JPH09157512A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin compsn. which contains a polycarbonate resin, a graft copolymer and a phenol resin as the essential components, does not generate any harmful substance during its molding or burning, has an improve resistance to discoloration due to light or heat, and is excellent in flame retardancy. SOLUTION: This resin compsn. is prepd. by compounding 100 pts.wt. resin component comprising 1-99wt.% polycarbonate resin, 1-50wt.% graft copolymer, and 0-98wt.% thermoplastic resin with 1-50 pts.wt. phosphorus compd., 1-50 pts.wt. phenol resin, and 0.01-15 pts.wt. at least one light stabilizer selected from among oxanilide, benzotriazole, benzophenone, salicylic acid, and cyanurate ultraviolet absorbers and a titanium oxide ultraviolet stabilizer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant resin composition containing a polycarbonate resin improved in flame retardancy and discoloration without using a brominated flame retardant and a graft copolymer as essential components.

[0002]

2. Description of the Related Art Conventionally, resin compositions containing polycarbonate resin and ABS resin as essential components (hereinafter referred to as PC / ABS
Alloys are abbreviated) and are used in a wide range of applications due to their excellent balance of physical properties and good moldability. However, depending on the application, it is necessary to have flame retardancy, and this can be said especially when used in products such as electric / electronic device parts, OA / home electric appliances, and the like. As a method for imparting flame retardancy to PC / ABS alloys, a halogen-based flame retardant is generally added, but during kneading and molding, part of the halogen-based flame retardant decomposes and gasifies, corroding processing equipment. In addition, it is pointed out that some halogen-based flame retardants generate toxic brominated dibenzodioxin, dibenzofuran, and the like in an extremely small amount during molding and burning. As a method for eliminating such a defect, it has been proposed to add a phosphorus compound, a phenol resin or the like to the PC / ABS alloy instead of the halogen-based flame retardant (JP-A-7-53846). However, since it contains a phenol resin, it has a problem that it is easily discolored by light or heat.

[0003]

The present invention has been made in view of the above problems, and there is no fear of generation of harmful substances during molding or combustion, and the discolorability to light and heat is high. An object of the present invention is to provide a flame-retardant resin composition containing a polycarbonate resin, a graft copolymer and a phenol resin, which are improved and have excellent flame retardancy, as essential components.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have aimed to improve the discolorability to light and heat in a resin composition comprising a polycarbonate resin, a graft copolymer and a phenol resin without lowering the flame retardancy. As a result of intensive studies, (1) it is effective to add a specific light stabilizer for improving the discoloration property against light, and (2) a specific antioxidant for improving the discoloration property against heat. And it is effective to blend a heat stabilizer composed of a specific phosphorus-based antioxidant,
(3) To simultaneously improve the discoloration properties against light and heat,
It is effective to use a specific light stabilizer and a heat stabilizer composed of a specific antioxidant and a specific phosphorus-based antioxidant in combination.
In addition, they have found that (4) when an imidized copolymer is blended with these light stabilizers and heat stabilizers, the discolorability with respect to light and heat is further improved, and the initial coloring can be suppressed, and the present invention has been reached. That is, in the present invention, as the component (1) (A), the polycarbonate resin is 1 to 99% by weight, (B)
1 to 50% by weight of the graft copolymer as a component, (C)
As a component, 1 to 50 parts by weight of a phosphorus compound as a component (D) and 1 to 50 parts by weight of a phenol resin as a component (E) with respect to 100 parts by weight of a resin component composed of 0 to 98% by weight of another thermoplastic resin. Part, as the component (F), an oxalic acid anilide type ultraviolet absorber, a benzotriazole type ultraviolet absorber,
It is characterized by containing 0.01 to 15 parts by weight of a light stabilizer containing at least one selected from a benzophenone type ultraviolet absorber, a salicylic acid type ultraviolet absorber, a cyanurate type ultraviolet absorber and a titanium oxide type ultraviolet stabilizer. Flame-retardant resin composition, (2) (A) and (B) described in (1),
In addition to the components (C), (D), and (E), as a component (G), an antioxidant of a phenol-based antioxidant and / or a sulfur-based antioxidant, a phosphite and / or a phosphonite Heat stabilizer consisting of phosphorus-based antioxidant 0.00
1 to 5 parts by weight of a flame-retardant resin composition, (3) (1) described (A), (B), (C),
In addition to the components (D), (E), and (F), as a component (G), an antioxidant of a phenol-based antioxidant and / or a sulfur-based antioxidant, a phosphite and / or a phosphonite Heat stabilizer consisting of phosphorus-based antioxidant 0.00
1 to 5 parts by weight of a flame-retardant resin composition, (4) the other thermoplastic resin of the component (C) is a rubbery polymer 0 to 40% by weight, aromatic vinyl unit amount Body residue 29.
5 to 69.5% by weight, unsaturated dicarboxylic acid imide monomer residue 30 to 60% by weight, unsaturated dicarboxylic acid anhydride residue 0.5 to 15% by weight, and vinyl monomer residue 0 other than these The flame-retardant resin composition according to any one of (1) to (3), wherein the flame-retardant resin composition is an imidized copolymer composed of 40 to 40% by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The (A) polycarbonate resin in the present invention is
It can be produced by reacting a dihydric phenol with phosgene or a carbonic acid diester. Examples of the dihydric phenol include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane and bis (4
-Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and the like, or nuclear alkylated derivatives thereof are preferred, but bisphenols are preferred, and 2,2-bis is particularly preferred. It is (4-hydroxyphenyl) propane. It may be a homopolymer of these dihydric phenols, a copolymer of two or more kinds, or a blended product thereof. If necessary, a branching agent (usually a polyfunctional aromatic compound) and a randomly branched polycarbonate obtained by reacting a dihydric phenol with phosgene or a carbonic acid diester are also included. These polyfunctional aromatic compounds contain at least three functional groups such as carboxy, hydroxy, carboxylic acid anhydrides, haloformyl and combinations thereof. Specific examples of the branching agent include trimellitic anhydride, trimellitic acid, 4-chloroformylphthalic anhydride, pyromellitic acid, phloroglucin, gallic acid, propyl gallate, mellitic acid, trimesic acid and benzophenone tetracarboxylic acid. Is mentioned.

The (B) graft copolymer in the present invention means an elastomer 100 having a glass transition temperature of 10 ° C. or lower.
In the presence of parts by weight, a monomer 5 comprising at least one kind of aromatic vinyl monomer, (meth) acrylic acid ester monomer, vinyl cyanide monomer, unsaturated dicarboxylic acid imide monomer, etc. It can be obtained by (co) polymerizing 2000 parts by weight. Further, an elastomer 100 having an epoxy group, an amino group, an acid anhydride group or the like and having a glass transition temperature of 10 ° C. or lower.
An amino group that reacts with parts by weight and the functional group, a ureido group,
At least one of an aromatic vinyl compound having a functional group such as an isocyanate group, a carboxyl group, an acid anhydride group, a hydroxyl group, a mercapto group, and an oxazoline group, a (meth) acrylic acid ester, a vinyl cyanide compound, and a maleimide compound. It can also be obtained by subjecting the contained (co) polymer to an extrusion reaction with 10 to 2000 parts by weight.

As the elastomer having a glass transition temperature of 10 ° C. or lower, for example, polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, hydrogenated butadiene-styrene block copolymer,
Butadiene rubber such as butadiene-acrylonitrile copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, isobutylene-isoprene copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer Examples thereof include polymers, polyurethane rubbers, polyamide rubbers, silicone rubbers and the like. Further, a composite rubber composed of silicone rubber and acrylic rubber or a composite rubber composed of butadiene rubber and acrylic rubber can be used. In the present invention, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber and the like are preferably used.

Examples of the aromatic vinyl monomer that can be used in the (B) graft copolymer of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, sodium styrenesulfonate and the like. Preferably, styrene, α-
It is methylstyrene. Examples of the (meth) acrylic acid ester monomer include methyl acrylate, ethyl acrylate,
Examples thereof include butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like, and preferably methyl methacrylate and the like are used. Vinyl cyanide monomers include acrylonitrile, methacrylonitrile, fumaronitrile,
α-Chloroacrylonitrile and the like can be mentioned, and acrylonitrile is preferably used. Examples of the unsaturated dicarboxylic acid imide monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N- (4-hydroxyphenyl). ) Maleimide, N- (alkyl-substituted phenyl) maleimide and the like can be mentioned, with preference given to N-phenylmaleimide and maleimide.

The proportion of the elastomer having a glass transition temperature of 10 ° C. or less in the graft copolymer is preferably in the range of 5 to 95% by weight, more preferably 10 to 95% by weight.
It is in the range of 90% by weight. If the proportion of the rubbery polymer is less than 5% by weight, the impact resistance is not sufficient, and if it exceeds 95% by weight, the graft ratio, the surface gloss of the resin, the moldability and the flame retardancy are lowered. The graft ratio of the graft copolymer is preferably 5 to 150% by weight, more preferably 10 to 120.
% By weight. When the graft ratio is less than 5% by weight, sufficient impact resistance cannot be obtained, and when it exceeds 150% by weight, dripping tends to occur during combustion.

It is also possible to use a core / shell type copolymer as the (B) graft copolymer. In this case, the core includes the above rubbery polymers such as polybutadiene, polyisoprene, acrylic rubber, and composite rubber composed of silicone rubber and acrylic rubber. The shell component preferably comprises a copolymer obtained from a mixture of the aromatic vinyl monomer and the (meth) acrylic acid ester monomer, a polymer obtained from only the (meth) acrylic acid ester, etc., but is required. Then vinyl acrylate,
Vinyl methacrylate, butylene diacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, divinylbenzene,
A crosslinkable monomer such as trivinylbenzene may be further used in combination, but is not limited thereto.

Specific examples of the graft copolymer which is particularly preferable in the present invention include the ABS graft copolymer, A
ES graft copolymer, AAS graft copolymer, MB
Examples thereof include a core / shell type copolymer of S, a copolymer having a composite rubber composed of silicone and acrylic rubber as a core and polymethylmethacrylate as a shell.

The method for producing the graft copolymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and reaction in an extruder can be used. In the case of emulsion polymerization, although there is an advantage that the rubber particle size can be easily controlled, impurities such as sodium, potassium, magnesium and calcium tend to remain, but it is desirable that these impurities be small.

As the other thermoplastic resin (C) in the present invention, a copolymer obtained by copolymerizing a monomer containing an aromatic vinyl monomer as an essential component, polyester, polyarylate, polyamide, polyphenylene. Examples thereof include oxides. The ratio of the monomers of the copolymer obtained by copolymerizing a monomer having an aromatic vinyl monomer as an essential component is as follows: aromatic vinyl compound / vinyl cyanide monomer, (meth) acrylic acid ester At least one monomer selected from monomers, unsaturated dicarboxylic acid imide monomers, unsaturated (di) carboxylic acid (anhydride) monomers, unsaturated carboxylic acid amide monomers, etc. = 10 / 90-99 / 1 (weight ratio), preferably 1
It is in the range of 5/85 to 95/5 (weight ratio). Incidentally, these aromatic vinyl monomers, vinyl cyanide monomers,
The (meth) acrylic acid ester monomer and the unsaturated dicarboxylic acid imide monomer may be those exemplified in the (B) graft copolymer, and as the unsaturated (di) carboxylic acid (anhydride) monomer. Examples of the unsaturated carboxylic acid amide include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, maleic acid, itaconic anhydride, citraconic anhydride, aconitic anhydride, monomethyl itaconic acid and monomethyl fumarate. Examples of the monomer include acrylic acid amide, methacrylic acid amide, dimethyl acrylamide, and diethyl acrylamide. Of these, maleic anhydride and methacrylic acid amide are preferable. Any of these monomers may be used alone or in combination of two or more. The method for producing these copolymers is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used.

Examples of polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polycyclohexane dimethylene terephthalate.
As polyarylate, bisphenol A or 4,4 '
-Aromatic polyesters synthesized from bisphenols such as dihydroxy-diphenyl ether and dibasic acids such as isophthalic acid and terephthalic acid or derivatives thereof, p-hydroxybenzoic acid / bisphenol / terephthalic acid, p-
Hydroxybenzoic acid / 6-hydroxy-2-naphthalenecarboxylic acid / terephthalic acid, p-hydroxybenzoic acid /
Examples of the liquid crystalline polyester such as polybutylene terephthalate.

As the polyamide, 6-nylon, 6,
Aliphatic nylons such as 6-nylon, 4,6-nylon and 10-nylon and metaxylylenediamine / adipic acid, polyphthalamide, hexamethylenediamine / terephthalic acid / caprolactam, hexamethylenediamine /
Aromatic nylons such as terephthalic acid / isophthalic acid, hexamethylenediamine / terephthalic acid / adipic acid and the like can be mentioned.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene) ether,
Examples thereof include a 2,6-dimethyl-1,4-phenyl / 2,3,6-trimethyl-1,4-phenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to the former two.

Specific examples of preferred (C) other thermoplastic resins include α-methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate copolymers, and styrene / N-. Phenylmaleimide copolymer, styrene /
N-phenylmaleimide / acrylonitrile copolymer,
Styrene / N-phenylmaleimide / maleic anhydride copolymer, polyethylene terephthalate, polybutylene terephthalate, polyarylate consisting of bisphenol A / phthalic acid, poly (2,6-dimethyl-1,4-phenylene) ether, metaxylenediamine / A polyamide of adipic acid may be mentioned.

Particularly preferable other thermoplastic resin (C) is 0 to 40% by weight of a rubbery polymer, 29.5 to 69.5% by weight of an aromatic vinyl monomer residue, and an unsaturated dicarboxylic acid imide unit. It is an imidized copolymer comprising 30 to 60% by weight of a monomer residue, 0.5 to 15% by weight of an unsaturated dicarboxylic acid anhydride residue, and 0 to 40% by weight of the remaining vinyl monomer. Examples of vinyl monomers other than these include the above-mentioned vinyl cyanide monomers, (meth) acrylic acid ester monomers, unsaturated carboxylic acid amide monomers, and the like. In a particularly preferred imidized copolymer, the proportion of aromatic vinyl monomer residues is less than 29.5% by weight or 69.
Exceeding 5% by weight, rubber polymer ratio is 40% by weight
Or the proportion of vinyl monomers other than these exceeds 40% by weight, the compatibility with the (A) polycarbonate resin and (B) graft copolymer is impaired.
A disadvantage is that the molded product is liable to have a poor appearance such as delamination.

The proportion of unsaturated dicarboxylic acid anhydride residues is
If it is less than 0.5% by weight, the effect of suppressing the initial coloration becomes poor, while if it exceeds 15% by weight, the stability of the imidized copolymer itself is lowered, and therefore the effect of improving discoloration to light and heat is improved. Becomes insufficient. If the proportion of unsaturated dicarboxylic acid imide monomer residues is less than 30% by weight or exceeds 60% by weight, the proportion of unsaturated dicarboxylic acid anhydride residues is 0.5 to 15% by weight. Even if it is in the range of (4), the compatibility with the (A) polycarbonate resin and (B) graft copolymer is insufficient, and the thermal stability of the imidized copolymer itself is insufficient. The improvement effect of is reduced.

The imidized copolymer can be produced by the first production method in the presence of a rubbery polymer, if necessary, in the presence of an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide monomer or an unsaturated dicarboxylic acid anhydride. And a method for copolymerizing a vinyl monomer mixture copolymerizable therewith with an aromatic vinyl monomer in the presence of a rubbery polymer as the second production method, if necessary.
A polymer obtained by copolymerizing an unsaturated dicarboxylic acid anhydride and a vinyl monomer mixture copolymerizable therewith with ammonia and / or a primary amine is reacted to give an acid anhydride group of 40
A method of converting about 99 mol% to an imide group,
An imidized copolymer can be obtained by any method.

The temperature of the imidization reaction is about 80 to 350 ° C.
And preferably 100 to 300 ° C. If the temperature is lower than 80 ° C., the reaction rate is low and the reaction requires a long time, which is not practical. On the other hand, if the temperature exceeds 350 ° C., the physical properties are deteriorated due to thermal decomposition of the polymer. The amount of acid anhydride residue is adjusted by the molar equivalent of ammonia and / or primary amine added to the acid anhydride group.

As the solvent for imidization in a solution state, there are acetone, methyl ethyl ketone, isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide and the like, and among them, methyl ethyl ketone and methyl isobutyl ketone are preferable. As the non-aqueous medium for imidization in suspension in a non-aqueous medium, heptane, hexane, pentane, octane, 2-
Examples of the rubber-like polymer used if necessary for the (A) imidized copolymer include aliphatic hydrocarbons such as methylpentane and cyclohexane, for example, polybutadiene,
Butadiene-styrene copolymer, butadiene-styrene block copolymer, butadiene-acrylonitrile copolymer, polyisoprene, isoprene-styrene copolymer, isobutylene-isoprene copolymer, hydrogenated butadiene-styrene block copolymer, hydrogen Examples thereof include a butadiene rubber such as an added isoprene-styrene block copolymer, an acrylic rubber, an ethylene-propylene (diene component) copolymer, and the like.

In the present invention, the blending ratio of (A) polycarbonate resin, (B) graft copolymer and (C) other thermoplastic resin is such that (A) component: (B) component: (C) component = 1 to 99: 1 to 5: 0 to 98% by weight, preferably
3 to 97: 2 to 40: 0 to 95% by weight, particularly preferably 5 to 95: 3 to 30: 0 to 90% by weight.
If the compounding ratio of the (A) polycarbonate resin is less than 1% by weight, the flame retardancy and impact resistance will deteriorate, while if it exceeds 99% by weight, the moldability will decrease and the impact strength will depend on the thickness. The disadvantage is that the property becomes too large. If the blending ratio of the (B) graft copolymer is less than 1% by weight, the impact strength is insufficient, and conversely, if it exceeds 50% by weight, the disadvantages of lowering the flame retardancy and heat resistance become remarkable. The moldability tends to be improved as the blending ratio of the other thermoplastic resin (C) increases, but if it exceeds 98% by weight, the impact strength decreases.

In the present invention, if necessary, (A) a polycarbonate resin, (B) a graft copolymer and (C) another thermoplastic resin, as long as they do not impair physical properties such as flame retardancy and impact resistance. It is also possible to contain a thermoplastic resin other than. To illustrate the representative ones among them, (denaturation)
Examples thereof include polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polymethylpentene, polyphenylene sulfide, polyacetal, polyetheresteramide, polyetherimide, polyetheretherketone, and polymethylmethacrylate. These resins can be used in combination of two or more kinds.

The phosphorus compound (D) used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, and phosphoric acid ester, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid. Examples thereof include diethyl, phosphazene compounds, red phosphorus and the like. An organic phosphorus compound represented by the general formula (I) is preferably used.

Embedded image (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an organic group, except when R ₁ = R ₂ = R ₃ = H. X represents a divalent or higher valent organic group. , Y is an oxygen source or a sulfur atom, Z is an alkoxy group or a mercapto group, p is 0 or 1, q is an integer of 1 to 30, r is an integer of 0 or more, and n is 1. In the above formula, examples of the organic group include an alkyl group which may be substituted or not, a cycloalkyl group, an aryl group and the like. When it is substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like, and a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or these substituents are oxygen. A group in which an atom, a sulfur atom, a nitrogen atom or the like is bonded and combined (eg, an arylsulfonylaryl group) may be used as a substituent.

The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups. Examples include alkylene groups, and preferably (substituted) phenylene groups, and those derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, bis (4-hydroxyphenyl) methane, 2,
2-bis (4-hydroxyphenyl) propane [bisphenol A], dihydroxydiphenyl, p, p′-dihydroxydiphenylsulfone, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis ( 4-hydroxyphenyl) ketone etc. are mentioned.

Examples of these phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate and tricresyl. Phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate,
Tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate xylenyldiphenylphosphate, diphenyl (2-
Ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2- Methacryloyloxyethyl acid phosphate, diphenyl-2-
Acryloyloxyethyl phosphate, diphenyl-
2-methacryloyloxyethyl phosphate and the like and condensates thereof, such as resorcinol bis (diphenyl phosphate resorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate). Examples thereof include bisphosphates such as hydroquinone bis (dixylenyl phosphate), biphenol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), and polyphosphate oligomers.

Further, a hydroxyl group-containing aromatic phosphoric acid ester containing one or more phenolic hydroxyl groups in triphenyl phosphate, tricresyl phosphate, condensed phosphoric acid ester thereof or the like can also be used as the phosphorus compound. . Examples of the hydroxyl group-containing aromatic phosphate ester include diphenyl resorcinol phosphate, phenyl diresorcinol phosphate, dicresyl resorcinol phosphate, and the like.

In the present invention, a phosphoric acid ester is preferably used as the organic phosphorus compound, and among them, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate and xyle are particularly preferable. Examples thereof include monophosphates such as nildiphenyl phosphate and di (isopropylphenyl) phenyl phosphate, and bisphosphates such as resorcinol bis (diphenyl phosphate) and bisphenol A bis (dicresyl phosphate). These phosphorus compounds may be used alone or in combination of two or more.

The amount of these phosphorus compounds blended is 1 to 50 parts by weight per 100 parts by weight of the resin component consisting of (A) polycarbonate resin, (B) graft copolymer, (C) other thermoplastic resin, It is preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight. If the amount is less than 1 part by weight, a sufficient flame retarding effect cannot be obtained, and if the amount is more than 50 parts by weight, the heat resistance and impact resistance of the resulting composition are remarkably lowered, and volatile components during molding are reduced. It causes harmful effects such as increase.

The (E) phenol resin used in the present invention is obtained by reacting phenols and aldehydes under an acidic or alkaline catalyst. As phenols,
Phenol, cresol, xylenol, ethylfunol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (hydroxyphenyl) pentane , Bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) butane, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl)
Examples include sulfide, dihydroxynaphthalene, bis (4-hydroxyphenyl) propane, and the like, and mixtures thereof.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal and the like. Further, an aromatic monoaldehyde having at least one phenolic hydroxyl group in one molecule can also be used. Examples of such aromatic monoaldehydes include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, β-resorcylaldehyde and vanillin.

Examples of the ketones include acetone and the like. These aldehydes and / or ketones may be used alone or in combination of two or more.

In the present invention, both a resol type resin and a novolac type phenolic resin can be used, but a novolac type phenolic resin is preferably used. The novolac-type phenol resin used in the present invention is obtained by reacting the above-mentioned phenols with the above-mentioned aldehydes and / or ketones under an acid catalyst by a known method. Further, in the present invention, a novolac type phenol resin obtained by substituting a part or all of the above aldehyde and / or ketone with dicyclopentadiene and reacting with the above phenol can also be used. Further, in the present invention, a novolac type phenol resin obtained by replacing a part or all of the aldehyde and / or ketone with an aralkyl halide and / or an aralkyl alcohol derivative and reacting with the phenol can be used.

Aralkyl halide and / or in the present invention
Alternatively, the aralkyl alcohol derivative has the general formula (II)

Embedded image In the formula, R is a compound which is a halogen atom such as chlorine or bromine, a hydroxyl group, or an alkoxy group, and the alkoxy group is preferably a lower alkoxy group having 4 or less carbon atoms. As the aralkyl halide preferably used, α, α '
-Dichloro-p-xylene, α, α'-dibromo-p-
Xylene, α, α′-diiodo-p-xylene, and the like, and aralkyl alcohol derivatives that are preferably used include α, α′-dihydroxy-p-xylene, α, α′-dimethoxy-p-xylene, α, α'-
Diethoxy-p-xylene, α, α′-dipropoxy-
p-xylene, α, α′-di-n-butoxy-p-xylene, αα′-di-sec-butoxy-p-xylene,
Examples include α, α′-di-isobutoxy-p-xylene. These phenol resins may be used alone or in combination of two or more.

The blending amount of these phenolic resins is
1 to 50 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 parts by weight based on 100 parts by weight of a resin component comprising (A) a polycarbonate resin, (B) a graft copolymer, and (C) another thermoplastic resin. ~ 30 parts by weight. If the amount is less than 1 part by weight, a sufficient dripping prevention effect cannot be obtained.
If the amount is more than the amount by weight, adverse effects such as a marked decrease in impact resistance of the obtained resin composition may occur.

In the present invention, the (F) light stabilizer for improving discoloration to light is an oxalic acid anilide type ultraviolet absorber,
A light stabilizer comprising at least one selected from bezotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid ultraviolet absorbers, cyanoacrylate ultraviolet absorbers and titanium oxide ultraviolet stabilizers. It is an agent.

Specific examples of preferable light stabilizers include 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid bisanilide, 2-ethoxy-2'-ethyl oxalic acid bisanilide, and 2;
-Ethoxy-4'-isodecylphenyl oxalic acid bisanilide and other oxalic acid anilide ultraviolet absorbers, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3 ', 5'-diamylphenyl)
Benzotriazole, 2- [2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-)
Benzotriazole-based UV absorbers such as tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobezophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-
Benzophenone-based UV absorbers such as carboxybenzophenone, salicylate-based UV absorbers such as phenyl salicylate, p-t-butylphenyl salicylate, p-octylphenyl salicylate, 2-ethylhexyl-2
-Cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, and other cyanoacrylate-based UV absorbers, rutile-type titanium oxide, anatase-type titanium oxide, alumina, silica, and silane coupling Examples thereof include titanium oxide-based UV stabilizers such as titanium oxide treated with a surface treatment agent such as an agent or a titanium-based coupling agent.

These light stabilizers may be used alone or, of course, may be used in combination. If you need more,
Other light stabilizers, for example, hindered amine stabilizers, external light stabilizers, nickel ultraviolet stabilizers, and pigments such as zinc oxide can be used in combination. However, when other light stabilizers and the like are used in combination, it is desirable to use them in such a ratio that the addition amount is not more than twice the addition amount of the light stabilizer which is the component (F) in the present invention. When the amount of the other light stabilizer exceeds twice the amount of the light stabilizer which is the component (F) in the present invention, the flame retardancy, impact strength and the like are markedly reduced.

(F) The amount of the light stabilizer added is from (A) to
0.0 with respect to 100 parts by weight of the resin component composed of (C)
1 to 15 parts by weight, preferably 0.02 to 12 parts by weight,
Particularly preferably, it is 0.03 to 10 parts by weight. (F)
If the added amount of the light stabilizer is less than 0.01 parts by weight, the effect of improving the discoloration property to light is poor, and if it exceeds 15 parts by weight, mechanical properties such as heat resistance and impact strength are lowered, or in some cases, The tendency that flame retardancy is lowered becomes remarkable.

In the present invention, the heat stabilizer (G) for improving discoloration to heat includes a phenol-based antioxidant and / or a sulfur-based antioxidant, and a phosphite- and / or phosphonite-based phosphorus-based antioxidant. It is a heat stabilizer composed of an antioxidant.

As the phenolic antioxidant, 2,6
-Di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Monophenolic antioxidants such as propionate, 2,2'-methylene-bis (4
-Methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4, 4'-butylidene-bis (3-methyl-6-t-butylphenol), 3,9- [1,1
-Dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5]
Undecane and other bisphenol antioxidants, 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol Ester, 1,3,5-
Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H,
Polymeric phenolic antioxidants such as 3H, 5H) trione and tocopherols can be mentioned.

As the sulfur type antioxidant, ditridecyl-3,3'-thiodipropionate, dilauryl-3,
3'-thiodipropionate, ditetradecyl-3,
3'-thiodipropionate, distearyl-3,3 '
-Thiodipropionate, dioctyl-3,3'-thiodipropionate and the like. The phosphite is represented by the general formula (III),

Embedded image (In the formula, R ¹ , R ² and R ³ independently have 1 to 2 carbon atoms.
5 represents a hydrocarbon group. ) Or the general formula (IV)

Embedded image (In the formula, R ⁴ and R ⁶ each independently represent a hydrocarbon group having 1 to 25 carbon atoms.) Specifically, trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite Fight, tributoxyethyl phosphite, trioctyl phosphite, tridecyl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, tris (isopropylphenyl) Phosphite, trisnonylphenylphosphite, tris (o-phenylphenyl) phosphite, tris (p-
Phenylphenyl) phosphite, trinaphthylphosphite, cresyldiphenylphosphite, xylenyldiphenylphosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenylphosphite, o-phenylphenyldicresylphosphite, dibutylphosphite Fight, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphite and their condensates, bis (tridecyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (noni Ruphenyl) pentaerythritol diphosphite, bis (di-t-butylphenyl)
Pentaerythritol diphosphite, bis (di-t-
Examples include butyl-4-methylphenyl) pentaerythritol diphosphite, bis (octadecyl) pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, and the like. Preferably, trioctyl phosphite, tridecyl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (octadecyl pentaerythritol diphosphite, bis (di -T-butylphenyl) pentaerythritol diphosphite, bis (di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and the like.

Phosphonite is represented by the general formula (V),

Embedded image (In the formula, R ¹ , R ² and R ³ independently have 1 to 2 carbon atoms.
5 represents a hydrocarbon group. R ³ may be a divalent or trivalent hydrocarbon group having 1 to 25 carbon atoms. ) Specific examples include diphenyl phenyl phosphonite, dinonyl phenyl octyl phosphonite, tetrakis (2,4
-Di-t-butylphenyl) 1,4-phenylene-di-
Phosphonite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphonite, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene and the like can be mentioned. To be

In the heat stabilizer (G) of the present invention,
The ratio of the phenol-based antioxidant and / or the sulfur-based antioxidant to the phosphite- and / or phosphonite-based phosphorus antioxidant is 10/90 to 90/10 by weight, and preferably 20 / 80 to 80/20 weight ratio, particularly preferably 30/70 to 70/30 weight ratio.
When the ratio is less than 10/90, the initial coloring during molding is small, but the effect of preventing discoloration when left at high temperature becomes poor. On the other hand, if the ratio exceeds 90/10, the initial coloring during molding tends to deteriorate.

The amount of the heat stabilizer (G) of the present invention added is
0.001 to 5 parts by weight, preferably 0.003 to 100 parts by weight of the resin component consisting of (A) to (C).
4 parts by weight, particularly preferably 0.005 to 3 parts by weight. (G) If the addition amount of the heat stabilizer is less than 0.001 part by weight, the effect of improving the discoloration property against heat is poor, and if it exceeds 5 parts by weight, mechanical properties such as heat resistance and impact strength are deteriorated. Depending on the situation, the tendency of the flame retardancy to decrease becomes remarkable.

The flame-retardant resin composition of the present invention does not use a compound containing bromine or chlorine as a flame-retardant component,
Although it exhibits an excellent flame retardant effect, a commonly used known flame retardant additive may be used in combination. The flame retardant additive is not particularly limited as long as it usually has a flame retardant effect, chlorine or bromine-containing compounds, antimony compounds, nitrogen-containing compounds, boron compounds, silicone compounds,
Flame retardant additives such as heat-expandable graphite, metal oxides, metal hydroxides, alkali (earth) metal salts, fluororesins, and sulfonic acid compounds can be used. These flame retardant additives may be used alone or in combination of two or more.

There is no particular limitation on the method of mixing the resin and the flame retardant, and any means can be adopted as long as it can uniformly mix them. For example, mixing, kneading, and the like using various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted.

At this time, if necessary, various fillers, additives and the like can be blended in amounts such that the effects are exhibited within a range that does not impair flame retardancy. Examples thereof include glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate whisker fibers, metal fibers, ceramic fibers, fibrous fillers such as boron whisker fibers, mica, silica, talc, clay, calcium carbonate, Glass beads,
Examples thereof include fillers such as glass balloons and glass flakes, and additives such as mold release agents, lubricants, plasticizers, antioxidants, heat stabilizers, antioxidants, and dye (face) agents. Further, an impact strength improver for improving the properties of the polymer blend, a compatibilizing component and the like can be added.

[0050]

The following examples are provided to further illustrate the present invention, but these examples are not intended to limit the invention in any way. Examples 1 to 24, Comparative Examples 1 to 8 With the formulations shown in Tables 1 to 3, mixed and stirred with a Henschel mixer, using a vented 30 mm φ twin-screw extruder (PCM-30, manufactured by Ikegai Tekko KK), 220 The mixture was melt-kneaded and extruded at 280 ° C, and pelletized by a pelletizer. After sufficiently drying the pellets thus obtained, a test piece was prepared by injection molding and evaluated and measured by the following methods. (1) Heat distortion temperature: Measured under a load of 18.6 kg / cm ² according to ASTM D648. (2) Izod impact strength: measured according to ASTM D256 using a notched test piece at 23 ° C. with a thickness of 1/8 inch. (3) Flame retardancy: Based on the UL-94 test method, the test piece having a thickness of 1/16 inch was used for evaluation. (4) Color difference measurement: Minolta color difference meter CR
-200b is used, JIS K7
In accordance with 105, the color difference ΔE was measured. The smaller the ΔE, the less the coloring is, which is preferable. Initial Coloring: The UL-94 test piece immediately after molding was wrapped with aluminum foil and stored. Photochromic property: UL-94 test piece was ATLAS
UVCONUV-1 type UV-600 was used to measure ΔE after irradiation for 48 hours at a set temperature of 20 ° C. Thermochromic property: The UL-94 test piece was subjected to heat treatment at 120 ° C. for 48 hours in a blow dryer to measure ΔE. The results are also shown in Tables 1 to 3.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

The resins, phosphorus compounds, phenolic resins, light stabilizers and heat stabilizers used in Tables 1 to 3 are as follows. (A) Polycarbonate resin PC resin Panlite K-1300W manufactured by Teijin Chemicals (B) Graft copolymer Graft copolymer (1): polybutadiene latex 8
Powder obtained by precipitating, washing with water, filtering, and drying a latex obtained by graft-copolymerizing 0 part (average particle size 320 μm, solid content concentration 50%) with 18 parts of acrylonitrile and 42 parts of styrene. Copolymer (2): Polymethylmethacrylate 15 in 85 parts of silicone / acrylic composite rubber as core
Copolymer Having Shell Structure of Part (C) Other Thermoplastic Resin Thermoplastic Resin (1): Acrylonitrile / Styrene (2
(8/72 ratio) Copolymer obtained by suspension polymerization of the mixture Thermoplastic resin (2): 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer and the system was replaced with nitrogen gas After that, the temperature was raised to 85 ° C., and a solution of 40 parts of maleic anhydride and 0.15 parts of benzoyl peroxide dissolved in 250 parts of methyl ethyl ketone was continuously added over 8 hours. After the addition, the temperature was maintained at 85 ° C for an additional 3 hours. 0.90 molar equivalents of aniline and 0.3 parts of triethylamine were added to the obtained copolymer solution with respect to maleic anhydride, and the mixture was reacted at 140 ° C. for 7 hours, cooled to room temperature, and vigorously stirred. Was poured into 1500 parts of methanol, precipitated, filtered, and dried to obtain an imidized copolymer. (D) Phosphorus compound Triphenyl phosphate (TPP) (E) Phenol resin (E) Phenol resin (1): Phenol novolac resin Softening point 92 ° C Phenol resin (2): Phenol aralkyl resin, p-xylene modified Novolak resin Weight average molecular weight 1700 (F) Light stabilizer Light stabilizer (1): anilide oxalic acid ultraviolet absorber (2-ethoxy-2-ethylbisanilide oxalate) Light stabilizer (2): benzotriazole ultraviolet absorber [ 2- (2'-hydroxy-5'-methylphenyl) benzotriazole] Light stabilizer (3): benzophenone-based ultraviolet absorber (2-
Hydroxy 4-methoxybenzophenone) Light stabilizer (4): Salicylic acid-based UV absorber (pt-)
Butylphenyl salicylate) Light stabilizer (5): Cyanurate ultraviolet absorber (ethyl-2-cyano-3,3-diphenyl acrylate) Light stabilizer (6): Titanium oxide ultraviolet stabilizer (Taika JR- 405) Light stabilizer (7): hindered amine ultraviolet stabilizer [bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate] Light stabilizer (8): Zinc oxide pigment (average particle size 0.4 μm
Zinc white) (G) Thermal stabilizer Thermal stabilizer (1): Phenolic antioxidant {tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-
4'-Hydroxyphenyl) propionate] methane} thermal stabilizer (2): sulfur-based antioxidant (dilauryl thiodipropionate) thermal stabilizer (3): phosphite [cyclic neopentanetetraylbis (2,4) -Di-t-butylphenyl) phosphite] heat stabilizer (4): phosphonai [tetrakis (2,4-
Di-t-butylphenyl) 4,4'-biphenylylene-
Di-phosphonite] Other additives Sulfonic acid compound: Dodecylbenzenesulfonic acid

[0055]

EFFECTS OF THE INVENTION According to the present invention, (1) a resin composition containing a polycarbonate resin, a graft copolymer, a phosphorus compound and a phenol resin as essential components, and if necessary, other thermoplastic resin, By adding a specific light stabilizer, the discolorability to light can be improved. (2) By adding a heat stabilizer composed of a specific antioxidant and a specific phosphorus-based antioxidant, the discolorability with respect to heat can be improved. (3) By using the light stabilizer of the present invention and the heat stabilizer in combination, the discolorability to light and heat can be improved at the same time. (4) Furthermore, by using an imidized copolymer as another thermoplastic resin, the discolorability to light and / or heat is further improved. (5) Since a resin composition having improved discoloration with respect to light and / or heat and excellent flame retardancy is provided, it is suitable for use in electronic / electrical products, OA equipment, and various parts materials. can do.

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Claims (4)

[Claims] 1. A component (A) is 1 to 99% by weight of a polycarbonate resin, a component (B) is 1 to 50% by weight of a graft copolymer, and a component (C) is 0 to 98% by weight of another thermoplastic resin. 1 to 50 parts by weight of the phosphorus compound as the component (D) with respect to 100 parts by weight of the resin component consisting of
As the component (E), 1 to 50 parts by weight of a phenol resin,
As the component (F), at least one selected from anilide oxalic acid ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid ultraviolet absorbers, cyanurate ultraviolet absorbers and titanium oxide ultraviolet stabilizers. A flame retardant resin composition comprising 0.01 to 15 parts by weight of a light stabilizer containing a seed. 2. (A), (B) according to claim 1,
In addition to the components (C), (D), and (E), as a component (G), an antioxidant of a phenol-based antioxidant and / or a sulfur-based antioxidant, a phosphite and / or a phosphonite Heat stabilizer consisting of phosphorus-based antioxidant 0.00
A flame-retardant resin composition containing 1 to 5 parts by weight. 3. (A), (B) according to claim 1,
In addition to the components (C), (D), (E), and (F),
As the component (G), an antioxidant such as a phenol-based antioxidant and / or a sulfur-based antioxidant, a phosphite and / or
Alternatively, a flame-retardant resin composition containing 0.001 to 5 parts by weight of a heat stabilizer composed of a phosphorus-based antioxidant of phosphonite. 4. The other thermoplastic resin as the component (C) comprises 0 to 40% by weight of a rubber-like polymer, and an aromatic vinyl monomer residue 2
9.5 to 69.5% by weight, unsaturated dicarboxylic acid imide monomer residue 30 to 60% by weight, unsaturated dicarboxylic acid anhydride residue 0.5 to 15% by weight, and vinyl monomer residue other than these The flame-retardant resin composition according to any one of claims 1 to 3, which is an imidized copolymer comprising 0 to 40% by weight of a group.