JPH01190755A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in electrical properties, mechanical properties, toughness, incinerability, etc., by mixing a specified resin mixture with a triazine compound, a bisphenol epoxy compound and/or an olefin polymer. CONSTITUTION:A resin mixture (A) is obtained by mixing 20-95wt.% polyamide resin obtained by polycondensing a three-membered or larger lactam, a polymerizable omega-amino acid, a dibasic acid, a diamine or the like with 80-5wt.% thermoplastic polyester resin based on a polyalkylene terephthalate obtained by polycondensing terephthalic acid (or its dialkyl ester) with an aliphatic glycol. 100 pts.wt. component A is mixed with 5-50 pts.wt. triazine compound (B) (e.g., melamine cyanurate), 0.01-3 pts.wt. bisphenol epoxy compound of a degree of polymerization >=3, comprising a condensate of a bisphenol A with an epichlorohydrin (C) and/or 2-40 pts.wt. olefin polymer (D) copolymerized with an alpha,beta-unsaturated carboxylic acid (derivative) or modified therewith.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel resin composition.

More specifically, the present invention is suitable for electrical/electronic parts and building material parts, has excellent electrical properties and mechanical properties, has little change in these properties due to moisture absorption, and has high toughness.
The present invention relates to a resin composition having excellent characteristics such as excellent flame retardancy and low metal corrosiveness.

[Prior art] Polyamide resin has excellent mechanical and electrical properties in a dry state, but it is highly hygroscopic, and its physical properties and dimensions change significantly due to moisture absorption, and in particular, the electrical properties deteriorate significantly. However, it has the drawback that its use in applications such as electrical and electronic components is subject to restrictions.

On the other hand, although thermoplastic polyester resin has the advantage of low hygroscopicity and little change in electrical properties, it is not easy to make it flame retardant, and halogenated flame retardants such as bromine compounds are required to make it flame retardant. Since the halogen-based flame retardant tends to corrode metal contacts, there are still restrictions on its use in electrical and electronic parts.

Furthermore, since thermoplastic polyester resin has inferior toughness compared to polyamide resin, it is difficult to use it as is for connectors such as snap fits and wire retention that utilize the toughness and elasticity of resin, and it is difficult to use it as is for such applications. For this purpose, elastomer components are usually blended, but in this case, the flame retardant properties are reduced, so it is necessary to increase the amount of flame release agent blended, and therefore it is not suitable for electrical and electronic parts. , the disadvantageous problem of increased metal corrosivity arises.

[Problems to be Solved by the Invention] Under these circumstances, the present invention provides a material that has excellent electrical and mechanical properties, has little change in these properties due to moisture absorption, has high toughness, and has excellent flammability. The purpose of this invention is to provide a resin composition which has excellent characteristics such as low metal corrosiveness and is suitable for use in electric/electronic parts, building material parts, etc.

[Means for Solving the Problems] As a result of intensive research to develop a resin composition having the above-mentioned excellent characteristics, the present inventors discovered that a polyamide resin and a thermoplastic polyester resin in a predetermined ratio were combined. Based on this finding, we discovered that a composition consisting of a mixture containing a triazine compound, a hisphenol-type epoxy compound, and/or a specific olefin polymer in a predetermined ratio is suitable for the purpose. This led to the completion of the present invention.

That is, the present invention provides (A) (a) polyamide resin 20 to
95% by weight and (b) thermoplastic polyester resin 80-5
(B) 5 to 50 parts by weight of a triazine compound, (C) a hisphenol-type epoxy compound with a degree of polymerization of 3 or more consisting of a condensate of hisphenols and epichlorohydrin, and 0.0% to 100 parts by weight of the resin mixture. 01 to 30 parts by weight, and/or (D) 2 to 40 parts by weight of an olefin polymer copolymerized with or modified with an α,β-unsaturated carboxylic acid or a derivative thereof. It is something to do.

The present invention will be explained in detail below.

In the composition of the present invention, a polyamide resin and a thermoplastic polyester resin are used as component (A). As the polyamide resin, a polyamide resin obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid, and a diamine can be used.

Specific examples of such polyamide resins include ε-caprolactam, aminocaproic acid, enantlactam, 7
-Aminhebutanoic acid, 11-aminoundecanoic acid, 9-
Polymers of aminononanoic acid, α-pyrrolidone, α-piperidone, diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dotecamethylene diamine, metaxylylene diamine, and terephthalic acid, isophthalic acid, adipine. Polymers formed by polycondensation of dicarboxylic acids such as acid, cepatic acid, dodecane dibasic acid, and geltaric acid, or copolymers thereof, such as nylon 4.6.7.8.11.12.6,6 .6,
9.6, 10.6, I+, 6. +2.6T, 6/6
, 6.6/12.6/6T, 6+/67, etc. One type of these polyamide resins may be used, or
You may use two or more types in combination.

On the other hand, as the thermoplastic polyester resin, polyalkylene terephthalate obtained by the polycondensation reaction of terephthalic acid or its dialkyl ester with aliphatic glycols, or a copolymer mainly composed of these, is used. , polyethylene terephthalate, polybutylene terephthalate, and the like.

Examples of the aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, etc.
3 for these aliphatic glycols as well as other diols or polyhydric alcohols, such as aliphatic glycols.
0% by weight or less of cyclohexane dimetatool, xylylene glycol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane 2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxyethoxyphenyl)
A mixture of 3,5-dibromophenyl)propane, glycerin, and pentaerythritol may be used.

In addition, together with terephthalic acid or its dialkyl ester, other dibasic acids, polybasic acids, or their alkyl esters, such as 7-thalic acid, isophthalic acid, naphthalene dicarboxylic acid, in an amount of not more than 30% by weight based on terephthalic acid or its dialkyl ester. , diphenyldicarboxylic acid, adipic acid, sebacic acid, trimesic acid, trimellitic acid, alkyl esters thereof, etc. may be used in combination.

One type of the thermoplastic polyester resin may be used, or
You may use two or more types in combination.

Regarding the blending ratio of the polyamide resin and thermoplastic polyester resin in the composition of the present invention, the polyamide resin is 20 to 95% by weight, preferably 40 to 80% by weight,
It is necessary to mix the thermoplastic polyester resin in a proportion of 80 to 5% by weight, preferably 60 to 20% by weight.

If this blending ratio deviates from the above range, a resin composition having desired physical properties will not be obtained, and the object of the present invention will not be fully achieved.

In order to improve the flame retardancy of the composition of the present invention,
A triazine compound is blended as component (B). This triazine compound is, for example, one represented by the general formula (in the formula, R1, R2, and R3 are each a hydrogen atom or an alkyl group, and they may be the same or different). Examples include compounds such as melamine, melamine cyanurate, and the like.

Specific examples of the compound represented by the general formula (I) include cyanuric acid, trimethyl cyanurate, triethyl cyanurate, methyl cyanurate, and diethyl cyanurate.
Specific examples of the compound represented by the general formula (II) include incyanuric acid, trimethyl isocyanurate, triethyl isocyanurate,
Examples include tri(n-propyl)ine cyanurate, diethyl isocyanurate-1-, and methylisone anurate.

On the other hand, the melamines include melamine, melamine derivatives, compounds having a similar structure to melamine, condensates of melamine, etc.; examples of such melamines include melamine, ammelide, ammeline, formoguanamine, and guanylmelamine. , ananomelamine, arylguanamine, melam, melem, melon, etc.

Further, the cyanuric acid melamine is an equimolar reaction product of cyanuric acid and melamine, for example, by mixing an aqueous solution of cyanuric acid and an aqueous solution of melamine.
It can be obtained by carrying out the reaction under stirring at 0.0 0.0000000000000 000 and filtering off the produced precipitate. This product is a white solid and is preferably used after being ground into a fine powder. Of course, commercially available products can be used as they are or after being crushed, and melamine cyanurate in which some of the amino groups or hydroxyl groups have been substituted with other substituents can also be used.

These triazine compounds may be used alone or in combination of two or more. Furthermore, among the triazine compounds, melamine and melamine cyanurate are preferred, and in particular, melamine cyanurate causes decomposition products to emerge on the surface of the molded article. This is preferable because there is no inconvenience such as so-called blooming.

In the composition of the present invention, the amount of the triazine compound as the component (B) is preferably 5 to 50 parts by weight, based on 100 parts by weight of the mixture of the polyamide resin and thermoplastic polyester resin as the component (A). The amount is selected in the range of 7 to 35 parts by weight. If this amount is less than 5 parts by weight, no effect of improving the flame retardance of the composition can be expected, and if it exceeds 50 parts by weight, the electrical properties, mechanical properties, etc. of the composition may deteriorate.

In the composition of the present invention, a bisphenol type epoxy compound as component (C) and/or an olefin polymer as component (D) are blended in order to improve its impact resistance and electrical properties. The bisphenol type epoxy compound of component (C) is composed of a condensate of hisphenols and epichlorohydrin, and has a high molecular weight with a degree of polymerization of 3 or more, preferably 15 or more.

This bisphenol type epoxy compound can be represented by the following general formula when the bisphenol is bisphenol A, for example.

(The following is a blank space) (n in the formula is a number of 3 or more, preferably 15 or more) The bisphenols include, for example, bisphenol A
1 Bisphenol F1 Bisphenol C1 Tetramethylbisphenol A1 Tetramethylbisphenol F
1 diisopropyl bisphenol A1 di-5ec-butylbisphenol A1 tetra-tert-butylbisphenol A1 tetra-tert-butylbisphenol F1 tetra-tert-butylhisphenol, 1. l
-ethylidene bisphenol, l, 1-imbutylidene bisphenol, methyl-ethyl-methylene bisphenol L=.

Methyl-isobutyl-methylenebisphenol, methyl-hexyl-methylenehisphenol, methyl-phenyl-methylenebisphenol, bisphenol z, p,
p'-bisphenol, methylenebis(2,4-di-t
ert-butyl-3-cresol), o, pl-bisphenol A1 methylpropinate diphenol, ethylpropinate diphenol, tetramethylbisphenol S, and the like.

In the composition of the present invention, the blending amount of the bisphenol-type epoxy compound as the component (C) is equal to 1% of the mixture of the polyamide resin and the thermoplastic polyester resin as the component (A).
0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight. This amount is 0,
If it is less than 0.01 parts by weight, no effect of improving impact resistance or electrical properties can be expected, and if it exceeds 30 parts by weight, the original physical properties of the mixed resin of polyamide resin and thermoplastic polyester resin will be impaired.

The olefinic polymer of component (1) above is a copolymerized or modified α,β-unsaturated carboxylic acid or its derivative, and as the α,β-unsaturated carboxylic acid or its derivative. is (1) an ethylenically unsaturated mono- or dicarboxylic acid having 3 to 12 carbon atoms, (2) an ester of an alcohol having 1 to 29 carbon atoms and a monocarboxylic acid,
Monoesters and diesters of the alcohol and dicarboxylic acid; (3) monocarboxylic acids in which some or all of the hydroxyl groups of the carboxyl groups are substituted with metal ions;
Examples include metal salts of dicarboxylic acids and dicarboxylic acid monoesters.

Specific examples of these include methyl methacrylate, butyl acrylate, ethyl acrylate, alkyl esters of acrylic and methacrylic acids, sodium methacrylate, zinc methacrylate, maleic acid, maleic anhydride, maleic acid monoethyl ester, maleic acid Examples include monoethyl ester metal salts, fumaric acid, fumaric acid monoethyl ester, metal salts of fumaric acid monoethyl ester, maleic acid, alkyl monoesters of fumaric acid having up to 29 carbon atoms, glycidyl methacrylate, and glycidyl acrylate.

The olefin polymer may be one in which these α,β-unsaturated carboxylic acids or derivatives thereof are randomly copolymerized with monomers such as ethylene, propylene, butene, or ethylene, propylene, butene, etc. It may be one obtained by graft polymerization or graft reaction with an olefin polymer such as. Specifically, ethylene/methacrylic acid or zinc salt of methacrylic acid, ethylene/isobutyl acrylate/zinc salt of methacrylic acid: monoethyl ester of ethylene/methyl acrylate/maleic anhydride and its 0
~100% neutralized zinc, sodium, calcium, lithium, antimony, and potassium salts diethylene/propylene/g - maleic anhydride: ethylene/phthene/
g-Maleic anhydride: ethylene/methyl acrylate/
Methacrylic acid and its zinc salt: ethylene/vinyl acetate/
Methacrylic acid and its zinc salt: ethylene/propylene/
1,4-hexadiene/g-maleic anhydride: ethylene/propylene/norbornadiene/g-maleic anhydride: ethylene/propylene/tetrahydroindene/g-
7 Malic acid: ethylene/glycidyl methacrylate: ethylene/propylene acetate/glycidyl methacrylate: ethylene/propylene 1 fug-tetrahydrofurfuryl methacrylate: ethylene/buty 2 fug-tetrahydrofurfuryl methacrylate: ethylene/furopylene/9-maleic anhydride Random copolymers or grafts such as acid/g-tetrahydrofurfuryl methacrylate: ethylene/butythene/g-maleic anhydride/7-titrahydrofurfuryl methacrylate (g means graft) can be mentioned.

In the case of random copolymerization of α,β-unsaturated carboxylic acids or derivatives thereof, the amount thereof is 50% by weight or less based on the total weight of all components, and in the case of grafting, the amount is 0.01 to 2
A weight percent range is preferred.

As for the olefin polymer used in the present invention, those having good flexibility to some extent have a remarkable impact resistance improvement effect, and therefore have a bending modulus of 100 to 5-150 GO/cm2,
Preferably, it is in the range of 200-8000 kg/cm2. Among the olefin polymers, metal ion-containing ethylene copolymers are particularly preferred. This metal ion-containing ethylene copolymer is a copolymer of ethylene and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, with metal ions such as sodium, zinc, or magnesium bound to it, and is generally combined with an ionomer. An example of such a resin is ionomer resin (trademark: Surlyn) manufactured by DuPont.

The blending amount of the olefin polymer as the component (D) is (A
2 to 40 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the mixture of polyamide resin and thermoplastic polyester resin (component). If this amount is less than 2 parts by weight, the impact resistance and electrical properties of the composition will not be sufficiently improved, and if it exceeds 40 parts by weight, the original physical properties of the mixed resin of polyamide resin and thermoplastic polyester resin will be impaired. There is a risk of being exposed.

=16- In addition to the above-mentioned components, the composition of the present invention may contain, as desired,
Various known additives, such as glass fibers, carbon fibers, reinforcing agents such as metal whiskers, silica, alumina, silica-alumina clay minerals, silica-magnesium clay minerals, calcium silicate, calcium carbonate, asbestos,
Fillers such as carbon black, other flooring agents, nucleating agents,
Antioxidants, flame retardants, antistatic agents, weathering agents, etc. may be added.

The composition of the present invention comprises the above-mentioned (A) component, (B) component, (C
It can be prepared by melt-kneading component ) and/or component (D), and various additives used as necessary, by a commonly used method. Examples of kneading machines used include extruders, Banbury mixers, super mixers, rolls, and kneaders.
Melt-kneading methods at temperatures in the range from 20 to 300°C are advantageous.

[Effects of the Invention] The resin composition of the present invention is a mixture of a polyamide resin and a thermoplastic polyester resin blended with a triazine compound, a specific bisphenol type epoxy compound, and/or an olefin polymer, It has excellent electrical and mechanical properties, and has little change in them due to moisture absorption.
It has excellent characteristics such as high toughness, excellent flame retardancy, and low metal corrosion, and is suitable for use in, for example, electrical/electronic parts and building material parts.

[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, each physical property of the composition was measured according to the following method.

(1) Combustion characteristics Using a 1/16 inch thick test piece, Obtained according to UL94.

(2) Using a test piece with a volume resistivity of 100 mm and a thickness of 113 mm, ASTM D
Measured according to 257.

(3) Using a test piece with a dielectric breakdown voltage of 100 mm and a thickness of 1.3 mm, ASTM D
149.

(4) In 100g of metal corrosive pellets, 2X3X0.5cm of 345C
After burying a manufactured test piece and leaving it in a constant temperature bath at 100°C for 96 hours, the surface of the test piece was visually observed and evaluated according to the following criteria.

Excellent: Slight loss of gloss, but no corrosion Good: 1 to 5 pits/cm2 of corrosion Poor: Corrosion on the entire surface (5) Flexural modulus Measured according to ASTM D 790.

(6) Izotsu impact value Using a 1/2 inch thick test piece, Measured according to ASTM D 256.

In addition, regarding changes in physical properties due to moisture absorption, test pieces were
Moisture absorption treatment was performed for 168 hours in an atmosphere of 195% RH, and the flexural modulus, Izot impact value, volume resistivity, and dielectric breakdown voltage before and after the treatment were compared.

Examples 1 to 7 Relative viscosity (JISK-6810
Using nylon 6 or nylon 66 resin with an Oswald viscosity tube of 3.0 (measured with an Oswald viscosity tube according to After compounding these resins with a bisphenol-type epoxy compound and a triazine-based compound so as to have the composition shown in Table 1, the resin temperature was increased to 2 using a 40 mm extruder.
After melting and mixing at a temperature of 40 to 290°C, the resulting composition was molded into a 5-ton injection molding machine with a mold clamping cuff [Toshiba Machine Co., Ltd.]
Injection molding was carried out using a model 1575 manufactured by Manufacturer Co., Ltd.

The physical properties of the thus obtained molded article were determined. The results are shown in Table 2.

Comparative Example 1.2 = 20- Each component was blended to have the composition shown in Table 1, except for either the hisphenol type epoxy compound or the triazine compound, and the composition was prepared in the same manner as Examples 1 to 7. Things,
After preparation, injection molding was performed, and various physical properties of this molded product were determined. The results are shown in Table 2.

Comparative Example 3.4 Using an epoxy compound other than the claims of the present invention, each component was blended to have the composition shown in Table 1, and the composition was prepared in the same manner as Examples 1 to 7. After preparation, injection molding was performed, and various physical properties of this molded product were determined. The results are shown in Table 2.

Comparative Examples 5 to 13 Using commonly used compounds shown in Table 1 as flame retardants,
Each component was blended so as to have the composition shown in the table, and Example 1
After preparing a composition in the same manner as in steps 7 to 7, injection molding was performed, and each physical property of the molded product was determined. The results are shown in Table 2.

Examples 8 to 15 Relative viscosity (JISK-6810
Nylon 6 or nylon 66 resin with a viscosity of 3.0 (measured with an Oswald viscosity tube according to After blending these resins with an olefin polymer and a triazine compound so as to have the composition shown in Table 3 using
After melt-kneading within the range of C, the resulting composition was injection molded using a 5 ton injection molding machine [manufactured by Toshiba Machinery Co., Ltd., model 1575].

Each physical property was determined for the molded article thus obtained. The results are shown in Table 4.

Comparative Example 14.15 A composition was prepared in the same manner as Examples 8 to 15, except for either the olefin polymer or the triazine compound, by blending each component so as to have the composition shown in Table 3. Afterwards, injection molding was performed, and various physical properties of this molded product were determined. The results are shown in Table 4.

Comparative Example 16 Using only nylon 6 without using a thermoplastic polyester resin, each component was blended to have the composition shown in Table 3, and a composition was prepared in the same manner as Examples 8 to 15.
Injection molding was performed, and each physical property of the molded product was determined.

The results are shown in Table 4.

Comparative Examples 17-23 Using commonly used compounds shown in Table 3 as flame retardants,
Each component was blended so as to have the composition shown in Table 3, and a composition was prepared in the same manner as in Examples 8 to 15. Then, injection molding was performed, and each physical property of the molded product was determined. The results are shown in Table 4.

(Left below) As is clear from the above results, the composition of the present invention shows little change in electrical and mechanical properties due to moisture absorption, has high toughness, and has a V-
It has a flammability of 1-V-2 and has extremely low metal corrosiveness.

Patent applicant: Mitsubishi Chemical Industries, Ltd.

Claims (1)

[Claims] (1) (B) 5 to 50 parts by weight of a triazine compound to 100 parts by weight of a resin mixture of (A) (a) 20 to 95% by weight of polyamide resin and (b) 80 to 5% by weight of thermoplastic polyester resin. , (C) 0.01 to 30 parts by weight of a bisphenol-type epoxy compound with a degree of polymerization of 3 or more consisting of a condensate of bisphenols and epichlorohydrin, and/or (D) an α,β-unsaturated carboxylic acid or a derivative thereof. Olefin polymers 2 to 4 polymerized or modified with these
A resin composition containing 0 parts by weight.