KR102577426B1 - Resin Composition, Manufacturing Method of Cured Body and Cured Body - Google Patents

Abstract

Providing a resin composition containing a polyamic acid that has excellent film forming properties and can stably form a cured product containing polyimide, a method for producing a cured product using the resin composition, and a cured product obtained by curing the resin composition. .
A resin composition containing a polyamic acid (A), a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in the molecule. One or more types selected from the group consisting of are mixed.

Description

Resin composition, manufacturing method of cured body and cured body {Resin Composition, Manufacturing Method of Cured Body and Cured Body}

The present invention relates to a resin composition containing polyamic acid, a method for producing a cured product using the resin composition, and a cured product obtained by curing the resin composition.

Because polyimide resin has characteristics such as excellent heat resistance, mechanical strength, insulation, and low dielectric constant, it is widely used as an insulating material or protective material in electrical and electronic components such as various types of devices and electronic boards such as multilayer wiring boards.

Generally, polyimide resin is formed by heat treating polyamic acid obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component in a polar organic solvent. Against this background, polyimide products for electronic materials are often supplied as a solution of a polyimide precursor such as polyamic acid. Specifically, when manufacturing electrical and electronic components, a solution of the polyimide precursor is supplied to the location where the insulating material or protective material is to be formed by methods such as coating or injection, and then the polyimide precursor solution is heat treated to form the insulating material or protective material. It is becoming.

Technologies for polyimide resin are also being pioneered.

For example, as an example in Patent Document 1, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3',4,4'-diphenylethertetracarboxylic dianhydride are used. A method for producing a polyimide resin is disclosed, which involves reacting in propylene glycol monomethyl ether acetate and imidizing at 150°C.

Patent Document 1: Japanese Patent Application Publication No. 2012-021133

Here, as a result of examination by the present inventors and others, it was found that if conditions are not appropriately set in the process of heat-curing the polyimide resin precursor, the curing behavior may not be stable and, as a result, film forming, etc. may not be performed well.

Since polyimide films with imperfect film formation have poor appearance, there has been strong anticipation for the development of a composition that can stably form a film.

The present invention was made in view of the above problems, and provides a resin composition containing a polyamic acid that has excellent film forming properties and can stably form a cured product containing polyimide, a method for producing a cured product using the resin composition, and the resin. The purpose is to provide a cured product obtained by curing the composition.

The present inventors and others have conducted diligent research to solve the above problems. As a result, the resin composition containing the polyamic acid (A) contained a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) that did not have a -CO-O- bond in the molecule. ), and completed the present invention by discovering that the above problems could be solved by combining one or more types selected from the group consisting of. Specifically, the present invention provides the following.

The first aspect of the present invention has the following formula (a1):

(In formula (a1), A is a tetravalent organic group having 6 to 50 carbon atoms, and B is a divalent organic group.)

A polyamic acid (A) having a structural unit represented by,

A resin containing at least one member selected from the group consisting of a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in the molecule. It is a composition.

A second aspect of the present invention includes a coating film forming step of forming a coating film by applying the resin composition according to the first aspect onto a substrate;

It is a method of producing a cured product including a heating process of heating the coating film at 70 to 550°C.

The third aspect of the present invention is a cured product obtained by curing the resin composition according to the first aspect.

According to the present invention, there is provided a resin composition containing a polyamic acid that has excellent film forming properties and can stably form a cured product containing polyimide, a method for producing a cured product using the resin composition, and a cured product obtained by curing the resin composition. Freight can be provided.

≪Resin composition≫

The resin composition of the first aspect of the present invention has the following formula (a1):

(In formula (a1), A is a tetravalent organic group having 6 to 50 carbon atoms, and B is a divalent organic group.)

A polyamic acid (A) having a structural unit represented by,

It contains at least one member selected from the group consisting of a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) that does not have a -CO-O- bond in the molecule. .

Here, a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in the molecule (hereinafter simply referred to as “carbonyloxy compound (B1)” )” or “Basic nitrogen-containing compound (B2)”) each has the effect of promoting the conversion of polyamic acid (A) to polyimide resin.

For this reason, when the resin composition is heated, imidization of the polyamic acid (A) proceeds uniformly and quickly, and as a result, irregularities, bends, cracks, etc. are unlikely to occur on the surface of the cured product, and it has a smooth surface and excellent appearance. A cured product can be formed.

As described above, the above resin composition cures at an appropriate rate to stably provide a cured product containing polyimide resin.

Hereinafter, essential or optional components contained in the resin composition will be described.

＜Polyamic acid (A)＞

The resin composition contains polyamic acid (A). Polyamic acid (A) is a precursor polymer for polyimide produced when the resin composition is cured.

Polyamic acid has a structural unit represented by the following formula (a1).

(In formula (a1), A is a tetravalent organic group having 6 to 50 carbon atoms, and B is a divalent organic group.)

The polyamic acid (A) mentioned above is usually obtained by condensing a diamine compound with tetracarboxylic dianhydride.

Hereinafter, the tetracarboxylic dianhydride used in the production of polyamic acid (A), the diamine compound, and the production method of polyamic acid (A) will be described.

[Tetracarboxylic dianhydride]

The tetracarboxylic dianhydride that produces the structural unit represented by formula (a1) is represented by the following formula (a1-1).

Tetracarboxylic dianhydride represented by formula (a1-1) reacts with a diamine compound described later to provide polyamic acid (A) having a structural unit represented by formula (a1). These tetracarboxylic dianhydrides may be used individually, or may be used in combination of two or more types.

(In formula (a1-1), A is a tetravalent organic group having 6 to 50 carbon atoms.)

In formula (a1-1), A is a tetravalent organic group having 6 to 50 carbon atoms, and in addition to the two acid anhydride groups represented by -CO-O-CO- in formula (a1-1), one or You may have multiple substituents.

Preferred examples of the substituent include a fluorine atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a fluorinated alkyl group with 1 to 6 carbon atoms, and a fluorinated alkoxy group with 1 to 6 carbon atoms. , In addition to the acid anhydride group represented by formula (a1-1), it may also contain a carboxyl group and a carboxylic acid ester group.

When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluorinated alkyl group or a perfluorinated alkoxy group.

Regarding the above substituents, the same can be said for one or more substituents that the aromatic group described later may have on the aromatic ring.

In formula (a1-1), A is a tetravalent organic group, the lower limit of the number of carbon atoms is 6, and the upper limit is 50.

The number of carbon atoms constituting A is more preferably 8 or more, and still more preferably 12 or more. Moreover, the number of carbon atoms constituting A is more preferably 40 or less, and even more preferably 30. A may be an aliphatic group, an aromatic group, or a combination of these structures. A may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When A contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N- , -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS- may be included in A or -O-, -CO-, -SO It is more preferable that it is included in A as a group selected from -, -SO ₂ -, -S-, and -SS-.

Tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydride conventionally used as a raw material for the synthesis of polyamic acids. Tetracarboxylic dianhydride may be aliphatic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride.

Examples of aliphatic tetracarboxylic dianhydride include 2,2-bis(3,4-dicarboxyl)propane dianhydride, bis(3,4-dicarboxyl)methane dianhydride, and , may contain an alicyclic structure. The above-mentioned alicyclic structure may be polycyclic, and examples of the polycyclic alicyclic structure include those having a cross-linked alicyclic structure such as bicyclo[2.2.1]heptane, for example, It may be condensed with a cross-linked alicyclic structure and/or a non-cross-linked alicyclic structure with a different formula, or a cross-linked alicyclic structure can be connected to a cross-linked alicyclic structure and/or a non-cross-linked alicyclic structure with a different formula through a spiro bond. It's okay too. When using aliphatic tetracarboxylic dianhydride, it tends to be easy to obtain a cured product with excellent transparency using the resin composition.

Additionally, as the aliphatic group constituting A in formula (a1-1), for example, a tetravalent group represented by the following formula (a2) can be employed. When such a group is used, it tends to be easy to obtain a transparent polyimide film.

In addition, n in the formula (a2) is preferably 5 or less, and more preferably 3 or less because the raw material compound can be easily purified. In addition, since the chemical stability of the raw material compound that gives the structure represented by formula (a1) is excellent, n is preferably 1 or more, and more preferably 2 or more.

In formula (a2), n is particularly preferably 2 or 3.

(In formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and a fluorine atom, and n is 0 to 12. It is an integer.)

Examples of aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxylphenoxy)benzene dianhydride, and 3,3',4,4'-oxybis. Phthalic acid dianhydride, 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-Biphenyltetracarboxylic acid dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, etc.

As the aromatic tetracarboxylic dianhydride, for example, those represented by the following general formulas (a1-2) to (a1-4) may be used.

In the above formulas (a1-2) and (a1-3), R ^a1 , R ^a2, and R ^a3 are each an aliphatic group that may be substituted with halogen, an oxygen atom, a sulfur atom, or an aliphatic group containing one or more divalent elements. It represents a divalent substituent composed of any aromatic group or a combination thereof. R ^a2 and R ^a3 may be the same or different.

That is, R ^a1 , R ^a2 and R ^a3 may include a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine), and 2,2-bis (3,4-dicarboxyltrifluorophenoxy)propane dianhydride, 1,4-bis(3,4-dicarboxyltrifluorophenoxy)benzene dianhydride, 1,4-bis(3,4-dicarhydride) Leboxyltrifluorophenoxy) tetrachlorobenzene dianhydride, 2,2',5,5',6,6'-hexafluoro-3,3',4,4',-biphenyltetracarboxylic acid dianhydride etc. can be mentioned.

In addition, in the above formula (a1-4), R ^a4 and R ^a5 are any of an aliphatic group that may be substituted with halogen, an aromatic group interposed by one or more divalent elements, and halogen, or a combination thereof. The constituting monovalent substituents may be the same or different, and difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, etc. can be used.

Examples of tetracarboxylic dianhydride for obtaining a fluorinated polyimide containing fluorine in the molecular structure include (trifluoromethyl)pyromellitic dianhydride, di(trifluoromethyl)pyromellitic dianhydride, and di( Heptafluoropropyl)pyromellitic dianhydride, pentafluorethylpyromellitic dianhydride, bis{3,5-di(trifluoromethyl)phenoxypyromellitic dianhydride, 2,2-bis(3,4-dicar) Leboxylphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxylbiphenyl dianhydride, 2,2',5,5'- Tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxylbiphenyl dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxyl Boxyl diphenyl ether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxylbenzophenone dianhydride, bis{(trifluoromethyl)dicarboxylphenoxy} Benzene dianhydride, bis(trifluoromethyl)dicarboxylphenoxyc(trifluoromethyl)benzene dianhydride, bis(dicarboxylphenoxy(trifluoromethyl)benzene dianhydride, bis(dicarboxylphenoxy) Bis(trifluoromethyl)benzene dianhydride, bis(dicarboxylphenoxy)tetrakis(trifluoromethyl)benzene dianhydride, 2,2-bis{4-(3,4-dicarboxylphenoxy)phenyl} Hexafluoropropane dianhydride, bis(trifluoromethyl)dicarboxylphenoxy｝biphenyl dianhydride, bis(trifluoromethyl)dicarboxylphenoxy｝bis(trifluoromethyl)biphenyl dianhydride, bis｛ (trifluoromethyl)dicarboxylphenoxy｝diphenyl ether dianhydride, bis(dicarboxylphenoxy)bis(trifluoromethyl)biphenyl dianhydride, difluoropyromellitic dianhydride, 1,4-bis( 3,4-dicarboxyltrifluorophenoxy)tetrafluorobenzene dianhydride, 1,4-bis(3,4-dicarboxyltrifluorophenoxy)octafluorobiphenyl dianhydride, etc.

As tetracarboxylic dianhydride, when considering the heat resistance, tensile elongation, chemical resistance, etc. of the obtained film or molded body, it is preferable to use aromatic tetracarboxylic dianhydride. In terms of price, availability, etc., 3,3',4 , 4'-biphenyltetracarboxylic dianhydride, and pyromellitic dianhydride are preferably used. In addition, acid chloride, ester chloride, etc. of tetracarboxylic acid having the same basic skeleton as these can also be used.

In this embodiment, tetracarboxylic dianhydride may be used in combination with dicarboxylic acid anhydride. When these carboxylic acid anhydrides are used together, the properties of the resulting imide ring-containing polymer such as polyimide resin may become even better. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorenedic anhydride, and methyltetrahydrophthalic acid. Phthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, etc. can be mentioned.

[Diamine compound]

The diamine compound represented by the following formula (a3-1) can typically be used. A diamine compound may be used individually by 1 type, or may be used in combination of 2 or more types.

H ₂ NB-NH ₂ … (a3-1)

(In formula (a3-1), B represents a divalent organic group.)

In formula (a3-1), B is a divalent organic group and may have one or more substituents in addition to the two amino groups in formula (a3-1).

Preferred examples of substituents include a fluorine atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a fluorinated alkyl group with 1 to 6 carbon atoms, a fluorinated alkoxy group with 1 to 6 carbon atoms, and a hydroxyl group. do.

When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluorinated alkyl group or a perfluorinated alkoxy group.

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

B may be an aliphatic group, but is preferably an organic group containing one or more aromatic rings.

When B is an organic group containing one or more aromatic rings, the organic group may be one aromatic group itself, and the two or more aromatic groups may be an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. It may be a group bonded through a bond containing . Bonds containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms contained in B include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O- , -CO-, -SO-, -SO ₂ -, -S-, and -SS-, and -O-, -CO-, -SO-, -SO ₂ -, -S-, and - SS- is preferred.

The aromatic ring bonded to the amino group in B is preferably a benzene ring. When the ring bonded to the amino group in B is a condensed ring containing two or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring.

Additionally, the aromatic ring contained in B may be an aromatic heterocycle.

When B is an organic group containing an aromatic ring, from the viewpoint of heat resistance of the cured product formed using the resin composition, the organic group is preferably at least one type of group represented by the following formulas (1) to (4).

(In formulas (1) to (4), R ¹¹ is one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group with 1 to 4 carbon atoms, and a halogenated alkyl group with 1 to 4 carbon atoms. In formula (4), Q is a 9,9'-fluoreneylidene group or formula:

-C ₆ H ₄ -, -CONH-C ₆ H ₄ -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -OCO-C ₆ H ₄ -COO-, -OCO-C ₆ H ₄ -C ₆ H ₄ -COO-, -OCO-, -O-, -S-, -CO-, -CONH-, -SO ₂ -, -C( CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -C(CF ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -, It represents one type selected from the group consisting of groups represented by -OC ₁₀ H ₆ -O-, -OC ₆ H ₄ -C ₆ H ₄ -O-, and -OC ₆ H ₄ -O-.

In the example of Q, -C ₆ H ₄ - is a phenylene group, m-phenylene group and p-phenylene group are preferable, and p-phenylene group is more preferable. In addition, -C ₁₀ H ₆ - is a naphthalenediyl group, naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group is preferred, naphthalene-1,4-diyl group, and naphthalene-2,6-diyl group are more preferred.)

R ¹¹ in formulas (1) to (4) is more preferably a hydrogen atom, a hydroxyl group, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, from the viewpoint of heat resistance of the cured product to be formed. is particularly preferable.

Q in formula (4) is 9,9'-fluoreneylidene group, -OC ₆ H ₄ -O-, -C(CF ₃ ) ₂ -, -O-, -C( CH ₃ ) ₂ -, -CH ₂ -, or -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -CONH- are preferred, -OC ₆ H ₄ -O-, - C(CF ₃ ) ₂ - or -O- is particularly preferred.

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

That is, the aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis( Trifluoromethyl) biphenyl, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1 ,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4- aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, and

4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, etc. can be mentioned. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferred in terms of price, availability, etc.

Additionally, as B, a silicon atom-containing group that may have a chain-shaped aliphatic group and/or an aromatic ring can be employed. Typically, the groups shown below can be used as such silicon atom-containing groups.

Additionally, from the viewpoint of further improving the mechanical properties of the obtained cured product, a group represented by the following formula (Si-1) can also be preferably used as B.

(In formula (Si-1), R ¹² and R ¹³ are each independently a single bond, a methylene group, an alkylene group with 2 to 20 carbon atoms, a cycloalkylene group with 3 to 20 carbon atoms, or a carbon atom number. 6 to 20 allylene groups, etc., and R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, or a 6 to 20 carbon atom group. an aryl group of 20, a group containing an amino group of 20 or less carbon atoms, a group represented by -OR ¹⁸ (R ¹⁸ is a hydrocarbon group of 1 to 20 carbon atoms), and one or more epoxy groups of 2 to 20 carbon atoms. It is an organic group that contains, and I is an integer of 3 to 50.)

The alkylene group having 2 to 20 carbon atoms for R ¹² and R ¹³ in the formula (Si-1) is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and is preferably a dimethylene group, Trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc. are mentioned.

The cycloalkylene group having 3 to 20 carbon atoms for R ¹² and R ¹³ in formula (Si-1) is preferably a cycloalkylene group having 3 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and a cyclobutylene group. , cyclopentylene group, cyclohexylene group, cycloheptylene group, etc.

The allylene group having 6 to 20 carbon atoms for R ¹² and R ¹³ in formula (Si-1) is preferably an aromatic group having 6 to 20 carbon atoms from the viewpoint of heat resistance and residual stress, and a phenylene group and a naphthylene group. etc. can be mentioned.

The alkyl group having 1 to 20 carbon atoms for R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in the formula (Si-1) is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, etc.

As the cycloalkyl group having 3 to 20 carbon atoms in R ¹³ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in formula (Si-1), a cycloalkyl group having 3 to 10 carbon atoms is preferable from the viewpoint of heat resistance and residual stress. And specifically, cyclopentyl group, cyclohexyl group, etc. can be mentioned.

The aryl group having 6 to 20 carbon atoms for R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in formula (Si-1) is preferably an aryl group having 6 to 12 carbon atoms from the viewpoint of heat resistance and residual stress, Specifically, phenyl group, tolyl group, naphthyl group, etc. can be mentioned.

Examples of groups containing an amino group having 20 or less carbon atoms at R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in formula (Si-1) include amino groups and substituted amino groups (for example, bis(trialkylsilyl)amino groups). ), etc.

The group represented by -OR ¹⁸ in R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in formula (Si-1) includes methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, Tolyloxy group, naphthyloxy group, propenyloxy group (for example, aryloxy group), and cyclohexyloxy group can be mentioned.

Among them, R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are preferably methyl, ethyl, propyl, or phenyl.

The group represented by the formula (Si-1) can be derived by reacting a silicon-containing compound having amino groups at both ends with an acid anhydride. Specific examples of such silicon-containing compounds include amino-modified methylphenyl silicone at both ends (e.g., X-22-1660B-3 (number average molecular weight approximately 4,400) and X-22-9409 (number average molecular weight approximately 1,300) manufactured by Shin-Etsu Chemical Co., Ltd. , amino-modified dimethyl silicone at both ends (e.g., X-22-161 A (number average molecular weight approximately 1,600), degree); BY16-835 U (number average molecular weight approximately 900) manufactured by Toray Dow Corning; and Cyraprene FM3311 (number average molecular weight approximately 1000) manufactured by JNC.

[Method for producing polyamic acid (A)]

Polyamic acid (A) having a structural unit represented by formula (a1) typically includes tetracarboxylic dianhydride represented by the above-mentioned formula (a1-1) and the above-mentioned formula (a3-1). It is a polymer obtained by reacting a diamine compound in a solvent, and may be a polymer obtained by using one type or two or more types of diamine compound and/or tetracarboxylic dianhydride, respectively. For example, it may be a polymer obtained by polycondensing a mixture containing a diamine compound and two or more types of tetracarboxylic dianhydrides. In addition, polyamic acid (A) can be used alone or in a mixture of two or more types.

The amount of tetracarboxylic dianhydride and diamine compound used when synthesizing polyamic acid (A) is not particularly limited, but it is preferable to use 0.50 to 1.50 mole of diamine compound per 1 mole of tetracarboxylic dianhydride, and 0.60 mole. It is more preferable to use ~1.30 mol, and it is especially preferable to use 0.70-1.20 mol.

In addition, the weight average molecular weight of the polyamic acid (A) obtained may be set appropriately according to the intended use, but for example, it is 5000 or more, preferably 7500 or more, and more preferably 10000 or more. On the other hand, the weight average molecular weight of the polyamic acid (A) obtained is, for example, 100,000 or less, preferably 80,000 or less, and more preferably 75,000 or less.

This weight average molecular weight can be set to the above-mentioned value by adjusting reaction conditions such as the compounding amount of tetracarboxylic dianhydride and diamine compound, solvent, and reaction temperature.

The reaction between tetracarboxylic dianhydride and a diamine compound is usually carried out in an organic solvent. The organic solvent used for the reaction between tetracarboxylic dianhydride and diamine compound is particularly limited as long as it can dissolve tetracarboxylic dianhydride and diamine compound and does not react with tetracarboxylic dianhydride and diamine compound. It doesn't work. Organic solvents can be used individually or in combination of two or more types.

Examples of organic solvents used in the reaction between tetracarboxylic dianhydride and diamine compounds include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-dimethyl. Nitrogen-containing polar solvents such as formamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea; Dimethyl sulfoxide; Acetonitrile; Diethylene glycol dimethyl Ether types include ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran.

Among these organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N, etc., due to the solubility of the produced polyamic acid (A) and polyimide resin. -Nitrogen-containing polar solvents such as dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea are preferred.

The temperature when reacting tetracarboxylic dianhydride and a diamine compound is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature between tetracarboxylic dianhydride and the diamine compound is preferably -5 to 150°C, more preferably 0 to 120°C, and particularly preferably 0 to 70°C. The time for reacting tetracarboxylic dianhydride and the diamine compound varies depending on the reaction temperature, but typically 1 to 50 hours is preferable, 2 to 40 hours is more preferable, and 5 to 30 hours is particularly preferable.

By the method described above, a solution containing polyamic acid (A) is obtained.

The method for preparing the resin composition according to the first aspect is not particularly limited, but is added to a solution containing the obtained polyamic acid (A), a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and - in the molecule - A method of mixing one or more types selected from the group consisting of basic nitrogen-containing compounds (B2) that do not have a CO-O-bond is preferred.

As described above, the solution containing the polyamic acid (A) can be used as is for the preparation of the resin composition, or the solution of the polyamic acid (A) can be prepared under reduced pressure at a low temperature such that conversion of the polyamic acid to polyimide resin does not occur. A paste or solid of polyamic acid obtained by removing at least part of the solvent can also be used to prepare a resin composition.

<Carbonyloxy compound (B1) and basic nitrogen-containing compound (B2)>

The resin composition contains at least one member selected from the group consisting of a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in the molecule. Includes. Carbonyloxy compound (B1) and basic nitrogen-containing compound (B2) are components that promote the production of polyimide from polyamic acid (A), respectively.

For this reason, when the resin composition according to the first aspect is used, the polyamic acid (A) is converted to polyimide at an appropriate rate, and it is easy to obtain a cured product with a stable shape.

The effect of promoting the production of polyimide can be obtained by using only either the carbonyloxy compound (B1) or the basic nitrogen-containing compound (B2), but the carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) can be used. It is preferable to mix them into a resin composition in combination from the viewpoint of curability of the resin composition.

Hereinafter, the carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) will be described, respectively.

[Carbonyloxy compound (B1)]

The carbonyloxy compound is not particularly limited as long as it is a compound having a -CO-O- bond in the molecule. The carbonyloxy compound (B1) promotes ring closure by dehydration in the polyamic acid (A), thereby favorably progressing curing of the resin composition.

Examples of the carbonyloxy compound (B1) include carboxylic acid, carboxylic acid ester, carboxylic acid anhydride, and carbonate.

Carbonyloxy compound (B1) may be used in combination of two or more types.

(carboxylic acid)

The carboxylic acid may be an aliphatic carboxylic acid or an aromatic carboxylic acid. In addition, the carboxylic acid may be a monovalent carboxylic acid having one carboxyl group, or may be a polyvalent carboxylic acid having two or more carboxyl groups.

Moreover, the number of carbon atoms of carboxylic acid is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 30.

Preferred specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lactic acid, acrylic acid, and methacrylic acid; Aliphatic polycarboxylic acids such as oxalic acid, maleic acid, adipic acid, sebacic acid, azelaic acid, fumaric acid, and itaconic acid; benzoic acid, salicylic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid Benzoic acid, m-chlorobenzoic acid, o-methylbenzoic acid, p-methylbenzoic acid, m-methylbenzoic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4 , 4'-dicarboxyl biphenyl, 4,4'-dicarboxyl diphenyl ether, and aromatic carboxylic acids such as trimellitic acid.

Additionally, compounds having a carboxyl group bonded to an aromatic group and an alkylene group are also preferable as carboxylic acids. Specific examples of such compounds include phenylacetic acid, 3-phenylpropionic acid, and 4-phenylbutanoic acid.

In addition, in this embodiment, examples of carboxylic acids preferably used include compounds represented by the following formula (b1-1).

(In formula (b1-1), R ^b0 , R ^b1 and R ^b2 are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, and sulfino group. group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group or organic group, and either of R ^b0 and R ^b1 is an aromatic group or alkyl group that may have a substituent.)

Examples of the organic group in formula (b1-1) include an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, and aralkyl group. This organic group may contain bonds or substituents other than hydrocarbon groups such as hetero atoms among the above-mentioned organic groups.

Additionally, this organic group may be linear, branched, or cyclic. This organic group is usually monovalent, but in cases such as when forming a cyclic structure, it may be a divalent or higher 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 include a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples of bonds containing heteroatoms include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, and imino bond (-N=C(-R)-, -C (=NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond, etc.

Bonds containing heteroatoms that the organic group may have include, from the viewpoint of heat resistance of the compound represented by formula (b1-1), ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, and urethane. A bond, an imino bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.

Specific examples of R ^b0 , R ^b1 , and R ^b2 include a halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group, and silyl group. , silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonate group, phosphino group, phosphino group. Examples include pynyl group, phosphonato group, alkyl ether group, alkenyl ether group, alkylthioether group, alkenylthioether group, arylether group, and arylthioether group. The hydrogen atom included in the substituent may be substituted by a hydrocarbon group. Additionally, the hydrocarbon group included in the substituent may be linear, branched, or cyclic.

In formula (b1-1), either R ^b0 or R ^b1 is an aromatic group or an alkyl group that may have a substituent. In formula (b1-1), when either R ^b0 or R ^b1 is an alkyl group, the alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, particularly preferably 1 to 10, more preferably 1 to 6, and most preferably 1 to 4.

R ^b2 may be an alkyl group, and in this case, the alkyl group is preferably the same as above.

In formula (b1-1), when either R ^b0 or R ^b1 is an aromatic group that may have a substituent, the type of substituent that the aromatic group may have is not particularly limited as long as it does not impair the purpose of the present invention. Preferred examples of the substituent include a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonato group or organic group. .

In formula (b1-1), when either R ^b0 or R ^b1 is an aromatic group that may have a substituent, the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and an aromatic hydrocarbon group is preferable. Preferred examples of aromatic groups include phenyl group, naphthyl group, biphenyl group, anthryl group, and phenanthryl group. Among these aromatic groups, phenyl group is preferable.

R ^b2 may be an aromatic group that may have a substituent. In this case, the aromatic group that may have a substituent is preferably the same as above.

Specific examples of substituents that the aromatic group may have are the same as those for R ^b0 , R ^b1 , and R ^b2 .

Among the compounds represented by formula (b1-1), preferred compounds include those represented by the following formula (b1-2).

(In formula (b1-2), R ^b1 and R ^b2 are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, alcohol Represents porosity, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group.R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 are each independently hydrogen atom, halogen Atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, Represents an amino group, an ammonium group, or an organic group. Two or more of R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 may be combined to form a cyclic structure, or may include a hetero atom bond. .)

The organic groups in R ^b1 and R ^b2 are the same as the organic groups described for formula (b1-1).

Among the above, R ^b1 and R ^b2 in formula (b1-2) each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 13 carbon atoms, and a cycloalkyl group with 4 to 13 carbon atoms. Alkenyl group, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having a cyano group, alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon Alkoxy group with 1 to 10 carbon atoms, amide group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, acyl group with 1 to 10 carbon atoms, aryl group with 6 to 20 carbon atoms, It is preferable that they are an aryl group having 6 to 20 carbon atoms substituted with an electron donating group and/or an electron withdrawing group, a benzyl group, a cyano group, or a methylthio group substituted with an electron donating group and/or an electron withdrawing group. More preferably, both R ^b1 and R ^b2 are hydrogen atoms, or R ^b1 is a methyl group and R ^b2 is a hydrogen atom.

Organic groups in R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 include those exemplified for R ^b1 and R ^b2 . As in the case of R ^b1 and R ^b2 , this organic group may contain bonds or substituents other than hydrocarbon groups such as hetero atoms. Additionally, this organic group may be linear, branched, or cyclic.

Two or more of R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 may be combined to form a cyclic structure, or may include a hetero atom bond. Examples of the cyclic structure include heterocycloalkyl groups and heteroaryl groups, and may be condensed rings. For example, R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 are two or more of them bonded, and the atom of the benzene ring to which R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 is bonded. may be shared to form a condensed ring of naphthalene, anthracene, phenanthrene, indene, etc.

Among the above, R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 13 carbon atoms, and 4 to 13 carbon atoms. cycloalkenyl group, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having a cyano group, alkyl group having 1 to 10 carbon atoms having a hydroxyl group. , alkoxy group with 1 to 10 carbon atoms, amide group with 2 to 11 carbon atoms, alkylthio group with 1 to 10 carbon atoms, acyl group with 1 to 10 carbon atoms, ester with 2 to 11 carbon atoms. group, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with an electron-donating group and/or an electron-withdrawing group, a benzyl group substituted with an electron-donating group and/or an electron-withdrawing group, and cyanogroup. It is preferable that they are a methylthio group or a nitro group.

In addition, as R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 , two or more of them are bonded and share the atom of the benzene ring to which R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 are bonded. Therefore, it is also preferable to form a condensed ring such as naphthalene, anthracene, phenanthrene, or indene.

Among the compounds represented by the above formula (b1-2), the compound represented by the following formula (b1-3) is preferable.

(In formula (b1-3), R ^b1 to R ^b6 have the same meaning as formula (b1-2). R ^b8 represents a hydrogen atom or an organic group. R ^b3 and R ^b4 do not become hydroxyl groups. R ^b3 , R ^b4 , R ^b5 , and R ^b6 may combine two or more of them to form a cyclic structure, or may include a hetero atom bond.)

Since the compound represented by formula (b1-3) has a substituent -OR ^b8 , it is easy to disperse or dissolve uniformly in the resin composition.

In formula (b1-3), R ^b8 is a hydrogen atom or an organic group. When R ^b8 is an organic group, examples of the organic group include those exemplified by R ^b1 and R ^b2 . This organic group may contain a hetero atom in the organic group. Additionally, this organic group may be linear, branched, or cyclic. As R ^b8 , a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group is more preferable.

Specific examples of particularly preferable compounds among the compounds represented by formula (b1-1) are shown below.

(carboxylic acid ester)

The carboxylic acid ester is not particularly limited as long as it is a compound having an ester bond. The carboxylic acid ester may have an aromatic group.

Examples of carboxylic acid esters include C ₁ -C ₁₀ alkyl esters, C ₃ -C ₁₀ cycloalkyl esters, phenyl esters, C ₆ -C ₁₀ alkylphenyl esters, and C ₇ -C ₁₀ of the above-mentioned carboxylic acids. alkoxyphenyl ester, naphthyl ester, C ₇ -C ₁₀ aralkyl ester, etc.

When the carboxylic acid ester is an ester of a polyhydric carboxylic acid, the carboxylic acid ester may have a carboxyl group along with the ester bond. For example, terephthalic acid monomethyl ester is also a carboxylic acid ester.

Preferred specific examples of carboxylic acid esters include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, sec-butyl formate, tert-butyl formate, n-pentyl formate, and n-formate. Hexyl, n-heptyl formate, n-octyl formate, cyclopropyl formate, cyclobutyl formate, cyclopentyl formate, cyclohexyl formate, cycloheptyl formate, cyclooctyl formate, phenyl formate, o-tolyl formate, m-tolyl formate, formic acid Formic acid esters such as p-tolyl, α-naphthyl formate, β-naphthyl formate, benzyl formate, and phenethyl formate; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl butyrate, acetic acid Isobutyl, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, acetic acid Acetic acid esters such as cycloheptyl, cyclooctyl acetate, phenyl acetate, o-tolyl acetate, m-tolyl acetate, p-tolyl acetate, α-naphthyl acetate, β-naphthyl acetate, benzyl acetate, and phenethyl acetate; propionic acid Methyl, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, n-pentyl propionate, n-hexyl propionate, n-heptyl propionate, n-propionate. -Octyl, cyclopropyl propionate, cyclobutyl propionate, cyclopentyl propionate, cyclohexyl propionate, cycloheptyl propionate, cyclooctyl propionate, phenyl propionate, o-tolyl propionate, m-tolyl propionate, p-tolyl propionate, α-naphthyl propionate. , propionate esters such as β-naphthyl propionate, benzyl propionate, and phenethyl propionate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert acrylate -Butyl, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, phenyl acrylate, Acrylic acid esters such as o-tolyl acrylate, m-tolyl acrylate, p-tolyl acrylate, α-naphthyl acrylate, β-naphthyl acrylate, benzyl acrylate, and phenethyl acrylate; methyl methacrylate, ethyl methacrylate, and metacrylate n-propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-methacrylate -Hexyl, n-heptyl methacrylate, n-octyl methacrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, methacrylic acid Cyclooctyl, phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, p-tolyl methacrylate, α-naphthyl methacrylate, β-naphthyl methacrylate, benzyl methacrylate, and methacrylic acid esters such as phenethyl methacrylate; methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, isobutyl benzoate, sec-butyl benzoate, tert-butyl benzoate, and n-pentyl benzoate. , n-hexyl benzoate, n-heptyl benzoate, n-octyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, cyclooctyl benzoate, phenyl benzoate, o-tolyl benzoate, m benzoate. -Benzoic acid esters such as tolyl, p-tolyl benzoate, α-naphthyl benzoate, β-naphthyl benzoate, benzyl benzoate, and phenethyl benzoate; dimethyl terephthalate, diethyl terephthalate, din-propyl terephthalate, diisopropyl terephthalate, Din-butyl terephthalate, diisobutyl terephthalate, disec-butyl terephthalate, ditert-butyl terephthalate, din-pentyl terephthalate, din-hexyl terephthalate, din-heptyl terephthalate, din-octyl terephthalate, dicyclo terephthalate. Propyl, dicyclobutyl terephthalate, dicyclopentyl terephthalate, dicyclohexyl terephthalate, dicycloheptyl terephthalate, dicyclooctyl terephthalate, diphenyl terephthalate, di-tolyl terephthalate, dim-tolyl terephthalate, dip-tolyl terephthalate, terephthalic acid. Terephthalic acid diesters such as diα-naphthyl, diβ-naphthyl terephthalate, dibenzyl terephthalate, and diphenethyl terephthalate; ethylene glycol monoacetate, ethylene glycol monopropionate, ethylene glycol monobutanoate, ethylene glycol monopenta Ethylene glycol esters such as noate, ethylene glycol monobenzoate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dibutanoate, ethylene glycol dipentanoate, and ethylene glycol dibenzoate; diethylene glycol Monoacetate, Diethylene Glycol Monopropionate, Diethylene Glycol Monobutanoate, Diethylene Glycol Monopentanoate, Diethylene Glycol Monobenzoate, Diethylene Glycol Diacetate, Diethylene Glycol Dipropionate, Diethylene Diethylene glycol esters such as glycol dibutanoate, diethylene glycol dipentanoate, and diethylene glycol dibenzoate; propylene glycol monoacetate, propylene glycol monopropionate, propylene glycol monobutanoate, propylene glycol mono Propylene glycol esters such as pentanoate, propylene glycol monobenzoate, propylene glycol diacetate, propylene glycol dipropionate, propylene glycol dibutanoate, propylene glycol dipentanoate, and propylene glycol dibenzoate; dipropylene Glycol Monoacetate, Dipropylene Glycol Monopropionate, Dipropylene Glycol Monobutanoate, Dipropylene Glycol Monopentanoate, Dipropylene Glycol Monobenzoate, Dipropylene Glycol Diacetate, Dipropylene Glycol Dipropionate, D Dipropylene glycol esters such as propylene glycol dibutanoate, dipropylene glycol dipentanoate, and dipropylene glycol dibenzoate; can be mentioned.

In addition, methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, and tert-butyl ester of the carboxylic acid represented by the above formula (b1-1). , n-pentyl ester, n-hexyl ester, n-heptyl ester, n-octyl ester, cyclopropyl ester, cyclobutyl ester, cyclopentyl ester, cyclohexyl ester, cycloheptyl ester, cyclooctyl ester, phenyl ester, o- Tolyl ester, m-tolyl ester, p-tolyl ester, α-naphthyl ester, β-naphthyl ester, benzyl ester, and phenethyl ester are also preferred as carboxylic acid esters.

(carboxylic acid anhydride)

The carboxylic acid anhydride is not particularly limited as long as it is a compound having a carboxylic acid anhydride group (-CO-O-CO-).

Preferred examples of carboxylic acid anhydride include acetic anhydride, propionic anhydride, butanoic anhydride, benzoic anhydride, phthalic anhydride, naphthalic anhydride, succinic anhydride, hetic anhydride, hymic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. , tetrabromophthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 5- (2,5-oxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and styrene maleic anhydride copolymer.

(carbonate)

Carbonate is not particularly limited as long as it is a compound having a carbonate bond (-O-CO-O-). The carbonate may be a linear carbonate such as dimethyl carbonate or a cyclic carbonate such as ethylene carbonate.

Preferred specific examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, din-propyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

Among the carbonyloxy compounds (B1) described above, the following formula (b1):

(In formula (b1), R ^b0 is an alkyl group or an aromatic group that may have a substituent, and R ^b9 is a hydrogen atom or an alkyl group.)

Compounds represented by are particularly preferable.

When R ^b9 is an alkyl group, the alkyl group is the same as the alkyl group of R ^b0 in formula (b1-1) described above.

Moreover, in this embodiment, it is especially preferable that R ^b9 is a hydrogen atom because the polyamic acid (A) can be converted into polyimide at an appropriate rate.

[Basic nitrogen-containing compound (B2)]

The basic nitrogen-containing compound (B2) is not particularly limited as long as it is a compound that contains a nitrogen atom and exhibits basicity as defined by Brønsted.

Examples of basic nitrogen-containing compounds (B2) include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, isobutylamine, n-butylamine, n-pentylamine, n-hexylamine, and dimethylamine. , diethylamine, din-propylamine, diisopropylamine, diisobutylamine, din-butylamine, din-pentylamine, din-hexylamine, trimethylamine, triethylamine, trin-propylamine Amine, triisopropylamine, triisobutylamine, trin-butylamine, trin-pentylamine, trin-hexylamine, aniline, o-toluidine, m-toluidine, p-toluidine, α-naphthylamine, and acyclic amines such as β-naphthylamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

Additionally, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, and aminoalkylmol. Porin and the like are also preferable as basic nitrogen-containing compounds (B2).

These may have a substituent, and preferred substituents include amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, and cyanogroup. Examples include anger, etc.

Particularly preferred organic basic compounds (B2) include guanidine, 1,1-dimethylguanidine, 1,1,3,3,-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N- Methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2 -Dimethylamino pyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5- Methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2- Aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl) p. Rollidine, pyrazole, 3-amino-5-methyl pyrazole, 5-amino-3-methyl-1-p-tolyl pyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2 , 4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-(2-aminoethyl) morpholine, and 1,8- Diazabicyclo[5.4.0]-7-undecene, etc. can be mentioned.

In the above, the basic nitrogen-containing compound (B2) was explained. However, among the basic nitrogen-containing compounds (B2), the imidazole compound containing an imidazole ring is used because it has a high effect of promoting curing of the polyamic acid (A). desirable. These imidazole compounds are typically represented by the following formula (b2-1).

(In formula (b2-1), R ^b10 , R ^b11 , and R ^b12 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, and a sulfo group. It is a nate group, phosphino group, phosphinyl group, phosphonato group, or organic group.)

Examples of the organic groups in R ^b10 , R ^b11 , and R ^b12 in formula (b2-1) include an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, and aralkyl group. This organic group may contain bonds or substituents other than hydrocarbon groups such as hetero atoms among the above-mentioned organic groups. Additionally, this organic group may be linear, branched, or cyclic. This organic group is usually monovalent, but in cases such as when forming a cyclic structure, it may be a divalent or higher organic group.

The organic groups in R ^b10 , R ^b11 , and R ^b12 in formula (b2-1) are the same as the organic groups in formula (b1-1).

R ^b10 , R ^b11 , and R ^b12 are preferably a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, an aryl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, and a halogen atom, and a hydrogen atom is preferable. It is more desirable.

The total amount of the carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) in the resin composition is not particularly limited as long as it does not impair the purpose of the present invention, but is 100 parts by mass of the polyamic acid (A). Relative to this, 0.01 to 30 parts by mass is preferable, 0.05 to 25 parts by mass is more preferable, and 0.2 to 20 parts by mass is particularly preferable.

In addition, when the carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) are used together, the ratio W _B1 / of the mass W _B1 of the carbonyloxy compound (B1) and the mass W _B2 of the basic nitrogen-containing compound (B2) W _B2 is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and especially preferably 15/85 to 85/15.

＜Solvent (S)＞

The resin composition preferably contains a solvent (S) from the viewpoint of applicability. The resin composition may be a paste containing a solid or may be a solution, but is preferably a solution. The solvent (S) can be used individually or in mixture of two or more types.

The type of solvent (S) is not particularly limited as long as it does not impair the purpose of the present invention. Examples of preferred solvents (S) are the same as those used for the reaction between tetracarboxylic dianhydride and diamine compounds described above.

Additionally, the solvent (S) may contain an alcohol-based solvent such as polyethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

When the solvent (S) contains an alcohol-based solvent, it is easy to form a cured product with excellent heat resistance.

The solvent (S) may also be a solvent containing the compound (S1) represented by the following formula (5).

(In formula (5), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is represented by the following formula (5-1) or the following formula (5-2):

It is a group represented by . In formula (5-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (5-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Among compounds (S1) represented by formula (5), specific examples when R ^S3 is a group represented by formula (5-1) include N,N,2-trimethylpropionic acid amide, N-ethyl-N,2-dimethyl Propionic acid amide, N,N-diethyl-2-methylpropionic acid amide, N,N,2-trimethyl-2-hydroxypropionic acid amide, N-ethyl-N,2-dimethyl-2-hydroxypropionic acid amide, and N,N-diethyl-2-hydroxy-2-methylpropionic acid amide, etc. can be mentioned.

Specific examples of compounds (S1) represented by formula (5) where R ^S3 is a group represented by formula (5-2) include N,N,N',N'-tetramethylurea, N,N,N ',N'-tetraethyl urea, etc. can be mentioned.

Among the above examples of compound (S1), N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are particularly preferred.

When the resin composition contains a solvent (S), the content of the above-mentioned compound (S1) in the solvent (S) is not particularly limited as long as it does not impair the purpose of the present invention. Typically, the ratio of compound (S1) to the mass of solvent is preferably 70% by mass or more, more preferably 80% by mass or more, and especially preferably 90% by mass or more, with respect to the total amount of solvent (S). It is most preferable that it is 100% by mass.

Organic solvents that can be used with compound (S1) include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, and 1,3-dimethyl. Nitrogen-containing polar solvents such as -2-imidazolidinone; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Cyclic ethers such as dioxane and tetrahydrofuran; Toluene, and Aromatic hydrocarbons such as xylene;

Sulfoxides such as dimethyl sulfoxide can be mentioned.

The content of the solvent (S) in the resin composition is not particularly limited as long as it does not impair the purpose of the present invention. The content of the solvent (S) in the resin composition is appropriately adjusted depending on the solid content in the resin composition. The solid content in the resin composition is preferably 5 to 70 mass%, and more preferably 10 to 60 mass%.

＜Other ingredients＞

The resin composition may contain other components in addition to the above components to the extent that they do not impair the purpose of the present invention. Examples of other ingredients include surfactants, plasticizers, viscosity modifiers, anti-foaming agents, and colorants.

≪Method for producing hardened product≫

The method for producing a cured product according to the second aspect is:

It includes a coating film forming step of applying the resin composition according to the first aspect onto a substrate to form a coating film, and a heating step of heating the coating film at 70 to 550°C.

In this method, since the coating film is formed using the resin composition according to the first aspect, a cured product containing polyimide is stably produced.

As a result, a cured product with a smooth surface with few irregularities, warping, or cracks and an excellent appearance is obtained.

＜Coat film formation process＞

In the forming process, the resin composition according to the first aspect is applied to the surface of the substrate to form a coating film. Examples of application methods include the dipping method, spray method, bar coat method, roll coat method, spin coat method, and curtain coat method.

After application, the coating film may be placed in a reduced pressure atmosphere for the purpose of promoting degassing and removal of the solvent (S) from the coating film. The degree of vacuum in the reduced pressure atmosphere is not particularly limited, but is preferably 300 Pa or less, more preferably 150 Pa or less, and even more preferably 100 Pa or less.

The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is preferably 2 to 100 μm, and more preferably 3 to 50 μm. The thickness of the coating film can be appropriately controlled by adjusting the application method or the solid content concentration or viscosity of the resin composition.

The material of the base material is not particularly limited as long as it does not cause thermal deterioration or deformation when the coating film is heated. The shape of the base material is not particularly limited as long as the resin composition can be applied thereto. Examples of the substrate include electronic devices such as semiconductor devices on which electrodes and wiring to be insulated are formed, intermediate products such as multilayer wiring boards, and various types of substrates. When the base is a substrate, preferred substrate materials include glass, silicon, aluminum (Al), aluminum-silicon (Al-Si), aluminum-copper (Al-Cu), and aluminum-silicon-copper (Al-Si). Aluminum alloys such as -Cu); Titanium (Ti); Titanium alloys such as titanium-tungsten (Ti-W); Titanium nitride (TiN); Tantalum (Ta); Tantalum nitride (TaN); Tungsten (W); Tungsten nitride. (WN); etc. can be mentioned.

Additionally, when heating the coating film at a low temperature, a substrate with low heat resistance made of a resin such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) may be used.

＜Heating process＞

The coating film formed in the coating film formation process is heated at 70 to 550°C in the heating process.

When heating the coating film, the heating temperature is set at, for example, 120 to 500°C, preferably 150 to 450°C. By heating the coating film at a temperature in this range, a cured product can be stably produced while suppressing thermal deterioration or thermal decomposition of the resulting polyimide.

In addition, when heating the coating film at a high temperature, a large amount of energy may be consumed and deterioration of processing equipment at high temperature over time may be accelerated. Therefore, it is also preferable to heat the coating film at a lower temperature. am.

The heating time depends on the composition of the resin composition, the thickness of the coating film, etc., but as a lower limit it is, for example, 5 minutes, preferably 10 minutes, more preferably 20 minutes, and as an upper limit it is, for example, 4 hours, preferably 3 hours. , more preferably 2.5 hours.

In addition, from the viewpoint of reducing the yellowness of the polyimide or converting polyamic acid (A) into polyimide more smoothly, the atmosphere at the time of heating (gas composition such as oxygen concentration) can be adjusted, or at the time of heating or before and after heating. Decompression processes can also be combined.

[Example]

Below, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples.

[Preparation of polyamic acid (A)]

Tetracarboxylic dianhydride and N-methyl-2-pyrrolidone of the structures shown below are placed in a separable flask equipped with a stirrer, stirring blade, reflux condenser, and nitrogen gas inlet tube, and the flask is injected through the nitrogen gas inlet tube. Nitrogen was introduced into the flask to create a nitrogen atmosphere. Next, the flask was immersed in an ice bath, and the N-methyl-2-pyrrolidone solution of p-phenylenediamine was slowly added dropwise in an amount of 1.0 mole based on tetracarboxylic dianhydride while stirring the contents.

After completion of dropwise addition, reaction was performed at 50°C for 20 hours to obtain a solution containing polyamic acid (A). In addition, tetracarboxylic dianhydride having the structure shown below was prepared according to the method described in Synthesis Example 1, Example 1, and Example 2 of International Publication No. 2011/099518, and the solution here was prepared by using the polyamic acid to be obtained. The solid content concentration of (A) was adjusted to 15% by mass.

[Example 1-3, Comparative Example 1]

In Example 1-3, the additives shown in Table 1 were added to the solution of polyamic acid (A) thus obtained to obtain a resin composition. The values (mass %) shown in parentheses in Table 1 are the ratio of additives to the amount of polyamic acid (A).

On the other hand, in Comparative Example 1, no additives were added to the solution of polyamic acid (A) obtained above.

In addition, p-methoxy cinnamic acid (cinnamic acid) was used from Tokyo Chemical Industry Co., Ltd., and imidazole was from Kishida Chemical Co., Ltd.

［Film forming performance evaluation］

The various resin compositions obtained in this way were evaluated for film forming properties as follows. That is, first, each resin composition was applied onto a glass substrate, and the pressure was reduced to 13 Pa. After returning to normal pressure, it was heated at 80°C for 10 minutes under air conditions, and then heated at 360°C for 30 minutes under conditions of an oxygen concentration of 100 ppm to obtain a cured product with a film thickness of 5 μm.

The cured product thus obtained was observed with the naked eye to see whether the shape was well formed. In addition, the evaluation was conducted based on the following standards.

◎: No roughness is observed when visually inspected.

○: Although the film was generally smooth, bending was observed at the edges.

Δ: It was observed that a part of the film was cracked.

X: Cracks were observed everywhere in the film.

From Table 1, it can be seen that by adding specific additives to the polyamic acid (A), a resin composition that has excellent film forming properties and can stably form a cured product containing polyimide can be obtained.

Claims (8)

Equation (a1) below:

(In formula (a1), A is a tetravalent polycyclic aliphatic group having 6 to 50 carbon atoms, and B is a divalent organic group containing one or more aromatic rings.)
A polyamic acid (A) having a structural unit represented by,
It includes a carbonyloxy compound (B1) having a -CO-O- bond in the molecule, and a basic nitrogen-containing compound (B2) that does not have a -CO-O- bond in the molecule,
As the carbonyloxy compound (B1), the following formula (b1):

(In formula (b1), R ^b0 is an aromatic group that may have a substituent, and R ^b9 is a hydrogen atom or an alkyl group.)
It includes compounds represented by
A resin composition containing a compound containing an imidazole ring as the basic nitrogen-containing compound (B2). In claim 1,
A resin composition in which A in the formula (a1) contains a tetravalent group represented by the following formula (a2).

(In formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and a fluorine atom, and n is 0 to 12. It is an integer.) In claim 1,
A resin composition in which R ^b9 in the formula (b1) is a hydrogen atom. In claim 1,
As the carbonyloxy compound (B1), the following formula (b1-2):

(In formula (b1-2), R ^b1 and R ^b2 are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, alcohol Represents a group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group.R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 are each independently a hydrogen atom or a halogen. Atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, Representing an amino group, an ammonio group, or an organic group.R ^b3 , R ^b4 , R ^b5 , R ^b6 , and R ^b7 may combine two or more of them to form a cyclic structure, or may include a hetero atom bond. )
A resin composition containing the compound represented by . In claim 1,
A resin composition containing an imidazole compound as the basic nitrogen-containing compound (B2). A coating film forming step of forming a coating film by applying the resin composition according to any one of claims 1 to 5 on a substrate, and
A method of producing a cured product comprising a heating process of heating the coating film at 70 to 550°C. A cured product obtained by curing the resin composition according to any one of claims 1 to 5. delete