JPH09169902A - Polyphenylene ether-based flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition suppressed in bleedout of the flame retardant contained and in fuming during its molding, and excellent in impact resistance and flame retaredancy, thus useful in the field of electronic equipment, by incorporating a polyphrnylene ether based resin (composition) with a specific flame retardant and a specific graft copolymer. SOLUTION: This composition is obtained by incorporating (A) 100 pts.wt. of a polyphenylene-based resin (and an aromatic vinyl-based resin) with (B) 1-30 pts.wt. of a condensed phosphoric ester-based flame retardant expressed by formula I or II(R<a-h> are each an alkyl, a phenyl or an alkylphenyl; X is a phenylene, a 1-6C alkylene or SO2 ; (p) and (q) are each an integer of 1-30), and (C) 0.5-30 pts.wt. of a composite rubber-based copolymer obtained by grafting a (epoxy group-containing) vinylic monomer to a composite rubber obtained by incorporating an organosiloxane robber component with a polyalkyl(meth)acrylate rubber component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition containing a polyphenylene ether (hereinafter sometimes referred to as PPE) resin.

[0002]

The PPE resin is attracting attention as an extremely useful engineering plastic material because it has excellent electrical and mechanical properties, high heat distortion temperature and self-extinguishing property. Generally, PPE resins have high melting temperatures and high melt viscosities, and therefore require high molding temperature and pressure during molding, which makes molding by melting difficult. Therefore, for example, as shown in JP-B-43-17812, the molding processability is imparted by blending with a polystyrene resin.

As a method of imparting flame retardancy to PPE resins, phosphoric acid ester flame retardants have hitherto been used. Triphenyl phosphate (hereinafter sometimes abbreviated as TPP) is generally used as the phosphoric acid ester flame retardant, but since TPP is a low molecular weight compound, it emits smoke during molding or bleeds out into the mold. It also has the drawback of contaminating molded products.

In order to improve the above-mentioned drawbacks of TPP, condensed phosphoric acid ester flame retardants have recently been used. Condensed phosphoric acid ester flame retardants include resorcin polyphenyl phosphate (JP-A-57-207641 and JP-A-57-207642), bisphenol A.
Polyphenyl phosphate, bisphenol A polycresyl phosphate (JP-A-55-118957 and JP-A-59-202240) and the like are known. The condensed phosphoric acid ester-based flame retardant described above can significantly improve smoke generation and mold contamination during molding. However, it has a drawback that the impact resistance of the obtained molded product is significantly reduced as compared with the case where TPP is blended. Therefore, there is a problem that it cannot be used in a recent application such as a housing of an OA device requiring high impact resistance.

In order to improve the impact resistance of the resin composition, a method of adding a rubber component is generally adopted. As the rubber component added to the PPE-based resin, an AB-A 'type elastomer block copolymer (A, A': aromatic vinyl compound, as disclosed in JP-A-48-62851) is used.
B: a conjugated diene), or a block having at least two polymer blocks X mainly containing an aromatic vinyl compound and at least one polymer block Y mainly containing a conjugated diene compound and being hydrogenated Copolymers and the like are known. When these rubber components are added to the PPE resin together with the above-mentioned condensed phosphoric acid ester flame retardant, it is possible to obtain impact resistance equal to or higher than that of TPP. However, the addition of all of the above rubber components significantly reduces the flame retardancy of the resin composition. Therefore, when the rubber component is added to improve the impact resistance, the amount of the flame retardant added must be further increased to improve the flame retardancy, which causes the impact resistance to decrease again. Fall into. Therefore, when the condensed phosphoric acid ester-based flame retardant is used for the PPE-based resin, a large amount of the flame retardant and the rubber component are added in order to obtain the same flame resistance and impact resistance as when TPP is used. Mechanical properties other than impact resistance, such as tensile strength, flexural strength,
Properties such as flexural modulus, thermal stability, and fluidity during molding will be greatly reduced.

The applicant of the present invention previously prepared by grafting a vinyl monomer onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate as disclosed in JP-A-64-79257. It has been found that when a composite rubber-based graft copolymer is blended with a PPE-based flame-retardant resin composition, impact resistance can be improved without relatively impairing the flame-retardant property (patent filed on November 28, 1995). ). This composite rubber-based graft copolymer does not significantly affect the flame retardancy unlike the conjugated diene-based block copolymer type rubber described above, but its compatibility with the PPE-based resin is not sufficient,
It was found that the improvement in impact resistance was still insufficient.

Therefore, an object of the present invention is to provide a PPE-based flame-retardant resin composition in which bleed-out of a flame retardant and smoke generation during molding are suppressed, and which has high impact resistance and excellent flame retardancy. .

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on a PPE-based flame-retardant resin composition, and as a result, PP
By adding a specific epoxy-modified polyorganosiloxane-based composite rubber graft copolymer together with a condensation type phosphoric acid ester-based flame retardant to an E-based resin, it is possible to greatly improve impact resistance without impairing flame retardancy. Heading out, the present invention was reached.

That is, the resin composition of the present invention comprises (A) a polyphenylene ether resin or 100 parts by weight of an aromatic vinyl resin and (B) the following formula (I):

[0010]

[Chemical 6] Or the following formula (II):

[0011]

Embedded image (In the above formula, R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R
^g and R ^h each independently represent an alkyl group, a phenyl group or an alkylphenyl group, X represents a phenylene group, an alkylene group having 1 to 6 carbon atoms or a —SO ₂ — group, and p and q each independently. 1 to 30 parts by weight of the condensed phosphoric acid ester-based flame retardant represented by the formula (1) to (30), and the (C) polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are separated from each other. 0.5 to 30 parts by weight of a composite rubber-based graft copolymer obtained by grafting one or more vinyl-based monomers containing at least an epoxy group-containing vinyl-based monomer onto a composite rubber having an integrated structure so that it cannot be integrated. including.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, known PPE resins can be used as the component (A). The PPE resin is, for example, a compound represented by the general formula (III):

[0013]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group or a nitro group, and n Is an integer representing the degree of polymerization), and may be a single polymer of the above general formula or a copolymer in which two or more polymers are combined. Good. Specific examples of R ₁ , R ₂ , R ₃ and R ₄ include chlorine, bromine, iodine, methyl, ethyl,
Groups such as propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, nitro and the like.

Specific examples of the polymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2- Methyl-6-ethyl-1,4-phenylene) ether, poly (2
-Methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ) Ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-dibromomethyl) -1,4-
Phenylene) ether, poly (2,6-diphenyl-1,4-)
Phenylene) ether, poly (2,6-ditolyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6-dibenzyl- 1,4-phenylene) ether and poly (2,5-dimethyl-1,4-phenylene) ether. A preferred PPE-based resin is a polymer in which R ₁ and R ₂ in the above formula (III) are alkyl groups, particularly alkyl groups having 1 to 4 carbon atoms, and n is usually preferably 50 or more. Examples of the PPE copolymer include copolymers in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. Further, a copolymer in which a styrene-based compound is grafted on these PPEs may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene or the like as the styrene-based compound on the above-mentioned PPE.

In the present invention, the component (A) is the above-mentioned PPE resin or the above and the aromatic vinyl resin.
Examples of the aromatic vinyl resin include styrene and derivatives thereof such as homopolymers and copolymers of p-methylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene, bromostyrene and the like. Further, rubber-modified polystyrene (HIPS) comprising 70 to 99% by weight of the above-mentioned aromatic vinyl compound and 1 to 30% by weight of a diene rubber can be used. Examples of the diene rubber constituting HIPS include a homopolymer of a conjugated diene compound such as butadiene, isoprene, and chloroprene, a copolymer of a conjugated diene compound and an unsaturated nitrile compound or an aromatic vinyl compound, and a natural rubber. And one or more kinds can be used. Particularly, polybutadiene and butadiene-styrene copolymer are preferred. HIPS is obtained by a method of emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof. In addition, polystyrene thermoplastic elastomers such as styrene-acrylonitrile-acrylate copolymer, FPDM rubber-modified polystyrene, acrylic rubber-modified styrene-acrylonitrile copolymer, hydrogenated styrene-butadiene block copolymer, etc. are also aromatic vinyl-based. Exemplified as a resin.

In the component (A), the PPE-based resin and the aromatic vinyl-based resin can be blended in any ratios, but the blending ratio is usually 99 to 1 part by weight of the PPE-based resin. 1 to 99 parts by weight. Preferably PP
20 to 20 parts by weight of E resin to 20 to 20 parts of aromatic vinyl resin
80 parts by weight.

The condensed phosphoric acid ester flame retardant (B) used in the present invention is represented by the above formula (I) or (II). In the formula (I) or (II), the alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkylphenyl group include a tolyl group, a xylyl group,
Examples thereof include a mesityl group and a cumenyl group.

Specifically, phenyl resorcin polyphosphate (R ^{a to} R ^d = phenyl group in the formula (I)), phenyl cresyl resorcin polyphosphate (R ^{a to} R ^d = in the formula (I)) Having both a phenyl group and a tolyl group), cresyl resorcin polyphosphate (R ^{a to} R ^d = tolyl group in formula (I)), phenyl hydroquinone polyphosphate (R ^{a to} R in formula (I)) ^d = phenyl group), phenyl
Bisphenol A / polyphosphate (R ^{e to} R ^h = phenyl group in formula (II), X = dimethylmethylene), phenyl / bisphenol S / polyphosphate (formula (II))
Where R ^{e to} R ^h = phenyl group, X = SO ₂ ), cresyl hydroquinone polyphosphate (R ^{a to} R ^d = tolyl group in formula (I)), cresyl bisphenol A polyphosphate (formula (II)) Where R ^{e to} R ^h =
Tolyl group, X = dimethylmethylene), cresyl bisphenol S.polyphosphate (R ^e ~ in formula (II))
R ^h = tolyl group, X = SO ₂ ) and the like can be mentioned.

Component (B) can be a mixture of two or more compounds and also a mixture of compounds having different degrees of polymerization.

The preferred component (B) is represented by the following formulas (i) and (i
i) and (iii):

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image (In the above formula, r is an integer of 1 to 30, preferably 1 to 10). r can be an average value.

The condensed phosphoric acid ester flame retardant (B) is 1 part by weight or more, preferably 5 parts by weight or more and 30 parts by weight or less, preferably 25 parts by weight or less, relative to 100 parts by weight of the component (A). Be compounded. If it is less than 1 part by weight, it does not reach a practical level as a flame retardant, and if it exceeds 30 parts by weight, extrusion processing becomes practically difficult due to the plasticizing effect.

Next, the component (C) used in the present invention
Is described. The component (C) is, for example, JP-A-7-207137.
Japanese Patent Laid-Open No. 7-207132 and a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are integrated so that they cannot be separated from each other, It is a composite rubber graft copolymer obtained by grafting at least one vinyl monomer containing at least an epoxy group-containing vinyl monomer.

Such epoxy-modified composite rubber-based graft copolymers are disclosed in JP-A-7-207137 and JP-A-7-20.
It can be produced using the method described in Japanese Patent No. 7132.

As the polyorganosiloxane rubber, use those obtained as fine particles by polymerizing by adding an organosiloxane and a crosslinking agent for polyorganosiloxane rubber, or a graft-crosslinking agent for polyorganosiloxane rubber to this. You can

As the organosiloxane, a cyclic organosiloxane having 3 or more membered rings can be mentioned.
A membered ring is preferably used. Specific examples of preferable cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenyl. Examples thereof include cyclotetrasiloxane, and these can be used alone or in combination of two or more kinds. The amount of cyclic organosiloxane used is preferably 60% by weight or more, and more preferably 70% by weight or more in the polyorganosiloxane rubber component.

As the polyorganosiloxane rubber crosslinking agent, a trifunctional or tetrafunctional silane crosslinking agent, that is, a silane compound having three or four alkoxy groups is used. Specific examples thereof include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Particularly, a tetrafunctional crosslinking agent is preferable, and among them, tetraethoxysilane is particularly preferable. The crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber component.
Is preferable, and more preferably 0.5 to 10% by weight. If the amount of the crosslinking agent used is too small, the impact strength of the molded product from the composition tends to be low, the appearance of the molded product tends to be poor, and if it is too large, there is no inconvenience, but in the formation of a further crosslinked structure Does not contribute.

The graft crossing agent for polyorganosiloxane rubber means that the siloxane part thereof is involved in the polymerization and is incorporated into the polyorganosiloxane rubber, but at this time it does not react and the polyorganosiloxane rubber for the preparation of the composite rubber thereafter. It is a siloxane having a functional group that reacts during the polymerization of a poly (meth) acrylate rubber in the presence. As a specific example, the following equations (a-1) to (a-4):

[0031]

Embedded image (In the above formula, R ¹ is a lower alkyl group such as a methyl group,
Represents an ethyl group, propyl group or phenyl group, R ²
Represents a hydrogen atom or a methyl group, and m is 0, 1 or 2
Represents, and f represents an integer of 1 to 6)

[0032]

Embedded image CH ₂ ═CH—SiR ³ _m O _{(3-m) / 2} (a-2) (wherein R ³ is a lower alkyl group such as a methyl group,
Represents an ethyl group, a propyl group or the like or a phenyl group, and m represents 0, 1 or 2.)

[0033]

Embedded image (In the above formula, R ⁴ is a lower alkyl group such as a methyl group,
R ⁵ represents an ethyl group, a propyl group, or a phenyl group.
Represents a hydrogen atom or a methyl group, and m is 0, 1 or 2
Represents)

[0034]

Embedded image HS- (CH ₂ ) _f —SiR ⁶ _m O _{(3-m) / 2} (a-4) (wherein R ⁶ is a lower alkyl group such as a methyl group,
A compound capable of forming a unit represented by an ethyl group, a propyl group or the like or a phenyl group, m represents 0, 1 or 2, and f represents an integer of 1 to 6).

A unit of the above formula (a-1) can be formed (meta)
Since acryloyloxysilane has high grafting efficiency,
It is possible to form an effective graft chain and is advantageous in that it exhibits high impact resistance. Note that the formula (a-
Methacryloyloxysilane is particularly preferable as a unit capable of forming the unit 1). Specific examples of methacryloyloxysilane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl. Ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-
Methacryloyloxybutyldiethoxymethylsilane and the like can be mentioned. Of these, γ-methacryloyloxypropyldimethoxymethylsilane and γ-methacryloyloxypropyltrimethoxysilane are preferable.

Examples of the unit capable of forming the unit of the above formula (a-2) include vinyltrimethoxysilane, vinylmethyldimethoxysilane and the like.

Examples of those capable of forming the unit of the above formula (a-3) include 4-vinylphenyldimethoxymethylsilane and 4-vinylphenyltrimethoxysilane.

As the unit capable of forming the unit of the above formula (a-4), for example, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyldiethoxyethylsilane and the like can be mentioned.

The amount of the graft crossing agent for polyorganosiloxane rubber used is preferably 0 to 10% by weight, more preferably 0 to 5% by weight in the polyorganosiloxane rubber component.

The polyorganosiloxane rubber component is
For example, it can be obtained as a latex by the method described in U.S. Pat. Nos. 289,1920 and 3,294,725. In the present invention, for example, a mixed solution obtained by adding a cross-linking agent for an organosiloxane and a polyorganosiloxane rubber and, if desired, a graft crossing agent for a polyorganosiloxane rubber is prepared in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid. Below,
For example, the polyorganosiloxane rubber is preferably produced by a method of shear mixing with water using a homogenizer or the like.

Alkylbenzene sulfonic acid is preferable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzene sulfonic acid in combination with an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt or the like, because it is effective in maintaining the polymer stably during the graft polymerization.

The termination of the polymerization can be carried out by neutralizing the latex with an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or sodium carbonate.

The composite rubber as the component (C) is obtained by adding to the above polyorganosiloxane rubber latex an alkyl (meth) acrylate, a crosslinker for a polyalkyl (meth) acrylate rubber and a graft crossing agent for a polyalkyl (meth) acrylate rubber. Then, the polyorganosiloxane rubber particles can be synthesized by impregnating these components with each other and then polymerizing.

As the alkyl (meth) acrylate,
Examples thereof include a linear or branched alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate having an alkyl group having 6 to 12 carbon atoms.
Specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 3-pentyl acrylate, Hexyl acrylate, n-heptyl acrylate, 2-heptyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, n-lauryl methacrylate, 2-ethylhexyl methacrylate, etc. You can Of these, n-butyl acrylate is preferred.

As the cross-linking agent for polyalkyl (meth) acrylate rubber, (meth) acrylate having two or more polymerizable unsaturated bonds is used, and examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate and 1,3-butylene. Examples thereof include glycol dimethacrylate and 1,4-butylene glycol dimethacrylate.

The graft-linking agent for polyalkyl (meth) acrylate rubber is polymerized with other components and incorporated into the rubber during the polymerization for producing the polyalkyl (meth) acrylate rubber. The polymerizable unsaturated groups remain unreacted, and the remaining unsaturated groups can be polymerized together with the graft branch component during the subsequent graft polymerization.
It is a monomer having three or more. Specific examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Allyl methacrylate is a polyalkyl (meth) acrylate rubber during polymerization, part of which both unsaturated groups react to form a crosslinked structure, and the rest react only one of the unsaturated groups,
The other unsaturated bond remains after the polymerization of the polyalkyl (meth) acrylate rubber, and during the subsequent graft polymerization, the remaining unsaturated bond reacts to form a graft bond, so both the cross-linking agent and the graft crossing agent are formed. Fulfill the function of.

The cross-linking agent and graft crossing agent for these polyalkyl (meth) acrylate rubbers may be used alone or in combination of two or more kinds. The amount of each of the cross-linking agent and the graft crossing agent used is preferably 0.1 to 10% by weight in the polyalkyl (meth) acrylate rubber component. When using allyl methacrylate alone as a cross-linking agent and a graft crossing agent, 0.2
It may be used up to 20% by weight. Polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate into a latex of polyorganosiloxane rubber neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. A crosslinking agent and a graft crossing agent for the polyalkyl (meth) acrylate rubber are added and impregnated into the polyorganosiloxane rubber particles, and then a normal radical polymerization initiator is allowed to act.

As the polymerization proceeds, a crosslinked network of polyalkyl (meth) acrylate rubbers entangled with each other in the crosslinked network of polyorganosiloxane rubber is formed, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate are substantially inseparable. A latex of a composite rubber composed of a rubber component is obtained. This composite rubber has a gel content when measured by extraction with toluene at 90 ° C for 4 hours.
It is preferably 80% or more.

As this composite rubber, a composite rubber in which the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane and the main skeleton of the polyalkyl (meth) acrylate rubber component has a repeating unit of n-butyl acrylate Is preferred. The ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the above composite rubber is preferably 1 to 99% by weight for the former and 99 to 1% by weight for the latter, and the former is 5% by weight. ~
More preferably, the latter is 95 to 5% by weight with respect to 95% by weight.

The component (C) is obtained by grafting the composite rubber obtained as described above with at least one vinyl monomer containing at least an epoxy group-containing vinyl monomer. In the present invention, "one or more vinyl-based monomers containing at least an epoxy group-containing vinyl-based monomer"
May be composed of only an epoxy group-containing vinyl monomer, or may be an epoxy group-containing vinyl monomer and another vinyl monomer copolymerizable with the epoxy group-containing vinyl monomer. It means that it may be a mixture with a monomer.

As the epoxy group-containing vinyl monomer,
For example, glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether,
Examples thereof include glycidyl ether of polyalkylene glycol (meth) acrylate, diglycidyl itaconate, and the like. These may be used alone or in combination of two or more kinds. Among these, a monomer selected from the group consisting of glycidyl (meth) acrylate and diglycidyl itaconate is preferable.

Other vinyl monomers copolymerizable with the epoxy group-containing vinyl monomer include, for example, methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate and the like. Acrylic esters; aromatic alkenyl compounds such as styrene, bromostyrene, p-methylstyrene, chlorostyrene, α-methylstyrene, vinyltoluene; various vinyl monomers such as acrylonitrile, methacrylonitrile and other cyanide vinyl compounds These may be used alone or in combination of two or more. Of these, methyl methacrylate, butyl acrylate and styrene are preferably used.

At least one vinyl monomer containing at least the epoxy group-containing vinyl monomer is graft-copolymerized with the above-mentioned composite rubber. The ratio of the epoxy group-containing vinyl monomer to the one or more vinyl monomers containing at least the epoxy group-containing vinyl monomer is 10
It is preferably not less than 20% by weight, more preferably not less than 20% by weight.

The amount of the epoxy group-containing vinyl monomer in the composite rubber-based graft copolymer is preferably 1 to 30% by weight, more preferably 2 to 20% by weight.
If the amount of the epoxy group-containing vinyl-based monomer in the composite rubber-based graft copolymer is too small, the impact strength will be insufficiently improved. There is no inconvenience if the amount is too large,
It does not contribute to the impact strength improvement effect.

Occupy in the composite rubber-based graft copolymer,
The amount of at least one vinyl-based monomer containing at least the epoxy group-containing vinyl-based monomer is preferably 2 to 50% by weight, more preferably 5 to 30% by weight. If this amount is too small, the compatibility of the component (C) with the component (A) becomes poor and the impact resistance becomes insufficient. On the other hand, if the amount is too large, the rubber content is reduced, so that the impact resistance is insufficient in this case as well.

The composite rubber-based graft copolymer is prepared by adding one or more vinyl-based monomers containing at least the epoxy group-containing vinyl-based monomer described above to the latex of the composite rubber described above and further carrying out a step of radical polymerization technique. Alternatively, the composite rubber-based graft copolymer latex obtained by multi-stage polymerization may be placed in hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and salted out and coagulated to separate and recover. it can.

If the average particle size of the composite rubber-based graft copolymer is less than 0.08 μm, the impact resistance of the resulting resin composition tends to be insufficient, and if it is more than 0.6 μm, the resistance of the resin composition also tends to be insufficient. Impact tends to be insufficient,
Further, since the surface appearance of the molded product from the resin composition tends to be deteriorated, the average particle diameter is preferably 0.08 to 0.6 μm. In order to obtain a composite rubber-based graft copolymer having such an average particle size, the polyorganosiloxane rubber or composite rubber used is preferably produced by emulsion polymerization.

The average particle size of the composite rubber-based graft copolymer can be measured by a quasi-elastic light scattering method using a latex diluted with water as a sample solution.

In the graft polymerization, a so-called free polymer, which is obtained by polymerizing only the branch component without grafting the component corresponding to the branch of the graft copolymer to the trunk component, is partially produced as a by-product and is free from the graft copolymer. Although it is obtained as a mixture of polymers, they are collectively referred to as a graft copolymer in the present invention.

The epoxy-modified composite rubber-based graft copolymer as described above can be obtained from, for example, Mitsubishi Rayon Co., Ltd.
It is commercially available as Metablen KS-4015.

Since the epoxy-modified composite rubber-based graft copolymer as described above has an epoxy group, the resin and the residual functional group of the PPE-based resin are not melted during melt kneading during the production of the resin composition. Upon reaction, a partial bond is generated between the component (A) and the component (C), which acts as a compatibilizing agent to improve the compatibility of the two, and as a result, a composite rubber-based graft not modified with epoxy. It is presumed that the impact strength of the resin composition is improved as compared with the case of using the copolymer.

The above-mentioned component (C) composite rubber graft copolymer is blended in an amount of 0.5 parts by weight or more and 30 parts by weight or less, preferably 20 parts by weight or less, relative to 100 parts by weight of (A). It If the amount of (C) is too small, the effect of the present invention will not be exhibited, and if it is too large, the rigidity of the molded body will decrease.

In the resin composition of the present invention, in addition to the above-mentioned components, when the resin is mixed as long as the physical properties are not impaired,
Other resins during molding, conventional additives such as pigments, dyes, reinforcing agents (glass fiber, carbon fiber, etc.), fillers (carbon black, silica, titanium oxide, mica, talc, etc.), heat-resistant agents, oxidative deterioration prevention Agents, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, compatibilizers (maleic anhydride, dicarboxylic acids such as citric acid and their anhydrides), antibacterial Agents and the like can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, the melt-kneading method is generally preferable. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include, in particular, an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The following compounds were used in the examples. Component (A): PPE resin: Intrinsic viscosity (chloroform, 25 ° C) 0.48d
1 / g of poly (2,6-dimethyl-1,4-phenylene) ether, manufactured by Nippon GE Plastics Co., Ltd. (hereinafter referred to as P
Aromatic vinyl resin: High impact polystyrene (H)
IPS) (trademark; Topolex 876-HF, manufactured by Mitsui Toatsu Chemicals, Inc.) (hereinafter referred to as HIPS) Component (B): B-1: Compound represented by the following formula (i), where r = 1
-10 mixture (trademark: CR733S, manufactured by Daihachi Chemical Co., Ltd.) B-2: compound represented by the following formula (ii), where r = 1
To 10 mixture (trademark: CR741, manufactured by Daihachi Chemical Co., Ltd.) B-3: compound represented by the following formula (iii), where r = 1
~ 10 mixture (trademark: CR741c, manufactured by Daihachi Chemical Co., Ltd.)

[0067]

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[0068]

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Embedded image In addition, the following compounds were used for comparison: TPP: triphenyl phosphate (manufactured by Daihachi Chemical Co., Ltd.) Component (C): Metabrene KS-4015: trade name, manufactured by Mitsubishi Rayon Co., Ltd., composite rubber (dimethyl siloxane) (Rubber component and n-butyl acrylate rubber component, composite rubber-based graft copolymer obtained by grafting epoxy group-containing methyl methacrylate) Further, the following rubber components were used for comparison: KRATON G1651; trademark, shell chemical Hydrogenated polystyrene (block X) -polybutadiene (block Y) block copolymer manufactured by the same company.

Metabrene S-2001: trade name, manufactured by Mitsubishi Rayon Co., Ltd., composite rubber (composite rubber-based graft copolymer obtained by grafting dimethylsiloxane rubber component and n-butyl acrylate rubber component with methyl methacrylate, epoxy group) Examples 1 to 3 and Comparative Examples 1 to 10 are not melted, and the components in the proportions (weight ratios) shown in Tables 1 and 2 are melt-kneaded at a kneading temperature of 280 ° C. and a rotation speed of 280 rpm in a 30 mm twin-screw extruder and pelletized. made. The pellets were injection molded under the conditions of a preset temperature of 260 ° C and a mold temperature of 80 ° C. The following characteristic evaluation was performed on the obtained molded product. The results are shown in Tables 1 and 2. (1) Deflection temperature under load According to ASTM D648, a test piece having a thickness of 1/4 inch was measured under a load of 18.6 kg / cm ² . (2) Izod impact strength Measured at 23 ° C. according to ASTM D256 with a thickness of 1/8 inch and a notch. (3) Tensile Strength Measured according to ASTM D638. (4) Flexural modulus Measured according to ASTM D790. (5) Flame retardancy test ( UL94 / V0, VI, VII test ) Five test rods (thickness: 1.6 mm) were used with Underwriters Laboratories Inc. Bretin 94 "Combustion test for material classification" (hereinafter, UL It is tested according to the test method shown in (-94). By this test method, the test material is UL-based based on the results of 5 samples.
-94 V-0, VI and VII were evaluated. The criteria for each V rating for UL-94 are as follows. V-0: Average flame holding time after removing the ignition flame is 5
It is less than a second, and all the samples do not fall the fine flame igniting the absorbent cotton. VI: Average flame holding time after removing the ignition flame is 25
It is less than a second, and all the samples do not fall the fine flame igniting the absorbent cotton. V-II: Average flame holding time after removing the ignition flame
It is less than 25 seconds, and these samples fall into a fine flame igniting absorbent cotton.

UL-94 also stipulates that all test rods must be classified in a particular V grade unless they pass the grade. If this condition is not met, the five test bars are given the rating of the single worst test bar. For example, if one test rod is classified as V-II, the rating for all five test rods is V-II. Further, HB is a grade that does not satisfy the above V-0, VI, and V-II regulations, and satisfies a separately prescribed horizontal combustion test. (6) Presence or absence of smoke during molding When the test piece was prepared, the amount of smoke at the nozzle of the injection molding machine was visually observed. (7) Presence or absence of contamination of mold and molded product Mold a box-shaped molded product (vertical 100 mm, horizontal 70 mm, height 20 mm, thickness 2 mm) with an injection molding machine and attach it to the mold and molded product. The kimono was visually observed.

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[Table 1]

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[Table 2] Component (B) flame retardant used alone (Comparative Examples 1-3)
In comparison with the case of using TPP (Comparative Example 7), it is possible to prevent smoke during molding and contamination of the mold and the molded product.
Izod impact strength is very low. Further, when the component (B) is used in combination with a conventional rubber component (Comparative Examples 4 to 6),
Izod impact strength is high, but flame retardancy is low. On the other hand, in the resin compositions of Examples 1 to 3 in which the components (B) and (C) were used in combination, the flame retardancy was excellent, the Izod impact strength was high, and the smoke and the mold during molding and It can be seen that there is no contamination of the molded product. Further, in Comparative Examples 8 to 10 using the composite rubber-based graft copolymer containing no epoxy group as the rubber component, the flame retardancy is excellent, and it is possible to prevent smoke during molding and contamination of the mold or molded product. However, it can be seen that the physical properties (particularly Izod impact strength) are inferior to those in Examples 1 to 3.

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The resin composition of the present invention is excellent in strength, flame retardancy and moldability. Therefore, it is extremely suitable for use in various fields such as printers, facsimiles, copiers, OA equipments such as computers, electronic equipments related to cathode ray tube peripheral parts, etc., whose demands are becoming stricter, and industrially. Very useful.

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Claims (4)

[Claims] 1. A polyphenylene ether resin or 100 parts by weight of an aromatic vinyl resin and (A) a polyphenylene ether resin, and (B) the following formula (I): Or the following formula (II): (In the above formula, R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R
^g and R ^h each independently represent an alkyl group, a phenyl group or an alkylphenyl group, X represents a phenylene group, an alkylene group having 1 to 6 carbon atoms or a —SO ₂ — group, and p and q each independently. 1 to 30 parts by weight of the condensed phosphoric acid ester-based flame retardant represented by the formula (1) to (30), and the (C) polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are separated from each other. 0.5 to 30 parts by weight of a composite rubber-based graft copolymer obtained by grafting one or more vinyl-based monomers containing at least an epoxy group-containing vinyl-based monomer onto a composite rubber having an integrated structure so that it cannot be integrated. A resin composition containing: 2. The resin composition according to claim 1, wherein the component (A) comprises 99 to 1 parts by weight of a polyphenylene ether resin and 1 to 99 parts by weight of an aromatic vinyl resin. 3. The component (B) has the following formulas (i), (ii) and (iii): Embedded image Embedded image The resin composition according to claim 1 or 2, which is selected from the group of compounds represented by the formula (r is an integer of 1 to 30). 4. The component (C), wherein the vinyl monomer is a compound selected from the group consisting of methacrylic acid ester, acrylic acid ester, aromatic alkenyl compound and vinyl cyanide compound. The resin composition according to claim 1.