JPH07331061A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in heat resistance, e.g. heat softening properties, thermal dimensional stability and heat decomposition properties, keeping the warkability and useful for an automobile component, an aircraft component, etc., by dispersing a metal oxide sol in a polyamide resin. CONSTITUTION:This heat-resistant resin composition is composed of (A) a polyamide resin (e.g. a polyamide resin having a molecular weight corresponding to 0.4 to 1.0dl/g logarithmic viscosity in N-methyl-2-pyrrolidone at 30 deg.C) containing (B) a metal oxide sol such as silica sol, alumina sol or zirconia sol dispersed therein. In addition, preparation of this resin composition is carried out preferably by reacting the component (A) with the component (C) in the presence of (C) a silane compound such as gamma-glycidoxypropylmethyldiethoxysilane in advance and subsequently dispersing the component (B) having 10 to 100nm particle diameter therein.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyamide resin composition having improved heat resistance. More specifically, it relates to a polyamide-imide resin having heat resistance that can be sufficiently used as a material related to a printed wiring board.

[0002]

2. Description of the Related Art Polyamide resins, particularly aromatic polyamide resins, are widely used as fibers, films, molding materials and the like because they are excellent in electrical properties, mechanical properties, heat resistance and processability. However, for example, when it is used as a related material for a printed wiring board, it must withstand a solder bath at 260 ° C or higher and thermocompression bonding at 300 ° C or higher. It does not have such heat resistance (heat softening property: elastic modulus at high temperature, etc.).
Furthermore, in general, polyamide resins are inferior in properties such as thermal decomposition characteristics and thermal expansion coefficient to polyimide resins or inorganic materials.

[0003]

An object of the present invention is to uniformly disperse a metal oxide in a polyamide resin so that heat softening characteristics (for example, at high temperature) can be obtained without impairing the good workability inherent in the polyamide resin. It is intended to improve heat resistance such as elastic modulus), thermal decomposition resistance, and thermal dimensional stability.

[0004]

The present inventors have accomplished the present invention as a result of earnest research for achieving the above object. That is, the present invention is a heat resistant resin composition in which a metal oxide sol is dispersed in a polyamide resin, and the metal oxide is present in the presence of a silane compound or after the silane compound is reacted with the polyamide resin in advance. A heat-resistant resin composition as described above, characterized in that a sol is dispersed, and further characterized in that the metal oxide sol has a particle size of 10 nm to 100 nm. It is a thing.

The polyamide resin used in the present invention can be synthesized by a conventionally known method. For example, there are a diisocyanate method, an acid chloride method, a direct polymerization method and the like. The industrially advantageous diisocyanate method can be obtained by reacting one or more diisocyanates with one or more dicarboxylic acids in an organic solvent at a temperature of 200 ° C. or lower.

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, and N-methyl-
Amides such as 2-pyrrolidone and dimethylacetamide,
Aromatic hydrocarbons such as xylene and toluene, sulfur such as dimethyl sulfoxide and sulfolane, phenol,
Examples thereof include phenols such as cresol and the like, and it is preferable to use them alone or as a mixture.

The reaction temperature is usually preferably 50 to 200 ° C., and the reaction is a catalyst for the reaction of isocyanate with an active hydrogen compound, such as triethylamine, lutidine,
Tertiary amines such as picoline, undecene and triethylenediamine, alkali metal such as lithium methylate, sodium methylate, potassium butoxite, potassium fluoride and sodium fluoride, alkaline earth metal compound,
Alternatively, it may be carried out in the presence of a metal such as cobalt, titanium, tin or zinc, or a metalloid compound.

The composition of the polyamide resin used in the present invention is not particularly limited, but one or more of the following acid components and isocyanate components (or amine components) can be preferably used.

As the acid component, oxalic acid, malonic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfidedicarboxylic acid, 1 of dicarboxylic acids such as diphenyl ether dicarboxylic acid, diphenyl sulfide dicarboxylic acid, diphenyl propane dicarboxylic acid and benzophenone dicarboxylic acid
Species or two or more species may be mentioned.

As the amine component, 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-diaminophenyl sulfone, 3,3-diaminodiphenyl sulfone, 4,4-diaminodiphenyl sulfide, 3,3-diaminodiphenyl sulfide, 4,4-
Diaminobenzophenone, 3,3-diaminobenzophenone, 3,4-diaminobiphenyl, 3,3-diaminobiphenyl, isopropylidene dianiline, 3,3-diaminodiphenylpropane, 2,4-tolylenediamine, 3,3-diamino Benzanilide, 4,4-diaminobenzanilide, 0-tolidine, 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-phenylene bis (1-methylethylidene)] bisaniline, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, bis [4- (3-aminophenoxy) 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)
Examples thereof include biphenyl, 4,4-bis (4-aminophenoxy) biphenyl, and the like, or one or a mixture of two or more of these diisocyanates.

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

In the heat-resistant resin composition of the present invention, the sol dispersed in the polyamide resin is, for example, one or more metal oxides such as silica, alumina, titanium, tin, boron and zirconia. A mixture may be mentioned, but silica sol is particularly preferable.

The average particle size of the metal oxide sol is preferably 10 nm to 100 nm, and the dispersion amount is 10 wt% to 4 nm.
0 wt% is preferable. When the particle size exceeds 100 nm, the heat resistance improving effect is small and the dispersibility is poor, so that the transparency of the molded product such as a film is significantly impaired. Moreover, if the dispersion amount exceeds 40 wt%, the mechanical properties of the molded product are impaired,
If it is 10 wt% or less, the effect of improving heat resistance is small.

In the heat-resistant resin composition of the present invention, the method for incorporating the metal oxide sol in the polyamide resin is, for example, N-methyl-2-pyrrolidone, dimethylacetamide, phenol, cresol, in an organic solvent of the polymer. Diethylene glycol dimethyl ether, xylene, cyclohexanone, dimethyl sulfoxide, γ-
Method for carrying out sol-gel reaction of metal alkoxide in polymer solution such as butyrolactone, or metal oxide sol solution such as methanol, isopropyl alcohol, butanol, ethylene glycol, xylene, toluene, methyl isobutyl ketone, dimethylformamide, dimethylacetamide , A sol solution or an aqueous solution of an organic solvent such as diethylene glycol diethyl ether, etc. may be directly blended and dispersed in the organic solvent solution of the above polymer, but the method is not particularly limited. Also, the concentration of the polymer solution and the concentration of the metal oxide sol solution are not particularly limited, but each is about 10 wt% to 50 w.
It is in the range of t%.

In the present invention, when the metal oxide sol is contained in the polyamide resin, in the presence of the silane compound,
Alternatively, a more uniform dispersibility can be obtained by previously reacting the polyamide resin with a silane compound. In addition, the introduction of a suitable reactive group into the silane compound causes a crosslinking reaction of the polymer, which further improves the heat resistance.

The silane compound used is γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane. Methoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl)
A silane coupling agent such as γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane or γ-mercaptopropyltrimethoxysilane, or Examples thereof include one or a mixture of two or more such as polysiloxane oil and varnish into which a suitable reactive group such as a carboxyl group, an amino group, a silanol group, a methoxy group, an acid anhydride group and an epoxy group is introduced.

When the silane compound is reacted with the polyamide resin in advance, the silane compound having a suitable reactive group is added before the polymer is polymerized and reacted at the same time as the polymerization, or after the completion of the polymerization, 50 to 2 as it is.
This can be achieved by reacting at a temperature of 00 ° C.

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

The heat-resistant resin composition of the present invention is obtained by molding the resin solution in which the metal oxide sol obtained as described above is dispersed by a known method such as solution casting, wet spinning, dry spinning or gel spinning. Can be processed.

The form of the molded product is not particularly limited, but it may be a molded product such as a film, a fiber, a hollow fiber, a pipe or a bottle. The application is also not particularly limited, but it can be used as parts and materials for automobiles, chemical plants, aviation / space, machinery, information, electric / electronics.

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

[0022]

【Example】

Example 1 Polymerization of Polyamideimide The following polymerization components were charged in a reaction vessel, and the temperature was raised to 180 ° C. under nitrogen with stirring for about 1 hour. Then, the mixture was stirred for about 3 hours to complete the polymerization. Polymerization component Azelaic acid 1 mol Isophorone diisocyanate 1 mol Lithium methylate 0.001 mol N-methyl-2-pyrrolidone 1.5 liter Dispersion of metal oxide sol Xylene solution of silica sol having an average particle diameter of 12.5 nm in the above-mentioned polymerization varnish. (Solid content concentration 30%) was blended so that the silica sol solid content was 20 wt% in the total solid content, and then dispersed by passing through a triple roll once. Preparation of Film The above polyamide / silica sol solution was applied on a releasable polyester film using an applicator so that the thickness after drying was 20 μm, and the temperature was 100 ° C. for 5 minutes.
After drying at 0 ° C. for 10 minutes, it was peeled from the release film. Then, under vacuum to completely remove the solvent, 160
It dried at 10 degreeC and 10 hours at 180 degreeC. Table 1 shows various characteristic values of the film thus obtained.

Examples 2 and 3 Films were prepared in the same manner as in Example 1 except that the polyamide resin and silica sol were changed as shown in Table 1. Table 1 shows various characteristic values.

Example 4 Polymerization of Polyamide A reactor was charged with the following polymerization components and a silane compound,
Under nitrogen, the temperature was raised to 180 ° C. over about 1 hour with stirring, and then the mixture was stirred for about 3 hours to complete the polymerization. Polymerization component Azelaic acid 1 mol Isophorone diisocyanate 1 mol Carboxyl-modified polydimethylsiloxane 1 wt% (Product name: X-22-162A manufactured by Shin-Etsu Chemical Co., Ltd.) Lithium methylate 0.001 mol N-methyl-2-pyrrolidone 1.5L Dispersion of metal oxide sol In the same manner as in Example 1, a dispersion solution of silica sol was prepared. Production of Film A film was produced in the same manner as in Example 1. The characteristic values of the obtained film are shown in Table 1.

Example 5 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 various characteristic values.

Comparative Example 1 A film was prepared in the same manner as in Example 1 except that the polymerization components shown in Table 1 were used. Table 1 shows various characteristic values.

[0027]

[Table 1]

[0028]

Since the heat-resistant resin composition of the present invention uniformly disperses the metal oxide sol in the polyamide resin, it has a heat-softening property (for example, 300) as compared with conventional polyamide resins without impairing processability. It is possible to remarkably improve heat resistance such as elastic modulus at ° C), thermal dimensional stability, and thermal decomposition characteristics.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroki Yamaguchi 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (3)

[Claims] 1. A heat resistant resin composition comprising a metal oxide sol dispersed in a polyamide resin. 2. The heat-resistant resin composition according to claim 1, wherein the metal oxide sol is dispersed in the presence of the silane compound or after the polyamide resin is reacted with the silane compound in advance. 3. The heat resistant resin composition according to claim 1, wherein the metal oxide sol has a particle size of 10 nm to 100 nm.