JPH08295796A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant resin composition that has an excellent flame retardancy and a good impact resistance and is excellent in the balance among physical properties. CONSTITUTION: The composition comprises (A) a thermoplastic resin comprising 99 to 5wt.% polycarbonate resin having such properties that the weight-average molecular weight is 72,000 to 110,000 and the melt flow rate (test temperature: 265 deg.C; test load: 10kgf) stipulated by JIS K-7210 is 5 to 29g/min and 1 to 95wt.% resin other than the polycarbonate resin, (B) a phosphorus compound, and (C) at least one member selected from among silicones, fluororesins, and phenolic resins.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, a flame-retardant resin having excellent impact resistance obtained by blending a thermoplastic resin containing a specific polycarbonate-based resin with a phosphorus compound and at least one selected from silicone, fluorine-based resin, and phenol-based resin. It relates to a composition.

[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, many polymer blends with other thermoplastic resins have been developed. Among them, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polyesters. Polymer alloys such as resin are widely used in the fields of automobiles, office automation equipment, electronic / electrical fields and the like. 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 resin components including 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 flame retardant effect is relatively large,
When a fire or incineration process occurs, a toxic or harmful substance is generated, which makes it difficult to perform emergency activities or fire fighting activities, or causes 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. But in this case,
In order to obtain sufficient flame retardancy, the compounding amount is increased, so that there is a problem that the physical properties such as impact resistance of the obtained flame retardant resin are significantly deteriorated.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to retain excellent flame retardancy and to have good impact resistance. Another object of the present invention is to provide a flame-retardant resin composition having an excellent physical property balance.

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to improve mechanical properties such as flame retardancy and impact resistance of a thermoplastic resin containing a polycarbonate resin as one component. As a result, surprisingly, by combining a polymer blend containing a specific polycarbonate-based resin with a phosphorus compound and at least one selected from a silicone, a fluorine-based resin, and a phenol-based resin, excellent difficulty can be obtained. The inventors have found that it is possible to dramatically improve impact resistance while maintaining flammability, and have reached the present invention. That is, the present invention provides (1) each of the following components (A) having a weight average molecular weight of 72,000 to 110000 and / or a melt flow rate (test temperature of 265 ° C., test load of 10 kgf) defined by JIS K-7210 of 5:
Thermoplastic resin containing 99 to 5% by weight of a polycarbonate resin having a characteristic of 29 g / 10 minutes and 1 to 95% by weight of a resin other than the polycarbonate resin (B) Phosphorus compound (C) Silicone, fluorine resin, and phenolic resin As the component (2) (A) selected from resins, the weight average molecular weight is 72,000.
˜110000 and / or 99-5 wt% polycarbonate resin having a melt flow rate (test temperature 265 ° C., test load 10 kgf) specified by JIS K-7210 of 5 to 29 g / 10 minutes and ABS resin 1
100 parts by weight of polymer blend consisting of
The component (B) contains 1 to 40 parts by weight of an organophosphorus compound, and the component (C) contains 0.01 to 5 parts by weight of a silicone and / or a fluorine-based resin. Flammable resin composition, (3) As the component (A), the weight average molecular weight is 72,000.
˜110000 and / or 99-5 wt% polycarbonate resin having a melt flow rate (test temperature 265 ° C., test load 10 kgf) specified by JIS K-7210 of 5 to 29 g / 10 minutes and ABS resin 1
100 parts by weight of polymer blend consisting of
The flame-retardant resin composition according to (1), which contains 1 to 40 parts by weight of an organic phosphorus compound as the component (B) and 1 to 30 parts by weight of a phenolic resin as the component (C). Is provided.

The present invention will be described in detail below. The polycarbonate resin 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 are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane and 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 those whose aromatic ring is substituted with an alkyl group, an aryl group, or the like. Preferred dihydric phenol is bis (4-hydroxyphenyl)
Alkane-based, more preferably bisphenol A
Is the main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like. Specifically, phosgene,
Diphenyl carbonate, dimethyl carbonate, dihaloformates of dihydric phenols and mixtures thereof. In producing a polycarbonate-based resin, one or more of these dihydric phenols can be used,
If necessary, an appropriate molecular weight regulator, 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 can also be used. . 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 polycarbonate resin used in the present invention has a weight average molecular weight of 72,000 to 110000 and / or a melt flow rate (test temperature of 265 ° C., test load of 10 kgf) defined by JIS K-7210 of 5 to 5.
It has a characteristic of 29 g / 10 minutes. One characteristic of the polycarbonate resin is that the weight average molecular weight is 72,000 to 110000, and preferably 7700.
0 to 110,000, particularly preferably 80,000 to 110
000. The weight average molecular weight in the present invention is obtained by gel permeation chromatography using tetrahydrofuran as a solvent and measurement in terms of polystyrene. Specifically, Shodex in the column
One KF-80M (Showa Denko) and Shodex
An example is one obtained by using one KF-8025 (manufactured by Showa Denko KK) and measuring it on a polystyrene basis under the following conditions. Conditions Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Detection: Ultraviolet detector Wavelength 272 nm Column temperature: 35 ° C.

Another characteristic of the polycarbonate resin is the melt flow rate (test temperature 265 ° C., test load 10 kg) specified in JIS K-7210.
f) is 5 to 29 g / 10 minutes, preferably 7 to 20
g / 10 minutes. The melt flow rate (MFR) in the present invention is a test temperature of 265 ° C. and a test load of 10 according to the method described in JIS K-7210.
Extrusion speed when a polycarbonate-based resin is extruded through a die having a specified length and diameter under the condition of kgf.
Expressed as mass (g) of sample extruded in 0 minutes.

In the present invention, a polycarbonate resin having only one of the above two characteristics may be used, or a polycarbonate resin having two characteristics at the same time may be used. Further, only one type of polycarbonate resin having these characteristics may be used, or two or more types may be used in combination.

The flame-retardant resin composition of the present invention is characterized by having a weight average molecular weight of 72,000 to 110000 and / or JI.
The melt flow rate (test temperature 265 ° C., test load 10 kgf) specified in SK-7210 is 5 to 29 g / 1.
By using a polycarbonate resin having a property of 0 minutes, it is possible to achieve a high level of flame retardancy without sacrificing impact resistance significantly.

When the weight average molecular weight of the polycarbonate resin used is in the range of 72,000 to 110000, and / or the melt flow rate specified in JIS K-7210 (test temperature 265 ° C., test load 10 kg).
When f) is in the range of 5 to 29 g / 10 minutes, it is possible to obtain a resin composition having good flame retardancy and excellent impact resistance and a good balance of physical properties. However, when the polycarbonate-based resin having the above characteristics is not used, problems such as a significant decrease in impact resistance of the resulting resin composition and poor moldability occur, and the resin drips or burns during combustion. The flame retardancy may be decreased, such as a long period of time, which is not preferable.

As the resin other than the polycarbonate resin used in the present invention, any thermoplastic resin can be effectively used without any particular limitation. Typical examples among them are polystyrene resin, ABS resin, polyester resin (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, polyether ester amide, polyether imide, polyether ether ketone, polymethyl methacrylate Etc. These resins are 2
It is also possible to use a combination of two or more species. Next, some of these will be described in more detail.

The polystyrene resin used in the present invention is a polymer obtained by polymerizing an unsaturated monomer containing an aromatic vinyl monomer, and further, the polymer is a rubber-based polymer. It also includes a polymer modified by coalescence.

Aromatic vinyl monomers used as unsaturated monomers include styrene, α-methylstyrene,
Examples include vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, sodium styrenesulfonate, and the like. Furthermore, with these monomers, (meth)
One or more kinds of monomers selected from acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, maleimide-based monomers, unsaturated dicarboxylic acid anhydride-based monomers and the like can be used. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. As the maleimide-based monomer, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, Examples thereof include N- (alkyl-substituted phenyl) maleimide. Examples of unsaturated dicarboxylic acid anhydride-based monomers include maleic anhydride. The method for producing the polystyrene resin is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used.

Specific examples of the polystyrene resin include polystyrene, α-methylstyrene / acrylonitrile copolymer, styrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, styrene / methacrylic acid copolymer, styrene / Maleic anhydride copolymer, α
-Methylstyrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / acrylonitrile / N-
Examples thereof include a phenylmaleimide copolymer, a styrene / N-phenylmaleimide copolymer, a styrene / N-phenylmaleimide / maleic anhydride copolymer, and rubber modified products thereof.

The ABS resin used in the present invention is a graft polymer obtained by graft-polymerizing a vinyl-based monomer containing an aromatic vinyl-based monomer to a rubber-like polymer. It also includes a blend of a polymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl monomer and the graft polymer.

The graft polymer has a glass transition temperature of 10
The rubbery polymer having a temperature of ℃ or below is selected from aromatic vinyl-based monomers and (meth) acrylonitrile, (meth) acrylic acid esters, maleimide-based monomers, unsaturated dicarboxylic acid anhydride-based monomers, and the like. It is obtained by graft-polymerizing one or more kinds of monomers.

Examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, sodium styrenesulfonate and the like, preferably styrene and α-methylstyrene. Etc. are used. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Examples thereof include ethyl methacrylate and butyl methacrylate. As the maleimide-based monomer, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-
Examples thereof include hydroxyphenyl) maleimide and N- (alkyl-substituted phenyl) maleimide. Examples of unsaturated dicarboxylic acid anhydride-based monomers include maleic anhydride. As one or more kinds of monomers selected from (meth) acrylonitrile, (meth) acrylic acid ester, maleimide-based monomer, unsaturated dicarboxylic acid anhydride-based monomer and the like, acrylonitrile and methyl methacrylate are preferable. N-phenylmaleimide, maleic anhydride, etc. are used. These monomers can be used in combination of two or more kinds.

1 selected from aromatic vinyl type monomers and (meth) acrylonitrile, (meth) acrylic acid ester, maleimide type monomers, unsaturated dicarboxylic acid anhydride type monomers and the like used for graft polymerization The ratio of at least one kind of monomer is selected from aromatic vinyl-based monomer / (meth) acrylonitrile, (meth) acrylic acid ester, maleimide-based monomer, unsaturated dicarboxylic acid anhydride-based monomer, etc. One or more kinds of monomers = 10/90 to 99/1 (weight ratio)
Is preferred. Within the above range, impact resistance,
A flame-retardant resin composition having further excellent physical properties such as heat resistance and moldability can be obtained.

Examples of the rubbery polymer used for the graft polymer include polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, hydrogenated butadiene-styrene block copolymer, butadiene-acrylonitrile copolymer. Such as butadiene rubber, acrylic rubber, ethylene-propylene (diene component) copolymer, isobutylene-isoprene copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, polyurethane rubber , Polyamide rubber, silicone rubber 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, preferably,
Polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber and the like are used.

The proportion of the rubber polymer in the graft polymer is preferably in the range of 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 polymer is preferably 5 to 95% by weight, more preferably 10 to 90% by weight.

The graft ratio of the graft polymer 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 graft polymer. 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 preferably comprises a copolymer of the aromatic vinyl monomer and a monomer containing a (meth) acrylic acid ester. Further, when a blended polymer obtained by polymerizing a graft polymer and a vinyl monomer containing an aromatic vinyl monomer is used as the ABS resin, a core / shell type copolymer is used. When used as a graft polymer, a core / shell type copolymer whose shell constituent does not contain an aromatic vinyl monomer and is a polymer of a monomer containing only (meth) acrylic acid ester is used. You can also do it.

The method for producing the graft polymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used.

As the polymer to be blended with the graft polymer, a polymer obtained by polymerizing the monomers used in the above graft polymer can be used. One or more selected from aromatic vinyl-based monomers and (meth) acrylonitrile, (meth) acrylic acid ester, maleimide-based monomers, unsaturated dicarboxylic acid anhydride-based monomers, etc. used as monomers The ratio of the monomer is one selected from aromatic vinyl monomer / (meth) acrylonitrile, (meth) acrylic acid ester, maleimide monomer, unsaturated dicarboxylic acid anhydride monomer, etc. Monomer above = 10
The range of / 90 to 99/1 (weight ratio) is preferable. 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.

As the polymer to be blended with the graft polymer, a polymer preferably used is α-methylstyrene /
Acrylonitrile copolymer, styrene / acrylonitrile copolymer, α-methylstyrene / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer, α
-Methylstyrene / acrylonitrile / N-phenylmaleimide copolymer, styrene / acrylonitrile / N-
Phenylmaleimide copolymer, styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / maleic anhydride copolymer, and the like, more preferably styrene / acrylonitrile copolymer, styrene / N-
Examples thereof include phenylmaleimide copolymer, styrene / N-phenylmaleimide / maleic anhydride 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. Also styrene /
For a copolymer obtained by polymerizing a vinyl-based monomer containing a maleimide-based monomer such as an N-phenylmaleimide / maleic anhydride copolymer, in place of the maleimide-based monomer in the first step, And a maleic anhydride in an amount corresponding to the maleimide-based monomer is copolymerized, and in the second step, a part or most of the maleic anhydride residue in the polymer corresponds to the desired maleimide-based monomer structure. It can also be produced by imidization with an amino compound such as aniline or an aniline derivative.

The ABS resin used in the present invention is a graft polymer obtained by graft-polymerizing a vinyl monomer containing an aromatic vinyl monomer to a rubber-like polymer, and further, It also includes a blend of a polymer obtained by polymerizing a vinyl-based monomer containing an aromatic vinyl-based monomer and the graft polymer. When a blend of a polymer obtained from a vinyl-based monomer containing an aromatic vinyl-based monomer and a graft polymer is used as the ABS-based resin, the content ratio is preferably the aromatic vinyl-based monomer. Copolymer / graft polymer obtained from contained vinyl-based monomer = 5/95 to 95/5 (weight ratio), and more preferably 10/90 to 90/10.
(Weight ratio). Within the above range, impact resistance,
A flame-retardant resin composition having a much better balance of physical properties such as heat resistance and moldability can be obtained.

Further, as a typical composition preferable as the ABS resin of the present invention, (a) styrene / acrylonitrile copolymer (b) styrene / N-phenylmaleimide / maleic anhydride copolymer and (c) styrene. / N
Examples thereof include a blend of at least one selected from a phenylmaleimide copolymer and a graft polymer obtained by graft-polymerizing a mixture of styrene and acrylonitrile with polybutadiene.

In the present invention, the blending ratio of the polymer blend of the polycarbonate resin and the resin other than the polycarbonate resin is polycarbonate resin / resin other than the polycarbonate resin = 99/1 to 5/95 (weight ratio)
Range, preferably 95/5 to 10/90 (weight ratio), and more preferably 90/10 to 20/80. If the proportion of the resin other than the polycarbonate resin exceeds 95 weight ratio, the original properties of the polycarbonate resin may not be maintained, and if it is less than 1 weight ratio, the workability and moldability of the polycarbonate resin are not improved.

The ABS resin is preferably used as a resin other than the polycarbonate resin in order to impart excellent flame retardancy and well-balanced physical properties to the obtained resin composition.

The phosphorus compound used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, but 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 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. 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, 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, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and the like.

Examples of the phosphorus compound (B) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, and tricle phosphate. Dil 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 dicresylphos Eto, 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, etc. 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), hydroquinone bis (diquin). Silenyl phosphate), biphenol bis (dixylenyl phosphate), bisphenol Bis (diphenyl phosphate), bisphosphate and polyphosphate oligomers such as bisphenol A bis (dicresyl phosphate), and the like.

In addition, triphenyl phosphate, tricresyl phosphate, condensed phosphoric acid esters thereof, etc.
A hydroxyl group-containing aromatic phosphoric acid ester containing one or two or more phenolic hydroxyl groups 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.

Other phosphorus compounds include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, phosphazene compounds and red phosphorus.

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 blending amount of these phosphorus compounds is 1 to 40 parts by weight, preferably 3 to 100 parts by weight of the component (A).
30 parts by weight, more preferably 5 to 25 parts by weight. 1
If it is less than 40 parts by weight, a sufficient flame retardant effect cannot be obtained, and if it is more than 40 parts by weight, the heat resistance and impact resistance of the resulting composition are remarkably lowered, and the volatile content during molding is increased. And the like. The phenomenon that the molten resin that burns when the resin burns drops is not a preferable phenomenon for disaster prevention.
For the purpose of preventing such resin dripping, silicone, fluorine resin, and phenol resin all work effectively.

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 fluorine resin 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,
You may use it in combination of 2 or more type. 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, its addition amount is 100 parts by weight of the component (A).
0.01-5 parts by weight, preferably 0.05-2 parts by weight,
More preferably, it is 0.1 to 1 part by weight. silicone,
When the amount of the fluorine-based resin is 0.01 parts by weight or less, a sufficient dripping prevention effect cannot be obtained, and when it exceeds 5 parts by weight, the appearance of the molded product of the compounded resin composition is poor, and defective phenomena such as increase in melt viscosity are caused. 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 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. The aralkyl halide and / or aralkyl alcohol derivative in the present invention is represented by 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.) 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 1 to 30 with respect to 100 parts by weight of the component (A).
Parts by weight, preferably in the range of 1 to 20 parts by weight. If 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 if it exceeds 30 parts by weight, the light resistance and impact resistance of the obtained resin composition are remarkably high. It is not preferable because it causes a problem such as reduction.

In the present invention, silicone, fluororesin,
Both of the phenolic resin and the phenolic resin effectively act to prevent the resin from dripping during combustion, but when a flame-retardant resin composition having excellent light resistance is obtained, a fluororesin and / or
Alternatively, it is preferable to use silicone.

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 15 and Comparative Examples 1 to 10 After mixing the components shown in Tables 1 to 3 at the compounding ratios shown in Tables 1 to 3 with a Henschel mixer, a 30 mmφ twin-screw extruder (PCM-30, manufactured by Ikegai Tekko KK). ) Was used, 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 by a UL combustion test. Izod impact strength was measured as an index of impact resistance of the resin composition. The results are also shown in Tables 1 to 3. For flame retardancy, a 127 mm x 12.7 mm x 1.6 mm combustion test piece was manufactured from the obtained pellets by injection molding,
It was measured according to a laboratory 94 subject UL (UL94) vertical combustion test. Izod impact strength is 3.2 width
A test piece with a notch of mm and a test piece with a notch of 6.4 mm in width were prepared and measured according to JIS K-7110.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

The symbols in Tables 1 to 3 are as follows. Polycarbonate resin (1): Panlite K-1300W manufactured by Teijin Chemicals Ltd. Weight average molecular weight: 102000 MFR:-Polycarbonate resin (2): Panlite K-1300 manufactured by Teijin Chemicals Ltd. Weight average molecular weight: 92000 MFR: 9g / 10 Min Polycarbonate resin (3): Sumitomo Dow Caliber 200-3 Weight average molecular weight: 83900 MFR: 10 g / 10 min Polycarbonate resin (4): Sumitomo Dow Caliber 200-5 Weight average molecular weight: 78000 MFR: 18 g / 10 min Polycarbonate resin (5): Sumitomo Dow Caliber 200-10 Weight average molecular weight: 71000 MFR: 30 g / 10 min Polycarbonate resin (6): Sumitomo Dow Caliber 200-13 Weight average molecular weight: 64200 MFR : 39 g / 10 min Polycarbonate resin (7): Caliber 200-20 manufactured by Sumitomo Dow Co., Ltd. Weight average molecular weight: 57900 MFR: 65 g / 10 minutes The weight average molecular weight of polycarbonate was determined by gel permeation chromatography using a column of Shodex KF.
-80M (Showa Denko) and Shodex KF-
One 8025 (manufactured by Showa Denko KK) was used, and the measurement was carried out based on polystyrene under the following conditions. Conditions Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Detection: Ultraviolet detector Wavelength 272 nm Column temperature: 35 ° C. Moreover, melt flow rate (MF of polycarbonate)
R) was measured in accordance with JIS K-7210 after sufficiently drying the sample and then under the conditions of a test temperature of 265 ° C. and a test load of 10 kgf.

Polycarbonate resin Resin (1) other than resin: 60% by weight of a styrene / acrylonitrile (weight ratio 75/25) mixture is grafted onto 40% by weight of polybutadiene rubber having an average particle size of 0.3 μm by emulsion polymerization. Copolymer Polycarbonate resin Resin other than resin (2): Copolymer obtained by suspension polymerization of styrene / acrylonitrile (weight ratio 72/28) mixture Resin other than polycarbonate resin Resin (3): Styrene / N-phenyl Copolymer obtained by solution polymerization of maleimide (weight ratio 47/53) Resin other than polycarbonate resin resin (4): styrene / N-phenylmaleimide / maleic anhydride (weight ratio
47 / 52.5 / 0.5) Copolymer obtained by solution polymerization of mixture Polycarbonate resin Resin other than resin (5): Suspension polymerization of styrene / acrylonitrile / N-phenylmaleimide (weight ratio 65/25/10) Copolymer obtained by the above method Resin other than polycarbonate resin (6): Silicone / acrylic rubber graft copolymer Metabrene S-2001 made by Mitsubishi Rayon Co., Ltd. Phosphorus compound (1): Triphenyl phosphate made by Daihachi Chemical Industry Co., Ltd. Phosphorus compound (2): Resorcinol bis (diphenyl phosphate CR-733S, made by Daihachi Chemical Industry Co., Ltd. Fluorine-based resin: Polytetrafluoroethylene Teflon 6J made by DuPont Mitsui Fluorochemicals Silicone: Polydimethylsiloxane SH-made by Toray Dow Corning Silicone 200 oil (viscosity 30000cs) Phenolic resin: Meiwa Kasei's novolac type phenolic resin MEH7800 weight average molecule The amount is 1000, and the average structural formula is represented by the general formula (III).

[Chemical 4] From Tables 1 to 3, the polycarbonate used has a weight average molecular weight of 72,000 to 110000, JIS
By satisfying any one of the characteristics that the melt flow rate specified in K-7210 (test temperature 265 ° C., test load 10 kgf) is 5 to 29 g / 10 minutes,
It can be seen that a resin composition having good Izod impact strength and high flame retardancy can be obtained. On the other hand, when a polycarbonate that does not satisfy the above properties is used, the Izod impact strength of the obtained resin composition is significantly lowered, and when the flame retardancy is lowered, such as dropping of the resin during combustion or a longer burning time. Is not preferable.

[0056]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a flame-retardant resin composition having excellent flame retardancy and good impact resistance and having an excellent balance of physical properties. Further, it can be suitably used for applications such as electronic / electrical products 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 C08L 55/02 LMF C08L 55/02 LMF 61/06 LMT 61/06 LMT LMY LMY LNA LNA LNB LNB 83/04 LRT 83/04 LRT LRY LRY 101/00 LSY 101/00 LSY

Claims (3)

[Claims] 1. A flame-retardant resin composition comprising the following components (A), (B), and (C). (A) The weight average molecular weight is 72,000 to 110000 and / or the melt flow rate (test temperature 265 ° C., test load 10 kgf) specified in JIS K-7210 is 5 to 5.
Thermoplastic resin containing 99 to 5% by weight of a polycarbonate resin having a characteristic of 29 g / 10 minutes and 1 to 95% by weight of a resin other than the polycarbonate resin (B) Phosphorus compound (C) Silicone, fluorine resin, and phenolic resin At least one selected from resins 2. The component (A) has a weight average molecular weight of 7
2000-110000 and / or JIS K-721
Melt flow rate (test temperature 265 ° C,
99 to 5% by weight of a polycarbonate-based resin and ABS having a test load of 10 kgf) to 5 to 29 g / 10 min
Polymer blend 100 consisting of 1 to 95% by weight of resin
1. 1 part by weight to 40 parts by weight of the organophosphorus compound as the component (B) and 0.01 to 5 parts by weight of the silicone and / or fluororesin as the component (C). The flame-retardant resin composition described. 3. The component (A) has a weight average molecular weight of 7
2000-110000 and / or JIS K-721
Melt flow rate (test temperature 265 ° C,
99 to 5% by weight of a polycarbonate-based resin and ABS having a test load of 10 kgf) to 5 to 29 g / 10 min
Polymer blend 100 consisting of 1 to 95% by weight of resin
The flame-retardant resin according to claim 1, characterized in that 1 part by weight to 40 parts by weight of the organophosphorus compound as the component (B) and 1 to 30 parts by weight of the phenolic resin as the component (C) are contained. Composition.