Polyimide resin composition

Abstract

Provided is a polyimide resin composition capable of forming a polyimide film which is excellent in transparency and heat resistance and has a low thermal linear expansion coefficient. The polyimide resin composition contains a polyimide resin produced by reacting (A) a tetracarboxylic dianhydride with (B) a diamine containing a phenolic hydroxyl group-containing diamine in an amount of from 5 to 100 mol % of the total diamine; and silica microparticles, in a ratio by mass of from 25/75 to 60/40.

Claims

1. A polyimide resin composition comprising: a polyimide resin produced by reactants consisting of (A) a tetracarboxylic dianhydride and (B) a diamine; and silica microparticles, in a ratio by mass of from 25/75 to 60/40; wherein the tetracarboxylic dianhydride (A) consists of at least one cycloalkanetetracarboxylic dianhydride; and wherein the diamine (B) consists of from 10 to 90 mol % of a phenolic hydroxyl group-containing diamine represented by the following formula (1) and from 10 to 90 mol % of a diamine other than the phenolic hydroxyl group-containing diamine; ##STR00005## wherein, in the formula, X.sub.1 represents a direct bond, CH.sub.2, O, S, SO.sub.2, CONH, CO, or C(CH.sub.3).sub.2; and wherein the diamine other than the phenolic hydroxyl group-containing diamine consists of 2,2-bis(trifluoromethyl)benzidine, 4,4-bis(4-aminophenoxy)biphenyl, or a combination of 2,2-bis(trifluoromethyl)benzidine and 4,4-diaminodiphenyl ether.

2. The polyimide resin composition according to claim 1, wherein the cycloalkanetetracarboxylic dianhydride is 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

3. The polyimide resin composition according to claim 1, wherein the diamine represented by the formula (1) is a diamine represented by the following formula (2): ##STR00006##

4. The polyimide resin composition according to claim 1, wherein the diamine (B) consists of from 10 to 90 mol % of the phenolic hydroxyl group-containing diamine represented by the formula (1) and from 10 to 90 mol % of 2,2-bis(trifluoromethyl)benzidine.

5. The polyimide resin composition according to claim 1, wherein the silica microparticles have a mean particle size of from 1 to 100 nm.

6. The polyimide resin composition according to claim 1, wherein the silica microparticles are ones surface-treated with an amino group-containing silane coupling agent.

7. A polyimide film formed using the polyimide resin composition of claim 1.

8. The polyimide film according to claim 7, which has a total light transmittance of 85% or more when having a thickness of 50 m.

9. A laminate comprising: a substrate selected from plastic film, silicon wafer, metal foil and glass; and a polyimide resin layer formed using the polyimide resin composition of claim 1.

10. The laminate according to claim 9, wherein the substrate is copper foil.

Description

DESCRIPTION OF EMBODIMENTS

(1) [Polyimide Resin Composition]

(2) The polyimide resin composition of the present invention contains: a polyimide resin produced by reacting (A) a tetracarboxylic dianhydride with (B) a diamine containing a phenolic hydroxyl group-containing diamine in an amount of from 5 to 100 mol % of the total diamine; and silica microparticles, in a ratio by mass of from 25/75 to 60/40.

(3) (Polyimide Resin)

(4) The polyimide resin contained in the polyimide resin composition of the present invention is one produced by reacting (A) a tetracarboxylic dianhydride with (B) a diamine containing a phenolic hydroxyl group-containing diamine in an amount of from 5 to 100 mol % of the total diamine.

(5) <Tetracarboxylic Dianhydride (A)>

(6) The tetracarboxylic dianhydride (A) for use in the present invention includes an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride.

(7) Specific examples of the aromatic tetracarboxylic dianhydride include 3,3,4,4-diphenylsulfone-tetracarboxylic dianhydride, 3,3,4,4-benzophenone-tetracarboxylic dianhydride, 4,4,-oxydiphthalic dianhydride, pyromellitic dianhydride, 2,2,3,3-benzophenone-tetracarboxylic dianhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4-(p-phenylenedioxy)diphthalic dianhydride, 4,4-(m-phenylenedioxy)diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. One alone or two or more of these may be used here either singly or as combined.

(8) The aliphatic tetracarboxylic dianhydride includes a cyclic or acyclic aliphatic tetracarboxylic dianhydride. The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include cycloalkane-tetracarboxylic dianhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, etc.; bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, and their regioisomers. One alone or two or more of these may be used here either singly or as combined.

(9) Specific examples of the alicyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, etc. One alone or two or more of these may be used here either singly or as combined.

(10) Of the above-mentioned tetracarboxylic dianhydrides, preferred is use of aliphatic tetracarboxylic dianhydrides from the viewpoint of transparency, heat resistance, low linear expansion coefficient and coloration resistance, and from the viewpoint of easiness in producing high-molecular weight polyimides. More preferred is use of cycloalkane-tetracarboxylic dianhydrides, even more preferred is use of cycloalkane-tetracarboxylic dianhydrides having a number of the ring-constituting carbon atoms of from 4 to 6, and still more preferred is use of 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

(11) In general, when an aliphatic diamine is used as the diamine (B) to be mentioned below as the raw material for a polyimide resin, polyamide acid produced as an intermediate product and the aliphatic diamine form a hard complex, and therefore a high-molecular weight polyimide is difficult to form. However, when a 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an aliphatic diamine are used, a complex in which the bonding between the polyamide acid and the aliphatic diamine is relatively weak is formed, and therefore the polyimide can be readily made to have an increased molecular weight.

(12) The polyimide resin for use in the present invention may be those further reacted with one or more compounds selected from a tetracarboxylic acid or any other tetracarboxylic acid derivative than the tetracarboxylic dianhydride (A), for example, pyromellitic acid, 3,3,4,4-biphenyltetracarboxylic acid, 2,3,3,4-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl)ether, bis(2,3-dicarboxyphenyl) ether, 3,3,4,4-benzophenonetetracarboxylic acid, 2,2,3,3-benzophenonetetracarboxylic acid, 4,4-(p-phenylenedioxy)diphthalic acid, 4,4-(m-phenylene dioxy)diphthalic acid, ethylenetetracarboxylic acid, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane and their derivatives, within a range not detracting from the physical properties of the resultant polyimide film.

(13) The amount to be used of the tetracarboxylic acid or the other tetracarboxylic acid derivative than the tetracarboxylic dianhydride (A) is preferably 10 mol % or less of the total tetracarboxylic dianhydride (A), more preferably 5 mol % or less, even more preferably 1 mol % or less.

(14) <Diamine (B)>

(15) The diamine (B) for use in the present invention includes a phenolic hydroxyl group-containing diamine in an amount of from 5 to 100 mol % of the total diamine.

(16) The phenolic hydroxyl group-containing diamine used here introduces the hydroxyl group into the structure of the polyimide resin for use in the present invention, therefore enhancing the affinity of the resultant resin with silica microparticles which is a kind of an inorganic material. Accordingly, the dispersibility of the silica microparticles in the polyimide resin composition is thereby bettered, and the content of the silica microparticles to be in the composition may be increased, and it is possible to provide a polyimide film excellent in transparency and heat resistance and having a small thermal linear expansion coefficient.

(17) [Phenolic Hydroxyl Group-Containing Diamine]

(18) The phenolic hydroxyl group-containing diamine to be contained in the diamine (B) is not specifically defined as long as the diamine has a phenolic skeleton in the molecule, but preferably, the phenolic hydroxyl group-containing diamine contains a diamine represented by the following general formula (1). The diamine represented by the general formula (1) is preferred from the viewpoint of realizing the advantageous effects of the present invention and from the viewpoint of easy availability thereof.

(19) ##STR00003##

(20) (In the formula, X.sub.1 represents a direct bond, CH.sub.2, O, S, SO.sub.2, CONH, CO, or C(CH.sub.3).sub.2.)

(21) In the above-mentioned general formula (1), preferably, X.sub.1 is at least one selected from a direct bond, CH.sub.2, O , SO.sub.2, CO and C(CH.sub.3).sub.2.

(22) The diamine represented by the above general formula (1) is preferably at least one selected from the diamines represented by the following general formulae (2) to (6); and from the viewpoint of the low thermal linear expansion coefficient thereof, more preferred is a diamine represented by the following general formula (2) (namely 3,3-dihydroxybenzidine).

(23) ##STR00004##

(24) One alone or two or more of the above-mentioned phenolic hydroxyl group-containing diamines may be used here either singly or as combined.

(25) The content of the phenolic hydroxyl group-containing diamine in the diamine (B) is from 5 to 100 mol % of the total diamine, preferably from 5 to 90 mol %, more preferably from 10 to 70 mol %, even more preferably from 10 to 50 mol %, still more preferably from 15 to 50 mol %, still further more preferably from 15 to 40 mol %, from the viewpoint of the transparency, the heat resistance and the low thermal linear expansion coefficient of the resultant polyimide resin composition and the polyimide film.

(26) [Other Diamines]

(27) The diamine (B) for use in the present invention may contain any other diamine than the above-mentioned phenolic hydroxyl group-containing diamine, from the viewpoint of the transparency, the heat resistance and the low thermal linear expansion coefficient of the resultant polyimide resin composition and the polyimide film.

(28) Not specifically defined, the other diamine may be an aliphatic diamine, an aromatic diamine or a mixture thereof. In the present invention, aromatic diamine means a diamine in which the amino group directly bonds to an aromatic ring, and the diamine of the type may contain an aliphatic group or any other substituent in a part of the structure thereof. The aromatic ring may be a single ring or a condensed ring, including, for example, a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a tetracene ring, etc. However, the invention is not limited to these. Of those, preferred is at least one selected from a benzene ring, a naphthalene ring and a fluorene ring, and more preferred is a benzene ring. Aliphatic diamine means a diamine in which the amino group directly bonds to an aliphatic group, and the diamine of the type may contain an aromatic ring and any other substituent in a part of the structure thereof.

(29) The aliphatic diamine includes, for example, acyclic aliphatic diamines such as ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl)ether, polypropylene glycol bis(3-aminopropyl)ether, etc.; cyclic aliphatic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, norbornanediamine, 4,4-diaminodicyclohexylmethane, etc.; and siloxanediamines, etc. One alone or two or more of these may be used here either singly or as combined.

(30) The aromatic diamine includes, for example, aromatic diamines having one aromatic ring, such as m-xylylenediamine, p-xylylenediamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-toluenediamine, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, etc.; aromatic diamines having two or more aromatic rings, such as 2,2-bis(trifluoromethyl)benzidine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-diaminodiphenyl sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(2-methyl-4-aminophenyl)fluorene, etc. One alone or two or more of these may be used here either singly or as combined.

(31) Of the other diamines mentioned above, preferred is use of aromatic diamines from the viewpoint of heat resistance and low thermal linear expansion coefficient; more preferred is use of aromatic diamines having two or more aromatic rings; even more preferred is use of one or more selected from 2,2-bis(trifluoromethyl)benzidine, 4,4-bis(4-aminophenoxy) biphenyl and 4,4-diaminodiphenyl ether; and from the viewpoint of transparency, further more preferred is use of 2,2-bis(trifluoromethyl)benzidine.

(32) From the viewpoint of colorless transparency and low thermal linear expansion coefficient, the diamine (B) for use in the present invention preferably contains from 10 to 95 mol % of a phenolic hydroxyl group-containing diamine and from 5 to 90 mol % of 2,2-bis(trifluoromethyl)benzidine. Preferred types of the phenolic hydroxyl group-containing diamine are the same as those mentioned hereinabove. In this case, the content of the phenolic hydroxyl group-containing diamine in the diamine (B) is more preferably from 10 to 70 mol %, even more preferably from 10 to 50 mol %, still more preferably from 15 to 50 mol %, still further more preferably from 15 to 40 mol %. The content of the 2,2-bis(trifluoromethyl)benzidine in the diamine (B) is more preferably from 30 to 90 mol %, even more preferably from 50 to 90 mol %, still more preferably from 50 to 85 mol %, still further more preferably from 60 to 85 mol %.

(33) From the viewpoint of colorless transparency and low thermal linear expansion coefficient, it is especially preferable that the diamine (B) for use in the present invention consists of from 10 to 95 mol % of a phenolic hydroxyl group-containing diamine represented by the above-mentioned general formula (1) and from 5 to 90 mol % of 2,2-bis(trifluoromethyl)benzidine.

(34) Preferred types of the phenolic hydroxyl group-containing diamine represented by the general formula (1) are the same as those mentioned above. In this case, the content of the phenolic hydroxyl group-containing diamine represented by the general formula (1) in the diamine (B) is more preferably from 10 to 70 mol %, even more preferably from 10 to 50 mol %, still more preferably from 15 to 50 mol %, still further more preferably from 15 to 40 mol %. The content of the 2,2-bis(trifluoromethyl)benzidine in the diamine (B) is more preferably from 30 to 90 mol %, even more preferably from 50 to 90 mol %, still more preferably from 50 to 85 mol %, still further more preferably from 60 to 85 mol %.

(35) <Production of Polyimide Resin>

(36) The method for producing the polyimide resin for use in the present invention, by reacting the above-mentioned tetracarboxylic dianhydride (A) with the diamine (B), is not specifically defined, for which employable is any known method.

(37) Concrete reaction methods include (1) a method of putting the tetracarboxylic dianhydride (A) and the diamine (B) into a reactor along with a reaction solvent thereinto, then stirring them at room temperature to 80 C. for 0.5 to 30 hours, and thereafter heating them for imidation, (2) a method of putting the diamine (B) and a reaction solvent into a reactor and dissolving them, then putting the tetracarboxylic dianhydride (A) thereinto, stirring them at room temperature to 80 C. for 0.5 to 30 hours, and thereafter heating them for imidation, (3) a method of putting the tetracarboxylic dianhydride (A) and the diamine (B) into a reactor along with a reaction solvent thereinto, and then immediately heating them for imidation.

(38) In producing the polyimide resin, the mixing ratio of the tetracarboxylic dianhydride (A) and the diamine (B) is preferably such that the amount of the diamine (B) is from 0.9 to 1.1 mols relative to 1 mol of the tetracarboxylic dianhydride (A).

(39) <Reaction Solvent>

(40) The reaction solvent for use in producing the polyimide resin in the present invention may be any one which is capable of dissolving the formed polyimide resin and does not interfere with the imidation reaction. For example, there are mentioned an aprotic solvent, a phenolic solvent, an ether solvent, a carbonate solvent, etc.

(41) Specific examples of the aprotic solvent include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, etc.; lactone solvents such as -butyrolactone, -valerolactone, etc.; phosphorus-containing amide solvents such as hexamethylphosphoric amide, hexamethylphosphine triamide, etc.; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, sulfolane, etc.; ketone solvents such as acetone, cyclohexane, methylcyclohexane, etc.; amine solvents such as picoline, pyridine, etc.; ester solvents such as (2-methoxy-1-methylethyl)acetate, etc.

(42) Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.

(43) Specific examples of the ether solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxyl)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc.

(44) Specific examples of the carbonate solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, etc.

(45) Of those reaction solvents, preferred are amide solvents and lactone solvents. One alone or two or more of these reaction solvents may be used here either singly or as combined.

(46) For the imidation, preferably, a Dean Stark apparatus or the like is used while removing water formed during the production process. The operation may increase the degree of polymerization and the imidation ratio.

(47) Any known imidation catalyst may be used in the imidation. The imidation catalyst includes a base catalyst and an acid catalyst.

(48) The base catalyst includes organic base catalysts such as pyridine, quinoline, isoquinoline, -picoline, -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline, etc.; inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate, etc.

(49) The acid catalyst includes crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc.

(50) Of the above, preferred is use of base catalysts from the viewpoint of the handleability thereof, more preferred is use of organic base catalysts, and even more preferred is use of triethylamine.

(51) The temperature of the imidation is preferably from 120 to 250 C., more preferably from 160 to 190 C., from the viewpoint of enhancing the reactivity and preventing gelation. Also preferably, the reaction time after the start of distillation of the produced water is from 0.5 to 10 hours.

(52) The polyimide resin for use in the present invention is obtained by reacting the tetracarboxylic dianhydride (A) with the diamine (B) preferably according to the above-mentioned method. The number-average molecular weight of the polyimide resin for use in the present invention is preferably from 5,000 to 500,000, from the viewpoint of the strength of the resultant polyimide film. The number-average molecular weight of the polyimide resin may be measured through gel permeation chromatography.

(53) (Silica Microparticles)

(54) The polyimide resin composition of the present invention contains the above-mentioned polyimide resin and silica microparticles.

(55) Silica for the silica microparticles is silicon dioxide (SiO.sub.2), and the morphology (crystalline morphology, amorphousness, etc.) thereof is not defined. The shape of the silica microparticles is not also defined, including spherical, oval, flat, rod-shaped, fibrous and the like ones.

(56) The silica microparticles for use in the present invention preferably have a small particle size, from the viewpoint of realizing high light transmittance of the polyimide resin composition and the polyimide film, and the mean particle size thereof is preferably from 1 to 100 nm, more preferably from 1 to 50 nm, even more preferably from 2 to 25 nm, still more preferably from 5 to 20 nm.

(57) The mean particle size of the silica microparticles may be measured, for example, according to a BET method.

(58) The silica microparticles may be surface-treated with a surface-treating agent such as a silane coupling agent or the like, from the viewpoint of the dispersibility thereof in polyimide resin.

(59) Any known silane coupling agent is usable here. From the viewpoint of the affinity thereof with polyimide resin, preferred is an amino group-containing silane coupling agent. The amino group-containing silane coupling agent includes, for example, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(3-aminopropylamino)propyltriethoxysilane, 3-(3-aminopropylamino)propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, etc. One alone or two or more of these may be used here either singly or as combined.

(60) The surface-treating method for the silica microparticles with a silane coupling agent is not specifically defined, for which, employable is any known method. For example, silica microparticles are dispersed in an organic solvent or the like to prepare a dispersion, and the above-mentioned silane coupling agent is added thereto, and stirred at a temperature falling between room temperature and 80 C. or so for several hours. A small amount of water may be added to the system to promote the treating reaction.

(61) The polyimide resin composition of the present invention contains the above-mentioned polyimide resin and silica microparticles in a ratio by mass of from 25/75 to 60/40. When the ratio by mass of the polyimide resin is less than 25, then the flexibility of the resultant polyimide film may lower; but when the ratio by mass of the polyimide resin is more than 60, then the heat resistance of the resultant polyimide resin composition and the polyimide film may lower and the thermal linear expansion coefficient thereof may increase.

(62) The ratio by mass of the polyimide resin and silica microparticles is preferably from 30/70 to 60/40, more preferably from 30/70 to 50/50, even more preferably from 40/60 to 50/50, from the viewpoint of realizing transparency, heat resistance and a low thermal linear expansion coefficient.

(63) (Other Components)

(64) The polyimide resin composition of the present invention may contain any other additive than the above-mentioned polyimide resin and silica microparticles, within a range not detracting from the advantageous effects of the present invention. For example, the composition may contain an antioxidant, a light stabilizer, a surfactant, a flame retardant, a plasticizer, a UV absorbent, any other polymer compound than the above-mentioned polyimide resin, etc.

(65) <Preparation of Polyimide Resin Composition>

(66) The method for preparing the polyimide resin composition of the present invention is not specifically defined. For example, the composition may be prepared by mixing and stirring the reaction liquid of polyimide resin obtained through reaction of the tetracarboxylic dianhydride (A) and the diamine (B) in the manner as mentioned above, with silica microparticles and any other optional component.

(67) In preparing the polyimide resin composition, a dispersion where silica microparticles are dispersed in an organic solvent or the like may be used, or a powder of silica microparticles produced as colloidal silica according to a vapor-phase method may be used.

(68) The organic solvent for use in the dispersion of silica microparticles includes methanol, isopropanol, ethylene glycol, methyl ethyl ketone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,N-dimethylacetamide, etc. From the viewpoint of the solubility therein of polyimide resin, preferred is at least one selected from N-methyl-2-pyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide.

(69) The solid concentration in the polyimide resin composition of the present invention may be suitably selected in accordance with the processability of the composition in forming polyimide films and laminates to be mentioned below. The solid concentration and the viscosity of the composition may be suitably controlled by adding an organic solvent thereto.

(70) Not specifically defined, the organic solvent may be any one capable of dissolving polyimide resin. From the viewpoint of the solubility therein of polyimide resin, preferred is at least one selected from N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, N, N-dimethylformamide and N,N-dimethylacetamide.

(71) [Polyimide Film]

(72) The polyimide film of the present invention is formed using the polyimide resin composition, and therefore has transparency and heat resistance and has a low thermal linear expansion coefficient.

(73) The method for forming the polyimide film of the present invention is not specifically defined, for which employable is any known method. For example, there is mentioned a method of forming the polyimide resin composition of the present invention containing an organic solvent into a film by coating or by shaping, and then removing the organic solvent. As the organic solvent, preferably used are the same solvents for reaction as those used in producing the polyimide resin in the above.

(74) The thickness of the polyimide film of the present invention may be suitably selected in accordance with the intended use thereof. Preferably, the thickness is from 0.1 to 500 m, more preferably from 1 to 250 m.

(75) The total light transmittance of the polyimide film of the present invention is preferably 85% or more, more preferably 90% or more, when the thickness thereof is 50 m.

(76) The thermal linear expansion coefficient of the polyimide film of the present invention is preferably 50 ppm/ C. or less, more preferably 40 ppm/ C. or less, even more preferably 35 ppm/ C. or less, and the glass transition temperature thereof is from the viewpoint of the heat resistance thereof, preferably 300 C. or higher, more preferably 320 C. or higher.

(77) The total light transmittance, the thermal linear expansion coefficient and the glass transition temperature of polyimide film can be measured concretely according to the methods described in the section of Examples.

(78) [Laminate]

(79) The present invention also provides a laminate having a substrate selected from plastic film, silicon wafer, metal foil and glass, and a polyimide resin layer formed using the polyimide resin composition of the present invention.

(80) <Substrate>

(81) The substrate for use in the laminate of the present invention is selected from plastic film, silicon wafer, metal foil and glass.

(82) The resin to constitute the plastic film includes, for example, polyolefins such as homopolymers or copolymers of ethylene, propylene, isobutene, etc.; amorphous polyolefins such as cyclic polyolefins, etc.; polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, etc.; polyamides such as nylon 6, nylon 66, nylon 12, copolymer nylon, etc.; polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyether imide, polysulfone, polyether sulfone, polyether ether ketone, polycarbonate, polyarylate, fluororesin, acrylic resin; biodegradable resins such as polylactic acid, etc. Of those, preferred are polyethylene 2,6-naphthalate, polyimide, polyether imide, polysulfone, polyether sulfone and polycarbonate, from the viewpoint of heat resistance and dimensional stability.

(83) As the metal which constitutes the metal foil, any metal may be used as long as it has electroconductivity. Examples thereof include gold, silver, copper, iron and nickel. Of those preferred is silver or copper, and more preferred is copper.

(84) Of the above-mentioned substrate, preferred is metal foil, and more preferred is copper foil.

(85) The thickness of the substrate may be suitably selected in accordance with the intended use of the laminate, and is preferably from 0.1 to 500 m, more preferably from 1 to 250 m.

(86) <Polyimide Resin Layer>

(87) The polyimide resin layer to be used for the laminate of the present invention is formed using the polyimide resin composition of the present invention, and the polyimide resin composition is as described hereinabove. The thickness of the polyimide resin layer may be suitably selected in accordance with the intended use of the laminate, and is preferably from 0.5 to 50 m, more preferably from 1 to 10 m.

(88) The production method for the laminate of the present invention is not specifically defined, for which employable is any known method. For example, there may be mentioned a method comprising applying the polyimide resin composition of the present invention containing an organic solvent onto a substrate, followed by removing the organic solvent.

(89) The polyimide resin composition and the polyimide film of the present invention are favorably used as films for various members. Concretely, there are mentioned color filters, flexible displays, semiconductor members, optical members, etc. The laminate of the present invention is favorably used as a substrate for printed-wiring assemblies.

EXAMPLES

(90) Examples of the present invention are described below; however, the present invention is not whatsoever limited by these Examples.

(91) The polyimide films produced in Examples and Comparative Examples were evaluated as follows:

(92) (1) Glass Transition Temperature

(93) Using a differential scanning thermometer (DSC 6200, manufactured by SII Nano Technology Inc.), DSC measurement was carried out under the condition of a heating rate of 10 C./min to obtain a glass transition temperature.

(94) (2) Thermal Linear Expansion Coefficient

(95) Using a thermal mechanical analyzer (TMA/SS 6100, manufactured by SII Nano Technology Inc.), TMA measurement was carried out under the condition of a heating rate of 10 C./min to obtain a thermal linear expansion coefficient in the range of from 100 to 200 C.

(96) (3) Total Light Transmittance

(97) Total light transmittance was measured using color/turbidity coincidence measuring instrument (COH 400, manufactured by Nippon Denshoku Industries Co., Ltd.).

(98) (4) Number-Average Molecular Weight

(99) The number-average molecular weight of the polyimide resin was measured using a gel permeation chromatography apparatus by Shimadzu Corporation (liquid feeding unit: LC-20AD, autosampler: SIL-10AXL) under the condition mentioned below.

(100) <Measurement Condition>

(101) Detector: differential refractivity detector RI, RI-8020 Model (by Tosoh Corporation)

(102) Column: TSKgel -M (by Tosoh Corporation)

(103) Column Temperature: 23 C.

(104) Flow Rate: 0.8 mL/min

(105) Standard Sample: monodispersed polystyrene (by Tosoh Corporation)

Production Example 1

Synthesis of 1,2,4,5-cyclohexanetetracarboxylic dianhydride

(106) 552 g of pyromellitic acid, 200 g of a catalyst of rhodium held on active carbon (by N.E. Chemcat Corporation), and 1656 g of water were put into a hastelloy (HC22) autoclave having an inner volume of 5 liters, and while stirring, the reactor was purged with nitrogen gas. Next, the reactor was purged with hydrogen gas so that the hydrogen pressure in the reactor could be 5.0 MPa, and heated up to 60 C. While the hydrogen pressure was kept at 5.0 MPa, this was reacted for 2 hours. The hydrogen gas in the reactor was purged with nitrogen gas, and the reaction liquid was taken out of the autoclave. The reaction liquid was filtered at a hot state to separate the catalyst from a filtrate. The filtrate was concentrated by evaporating water under reduced pressure with a rotary evaporator, thereby precipitating a crystal. The precipitated crystal was separated through solid-liquid separation at room temperature and dried to give 481 g of 1,2,4,5-cyclohexanetetracarboxylic acid (yield 85.0%).

(107) Subsequently, 450 g of the resultant 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were put into a 5-liter separable glass flask (equipped with a Dimroth condenser), and while stirring, the reactor was purged with nitrogen gas. This was heated up to the reflux temperature of the solvent under the nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, this was cooled to room temperature to precipitate a crystal. The precipitated crystal was separated through solid-liquid separation and dried to give a primary crystal. Further, the separated mother liquid was concentrated under reduced pressure using a rotary evaporator to precipitate a crystal. The crystal was separated through solid-liquid separation and dried to give a secondary crystal. The primary crystal and the secondary crystal were combined to give 375 g of 1,2,4,5-cyclohexanetetracarboxylic anhydride (yield in anhydration, 96.6%).

Example 1

(108) In a nitrogen stream atmosphere, as a diamine, 20.697 g (0.065 mol) of 2,2-bis(trifluoromethyl)benzidine, 5.998 g (0.028 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and as an organic solvent, 62.73 g of -butyrolactone were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 20.688 g (0.092 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 4.67 g (0.05 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 2 hours while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution. The number-average molecular weight of the polyimide resin was 48,900.

(109) After this was cooled, 220 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(110) The resultant polyimide resin composition was coated onto a glass plate, and held on a hot plate at 100 C. for 60 minutes to remove the organic solvent through evaporation, thereby giving a self-supporting colorless transparent primary-dried film. The film was fixed on a stainless frame, and heated in a hot air drier at 250 C. for 2 hours to evaporate the organic solvent thereby giving a polyimide film having a thickness of 50 m. The results are shown in Table 1.

Example 2

(111) In a nitrogen stream atmosphere, as a diamine, 18.515 g (0.050 mol) of 4,4-bis(4-aminophenoxy)biphenyl, 2.719 g (0.013 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and as organic solvents, 42.31 g of -butyrolactone and 10.58 g of N,N-dimethylacetamide were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 14.072 g (0.063 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 0.3 g (0.005 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 1 hour while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution. The number-average molecular weight of the polyimide resin was 385,000.

(112) After this was cooled to 60 C., 165 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(113) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Example 3

(114) In a nitrogen stream atmosphere, as a diamine, 20.244 g (0.055 mol) of 4,4-bis(4-aminophenoxy)biphenyl, 1.321 g (0.006 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and as organic solvents, 42.24 g of -butyrolactone and 10.56 g of N,N-dimethylacetamide were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 13.676 g (0.061 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 0.3 g (0.005 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 1 hour while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution. The number-average molecular weight of the polyimide resin was 423,000.

(115) After this was cooled to 60 C., 165 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(116) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Example 4

(117) In a nitrogen stream atmosphere, as a diamine, 15.523 g (0.048 mol) of 2,2-bis(trifluoromethyl)benzidine, 4.498 g (0.021 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and as an organic solvent, 65.91 g of -butyrolactone were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 15.516 g (0.069 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 3.50 g (0.05 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 170 C., and refluxed for 5 hours while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution. The number-average molecular weight of the polyimide resin was 48,900.

(118) After this was cooled to 60 C., 110 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(119) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Example 5

(120) In a nitrogen stream atmosphere, as diamines, 13.696 g (0.043 mol) of 2,2-bis(trifluoromethyl)benzidine and 2.851 g (0.014 mol) of 4,4-diaminodiphenyl ether, 3.087 g (0.014 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and as an organic solvent, 66.05 g of -butyrolactone were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 15.971 g (0.071 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 3.60 g (0.05 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 170 C., and refluxed for 5 hours while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution.

(121) After this was cooled to 60 C. 110 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(122) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Example 6

(123) A polyimide resin solution was produced in the same manner as in Example 2, and 385 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(124) Using the resultant polyimide resin composition and in the same manner as in Example 2, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Comparative Example 1

(125) In a nitrogen stream atmosphere, as a diamine, 21.728 g (0.059 mol) of 4,4-bis(4-aminophenoxy)biphenyl, and, as organic solvents, 65.64 g of -butyrolactone and 16.41 g of N,N-dimethylacetamide were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 13.481 g (0.060 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and an imidation catalyst, 0.3 g (0.005 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 3 hours while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution.

(126) After this was cooled to 60 C., 165 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(127) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Comparative Example 2

(128) In a nitrogen stream atmosphere, 16.024 g (0.043 mol) of 4,4-bis(4-aminophenoxy)biphenyl and 5.343 g (0.019 mol) of 3,3-dicarboxy-4,4-diaminodiphenylmethane as diamines, and, as organic solvents, 52.35 g of -butyrolactone and 13.09 g of N,N-dimethylacetamide were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, a nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 13.919 g (0.062 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 0.3 g (0.005 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 1 hour while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution.

(129) After this was cooled to 60 C., 165 g of silica microparticles DMAC-ST (mean particle size 11 nm, silica content 20% by mass, N,N-dimethylacetamide solution: by Nissan Chemical Industries, Ltd.) were added, and stirred for 2 hours to give a polyimide resin composition.

(130) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

Comparative Example 3

(131) In a nitrogen stream atmosphere, as a diamine, 18.816 g (0.059 mol) of 2,2-bis(trifluoromethyl)benzidine, 5.452 g (0.025 mol) of 3,3-dihydroxybenzidine as a phenolic hydroxyl group-containing diamine, and an organic solvent, 64.53 g of -butyrolactone, were put into a 500-mL five-neck flask equipped with a thermometer, a stirrer, nitrogen-introducing duct, a side tube-having dropping funnel, a Dean Stark unit and a condenser, and dissolved therein. 18.807 g (0.084 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride synthesized in Production Example 1 and as an imidation catalyst, 4.24 g (0.05 mol) of trimethylamine, were dropwise added thereto in one operation. After the addition, this was heated up to 180 C., and refluxed for 5 hours while the distillate was removed as needed. The finish of water distillation was confirmed, and this was cooled to 60 C. to give a polyimide resin solution.

(132) After this was cooled to 60 C., 110 g N,N-dimethylacetamide was added, and stirred for 2 hours to give a polyimide resin composition.

(133) Using the resultant polyimide resin composition and in the same manner as in Example 1, a polyimide film having a thickness of 50 m was produced. The results are shown in Table 1.

(134) TABLE-US-00001 TABLE 1 Polyimide Resin Composition Constitution of Polyimide Resin Diamine (B) Results of Film Evaluation Phenolic Hydroxyl Polyimide Thermal Linear Tetracarboxylic Group-Containing Other Resin/Silica Total Light Expansion Glass Transition Dianhydride (A) Diamine Diamine Microparticles transmittance Coefficient Temperature (molar ratio) (molar ratio) (molar ratio) (ratio by mass) (%) (ppm/ C.) ( C.) Example 1 HPMDA HAB TFMB 50/50 91.2 27 410 100 30 70 Example 2 HPMDA HAB BAPB 50/50 87.4 30 318 100 20 80 Example 3 HPMDA HAB BAPB 50/50 88.0 31 306 100 10 90 Example 4 HPMDA HAB TFMB 60/40 90.7 35 410 100 30 70 Example 5 HPMDA HAB TFMB/ODA 60/40 90.9 36 369 100 20 60/20 Example 6 HPMDA HAB BAPB 30/70 89.8 21 320 100 20 80 Comparative HPMDA BAPB 50/50 cloudy immeasurable* immeasurable* Example 1 100 100 Comparative HPMDA BAPB/MBAA 50/50 cloudy immeasurable* immeasurable* Example 2 100 70/30 Comparative HPMDA HAB TFMB 100/0 89.1 52 410 Example 3 100 30 70 *The film was too brittle to be analyzed.

(135) The abbreviations in the Table are as follows:

(136) HPMDA: 1,2,4,5-cyclohexanetetracarboxylic anhydride

(137) HAB: 3,3-dihydroxybenzidine

(138) TFMB: 2,2-bis(trifluoromethyl)benzidine

(139) BAPB: 4,4-bis(4-aminophenoxy)biphenyl

(140) MBAA: 3,3-dicarboxy-4,4-diaminodiphenylmethane

(141) ODA: 4,4-diaminodiphenyl ether

INDUSTRIAL APPLICABILITY

(142) The polyimide film formed using the polyimide resin composition of the present invention is excellent in transparency and heat resistance and has a low thermal linear expansion coefficient, and is therefore free from dimensional change by heat, and consequently, this is favorably used as films for various members. Concretely, the film is expected to be used in color filters, flexible displays, semiconductor members, optical members and the like. In addition, the laminate of the present invention is favorably used as a substrate for printed-wiring assemblies.