are hydrogen atoms, or R^b1Is methyl and R^b2Is a hydrogen atom.

In the formula (B2), R^b3、R^b4、R^b5、R^b6And R^b7Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate ester group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate ester group, an amino group, an ammonium group, or an organic group.

As R^b3、R^b4、R^b5、R^b6And R^b7Examples of the organic group in (1) include R¹、R²And R³The groups exemplified in (1). With respect to the organic group, with R¹、R²And R³Similarly, the organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. In addition, the organic group mayThe polymer may be linear, branched or cyclic.

With respect to R^b3、R^b4、R^b5、R^b6And R^b7Two or more of them may be bonded to form a ring structure. R^b3、R^b4、R^b5、R^b6And R^b7Each may comprise a bond comprising a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group, a heteroaryl group, and a condensed ring. For example, with respect to R^b3、R^b4、R^b5、R^b6And R^b7Two or more of them may be bonded to share R^b3、R^b4、R^b5、R^b6And R^b7Atoms of the bonded benzene rings form condensed rings such as naphthalene, anthracene, phenanthrene, indene, and the like. When a condensed ring is formed, the absorption wavelength is preferably long in this respect.

In the above, as R^b3、R^b4、R^b5、R^b6And R^b7Each of which is independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms and having a cyano group, an alkyl group having 1 to 10 carbon atoms and having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms and being substituted with an electron donating group and/or an electron withdrawing group, a benzyl group, a group, cyano, and nitro.

Among the compounds represented by the above formula (B2), compounds represented by the following formula (B3) are preferred:

(in the formula (B3), R¹、R²And R³The same as those of the formulae (B1) and (B2). R^b1～R^b6The same as in the formula (B2). R^b8Represents a hydrogen atom or an organic group. R^b3And R^b4Will not be hydroxyl. For R ^b3、R^b4、R^b5And R^b6Two or more of them may be bonded to form a cyclic structure, or may contain a bond of a hetero atom. ).

The compound represented by the formula (B3) has a substituent-O-R^b8Therefore, the solubility in the solvent (S) is excellent.

In the formula (B3), R^b8Is a hydrogen atom or an organic group. R^b8In the case of an organic group, the organic group may be R¹、R²And R³The groups exemplified in (1). As the organic group, a hetero atom may be contained in the organic group. The organic group may be linear, branched, or cyclic. As R^b8The alkyl group is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

Specific examples of compounds particularly suitable as the thermoalcogenating agent (B) among the compounds represented by the formula (B1) are shown below.

Also, an imidazole compound represented by the following formula (B4) is suitable as the thermoalcogenating agent (B).

(in the formula (B4), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b9Represents a hydrogen atom or a monovalent organic group, R^b10Represents an aromatic group which may have a substituent, R^b9Can be combined withAnother R^b9Or R^b10Bonded to form a ring structure. )

In the formula (B4), R^b9Is a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and may be, for example, an alkyl group which may have a substituent, an aromatic group which may have a substituent, or the like. R ^b9In the case of an alkyl group, the alkyl group may have an ester bond or the like in the chain.

The alkyl group may be, for example, R in the formula (B4a) described later^b11Etc. are the same. The number of carbon atoms of the alkyl group is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, particularly preferably 1 or more and 20 or less, and most preferably 1 or more and 10 or less.

The substituent which the alkyl group may have may be, for example, R in the formula (B4a) described later^b11The same applies to the substituents which the alkylene group of (1) may have.

The aromatic group which may have a substituent(s) is preferably the same as R in the formula (B4a) described later^b10Also, aryl groups are preferred, and phenyl groups are more preferred. As R^b9The aromatic group which may have a substituent(s) may be reacted with R^b10The same or different.

In the formula (B4), one R is preferred^b9Is a hydrogen atom, more preferably an R^b9Is a hydrogen atom and another R^b9Is an alkyl group which may have a substituent or an aromatic group which may have a substituent.

In the formula (B4), R^b9May be reacted with another R^b9Or R^b10Bonded to form a ring structure. For example, at least one R^b9When it is an alkyl group which may have a substituent(s), R^b9May be reacted with another R^b9Or R^b10Bonded to form a ring structure.

The imidazole compound represented by formula (B4) may be a compound represented by formula (B4a) below.

(in the formula (B4a), R¹、R²And R³And in formula (B1)R¹、R²And R³Likewise, R^b11Is a hydrogen atom or an alkyl group, R^b10Is an aromatic group which may have a substituent, R^b12Is alkylene which may have a substituent, R^b12Can be reacted with R^b10Bonded to form a ring structure. )

In the formula (B4a), R^b11Is a hydrogen atom or an alkyl group. R^b11When the alkyl group is used, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

With respect to as R^b11Specific examples of the preferred alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a 2-ethyl-n-hexyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, and a n-eicosyl group.

In the formula (B4a), R^b10Is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or may be an aromatic heterocyclic group which may have a substituent.

The kind of the aromatic hydrocarbon group is not particularly limited within a range not impairing the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be a group formed by fusing 2 or more aromatic hydrocarbon groups, and may be a group formed by bonding 2 or more aromatic hydrocarbon groups by a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group are preferable.

The kind of the aromatic heterocyclic group is not particularly limited within a range not impairing the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group are preferable.

Examples of the substituent which the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, and an organic group. When the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than the hydrocarbon group, such as a heteroatom. The organic group may be linear, branched, cyclic, or a combination of these structures. The organic group is usually monovalent, and may be divalent or more in the case of forming a cyclic structure or the like.

When the aromatic group has a substituent on adjacent carbon atoms, 2 substituents bonded to the adjacent carbon atoms may be bonded to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group may contain a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, a silicon atom, or the like. Specific examples of the heteroatom-containing bond include an ether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a carbamate bond, an imino bond (-N-C (-R) -, -C (-NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, an azo bond, and the like.

The heteroatom-containing bond that the organic group may have is preferably an ether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, an amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group), a carbamate bond, an imino bond (-N ═ C (-R) -, -C (═ NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, or a sulfonyl bond, from the viewpoint of heat resistance of the imidazole compound represented by formula (B4) or formula (B4 a).

When the organic group is a substituent other than a hydrocarbon group, the kind of the substituent other than a hydrocarbon group is not particularly limited within a range not impairing the object of the present invention. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, an cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, an alkyl ether group, an alkenyl ether group, and an aryl ether group. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. The hydrocarbon group included in the substituent may be linear, branched, or cyclic.

The substituent group of the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.

As R^b10The imidazole compound represented by formula (B4) or formula (B4a) is preferably a phenyl group, a furyl group, or a thienyl group, each of which may have a substituent, from the viewpoint that the imidazole compound can be synthesized at low cost and easily and has good solubility in water or an organic solvent.

In the formula (B4a), R^b12Is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited within a range not impairing the object of the present invention. Specific examples of the substituent which the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom and the like. The alkylene group may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The number of carbon atoms of the alkylene group does not include the carbon atoms of the substituent bonded to the alkylene group.

The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as the substituent is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

With respect to as R^b12Specific examples of suitable alkylene groups include methylene, ethane-1, 2-diyl, n-propane-1, 3-diyl, n-propane-2, 2-diyl, n-butane-1, 4-diyl, n-pentane-1, 5-diyl, n-hexane-1, 6-diyl, n-heptane-1, 7-diyl, n-octane-1, 8-diyl, n-nonane-1, 9-diyl, n-decane-1, 10-diyl, n-undecane-1, 11-diyl, n-dodecane-1, 12-diyl, n-tridecane-1, 13-diyl, n-tetradecane-1, 14-diyl, n-pentadecane-1, 15-diyl, n-hexadecane-1, 16-diyl, n-heptadecane-1, 17-diyl, n-octadecane-1, 18-diyl, n-nonadecane-1, 19-diyl and n-eicosane-1, 20-diyl.

Among the imidazole compounds represented by the above formula (B4), compounds represented by the following formula (B4-1a) are preferable in terms of being able to be synthesized inexpensively and easily.

(in the formula (B4-1a), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b9R is the same as in the formula (B4)^b13、R^b14、R^b15、R^b16And R^b17Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, or an organic group. R^b13、R^b14、R^b15、R^b16And R^b17At least two of which may be bonded to form a ring structure. R^b9Can be reacted with R^b15Bonded to form a ring structure. )

In the formula (B4-1a), R^b13、R^b14、R^b15、R^b16And R^b17May be all hydrogen atoms. In addition, R is preferably R from the viewpoint of solubility of the compound represented by the formula (B4-1) in the solvent (S)^b13、R^b14、R^b15、R^b16And R^b17At least one of them is a group other than a hydrogen atom.

R^b13、R^b14、R^b15、R^b16And R^b17The same applies to those in the formula (B4-1) described later. In the formula (B4-1a), R^b9Can be reacted with R^b15Bonded to form a ring structure. For example, R^b9When it is an alkyl group which may have a substituent(s), R^b9Can be reacted with R^b15Bonded to form a ring structure.

Among the imidazole compounds represented by the above formula (B4a) or formula (B4-1a), the compound represented by the following formula (B4-1) is preferable, and the compound represented by the formula (B4-1) is more preferable, since it can be synthesized easily at low cost and has excellent solubility in water or organic solvents ^b12A compound which is methylene.

(in the formula (B4-1), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b11And R^b12And R in the formula (B4a)^b11And R^b12Likewise, R^b13、R^b14、R^b15、R^b16And R^b17Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, or an organic group. R^b13、R^b14、R^b15、R^b16And R^b17At least two of which may be bonded to form a ring structure. R^b12Can be reacted with R^b15Bonded to form a ring structure. )

In the formula (B4-1), R^b13、R^b14、R^b15、R^b16And R^b17May be all hydrogen atoms. In addition, R is preferably R from the viewpoint of solubility of the compound represented by the formula (B4-1) in the solvent (S)^b13、R^b14、R^b15、R^b16And R^b17At least one of them is a group other than a hydrogen atom.

R^b13、R^b14、R^b15、R^b16And R^b17When it is an organic group, the organic group is bonded to R in the formula (B4a)^b10The same applies to the organic group which may be present as a substituent. From the viewpoint of solubility of the imidazole compound in the solvent (S), R^b13、R^b14、R^b15And R^b16Preferably a hydrogen atom.

Among them, R is preferred^b13、R^b14、R^b15、R^b16And R^b17At least one of them is the following substituent, with R being particularly preferred^b17The following substituents are used. R^b17When the following substituents are present, R ^b13、R^b14、R^b15And R^b16Preferably a hydrogen atom.

-O-R^b18

(R^b18Is a hydrogen atom or an organic group. )

R^b18When it is an organic group, the organic group is bonded to R in the formula (B4a)^b10The same applies to the organic group which may be present as a substituent. As R^b18The alkyl group is preferable, the alkyl group having 1 to 8 carbon atoms is more preferable, the alkyl group having 1 to 3 carbon atoms is particularly preferable, and the methyl group is most preferable.

Among the compounds represented by the above formula (B4-1), the compounds represented by the following formula (B4-1-1) are preferred.

(in the formula (B4-1-1), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b11R is the same as in the formula (B4a)^b19、R^b20、R^b21、R^b22And R^b23Each independently is a hydrogen atom, hydroxyl group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate ester group, phosphino group, phosphinyl group, phosphonyl group, phosphonate ester group, amino group, ammonium group, or organic group. Wherein R is^b19、R^b20、R^b21、R^b22And R^b23At least one of them is a group other than a hydrogen atom. )

Among the compounds represented by the formula (B4-1-1), R is preferred^b19、R^b20、R^b21、R^b22And R^b23At least one of which is the above-mentioned-O-R^b18The group represented by, particularly preferably R^b23is-O-R^b18The group shown. R^b23is-O-R^b18When represents a group, R^b19、R^b20、R^b21And R^b22Preferably a hydrogen atom.

Preferred specific examples of the imidazole compound represented by formula (B4) or formula (B4a) include the following compounds.

The content of the thermal alkali generator (B) in the varnish composition is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less, with respect to the mass of the varnish composition. By using the thermal alkali-producing agent (B) in an amount within this range, the production of a polyamide resin from the polyamic acid (a) can be effectively promoted without excessive volatilization or sublimation of a thermal decomposition product of the thermal alkali-producing agent (B).

< other ingredients >

The varnish composition may contain various additives as required. Examples of the additives include a colorant, a dispersant, a sensitizer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, an antifoaming agent, and a surfactant. In addition, the varnish composition may contain various filler materials or reinforcing materials as needed.

The amount of each additive used is not particularly limited within a range not impairing the object of the present invention. The content of the solid content in the varnish composition may be appropriately adjusted within a range of, for example, 0.001 to 60 mass%, and is preferably 0.05 to 5 mass%.

The amount of the filler or the reinforcing material to be used is not particularly limited within a range not impairing the object of the present invention. Typically, the amount of the filler or the reinforcing material used is preferably 1% by mass or more and 300% by mass or less, more preferably 5% by mass or more and 200% by mass or less, and further preferably 10% by mass or more and 100% by mass or less, with respect to the mass of the polyamic acid (a).

As described above, when the varnish composition is used, a polyimide resin having improved physical properties such as a thermal expansion coefficient, elongation at break, and tensile strength can be obtained.

Method for producing polyimide resin

The polyimide resin can be produced by a method comprising the steps of:

a molding step of molding the varnish composition described above; and

When the varnish composition is molded, the shape of the molded varnish composition is not particularly limited. The method for molding the varnish composition is not particularly limited. Examples thereof include: a method of injecting the varnish composition into a mold of a desired shape; a method of filling a varnish composition into a mold using a squeegee or the like; a method of applying a varnish composition to a substrate; and so on.

Among these methods, a method of coating a varnish composition on a substrate is preferable in terms of a large demand for a polyimide resin film, ease of good removal of the solvent (S) from the varnish composition in the production of a polyimide resin, and the like.

After the varnish composition is applied, the coated film is dried in a heated and/or vacuum or reduced pressure environment to form a dried film.

The temperature at which the varnish composition or the varnish composition after the drying step is heated is not particularly limited as long as the polyimide resin having desired properties can be obtained. The temperature for heating the polyamic acid is preferably 120 ℃ or more and 430 ℃ or less, and more preferably 150 ℃ or more and 420 ℃ or less. By heating the varnish composition at a temperature in such a range, the solvent (S) can be removed while suppressing thermal degradation and thermal decomposition of the polyimide resin to be produced, and the polyimide resin can be produced.

Further, from the viewpoint of easy formation of a polyimide resin having a high glass transition temperature and tensile strength, a low thermal expansion coefficient, and little coloration, it is also preferable to heat the polyamic acid in stages at a temperature of 70 ℃ to 120 ℃ for about 10 minutes to 2 hours, and further at a temperature of 150 ℃ to 420 ℃ for about 10 minutes to 2 hours, to produce a polyimide resin.

According to the above-described method for producing a polyimide resin, a polyimide resin having improved physical properties such as a thermal expansion coefficient, elongation at break, and tensile strength can be produced.

Additives for food

The additive is used for compounding into a polyamic acid-containing liquid containing a polyamic acid (a) and a solvent (S) to obtain a varnish composition for forming a polyimide resin. The additive contains an amide compound (C). As for the additives, the polyamic acid (a), the solvent (S), and the amide compound (C) are as described above for the varnish composition. In addition, the optional components described above for the varnish composition for forming the polyimide resin may be appropriately blended with the polyamic acid-containing liquid or the varnish composition to which the additive is added.

In the case where the varnish composition containing the additive is heated to obtain a polyimide resin, at least one of a reduction in thermal expansion coefficient, an improvement in elongation at break, and an improvement in tensile strength can be achieved in the obtained polyimide resin, as compared with the case where a polyamic acid-containing liquid is heated to obtain a polyimide resin. Preferably, the use of the additive causes all of a decrease in the coefficient of thermal expansion, an increase in the elongation at break, and an increase in the tensile strength.

The form of the additive is not particularly limited. The additive may be in a solid state or a liquid state. When the additive is in a solid state, the amide compound (C) may be mixed with at least one component selected from a colorant, a dispersant, a sensitizer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, an antifoaming agent, a surfactant, and the like, and processed into a form of granules or the like. When the additive is a liquid, it is preferable to disperse or dissolve the amide compound (C) in the solvent (S). The liquid additive may contain at least one component selected from the group consisting of a colorant, a dispersant, a sensitizer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, an antifoaming agent, a surfactant and the like together with the amide compound (C).

The amount of the additive to be used is not particularly limited as long as the desired effect by the use of the additive can be obtained. The amount of the additive to be used is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, and still more preferably 5 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the polyamic acid (a) contained in the polyamic acid-containing liquid.

In addition, the amide compound (C) as an additive may be combined with the thermal alkali generator (B) in a mass ratio of the thermal alkali generator (B) to the amide compound (C) ((B): C)) of, for example, 100: 30-100: 500, more preferably 100: 100-100: 300. the thermal alkali generator (B) is preferably a compound represented by formula (B1), formula (B2), or formula (B4) described later, and more preferably a compound represented by formula (B4).

Examples

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[ preparation example 1 ]

First, a three-necked flask having a capacity of 30mL was heated with a heat gun to sufficiently dry the flask. Then, the atmosphere in the three-necked flask was replaced with nitrogen to make the atmosphere in the three-necked flask a nitrogen atmosphere. To a three-necked flask, 0.2045g (0.90 mmol: DABAN, manufactured by Nippon Kagaku K.K.) of 4,4 ' -diaminobenzanilide was added, and then N, N, N ', N ' -Tetramethylurea (TMU) was added. The contents of the three-necked flask were stirred to obtain a slurry solution in which an aromatic Diamine (DABAN) was dispersed in TMU.

Next, 0.3459g (0.90mmol) of tetracarboxylic dianhydride of the following formula was added to the three-necked flask, and then the contents of the flask were stirred at room temperature (25 ℃) for 12 hours under a nitrogen atmosphere to obtain a reaction solution. Thus, a polyamic acid solution containing polyamic acid A-1 at a solid content concentration of 18 mass% was obtained. The obtained polyamic acid A-1 can form a transparent polyimide resin.

[ preparation example 2 ]

A polyamic acid solution containing polyamic acid a-2 at a solid content concentration of 18 mass% was obtained in the same manner as in preparation example 1, except that the diamine component was changed to 4, 4' -diaminodiphenyl ether, the tetracarboxylic dianhydride component was changed to pyromellitic dianhydride, and the solvent was changed to N-methyl-2-pyrrolidone (NMP). The obtained polyamic acid A-2 can form an opaque polyimide resin.

[ examples 1 to 9 ]

The varnish compositions of examples 1 to 9 were obtained by mixing a polyamic acid solution containing 80 parts by mass of a polyamic acid (a) of the type shown in table 1, 10 parts by mass of a thermal alkali generator (B) as a compound having the following structure, and 10 parts by mass of an amide compound (C) of the type shown in table 1, and then diluting the mixture with a solvent (S) of the type shown in table 1 to a solid content concentration of 15% by mass.

[ comparative example 1 ]

A polyamic acid solution containing 80 parts by mass of polyamic acid a-1 and 20 parts by mass of the thermal alkali generator (B) used in example were mixed, and then the mixture was diluted with a solvent (S) of the type shown in table 1 to a solid content concentration of 15% by mass, to obtain a varnish composition of comparative example 1.

[ comparative example 2 ]

A polyamic acid solution containing 90 parts by mass of polyamic acid a-1 and 10 parts by mass of the thermal alkali generator (B) used in example were mixed, and then the mixture was diluted with a solvent (S) of the type shown in table 1 to a solid content concentration of 15% by mass, to obtain a varnish composition of comparative example 2.

[ comparative example 3 ]

The polyamic acid solution containing polyamic acid A-1 was diluted to a solid content concentration of 15% by mass with the solvent (S) of the type described in Table 1 to obtain a varnish composition of comparative example 3.

[ comparative example 4 ]

A polyamic acid solution containing 80 parts by mass of polyamic acid a-2 and 20 parts by mass of the thermal alkali generator (B) used in example were mixed, and then the mixture was diluted with a solvent (S) of the type shown in table 1 to a solid content concentration of 15% by mass, to obtain a varnish composition of comparative example 4.

The varnish compositions of the examples and comparative examples obtained in the above manner were used to evaluate the storage stability of the varnish compositions in the following manner. The polyimide resin was formed using the varnish composition after the evaluation of storage stability, and the formed polyimide resin was evaluated for haze, Yellowness Index (YI), light transmittance, Coefficient of Thermal Expansion (CTE), elongation at break, and tensile strength by the following methods. The varnish composition of comparative example 1 was not evaluated for a polyimide resin because the film could not be formed due to thickening during storage.

< storage stability >

The varnish compositions of the examples and comparative examples prepared in the above manner were stored at 23 ℃ for 10 days, and the varnish compositions after storage were observed. The varnish after storage was judged to be good when neither cloudiness nor gelation occurred, and the varnish after storage was judged to be poor when at least one of cloudiness and gelation occurred.

With respect to the varnish compositions of examples 1 to 6, comparative examples 2 and comparative example 3, a polyimide resin film was formed in the following manner using the varnish composition after storage for a predetermined period of time.

< method for Forming polyimide resin film >

The varnish composition after storage obtained in the above manner was spin-coated on a glass substrate (100 mm in length, 100mm in width, and 1.3mm in thickness) so that the thickness of the coating film after heat curing became 13 μm, to form a coating film. Subsequently, the glass substrate having the coating film was vacuum-dried at a temperature of 50 ℃ and a pressure of 13Pa to remove the solvent in the coating film.

After the solvent was removed, the glass substrate provided with the coating film was put into an inert oven in which nitrogen was flowed at a flow rate of 3L/min. The resultant was allowed to stand for 0.5 hour under a nitrogen atmosphere at a temperature of 80 ℃ and then further heated at a temperature of 400 ℃ (final heating temperature) for 0.5 hour in an inert oven to cure the coating film, thereby obtaining a polyimide-coated glass coated with a thin film (polyimide film) formed of polyimide.

The obtained polyimide-coated glass was immersed in hot water at 90 ℃ to peel the polyimide film from the glass substrate, thereby obtaining a polyimide film (film having a size of 100mm in length, 100mm in width and 13 μm in thickness).

< haze, Yellowness Index (YI), light (all-light) transmittance >

The haze, Yellowness Index (YI) and total light transmittance (light transmittance) values (unit:%) of the polyimide films of the examples and comparative examples were determined as follows: measurement was carried out in accordance with JIS K7361-1 (published in 1997) using a measurement apparatus of "Hazemeter NDH-5000", a trade name of Nippon Denshoku industries Co., Ltd.

< Coefficient of Thermal Expansion (CTE) >

The polyimide films of the examples and comparative examples were grown: 20mm, width: a membrane for measuring 5mm in size.

Then, the obtained film for measurement was heated from 30 ℃ to 200 ℃ at a heating rate of 10 ℃/min, temporarily cooled to 30 ℃, heated from 30 ℃ to 500 ℃ again at a heating rate of 10 ℃/min, and the change in length of the sample at 100 ℃ to 350 ℃ was measured by using a thermomechanical analyzer (trade name "TMA-60" manufactured by shimadzu corporation) as a measuring device, and the average value of the change in length at 1 ℃ in 100 ℃ to 350 ℃ was determined. The stretching mode was set to 49 mN.

< elongation at Break and tensile Strength >

For the polyimide films of the examples and comparative examples, a product name "Super dumpbell cutter (model: SDMK-1000-D, conforming to a22 standard of JIS K7139 (published in 2009)" manufactured by dumpbell co., Ltd was attached to an SD lever type sample cutter (model: sdlbell co., Ltd, model SDL-200)) so that the polyimide film had a size of the full length: 75mm, tab (tab) portion spacing: 57mm, length of parallel portion: 30mm, radius of shoulder: 30mm, width of end portion: 10mm, width of central parallel portion: 5mm, thickness: the sheet was cut to 13 μm, and a dumbbell-shaped test piece (a test piece following the JIS K7139 type a22 (scale-down test piece) except that the thickness was set to 13 μm) was prepared as a measurement sample.

Then, the measurement sample was arranged so that the width between the clamps was 57mm and the width of the clamped portion was 10mm (the total width of the end portions) using a Tensilon type universal tester (model "UCT-10T" manufactured by a & D Company), and then a tensile test of the tensile measurement sample was performed under conditions of a full load of 0.05kN and a test speed of 1 to 300 mm/min, to obtain values of tensile strength and elongation at break.

The above test was carried out in accordance with JIS K7162 (published in 1994).

The value (%) of the elongation at break was calculated by assuming that the length of the parallel portion of the test piece (length of the parallel portion: 30mm) was L0 and the length of the parallel portion of the test piece until breaking (length of the parallel portion of the test piece at the time of breaking: 30mm + α) was L:

[ elongation at break (%) ] { (L-L0)/L0} × 100.

In table 1 below, the kind of the amide compound (C) is as follows.

C-1: cinnamic acid amides

C-2: benzamide derivatives

C-3: phenylacetamides

C-4: butenamides

C-5: n-methylacetamide

C-6: 1,2, 3-propane trimethanamide

In the examples and comparative examples, when the varnish compositions containing the same polyamic acid (a) were compared, it was found that the polyimide resin formed using the varnish composition had a decreased thermal expansion coefficient and improved elongation at break and tensile strength when the amide compound (C) was contained.

In addition, as is clear from the comparative examples, when the varnish composition does not contain the amide compound (C), cloudiness and gelation may occur when the varnish composition is stored at room temperature.

On the other hand, the varnish composition of the example containing the amide compound (C) was stable even when stored at room temperature for a certain period of time.

Further, from the evaluation results of the varnish compositions of examples 1 to 6, comparative example 2 and comparative example 3 containing polyamic acid A-1 capable of forming a transparent polyimide resin, it was found that a highly transparent polyimide resin having no haze, less coloration and high light transmittance can be formed by using the varnish compositions of examples 1 to 6 containing the amide compound (C).

Claims

1. A varnish composition for forming a polyimide resin, comprising a polyamic acid (A), an amide compound (C), and a solvent (S),

the amide compound (C) is a compound represented by the following formula (C1):

R^c1-(-CO-NH-R^c2)_n···(C1)

in the formula (C1), R^c1Is an n-valent organic radical bonded to the carbonyl group via a carbon-carbon bond, R^c2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4.

2. The varnish composition of claim 1 wherein the amide compound (C) comprises R^c1Is a benzyl group, and n is 1.

3. The varnish composition of claim 1 wherein the amide compound (C) comprises a compound wherein n is 3 or 4.

4. The varnish composition according to any one of claims 1 to 3, comprising a thermal base generator (B) that generates a basic nitrogen-containing heterocyclic compound by heating.

5. The varnish composition according to claim 4, wherein the basic nitrogen-containing heterocyclic compound is a compound represented by the following formula (B1):

in the formula (B1), R¹、R²And R³Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group.

6. The varnish composition according to claim 5, wherein the thermoalcogenating agent (B) is at least 1 selected from the group consisting of a compound represented by the following formula (B2) and a compound represented by the following formula (B4),

in the formula (B2), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b1And R^b2Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, R^b3、R^b4、R^b5、R^b6And R^b7Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group, or an organic group, for R ^b3、R^b4、R^b5、R^b6And R^b7In other words, two of them are presentMay be bonded to form a cyclic structure or may contain a heteroatom bond,

in the formula (B4), R¹、R²And R³And R in the formula (B1)¹、R²And R³Likewise, R^b9Represents a hydrogen atom or a monovalent organic group, R^b10Represents an aromatic group which may have a substituent, the R^b9May be reacted with another R^b9Or R^b10Bonded to form a ring structure.

7. The varnish composition according to any one of claims 1 to 3, wherein the content of the amide compound (C) is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the entire solid content.

8. A method for producing a polyimide resin, comprising the steps of:

a molding step of molding the varnish composition according to any one of claims 1 to 7; and

and an imidization step of heating the molded varnish composition to imidize the composition.

9. An additive for compounding into a polyamic acid-containing liquid containing a polyamic acid (A) and a solvent (S) to obtain a varnish composition for forming a polyimide resin,

the additive comprises an amide compound (C),

the amide compound (C) is a compound represented by the following formula (C1):

R^c1-(-CO-NH-R^c2)_n···(C1)

In the formula (C1), R^c1Is an n-valent organic radical bonded to the carbonyl group via a carbon-carbon bond, R^c2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is 1 or moreAn integer of up to and 4 or less,

in the case where the varnish composition is heated to obtain a polyimide resin, at least one of a decrease in thermal expansion coefficient, an increase in elongation at break, and an increase in tensile strength is caused in the obtained polyimide resin, as compared with the case where the polyamic acid-containing liquid is heated to obtain a polyimide resin.