JPH09169885A - Flame resistant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame resistant thermoplastic resin composition which has a superior light fastness and sticks lightly to a metal in kneading and molding processes by adding a specific compound together with a halogenated epoxy compound to a styrene resin. SOLUTION: This is a flame resistant thermoplastic resin composition prepared by blending 1-30 pts.wt. compound as represented by formula I [wherein (n) is 0-15; X is bromine or chlorine; R1 is isopropylidene, methylene or sulfonic; R2 , R3 are each 2,3-epoxypropyl or -CH2 CH(OH)CH2 OR4 (wherein R4 is a (bromine or chlorine substd.) alkyl or allyl)] and 0.05-5 pts.wt. compound as represented by formula II [wherein R5 -R10 are each H, -COR' (R' is a 4-30C alkyl or alkenyl); (n) is 0-2] with 10-100 pts.wt. graft copolymer of the mixture of 60-100wt.% aromatic vinyl monomer and 0-40wt.% another monomer and a rubbery polymer and 100 pts.wt. resin mixture composed of 0-90wt.% copolymer of the mixture of 60-100wt.% aromatic vinyl monomer and 0-40wt.% another monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermoplastic resin composition having excellent light resistance and little adhesion to metal during kneading and molding. More specifically, it relates to a thermoplastic resin composition having excellent flame retardancy, thermal stability, and light resistance, and having little adhesion to a metal during kneading and molding.

[0002]

2. Description of the Related Art Styrenic resins represented by ABS and HIPS are widely used for electric appliances, office automation equipment, office equipment, etc. due to their excellent characteristics such as moldability, mechanical properties and appearance. . In these applications, heat generated by internal components,
Due to problems such as ignition sources, it is necessary to make the resin flame-retardant, and an organic compound containing a halogen element such as bromine or chlorine is blended as a flame retardant. Further, in order to prevent discoloration due to light such as a fluorescent lamp and sunlight, light resistance is required in addition to flame resistance and impact resistance in applications such as computers and facsimiles.
For example, JP-A-61-211354 discloses a technique of obtaining a thermoplastic resin having excellent light resistance by using a halogenated epoxy compound having epoxy groups at both ends. However, when the halogenated epoxy compound as described above is used, the resin adheres to the metal screw surface of the processing machine during the kneading process and the molding process to cause a gelation reaction of the epoxy compound, and further discoloration and carbonization of the resin. However, there is a problem in that the characteristics of the molded product are remarkably deteriorated due to such problems.

As a technique for suppressing the gelation reaction of an epoxy compound, JP-A-1-01350 discloses that a halogenated epoxy compound having an epoxy group at the end is added together with a basic inorganic compound such as antimony trioxide and hydrotalcite. A technique for improving thermal stability is also disclosed in JP-A-6-93156.
Japanese Patent Publication discloses a technique of improving thermal stability by adding a halogenated epoxy compound having an epoxy group at a terminal together with zeolite and a metal salt of ethylenediaminetetraacetic acid, but a decrease in impact resistance due to addition of a filler, and Since these compounds are hydrates, there have been problems such as appearance defects such as silver streaks and foaming during molding.

On the other hand, as a technique for suppressing the adhesion of the resin to the metal during the kneading process and the molding process, Japanese Patent Laid-Open No. 5-117463
Japanese Patent Publication discloses a technique of using a mixture obtained by melt-mixing a halogenated epoxy compound and a compound having a structure in which a part or all of the epoxy groups of an epoxy resin is sealed with a long-chain aliphatic carboxylic acid, In order to obtain such an effect, the amount of the long-chain aliphatic carboxylic acid added to the mixture must be increased, and decomposition gas is generated from the additive or the reaction compound during the molding process, resulting in defects such as silver streak. There was a problem. In addition, when the melting point of the reaction compound such as the ester obtained above is around room temperature, there is a problem that workability during kneading is significantly reduced.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a flame-retardant thermoplastic resin composition containing a halogenated epoxy compound and having excellent light resistance, such as defects such as silver streaks during molding and reduction in impact strength. It is an object of the present invention to provide a composition which is prevented from adhering to a metal screw or a metal roll during kneading processing and molding processing without causing the above phenomenon.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a resin composition containing the epoxy compound is obtained by adding a pentaerythritol fatty acid ester together with a halogenated epoxy compound to a styrene resin. The thermal stability of is improved significantly, and defects such as silver streaks do not occur during kneading and molding.
It has been found that the adhesion of the metal of the resin composition to a screw or a metal roll is suppressed. Further, the effect is synergistically improved by adding a higher fatty acid amide as needed, and the epoxy compound has one end having an epoxy group and the other end having an epoxy group brominated or chlorinated. It has been found that when a halogenated epoxy compound to which good alcohols and / or phenols are added is contained, a higher effect can be obtained.

[0007]

[Means for Solving the Problems] That is, the present invention provides a monomer containing 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer. The mixture was polymerized in the presence of a rubbery polymer (A) 10 to 100 parts by weight of a graft copolymer, and an aromatic vinyl monomer 6
A resin mixture 10 comprising 0 to 90 parts by weight of a (B) copolymer obtained by polymerizing a monomer mixture of 0 to 100% by weight and a monomer copolymerizable with an aromatic vinyl monomer 0 to 40% by weight.
0 parts by weight of (C) the following general formula

[0008]

Embedded image (In the formula, n is an integer of 0 to 15, X is bromine or chlorine, a,
b, c and d are integers of 1 to 4, R ₁ is an isopropylidene group, a methylene group or a sulfone group, and R ₂ and R ₃ are 2,3 epoxypropyl group and / or --CH ₂ .CH (OH ) · CH ₂ —OR ₄ group [R ₄ is an alkyl group or allyl group which may be substituted with bromine or chlorine]. )

The halogenated epoxy compound represented by
To 30 parts by weight, and (D) the following general formula

[0010]

Embedded image (In the formula, R _{5 to} R ₁₀ are each hydrogen or an alkylcarbonyl group and / or an alkenylcarbonyl group represented by —CO—R ′ [wherein R ′ is an alkyl group and / or an alkenyl group having 4 to 30 carbon atoms]; ], N shows the integer of 0-2.)

A flame-retardant thermoplastic resin composition comprising 0.05 to 5 parts by weight of a pentaerythritol fatty acid ester represented by the formula: Further, in claim 2, (C) the halogenated epoxy compound according to claim 1 is represented by the following general formula:

[0012]

[Chemical 6] (In the formula, n is an integer of 0 to 15, X is bromine or chlorine, a,
b, c and d are integers of 1 to 4 and R ₁ is an isopropylidene group, a methylene group or a sulfone group. )

A flame-retardant thermoplastic resin composition according to claim 1, which is a halogenated epoxy compound having a structure represented by:

In claim 3, (C) according to claim 1
The halogenated epoxy compound is a reaction product of 35 to 85 mol% of the halogenated epoxy compound according to claim 2 and 15 to 65 mol% of an optionally brominated or chlorinated alcohol and / or phenol. The flame-retardant thermoplastic resin composition according to claim 1 is provided.

Furthermore, the present invention provides the flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein
The present invention provides a flame-retardant thermoplastic resin composition characterized by further comprising 0.05 to 5 parts by weight of (E) a higher fatty acid amide based on 100 parts by weight of the resin mixture described.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The (A) graft copolymer in the present invention means a monomer mixture of 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer. ,
A graft copolymer obtained by polymerizing in the presence of a rubbery polymer having a glass transition temperature of 0 ° C or lower, preferably -20 ° C or lower. The resin composition of the present invention has excellent physical properties,
In order to have flame retardancy and processability, the rubbery polymer contained in the (A) graft copolymer preferably has a rubber weight average particle diameter of 0.1 to 3 μm, and further has a rubber content of 5 It is preferably about 70% by weight. If these values are less than the above range, the impact resistance of the resin finally obtained will be lowered, and if it exceeds the above range, the flame retardancy of the resin finally obtained will be lowered, which is not preferable.

The rubbery polymer used in (A) the graft copolymer is one having a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower. For example, polybutadiene,
Examples thereof include a rubbery polymer made of a copolymer of butadiene and another monomer. Specific examples of the aromatic vinyl monomer that is a constituent component of the present invention include styrene and
Examples include α-alkylstyrenes such as α-methylstyrene, nucleus-substituted alkylstyrenes such as p-methylstyrene, vinylnaphthalene, and the like. These may be one kind or a mixture of two or more kinds. Specific examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, and butyl acrylate which is an alkyl ester thereof. Examples thereof include acrylic monomers such as methyl methacrylate and cyclohexyl methacrylate, maleic anhydride, and unsaturated anhydride derivative-based monomers such as maleimide and N-phenylmaleimide. These may be one kind or a mixture of two or more kinds. (A)
The ratio of the aromatic vinyl monomer component in the monomer mixture used for the graft copolymer is in the range of 60 to 100% by weight. If it is less than 60% by weight, heat resistance, impact resistance, color tone and the like of the obtained resin composition are deteriorated, which is not preferable.

Specific examples of the (A) graft copolymer include high impact polystyrene (HIPS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin). ), Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS
Resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), acrylonitrile / chlorinated polyethylene / styrene copolymer (ACS resin), etc. , Or a mixture thereof. The (A) graft copolymer is prepared by batch-processing the above-mentioned monomer or a mixture of the monomers by a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method or a bulk polymerization method. It can be manufactured in a continuous or continuous manner.

The (B) copolymer in the present invention is a monomer consisting of 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer. It refers to a copolymer obtained by polymerizing a body mixture. As the aromatic vinyl monomer (B) which is a constituent of the copolymer and the monomer copolymerizable therewith, the same examples as those mentioned in the above (A) graft copolymer may be used. You can The types and mixing ratios of the constituent monomers of the (B) copolymer may be within the scope of the claims, and they are not necessarily the same as the constituent monomers of the (A) graft copolymer. There is no. The mixing ratio of the aromatic vinyl monomer component in the copolymer (B) is in the range of 60 to 100% by weight. If it is less than 60% by weight, heat resistance, impact resistance, color tone and the like of the obtained resin composition are deteriorated, which is not preferable.

This (B) copolymer can be prepared, for example, according to a known technique for producing an acrylonitrile / styrene copolymer,
It can be produced by a batch system or a continuous system using methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method and a bulk polymerization method. Further, the (B) copolymer can be produced or by-produced in the same polymerization system at the same time in the polymerization operation of the (A) graft copolymer, or can be produced by separately setting the polymerization method and the polymerization conditions. You can also The blending ratio of each resin in the resin composition of the present invention is 10 to 100% by weight of (A) graft copolymer and 0 to 90 (B) copolymer.
Must be in the wt% range. If the amount is out of this range, the resin composition obtained cannot have sufficient flame retardancy and physical properties. When the (A) graft copolymer or (B) copolymer is produced by an emulsion polymerization method, an emulsifier,
It is preferable to reduce the residue of fatty acid or metal salt derived from a salting-out agent or the like, because the resulting resin composition has improved thermal stability and mechanical strength. If desired, any other resin can be further added to the resin composition of the present invention. Examples of other resins that can be added include polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyamide resins, polyphenylene oxide resins, and the like.

The (C) halogenated epoxy compound in the present invention is a reaction product of a halogenated bisphenol and a diglycidyl ether of a halogenated bisphenol or epihalohydrin and is represented by the following general formula.

[0022]

Embedded image (In the formula, n is an integer of 0 to 15, X is bromine or chlorine, a,
b, c and d are integers of 1 to 4, R ₁ is an isopropylidene group, a methylene group or a sulfone group, and R ₂ and R ₃ are 2,3 epoxypropyl group and / or --CH ₂ .CH (OH ) · CH ₂ —OR ₄ group [R ₄ is an alkyl group or allyl group which may be substituted with bromine or chlorine]. )

Specific examples of the halogenated bisphenol (C) used for producing the halogenated epoxy compound include tetrabromobisphenol A, dibromobisphenol A, tetrachlorobisphenol A, dichlorobisphenol A, tetrabromobisphenol F and dibromobisphenol. F, tetrachlorobisphenol F, dichlorobisphenol F, tetrabromobisphenol S, dibromobisphenol S, tetrachlorobisphenol S, dichlorobisphenol S and the like. These may be one kind or a mixture of two or more kinds.

The degree of polymerization n of the halogenated epoxy compound (C) in the composition of the present invention is an integer of 0-15. When the degree of polymerization n exceeds 15, the impact resistance and the light resistance of the resin composition obtained are deteriorated, which is not preferable. These may be a mixture of two or more kinds having different polymerization degrees n. (C) The terminal of the halogenated epoxy compound may be an epoxy group, or the epoxy group may be substituted with an alcohol or the like by an ether group bonded to an allyl group, an alkyl group or the like and sealed. The allyl group or alkyl group to be stopped may be modified with a halogen element such as chlorine or bromine, if necessary. Specific examples of the terminal blocking group include unsubstituted allyl groups such as phenyl group and naphthyl group, tribromophenyl group, pentabromophenyl group, trichlorophenyl group, halogenated allyl groups such as pentachlorophenyl group and stearyl group. And other alkyl groups.

The terminal of the (C) halogenated epoxy compound used in the present invention is not limited as long as it is within the above range,
The structure of one end and the other end may be the same or different. In particular, when using (C) a halogenated epoxy compound in which one end is an epoxy group and the other end is sealed with an optionally brominated or chlorinated alkyl group or allyl group, The effect of the invention can be further improved. Such (C) halogenated epoxy compound can be obtained by reacting a halogenated epoxy compound having epoxy groups at both ends with a small amount of alcohols or phenols which may be brominated or chlorinated. it can. As a specifically preferable reaction charging ratio, alcohols which may be brominated or chlorinated with respect to halogenated epoxy compounds having epoxy groups at both ends of 35 to 85 mol%, more preferably 40 to 75 mol% Or phenols 15-65
A suitable reaction product can be obtained by adjusting the content to be mol%, more preferably 25 to 60 mol%.

The amount of the halogenated epoxy compound (C) added is 1 to 30 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the resin mixture of the copolymers (A) and (B). . If the amount added exceeds 30 parts by weight, not only is it economically disadvantageous, but the physical properties of the resulting resin composition deteriorate. If the addition amount is less than 5 parts by weight, sufficient flame retardancy cannot be imparted to the obtained resin composition, which is not preferable.

The (D) pentaerythritol fatty acid ester used in the present invention is pentaerythritol and / or
Or an oligomer thereof, stearic acid, palmitic acid,
Myristic acid, lauric acid, capric acid, oleic acid,
An ester of a fatty acid having 4 to 30 carbon atoms such as behenic acid, coconut oil-based fatty acid, palm oil-based fatty acid, and beef tallow-based fatty acid, which is generally commercially available, can be used. The fatty acids used in the same molecule may be the same or different. Further, either saturated fatty acids or unsaturated fatty acids can be used, but saturated fatty acids are more preferably used. All of the hydroxyl groups of pentaerythritol and / or its oligomer do not have to be esterified with a fatty acid, but as the number of hydroxyl groups remaining without being esterified is smaller, (C) a gelling reaction with a halogenated epoxy compound. Is preferable because it suppresses

Specific examples of (D) pentaerythritol fatty acid ester include, for example, dipentaerythritol hexastearate, dipentaerythritol tetrastearate, dipentaerythritol hexalaurate,
Dipentaerythritol fatty acid ester such as dipentaerythritol tetralaurate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monostearate, pentaerythritol tetralaurate, pentaerythritol trilaurate, Examples thereof include monopentaerythritol fatty acid esters such as pentaerythritol dilaurate and pentaerythritol monolaurate. These may be one kind or a mixture of two or more kinds. The blending amount of (D) pentaerythritol fatty acid ester in the present invention is in the range of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight. If the blending amount is less than 0.05 parts by weight, a sufficient suppressing effect on metal adhesion cannot be obtained, and if it exceeds 5 parts by weight, defects such as silver streaks are likely to occur during molding.

The (E) higher fatty acid amide used in the present invention is an amide of an alkylenediamine and a higher fatty acid having 4 to 30 carbon atoms, and a commercially available one can be used. Specific examples of the higher fatty acid amide (E) include ethylenebisstearylamide, ethylenebislaurylamide, and methylenebisstearylamide. The amount of the higher fatty acid amide (E) used in the present invention is 0 to 5 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the resin mixture. Is the range. If the blending amount is less than 0.05 parts by weight, a sufficient effect of suppressing screw adhesion cannot be obtained, and if it exceeds 5 parts by weight, defects such as silver streaks may occur during molding, which is not preferable.

The resin composition according to the present invention comprises (A) a graft copolymer, (B) a copolymer, (C) a halogenated epoxy compound, (D) a pentaerythritol fatty acid ester, and optionally (E). ) A higher fatty acid amide can be obtained by weighing it within the range described above and mixing and kneading it by a known method. For example, a mixture of the constituents in the form of powder, beads, flakes or pellets can be fed to a single-screw extruder,
The resin composition can be obtained by melt-kneading using an extruder such as a twin-screw extruder or a kneading machine such as a Banbury mixer, a pressure kneader, or a twin roll. When it is necessary to mix the liquid, the kneading may be performed by the above method using a known liquid injection device. Further, at that time, if necessary, a type and amount of a lubricant, a release agent, a colorant, an antistatic agent, an antioxidant, which do not impair the properties of the present resin composition,
Various flame retardants, flame retardant aids such as antimony trioxide, drip (dripping of fire species during combustion) inhibitors such as polytetrafluoroethylene, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, etc. A resin additive, a filler such as talc, a reinforcing material such as glass fiber, carbon fiber, and whiskers can be appropriately combined and added.

[0031]

EXAMPLES The present invention will now be specifically described based on examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “part” is an abbreviation for “part by weight”.

(1) Production of (A) Graft Copolymer Acetic anhydride was used in a reactor having a capacity of 5 L equipped with a stirrer, a heating / cooling device, each raw material and an auxiliary charging device, and 0.25.
100 parts of a conjugated diene rubbery polymer latex having a particle size enlarged to μm as a solid content and 270 parts of deionized water (including water in the latex) were charged, and the temperature was raised to 70 ° C. During the heating, at 60 ° C., 1.0 part of sodium pyrophosphate, 0.5 part of dextrose and 0.01 part of ferrous sulfate dissolved in 45 parts of water were added. Over a period of 2.5 hours from the time when the temperature reached 70 ° C., 70 parts of styrene, 30 parts of acrylonitrile, 1.1 parts of t-dodecyl mercaptan, 0.5 part of cumene hydroperoxide, and disproportionated potassium rosinate soap 1. 8 parts, potassium hydroxide 0.37 parts and deionized water 35 parts were added. After the addition was completed, the reaction was continued for another 30 minutes and cooled to complete the reaction. After adding 5 parts of an antioxidant to this graft copolymer latex, the mixture is added to an aqueous magnesium sulfate solution heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to obtain a white powdered graft copolymer. Obtained.

(2) Copolymer of (B) Styrene / acrylonitrile = 70/30 weight ratio and a molecular weight of 120,000 were used.

(3) (C) Halogenated Epoxy Compound (C-1) End-Uncapped Type Commercially Available End-Uncapped Type Tetrabromobisphenol A-Type Epoxy Oligomer (Epotote YDB406, Toto Kasei Co., Ltd.) It was used. The structural formula is shown below.

[0035]

Embedded image (However, a mixture of n = 0 and 1)

(C-2) Terminal-end-capped type Commercially available terminal-end-capped type tetra-capped type, which is a reaction product of 50 mol% of non-end-capped tetrabromobisphenol A type epoxy oligomer and 50 mol% of tribromophenol A bromobisphenol A type epoxy oligomer (manufactured by Tohto Kasei Co., Ltd., trade name Epototo YDB416) was used. The structural formula is shown below.

[0037]

Embedded image (It is a mixture of A, B and C, and the molar ratio is A: B: C =
1: 2: 1. A, B, C are each a mixture of n = 0 and 1. )

(C-3) Lubricant addition (end uncapped) type As a comparative example, a molten mixture of a commercially available end-capped tetrabromobisphenol A type epoxy oligomer and an aromatic higher fatty acid ester-based lubricant (Dainippon Ink Chemical industry Co., Ltd. make, the brand name Pratherm EPR-13) was used.

(4) (D) Pentaerythritol fatty acid ester (D-1) dimer type Commercially available dipentaerythritol hexastearate (manufactured by Riken Vitamin Co., Ltd., trade name: LIKESTER SL02) was used. The structural formula is shown below.

[0040]

Embedded image

(D-2) Monomer type Commercially available pentaerythritol distearate (manufactured by NOF CORPORATION, trade name Unistar H476D) was used. The structural formula is shown below.

[0042]

Embedded image

(5) (E) Higher fatty acid amide Commercially available ethylenebisstearylamide (manufactured by Kao Corporation,
The product name Kaowax EB-P) was used.

(6) (F) Magnesium stearate As a comparative example, commercially available magnesium stearate was used.

(7) (G) Antimony trioxide As a flame retardant aid, a commercially available antimony trioxide (trade name: Fireshield H0, manufactured by Laurel Industry Co., Ltd.) is used.
7) was used.

(8) Evaluation Method of Physical Properties of Resin Composition The physical properties of the resin composition are measured on the test pieces prepared by the injection molding method by the following methods for metal adhesion, Izod impact strength and UL combustion standard. did.

Metal adhesion test 20 mm × 20 mm cut out from a press-molded product having a thickness of 3 mm
The test piece of 1 was fixed between two stainless steel plates and heated in a gear oven at 200 ° C. for 6 hours. After cooling, peel strength between steel plate and resin with an Instron universal testing machine (kg)
Was measured and used as an index of metal adhesion.

Silver streak The surface of the molded product was visually evaluated by ◯ (good) and × (defective). UL burning test UL-94 issued by Underwriter Laboratories, USA
A vertical combustion test was performed by a method in conformity with (1) and was used as an index of flame retardancy (test piece thickness: 1/12 inch).・ Izod impact strength Measured at 23 ° C by a method based on JIS-K7110,
It was used as an index of impact resistance (test piece thickness: 1/8 inch, with V notch).

Examples 1 to 6, Comparative Examples 1 to 7 (A) Graft copolymer obtained by the above method, (B)
The copolymer, (C) halogenated epoxy compound, (D) pentaerythritol fatty acid ester, (E) higher fatty acid amide, (F) magnesium stearate and (G) antimony trioxide are shown in Tables 1 to 3. The ingredients were weighed in the stated blending ratio (parts by weight) and mixed in a tumbler. The obtained mixture was kneaded with a vented twin-screw extruder while removing volatile components to prepare pellets of the resin composition. Test pieces were prepared from the pellets of the resin composition by an injection molding method, and physical properties were measured. The results are shown in Tables 1 to 3.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

From Tables 1 and 2, the resin composition according to the present invention, by incorporating (D) pentaerythritol fatty acid ester, retains excellent impact resistance and flame retardancy, and has a silver streak. It is possible to obtain a resin composition containing a halogenated epoxy compound (C) without causing defects such as the following. The resin composition suppresses metal adhesion and has extremely excellent thermal stability. Understand (Example 1
4). On the other hand, when (D) pentaerythritol fatty acid ester was not added, metal adhesion was observed (Comparative Examples 1 and 5), and (E) ethylenebisstearylamide, instead of (D) pentaerythritol fatty acid ester,
(F) When only a lubricant such as magnesium stearate was added, the metal adhesion was not improved (Comparative Examples 2, 3,
6, 7), and when only (E) ethylenebisstearylamide is used, the flame retardancy also decreases (Comparative Examples 2 and 6). Further, a halogenated epoxy compound (C-3) to which an aromatic higher fatty acid ester lubricant is added
Also when using, the metal adhesion is not improved and silver streaks occur (Comparative Example 4).

Further, from the comparison between Examples 3 and 4 in Table 2 and Examples 1 and 2 in Table 1, when the semi-encapsulated halogenated epoxy compound (C-2) was used, it was unencapsulated. It can be seen that the metal adhesion is further improved as compared with the halogenated epoxy compound (C-1) of the type. From Table 3, it can be seen that the combined use of (D) pentaerythritol fatty acid ester and (E) higher fatty acid amide synergistically improves the metal adhesion as compared with the case of using (D) pentaerythritol fatty acid ester alone ( Examples 5 and 6).

[0055]

The resin composition of the present invention comprises (A) a graft polymer, (B) a copolymer, (C) a halogenated epoxy compound, (D) a pentaerythritol fatty acid ester, and optionally (E). ) A flame-retardant thermoplastic resin containing a higher fatty acid amide, which suppresses adhesion to metal screws and metal rolls during kneading and molding, and suppresses defects such as silver streaks during molding. It can be used as a material, and its industrial utility value is extremely high.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 71:00)

Claims (4)

[Claims] 1. A monomer mixture comprising 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with an aromatic vinyl monomer in the presence of a rubbery polymer. 10 to 100 parts by weight of the (A) graft copolymer polymerized with the above, 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer. To 100 parts by weight of a resin mixture consisting of 0 to 90 parts by weight of a copolymer (B) obtained by polymerizing a monomer mixture, (C) the following general formula: (In the formula, n is an integer of 0 to 15, X is bromine or chlorine, a,
b, c and d are integers of 1 to 4, R ₁ is an isopropylidene group, a methylene group or a sulfone group, and R ₂ and R ₃ are 2,3 epoxypropyl group and / or --CH ₂ .CH (OH ) · CH ₂ —OR ₄ group [R ₄ is an alkyl group or allyl group which may be substituted with bromine or chlorine]. 1 to 30 parts by weight of a halogenated epoxy compound represented by the formula (1), and (D) the following general formula: (In the formula, R _{5 to} R ₁₀ are each hydrogen or an alkylcarbonyl group and / or an alkenylcarbonyl group represented by —CO—R ′ [wherein R ′ is an alkyl group and / or an alkenyl group having 4 to 30 carbon atoms]; ], N shows the integer of 0-2.) The pentaerythritol fatty acid ester represented by 0.05-0.05
A flame-retardant thermoplastic resin composition comprising 5 parts by weight. 2. The halogenated epoxy compound (C) according to claim 1 has the following general formula: (In the formula, n is an integer of 0 to 15, X is bromine or chlorine, a,
b, c and d are integers of 1 to 4 and R ₁ is an isopropylidene group, a methylene group or a sulfone group. The flame-retardant thermoplastic resin composition according to claim 1, which is a halogenated epoxy compound having a structure represented by the formula (1). 3. The halogenated epoxy compound (C) according to claim 1 is the halogenated epoxy compound 3 according to claim 2.
The flame-retardant thermoplastic according to claim 1, which is a reaction product of 5 to 85 mol% of an optionally brominated or chlorinated alcohol and / or a phenol of 15 to 65 mol%. Resin composition. 4. The flame-retardant thermoplastic resin composition according to claim 1, wherein the resin mixture 1 according to claim 1.
(E) higher fatty acid amide 0.05 to 100 parts by weight
A flame-retardant thermoplastic resin composition, further comprising 5 parts by weight.