KR20180036623A - Resin Composition, Manufacturing Method of Cured Body and Cured Body - Google Patents

Abstract

The present invention aims to provide: a resin composition containing a polyamic acid capable of stably forming a cured product containing polyimide and excellent in film formability; a method for manufacturing a cured product using the resin composition; and a cured product obtained by curing the resin composition. In the resin composition containing the polyamic acid (A), at least one of a carbonyloxy compound (B1) having -CO-O- bond in a molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in the molecule are mixed.

Description

[0001] The present invention relates to a resin composition, a process for producing the same,

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

BACKGROUND ART Polyimide resins are widely used as insulating materials and protective materials in electric and electronic parts such as electronic devices such as various kinds of devices and multilayer wiring boards because they have excellent heat resistance, mechanical strength, insulation properties and low dielectric constant.

Generally, the polyimide resin is formed by heat-treating a polyamic acid obtained by polymerizing a tetracarboxylic acid dianhydride component and a diamine component in a polar organic solvent. In view of this background, polyimide products for electronic materials are often supplied as solutions of polyimide precursors such as polyamic acid. Specifically, in the production of electric and electronic parts, after the solution of the polyimide precursor is supplied to the place where the insulating material or the protecting material is formed by a method such as coating or injection, the solution of the polyimide precursor is heat- .

The technical development of such a polyimide resin is being worked hard.

For example, as an example of Patent Document 1, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3 ', 4,4'-diphenylether tetracarboxylic acid dianhydride Propyleneglycol monomethyl ether acetate, and imidization is carried out at 150 占 폚.

Patent Document 1: Japanese Patent Application Laid-Open No. 2012-021133

As a result of the studies conducted by the inventors of the present invention, it has been found that if the conditions are not appropriately set in the process of heating and curing the polyimide resin precursor, the curing behavior is not stabilized and, consequently, the film formation can not be performed well.

Since the appearance of the polyimide film with incomplete film formation is inferior, it has been strongly expected to pioneer a composition capable of forming a film stably.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition containing a polyamic acid capable of stably forming a cured product containing polyimide and excellent in film formability, a method of producing a cured product using the resin composition, It is an object of the present invention to provide a cured product obtained by curing a composition.

The present inventors have studied hard to solve the above problems. As a result, it was confirmed that a carbonyloxy compound (B1) having -CO-O- bond in the molecule and a basic nitrogen-containing compound (B2) having no -CO-O-bond in the molecule were added to the resin composition containing the polyamic acid ). The present invention has been accomplished based on this discovery. Specifically, the present invention provides the following.

A first aspect of the present invention relates to a method for producing a compound represented by the following formula (a1):

(In the 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 the formula

(B1) having a -CO-O- bond in a molecule, and a basic nitrogen-nitrogen compound (B2) having no -CO-O- .

According to a second aspect of the present invention, there is provided a process for producing a resin composition, comprising the step of forming a coating film by applying the resin composition according to the first aspect onto a substrate,

And a heating step of heating the coating film at 70 to 550 占 폚.

A 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 capable of stably forming a cured product containing polyimide excellent in film formability, a method of producing a cured product using the resin composition, Cargo can be provided.

≪ Resin composition &

The resin composition, which is the first aspect of the present invention, is represented by the following formula (a1):

(In the 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 the formula

A carbonyloxy compound (B1) having a -CO-O- bond in a molecule, and a basic nitrogen-containing compound (B2) having no -CO-O- bond in a molecule. .

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

As a result, imidization of the polyamic acid (A) progresses uniformly and quickly at the time of heating the resin composition. As a result, unevenness, warpage, cracks and the like are hardly generated on the surface of the cured product, A cured product can be formed.

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

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

<Polyamic acid (A)>

The resin composition includes a polyamic acid (A). The polyamic acid (A) is a precursor polymer of polyimide which is produced when the resin composition is cured.

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

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

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

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

[Tetracarboxylic acid dianhydride]

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

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

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

In the formula (a1-1), A is a quaternary 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) And may have a plurality of substituents.

Preferable 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 fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy group having 1 to 6 carbon atoms, , An acid anhydride group represented by the formula (a1-1), 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 perfluoroalkyl group or a perfluoroalkoxy group.

With regard to the above substituents, it can be said that the aromatic group described later is the same for one or a plurality of substituents which may be present on the aromatic ring.

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

The number of carbon atoms constituting A is more preferably 8 or more, and still more preferably 12 or more. The number of carbon atoms constituting A is more preferably 40 or less, and still more preferably 30. A may be an aliphatic group or an aromatic group, or a group combining 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, an oxygen atom, a nitrogen atom, or a sulfur atom may be a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N-, , -CO-, -SO-, -SO ₂ -, -S-, and -SS-, which may be included in A or may be -O-, -CO-, -SO -, -SO ₂ -, -S-, and -SS-, and is more preferably contained in A.

The tetracarboxylic acid dianhydride can be appropriately selected from tetracarboxylic acid dianhydrides conventionally used as a starting material for the synthesis of polyamic acid. The tetracarboxylic acid dianhydride may be an aliphatic tetracarboxylic acid dianhydride or an aromatic tetracarboxylic acid dianhydride.

Examples of the aliphatic tetracarboxylic acid dianhydride include 2,2-bis (3,4-dicarboxyl) propane dianhydride and bis (3,4-dicarboxyl) methane dianhydride. , Or an alicyclic structure. Such alicyclic structure may be polycyclic, and examples of the polycyclic alicyclic structure include those having a bridged alicyclic structure such as bicyclo [2.2.1] heptane and the like, and for example, May be condensed with a crosslinking alicyclic structure and / or a non-crosslinking alicyclic structure having a different structure from that of the crosslinking alicyclic structure and / or with a crosslinking alicyclic structure and / or a non-crosslinkable alicyclic structure . When an aliphatic tetracarboxylic acid dianhydride is used, there is a tendency that a cured product excellent in transparency tends to be obtained by using a resin composition.

As the aliphatic group constituting A in the formula (a1-1), for example, a tetravalent group represented by the following formula (a2) can be adopted. When such a group is used, a polyimide film having transparency tends to be easily obtained.

Further, n in the formula (a2) is preferably 5 or less, and more preferably 3 or less, since the raw material compound can be easily purified. Further, n is preferably 1 or more, and more preferably 2 or more, from the viewpoint of excellent chemical stability of the raw material compound imparting the structure represented by formula (a1).

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

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

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 1,4-bis (3,4-dicarboxylphenoxy) benzene dianhydride, 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 acid dianhydride, and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride.

The aromatic tetracarboxylic acid dianhydride may also be represented by, for example, the following general formulas (a1-2) to (a1-4).

In the formulas (a1-2) and (a1-3), R ^a1 , R ^a2 and R ^a3 each represent an aliphatic group which may be substituted with halogen, an oxygen atom, a sulfur atom, An aromatic group, or a bivalent substituent constituted by such a combination. R ^a2 and R ^a3 may be the same or different.

That is, R ^a1 , R ^a2 and R ^a3 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond or a halogen element (fluorine, chlorine, bromine, iodine) (3,4-dicarboxylic triflurophenoxy) propane dianhydride, 1,4-bis (3,4-dicarboxylic triflurophenoxy) benzene dianhydride, 1,4-bis Tetrafluorobenzene dianhydride, 2,2 ', 5,5', 6,6'-hexafluoro-3,3 ', 4,4', -biphenyltetracarboxylic acid dianhydride And the like.

In the formula (a1-4), R ^a4 and R ^a5 may be any of an aliphatic group which may be substituted with halogen, an aromatic group which contains at least one divalent element and halogen, or a combination thereof And may be the same or different, and difluoropyromellitic acid dianhydride, dichloropyromellitic acid dianhydride, and the like can also be used.

Examples of the tetracarboxylic acid dianhydride for obtaining the fluorine-containing polyimide containing fluorine in the molecular structure include (trifluoromethyl) pyromellitic dianhydride, di (trifluoromethyl) pyromellitic dianhydride, di Heptafluoropropyl) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride, bis {3,5-di (trifluoromethyl) phenoxy pyromellitic dianhydride, 2,2-bis Bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxyl biphenyl dianhydride, 2,2', 5,5'-bis (trifluoromethyl) Tetrakis (triphenylmethyl) -3,3 ', 4,4'-tetracarboxylbiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3,3' (Trifluoromethyl) dicarboxylphenoxy} bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxylbenzophenone dianhydride, bis { Benzene 2 (Dicyanomethyl) benzene dianhydride, bis (dicarboxylphenoxy) bis (dicarboxylic acid) benzene dianhydride, bis (Trifluoromethyl) benzene dianhydride, bis (dicarboxylphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2,2-bis {4- (3,4-dicarboxylphenoxy) phenyl} hexafluoride Propane dianhydride, bis {(trifluoromethyl) dicarboxylphenoxy} biphenyl dianhydride, bis {(trifluoromethyl) dicarboxylphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis { Bis (dicarboxylphenoxy) bis (trifluoromethyl) biphenyl dianhydride, difluoro pyromellitic acid dianhydride, 1,4-bis (3,3-dihydroxyphenyl) dicarbonylphenoxy} diphenyl ether dianhydride, 4-dicarboxyltrifluorophenoxy) tetrafluorobenzene dianhydride, 1,4-bis (3,4 -Dicarboxyltrifluorophenoxy) octafluorobiphenyl dianhydride and the like.

As the tetracarboxylic acid dianhydride, it is preferable to use an aromatic tetracarboxylic acid dianhydride in view of the heat resistance, tensile elongation, chemical resistance, etc. of the obtained film or molded article, and it is preferable to use 3,3 ', 4 , 4'-biphenyltetracarboxylic acid dianhydride, and pyromellitic dianhydride are preferably used. Acid chlorides, esters and the like of tetracarboxylic acids having the same basic skeleton as these may also be used.

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

[Diamine compound]

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

H ₂ NB-NH ₂ ... (a3-1)

(In the 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).

Preferable 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 fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 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 perfluoroalkyl group or a perfluoroalkoxy group.

In the 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, more preferably 30.

B may be an aliphatic group, but is preferably an organic group containing at least one aromatic ring.

When B is an organic group containing at least one aromatic ring, the organic group may be an aromatic group itself, and two or more aromatic groups may be replaced by an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, a hetero atom such as an oxygen atom, a sulfur atom, May be combined through a bond including a bond. Examples of the bond containing hetero atom such as oxygen atom, sulfur atom and nitrogen atom included in B include -CONH-, -NH-, -N═N-, -CH═N-, -COO-, -O- _{, -CO-, -SO-, -SO 2 -} , and the like -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 bonding to the amino group in B is a condensed ring containing two or more rings, it is preferable that the ring bonding with the amino group in the condensed ring is a benzene ring.

The aromatic ring included in B may be an aromatic heterocycle.

When B is an organic group containing an aromatic ring, it is preferable that the organic group is at least one of the groups represented by the following formulas (1) to (4) in view of the heat resistance of the cured product formed using the resin composition.

(In the formulas (1) to (4), R ¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms In the formula (4), Q represents a 9,9'-fluorenylidene group or a group represented by the 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 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 - A group 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, and m-phenylene group and p-phenylene group are preferable, and p-phenylene group is more preferable. Further, -C ₁₀ H ₆ - is a naphthalene diyl group, and naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-2,3-diyl group, And naphthalene-2,7-diyl group are preferable, and naphthalene-1,4-diyl group and naphthalene-2,6-diyl group are more preferable.

R ¹¹ in the 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 a cured product to be formed, a hydrogen atom, a hydroxyl group or a trifluoromethyl group Is particularly preferable.

Q in the formula (4) is preferably 9,9'-fluorenylidene 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- is preferable, -OC ₆ H ₄ -O-, C (CF _{3) 2} -, or it is particularly preferably -O-.

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

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis Trifluormethyl) biphenyl, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- Bis (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene, 9,9-

4,4 '- [1,4-phenylenebis (1-methylethane-1,1-diyl)] dianiline. Of these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable in terms of price and availability.

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

From the viewpoint of further improving the mechanical properties of the resulting cured product, B can be preferably used as the airway represented by the following formula (Si-1).

(In the formula (Si-1), R ¹² and R ¹³ each independently represent 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, And R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent 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, An aryl group having 1 to 20 carbon atoms, an amino group having 20 or less carbon atoms, a group represented by -OR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to 20 carbon atoms), at least one epoxy group having 2 to 20 carbon atoms, And I is an integer from 3 to 50.)

The alkylene group having 2 to 20 carbon atoms in R ¹² and R ¹³ in the formula (Si-1) is preferably an alkylene group having 2 to 10 carbon atoms in terms of heat resistance and residual stress, A trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

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

The allylene group having 6 to 20 carbon atoms in R ¹² and R ¹³ in the 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, a naphthylene group And the like.

The alkyl group having 1 to 20 carbon atoms in 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 in terms of heat resistance and residual stress, Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl.

The cycloalkyl group having 3 to 20 carbon atoms in R ¹³ , R ¹⁵ , R ¹⁶ and R ¹⁷ in the formula (Si-1) is preferably a cycloalkyl group having 3 to 10 carbon atoms in terms of heat resistance and residual stress And specific examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group having 6 to 20 carbon atoms in R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ in the formula (Si-1) is preferably an aryl group having 6 to 12 carbon atoms in view of heat resistance and residual stress, Specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

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

Examples of the group represented by -OR ¹⁸ in R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ in the formula (Si-1) include methoxy, ethoxy, propoxy, isopropyloxy, Naphthyloxy group, propenyloxy group (for example, aryloxy group), cyclohexyloxy group, and the like.

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

The group represented by the formula (Si-1) can be derived by reacting a silicon-containing compound having an amino group at both terminals with an acid anhydride. Specific examples of such a silicon-containing compound include amino-modified methylphenyl silicone at both ends (for example, X-22-1660B-3 (number average molecular weight of about 4,400) and X-22-9409 (number average molecular weight of about 1,300) , X-22-161 A (number average molecular weight of about 1,600), X-22-161 B (number average molecular weight of about 3,000) and KF8012 (number average molecular weight of 4,400 BY16-835 U (number average molecular weight of about 900) manufactured by Toray Dow Corning Inc. and Siranaprene FM3311 (number average molecular weight of about 1000) manufactured by JNC).

[Process for producing polyamic acid (A)]

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

The amount of the tetracarboxylic acid dianhydride and the diamine compound used in the synthesis of the polyamic acid (A) is not particularly limited, but it is preferable to use the diamine compound in an amount of 0.50 to 1.50 moles per mole of the tetracarboxylic acid dianhydride, To 1.30 moles, and particularly preferably 0.70 to 1.20 moles.

The weight average molecular weight of the polyamic acid (A) to be obtained may be suitably set in accordance with the intended use, but is preferably 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, 100,000 or less, preferably 80,000 or less, more preferably 75,000 or less.

The weight average molecular weight may be adjusted to the above values by adjusting reaction conditions such as the amount of the tetracarboxylic acid dianhydride and the diamine compound or the solvent or the reaction temperature.

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

Examples of the organic solvent used in the reaction of the tetracarboxylic acid dianhydride with the diamine compound include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, Nitrogen polar solvents such as formamide, N, N-diethylformamide, N-methylcaprolactam and N, N, N ', N'-tetramethylurea; dimethyl sulfoxide; acetonitrile; diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran.

Among these organic solvents, the solubility of the polyamic acid (A) or the polyimide resin to be produced is preferably selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Nitrogen polar solvents such as dimethylformamide, N, N-diethylformamide, N-methylcaprolactam and N, N, N ', N'-tetramethylurea are preferable.

The temperature at which the tetracarboxylic acid dianhydride is reacted with the diamine compound is not particularly limited as long as the reaction proceeds satisfactorily. Typically, the reaction temperature of the 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 reaction time of the tetracarboxylic acid dianhydride and the diamine compound varies depending on the reaction temperature, but is typically 1 to 50 hours, preferably 2 to 40 hours, particularly preferably 5 to 30 hours.

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

The method for preparing the resin composition according to the first aspect is not particularly limited, but it is preferable that the solution containing the obtained polyamic acid (A) contains a carbonyloxy compound (B1) having -CO-O- And a basic nitrogen-nitrogen compound (B2) having no CO-O- bond are preferably blended.

As described above, the solution containing the polyamic acid (A) can be used as it is for the preparation of the resin composition as it is, and the solution of the polyamic acid (A) at a low temperature at which the conversion of the polyamic acid into the polyimide resin does not occur, A paste or a solid of polyamic acid obtained by removing at least a part of the solvent from the polyamic acid may be used for preparing the resin composition.

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

The resin composition may contain at least one 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- . The carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) are components that promote the formation of polyimide in the polyamic acid (A), respectively.

Therefore, when the resin composition according to the first aspect is used, the polyamic acid (A) is converted into the polyimide at an appropriate rate, and a cured product having a stable shape is easily obtained.

(B1) and the basic nitrogen-containing compound (B2), the effect of promoting the formation of polyimide can be obtained. However, when the carbonyloxy compound (B1) and the basic nitrogen compound (B2) It is preferable to blend them in the resin composition in view of the curability of the resin composition.

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

[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) accelerates the ring-opening by dehydration in the polyamic acid (A), thereby favorably accelerating the curing of the resin composition.

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

The carbonyloxy compound (B1) may be used in combination of two or more.

(Carboxylic acid)

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

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

Specific preferred examples of the carboxylic acid 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 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-naphthalene dicarboxylic acid, , 4'-dicarboxylic biphenyl, 4,4'-dicarboxylic diphenyl ether, and trimellitic acid.

A compound having a carboxyl group bonded to an aromatic group and an alkylene group is also preferable as the carboxylic acid. Specific examples of such a compound include phenylacetic acid, 3-phenylpropionic acid, 4-phenylbutanoic acid, and the like.

In the present embodiment, examples of the carboxylic acid preferably used include compounds represented by the following formula (b1-1).

(Wherein R ^b0 , R ^b1 and R ^b2 each independently represent 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 phosphono group, a phosphono group, a phosphonato group or an organic group, and any of R ^b0 and R ^b1 is an aromatic group or an alkyl group which may have a substituent.

Examples of the organic group in the formula (b1-1) 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 a hydrocarbon group such as a hetero atom in the organic group.

The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

The bond included 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 including a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples of the bond including a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (= NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.

From the viewpoint of the heat resistance of the compound represented by the formula (b1-1), the bond containing the hetero atom which the organic group may have is preferably an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, 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 or a sulfinyl bond.

Specific examples of R ^b0 , R ^b1 and R ^b2 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, , A silanol group, an alkoxy group, an alkoxycarbonyl 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, An alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, an arylether group, and an arylthioether group. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

In formula (b1-1), any of R ^b0 and R ^b1 is an aromatic group or an alkyl group which may have a substituent. In formula (b1-1), R ^b0 and R ^b1 Is an alkyl group, the alkyl group may be straight chain or branched chain. The number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 10, even more preferably from 1 to 6, most preferably from 1 to 4.

In some cases, R ^b2 is an alkyl group, and the alkyl group in this case is preferably the same group as described above.

In formula (b1-1), R ^b0 and R ^b1 Is an aromatic group which may have a substituent, the kind of the substituent which the aromatic group may have is not particularly limited within the range not hindering the object of the present invention. Preferred examples of the substituent include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, nitroso groups, sulfonate groups, .

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

R ^b2 may be an aromatic group which may have a substituent, and in this case, the aromatic group which may have a substituent is preferably the same group as described above.

Specific examples of the substituent which the aromatic group may have are the same as the specific examples of R ^b0 , R ^b1 and R ^b2 .

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

(Wherein R ^b1 and R ^b2 each independently represent 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, R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 each independently represent a hydrogen atom, a halogen atom, a halogen atom, a cyano group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A silyl group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 may combine with each other to form a cyclic structure or may contain a bond of a heteroatom .)

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

Among them, R ^b1 and R ^b2 in the formula (b1-2) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkyl 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 having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, a carbon An alkoxy group having 1 to 10 atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, It is preferable that the electron-donating group and / or the electron-withdrawing group is substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or a benzyl group substituted with an electron-withdrawing group, a cyano group or a methylthio 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.

Examples of the organic groups in R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 include those exemplified for R ^b1 and R ^b2 . The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group as in the case of R ^b1 and R ^b2 . The organic group may be any of linear, branched and cyclic.

R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 may combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For ^{example, R b3, R b4, R} b5, R b6, and R ^b7 have the benzene ring atoms that are combined these two or more ^{and, R b3, R b4, R} b5, R b6, and R ^b7 are combined To form a condensed ring such as naphthalene, anthracene, phenanthrene, or indene.

R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkyl 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 a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group , An alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester having 2 to 11 carbon atoms An aryl group having 6 to 20 carbon atoms, an electron-donating group and / or an aryl group having 6 to 20 carbon atoms substituted with an electron-withdrawing group, a benzyl group substituted with an electron-donating group and / Anthio group, a methylthio group, and a nitro group.

In ^{addition, R b3, R b4, R} b5, R b6, and R ^b7 As to the combination of these 2 or ^{more, R b3, R b4, R} b5, R b6, and R ^b7 share a benzene ring atom bonded To form a condensed ring such as naphthalene, anthracene, phenanthrene, or indene.

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

(B1-3), R ^b1 to R ^b6 have the same meanings as in formula (b1-2), R ^b8 represents a hydrogen atom or an organic group, R ^b3 and R ^b4 do not represent a hydroxyl group, R ^b3 , R ^b4 , R ^b5 and R ^b6 may combine with each other to form a cyclic structure or may contain a bond of a hetero atom.)

The compound represented by the formula (b1-3) has a substituent -OR ^b8 and is therefore likely to be uniformly dispersed or dissolved 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 as R ^b1 and R ^b2 . The organic group may contain a hetero atom in the organic group. The organic group may be any of linear, branched and 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 the 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 the carboxylic acid ester include C ₁ -C ₁₀ alkyl esters of the aforementioned carboxylic acids, C ₃ -C ₁₀ cycloalkyl esters, phenyl esters, C ₆ -C ₁₀ alkylphenyl esters, C ₇ -C ₁₀ Naphthyl esters, C ₇ -C ₁₀ aralkyl esters, and the like.

When the carboxylic acid ester is an ester of a polycarboxylic acid, the carboxylic acid ester may have a carboxyl group together with an ester bond. For example, terephthalic acid monomethyl ester and the like are also carboxylic acid esters.

Specific preferred examples of the carboxylic acid ester include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, sec-butyl formate, tert-butyl formate, n- 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; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, Butyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, cyclopropyl acetate, cyclobutyl acetate, acetic acid Cyclohexyl acetate, cyclooctyl acetate, phenyl acetate, o-tolyl acetate, m-tolyl acetate, p-tolyl acetate,? -Naphthyl acetic acid,? -Naphthyl acetate, benzyl acetate, Butyl acetate, tert-butyl propionate, n-pentyl propionate, n-propyl propionate, n-butyl acetate, n-butyl acetate, isopropyl Hexyl, n-heptyl propionate, n-octyl propionate, cyclopropyl propionate, cyclobutyl propionate, cyclopentyl propionate, cyclohexyl propionate, cycloheptyl propionate, cyclooctyl propionate, phenyl propionate, o-tolyl propionate, P-tolyl propionate,? -Naphthyl propionate,? -Naphthyl propionate, Ethyl propionate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, N-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, cyclopropyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, phenyl acrylate, Acrylic esters such as m-tolyl acrylate, p-tolyl acrylate,? -Naphthyl acrylate,? -Naphthyl acrylate, benzyl acrylate, and phenethyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, , Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, Octyl methacrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-heptyl methacrylate, , Cyclooctyl methacrylate, phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, p-tolyl methacrylate,? -Naphthyl methacrylate,? -Naphthyl methacrylate, Propyl benzoate, isopropyl benzoate, n-butyl benzoate, isobutyl benzoate, sec-butyl benzoate, tert-butyl benzoate, benzoyl peroxide, N-pentyl benzoate, n-heptyl benzoate, n-heptyl benzoate, n-octyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, cyclooctyl benzoate, phenyl benzoate, Tolyl, benzoic acid m-tolyl, benzoic acid p-tolyl, benzoic acid &lt; RTI ID = Benzoic acid esters such as naphthyl,? -Naphthyl benzoate, benzoyl benzoate, and phenethyl benzoate; esters such as dimethyl terephthalate, diethyl terephthalate, di-terephthalate, diisopropyl terephthalate, diisobutyl terephthalate, Terephthalic acid di-sec-butyl terephthalate, di-tert-butyl terephthalate, di-n-pentyl terephthalate, dihexyl terephthalate, di-n-heptyl terephthalate, di-n-octyl terephthalate, dicyclopropyl terephthalate, dicyclopentyl terephthalate Terephthalic acid dicyclohexyl, terephthalic acid dicycloheptyl, terephthalic acid dicyclooctyl, terephthalic acid diphenyl, terephthalic acid di-tolyl, terephthalic acid di-m-tolyl, terephthalic acid di-p- tolyl, terephthalic acid di-naphthyl, terephthalic acid di- Terephthalic acid dibenzyl, terephthalic acid dibenzyl, and terephthalic acid diphenetyl; terephthalic acid diesters such as ethylene glycol monoacetate, ethylene glycol Ethylene glycol monopentanoate, ethylene glycol monobenzoate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dibutanoate, ethylene glycol dipentanoate, ethylene glycol monopentanoate, ethylene glycol monopentanoate, ethylene glycol monopentanoate, , And ethylene glycol dibenzoate; polyhydric alcohols such as diethylene glycol monoacetate, diethylene glycol monopropionate, diethylene glycol monobutanoate, diethylene glycol monopentanoate, diethylene glycol monobenzoate, Diethylene glycol esters such as diethylene glycol diacetate, diethylene glycol dipropionate, diethylene glycol dibutanoate, diethylene glycol dipentanoate, and diethylene glycol dibenzoate, propylene glycol monoacetate, propylene glycol monoacetate, Glycol monopropionate, pro Propylene glycol monopentanoate, propylene glycol monobenzoate, propylene glycol diacetate, propylene glycol dipropionate, propylene glycol dibutanoate, propylene glycol dipentanoate, and propylene glycol di Propylene glycol esters such as benzoate, dipropylene glycol monoacetate, dipropylene glycol monopropionate, dipropylene glycol monobutanoate, dipropylene glycol monopentanoate, dipropylene glycol monobenzoate, dipropylene glycol diacetate , Dipropylene glycol esters such as dipropylene glycol dipropionate, dipropylene glycol dibutanoate, dipropylene glycol dipentanoate, and dipropylene glycol dibenzoate.

In addition, the 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-mentioned 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, Tolyl esters, m-tolyl esters, p-tolyl esters,? -Naphthyl esters,? -Naphthyl esters, benzyl esters and phenethyl esters 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 the carboxylic acid anhydride include carboxylic anhydrides such as acetic anhydride, propionic anhydride, butanoic anhydride, benzoic anhydride, phthalic anhydride, naphthalic anhydride, succinic anhydride, hic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Tetrabromophthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and 5- (2,5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and styrene maleic anhydride copolymer.

(Carbonate)

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

Specific preferred examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

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

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

Are particularly preferable.

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

In the present embodiment, it is particularly preferable that R ^b9 is a hydrogen atom in that 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 contains a nitrogen atom and exhibits a basicity in the definition of Bronsted.

Examples of the basic nitrogen compound (B2) include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, isobutylamine, n-butylamine, n-pentylamine, n-hexylamine, , Diethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-n-butylamine, di-n-pentylamine, dihexylamine, trimethylamine, And examples thereof include an amine, triisopropylamine, triisobutylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, aniline, o-toluidine, m-toluidine, naphthylamine, and acyclic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and the like.

In addition, it is also possible to use an aminopyridine compound such as guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, And the like are also preferable as the basic nitrogen-containing compound (B2).

These substituents may have a substituent and preferable substituents include amino, aminoalkyl, alkylamino, aminoaryl, arylamino, alkyl, alkoxy, acyl, acyloxy, aryl, aryloxy, nitro, Anger, and the like.

Particularly preferred organic basic compounds (B2) are guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4- Aminopyridine, 4-aminopyridine, 2-aminopyridine, 2-aminopyridine, 2-phenylimidazole, Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2- Aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethylpiperidine, Aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, , Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2- pyrazoline, 3- Morpholine, N- (2-aminoethyl) morpholine, and 1,8-diazabicyclo [5.4.0] -7-undecene.

As described above, the basic nitrogen-containing compound (B2) has been described. However, among the basic nitrogen-containing compounds (B2), an imidazole compound containing an imidazole ring is preferable because it has a high effect of accelerating the curing of the polyamic acid desirable. Such an imidazole compound is typically represented by the following formula (b2-1).

(Wherein R ^b10 , R ^b11 and R ^b12 each independently represents 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 phosphino group, a phosphono group, or an organic group).

Examples of the organic group at R ^b10 , R ^b11 and R ^b12 in the formula (b2-1) 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 a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

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

As R ^b10 , R ^b11 and R ^b12 , a hydrogen atom, 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, and a halogen atom are preferable, More preferable.

The total amount of the content of the carbonyloxy compound (B1) and the content of the basic nitrogen compound (B2) in the resin composition is not particularly limited as long as the object of the present invention is not impaired. However, it is preferable that 100 parts by mass of the polyamic acid More preferably from 0.05 to 25 parts by mass, and particularly preferably from 0.2 to 20 parts by mass.

When the carbonyloxy compound (B1) and the basic nitrogen compound (B2) are used in combination, the ratio W _B1 / W _B2 of the mass W _B1 of the carbonyloxy compound (B1) to the mass W _B2 of the basic nitrogen compound (B2) W _B2 is preferably from 1/99 to 99/1, more preferably from 5/95 to 95/5, and particularly preferably from 15/85 to 85/15.

&Lt; Solvent (S) &gt;

The resin composition preferably contains a solvent (S) in view of coating properties. The resin composition may be a paste containing a solid or a solution, but it is preferably a solution. The solvent (S) may be used alone or in combination of two or more.

The kind of the solvent (S) is not particularly limited as long as it does not impair the object of the present invention. Examples of the preferable solvent (S) are the same as the examples of the solvent used for the reaction of the above-mentioned tetracarboxylic acid dianhydride with the diamine compound.

The solvent (S) may also include alcohol solvents 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 having excellent heat resistance.

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

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

Lt; / RTI &gt; In the formula (5-1), R ^S4 is a hydrogen atom or a hydroxyl group, and each of R ^S5 and R ^S6 is independently an alkyl group having 1 to 3 carbon atoms. In the formula (5-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Specific examples of the compound (S1) represented by the formula (5) in which R ^S3 is a group represented by the formula (5-1) include N, N, 2-trimethylpropionic acid amide, N- N, N-diethyl-2-hydroxypropionic acid amide, N, N, 2-trimethyl-2-hydroxypropionic acid amide, N- N, N-diethyl-2-hydroxy-2-methylpropionic acid amide and the like.

In the compound (S1) represented by the formula (5), specific examples of the case where R ^S3 is a group represented by the formula (5-2) include N, N, N ', N'-tetramethylurea, N, N, N ', N'-tetraethylurea, and the like.

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

When the resin composition contains the solvent (S), the content of the above-mentioned compound (S1) in the solvent (S) is not particularly limited within the range not hindering the object of the present invention. The ratio of the compound (S1) to the mass of the solvent is typically at least 70% by mass, more preferably at least 80% by mass, particularly preferably at least 90% by mass, based on the total amount of the solvent (S) Most preferably 100% by mass.

Examples of the organic solvent usable in combination with the compound (S1) include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, Imidazolidinone and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; cyclic ether types such as dioxane and tetrahydrofuran; Aromatic hydrocarbons such as xylene;

And sulfoxides such as dimethyl sulfoxide.

The content of the solvent (S) in the resin composition is not particularly limited within the range not hindering the object of the present invention. The content of the solvent (S) in the resin composition is appropriately adjusted according to the solid content in the resin composition. The solid content in the resin composition is preferably 5 to 70 mass%, more preferably 10 to 60 mass%.

<Other components>

The resin composition may contain other components in addition to the above components to the extent that the object of the present invention is not impaired. Examples of the other components include a surfactant, a plasticizer, a viscosity adjusting agent, a defoaming agent, and a coloring agent.

&Lt; Process for producing cured product &

The method for producing the cured product according to the second aspect,

A coating film forming step of applying a 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 캜.

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 having a smooth surface with little unevenness, warpage, and cracks and excellent appearance can be obtained.

<Coating Formation Step>

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

After application, the coating film may be placed in a reduced-pressure atmosphere for the purpose of promoting the removal of the solvent from the coating film or the removal of the solvent (S). The vacuum degree of the reduced pressure atmosphere is not particularly limited, but is preferably 300 Pa or less, more preferably 150 Pa or less, and further 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 mu m, more preferably 3 to 50 mu m. The thickness of the coating film can be appropriately controlled by adjusting the coating method and the solid content concentration and 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 substrate is not particularly limited as long as the resin composition can be applied. Examples of the substrate include intermediate products such as electronic elements such as semiconductor elements and multilayer wiring boards formed with electrodes or wirings to be insulated, and various types of substrates. As the material of the substrate in the case where the substrate is a substrate, preferable examples of the substrate include glass, silicon, aluminum (Al), aluminum-silicon (Al-Si), aluminum- (Ti), titanium-titanium (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN); and the like.

When the coating film is heated at a low temperature, a substrate having 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 forming step is heated at 70 to 550 DEG C in the heating step.

When the coating film is heated, the heating temperature is set at, for example, 120 to 500 ° C, preferably 150 to 450 ° C. By heating the coating film at such a temperature range, it is possible to stably produce a cured product while suppressing thermal deterioration or pyrolysis of the resulting polyimide.

Further, when the coating film is heated at a high temperature, consumption of a large amount of energy and deterioration with time of the processing equipment at a high temperature are promoted. Therefore, it is also preferable to conduct the heating of the coating film at a lower temperature to be.

The heating time depends on the composition of the resin composition, the thickness of the coating film, and the like. The lower limit value is, for example, 5 minutes, preferably 10 minutes, more preferably 20 minutes and the upper limit value is 4 hours, , And more preferably 2.5 hours.

In addition, from the viewpoint of reducing the yellowing degree of the polyimide or adjusting the atmosphere (gas composition such as oxygen concentration) at the time of heating in view of more smoothly converting polyimic acid (A) into polyimide, The depressurization step may be combined.

[Example]

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

[Preparation of polyamic acid (A)] [

A tetracarboxylic acid dianhydride and N-methyl-2-pyrrolidone having the structures shown below were placed in a separable flask equipped with a stirrer, a stirrer, a reflux condenser and a nitrogen gas introducing tube. And nitrogen was introduced into the flask. Next, the flask was immersed in an ice bath, and while stirring the contents, an N-methyl-2-pyrrolidone solution of p-phenylenediamine was slowly added dropwise in 1.0 mol of the tetracarboxylic acid dianhydride.

After completion of dropwise addition, the mixture was reacted at 50 DEG C for 20 hours to obtain a solution containing the polyamic acid (A). The tetracarboxylic acid 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, (A) was adjusted to be 15% by mass.

[Example 1-3, Comparative Example 1]

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

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

Further, p-methoxycinnamic acid (cinnamic acid) was purchased from Tokyo Chemical Industry Co., Ltd., and imidazole was purchased from Kishida Chemical Co., Ltd.

[Evaluation of film formability]

Various resin compositions thus obtained were evaluated for film formability in accordance with the following. That is, first, each resin composition was coated on a glass substrate, and the pressure was reduced to 13 Pa. After returning to atmospheric pressure, it was heated at 80 캜 for 10 minutes under air condition, and then heated at 360 캜 for 30 minutes under the condition of an oxygen concentration of 100 ppm to obtain a cured product having a thickness of 5 탆.

The thus obtained cured product was visually observed to see whether the film was well formed. The evaluation was carried out based on the following criteria.

◎: No roughness was observed with naked eyes.

O: Generally, it was a smooth film, but warp was observed at the edge portion.

DELTA: Cracks were observed in a part of the film.

X: It was observed that cracks were present all over the membrane.

It can be seen from Table 1 that by adding a specific additive to the polyamic acid (A), it is possible to obtain a resin composition which is excellent in film formability and can stably form a cured product containing polyimide.

Claims (8)

(A1): &lt; EMI ID =

(In the 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 the formula
(B1) having a -CO-O- bond in a molecule, and a basic nitrogen-nitrogen compound (B2) having no -CO-O- Composition. The method according to claim 1,
As the carbonyloxy compound (B1), a compound represented by the following formula (b1):

(In the formula (b1), R ^b0 is an alkyl group or an aromatic group which may have a substituent, and R ^b9 is a hydrogen atom or an alkyl group.)
&Lt; / RTI &gt; The method of claim 2,
Wherein R ^b9 in the formula (b1) is a hydrogen atom. The method according to claim 1,
As the carbonyloxy compound (B1), a compound represented by the following formula (b1-2):

(Wherein R ^b1 and R ^b2 each independently represent 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, R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 each independently represent a hydrogen atom, a halogen atom, a halogen atom, a cyano group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A silyl group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, R ^b3 , R ^b4 , R ^b5 , R ^b6 and R ^b7 may combine with each other to form a cyclic structure or may contain a heteroatom bond. )
&Lt; / RTI &gt; The method according to claim 1,
Wherein the carbonyloxy compound (B1) and the basic nitrogen-containing compound (B2) are both contained. The method according to claim 1,
Wherein the basic nitrogen-containing compound (B2) comprises an imidazole compound. A coating film forming process for forming a coating film by applying the resin composition according to any one of claims 1 to 6 on a substrate,
And heating the coating film at 70 to 550 占 폚. A cured product obtained by curing the resin composition according to any one of claims 1 to 6.