JPH09137032A - Flame-retardant resin composition with improved thermal stability - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a flame-retardant resin composition having a high degree of thermal stability without using a halogen compound, and having excellent appearance, printing / paintability and mechanical properties. SOLUTION: (A) a rubber-modified styrene resin and (B)
Mixed resin 100 made of polyphenylene ether resin
0.1 to 30 parts by weight of (C) organic phosphate ester flame retardant, 0.1 to 30 parts by weight of (D) triazine skeleton-containing compound, and 0.0) of (E) coupling agent based on parts by weight.
A flame-retardant resin composition containing 0.1 to 3 parts by weight, in particular, the component (D) is surface-treated with a coupling agent of component (E).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition having excellent thermal stability, which is used in injection molding, extrusion molding, compression molding and the like.

[0002]

2. Description of the Related Art Styrene-based resins have good moldability, dimensional stability,
Because it has excellent impact resistance, rigidity, electrical insulation, etc.,
It is used in a wide variety of fields including home appliance parts and OA equipment. In recent years, there is a strong demand for flame retardancy in these application fields, and flame retardant resins occupy a large position. Various methods have been devised as a method for imparting flame retardancy to a flammable resin such as a styrene resin, but in general,
A method of adding a halogen-based flame retardant such as a bromine compound having a high flame retarding effect and, if necessary, antimony oxide to a resin is adopted. However, it has been pointed out that when a halogen-based flame retardant is used, a large amount of gas harmful to the human body is generated due to decomposition of the halogen compound during combustion.

Therefore, as a method for flame retarding without using a halogen-based flame retardant, a flame-retardant resin composition comprising a vinyl aromatic resin, a polyphenylene ether resin, a phosphorus-containing compound and a triazine skeleton-containing compound is disclosed in Japanese Patent Laid-Open Publication No. 54-38
No. 348, JP-A-54-38349, JP-A-5-287119, and JP-A-5-339417. However, the flame-retardant resin composition produced according to the technique disclosed in these is low in thermal stability because the phosphorus-containing compound decomposes due to the interaction between the triazine skeleton-containing compound and the phosphorus-containing compound, When performing large-scale molding or thin-wall molding, there is a drawback that the molded product is significantly discolored when the processing temperature rises.

On the other hand, a resin composition comprising a styrene-based resin and a polyphenylene ether-based resin has a lack of polarity. Therefore, when a cooling / heating cycle test is carried out, a defective phenomenon such as printing or peeling of a coating film due to insufficient adhesive strength occurs. In addition, there is a problem that when the triazine skeleton-containing compound and the phosphorus-containing compound are blended together with this resin composition, the printability and paintability are further deteriorated. Therefore, although the flame retardancy is improved by adding the triazine skeleton compound according to the conventionally disclosed technique, the improvement effect is not satisfactory, and the problem of deterioration in printing / paintability has not been solved, There was nothing satisfactory in terms of mechanical properties. As described above, the techniques disclosed in the related art have various problems in industrial implementation.

[0005]

DISCLOSURE OF THE INVENTION The present invention has a high degree of thermal stability, excellent flame retardancy without using a halogen compound, and excellent appearance, printing / paintability and mechanical properties. It is to provide a flame-retardant resin composition.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a rubber-modified styrene resin, a polyphenylene ether resin, an organic phosphate ester flame retardant, a triazine skeleton. In the resin composition comprising the compound containing, especially by surface-treating the triazine skeleton-containing compound with a coupling agent, it has a high degree of thermal stability, little discoloration of the resin even at the time of molding at high temperature,
It has been found that a flame-retardant resin composition having improved appearance and printing / paintability and excellent mechanical properties can be obtained, and the present invention has been completed.

That is, the present invention is based on 100 parts by weight of the component (A): 1 to 99 parts by weight of the rubber-modified styrenic resin and 99 to 1 parts by weight of the component (B): polyphenylene ether resin. ) Component: organic phosphate ester flame retardant 0.1 to 30 parts by weight, component (D): triazine skeleton-containing compound 0.1 to 30 parts by weight and (E)
Component: at least one coupling agent selected from the group consisting of a silane coupling agent, an aluminum coupling agent and a titanium coupling agent 0.001 to 3
The present invention relates to a flame-retardant resin composition containing parts by weight. Further, the above-mentioned component (D) relates to a flame-retardant resin composition characterized in that the component (E) is surface-treated with a coupling agent as the component (E).

Hereinafter, the present invention will be described in detail. The rubber-modified styrenic resin as the component (A) is the main component of the resin composition of the present invention and plays a role of maintaining the strength of the resin composition. The polyphenylene ether resin as the component (B) imparts heat resistance to the component (A) and (C).
Organic phosphate ester flame retardant as a component, and (D)
It is a resin component for imparting flame retardancy synergistically with a triazine skeleton-containing compound as a component. The components (C) and (D) of the present invention are main flame retardant components, and are components that act synergistically with the component (B) to impart flame retardancy to the component (A). Further, the coupling agent as the component (E) of the present invention is a component which is the core of the present invention,
It is a component not only for improving the thermal stability between the component (C) and the component (D) but also for improving the appearance and printability / paintability.

The component (A) used in the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix resin composed of a vinyl aromatic polymer, and the presence of the rubber-like polymer. The aromatic vinyl monomer and a vinyl monomer copolymerizable therewith are added to the bottom of the mixture to obtain a monomer mixture by known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. Examples of such resins include HI resin (rubber reinforced polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like. Here, the rubber-like polymer has a glass transition temperature (Tg) of 0.
The temperature is preferably ℃ or less, more preferably -30 ℃ or less. If the Tg of the rubber-like polymer exceeds 0 ° C., the impact resistance decreases, which is not preferable. Examples of such rubbery polymers include polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-
Diene rubber such as butadiene) and saturated rubber obtained by hydrogenating the above diene rubber, isoprene rubber, chloroprene rubber, acrylic rubber such as polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EP
DM) can be mentioned, and diene rubber is particularly desirable.

The structure of the rubber particles of the rubber-modified styrenic resin used in the present invention is not particularly limited, and those having a salami structure and those having a single occlusion structure are typical. Further, within the scope of the present invention, the average particle size distribution of the rubber may have a particle size distribution consisting of two or more peaks of a small particle portion and a large particle portion. The rubber-modified styrenic resin of the present invention is preferably such that the matrix resin portion is graft-copolymerized with the rubber-like polymer, but a dry blend of the matrix resin portion and the rubber-like polymer is prepared by using a Henschel mixer or Banbury. It may be kneaded by a known kneader such as a mixer, a single-screw extruder or a twin-screw extruder.

The aromatic vinyl monomer referred to here is, in addition to styrene, α-alkyl-substituted styrene such as α-methylstyrene and α-methyl-p-methylstyrene, p-methylstyrene, o-methylstyrene, Nuclear alkyl-substituted styrenes such as m-methyl styrene, 2,4-dimethyl styrene, p-tertiary butyl styrene and the like, and styrene is most preferable, but styrene is mainly used and one of the above-mentioned other aromatic vinyl monomers is used. Alternatively, two or more kinds may be copolymerized. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced into the rubber-modified styrene resin of the present invention. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to lower the melt viscosity at the time of blending, an acrylate having an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to increase the heat resistance of the polymer composition, α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, N
-N-substituted maleimide monomers such as phenylmaleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0 to
40% by weight.

The proportion of the rubber-like polymer in this rubber-modified styrene resin is preferably 1 to 60% by weight, more preferably 5 to 25% by weight. The proportion of the vinyl aromatic monomer and the vinyl monomer copolymerizable with the vinyl aromatic monomer is preferably 99 to 40% by weight,
It is more preferably in the range of 95 to 75% by weight. Outside of this range, the impact resistance and rigidity of the desired polymer composition cannot be balanced, which is not preferable. The weight average particle size of the rubber particles dispersed in the matrix resin of the rubber-modified styrene resin is preferably 0.5 to 4.0 μm. Particularly preferably 1.0 to 3.0 μm
Range. When the weight average rubber particle diameter is within the above range, not only the impact strength of the rubber-modified styrene resin itself is improved, but also the color between the rubber-modified styrene resin and the triazine skeleton-containing compound of the component (D) is increased. The synergistic effect on the coloring property of the agent can be increased,
It is preferable from the viewpoint of balancing high flame retardancy with coloring properties and mechanical properties.

The weight average particle size of the dispersed rubber particles in the rubber-modified styrene-based resin as used herein means the matrix of the rubber-modified styrene-based resin pellets prepared by using a mixed solution of MEK / acetone of 50/50% by volume. After dissolving only the polystyrene part forming the, the undissolved rubber particle part was separated by a centrifuge (rotation speed 18000 rpm), and then dispersed in a DMF electrolyte solution at an appropriate concentration. It is measured using a Coulter Multi-Riser II type).

The gel content of the rubber-modified styrenic resin used as the component (A) in the present invention is 20 to 80% by weight.
Is preferred and 22 to 60% by weight is more preferred. Particularly preferably, it is in the range of 25 to 50% by weight. When the gel content is within the above range, not only the impact strength of the rubber-modified styrenic resin itself becomes high, but also the coloring property between the rubber-modified styrenic resin and the triazine skeleton-containing compound of the component (D) due to a coloring agent. Because the synergistic effect on
It is preferable because it provides a good balance of high flame retardancy, coloring properties and mechanical properties. The gel content of the component (A) as used herein means that after the rubber-modified styrene resin pellets are mixed with a 50/50% by volume mixed solution of MEK / acetone, only the polystyrene portion forming the matrix is dissolved, Separated from the undissolved rubber particle portion by a centrifuge (rotation speed 18000 rpm), then dried under reduced pressure at 60 ° C., and refers to the weight% of the dried gel based on the original weight of the rubber-modified styrene resin. .

Further, the component (A) used in the present invention is
The reduced viscosity (0.4 g / dl, toluene solution, measured at 30 ° C.), which is a measure of molecular weight, is preferably in the range of 0.3 to 1.2 dl / g, and 0.5 to 1.0 dl / g. It is more preferable to be in the range. When the reduced viscosity of the component (A) is within the above range, the synergistic effect between the components (A) to (D) becomes large due to the decrease in the melt-dripping property of the rubber-modified styrene resin. Therefore, it is possible to reduce the compounding amount of the organophosphate ester flame retardant of the component (C) and the triazine skeleton-containing compound of the component (D) for achieving a high degree of flame retardancy, and to improve mechanical properties. And is preferable.

The blending amount of the component (A) is determined according to the required mechanical strength, moldability and heat resistance. Specifically, in the total 100 parts by weight of the component (A) and the component (B), 1 to
It is necessary to mix 99 parts by weight, preferably 40 to 95 parts by weight, and particularly preferably 60 to 90 parts by weight.

Next, in the present invention, the polyphenylene ether resin blended as the component (B) has the following general formula (I).

Embedded image (Wherein Q _{1 to} Q ₄ are each independently selected from the group consisting of hydrogen and a hydrocarbon residue having 1 to 12 carbon atoms, and m is 3
Indicates an integer of 0 or more. ) A homopolymer or copolymer having a unit represented by

Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4-phenyl).
Phenylene) ether, poly (2,6-dipropyl-
1,4-phenylene) ether, poly (2-methyl-6)
-Ethyl-1,4-phenylene) ether, poly (2-
Methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, (2,6-dimethyl-1,4-phenylene) ether 1 Tell and (2,3,6-trimethyl-1,4-
Copolymer with phenylene) ether, copolymerization with (2,6-diethyl-1,4-phenylene) ether and (2,3,6-trimethyl-1,4-phenylene) ether Combined, (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-triethyl-1,4-phenylene)
And copolymers with ether. Especially poly (2,
6-Dimethyl-1,4-phenylene) ether is preferred.

Further, the reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.), which is a measure of the molecular weight of this polyphenylene ether resin, is 0.2 to 0.7 dl.
/ G is preferably in the range of 0.3 to 0.6 dl
/ G is more preferable. When the reduced viscosity of the rubber-modified styrene resin component (A) is within the above range,
It is preferable because it is excellent in molding processability and balance of mechanical properties. The blending amount of the polyphenylene ether resin as the component (B) is determined according to the required mechanical strength, moldability and heat resistance. Specifically, it is necessary to add 99 to 1 parts by weight, preferably 60 to 5 parts by weight, and 40 to 10 parts by weight, in 100 parts by weight of the total of the components (A) and (B). It is particularly preferable to blend.

Next, as the organophosphate ester flame retardant as the component (C), an organophosphate ester flame retardant is used. Among these, compounds having at least one of the structural units represented by the following general formulas (II) to (V) are preferable.

Embedded image (In the formula, R _{1 to} R ₃ each represent a hydrocarbon residue having 1 to 12 carbon atoms, and q _{1 to} q ₃ represent 0 or 1.)

[0021]

Embedded image (Wherein, R _{1 to} R ₄ are each a hydrocarbon residue having 1 to 12 carbon atoms, R _{5 to} R ₈ are a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, q _{1 to} q ₆ are 0 or 1, n is a degree of polymerization of 1 to 30
Indicates the number of )

[0022]

Embedded image (In the formula, R ₁ , R ₂ , R ₄ , and R ₅ are hydrocarbon residues having 1 to 12 carbon atoms, and R ₃ is —C (CH ₃ ) ₂ —, —CH ₂ —, and —SO ₂
Represents a group selected from —, —CO— and —O—, and R ₆ to
R ₁₃ is a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms,
q _{1 to} q ₇ represent 0 or 1, and n represents a number having a degree of polymerization of 1 to 30. )

[0023]

Embedded image (Wherein, R _{1 to} R ₆ are a hydrocarbon residue having 1 to 12 carbon atoms;
_{7 to} R ₉ represent a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms, and q _{1 to} q ₉ represent 0 or 1. )

These organic phosphate ester flame retardants as the component (C) may be used alone or in admixture of two or more. As the organophosphate ester flame retardant used as the component (C) in the present invention, triphenyl phosphate, tricresyl phosphate, resorcinol bis (diphenyl phosphate) and the like are particularly preferable. Further, the blending amount of these components (C) is determined according to the required flame retardancy and heat resistance. In particular,
For the total of 100 parts by weight of the components (A) and (B),
The component (C) must be added in an amount of 0.1 to 30 parts by weight, preferably 3 to 25 parts by weight, and 5-2.
It is particularly preferable to add 0 part by weight.

The triazine skeleton-containing compound of the component (D) used in the present invention is a component for imparting flame retardancy to the component (A). The component (D) of the present invention is blended in combination with at least one coupling agent selected from the group consisting of a silane coupling agent, an aluminum coupling agent and a titanium coupling agent, which is the component (E). In particular, the component (D) is preferably surface-treated with the component (E). The component (E) of the present invention is the main component of the present invention, and improves the thermal stability between the organophosphate ester flame retardant which is the component (C) and the triazine skeleton-containing compound which is the component (D). It is a component that not only improves the appearance, but also improves the appearance and printability / paintability.

The triazine skeleton-containing compound of the component (D) used in the present invention includes aminotriazine sulfate compounds, aminotriazine cyanurate compounds, aminotriazine borate compounds, aminotriazine diborate compounds, aminotriazine condensed borate compounds, A nitrogen-containing compound having a triazine skeleton such as an organic sulfonic acid aminotriazine compound. These may be used alone or in combination of two or more.

Specific examples of these triazine skeleton-containing compounds include melamine sulfate, melamine cyanurate, melamine borate, melamine diborate, melamine condensed borate,
Melamine p-toluenesulfonate, benzoguanamine sulfate, benzoguanamine cyanurate, benzoguanamine borate, benzoguanamine fused borate, benzoguanamine p-toluenesulfonate, acetoguanamine sulfate, acetoguanyanate borate, acetoguanamine borate, acetoguanamine fused borate, Acetoguanamine p-toluene sulfonate, guanyl melamine sulfate, guanyl melamine cyanurate, guanyl melamine borate, guanyl melamine fused borate, guanyl melamine p-toluene sulfonate, melam sulfate, melam cyanurate, melam borate, condensed boric acid Melam, p-toluene sulfonic acid melam, melem sulfate, melan cyanurate, melem borate, melem condensed borate, melem p-toluene sulfonate, etc. can be mentioned.

Of these compounds, melamine sulfate is not particularly preferable in view of flame retardancy, printability / paintability and economical efficiency, and has a great synergistic effect with a rubber-modified styrene resin in terms of colorability with a coloring agent. Therefore, it is preferable. The average particle size of the triazine skeleton-containing compound is preferably 50 μm or less because a molded product having a glossy and good appearance can be obtained. Further, it is preferably 0.01 to 30 μm, and particularly preferably 0.1 to 10 μm.

As the triazine skeleton-containing compound used in the present invention, if necessary, a suitable dispersant, a lubricant and the like are added after a part of the fine pulverization treatment step and / or after the treatment so that the fine pulverized product is reaggregated. It is possible to use a material that prevents coarsening. Examples of such dispersants include white carbon, alkali metal stearates, and fatty acid amides. The mixing of the dispersant and the lubricant may be performed several times in any step of the fine pulverization treatment step.

The added amount of the component (D) must be 1 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Parts, particularly preferably 5 to 20 parts by weight. It is preferable that the addition amount of the component (D) is within the above range in order to achieve the flame retarding effect of the resin and to maintain the balance between the effect of improving the printability / paintability and the mechanical properties.

Further, in the present invention, the organic phosphate ester flame retardant of the component (C) and the triazine skeleton-containing compound of the component (D) act synergistically with the polyphenylene ether resin of the component (B) to give a resin. Since flame retardancy is imparted to the composition, the ratio of the amounts of the component (C) and the component (D) added is important for exhibiting a high degree of flame retardancy. The weight ratio of the component (C) and the component (D) is (C) / (D) = 10/90.
It is preferably from 90/10. More preferably (C) / (D) = 20/80 to 85/15. Particularly preferably, (C) / (D) = 30/70 to 80/20.

The coupling agent used as the component (E) in the present invention is at least one coupling agent selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents. It is an agent. By using the coupling agent of the present invention to surface-treat the triazine skeleton-containing compound as the component (D), the thermal stability of both components is improved, and the appearance and printing
A flame-retardant resin composition with improved paintability can be obtained.

Specific examples of the coupling agent as the component (E) of the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxy. Silane, vinyl-tris (2-methoxyethoxy) silane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxy-cyclohexyl) ethyltrimethoxy Silane, hexamethyldisilazane, γ
-Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyl Triethoxysilane, tetraethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, alkoxysilyl group, epoxy group, carboxyl group and / Or carbinol group-containing silicone macromolecular coupling agent, isopropyltristearoyl titanate, isopropyl Tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate , Tetraisopropyl bis (dioctyl phosphite) titanate , Dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, tetraisopropoxy titanium,
Tetra n-butoxy titanium, tetra stearoxy titanium, tetraisopropoxy titanium polymer, tetra n-
Butoxytitanium polymer, tri-n-butoxytitanium stearate, isopropoxytitanium tristearate, diisopropoxytitanium bisacetylacetonate, dihydroxybislactatotitanium, acetoalkoxyaluminum diisopropylate, aluminum ethylate, aluminum isopropylate, mono sec-Butoxyaluminium diisopropylate, aluminum s
ec-butyrate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, cyclic aluminum oxide iso Examples thereof include stearates and the like and mixtures thereof.

Among these compounds, the silane coupling agent having a vinyl group or a methacryl group is not particularly preferable in terms of thermal stability, physical properties, printing / paintability and economical efficiency, and is also colored by a colorant. It is preferable because the improvement effect is large.

The added amount of the coupling agent as the component (E) used in the present invention is 0.001 to 3 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Is necessary, and preferably 0.05 to 1.5 parts by weight. The addition amount of the component (E) being within the above range improves the thermal stability between the organophosphate ester flame retardant of the component (C) and the triazine skeleton-containing compound of the component (D), and the appearance It is also preferable for improving printability / paintability and maintaining the balance of mechanical properties.

Further, in the present invention, since the component (E) protects the surface of the component (D), it exhibits the effects of improving the thermal stability and improving the appearance and printing / paintability.
The ratio of the added amount of the component to the component (D) is important for exhibiting a high degree of thermal stability, appearance and printability / paintability.
The weight ratio of the (E) component to the (D) component is (E) / (D) =
It is preferably 0.1 / 99.9 to 10/90.
More preferably (E) / (D) = 0.5 / 99.5-
5/95, particularly preferably (E) / (D) = 1/99 to
It is 3/97.

Usually, as a method for treating the coupling agent, a method of pre-treating the component (D) with the component (E) as a pretreatment method and a resin composition of the component (E) as an integral blending method. Although there is a method of addition, a pretreatment method is preferable from the viewpoints of heat stability of the resin composition, appearance and printability / paintability. Further, the pretreatment method includes a dry method and a wet method, and the pretreatment method can be properly used depending on the application of the resin composition.

Next, if necessary, an anti-dripping agent can be added as the component (F) to the resin composition of the present invention within a range that does not impair the effects of the present invention. The component (F) enhances flame retardancy without significantly lowering the thermal stability, printability / paintability, impact resistance and colorability of the molded article of the resin composition of the present invention, and improves the dripping phenomenon. Examples of the component (F) used include fluorine-based resins and silicone-based resins. The blending amount of the component (F) is from (A) to
0 to 20 parts by weight based on 100 parts by weight of (E) in total,
It is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 5 parts by weight. The compounding amount of the component (F) is 2
If it exceeds 0 parts by weight, the impact resistance as a resin and the appearance of molding are impaired.

If necessary, a lubricant may be added to the flame-retardant resin composition of the present invention as the component (G) within a range that does not impair the effects of the present invention. The component (G) is not only a component that improves the moldability of the present invention by improving the fluidity while maintaining the printability / paintability and flame retardancy, but also plasticizes the resin of the component (A). This is a component for improving the effect of the present invention by improving the dispersibility of the triazine skeleton-containing compound of the component (D) of the present invention. Examples of the component (G) used include higher fatty acid amide compounds, higher fatty acids, higher fatty acid ester compounds, higher aliphatic alcohols and higher fatty acid metal salts. Preferred are higher fatty acid amide compounds, higher fatty acid ester compounds, and higher fatty acid metal salts, and usually 0.01 to 100 parts by weight of the total of (A) to (E).
~ 3 parts by weight are blended.

The flame-retardant resin composition of the present invention further comprises halogen other than the organophosphate ester flame retardant of the component (C) and the triazine skeleton-containing compound of the component (D) within a range not impairing the effects of the present invention. Flame retardants that do not contain atoms can be included as needed. Examples of such flame retardants include phosphorus-containing nitrogen-containing compounds such as red phosphorus, polyphosphazene, ammonium polyphosphate, boric acid compounds such as zinc borate and barium metaborate, and metal hydroxides such as magnesium hydroxide. .

For the purpose of modifying the resin, the flame-retardant resin composition of the present invention contains other thermoplastic resins, thermosetting resins, usual additives such as antistatic agents, antioxidants, and ultraviolet absorbers. Agents, colorants, surface modifiers, dispersants, plasticizers, organotin compounds, light stabilizers, processing aids, foaming agents, glass fibers,
An inorganic filler such as talc can be added. The method for producing the flame-retardant resin composition according to the present invention is not particularly limited, but the flame-retardant resin composition can be produced by an ordinary method, for example, melt blending by extruder kneading. The flame-retardant resin composition of the present invention thus obtained can be molded into a molded product by a molding method such as injection molding, extrusion molding or compression molding.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, (A) used in the following examples
Each of the components (G) to (G) has the following characteristics.

The following HIPS was used as the rubber-modified styrene resin as the component (A). Rubber-modified styrene-based resin-A: rubber content 9.2% by weight Weight-average rubber particle diameter 2.6 μm Gel content 28% by weight Reduced viscosity 0.75 dl / g Rubber-modified styrene-based resin-B: rubber content 14.7% by weight Weight average rubber particle diameter 2.7 μm Gel content 38% by weight Reduced viscosity 0.71 dl / g Rubber modified styrenic resin-C: Rubber content 7.9% by weight Weight average rubber particle diameter 2.3 μm Gel content 25% by weight Reduced viscosity 0.78 dl / g Rubber-modified styrenic resin-D: Rubber content 6.5 wt% Weight average rubber particle size 4.8 μm Gel content 18 wt% Reduced viscosity 0.70 dl / g

Component (B) polyphenylene ether (P
PE) -based resin, poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity ηsp / c of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl; PPE-based resin- A was used.

The following were used as the organic phosphate ester flame retardant as the component (C). Flame Retardant-A: Triphenyl Phosphate Flame Retardant-B: Phenylresorcinol Polyphosphate

As the triazine skeleton-containing compound of the component (D), the triazine skeleton-containing compounds A to D, F and H surface-treated with the coupling agent of the component (E) and the untreated triazine skeleton-containing compounds E, G, and I was used. Triazine compound-A: Melamine sulfate, part by weight average particle size: 15 μm, silane coupling agent treatment (γ-methacryloxypropyltrimethoxysilane, 2%, dry method treatment) Triazine compound-B: melamine sulfate, part by weight average particle Diameter: 15 μm, silane coupling agent treatment (vinyltrimethoxysilane, 1%, dry method treatment) Triazine compound-C: melamine sulfate, weight part average particle diameter: 3 μm, silane coupling agent treatment (Nippon Unicar: UCARSIL FR -1A, 3%, dry method treatment) Triazine compound-D: melamine sulfate, weight part average particle diameter: 15 μm, titanium coupling agent treatment (bis (dioctylpyrophosphate) ethylene titanate, 2%,
Dry method treatment) Triazine compound-E: melamine sulfate, weight part average particle diameter: 15 μm Triazine compound-F: melamine cyanurate, weight part average particle diameter: 3 μm, silane coupling agent treatment (γ-
Methacryloxypropyltrimethoxysilane, 2%, dry method treatment) Triazine compound-G: melamine cyanurate, weight part average particle diameter: 3 μm, triazine compound-H: melamine phosphate, weight part average particle diameter: 15 μm, silane cup Ring agent treatment (γ-methacryloxypropyltrimethoxysilane, 3%, wet method treatment) Triazine compound-I: melamine phosphate, part by weight average particle diameter: 15 μm,

The following fluorine-based resin was used as the anti-dripping agent for the component (F). Anti-drip agent-A: Mitsui Dupont Fluorochemical Co., Ltd.
The following lubricant was used as a lubricant for the Teflon 6-J (G) component manufactured by Teflon Corporation. Lubricant-A: Ethylenebisstearic acid amide

The characteristics of the examples and comparative examples were measured by the following methods. (1) Thermal stability Evaluation of thermal stability was performed by changing the color tone between a molded product formed by injection molding of a resin retained for 20 minutes at a cylinder temperature of 280 ° C. and a molded product molded with a resin not retained (Δ). YI) is a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., color difference meter SZ-Σ90)
The evaluation was carried out by measuring with.

(2) Printing / Paintability The printing / paintability was evaluated based on the strength of adhesion of silk screen printing after the thermal cycle test. First, silk screen printing was performed on a 160 mm × 160 mm × 3 mm flat plate made by injection molding using a printing ink for polystyrene, dried at 90 ° C. for 1 hour, and further left at room temperature for 1 day. did. The test piece prepared in this manner was heated at 23 ° C. and 60 RH% (relative humidity).
The sample was placed in a thermo-hygrostat set under the conditions, kept under these conditions for 1 hour, and then cooled down to -40 ° C. at a rate of 5 ° C./min. After maintaining at −40 ° C. for 2 hours, the temperature was raised to 60 ° C. at a rate of 5 ° C./min. After holding at 60 ° C for 2 hours,
The temperature was lowered to 23 ° C. at a rate of 5 ° C./min.

Then, the test piece was taken out from the thermostat / humidity chamber, and then a checkerboard-like scratch was made on the printing surface of this flat plate with a cutter, and then cellophane tape was applied, and the surface was pressed sufficiently with the force of a finger to bring it into close contact. After that, by pulling at an angle of 45 ° from the surface, the peeling state of the printed surface was evaluated by an optical microscope and visual observation. A: No peeling of the printed surface occurs. ：: No peeling of the printed surface occurs, but slight peeling occurs at the cutting end face by the cutter. Δ: The printed surface slightly peels off. X: The printed surface is peeled off in a wide range.

(3) Colorability The colorability was evaluated by visually observing the colorability of the molded product obtained by adding 1 part by weight of a dark blue colorant to 100 parts by weight of the resin composition, and judging by the following criteria. did. ：: Vivid dark blue color. ○: Dark blue color. Δ: Slightly whitish dark blue. ×: Navy dark blue color.

(4) Izod impact value The Izod impact value was measured at 23 ° C. by a method according to ASTM-D256 (V notch, 1/4 inch test piece). (5) Deflection temperature under load (DTUL) Measured by a method based on ASTM-D648 (1/4)
Inch specimen).

(6) Flame retardance VB (Vertical Bur) compliant with UL-94
ing) method and HB (Horizontal Bur)
The thickness of the test piece (1/8 inch, 1
/ 12 inch and 1/16 inch).
The 0, V1, V2 and HB grades were determined.

[0054]

[Embodiment] Each component shown in Tables 1 to 4 was prepared according to Ikegai Iron Works Ltd.
Using a manufactured 30 mmφ twin-screw extruder, the mixture was kneaded at a cylinder temperature of 220 to 300 ° C. to obtain pellets of the target styrene resin composition. After pre-drying the obtained pellets, test pieces were prepared using a 100t injection molding machine manufactured by Japan Steel Works, Ltd. and a 40t injection molding machine manufactured by Nissei Plastic Co., Ltd., and thermal stability, printing / paintability , Colorability, Izod impact value, and flame retardancy were evaluated. The results are shown in Tables 1 to 4.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION According to the present invention, a flame-retardant resin composition having a high degree of thermal stability and excellent in flame retardancy, appearance, printing / paintability and mechanical properties without using a halogen compound. You can get things. The flame-retardant resin composition provided can be widely used, including parts in the electric and electronic fields where flame retardancy is required. In addition, since the occurrence of burn-off during molding, which has been a problem in the past, can be suppressed, the yield when commercialized as a molded product is improved, and its industrial utility value is extremely high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takashi Matsuda 1-5-1 Kuriya, Tama-ku, Kawasaki City, Kanagawa Prefecture (72) Toshimasa Tanaka 1618 Ida, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Nippon Steel Corp. Technology Within the development headquarters

Claims (5)

[Claims] 1. Component (A): rubber-modified styrene resin
1 to 99 parts by weight and (B) component: polyphenylene ether resin 99 to 1 part by weight to 100 parts by weight in total, (C) component: organic phosphate ester flame retardant
0.1 to 30 parts by weight, component (D): triazine skeleton-containing compound 0.1 to 30 parts by weight and component (E): selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents. A flame-retardant resin composition containing 0.001 to 3 parts by weight of at least one coupling agent. 2. The flame-retardant resin composition according to claim 1, wherein the component (D) is surface-treated with the component (E). 3. The flame-retardant resin composition according to claim 1, wherein the component (D) is melamine sulfate. 4. The flame-retardant resin composition according to claim 1 or 2, wherein the component (E) is a silane coupling agent having a vinyl group or a methacryl group. 5. The gel content of the component (A) is 20 to 80% by weight, and the weight average particle diameter of the dispersed rubber particles dispersed in the matrix resin is 0.5 to 4 μm. The flame-retardant resin composition described.