JPH05125238A - Flame-retarding styrene resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in tensile strength, impact resistance and flame retardancy and good in heat resistance, weathering resistance and antiblooming properties. CONSTITUTION:The title composition comprises 100 pts.wt. styrene resin (A), 6-50 pts.wt. brominated epoxy compound (B1) of a bromine content of 40wt.% or above [flame retardant (I)], 1-30 pts.wt. brominated imide compound (B2) having a bromine content of 50wt.% or above [flame retardant (II)] and 1-30 pts.wt. antimony trioxide (C), wherein the weight ratio of the flame retardant (I) to the flame retardant (II) is 0.2-20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant styrene resin composition having good flame retardancy, high tensile strength and impact resistance, and also excellent in heat resistance, anti-blooming property and weather resistance. It is a thing.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Styrenic resins are widely used in electrical products due to their excellent mechanical and electrical properties. On the other hand, in recent years, TVs, CRTs, various computers, OA equipment, home appliances, etc. are required to meet the UL94 flame retardancy standard. In order to make a styrene resin such as an acrylonitrile-butadiene-styrene resin, that is, an ABS resin flame-retardant, a brominated diphenyl ether such as decabromodiphenyl ether, octabromodiphenyl ether, or a halogen-based tetrabromobisphenol A is generally used. Flame retardant and antimony trioxide (Sb ₂ O ₃ )
A method of blending and with a styrene resin is widely used.

However, when the brominated diphenyl ether is used, the weather resistance (discoloration) is poor, and the flame-retardant resin using the brominated diphenyl ether is used as a waste during molding, during use of the molded product or as waste. Problems such as generation of highly toxic brominated dioxins when burning are pointed out. Further, when decabromodiphenyl ether, which is particularly preferable in terms of physical properties, is used, it has a major drawback that the decabromodiphenyl ether exudes on the surface of the molded product, that is, a blooming phenomenon. Further, when tetrabromobisphenol A, which is most widely used, is used, the heat resistance of the molded article is significantly reduced and the weather resistance (discoloration) is not good, which is a major limitation in terms of application.

In order to solve such a problem, Japanese Patent Laid-Open No.
JP-A-101350 describes a method of adding a brominated epoxy type resin as a flame retardant to an ABS resin. It is known that this flame retardant can improve heat resistance and weather resistance of the ABS resin and has anti-blooming property. However, when the brominated epoxy type resin is added to the ABS resin as a flame retardant by the above-mentioned known method, the weather resistance, heat resistance and anti-blooming property are good, but the flame resistance is not sufficient. That is, if the addition amount of ABS resin is about 32 parts by weight or less, UL94 (V
-0) It is difficult to pass the test, and if it exceeds about 32 parts by weight,
Although it can normally pass the UL94 (V-0) test, its use is limited because the impact resistance and tensile strength are significantly impaired and the cost is increased.

An object of the present invention is to provide a flame-retardant styrene resin composition having excellent high tensile strength, impact resistance and flame retardancy as well as good heat resistance, weather resistance and anti-blooming property. To do.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems, and as a result, have found that a specific organic bromine compound and antimony trioxide are added to a styrene resin at specific ratios. By blending, high tensile strength,
It is even more excellent that a resin composition having excellent impact resistance, flame retardancy, heat resistance, weather resistance, and anti-blooming properties can be obtained, and that silicone oil or chlorinated polyethylene is further added to the resin composition. The inventors have found that performance can be obtained and completed the present invention.

That is, the present invention relates to (A) styrene resin 1
00 parts by weight, (B ₁ ) 6 to 50 parts by weight of a brominated epoxy compound [flame retardant (I)] having a bromine content of 40% by weight or more, (B ₂ )
Brominated imide compound having a bromine content of 50% by weight or more [flame retardant (II)] 1 to 30 parts by weight, and (C) antimony trioxide 1 to 30 parts by weight, and flame retardant (I) / flame retardant The present invention relates to a flame-retardant styrenic resin composition characterized in that the weight ratio of the flame retardant (II) is 0.2 to 20. Further improvement can be achieved by adding silicone oil or chlorinated polyethylene thereto. To do.

The styrene resin used in the present invention is
As the monomer, a styrenic monomer such as α
-Methylstyrene, o-methylstyrene, p-chlorostyrene, a mixture of two or more of 2,4,6-tribromostyrene, and 40% by weight or more, preferably 50% by weight or more of a styrene monomer, A monomer mixture containing less than 60% by weight, preferably less than 50% by weight, of a monomer copolymerizable with them, for example, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, maleic anhydride, N-phenylmaleimide, etc. A styrene-based polymer obtained by polymerization, and an impact-resistant resin obtained by further modifying these polymers with a rubber-like material such as polybutadiene-based rubber, ethylene-propylene-based rubber (EPDM, etc.), acrylate-based rubber, etc. are meant. ..
Examples of such impact resistant resins include rubber-modified polystyrene, ABS resin, AES resin, AAS resin, MBS resin, rubber-modified styrene-maleic anhydride copolymer resin, and styrene-based polymers such as ABS resin and AES resin. In particular, those obtained by copolymerizing acrylonitrile and styrene with other copolymerization components such as phenylmaleimide, alphamethylstyrene, tribromostyrene and methyl methacrylate are preferable from the viewpoint of impact strength.

The impact-resistant resin used in the present invention is the same as that produced by graft-copolymerizing the above rubber-like material with a styrene monomer and, if necessary, a monomer copolymerizable therewith. It is used or made by mixing the graft polymer obtained by graft polymerization with a rubber-free styrenic polymer. Graft polymerization methods include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a method of combining these graft polymerization methods (for example, a method of performing bulk polymerization and then suspension polymerization). The proportion of the rubber-like substance used in the polymerization is usually 10 to 80% by weight of the graft polymer, and the balance is the styrene monomer and the monomer copolymerizable therewith. The amount of the rubber-like material used for producing 100 parts by weight of the impact resistant resin is usually 5 to 40 parts by weight, and 7 to 35 parts by weight is preferable from the viewpoint of balance between tensile strength and impact resistance.

Preferred examples of the styrene-based polymer used in the present invention include AS-based resin, that is, acrylonitrile and styrene, and other copolymerization components as required, such as phenylmaleimide, alphamethylstyrene, dibromostyrene, tribromostyrene, Resins copolymerized with methyl methacrylate, maleic anhydride, methacrylic acid, and the like, and MS-based resins, that is, methyl methacrylate and styrene, if necessary, other copolymerization components such as phenylmaleimide, tribromostyrene, and anhydrous. Maleic acid,
There are resins copolymerized with methacrylic acid and the like. These AS
The resin and MS resin are produced by various polymerization methods similar to the above graft polymerization.

The brominated epoxy compound (hereinafter referred to as flame retardant (I)) and the brominated imide compound (hereinafter referred to as flame retardant (II)) used in the present invention are both blended in a styrene resin. The bromine content is 40% by weight or more and 50 to 50% by weight or more, preferably about 45 to 63% by weight and about 65 to 68% by weight, respectively, and the bromine content is 40% by weight and 50% by weight, respectively. If it is less than%, a styrene resin composition having excellent flame retardancy cannot be obtained. The flame retardant (I) generally has a weight average molecular weight of 500.
~ 20,000 compounds. When the molecular weight is less than 500, it is difficult to obtain a resin composition having sufficient heat resistance. On the other hand, if the molecular weight exceeds 20000, the compatibility tends to deteriorate, and the impact resistance of the product tends to decrease. Flame retardant (II)
Those having a molecular weight of about 950 to 1000 are usually used.

A typical compound of the flame retardant (I) used in the present invention is a brominated epoxy resin. The brominated epoxy resin is obtained by reacting bromine-containing bisphenol A with epichlorohydrin. Further, a high molecular weight brominated epoxy resin having an epoxy group or a phenol group at the terminal, which is obtained by the reaction of this bromine-containing epoxy resin and bromine-containing bisphenol A, can also be used in the present invention. In addition, a terminal obtained by reacting a brominated epoxy resin having an epoxy group with phenol, alkylphenol, brominated phenol, tribromophenol, trichlorophenol, pentapromphenol, pentachlorophenol, etc. is phenyl etherified. May be.

Examples of the flame retardant (II) used in the present invention include alkylenebistetrabromophthalimide compounds obtained by the reaction of alkylenediamine and tetrabromo-phthalic anhydride, and ethylenebistetrabromophthalimide compounds and butylene. The bistetrabromophthalimide compound is a preferred example thereof, and ethylene bistetrabromophthalimide is most preferred.

Generally, the amount of flame retardant (I) used is 6 to 50 parts by weight per 100 parts by weight of styrene resin (A),
Particularly, 10 to 30 parts by weight is preferable. Also flame retardant (II)
The amount used is 1 for 100 parts by weight of styrene resin (A).
-30 parts by weight, and particularly preferably 2-20 parts by weight.
The blending weight ratio of flame retardant (I) / flame retardant (II) is 0.2.
-20, preferably 0.5-10. If this ratio is less than 0.2, impact resistance will be insufficient, and if it exceeds 20, flame retardancy will be insufficient. These flame retardants (I) and (II) are styrenic resins (A) having a shape such as powder, flakes or pellets.
Used by blending with.

In the present invention, it is necessary to use antimony trioxide in order to obtain sufficient flame retardancy. The amount used is 1 to 30 parts by weight, preferably 2 to 20 parts by weight, and particularly preferably 4 to 12 parts by weight, based on 100 parts by weight of the styrene resin (A). Further, in the present invention, it is particularly preferable to add an appropriate amount of silicone oil. The silicone oil that can be used in the present invention has the formula

[0016]

[Chemical 1]

(Wherein R represents a methyl group, a phenyl group, or a hydrogen atom) means a polymer having a skeleton represented by the formula and substituted products thereof, and polydimethylsiloxane in which all R 2 are methyl groups, and methyl as R 1 Groups having both a phenyl group and a phenyl group, polymethyl hydrogen siloxane having both a methyl group and a hydrogen atom as R, and modified poly- mers having various substituents at the molecular ends or in the middle of these polymers. Siloxane,
For example, there are those having a group such as an amino group, a hydroxyl group, a carboxyl group, a mercapto group, an epoxy group, a polyoxyethylene group, and a polyoxypropylene group, and polydimethylsiloxane is particularly preferable from the viewpoint of cost.
The silicone oil preferably has a viscosity at 25 ° C. of 100 to 60,000 centistokes. When the silicone oil is used in the present invention, the amount thereof used is 0.02 to 3 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the styrene resin (A). If it is less than 0.02 part by weight, the impact resistance improving effect is low, and if it exceeds 3 parts by weight, a slip phenomenon is likely to occur during the kneading and manufacturing of the composition, and the thermal stability and the tensile strength are lowered.

In the present invention, the impact strength can be further improved by adding 1 to 20 parts by weight of chlorinated polyethylene to 100 parts by weight of the styrene resin (A). If the amount of chlorinated polyethylene used is less than 1 part by weight, the effect of improving impact resistance is poor, and if it exceeds 20 parts by weight, tensile strength is unfavorable. As the chlorinated polyethylene, those having a crystallinity of 10 to 45% and a chlorine content of 20 to 50% by weight are particularly preferable from the viewpoint of impact strength.

Generally, a halogen atom contained in a bromine-based compound or chlorinated polyethylene has a tendency to be liberated as a hydrogen halide when heated, and the hydrogen halide promotes deterioration of the flame-retardant styrene-based resin, resulting in remarkable heat generation. Cause discoloration. In order to suppress or prevent this phenomenon, 0.1 to 10 parts by weight of a dehydrohalogenating inhibitor including a metal soap, a metal oxide, an organic tin compound, etc. as a heat stabilizer is usually added to the styrene resin composition of the present invention. To do. In addition, it is usual to add 0.01 to 7 parts by weight of a phenolic antioxidant, a thiopropionate antioxidant, a lubricant, a dispersant and the like to the styrene resin composition of the present invention, if necessary.

The resin composition of the present invention comprises a styrene resin,
Flame retardants (I) and (II), antimony trioxide, preferably together with silicone oil, chlorinated polyethylene,
Further, if necessary, a dehydrohalogenation inhibitor and a phenol-based or thiopropionate-based antioxidant and the like are blended to obtain a resin composition having predetermined properties. In addition, light stabilizers, fillers, colorants, lubricants, plasticizers and antistatic agents used for improving the moldability of the thermoplastic resin may be added appropriately.

In addition to the above, in the resin composition of the present invention, a resin for polymer alloy, for example, polycarbonate, polyamide, polyester (PET, PBT, etc.), polyphenylene ether, polyvinyl chloride, methyl polymethacrylate, ethylene-methacrylate. It is also possible to use a mixture of a methyl acrylate copolymer, polypropylene, a styrene-butadiene block copolymer, a hydrogenated acrylonitrile-butadiene copolymer, a hydrogenated styrene-butadiene block copolymer and the like. When these are used, the compounding amount is generally 5 to 200 parts by weight with respect to 100 parts by weight of the styrene resin (A).

As a mixing method for obtaining the resin composition of the present invention, a blending machine generally used in the field of synthetic resins, such as a Henschel mixer, is used for dry blending, followed by extruding blending machine, kneader or Banbury mixer. A typical method is to use a mixer to melt and mix. Among the above mixing methods, when melt kneading, or when molded by the molding method described below, when a high temperature is applied to the resin composition of the present invention, thermal decomposition or dehydrohalogenation reaction occurs, so that 2
Preference is given to carrying out at a temperature of 30 ° C. For molding using the resin composition of the present invention, generally, an injection molding method,
A molding method such as an extrusion molding method, a compression molding method, or a hollow molding method is applied.

[0023]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited thereto. All parts and% in the examples are based on weight.

Example 1 ABS resin made by Chimi Industrial Co., Ltd. as a styrene resin, trade name Polylac PA-747 (Acrylonitrile 22
%, Styrene 57%, butadiene 21%, average rubber particle size 0.31
μm), a bromine content of 58%, a molecular weight of about 1500 and a brominated epoxy resin (flame retardant (I)), ethylenebistetrabromophthalimide (flame retardant (II)), and Sb ₂ O ₃ are used in the amounts shown in Table 1, respectively. , Dry-blended with a Henschel mixer with 1.0 part of heat stabilizer, dibutyltin maleate, and pelletized flame-retardant resin using a twin-screw extruder with a vent set to a cylinder temperature of 200-210 ° C and a die temperature of 220 ° C. A composition was obtained. Next, using this pellet, tensile test, heat resistance test (heat distortion temperature), Izod impact strength, and flame retardancy test were performed for ASTM D-638, DSTM D-648, ASTM D-256 (with notch), UL, respectively. The test was performed according to the method of vertical combustion test (thickness 1/16 inch). The results are shown in Table 1.

[0025]

[Table 1]

Example 2 Polylac PA-747 as an ABS resin, the same brominated epoxy resin (flame retardant (I)) used in Example 1, ethylenebistetrabromophthalimide (flame retardant (II)),
Sb ₂ O ₃ , polydimethylsiloxane (silicone oil) with a viscosity of 1000 centistokes at 25 ° C, crystallinity 25
%, Chlorinated polyethylene (CPE) with a chlorine content of 35% is used in the amounts shown in Table 2, and dibutyltin maleate 1.0
A flame-retardant resin composition was obtained in the same manner as in Example 1 together with the parts and tested in the same manner. The results are shown in Table 2. or,
Furthermore, a weather resistance test and a blooming test were performed on each sample. At this time, as a comparison product, Polylac PA-
100 parts of 747, 24 parts of decabromodiphenyl ether, Sb
_A mixture of 8 parts of ₂ O _{3 and} 1.0 part of dibutyltin maleate in the same manner as in Example 1 was used as Experiment No. 5 for comparison. The results are shown in Table 3. In the weather resistance test, the hue was observed by exposing the test piece to a weatherometer for 100 hours and 150 hours. The anti-blooming property was determined by observing the presence or absence of blooming on the surface after the test piece was left in an atmosphere of 70 ° C. for 1 week.

[0027]

[Table 2]

[0028]

[Table 3]

Example 3 A styrene resin, a flame retardant (I), the same flame retardant (II) as used in Example 1, Sb ₂ O ₃ , silicone oil and CPE were used as described in Table 3, and dibutyl tin was used. Maleate 1
A flame-retardant resin composition was obtained in the same manner as in Example 1 together with the parts and tested in the same manner. The results are shown in Table 4.

[0030]

[Table 4]

Note) S ₁ : Polylac PA-747 S ₂ : AES resin (acrylonitrile 20% _, styrene 56%)
_, EPDM 24% _, average rubber particle size 0.3 μm) S ₃ : ABS resin (acrylonitrile 18% _, styrene 50%
_, Phenylmaleimide 2% _, Alphamethylstyrene 3
% _, Methyl methacrylate 2% _, butadiene 25% _, average rubber particle diameter 0.3 μm) E ₁ : brominated epoxy resin E ₂ having a bromine content of 54% and an average molecular weight of about 1700: the same as that used in Example 1 x ₁ : polydimethylsiloxane having a viscosity of 2000 centistokes at 25 ° C. x ₂ : polydimethylsiloxane having a viscosity of 5000 centistokes at 25 ° C. C ₁ : the same CPE used in Example 2 C ₂ : crystallinity 28 %, CPE with chlorine content of 32%

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[Procedure amendment]

[Submission date] May 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the present invention, the impact strength can be further improved by adding 1 to 20 parts by weight of chlorinated polyethylene to 100 parts by weight of the styrene resin (A). If the amount of chlorinated polyethylene used is less than 1 part by weight, the effect of improving impact resistance is poor, and if it exceeds 20 parts by weight, tensile strength is unfavorable. Chlorinated polyethylene has a crystallinity of 1.0 to 45% and a chlorine content of 20 to 50% by weight.
From the viewpoint of impact strength, the above is preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Example 2 Polylac PA-747 as an ABS resin, the same brominated epoxy resin (flame retardant (I)) used in Example 1, ethylenebistetrabromophthalimide (flame retardant (II)),
Sb ₂ O ₃ , polydimethylsiloxane (silicone oil) with a viscosity of 1000 centistokes at 25 ° C, crystallinity
Chlorinated polyethylene with 2.5 % and chlorine content of 35% (CP
A flame-retardant resin composition was obtained in the same manner as in Example 1 except that E) was used in the amounts shown in Table 2 together with 1.0 part of dibutyltin maleate, and the same test was conducted. The results are shown in Table 2.
Moreover, a weather resistance test and a blooming test were performed on each sample. Polylac P as a comparison product
100 parts of A-747, decabromodiphenyl ether 24
Part, Sb ₂ O ₃ 8 parts, and dibutyltin maleate 1.0 part were mixed in the same manner as in Example 1, and an experiment No. 5 was carried out for comparison. The results are shown in Table 3. In the weather resistance test, the hue was observed by exposing the test piece to a weatherometer for 100 hours and 150 hours. The anti-blooming property of the test piece was 70 ° C.
After left for 1 week in the atmosphere, the presence or absence of blooming on the surface was observed and judged.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

Note) S ₁ : Polylac PA-747 S ₂ : AES resin (acrylonitrile 20% _, styrene 56%)
_, EPDM 24% _, average rubber particle size 0.3 μm) S ₃ : ABS resin (acrylonitrile 18% _, styrene 50%
_, Phenylmaleimide 2% _, Alphamethylstyrene 3
% _, Methyl methacrylate 2% _, butadiene 25% _, average rubber particle diameter 0.3 μm) E ₁ : brominated epoxy resin E ₂ having a bromine content of 54% and an average molecular weight of about 1700: the same as that used in Example 1 x _1: 25 ° C. a viscosity of polydimethylsiloxane x ₂ is a 2000 centistokes: 25 viscosity ° C. is 5000 cSt polydimethylsiloxane C _1: example 2 the same CPE as used in C _2: crystallinity 2.8 %, CPE with chlorine content of 32%

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Claims (3)

[Claims] 1. (A) 100 parts by weight of a styrene resin, (B ₁ ) 6 to 50 parts by weight of a brominated epoxy compound [flame retardant (I)] having a bromine content of 40% by weight or more, (B ₂ ) bromine 50% by weight
The above is a brominated imide compound [flame retardant (II)] 1 to 30
And 1 to 30 parts by weight of (C) antimony trioxide, and the weight ratio of flame retardant (I) / flame retardant (II) is 0.
A flame-retardant styrene-based resin composition, which is 2 to 20. 2. The composition according to claim 1, which further comprises 0.02 to 3 parts by weight of silicone oil based on 100 parts by weight of the styrene resin. 3. The composition according to claim 1, which further comprises 1 to 20 parts by weight of chlorinated polyethylene with respect to 100 parts by weight of the styrene resin.