Heat-resistant resin composition

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Industrial application field]

The present invention relates to a polyimide resin composition having improved heat resistance. More specifically, the present invention relates to a polyimide resin composition having heat resistance that can be sufficiently used as a related material for a printed wiring board.

【0002】

[Conventional technology]

Polyimide resin is widely used as a fiber, a film, a molding material, etc. because of its excellent electrical properties, mechanical properties, and heat resistance. However, when used as a related material for printed wiring boards, for example, it can withstand a soldering iron of about 400 ° C, and when used as a substrate film, it has thermal dimensional stability close to that of an inorganic material (for example, copper). Although it is desirable to have it, the currently known polyimide resin does not have such heat resistance.

【0003】

[Problems to be Solved by the Invention]

An object of the present invention is to uniformly disperse a metal oxide sol in a polyimide resin, so that heat-resistant softening characteristics (for example, elastic modulus at high temperature) and thermal dimensional stability are not impaired without impairing the good processability inherent in the polyimide resin. Or, to improve heat resistance such as thermal decomposition characteristics.

【0004】

[Means for solving problems]

The present inventors have arrived at the present invention as a result of diligent research to achieve the above object. That is, the present invention is a heat-resistant resin composition in which a metal oxide sol is dispersed in a polyimide resin, and the silane compound is reacted with the polyimide resin or / and the polyamic acid resin in the presence of the silane compound or in advance. The heat-resistant resin composition is characterized in that the metal oxide sol is dispersed thereafter, and further, the heat-resistant resin is characterized in that the particle size of the metal oxide sol is 10 nm to 100 nm. It relates to a composition.

【0005】

The polyimide resin used in the present invention can be synthesized by a conventionally known method. For example, there are a diisocyanate method, a diamine method and the like. In the case of the industrially advantageous diisocyanate method, one or more diisocyanates and one or more polycarboxylic acid anhydrides are reacted with each other in an organic solvent at a temperature of 200 ° C. or less. Obtained by.

【0006】

Examples of the organic polar solvent used in the reaction include ethers such as diethylene glycol diethyl ether and diethylene glycol dimethyl ether, ketones such as cyclohexanone and methyl ethyl ketone, esters such as γ-butyrolactone and cellosolve acetate, N-methyl-2-pyrrolidone and dimethylacetamide. , Amides such as dimethylformamide, aromatic hydrocarbons such as xylene and toluene, sulfur type such as dimethylsulfooxide and sulfolane, phenol type such as phenol and cresol, etc., and it is preferable to use them alone or as a mixture. ..

【0007】

The reaction temperature is usually preferably 50 to 200 ° C, and the reaction is a catalyst for the reaction of isocyanate and an active hydrogen compound, for example, tertiary amines such as triethylamine, lutidine, picolin, undecene, triethylenediamine, lithium methylate, sodium methylate. , Potassium butoxite, alkali metals such as potassium fluoride and sodium fluoride, alkaline earth metal compounds, or metals such as cobalt, titanium, tin and zinc, and semi-metal compounds may be used.

【0008】

In the case of the diamine method, one kind or two or more kinds of tetracarboxylic dianhydride and one kind or two or more kinds of diamine in the above-mentioned organic polar solvent at room temperature or a temperature of about 5 ° C. By reacting the two with each other, a polyamic acid solution as a precursor is obtained. Further, a polyimide solution can be obtained by dehydration imidization in the solution as it is by chemical or heating.

【0009】

The composition of the polyimide resin used in the present invention is not particularly limited, but one or more of the acid components shown below and one or more of the amine components (or isocyanate components) are preferably used. it can.

【0010】

The acid components include butanetetracarboxylic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, diphenylsulfonetetracarboxylic acid anhydride, diphenylethertetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, and diphenylpropanetetra. One or more of tetracarboxylic acid anhydrides such as carboxylic acid anhydride and diphenylhexafluoropropane tetracarboxylic acid anhydride can be mentioned.

【0011】

As amine components, hexamethylenediamine, tetramethylenediamine, 4,4-diaminocyclohexane, 4,4-diaminodicyclohexylmethane, 1,3-bis- (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane , P-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 3,3-diaminodiphenylmethane, 2,4-dimethylmetaphenylenediamine, 5- Nitro-metaphenylenediamine, 5-chloro-metaphenylenediamine, 4,4-diaminodiphenylhexafluoropropane, 3,3-diaminodiphenylhexafluoropropane, 4,4-diaminodiphenylsulfone, 3,3-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfide, 3,3-diaminodiphenylsulfide, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone, 3,4-diaminobiphenyl, 3,3-diaminobiphenyl, isopropyridene dianiline, 3 , 3-Diaminodiphenylpropane, 2,4-tolylene diamine, 3,3-diaminobenzanilidero, 4,4-diaminobenzanilide, O-trizine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-) Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4- [1,3-phenylenebis (1-methylethylidene)] bisaniline , 4,4- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,3- [1,3-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4-( 4-Aminophenoxy) phenyl] propane, bis [4- (3-ami)Nophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4, (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, bis [4, (3-aminophenoxy) phenyl] sulfone, 4,4-bis (3-aminophenoxy) biphenyl, 4,4-bis (4-aminophenoxy) biphenyl, etc., or these Examples thereof include one type or a mixture of two or more types of diisocyanate.

【0012】

The optimum value of the molecular weight of the polyimide resin used in the present invention varies depending on each composition and application, but is 0.1 to 3.0 dl / g, preferably 0.4 to 1.0 in logarithmic viscosity value at 30 ° C. in N-methyl-2-pyrrolidone. It is in the range of dl / g.

【0013】

In the heat-resistant resin composition of the present invention, examples of the sol dispersed in the polyimide resin include one or a mixture of two or more metal oxides such as silica, alumina, titanium, tin, boron, and zirconia. However, silica sol is particularly preferable.

【0014】

The average particle system of the metal oxide sol is preferably 10 nm to 100 nm, and the fork dispersion amount is preferably 10 wt% to 40 wt%. If the particle system exceeds 100 nm, the effect of improving the heat resistance is small, and the dispersibility is deteriorated, so that the transparency of the molded product such as a film is significantly impaired. Further, if the dispersion amount exceeds 40 wt%, the mechanical properties of the molded product are impaired, and if it is 10 wt% or less, the effect of improving the heat resistance is small.

【0015】

In the heat-resistant resin composition of the present invention, as a method for containing a metal oxide sol in the polyimide resin, for example, N-methyl-2-pyrrolidone, dimethylacetamide, phenol, cresol, diethylene glycol dimethyl ether, etc. A method of performing a sol-gel reaction of a metal alkoxide in a polymer solution such as xylene, cyclohexanone, dimethylsulfooxide, γ-butyrolactone, or a metal oxide sol solution such as methanol, isopropyl alcohol, butanol, ethylene glycol, xylene, toluene, methyl. A solution of an organic solvent such as isobutyl ketone, dimethylformamide, dimethylacetamide, or diethylene glycol diethyl ether, or a method of directly blending and dispersing the aqueous solution in the solution of the organic solvent of the above polymer is available, but is not particularly limited. Further, the above-mentioned polymer solution concentration and metal oxide sol solution concentration are also not particularly limited, but are in the range of about 10 wt% to 50 wt%, respectively. Alternatively, the above method may be carried out using a polyamic acid resin solution which is a precursor of polyimide.

【0016】

In the present invention, when the metal oxide sol is contained in the polyimide resin or / and the polyamic acid resin, the silane compound is reacted with the polyimide resin or / and the polyamic acid resin in the presence of the silane compound or in advance. By doing so, more uniform dispersibility can be obtained. Further, by introducing an appropriate reactive group into the silane compound, a cross-linking reaction of the polymer occurs, so that the heat resistance is further improved.

【0017】

Examples of the silane compound used include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. γ-Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Silane coupling agents such as γ-mercaptopropyltrimethoxysilane, or polysiloxane oils and varnishes with appropriate reactive groups such as carboxyl groups, amino groups, silanol groups, methoxy groups, acid anhydride groups, and epoxy groups. One kind or a mixture of two or more kinds such as.

【0018】

When the silane compound is reacted with the polyimide resin or / and the polyamic acid resin in advance, a silane compound having an appropriate reactive group is added before the polymer polymerization and reacted at the same time as the polymerization, or added after the polymerization is completed. This can be achieved by reacting as it is at an appropriate temperature.

【0019】

The optimum value of the addition amount of the silane compound depends on the composition and molecular weight of the polyimide resin and the silane compound, but is in the range of 1 to 50 wt%, preferably 1 to 10 wt% in the solid content of the polyimide resin.

【0020】

In the heat-resistant resin composition of the present invention, the resin solution in which the metal oxide sol obtained as described above is dispersed can be directly molded by a conventionally known method such as solution casting, wet spinning, dry spinning, and gel spinning. Further, in the case of a resin solution prepared using a polyamic acid resin, it is necessary to dehydrate and imide at a temperature of Tg or higher of the polyimide resin after molding.

【0021】

The form of the molded product is not particularly limited, but is a molded product such as a film, a fiber, a hollow fiber, a pipe, and a bottle. The application is not particularly limited, but it can be used as parts and materials for automobiles, chemical plants, aerospace, machinery, information, electrical / electronic.

【0022】

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

【0023】

[Example]

Example 1 Polymerization of polyimide resin The following polymerization components were charged in a reaction vessel, and the temperature was raised to 100 ° C. over about 1 hour with stirring under nitrogen. After that, the mixture was stirred for about 3 hours to complete the polymerization. Polymerized component 1 mol of benzophenone tetracarboxylic dianhydride 4,4-Dicyclohexylmethane Diisocyanate 1 mol 0.001 mol of sodium methylate N-methyl-2-pyrrolidone 1.5 liters Dispersion of metal oxide sol A xylene solution (solid content concentration of 30%) of silica sol having an average particle diameter of 12.5 nm was added to the above-mentioned polymerized varnish so that the silica sol solid content was 20 wt% in the total solid content, and then dispersed once through three rolls. did. Film making The above polyimide / silica sol solution is applied onto a releasable polyester film using an applicator so that the thickness after drying is 20 μm, dried at 100 ° C for 5 minutes, and then dried at 140 ° C for 10 minutes. It was peeled off from the releasable film. Then, it was dried under vacuum at 200 ° C. for 10 hours in order to completely remove the solvent. Table 1 shows various characteristic values of the film thus obtained.

【0024】

Examples 2 and 3 A film was prepared in the same manner as in Example 1 except that the polyimide resin and silica sol were changed as shown in Table 1. Table 1 shows the various characteristic values obtained.

【0025】

Example 4 Polymerization of polyimide resin The following polymerization component and silane compound were charged in the reaction vessel, and the temperature was raised to 100 ° C. over about 1 hour with stirring under nitrogen. After that, the mixture was stirred for about 3 hours to complete the polymerization. Polymerized component 1 mol of aqueous benzophenone tetracarboxylic acid 4,4-Dicyclohexylmethane Diisocyanate 1 mol Carboxy-modified polydimethylsiloxane 1wt% (Product name: X-22-162A manufactured by Shin-Etsu Chemical Co., Ltd.) 0.001 mol of sodium methylate N-methyl-2-pyrrolidone 1.5 liters Dispersion of metal oxide sol A silica sol dispersion solution was prepared in the same manner as in Example 1. Film making A film was prepared in the same manner as in Example 1. The obtained characteristic values are shown in Table 1.

【0026】

Examples 5, 6 A film was prepared in the same manner as in Example 4 except that the silane compound and the silica sol as the polymerization components were changed as shown in Table 1. Table 1 shows the various characteristic values obtained.

【0027】

Comparative Examples 1 and 2 A film was prepared in the same manner as in Example 1 except that the polymerization components were as shown in Table 1. Table 1 shows the various characteristic values obtained. [0028]

[table 1]

<img file="JPH07331069A_D0001.tif" />【0029】

[Effect of the invention]

Since the heat-resistant resin composition of the present invention uniformly disperses the metal oxide sol in the polyimide resin, it does not impair the processability as compared with the conventional polyimide resin, and has thermal softening characteristics (for example, elastic modulus at 350 ° C). ), Thermal dimensional stability, thermal decomposition characteristics, and other heat resistance are significantly improved.