JPH06322200A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition harmless to environment, having excellent heat-resistance and flame retardancy and useful for household appliances, automobile parts, etc., by compounding a styrene-based resin, a polyphenyl sulfide resin, red phosphorus and a specific silane compound at specific ratios. CONSTITUTION:The objective composition can be produced by compounding (A) 50-99wt.% of a styrene-based resin, (B) 1-50wt.% of a polyphenyl sulfide resin, (C) 1-25 pts.wt. (based on 100 pts.wt. of A+B) of red phosphorus and (D) 0-0.5 pts.wt. of a silane compound or silicone oil having amino, epoxy, hydroxyl and/or carboxyl groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent flame retardancy and containing no halogen compound, and more particularly to a flame retardant styrene resin composition having excellent drip preventing property.

[0002]

BACKGROUND OF THE INVENTION Styrenic resins have excellent mechanical properties,
It is used in a wide range of fields including home electric appliances, office automation equipment, automobiles and other parts due to its moldability and electrical insulation. However, styrene-based resins are flammable, and various techniques have been devised for flame retardation due to safety issues.

In general, a method has been adopted in which a halogen-based flame retardant such as a bromine compound having a high flame retarding efficiency and antimony oxide are blended with a resin to make the flame retardant.

Further, as a non-halogen flame-retardant resin containing no halogen-based flame retardant in connection with recent environmental problems,
A method of blending red phosphorus and a metal oxide with a styrene resin (JP-A-4-106140), and a method of blending red phosphorus, melamine and a heat-crosslinkable curable resin with an ABS resin (JP-A-61-291643). Gazette) has been proposed.

[0005]

However, in the method of using a halogen-based flame retardant, since the flame retardant is added in an increased amount to prevent the drop (drip) of the fire species during combustion, the mechanical properties and heat resistance of the resin composition are reduced. However, there is a problem that a toxic gas is generated due to decomposition of a halogen compound during molding or combustion.

Further, since the composition described in JP-A-4-106140 contains a large amount of an inorganic metal which is incompatible with the resin, the impact resistance is poor, and the composition described in JP-A-61-291643 is Since a large amount of various flame retardants are added, the original properties of the resin such as impact resistance cannot be obtained, which is not satisfactory.

An object of the present invention is to provide a styrene-based resin having excellent flame retardancy without using a halogen compound while utilizing the original characteristics of the resin.

[0008]

Means for Solving the Problems As a result of extensive studies to solve the above-mentioned problems, the present invention aims to achieve the above-mentioned object by adding red phosphorus and a specific silane compound to a mixture of a styrene resin and a polyphenylene sulfide resin. The present invention has been found to be efficiently achieved.

That is, the present invention provides (A) styrene resin 5
0 to 99% by weight and (B) polyphenylene sulfide resin 1
1 to 25 parts by weight of (C) red phosphorus and (D) an amino group, an epoxy group, a hydroxyl group, based on a resin composition (total amount of 100 parts by weight of (A) and (B)) consisting of A thermoplastic resin composition comprising 0 to 5.0 parts by weight of a silane compound or silicone oil containing at least one functional group selected from a carboxyl group.

The present invention will be described in detail below.

The styrene resin (A) in the present invention means a (co) polymer containing 10% by weight or more of a styrene unit, or a monomer or a unit amount of 1 to 80 parts by weight of a rubbery polymer containing 10% by weight or more of styrene. A graft (co) polymer obtained by graft-polymerizing 99 to 20 parts by weight of a body mixture and a mixture thereof.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or lower are preferable, and specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and styrene-butadiene block are preferred. Examples thereof include copolymers, diene rubbers such as butyl acrylate-butadiene copolymers, acrylic rubbers such as polybutyl acrylate, polyisoprene, ethylene-propylene-diene terpolymers, and the like.

Specific examples of the styrene resin (A) in the present invention include polystyrene, rubber-modified polystyrene (HI-PS resin), styrene-acrylonitrile copolymer, styrene-rubber polymer-acrylonitrile copolymer ( ABS resin, AES resin, AAS resin) and the like. Two or more of these may be used. Further, a part of these styrenes and / or a part or all of acrylonitrile is α-methylstyrene, P-methylstyrene, Pt-butylstyrene, (meth) acrylic acid methyl, ethyl, propyl, n-butyl. Ester compounds such as, maleimide, N-methylmaleimide, N
-Maleic monomers such as cyclohexylmaleimide and N-phenylmaleimide, vinylic monomers containing carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, glycidyl acrylate , Glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate, allyl glycidyl ether, styrene-P-glycidyl ether,
Epoxy group-containing vinyl monomers such as P-glycidyl styrene, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylamino methacrylate Ethyl, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-
Vinyl-based monomers containing amino groups or substituted amino groups such as methylallylamine, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, P-aminostyrene, aminostyrene, acrylic acid 2 -Hydroxyethyl, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4, methacrylic acid
5,6-pentahydroxyhexyl, acrylic acid 2,
3,4,5-tetrahydroxypentyl, 2,3,4,5-tetrahydroxypentyl methacrylate, 3-hydroxy-1-propene, 4-hydroxy-1-butene,
Cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-
1-propene, cis-5-hydroxy-2-pentene,
Includes those substituted with vinyl monomers that are copolymerizable with styrene, such as vinyl monomers containing hydroxyl groups such as trans-5-hydroxy-2-pentene and 4-dihydroxy-2-butene. Be done.

Here, as the styrene resin, particularly H
I-PS resin, ABS resin, AES resin, AAS resin,
MBS resin and the like are preferably used. In that case, the content of the rubbery polymer in the resin composition is 40% by weight or less, preferably 30% by weight or less. If it exceeds 40% by weight, the resin composition becomes soft, which is not preferable.

The method for producing the (A) styrene resin is not particularly limited, and a usual method such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk-suspension polymerization method or a solution-bulk polymerization method may be used. You can

The polyphenylene sulfide resin (B) in the present invention means a structural formula (hereinafter abbreviated as PPS resin).
The repeating unit represented by (I)

[Chemical 1] It is a polymer containing. In order to effectively achieve the present invention, a polymer containing 50 mol% or more, particularly 70 mol% or more of the repeating unit of the structural formula (I) is preferable. PPS resins include those containing the following structural formula (II) as a repeating unit other than the above.

[0017]

[Chemical 2] Such a PPS resin can be prepared by a known method, that is, Japanese Patent Publication No.
No. 3368, a method for obtaining a polymer having a relatively small molecular weight, or a method for obtaining a polymer having a relatively large molecular weight described in JP-B-52-12240 and JP-A-61-7332. Can be manufactured by.
In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, washed with an organic solvent, hot water, an aqueous acid solution, etc., activated with a functional group-containing compound such as an acid anhydride or isocyanate. Of course, it is possible to use it after performing various treatments.

(A) Styrenic resin in the present invention, (B)
The ratio of polyphenylene sulfide resin is (A) component and (B)
50 to 99% by weight of the component (A) with respect to the total amount of the components,
It is preferably 60 to 95% by weight, and the component (B) is 1 to 50% by weight, preferably 5 to 40% by weight.

If (A) the styrene resin is less than 50% by weight, the resin composition becomes brittle, and if it exceeds 99% by weight, the flame retardancy deteriorates, which is not preferable. (B) If the polyphenylene sulfide resin is less than 1% by weight, the flame retardancy becomes poor, and
When it exceeds the weight%, the resin composition becomes brittle, which is not preferable.

Examples of (C) red phosphorus in the present invention include those obtained by surface-treating a single substance or red phosphorus particles with a resin, an inorganic compound, mineral oil, etc., and particularly, a surface-treated with a thermosetting resin or an inorganic compound. Those are preferable from the viewpoint of safety.

The particle size of red phosphorus is not particularly limited, but fine particles are preferred because of their excellent flame retarding efficiency.

The blending amount of (C) red phosphorus in the present invention is (A)
It is 1 to 25 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of the styrene resin and the polyphenylene sulfide resin (B).

If the compounding amount of (C) red phosphorus is less than 1 part by weight, the resin composition cannot obtain sufficient flame retardancy, and if it exceeds 25% by weight, the flame retardancy is deteriorated, which is not preferable.

The (D) silane compound or silicone oil (hereinafter referred to as modified silane compound) containing at least one functional group selected from amino group, epoxy group, hydroxyl group and carboxyl group in the present invention is A silane compound or silicone oil having at least one functional group selected from an amino group, an epoxy group, a hydroxyl group and a carboxyl group in the molecule. Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, γ
-Ureidopropyltriethoxysilane, amino-modified silicone oil, γ-glycidoxypropyltrimethoxysilane, epoxy-modified silicone oil, hydroxypropyltrimethoxysilane, phenol-modified silicone oil, carboxy-modified silicone oil and the like, particularly γ- (2-Aminoethyl) aminopropyltrimethoxysilane, amino-modified silicone oil, γ-
Glycidoxypropyl methoxysilane and phenol-modified silicone oil are preferred because they have excellent drip prevention properties and flame retardancy.

The compounding amount of the (D) modified silane compound in the present invention is 0 to 5.0 parts by weight, preferably 0.1 to 3 parts by weight based on the total amount of the (A) styrene resin and (B) polyphenylene sulfide resin. 0.0 parts by weight.

If the compounding amount of the (D) modified silane compound exceeds 5.0 parts by weight, the flame retardancy deteriorates, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited. For example, a mixture of (A) styrene resin, (B) polyphenylene sulfide resin, (C) red phosphorus and (D) modified silane compound is Banbury. Mixer, roll,
It is made into a product by melt-kneading with an extruder or a kneader.

The resin composition of the present invention may be another thermoplastic resin compatible with the resin composition of the present invention, such as polycarbonate, polyphenylene ether, polyglutarimide,
Impact resistance and heat resistance can be improved by mixing with polycyclohexane dimethylene terephthalate or the like, and chemical resistance can be improved by mixing with polyolefin, polybutylene terephthalate, polyethylene terephthalate, polyamide or the like.

If desired, various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers may be added.

[0030]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below. In addition, the part number and% in an Example show a weight part and weight%, respectively.

Reference Example (1) Preparation of (A) Styrene Resin (a1) Graft Copolymer A-1: Polybutadiene Latex (Rubber Particle Diameter 0.3
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion-polymerized in the presence of 60 parts (solid content) of 0 μ and a gel content of 88%.

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (A-1).

(A2) Preparation of Copolymer a-1: A copolymer (a-1) was prepared by suspension polymerization of a monomer mixture of 70% styrene and 30% acrylonitrile.

A-2: A copolymer (A-2) was prepared by suspension polymerization of a monomer mixture of 70% styrene, 25% acrylonitrile and 5% methacrylic acid.

A-3: A copolymer (a-3) was prepared by suspension polymerization of a monomer mixture of 72% styrene, 27% acrylonitrile and 1% glycidyl methacrylate.

(2) Preparation of (B) polyphenylene sulfide resin B-1: PPS (B-1) comprising 80 mol% of P-dichlorobenzene and 20 mol% of m-dichlorobenzene was prepared. The melting point of the obtained PPS was 218 ° C.

B-2: PPS comprising 70 mol% of P-dichlorobenzene and 30 mol% of m-dichlorobenzene
(B-2) was prepared. The melting point of the obtained PPS is 160
It was ℃.

(3) (C) Preparation of red phosphorus C-1: Novaret # 120 (red phosphorus content = 85%, manufactured by Rin Kagaku Kogyo Co., Ltd.) was used.

C-2: Novaret # 280A (red phosphorus content = 48%, manufactured by Rin Kagaku Kogyo Co., Ltd.) was used.

(4) Preparation of (D) Modified Silane Compound D-1: SH6020 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was used.

D-2: SH6040 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was used.

Examples 1 to 8 The (A) styrene resin, (B) polyphenylene sulfide resin, (C) red phosphorus, and (D) modified silane compound prepared in Reference Examples were mixed at the compounding ratio shown in Table 1. A pelletized polymer was produced by melt-kneading and extruding at a resin temperature of 230 ° C. with a vented 40 mmφ extruder. Then, using an injection molding machine, the cylinder temperature is 230 ° C. and the mold temperature is 60.
A test piece was molded at ℃, and the physical properties were measured under the following conditions.

1/2 "Izod impact strength: ASTM
D256-56A Flame Retardance: In accordance with UL94 standard, vertical combustion test 1 /
A 16 ″ × 1/2 ″ × 5 ″ combustion test piece was used.

The measurement results are shown in Table 2.

[0045]

[Table 1]

[0046]

[Table 2]

Comparative Examples 1 to 6 The (A) styrene resin, (B) polyphenylene sulfide resin, (C) red phosphorus, and (D) modified silane compound prepared in Reference Examples were mixed at the compounding ratio shown in Table 1. Each physical property was measured in the same manner as in the examples. The measurement results are shown in Table 2.

From the results shown in Table 2, the following is clear.
The resin compositions (Examples 1 to 8) of the present invention are excellent in impact resistance and flame retardancy in balance.

On the other hand, polyphenylene sulfide resin (B)
When the compounding amount is less than 1% by weight (Comparative Examples 1 and 5), the flame retardancy is poor, and when it exceeds 50% by weight (Comparative Examples 2 and 6), the impact resistance is poor, which is not preferable.

Further, when the content of red phosphorus is less than 1 part by weight (Comparative Example 3), the flame retardancy is poor, and when it exceeds 25 parts by weight (Comparative Example 4), the flame retardancy is deteriorated, which is not preferable. .

[0051]

The thermoplastic resin composition of the present invention exhibits excellent flame retardancy and impact resistance.

According to the present invention, it is possible to provide a flame-retardant resin containing no halogen compound.

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Claims (1)

[Claims] 1. (A) 50 to 99% by weight of styrene resin
(B) 1 to 50 parts by weight of a polyphenylene sulfide resin (100 parts by weight of the total amount of (A) and (B)) to (C) 1 to 25 parts by weight of red phosphorus and (D) an amino group. ,
A thermoplastic resin composition comprising 0 to 5.0 parts by weight of a silane compound or silicone oil containing at least one functional group selected from an epoxy group, a hydroxyl group and a carboxyl group.