JPH0959502A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which is produced by formulating a metal-inactivating compound together with a phosphorus compound and a silicone to the resin to develop synergistic flame-retarding action and reveal excellent flame retardance with reduced use of the flame retarder, and is useful as electric and electronic products. SOLUTION: One hundred pts.wt. of a polymer blend of (A) 99-5wt.% of a polycarbonate resin and (B) 1-95wt.% of a resin other than polycarbonate contains (C) 1-40 pts.wt. of a phosphorus compound, (D) 0.01-5 pts.wt. of a silicone and/or a fluorine resin, or preferably 1-30 pts.wt. of a phenolic resin and (E) 0.001-5 pts.wt. of a metal inactivating agent. As a component (E), is preferably cited a thiazole of formula I such as 2-mercaptobenzothiazole, or a triazole of formula II or formula III such as l, 2, 3-benzotriazole.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition. More specifically, a flame-retardant resin composition obtained by blending a polymer blend containing a polycarbonate resin with a phosphorus compound, at least one selected from silicone, a fluorine resin, and a phenol resin, and a metal deactivator. It is about things.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, since it has a problem of high melt viscosity and poor moldability, polymer blends with thermoplastic resins other than polycarbonate resins such as styrene resins (acrylonitrile-butadiene-styrene (ABS) resins etc.) Many have been developed and widely used in the fields of automobiles, office automation equipment, electronics and electricity, etc. On the other hand, in recent years, there has been a strong demand for flame-retardant resin materials used mainly for applications such as office automation equipment and home electric appliances, and many flame-retardant resins have been developed and studied in order to meet these demands. Conventionally, chlorine- or bromine-containing compounds have been mainly used for flame-retarding polymer blends containing polycarbonate-based resins, and in many cases, antimony trioxide or the like is also used as a flame-retardant aid in addition to those flame-retardants. Has been done. However, when such a chlorine- or bromine-containing compound is used, the effect of flame retardancy is relatively large, but in the event of a fire or incineration process, a toxic or harmful substance is generated, so emergency activities or fire extinguishing It has problems such as making activities difficult or causing environmental pollution. Therefore, it is desired to develop a flame-retardant resin containing no chlorine or bromine-containing compound or containing a small amount of chlorine or bromine-containing compound. Therefore, a flame retarding method using a phosphorus compound as a flame retardant other than the chlorine- or bromine-containing compound has been proposed. However, in this case, in order to obtain sufficient flame retardancy, the blending amount becomes large,
The obtained flame-retardant resin has a problem that the mechanical properties, heat resistance, etc. are significantly reduced.

[0003]

The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition having excellent flame retardancy.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to improve the flame retardancy of a polymer blend containing a polycarbonate resin, surprisingly,
Phosphorus compounds and silicones, fluorinated resins as flame retardants,
The inventors have found that flame retardancy is dramatically improved by adding a metal deactivator to a polymer blend containing at least one selected from the group consisting of a phenolic resin and a phenol resin. That is, the present invention is: (1) A flame-retardant resin composition comprising the following components (A) to (E). (A) Polycarbonate-based resin (B) Resin other than polycarbonate-based resin (C) Phosphorus compound (D) At least one selected from silicone, fluorine-based resin, and phenol-based resin (E) Metal deactivator, 2) Polycarbonate resin 99 as component (A)
To 5 parts by weight and 100 parts by weight of a polymer blend consisting of 1 to 95% by weight of a resin other than a polycarbonate resin as the component (B), the phosphorus compound 1 as the component (C).
To 40 parts by weight, 0.01 to 5 parts by weight of silicone and / or fluororesin as the component (D), and 0.001 to 5 parts by weight of metal deactivator as the component (E). (1) Polycarbonate resin 99 as component (A)
1 to 40 parts by weight of the phosphorus compound as the component (C), relative to 100 parts by weight of the polymer blend consisting of 1 to 95% by weight of the resin other than the polycarbonate-based resin as the component (B) and 1 to 95% by weight of the component (B). 1 to 30 parts by weight of a phenolic resin as a component and 0.001 to 5 parts by weight of a metal deactivator as a component (E), the flame-retardant resin composition according to (1), (4) At least one selected from a thiazole compound, a triazole compound, an imidazole compound, a sulfur / nitrogen-containing compound, a phenol compound, a hydrotalcite compound, and an antimony compound in which the metal deactivator has a specific structure. (1)-
The flame-retardant resin composition according to any one of (3) is provided.

Hereinafter, the present invention will be described in detail. The polycarbonate resin (A) used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Typical examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and the like, and an alkyl group on its aromatic ring, The thing in which the aryl group etc. were substituted is mentioned.
A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane-based one, and more preferably one containing bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dimethyl carbonate,
The dihaloformates of dihydric phenols and mixtures thereof. In manufacturing polycarbonate resin,
One or more of these dihydric phenols can be used, and if necessary, an appropriate molecular weight modifier, a catalyst for accelerating the reaction and the like can be used. As the polycarbonate resin of the present invention, a branched polycarbonate resin obtained by copolymerizing a polyfunctional compound or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid having 8 or more carbon atoms may be used. it can. The polycarbonate-based resin thus obtained may be used alone or in combination of two or more. In the present invention, a halogen-free polycarbonate is preferably used.

The resin (B) other than the polycarbonate resin used in the present invention can be used without particular limitation as long as it is a thermoplastic resin. Representative examples of these include polyester resins (polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyarylate, liquid crystalline aromatic polyester, etc.), (modified) polyethylene, ( Modified polypropylene, (modified) ethylene / propylene copolymer resin, polyamide resin, polyphenylene sulfide, polyphenylene ether, polyacetal, polyetheresteramide, polyetherimide, polyetheretherketone, polymethylmethacrylate, styrene resin, etc. Can be mentioned. These resins can be used in combination of two or more kinds. Of these, styrene resins are preferably used. Hereinafter, the styrene resin will be described in detail.

The styrene resin preferably used in the present invention contains the following components (B-1) and (B-2). (B-1) A copolymer obtained by copolymerizing an aromatic vinyl compound and a vinyl compound copolymerizable with an aromatic vinyl compound (B-2) Obtained by grafting a vinyl compound onto a rubber-like polymer Graft Copolymer As the aromatic vinyl compound used for the copolymer (B-1) in the styrene resin, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, styrene sulfonic acid can be used. Examples thereof include sodium, and preferably styrene, α-methylstyrene and the like. As the vinyl compound copolymerizable with the aromatic vinyl compound, acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate,
(Meth) acrylic acid ester such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N
-Propylmaleimide, N-hexylmaleimide, N-
Cyclohexylmaleimide, N-phenylmaleimide,
Maleimide-based compounds such as N- (4-hydroxyphenyl) maleimide and N- (alkyl-substituted phenyl) maleimide, and unsaturated dicarboxylic acid anhydride-based compounds such as maleic anhydride, and the like, preferably acrylonitrile,
Methyl methacrylate, N-phenylmaleimide, maleic anhydride, etc. are used. The above aromatic vinyl compound,
Any of the vinyl compounds copolymerizable with the aromatic vinyl compound may be used alone or in combination of two or more kinds. The ratio of the aromatic vinyl compound (x ₁ ) used in the copolymer (B-1) in the styrene resin and the vinyl compound (x ₂ ) copolymerizable with the aromatic vinyl compound is (x ₁ ) + (x _{When (2} ) is 100% by weight, (x ₁ ) is preferably 10 to 95% by weight, (x ₂ ) is preferably 5 to 90% by weight, more preferably (x ₁ ) is 40 to 90% by weight, (X ₂ ) is 1
It is in the range of 0 to 60% by weight, particularly preferably (x ₁ )
Is in the range of 45 to 80% by weight, and (x ₂ ) is in the range of 20 to 55% by weight. Within the above range, impact resistance, heat resistance,
A flame-retardant resin composition having more excellent physical properties such as moldability can be obtained.

Copolymers preferably used as the copolymer (B-1) of the present invention are α-methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate copolymers. , Α-methylstyrene / acrylonitrile /
Methyl methacrylate copolymer, α-methylstyrene / N
-Phenylmaleimide copolymer, styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / acrylonitrile copolymer, α-methylstyrene / N-phenylmaleimide / acrylonitrile copolymer, styrene / N-phenylmaleimide / Maleic anhydride copolymer, α-methylstyrene / N-phenylmaleimide / maleic anhydride copolymer and the like, more preferably styrene / acrylonitrile copolymer, styrene / N.
-Phenylmaleimide / maleic anhydride copolymer, styrene / N-phenylmaleimide copolymer and the like. These polymers may be used alone or in combination of two or more.

The method for producing these polymers is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. Further, a copolymer obtained by selecting a vinyl compound containing a maleimide compound as a vinyl compound copolymerizable with an aromatic vinyl compound, such as a styrene / N-phenylmaleimide / maleic anhydride copolymer, is In the first step, maleic anhydride in an amount corresponding to the maleimide compound is copolymerized in place of the maleimide compound, and in the second step, a part or most of the maleic anhydride residue in the polymer is converted into the desired maleimide compound. It can also be produced by imidization with an amino compound such as aniline or an aniline derivative corresponding to the compound structure.

According to the present invention, a resin composition having excellent flame retardancy can be obtained, but when it is desired to obtain a flame retardant resin composition having an excellent balance of physical properties, which also imparts good heat resistance. In particular, it is particularly preferable that the styrene resin contains the copolymer (B-1) obtained by selecting a maleimide compound as the vinyl compound copolymerizable with the aromatic vinyl compound. By incorporating the copolymer (B-1) having a maleimide compound as a monomer unit structure, a resin composition having excellent flame retardancy and heat resistance and a good balance of physical properties can be obtained.

The rubber-like polymer used for the graft copolymer (B-2) in the styrene resin is a rubber-like polymer having a glass transition temperature of 10 ° C. or lower.
Butadiene rubber such as polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, hydrogenated butadiene-styrene block copolymer, butadiene-acrylonitrile copolymer, acrylic rubber, ethylene-propylene (diene component) ) Copolymer,
Examples thereof include isobutylene-isoprene copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, polyurethane rubber, polyamide rubber, and silicone rubber. 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, preferably polybutadiene,
Butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber and the like are used.

As the vinyl compound used in the graft copolymer (B-2), an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester, a maleimide compound, an unsaturated dicarboxylic acid anhydride compound, etc. Is mentioned. As the aromatic vinyl compound, styrene,
Examples thereof include α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, sodium styrenesulfonate, and the like, and styrene and α-methylstyrene are preferably used. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferably used. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, and preferably methyl methacrylate and the like are used.

As the maleimide compound, maleimide,
N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-
Examples thereof include (4-hydroxyphenyl) maleimide and N- (alkyl-substituted phenyl) maleimide, and N-phenylmaleimide is preferably used.

Examples of unsaturated dicarboxylic acid anhydride compounds include maleic anhydride. The above vinyl compounds may be used alone or in combination of two or more. Of these, a mixture of at least one selected from vinyl cyanide compounds, (meth) acrylic acid esters, maleimide compounds and unsaturated dicarboxylic acid anhydride compounds, and aromatic vinyl compounds is preferably used. Specifically,
Examples thereof include a mixture of styrene and one selected from acrylonitrile, methyl methacrylate, N-phenylmaleimide, and maleic anhydride. Further, particularly preferably, a mixture of an aromatic vinyl compound and a vinyl cyanide compound is used, and specific examples thereof include a mixture of styrene and acrylonitrile.

It is also possible to use a core / shell type copolymer as the graft copolymer (B-2). 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 constituent material is preferably a copolymer obtained from a mixture of the aromatic vinyl compound and the (meth) acrylic acid ester or a polymer obtained from only the (meth) acrylic acid ester, but is not limited thereto. Not a thing.

The proportion of the rubbery polymer in the graft copolymer (B-2) is preferably 5 to 95% by weight, more preferably 10 to 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 proportion of the graft component in the graft copolymer (B-2) is preferably 5 to 95% by weight, more preferably 10 to 90.
% By weight.

The graft ratio of the graft copolymer (B-2) is preferably 5 to 150% by weight, more preferably 10%.
~ 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.

As the vinyl compound used in the graft copolymer (B-2), a vinyl cyanide compound, (meth)
When using a mixture of at least one selected from an acrylic ester, a maleimide compound and an unsaturated dicarboxylic anhydride compound and an aromatic vinyl compound,
The proportion of at least one kind (y ₂ ) selected from an aromatic vinyl compound (y ₁ ) and a vinyl cyanide compound, a (meth) acrylic acid ester, a maleimide compound and an unsaturated dicarboxylic acid anhydride compound is (y ₁ ) + (y ₂ ) is 100
(Y ₁ ) is 10 to 95% by weight, (y ₂ )
Is preferably in the range of 5 to 90% by weight, more preferably (y ₁ ) is 50 to 90% by weight and (y ₂ ) is 10 to 50% by weight.
And particularly preferably (y ₁ ) is in the range of 60 to 80% by weight and (y ₂ ) is in the range of 20 to 40% by weight. Within the above range, a flame-retardant resin composition having more excellent physical properties such as impact resistance, heat resistance, and moldability can be obtained.

The graft copolymer (B-2) of the present invention is 1
Only one kind may be used, or two or more kinds may be used in combination. The method for producing the graft copolymer (B-2) is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used.

Copolymer (B-
1), the content ratio of the graft copolymer (B-2) is 100 for the copolymer (B-1) + the graft copolymer (B-2).
When it is defined as weight%, it is preferably copolymer (B-1) / graft copolymer (B-2) = 5/95 to 95/5 (weight ratio), and more preferably 10/90 to 90 /. 10
(Weight ratio). Within the above range, a flame-retardant resin composition having a much better balance of physical properties such as flame retardancy, impact resistance and heat resistance can be obtained.

Further, as a typical composition preferable as the styrene-based resin of the present invention, a styrene / acrylonitrile copolymer and styrene / N- can be used as the copolymer (B-1).
At least one selected from phenylmaleimide / maleic anhydride copolymer and styrene / N-phenylmaleimide copolymer, and graft polymerization of a mixture of styrene and acrylonitrile onto polybutadiene as a graft copolymer (B-2). Examples thereof include a styrene resin containing a graft copolymer obtained.

In the present invention, the blending ratio of the polymer blend of the polycarbonate resin (A) and the resin (B) other than the polycarbonate resin is as follows: polycarbonate resin / resin other than polycarbonate resin = 99/1 to 5
/ 95 (weight ratio), preferably 95/5 to
10/90 (weight ratio) range, more preferably 90/1
It is in the range of 0 to 20/80. If the ratio of resins other than polycarbonate resin exceeds 95 weight ratio, impact resistance,
In some cases, properties such as heat resistance and flame retardancy may not be sufficiently obtained, and if it is less than 1 weight ratio, good workability and moldability may not be obtained.

The phosphorus compound used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, and inorganic phosphorus compounds such as red phosphorus and ammonium polyphosphate, triphenylphosphine oxide, tricresylphosphine oxide and methane. Examples thereof include organic phosphorus compounds such as diphenyl phosphonate, diethyl phenylphosphonate, phosphazene compounds, phosphoric acid esters, and phosphorous acid esters.

Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, 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 Mono-butyl 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, for example. Resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (dixylenyl phosphate), biphenol bis (Dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) , Bisphosphate and polyphosphate oligomers such as bisphenol A bis (dicresyl phosphate), and the like.

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.

Examples of the phosphite include trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tributoxyethylphosphite, trioleylphosphite, triphenylphosphite, tricresylphosphite. Fight, trixylenylphosphite, tris (isopropylphenyl) phosphite, trisnonylphenylphosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite, trinaphthylphosphite, cresyldiphenyl Phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenylphenyl dicresi Phosphite, dibutyl phosphite, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphites and condensates thereof and the like.

An organic phosphorus compound is preferably used as the phosphorus compound in the flame-retardant resin composition of the present invention, and among them, the organic compound represented by the general formula (VII) is particularly preferable.

[Chemical 7] (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 is a divalent or higher valent organic group. , Y is an oxygen atom 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, and r is r.
Is an integer of 0 or more, and n is 0 or 1. However, it is not limited to these. In the above formula, the organic group is, for example, an alkyl group which may or may not be substituted, 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. Further, the divalent or higher valent organic group, from the above organic groups,
It means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom. Examples include alkylene groups, and preferably (substituted) phenylene groups, 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'-dihydroxydiphenyl sulfone, dihydroxynaphthalene,
Examples thereof include bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and bis (4-hydroxyphenyl) ketone.

Among the organic phosphorus compounds represented by the general formula (VII), phosphoric acid esters are preferably used, and among them, triphenyl phosphate, tricresyl phosphate,
Monophosphates such as trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, di (isopropylphenyl) phenylphosphate, resorcinol bis (diphenylphosphate), bisphenol A bis (dicresylphosphate) Particularly preferred are bisphosphates such as). The phosphorus compound used in the flame-retardant resin composition of the present invention may be used alone or in combination of two or more. The blending amount of these phosphorus compounds is (A) component and (B)
It is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight, based on 100 parts by weight of the total of the components. 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 40 parts by weight, the heat resistance and impact resistance of the obtained composition are remarkably deteriorated, and volatile components during molding are reduced. It causes harmful effects such as increase.

In the present invention, at least one selected from the above (D) silicone, fluororesin, and phenolic resin is used in order to reduce or prevent dripping of molten resin at the time of combustion to enhance flame retardancy. Is added to the resin composition.

The silicone used in the present invention, in principle, has in its molecular structure

Embedded image There is no particular limitation as long as it has a skeleton. Examples of the silicone used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, amino-modified silicone, mercapto-modified silicone, and epoxy-modified silicone. These may be used alone or in combination of two or more. Furthermore, these silicones can be used in a wide range of molecular weights of several hundreds to several millions, and their forms are oily, varnish-like, gum-like,
It may be in any form such as resin. In the present invention, polydimethylsiloxane is preferably used.

The fluororesin used in the present invention is not particularly limited as long as it is a resin containing a fluorine atom. Examples of the fluorine-based resin used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene. Examples thereof include copolymers, polytrifluorochloroethylene, and polyvinylidene fluoride. You may use only 1 type of these,
Two or more kinds may be used in combination. The form of the fluororesin is emulsion, suspension, microfibril,
It may be in the form of powder, particles or the like. In the present invention, polytetrafluoroethylene is preferably used.

When silicone or a fluororesin is used in the present invention, the addition amount is 1 in total of the components (A) and (B).
It is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and particularly preferably 0.1 to 1 part by weight, relative to 00 parts by weight. If the amount of silicone or fluorine-based resin is 0.01 parts by weight or less, a sufficient anti-dripping effect cannot be obtained, and if it exceeds 5 parts by weight, the appearance of the molded product of the compounded resin composition may be poor and the melt viscosity may increase. A defective phenomenon may occur.

The phenolic resin used in the present invention is
It is obtained by reacting phenols and aldehydes under an acidic or alkaline catalyst. Examples of phenols include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, dihydroxydiphenyl, 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 ketones include acetone. 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 substituting a part or all of the above aldehyde and / or ketone with an aralkyl halide and / or aralkyl alcohol derivative and reacting with the above phenol can also be used. it can. The aralkyl halide and / or aralkyl alcohol derivative in the present invention has the general formula (IX)

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.) As the alkoxy group, a lower alkoxy group having 4 or less carbon atoms is preferable.
The aralkyl halide preferably used is α,
α'-dichloro-p-xylene, α, α'-dibromo-
P-xylene, α, α′-diiodo-p-xylene and the like can be mentioned, and preferable aralkyl alcohol derivatives are α, α′-dihydroxy-p-xylene and α, α′-dimethoxy-p-. Xylene, α, α '
-Diethoxy-p-xylene, α, α'-dipropoxy-p-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-sec-butoxy-p-xylene, α, Examples include α'-di-isobutoxy-p-xylene.

When the phenolic resin is used in the present invention, the addition amount thereof is in the range of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). is there. When the amount of the phenolic resin is less than 1 part by weight, the anti-dripping effect is not sufficiently obtained and the flame retardancy is poor, and when the amount exceeds 30 parts by weight, the light resistance and impact resistance of the obtained resin composition are remarkable. There may be a problem such as deterioration.

In the present invention, silicone, fluorine resin,
And the phenolic resin both effectively act to reduce or prevent the dropping of the resin at the time of combustion, but especially when it is desired to obtain a flame-retardant resin composition having excellent light resistance, a fluororesin and It is preferable to use silicone and / or silicone.

Metal deactivator (E) used in the present invention
Means an organic compound having a functional group having a property of interacting with a metal ion and / or a metal atom, and the functional group having a property of interacting with a metal ion and / or a metal atom includes a carboxylic acid group and a sulfonic acid group. Group, amino group, phenolic hydroxyl group, alcoholic hydroxyl group, phosphino group,
Examples thereof include an amide group, an ester group, a mercapto group and a thiocarbamate group. Also included are organic compounds having the property of acting with metal ions and / or metal atoms to form metal complex compounds and / or metal salts, such as glycine,
Compounds capable of forming metal chelates such as oxalic acid, ethylenediaminetetraacetic acid and acetylacetone, compounds serving as ligands having a cyclic structure such as crown ether, porphyrin and phthalocyanine, triazole derivatives, thiazole derivatives and imidazoles. Examples thereof include compounds having a nitrogen atom and / or a sulfur atom such as derivatives.

Furthermore, an inorganic compound which deactivates a metal ion and / or a metal atom by adsorbing a metal ion and / or a metal atom, or by ion-exchanging a metal ion, also deactivates the metal deactivating compound of the present invention. Included in the agent. Such inorganic compounds include hydrotalcite compounds, acid clay, dolomite, zeolites, antimony compounds such as antimony pentoxide and diantimony tetroxide, zirconium compounds, tin compounds, bismuth compounds,
Examples thereof include titanium compounds and aluminum compounds.

The metal deactivator preferably used in the present invention is represented by the general formula (I)

Embedded image Compounds having general formula (II) or (III)

Embedded image

[Chemical 12] A triazole-based compound having the general formula (IV)

Embedded image Imidazole compounds having the general formula (V)

Embedded image Sulfur / nitrogen containing compounds having the general formula (VI)

Embedded image Examples thereof include phenol compounds, hydrotalcite compounds, and antimony compounds.

Specific examples of these metal deactivators include thiazole-based compounds such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexylbenzothiazole sulfenamide and N-oxydiethylenebenzothiazole sulfenamide. Compound or
1,2,3-benzotriazole, methylbenzotriazole, 2- (2-hydroxy-5-methylphenyl)
Triazole compounds such as benzotriazole, 2-
Imidazole compounds such as mercaptobenzimidazole, diphenylthiocarbazone, tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Sulfur / nitrogen-containing compounds such as tetramethylthiuram monosulfide, phenolic compounds such as salicylic acid, phenyl salicylate, methyl salicylate, salicylamide, salicylanilide, compounds represented by the general formula (X),

Embedded image Furthermore, hydrotalcites (including those obtained by calcining hydrotalcite), antimony compounds such as antimony pentoxide, and the like can be mentioned.

Particularly preferred among the metal deactivators of the present invention are 2-mercaptobenzothiazole, 1,2,3-
Benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-mercaptobenzimidazole, diphenylthiocarbazone, salicylic acid, phenyl salicylate, methyl salicylate, salicylamide, salicylanilide, represented by formula (X) Compound, hydrotalcite, antimony pentoxide and the like are used, more preferably methyl salicylate, phenyl salicylate and a compound represented by the formula (X) are used, and particularly preferably, a compound represented by the formula (X) Is used. These metal deactivators may be used alone or in combination of two or more.

The flame-retardant resin composition of the present invention is synergistically prepared by blending the metal deactivator with the resin together with at least one selected from the group consisting of a phosphorus compound and silicone, a fluororesin, and a phenolic resin. The flame retarding effect is obtained, and thus the amount of the flame retardant compounded can be smaller than in the conventional case, so that the deterioration of the physical properties of the resin resulting from the compounding of the flame retardant can be suppressed to the minimum.

The addition amount of the metal deactivator of the present invention is
The total amount of the components (A) and (B) is 100 parts by weight, preferably 0.001 to 5 parts by weight, particularly preferably 0.0.
It is in the range of 05 to 2 parts by weight, more preferably 0.01 to 1 part by weight. If the amount of the metal deactivator is less than 0.001 part by weight, the flame retardancy may be poor, and if it exceeds 5 parts by weight, mechanical properties such as impact resistance may be deteriorated.

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 has a flame retardant effect, chlorine or bromine-containing compounds, antimony compounds, nitrogen compounds, thermally expandable graphite, carboxylic acid metal salts, sulfonic acid metal salts, Flame retardant additives such as boric acid metal salt, metal oxide, metal hydroxide, ferrocene, guanamine resin, melamine resin and urea resin 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 the time of kneading, each component may be kneaded at once, or any component may be kneaded and then the remaining components may be added and kneaded. A preferable kneading method is a method using an extruder, and a twin-screw extruder is particularly preferable as the extruder.

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,
Fillers such as glass balloons and glass flakes, release agents, lubricants, plasticizers, dispersants, UV absorbers, light stabilizers,
Examples thereof include additives such as antioxidants, heat resistance stabilizers, antioxidants, and dyes (face). 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 18 below
And what was used for the compounding prescription of Comparative Examples 1-9 is shown. Polycarbonate resin: Teijin Chemicals Panlite K-
As a resin other than the polycarbonate-based resin, a styrene-based resin was used as a typical one. Copolymer (B-1) constituting the styrene resin, graft copolymer (B-
The following was used as 2). Copolymer of component (B-1): (b-1-1) Styrene / acrylonitrile (weight ratio 7
5/25) A copolymer obtained by emulsion polymerization of the mixture. Reduced viscosity (in methyl ethyl ketone, concentration 0.01 g / ml, 3
Measured at 0 ° C) is 0.55 dl / g. (B-1-2) A copolymer obtained by solution polymerization of styrene / N-phenylmaleimide / maleic anhydride (weight ratio 49 / 50.7 / 0.3). Reduced viscosity (measured in methyl ethyl ketone at a concentration of 0.01 g / ml at 30 ° C) of 0.34
dl / g. Component (B-2) Graft Copolymer: (b-2-1) Polybutadiene latex (average particle size: 50 parts by weight in terms of solid content) by a known emulsion polymerization method using a reactor equipped with a stirrer. 0.35 μm, gel content 9
(2%) in the presence of 37.5 parts by weight of styrene and 12.5 parts by weight of acrylonitrile, polymerization was carried out using cumene hydroperoxide as a polymerization initiator to complete the reaction. The obtained polymer latex is coagulated with calcium chloride, washed with water, filtered and dried to obtain the graft copolymer (b-
2-1) was obtained. Phosphorus compound (1): Triphenyl phosphate manufactured by Daihachi Chemical Co., Ltd. Phosphorus compound (2): Resorcinol bis (diphenyl phosphate) CR-733S manufactured by Daihachi Chemical Co., Ltd. Fluorine-based resin: Polytetrafluoroethylene manufactured by Mitsui DuPont Fluorochemical Ethylene Teflon 6J Silicone: Toray Dow Corning Silicone Polydimethylsiloxane SH-200 Oil (viscosity 30000cs) Metal deactivator (1): Wako Pure Chemical Industries, 1, 2, 3-
Benzotriazole metal deactivator (2): 2-mercaptobenzimidazole metal deactivator manufactured by Wako Pure Chemical Industries, Ltd. (3): 2-mercaptobenzothiazole metal deactivator manufactured by Wako Pure Chemical Industries (4) : Wako Pure Chemical Industries, Ltd. diphenylthiocarbazone metal deactivator (5): Wako Pure Chemical Industries, Ltd. salicylic acid metal deactivator (6): Wako Pure Chemical Industries, Ltd. phenyl salicylate metal deactivator ( 7): Methyl salicylate metal deactivator manufactured by Wako Pure Chemical Industries (8): Salicylamide metal deactivator manufactured by Wako Pure Chemical Industries (9): Salicylanilide metal deactivator manufactured by Wako Pure Chemical Industries, Ltd. (10): Adeka Stub manufactured by Asahi Denka Co., Ltd.
CDA-1 This structural formula is represented by the general formula (X).

Embedded image Examples 1 to 18 and Comparative Examples 1 to 9 After mixing the components shown in Table 1 and Table 2 in the proportions shown in Table 1 and Table 2 with a Henschel mixer, a 30 mmφ twin-screw extruder (made by Ikegai Tekko KK, PCM -30) is used and 250-
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 the flame retardancy of the resin composition was evaluated. The results are also shown in Tables 1 and 2. Flame retardancy is 12 by injection molding from the obtained pellets.
A 7 mm × 12.7 mm × 1.6 mm combustion test piece was prepared and measured according to Subject 94 (UL94) vertical combustion test of Underwriters Laboratory, Inc., USA.

[0051]

[Table 1]

[0052]

[Table 2]

Hereinafter, Examples 19 to 22 and Comparative Examples 10 to 10 will be described.
It shows what was used for 14 compounding prescriptions. Polycarbonate resin: Teijin Chemicals Panlite K-
As a resin other than the polycarbonate-based resin, a styrene-based resin was used as a typical one. Copolymer (B-1) constituting the styrene resin, graft copolymer (B-
The following was used as 2). Copolymer of component (B-1): (b-1-1) Styrene / acrylonitrile (weight ratio 7
5/25) A copolymer obtained by emulsion polymerization of the mixture. Reduced viscosity (in methyl ethyl ketone, concentration 0.01 g / ml, 3
Measured at 0 ° C) is 0.55 dl / g. (B-1-2) A copolymer obtained by solution polymerization of styrene / N-phenylmaleimide / maleic anhydride (weight ratio 49 / 50.7 / 0.3). Reduced viscosity (measured in methyl ethyl ketone at a concentration of 0.01 g / ml at 30 ° C) of 0.34
dl / g. Component (B-2) Graft Copolymer: (b-2-1) Polybutadiene latex (average particle size: 50 parts by weight in terms of solid content) by a known emulsion polymerization method using a reactor equipped with a stirrer. 0.35 μm, gel content 9
(2%) in the presence of 37.5 parts by weight of styrene and 12.5 parts by weight of acrylonitrile, polymerization was carried out using cumene hydroperoxide as a polymerization initiator to complete the reaction. The obtained polymer latex is coagulated with calcium chloride, washed with water, filtered and dried to obtain the graft copolymer (b-
2-1) was obtained. (B-2-2) Mitsubishi Rayon Co., Ltd. Silicone / Acrylic Rubber Graft Copolymer Metabrene S-2001 Phosphorus Compound: Triphenyl Phosphate from Daihachi Chemical Industry Phenolic Resin: Novolac Phenolic Resin from Showa High Polymer Co., Ltd. BRG-555 has a weight average molecular weight of 900 and an average structural formula represented by the general formula (XI).

Embedded image Metal deactivator (11): ADEKA STAB made by Asahi Denka Co., Ltd.
CDA-1 Metal deactivator (12): Antimony pentoxide manufactured by Nissan Chemical Industries Sun Epoch NA-1030 Metal deactivator (13): Hydrotalcite manufactured by Kyowa Chemical Industry (chemical composition Mg _0.7 Al _0.3 O _1.15 ) KYOWARD KW
-2000

Examples 19 to 22 and Comparative Examples 10 to 14 After mixing the components shown in Table 3 at the compounding ratio shown in Table 3 in a Henschel mixer, a 30 mmφ twin-screw extruder (PCM-30, manufactured by Ikegai Tekko KK). Was melt-kneaded and extruded at 250 to 280 ° C., and pelletized by a pelletizer. After sufficiently drying the pellets thus obtained, a test piece was prepared by injection molding, and the flame retardancy of the resin composition was evaluated.
The results are also shown in Table 3. Flame retardance is 127 mm x 12.7 mm x by injection molding from the obtained pellets
A 1.6 mm combustion test piece was manufactured and subject 94 (UL) of Underwriters Laboratory, Inc.
94) Measured according to the vertical burning test.

[0055]

[Table 3]

[0056]

According to the present invention, a metal deactivator is blended in a resin together with a phosphorus compound and at least one selected from silicone, a fluorine-based resin, and a phenol-based resin. Since the flame-retardant action can be obtained, the amount of the flame retardant compounded can be smaller than the conventional amount, and therefore the deterioration of the physical properties of the resin due to the compounding of the flame retardant can be suppressed to a minimum. Furthermore, a resin composition showing excellent flame retardancy is provided,
It can be suitably used for applications such as electric appliances and office automation equipment, and as materials for various parts.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08K 5/47 KKL C08K 5/47 KKL 5/49 KKM 5/49 KKM C08L 101/00 LTA C08L 101/00 LTA // (C08L 69/00 83:04 27:12 61:04)

Claims (4)

[Claims] 1. A flame-retardant resin composition comprising the following components (A) to (E). (A) Polycarbonate-based resin (B) Resin other than polycarbonate-based resin (C) Phosphorus compound (D) At least one selected from silicone, fluorine-based resin, and phenol-based resin (E) Metal deactivator 2. A polymer blend comprising 99 to 5% by weight of a polycarbonate resin as the component (A) and 1 to 95% by weight of a resin other than the polycarbonate resin as the component (B), relative to 100 parts by weight of the polymer blend (C). 1 to 40 parts by weight of a phosphorus compound as a component, 0.01 to 5 parts by weight of a silicone and / or a fluororesin as a component (D), and (E)
The flame-retardant resin composition according to claim 1, which contains 0.001 to 5 parts by weight of a metal deactivator as a component. 3. A polymer blend comprising 99 to 5% by weight of a polycarbonate resin as the component (A) and 1 to 95% by weight of a resin other than the polycarbonate resin as the component (B) with respect to 100 parts by weight of the polymer blend (C). ) As an ingredient,
1 to 40 parts by weight of a phosphorus compound, 1 to 30 parts by weight of a phenolic resin as the component (D), and 0.001 to 5 parts by weight of a metal deactivator as the component (E). Item 1. The flame-retardant resin composition according to item 1. 4. The metal deactivator is represented by the general formula (I): A thiazole compound having the general formula (II) or (III) Embedded image A triazole-based compound having the general formula (IV): An imidazole compound having a general formula (V): Sulfur / nitrogen containing compounds having the general formula (VI): The flame-retardant resin composition according to any one of claims 1 to 3, wherein the flame-retardant resin composition is at least one selected from the group consisting of a phenol compound, a hydrotalcite compound, and an antimony compound.