CN1370803A - Fire-retardant resin composition and its molded product - Google Patents

Abstract

A flame resistant resin composition, high in heat resistance, excellent in impact resistance, and having a high flame resistance. The polycarbonate based flame resistant resin composition is composed of (A-1) a polycarbonate based resin, (A-2) a thermoplastic resin excepting the polycarbonate based resin, (B) a silicone resin, (C) a phosphate ester represented by chemical formula 1, and (D) an epoxy stabilizer.

Description

Flame-retardant resin composition and molded product thereof

field of invention

The invention relates to a flame-retardant carbonate polymer.

Background of the invention

Polycarbonate resins are used globally in the fields of electricity, electronics, and office automation (OA) as engineering plastics having excellent transparency, impact resistance, heat resistance, and electrical properties. In these electrical, electronic and OA fields, as in the case of the personal computer outer packaging part, a high degree of flame retardancy (UL94V) or impact resistance is required.

Polycarbonate resin is a plastic material with high flame retardancy and self-quenching properties. However, in the fields of electricity, electronics, and OA, higher flame retardancy is still required in order to achieve a higher degree of safety consistent with UL94V or 94V-1.

Therefore, in the past, in order to improve the flame retardancy of polycarbonate, a method of compounding a large amount of oligomers or polymers of polycarbonate derivatives of bisphenol A bromide with polycarbonate was used. However, this suffers from the problems of reduced impact resistance and easy generation of cracks in molded articles. Moreover, since a halogen compound containing a large amount of bromine is compounded, the generation of halogen-containing gas during combustion is also an environmental concern.

Phosphate esters and silicones are known halogen-free flame retardants. For example, in the patent gazette of Japanese Patent Laid-Open Sho 62-25706, it has been proposed to add phosphoric acid esters to polycarbonate resins. However, if a phosphate ester is added to a polycarbonate composition, there arises a problem of lowering heat resistance or impact resistance when molding materials are prepared.

For this purpose, silicon compounds are used as flame retardants for thermoplastic resins such as polycarbonate because silicon compounds have high heat resistance. No toxic gas is produced when burning, and the stability of the silicone resin material is also high. The silicon compound used as a flame retardant is a polymer formed by polymerizing at least one of the following four types of siloxane units (M unit, D unit, T unit, and Q unit).

In another reference, Japanese Patent Publication Sho 62-60421 discloses a flame retardant resin composition to which a silicone resin having more than 80% by weight of T units is added. Japanese Patent No. Hei 5-86295 discloses a flame retardant resin composition, such as polycarbonate, which has added 30-99mol% T unit, 0-80mol% D unit, 1-70mol% M unit and 0-50mol% Q Unit of silicone.

In the prior art references, a large amount of silicone resin needs to be added to meet the strict flame retardant standards related to electrical and electronic machinery. As a result, other properties of the thermoplastic composition are affected, such as moldability, kneadability, and other properties desired for thermoplastics, and moreover, this becomes impractical because of the cost.

Furthermore, as an attempt to improve the flame-retardant effect of the silicon compound itself and to reduce the required amount of the silicon compound, the use of metal salts together with the silicon compound has been proposed. For example, Japanese Published Patent Application Sho 56-100853 discloses a flame retardant resin composition in which a silicon compound composed of a D unit and a Group IIa metal carbonate having 14-20 carbon atoms is mixed with polycarbonate, etc. polymer compound. In another publication (Japanese Patent No. Hei 3-48947), a flame-retardant resin composition is disclosed in which a silicone resin composed of M units and Q units is compounded with other silicone resins and a group IIa metal salt of carbonic acid. Even if silicon compounds and metal salts are used together, in order to provide a satisfactory flame retardant effect, the amount of silicone resin is still high. Also, it is also necessary to use an inorganic flame-retardant filler material such as aluminum hydroxide or a halogen or phosphorus compound in combination.

Therefore, in the prior art practice of adding silicone resin as a flame retardant, a sufficient flame retardant effect cannot be obtained unless the amount added is very high. In addition, if a large amount of silicone resin is added, various properties of the resin composition such as moldability, appearance of molded articles or mechanical strength are adversely affected. In addition, since the silicone resin material itself is expensive, there is also a high material cost. There is still a need for silicone resin additives that have a high flame retardancy effect, or for an additive that is used together with silicone resins to affect flame retardancy.

Japanese Patent No. Hei 8-176425 discloses a flame retardant composition in which an epoxy group-containing organopolysiloxane and an alkali metal salt of an organic sulfonic acid are added. Japanese Patent No. Hei 8-176427 has disclosed a flame retardant composition containing polycarbonate resin modified by organopolysiloxane, containing phenolic hydroxyl group and organic alkali metal salt. Also, a composition having an improved flame retardant effect has been disclosed in Japanese Patent No. Hei 9-169914 by using petroleum heavy oil or various kinds of bitumen together with a silicon compound. However, in these cases, expensive silicones need to be used and a sufficient flame retardant effect is not obtained in view of the complexity involved in the production stage. In addition, the dispersibility and compatibility with polycarbonate resin were not satisfactory.

In Japanese Patent No. Hei 10-139964, the molecular weight (weight average MW) of the flame retardant composition is in the range of 10,000-270,000, wherein the silicone resin containing D and T units shown in the following formula is compounded with aromatic polycarbonate.

Also, Japanese Laid-Open Patent No. Hei 11-140294 discloses a flame-retardant polycarbonate resin composition, wherein a silicone resin containing 50-90mole% T units and 10-50mole% D units has been compounded, and among these units More than 80 mole % of the total organic substituents have been occupied by phenyl groups.

However, in both references, the burning lasts for a long time, and the drip characteristic is insufficient, and the flame retardancy obtained in the burning test extensively evaluated based on UL94 is still unsatisfactory.

In another reference, Japanese Patent No. Hei 11-217494 discloses a flame-retardant polycarbonate resin composition in which a silicon compound has the following structure, that is, has a D unit as its main structural unit, composed of D units Metal salts and polymers consisting of T units and/or Q units and additionally having aromatic groups as organic functional groups and aromatic sulfur compounds.

In the above formula, R and X are organofunctional groups. And in the above references, the softening point of the silicone resin containing these D units as an essential component is remarkably low. As a result, silicone resins more readily convert to a liquid form at room temperature, which makes compounding with polycarbonate resins particularly difficult. Also, due to the high molecular weight, a solid silicone resin can be obtained at room temperature even in the form of a silicone resin containing D units as an essential component. Therefore, in order to increase the molecular weight of the silicone resin, a longer polymerization time is required, and the flame retardant effect is not high.

Japanese Laid-Open Patent No. Hei 11-222559 discloses a flame-retardant resin composition containing 100 parts by weight of synthetic resin, which contains an aromatic ring in the molecule, such as introducing an aromatic polycarbonate resin, phenyl as shown in the structural formula Shown: R1mR2nSi(OR3)p(OH)qO(4-m-n-p-q)/2, and 0.1-10 parts by weight of organosiloxane containing alkoxy groups. In the formula, R1 represents a phenyl group, R2 represents a monovalent hydrocarbon group with 1-6 carbon atoms (excluding the phenyl group), R3 represents a monovalent hydrocarbon group with 1-4 carbon atoms, and the following range: 0.5<= m<=2.0, 0<=n<=0.9, 0.42<=p<=2.5, 0<q<=0.35, 0.92<=+m+n+p+q<=2.8.

Also, Japanese Published Patent Application No. 2000-159996 discloses a flame retardant resin composition containing aromatic polycarbonate, a silicate shown in the following formula, and a flame retardant such as a metal group, a halogen group, or an inorganic group Flame retardants, compounds containing three azine skeletons, silicone resins, silicone oils, silicon dioxide, aramid resins, polyacrylonitrile fibers, fluorine resins, norvolac resins, etc.:

In the above formula, R1 to R4 represent hydrocarbons having 1 to 20 carbon atoms, and R1 and R4 form a ring. p and q are 0 or 1, and cannot be 0 at the same time. n is an integer greater than 1.

However, in these prior art flame retardant resin compositions, materials having satisfactory flame retardancy, fluidity and various satisfactory properties such as heat resistance, hydrolysis resistance or impact resistance cannot be obtained. Molded products with other characteristics.

The applicant has surprisingly found a resin composition which is highly flame retardant and all of the above problems have been solved by the synergistic use of silicone resins and specially structured phosphate esters and additionally by the combination of epoxy stabilizers and anti-drip agent and compounded with polycarbonate resin to solve. The composition of the present invention has heat resistance, excellent impact resistance and hydrolysis resistance, and has excellent flame retardancy.

Summary of the invention

The present invention relates to a flame-retardant polycarbonate composition, containing polycarbonate (A-1); a thermoplastic resin (A-2) different from polycarbonate; a silicone resin (B); and the following formula A phosphate ester compound (C) as shown: Wherein, each of R1, R2, R3 and R4 represents a hydrocarbon with 1-30 carbon atoms; X represents a divalent organic group with 1-30 carbon atoms, which may even contain oxygen atoms and/or nitrogen atoms and m represents an integer of 0-5; and an epoxy stabilizer (D),

The composition is characterized in that the weight ratio (A-1:A-2) of the polycarbonate resin (A-1) to the thermoplastic resin (A-2) is in the range of 99:1-1:99, and

The silicon family resin (B) is 0.1-15 parts by weight relative to the total amount of 100 parts by weight of the polycarbonate family resin (A-1) and the thermoplastic resin (A-2),

The ratio of the phosphate ester compound (C) is 1-30 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2), and

Described epoxy stabilizer (D) is the proportion of 0.01-10 weight part relative to the polycarbonate family resin (A-1) and thermoplastic resin (A-2) of 100 weight parts of total amount, wherein said silicon The resin (B), the phosphate ester compound (C) and the epoxy stabilizer (D) provide a synergistic effect.

In one embodiment, thermoplastic resin (A-2) is selected from the following group:

a) A polymer containing (a) an aromatic vinyl unimer component (unimer) as its structural component;

b) a copolymer containing (a) an aromatic vinyl single-mer component and (b) a vinyl cyanide single-mer component as its structural components;

c) containing (a) aromatic vinyl single-mer components, (b) vinyl cyanide single-mer components, and

(c) copolymers with rubbery polymers as their structural constituents;

d) aromatic polyesters;

e) polyphenylene ether (polyphenylene ether);

f) polyetherimide; and

g) polyphenylene sulfide.

In another embodiment, the thermoplastic resin (A-2) is selected from ABS resin, AES resin, ACS resin, AAS resin and polystyrene resin.

In another embodiment, the silicone resin (B) is a silicone resin containing at least 2 types of siloxane units selected from the group consisting of siloxane units represented by RSiO1.5 (T units), R3SiO1 A siloxane unit represented by .0 (D unit), a siloxane unit represented by R3SiO0.5 (M unit) and a siloxane unit represented by SiO2.0 (Q unit), where R represents a monovalent unsubstituted or Substituted hydrocarbyl groups having 1 to 10 carbon atoms. The above-mentioned silicone resin (B) is as a silicone resin composed of T units and M units or as a silicone resin composed of T units and M units and SiO2.0 (Q units, wherein R represents monovalent non-substituted or substituted 1-10 The presence of a silicone resin consisting of a hydrocarbon group of 2 carbon atoms) is ideal. In another embodiment, at least 20 mole % of aromatic groups are present in the organofunctional group R contained in the above-mentioned silicone resin (B).

In another embodiment, the phosphate compound (C) is bisphenol A-tetraphenyl diphosphate or bisphenol A-tetrahydroxycresyl diphosphate; epoxy stabilizer (D) is 3,4- Epoxy cyclohexyl methyl-3', 4'-epoxy cyclohexane carbonate or two (3,4-epoxy cyclohexyl) adipate; In the present invention, anti-dripping agent (E ) is polytetrafluoroethylene (PTFE), with respect to 100 parts by weight of the polycarbonate family resin (A-1) or the total polycarbonate family resin (A-1) and thermoplastic resin (A-2), its It is present in proportions of 0.01-10 parts by weight.

The present invention also relates to articles including electrical and electronic machinery and home decoration formed from the above flame retardant resin composition. Detailed description of the invention

The flame retardant resin composition that the present invention relates to is characterized in that containing polycarbonate family resin (A-1), thermoplastic resin (A-2), silicone resin (B), phosphate ester compound (C) and epoxy stabilizer (D ).

Polycarbonate-based resin (A-1). The polycarbonate family resin (A) used in the present invention is an aromatic homopolycarbonate or an aromatic copolycarbonate obtained from the reaction between an aromatic dihydroxy compound and a carbonate precursor.

Polycarbonate resins generally have repeating structural units represented by the following formula (1),

O-A-O-C ...(1) where A is a divalent residue derived from an aromatic dihydroxy compound.

Aromatic dihydroxy compounds exist as mononuclear or polynuclear aromatic compounds with 2 hydroxyl functional units and wherein each hydroxyl group is directly bonded to a carbon atom of the aromatic nucleus.

A bisphenol compound represented by the following formula (2) can be given as an example of the aromatic dihydroxy compound.

Wherein Ra and Rb may be the same or different, and are respectively a halogen atom or a monovalent hydrocarbon group, and m and n are integers of 0-4. x is

Rc and Rd are hydrogen atoms or monovalent hydrocarbon groups, Rc and Rd can form a ring structure, and Re is a divalent hydrocarbon group.

Examples of these aromatic dihydroxy compounds represented by the formula (2) include bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (known as bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane , Bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxy-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, etc.; bis(hydroxyaryl)cycloalkanes, such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc.; dihydroxyaryl ethers, such as 4,4'-dihydroxydiphenyl Ether, 4,4'-dihydroxy-3,3'-diphenyl ether, etc.; dihydroxydiaryl sulfide, such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy -3,3'-diphenylsulfide, etc.; dihydroxydiarylsulfoxide, such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyl Dihydroxydiarylsulfone, such as 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-diphenylsulfone, etc. However, it should be noted that the aromatic dihydroxy compound is not limited to the above examples.

其中每个R1独立地是C₁-C₁₀烃基、卤原子或卤代烃基，其中至少一个所述的烃基被卤原子取代，p是0-4的整数。In one embodiment, the aromatic dihydroxy compound is 2,2-bis(4-hydroxyphenyl)propane (known as bisphenol A). Also, in addition to those represented by the above-mentioned formula (2), aromatic dihydroxy compounds represented by the following formula (3) can also be used as the aromatic dihydroxy compound.

Wherein each R1 is independently a C ₁ -C ₁₀ hydrocarbon group, a halogen atom or a halogenated hydrocarbon group, wherein at least one of said hydrocarbon groups is substituted by a halogen atom, and p is an integer of 0-4.

Examples of these compounds include resorcinol; substituted resorcinols such as 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol Hydroquinone, 3-tert-butylresorcinol, 3-phenylresorcinol, 3-cumylresorcinol, 2,3,4,6-tetrafluororesorcinol and 2,3 , 4,6-tetrabromoresorcinol; catechol; and hydroquinones and substituted hydroquinones such as 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3- Butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone.

In addition to the above formula (2), those other aromatic dihydroxy compounds are 2,2,2',2'-tetrahydro-3,3,3',3'-tetramethyl-1 represented by the following formula , 1'-spiro-bis[1H-indene]-7,7'-diol:

These aromatic dihydroxy compounds may be used alone or in combination of two. Polycarbonates can be linear or branched. Mixtures of linear polycarbonates and branched polycarbonates are also possible.

Branched polycarbonates can be obtained by reacting polyfunctional aromatic compounds with aromatic dihydroxy compounds and carbonate precursors. Typical examples of such polyfunctional aromatic compounds are listed in US Pat. Specific examples include 1,1,1-tris(4-hydroxyphenyl)ethane, 2,2′,2″-tris(4-hydroxyphenyl)diisopropylbenzene, (α-methyl-α , α′,α′-tris(4-hydroxyphenyl)-1,4-diethylbenzene, α,α′,α″-tris(4-hydroxyphenyl)-1,3,5-triiso Propylbenzene, Fluoroglycine, 4,6-Dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane-2, 1,3,5-tris(4-hydroxyphenyl)benzene , 2,2-bis[4,4-(4,4'-dihydroxyphenyl)cyclohexyl]-propane, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid and homo pyromellitic acid. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α′,α″-tris(4-hydroxyphenyl)-1,3,5-triiso Propylbenzene, etc.

The intrinsic viscosity of the polycarbonate-based resin measured in methylene chloride at 25°C is not particularly limited, and may be appropriately selected according to the desired use and moldability, but is usually at least 0.26 dL/g, preferably 0.30- 0.98dL/g, more preferably 0.34-0.64dL/g. When the average molecular weight viscosity is calculated, it should generally be at least 10,000, preferably 12,000-50,000, more preferably 14,000-30,000. Mixtures of polycarbonate resins having different intrinsic viscosities can also be used. By measuring the intrinsic viscosity (intrinsic viscosity [number] η) at 20°C in dichloromethane, then calculate the average molecular weight viscosity (Mv) according to the Mark-Houwink viscosity formula:

η=K×(Mv) ^a (K=1.23×10 ^-4 , a=0.83)

The polycarbonate-based resins used in the present invention are produced by known methods. Included examples are the following:

(1) A method in which polycarbonate is synthesized by subjecting an aromatic dihydroxy compound and a carbonate precursor (such as a carbonic acid diester) to a transesterification reaction in a melt (melt method).

(2) A method in which an aromatic dihydroxy compound and a carbonate precursor (such as phosgene) react in a solution (interfacial method).

These production methods are described in, for example, Japanese Patent Applications H2-175723 and H2-124934, US Patents 4,001,184, 4,238,569, 4,238,597, and 4,474,999, and the like. Thermoplastic resins other than polycarbonate family resins (A-2)

In the present invention, a thermoplastic resin other than carbonate (hereinafter simply referred to as a thermoplastic resin) may be contained together with the above-mentioned polycarbonate. Any thermoplastic resin other than polycarbonate can be used as the thermoplastic resin (A-2) without specific limitation, but it is preferable to use one or more resins selected from the following:

(1) A polymer comprising (a) an aromatic vinyl monomer component as a structural component

(2) A copolymer comprising (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as structural components

(3) A copolymer comprising (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubber-like polymer as structural components

(4) Aromatic polyester

(5) Polyphenylene ether

(6) Polyester imide

(7) Polyphenylene sulfide

All of the above-mentioned resins are commercially available, and there are no particular limitations on production methods and the like.

(Co)polymer (1) Firstly, a polymer including (a) aromatic vinyl monomer component (1) will be described. Examples of the aromatic vinyl monomer component (a) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene , monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene and vinylnaphthalene. The polymer used in the present invention may be a homopolymer of one of these monomers, or may be a copolymer of two or more different monomers. Of these monomers, styrene and α-methylstyrene are particularly preferred. In one embodiment, a styrene resin is used.

There is no particular limitation on the method of producing such (co)polymers, and any commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization may be used. (Co)polymers can also be obtained by separately mixing polymerized resins.

Polymer (2) The following describes a copolymer (2) comprising (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component. Examples of the aromatic vinyl monomer component (a) are the same as above. Examples of the vinyl cyanide monomer component (b) include acrylonitrile and methacrylonitrile. One or more of these components may be contained in the copolymer.

There is no particular limitation on the composition ratio (a)/(b), which is selected according to the application. (a)/(b) is preferably 50-95% by weight of (a) and 5-50% by weight of (b), more preferably 65-92% by weight of (a) and 8-35% by weight of (b) .

A preferable example of the aforementioned polymer is SAN resin (styrene-acrylonitrile copolymer). There is no particular limitation on the production method of the copolymer, and any commonly known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization may be used. It is also possible to obtain the desired copolymer by separately mixing polymerized resins.

Copolymer (3), a copolymer comprising (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubber-like polymer is described below. Examples of the aromatic vinyl monomer component (a) and the vinyl cyanide monomer component (b) are the same as above.

Examples of rubber-like polymers (c) include polybutadiene, polyisoprene, styrene-butadiene random and block copolymers, butadiene-isoprene copolymers and others based on Diene rubber; ethylene-propylene random and block copolymers, copolymers of ethylene and alpha-olefins, ethylene-methacrylate, ethylene-butyl acrylate and other copolymers of ethylene and unsaturated carboxylic acid esters acrylate-butadiene copolymers, such as butyl acrylate-butadiene copolymer, and other acrylic elastomeric polymers; ethylene-vinyl acetate and other copolymers of ethylene and fatty acid vinyl [salts]; ethylene - Propylene-hexadiene copolymers and other terpolymers of ethylene-propylene non-conjugated dienes; butene-isoprene copolymers and chlorinated polyethylene. These can be used alone or in combination. Preferred rubber-like polymers are terpolymers of ethylene-propylene non-conjugated dienes, diene rubbers and acrylic elastomeric polymers, with polybutadiene and styrene-butadiene copolymers being particularly preferred. In one embodiment, styrene is 50% by weight or less.

Such a copolymer (3) is preferably a graft copolymer obtained by graft-polymerizing other components in the presence of the rubber-like polymer (3). Particularly preferred are ABS resins (acrylonitrile-butadiene-styrene copolymers), AES resins (acrylonitrile-ethylene-styrene copolymers), ACS resins (acrylonitrile-chlorinated polyethylene-styrene copolymers) and AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer) resin.

The weight average molecular weight (Mw) of the above-mentioned (co)polymer (1) and copolymers (2) and (3) is preferably 30,000-200,000, more preferably 30,000-150,000, particularly preferably 30,000-110,000.

In one embodiment of the present invention, the monomers copolymerizable with the above-mentioned components (a), (b) and (c) can also be mixed with these components in the above-mentioned (co)polymer (1) and copolymer (2) and (3) Copolymerization. Examples of such copolymerizable monomers include acrylic acid, methacrylic acid and other α,β-unsaturated carboxylic acids, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( Butyl meth)acrylate, 2-ethyl (meth)acrylate, 2-ethylhexyl methacrylate and other α,β-unsaturated carboxylic acid esters; maleic anhydride, itaconic anhydride and other α,β - unsaturated dicarboxylic anhydrides; and maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenyl Maleimide and other α,β-unsaturated dicarboxylic acid imide compounds. These monomers can be used alone or in combination.

There is no particular limitation on the production method of these copolymers, which may be produced using bulk polymerization, bulk suspension polymerization, or solution polymerization.

Aromatic Polyester (4) Aromatic polyester is known per se and is a polyester having an aromatic ring on a chain unit of a polymer. These polymers and copolymers are obtained by polycondensation reactions in which the main components are aromatic dicarboxylic acids and diols (or their ester-forming derivatives).

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid Acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, biphenylsulfone-4,4'-dicarboxylic acid , diphenylisopylidene-4,4'-dicarboxylic acid, 1,2-di(phenoxy)ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6- Dicarboxylic acid, p-terphenyl-4,4'-dicarboxylic acid and pyridine-2,5-dicarboxylic acid. Terephthalic acid is preferred.

These aromatic dicarboxylic acids may also be used in admixture of two or more. Also, as long as the amount used is small, one or more aliphatic dicarboxylic acids—such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid—or one or more aliphatic dicarboxylic acids Acids, such as cyclohexanedicarboxylic acid, may be mixed with the aforementioned aromatic dihydroxycarboxylic acids.

Examples of diol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, triethylene glycol, and other aliphatic glycols , and cyclohexane-1,4-dimethanol and other alicyclic diols, and mixtures of these diols. Also, one or more long-chain diols having a molecular weight of 400-6000, such as polyethylene glycol, poly-1,3-propylene glycol or poly-1,4-butylene glycol, can be copolymerized as long as the amount used is small.

Specific examples of the aromatic polyester resin include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, Polybutylene naphthalate, Polyethylene 1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, and Polycyclohexanedimethylene terephthalate. In one embodiment, PBT or PET is used.

Polyphenylene ether (5) Polyphenylene ether (PPE) is a known resin having substituted or unsubstituted phenylene ether repeating units. Specific examples include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl -6-Ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1, 4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether , poly(2,6-dichloromethyl-1,4-phenylene) ether, poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-di Phenyl-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether, poly(2,6-dichloroyl)-1,4 -phenylene) ether, poly(2,6-dibenzyl-1,4-phenylene) ether and poly(2,6-dimethyl-1,4-phenylene) ether.

The PPE copolymer may be a copolymer containing a phenol trisubstituted with an alkyl group, such as 2,3,6-trimethylphenol, in some of the phenylene ether repeating units. Also possible are copolymers in which styrene compounds have been grafted onto PPE. The polyphenylene ether grafted with a styrene compound includes a copolymer obtained by graft-polymerizing one of the above-mentioned PPEs with a styrene compound such as styrene, α-methylstyrene, vinyltoluene, or chlorostyrene. PPE is commercially available as Noryl produced by GE Plastics Japan.

Polyetherimides (6) Polyetherimides are known resins such as those available under the trademark Ultem from GE Plastics Japan.

Polyphenylene Sulfide (7) Polyphenylene sulfide (PPS) is a known resin having substituted or unsubstituted phenylene sulfide repeating units. Examples include those commercially available from Phillips Petroleum, Tosoh Susteel Tohpren, Kureha Chemical, and the like.

Copolymers (1) and (3) are preferably used in the present invention as thermoplastic resins, more preferably used selected from HIPS (high impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer) and AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer). ABS resin and HIPS are particularly preferred.

For the thermoplastic resin (A-2), its weight ratio (A-1:A-2) to the polycarbonate-based resin (A-1) is advantageously 99:1-1:99, preferably 30:70 -70:30.

Component B - Silicone Resin There is no particular limitation on the silicone resin used as component (B) present in the present invention. In one embodiment, the silicone resin used contains at least 2 siloxane units selected from siloxane units represented by RSiO1.5 (T units), siloxane units represented by R3SiO1.0 (D units), Siloxane units (Q units) represented by SiO2.0 and siloxane units (M units) represented by R3SiO0.5 (wherein R represents a monovalent unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms).

The organic groups constituting the silicone resins may be the same or different. In one embodiment, alkyl groups such as methyl, ethyl, propyl, butyl, etc., alkenyl groups such as vinyl, allyl, etc., aryl groups such as phenyl, toluoyl, etc. are used.

Among these types of organic group R, a silicone resin having a methyl group and/or a phenyl group as the organic group R is particularly desirable from the viewpoint of dispersibility to polycarbonate-based resins and flame retardancy, and because In this case it is readily available as silicone. In particular, silicone resins with phenyl groups have particularly good flame retardancy in addition to their excellent compatibility with polycarbonate and increase the transparency of polycarbonate. It is desirable that such phenyl groups exist in a ratio of greater than 20 mol % relative to the entire organic groups in the silicone resin, and more desirably exist in a ratio of greater than 40 mol % relative to the entire organic groups.

The molecular weight of the silicone resin used in the flame retardant resin composition of the present invention is ideal in the range of 1000-50000, more ideally should be in the range of 2000-20000, the silicone resin used in the flame retardant resin composition of the present invention Particularly desirable molecular weights for silicone resins are in the range of 3000-10000. If the molecular weight is less than 1,000, it is difficult to maintain a solid state under the conditions used, and if the molecular weight exceeds 50,000, the processability decreases and the dispersibility to polycarbonate decreases.

In one embodiment, a silicone resin composed of T and M units or a silicone resin composed of T, M and Q units is used as the silicone resin (B) used in the present invention.

It is desirable to contain 0.03-1 mol of M units with respect to 1 mol of T units in a silicone resin, More preferably, the amount of 0.05-0.3 mol is contained. Also, when the silicone resin contains Q units, the content of these Q units is preferably 0.001-0.5 mol, more preferably 0.01-0.05 mol, based on 1 mol of T units. Containing Q units with a high degree of oxidation in a higher amount is beneficial for achieving flame retardancy, but if the amount of Q units in the siloxane becomes high, the dispersibility to polycarbonate family resins becomes unsatisfactory because The properties of materials that become inorganic particles become very strong. Therefore, it is necessary to control the compounding ratio so as to be within the above-mentioned range.

In consideration of the balance between flame retardancy, processability and molded product characteristics, it is desirable to select a range from the content range of the above-mentioned siloxane unit so that the proportion of the T unit is 50-50% of the weight of the entire silicone resin. 97 mol%.

Such silicone resins can be synthesized by known methods. For example, it can be obtained by subjecting organochlorosilane or organoalkoxysilane to hydrolysis condensation reaction with excess water. In one embodiment, a silicone resin containing silanol groups is prepared by subjecting a silane compound formed from T, Q and D units to a hydrolytic condensation reaction with water, and then, if the silanol group is formed by using a compound formed from M units, the silanol group Triorganosilanization of groups to make silicone resins, in which case molecular weight control becomes easy, as this case is ideal.

In an example of a production method of a silicone resin formed of T and M units, wherein 5-100 parts by weight are shown as (R13Si)aZ (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group that is the same or different from each other, a is an integer of 1-3, when a is 1, Z is a hydrogen atom, a halogen atom, a hydroxyl group or a hydrolyzable group, when a is 2, Z is -O-, -NX- or -S-, when a When it is 3, Z is -N-. Also, X is a hydrogen atom, a monovalent hydrocarbon group with 1-4 carbon atoms) silicon compound (b) and 100 parts by weight containing (a) [RSiO1.5] T The unit forms the silanol group of the silicone resin in reaction. The silicone resin containing the silanol group of the component (a) can be synthesized by a known method. For example, it can be obtained by hydrolyzing and condensing organochlorosilane or organoalkoxysilane with excess water. In this type of reaction, silicone resins with different degrees of polymerization can be obtained by adjusting the amount of water or controlling the amount and type of hydrolysis catalyst, duration or temperature of condensation reaction, etc. The silicone resins thus obtained generally contain silanol groups (—SiOH).

The silicon compound of component (b) represented by (R13Si)aZ is a compound in which the silanol group present in component (a) has been silylated. Examples of the hydrolyzed group for Z can be given such as methoxy, ethoxy, propoxy, isopropoxy, alkoxy such as butoxy, halogen such as chlorine, bromine, etc., such as propenyloxy, etc. Alkenyloxy group, acyloxy group such as acetoxy group, benzoyloxy group, organic oxime group such as acetone oxime group, butanone oxime group, etc., such as dimethylaminooxy group, diethylaminooxy group, etc. Organic aminooxy group, organic amino group such as dimethylamino group, cyclohexylamino group, etc., organic amide group such as N-methylacetamido group.

Examples of component (b) include hydrodiene silanes such as trimethylsilane, triethylsilane, etc., trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, etc. Chlorosilanes, silanols such as trimethylsilanol, alkoxysilanes such as trimethylmethoxysilane, triethylmethoxysilane, etc., such as (CH3)3SiNHCH3, (CH3)3SiNHC2H5 , (CH3)3SiNH(CH3)2, (CH3)3SiNH(C2H5)2, etc., acyloxysilanes such as (CH3)3SiOCOCH3, such as [(CH3)3Si]NH, 1,3-diethylene Disilazanes such as tetramethyldisilazane, and trimethylsilazane such as nonamethyltrimethylsilazane [(CH3)3Si]3N. In these examples, silazanes or chlorosilanes are ideally employed because it is easy to control the reaction or remove unreacted compounds.

The reaction between the above-mentioned component (a) and component (b) can be carried out under known conditions for converting silanols into silyl groups (silylation). For example, in the case where component (b) is silazane or chlorosilane, the reaction proceeds easily only by heating the mixed components (a) and (b). In this case, it is desirable that the ratio of component (b) used is within a range of 5 to 100 parts by weight relative to 100 parts by weight of component (a). And, if the proportion of the ingredient (b) is less than 5 parts by weight, the silanol group of the ingredient (a) cannot be satisfactorily silylated to be distorted during the reaction, such as to generate a gel. Also, if the proportion of the component (b) is more than 100 parts by weight, the economy from the viewpoint of raw materials is poor because a large amount of unreacted components exist as residues, and it takes longer time for removal of unreacted components. Component (b), so that the process becomes complicated.

In addition, it is desirable that the above-mentioned silylation reaction be carried out in an organic solvent while controlling the reaction temperature so as to control the occurrence of side reactions of dehydration condensation. As examples of such organic solvents to be used, hydrocarbon solvents such as toluene, xylene, hexane, industrial gasoline, mineral spirits, kerosene, etc., ether solvents such as tetrahydrofuran, dioxane, etc., dichloromethane, etc. Chlorinated hydrocarbon solvents such as methane and dichloroethane. There are no particular restrictions on the reaction temperature, but a range from room temperature up to 120°C is suitable. Hydrochloric acid, ammonia, ammonium chloride, alcohol, etc. generated during the reaction can be removed by washing with water, or removed simultaneously with the solvent.

The silicone resin obtained by the above method usually exists in the form of a liquid or a solid substance at room temperature. It is desirable that the silicone resin compounded with the polycarbonate-based resin exists in a solid state because it can be uniformly dispersed in the polycarbonate-based resin. Solid silicone resins with a softening point greater than 400C, ideally 70-2500C, are particularly suitable. In addition, the softening point of the silicone resin can be adjusted by mixing two kinds of silicone resins having different softening points.

The molecular weight of the silicone resin can be controlled by controlling the molecular weight of the silanol group-containing silicone resin used as component (a), the silanol group to be silylated, and by controlling the type of component (b) that becomes a silylating agent.

If the silicone resin used in the present invention has a D unit, the softening point of the silicone resin is significantly lowered since it is easily converted into a liquid substance at room temperature. As a result, compounding it with polycarbonate becomes difficult. Also, if the molecular weight is increased, a silicone resin in the form of a solid substance at room temperature can be obtained even if it exists in the form of a silicone resin having a D unit. However, in this case, the polymerization time required to increase the molecular weight becomes longer, and the final flame retardant effect is lower compared to a silicone resin composed of T and M units or a silicone resin composed of T, M and Q units .

The silicone resin used in the present invention may contain a small amount of silanol groups, but a smaller amount of silanol groups is desirable from the standpoint of storage stability, stability during melt processing, or flame retardancy. The amount of silanol groups contained in the silicone resin is desirably less than 0.5% by weight, more desirably less than 0.3% by weight.

In the flame retardant resin composition of the present invention, the amount of the compounded silicone resin is 0.1-15 wt. parts, preferably 0.1-5 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2). If the amount of the silicone resin is less than 0.1 parts by weight, satisfactory flame retardancy cannot be obtained, and if it exceeds 15 parts by weight, not only cannot improved flame retardancy be achieved but also adversely affect the appearance and optical clarity or strength of molded articles. In addition, none of these silicones generate noxious gas when burned.

Phosphate compound (C) A compound represented by the following formula is used as a phosphoric acid ester:

In the formula, R ¹ , R ² , R ³ and R ⁴ are independently a hydrocarbon group having 1-30 carbon atoms, preferably 1-5 carbon atoms, preferably a substituted or unsubstituted aromatic hydrocarbon group. If substituted, examples of substituents include alkyl, alkoxy, alkylthio, halogen, aryl and aryloxy.

Here, examples of R ¹ , R ² , R ³ and R ⁴ include phenyl, hydroxytolyl, xylyl (such as 2,6-xylyl), trimethylphenyl, ethylphenyl, cumyl and butylphenyl. If a hydrocarbon group is thus contained, the resulting resin composition is particularly excellent in flame retardancy.

m是0-5的整数。X is a C ₁ -C ₃₀ divalent organic group which may contain an oxygen atom and/or a nitrogen atom. The X is, for example, -OY ¹ -O- (wherein Y ¹ is a substituted or unsubstituted aromatic hydrocarbon group, preferably 1,4-phenylene, 1,3-phenylene, etc.) or -OY ² -R ⁵ -Y ³ -O- (wherein Y ² and Y ³ are divalent substituted or unsubstituted aromatic hydrocarbon groups, specific examples of which include substituted or unsubstituted phenylene; R ⁵ is C ₁ -C ₈ di Hydrocarbon group or oxyhydrocarbyl group (-R ⁶ -O-; wherein R ⁶ is C ₁ -C ₈ divalent hydrocarbon group), more particularly C ₁ -C ₉ divalent aliphatic hydrocarbon group, such as 2,2'-propylene base). X may be an organic group in which the nitrogen atom is directly bonded to the phosphorus atom, such as 1,4-piperidinediyl (formula below):

m is an integer of 0-5.

Examples of phosphate esters include bisphenol A tetraphenyl diphosphate (BPADP), triphenyl phosphate, tricresyl phosphate, cresol diphenyl phosphate, bisphenol A tetracresol diphosphate, resorcinol tetra (2,6-dimethylphenyl)phosphate and tetrakis(xylyl)piperidine phosphate amide. Among them, bisphenol A tetraphenyl diphosphate (BPADP) and bisphenol A tetracresol diphosphate are preferred as phosphoric acid esters.

If the phosphate ester compound (C) is added together with the above-mentioned silicone resin (B), a molded product having excellent impact resistance and heat resistance as well as excellent flame retardancy can be formed.

The amount of the compounded phosphate ester compound (C) in the flame retardant resin composition of the present invention is 1-30 relative to the polycarbonate family resin (A-1) and thermoplastic resin (A-2) of 100 parts by weight in total. The weight part is desirably 1 to 10 parts by weight relative to 100 parts by weight in total of the polycarbonate resin (A-1) and the thermoplastic resin (A-2). If the amount of the phosphate ester compound (C) is less than 1 part by weight, (sufficient flame retardancy cannot be obtained), whereas if it exceeds 30 parts by weight, heat resistance is lost.

Epoxy Stabilizer (D) The epoxy stabilizer (D) is further added to the flame retardant resin composition according to the present invention. Examples of such epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3 , 4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6 "-Methylcyclohexyl carboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 4-(3,4-epoxy-5-methylcyclo Hexyl)butyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexyloxirane, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3 , 4-epoxy-6-methylcyclohexylmethyl-6”-methylcyclohexyl carboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl phthalate ether, diglycidyl ether of hexahydrophthalic acid, bis-epoxydicyclopentadiene ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxy compound, tetraphenyloxirane, octyl epoxy phthalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-Dimethyl-1,2-epoxycyclohexane, 3-methyl-5-tert-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl- 3,4-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-cyclo Oxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate Ester, 2-ethylhexyl-3', 4'-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3', 4'-epoxycyclohexyl carboxylate Ester, 4,5-epoxy anhydrous tetrahydrophthalic acid, 3-tert-butyl-4,5-epoxy anhydrous tetrahydrophthalic acid, diethyl-4,5-epoxy- cis-1,2-cyclohexylcarboxylate, di-n-butyl-3-tert-butyl-4,5-epoxy-cis-1,2-cyclohexylcarboxylate and the like.

In one embodiment, the epoxy stabilizer (D) is a cycloaliphatic epoxy resin. In another embodiment, is 3,4-epoxycyclohexylmethyl-3&apos;,4&apos;-epoxycyclohexanecarboxylate or bis(3,4-epoxycyclohexyl)adipate.

The cycloaliphatic epoxy stabilizer is commercially available from Asahi Denka Kogyo Kabushiki Kaisha (Asahi Electrochemicals Co. Ltd.) under the trademark R-51, or from Daicel Kagaku Kogyo Kabushiki Kaisha (Daicel Chemical Industries Co. Ltd.) as Celoxide 2021P or Celoxide 2080 purchase.

It was found that the hydrolysis resistance of the resin composition was improved by adding epoxy stabilizers. In one embodiment, the amount of the epoxy stabilizer added is relative to the polycarbonate family resin (A-1) of 100 parts by weight in the case of using the polycarbonate family resin (A-1) alone, or in polycarbonate family resin (A-1) When the carbonate resin (A-1) is used together with the thermoplastic resin (A-2), it is about 0.01 to 10 parts by weight relative to 100 parts by weight of (A-1) and (A-2). In one embodiment, the amount is 0.1-5 parts by weight. For optimal hydrolysis resistance, the amount of epoxy stabilizer is greater than 0.01 parts by weight. However, if the amount exceeds 10 parts by weight, the mechanical strength of the molded article is affected.

Anti-Dripping Agent (E) The resin composition of the present invention may contain an anti-dripping agent. The anti-dripping agent is an additive that suppresses dripping during combustion, and any known agent may be used. In one embodiment, the anti-dripping agent forms a fibrous structure in a polycarbonate-based resin, typically using polytetrafluoroethylene (PTFE) and tetrafluoroethylene copolymers such as PTFE/hexafluoropropylene copolymer).

Among various types of polytetrafluoroethylene (PTFE) available, one having excellent dispersibility, such as one in which PTFE is emulsified and dispersed in an aqueous solution or the like, or one in which PTFE has been mixed with, for example, polycarbonate Resin encapsulation of esters and styrene-acrylonitrile copolymers, or masterbatches of PTFE and resins such as polycarbonate and styrene-acrylonitrile copolymers, as it gives molded articles composed of polycarbonate compositions Good surface appearance. If a material is used in which PTFE has been dispersed by emulsification in a solution such as water, it is not particularly limited, but a PTFE material having an average particle diameter of less than 1 micron is desirable, and it is particularly desirable to use one of less than 0.5 micron.

As detailed examples of commercially available PTFE materials, Teflon 30J (trademark, Mitsubishi DuponFluoro Chemicals (Kabushiki Kaisha (Mitsubishi Dupon Fluoro Chemicals Co.Ltd.)), Polyflon D-2C (trademark, Daikin Kagaku Kogyo (Kabushiki Kaisha (KaikinChemical) Industries Co. Ltd.)), Aflon AD1 (trademark, Asahi Glass (Kabushiki Kaisha (Asahi Glass Co. Ltd.)).

The amount of anti-dripping agent added is ideal for 0.01-10 parts by weight relative to the polycarbonate family resin (A-1) and thermoplastic resin (A-2) of 100 parts by weight of the total amount, and it is more desirable to add 0.05- 2 parts by weight, ideally 0.1-0.5 parts by weight.

If the amount of component (E) is less than the above range, a polycarbonate resin composition having excellent flame retardancy cannot be obtained, and if it is more than the above range, fluidity is lost.

Also, the molecular weight of the polytetrafluoroethylene should be greater than 500,000, ideally 1,000,000-5,000,000.

The resin composition compounded with polytetrafluoroethylene controls the occurrence of dripping during combustion. Also, if PTFE and silicone are used together, dripping is further controlled and, in addition, the burning time is shortened compared to the case of adding only PTFE.

In the present invention, as the anti-dripping agent, polyphenylene ether (PPE) may be used together with the above-mentioned polytetrafluoroethylene. Examples of PPE can be given including poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2 -Methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl -1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether wait. A particularly desirable PPE family resin is poly(2,6-dimethyl-1,4-phenylene) ether. Also, regarding polyphenylene ether copolymers, the copolymers have alkyl trisubstituted phenols in the phenylene ether repeating unit, for example, especially 2,3,6-trimethylphenol. In one embodiment, the copolymer wherein a styrenic compound is grafted into the polyphenylene ether. Regarding polyphenylene ethers grafted with styrenic compounds, there can be given styrenic compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. by graft polymerization in the above-mentioned polyphenylene ethers. obtained copolymer.

In addition, regarding the anti-dripping agent, an inorganic group anti-dripping agent may also be used together with the above-mentioned polytetrafluoroethylene. Silica, quartz, aluminum silicate, mica, alumina, alumina, calcium carbonate, talc, silicon carbide, silicon nitride, titanium dioxide, iron oxide, carbon black and the like can be given as the above-mentioned inorganic anti-dripping agent.

Other Components The resin composition of the present invention may further contain a UV absorber, a hindered phenol-based antioxidant, a release agent, and the like. Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and salicylate-based UV absorbers.

Known additives may also be added to the flame retardant resin composition of the present invention without losing its material properties when the resin composition is mixed or molded into an article. For example, coloring agents (decoratives, pigments such as carbon black, titanium dioxide, etc.), fillers, reinforcing agents (glass fibers, carbon fibers, talc, clay, mica, glass flakes, ground glass, glass beads), lubricating agent, plasticizer, flame retardant, flow property improver, etc.

There is no particular limitation on the method for preparing the resin composition of the present invention, and any known method may be used. However, it is particularly desirable to use the melt mixing method. A small amount of solvent may also be added when producing the resin composition.

As for the apparatus that can be used, extruders, bombarding mixers, rolls, kneaders, etc. can be particularly exemplified, which can be operated in a batchwise or continuous manner. At this time, there is no particular limitation on the order in which the ingredients are mixed.

The flame retardant resin composition of the present invention has excellent flame retardancy and does not drip when burned.

For example, the flame retardant resin composition involved in the present invention meets the UL-94 V-0 level in the UL-94 V assessment, and the UL-94 V assessment is based on the Bleten 94 "Combustion test for material classification" of the Under Writer Laboratory Incorporation (hereinafter called UL-94) Indicated test method is carried out, wherein a test plate with a thickness of 1/16th is prepared. In addition, the standards for each V class in UL-94 are shown in Table 1 below: Table 1 level V-0 V-1 V-1 Flame remaining time for each test sample less than 10 seconds less than 30 seconds less than 30 seconds Total flame residual time of 5 test samples less than 50 seconds less than 250 seconds less than 250 seconds Ignite cotton by trickle does not exist does not exist exist

The flame retardant resin composition related to the present invention can be molded into any desired form by any desired molding method, such as using injection molding, extrusion molding, blow molding and the like.

The molded article thus obtained has excellent impact resistance and high heat resistance, and has excellent flame retardancy. Therefore, molded articles of the resin composition of the present invention can be suitably used as outer panels of OA equipment or home appliances or as house decoration parts, electronic and electromechanical parts.

The flame retardant resin composition of the present invention has high flame retardancy without loss of impact resistance or moldability due to the specific phosphoric acid ester and silicone resin contained, and there is no need to worry about the corresponding flame retardants producing halogens when burning. The gas, since it does not contain flame retardants formed of chlorine, bromine compounds, etc., has an excellent function from the viewpoint of environmental protection. Also, since a specific epoxy stabilizer has been added therein, the polycarbonate family resin itself has improved hydrolysis resistance, and molded articles having excellent impact resistance can be produced.

Therefore, the flame retardant resin composition is particularly useful in applications requiring high heat resistance, such as parts for home appliances such as televisions, printers, copiers, facsimile machines, personal computers, house decoration and OA equipment, in Materials used in internal components such as battery packs, liquid crystal reflectors, and automobiles.

Example

The invention is described in more detail below with the aid of examples. However, the present invention is not limited by these Examples.

In addition, in the examples, parts are parts by weight and % is % by weight unless otherwise specified. In addition, the following compounds were used as each component.

Polycarbonate family resin (PC): polycarbonate of bisphenol A: LEXAN (trademark, NipponGE: Plastics Kabushiki Kaisha (Japan GE Plastics Co. Ltd.) production), intrinsic viscosity measured in dichloromethane at 250C = 0.49dl/g, viscosity average molecular weight (Mv) = 21760 (calculated).

ABS resin: material with rubber content = 20%, MI = 2.5 g/10 sec.

Phosphate compound (C) group compound: bisphenol A-tetraphenyl phosphate, CR741S (trademark, manufactured by Daihachi Kagaku Kabushiki Kaisha (Daihachi Chemical Co. Ltd.)).

Epoxy stabilizer: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carbonate (Celoxide 2021P, trademark, produced by Daicel Kagaku Kogyo Kabushiki Kaisha (Daicel Chemical Industries Co.Ltd.)).

Polytetrafluoroethylene (PTFE): Polyflon D-2C (trademark, Daikin Kagaku Kogyo (KabushikiKaisha (Daikin Chemical Industreis Co. Ltd.))). In the material, PTFE is emulsified and dispersed in water, and the PTFE content is 60% by weight. In addition, Polyflon D-2C was added in an amount of 0.5% by weight relative to the polycarbonate resin, because the actual amount of PTFE added was 0.3%. Also, water is evaporated when preparing the resin composition.

Silicone: A silicone material with the composition shown in Table 2 below was used. Table 2 Silicone A-1 A-2 B-1 nature Structural units T and M T and M T, D, M Ph/Me molar ratio 65/35 70/30 70/30 Weight average molecular weight 7800 7500 75000 Softening point[℃] 160 140 85 OH residue 0 0 0

Ph/Me molar ratio: the molar ratio of phenyl and methyl groups present in the silicone resin except for M units (T, D units).

Example 1

Mix 90 parts by weight of polycarbonate, 10 parts by weight of ABS resin, 1 part by weight of silicone resin (A-1), 6 parts by weight of phosphate ester (CR741S), 0.3 parts by weight of epoxy stabilizer and 0.5 parts by weight of PTFE, and use a biaxial An extruder (TEX44aII, produced by Nippon Sei Kojo (Kabushiki Kaisha) (Japan Steel Manufacturing Works Ltd.)) was extruded at a screw speed of 300rpm at a bore temperature of 250-260°C, and pellets of a specific length were cut. These pellets are used to inject test panels of specific sizes through a 100t injection molding machine under the molding conditions of a bore temperature of 260°C and a metal mold temperature of 50°C. The performance test of the molded article obtained was carried out as follows.

(1) Evaluation of impact resistance. Based on ASTM-1, the Izod impact strength was evaluated with a test panel at 1/8th thickness.

(2) Load deflection temperature (heat resistance). Based on ASTM-D-648, test the compliance temperature at a load of 18.6kg with a test panel of 1/4 thickness.

(3) Hydrolysis resistance. The original weight-average molecular weight of the polycarbonate in the prepared resin composition and the weight-average molecular weight of the polycarbonate in the resin composition after being held at 121° C. at 100 RH atmospheric pressure for 48 hours were measured. The measurement of the weight average molecular weight is performed by GPC. Also, a low weight average molecular weight indicates low hydrolysis resistance.

(4) Evaluation of flame retardancy. According to the test based on the above-mentioned UL-94, that is, according to the test method indicated in Bleten 94 "Combustion test for material classification" of the Under Writer Laboratory Incorporation (hereinafter referred to as UL-94), the flame retardancy of molded articles with a thickness of 1.6mm is measured sex. And, the burning time is the total burning time of 5 test materials.

The results are shown in Table 3.

Example 2-3

In Example 1, the silicone resin (A-1) was replaced with the silicone resin (A-2) or (B-1). Except for this change, the reaction was carried out in a manner similar to that of Example 1, and the properties of the particles thus obtained were evaluated.

The results are shown in Table 3. Comparative Examples 1-4

The compositions shown in Table 3 were used. Except for this change, the reaction was carried out in a manner similar to that of Example 1, and the properties of the particles thus obtained were evaluated.

The results are shown in Table 3.

table 3 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 composition PC 90 90 90 90 90 90 90 ABS 10 10 10 10 10 10 10 CR741S (Phosphate) 6 5 6 6 6 6 - Silicone resin (A-1) 1 - - - - 1 5 Silicone resin (A-2) - 1 - - - - Silicone resin (B-1) - - 1 - - - - PTFE 0.5 0.5 0.5 0.5 0.5 0.5 0.5 epoxy stabilizer 0.3 0.3 0.3 - 0.3 - 0.3 Impact resistance IZOD(kg/cm) 80 85 80 75 75 80 80 Load deflection temperature (°C) 106 109 106 106 106 106 120 UL UL94-1.6 ^* 1 Burning time-seconds 8 twenty four twenty three 50 50 11 240 UL class V-0 V-0 V-0 V-1 V-1 V-0 V-2 Hydrolysis resistance start 45000 45000 45000 45000 45000 45000 45000 after aging 43000 43000 42000 30000 42000 29000 43000 ^* 1) 1.6 is 1.6mm thickness

As shown in Table 3, the resin composition of the present invention has a short burning time because an epoxy stabilizer and an anti-dripping agent have been added together with the polycarbonate family resin, silicone resin and phosphoric acid ester compound (C) compound therein, and It controls dripping and is highly flame retardant (UL-94 V-0). Also, the resin composition of the present invention has excellent hydrolysis resistance because it is not hydrolyzed even when heated.

The resin composition of Comparative Example 1 not containing the silicone resin and the epoxy stabilizer was insufficient in flame retardancy and hydrolysis resistance. Whereas, the resin composition containing no silicone resin of Comparative Example 2 was insufficient in flame retardancy. In addition, the resin composition containing no epoxy stabilizer of Comparative Example 3 was insufficient in hydrolysis resistance. Also, the phosphate-free resin composition of Comparative Example 4 had low flame retardancy even though the amount of silicone resin was increased. Therefore, multiple effects on the flame retardancy of the resin composition can be achieved by combining phosphate ester and silicone resin and adding them to polycarbonate family resins.

Claims (13)

1. A flame retardant composition comprising: a) polycarbonate resin (A-1); b) a thermoplastic resin other than polycarbonate (A-2); c) a silicone resin (B); d) a phosphate compound (C) represented by the following formula:

Wherein, each of R ¹ , R ² , R ³ and R ⁴ represents a C ₁ -C ₃₀ hydrocarbon; X represents a C ₁ -C ₃₀ divalent organic group that may contain an oxygen atom and/or a nitrogen atom; and m represents integers from 0-5; and e) an epoxy stabilizer (D), Wherein the weight ratio (A-1:A-2) of the polycarbonate resin (A-1) to the thermoplastic resin (A-2) is in the range of 99:1-1:99, The silicone resin (B) is present in an amount of 0.1-15 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2), The phosphate ester compound (C) exists in an amount of 1-30 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2), and The epoxy stabilizer (D) is present in an amount of 0.01-10 parts by weight relative to the total amount of 100 parts by weight of the polycarbonate resin (A-1) and the thermoplastic resin (A-2). 2. The flame retardant composition of claim 1, wherein said thermoplastic resin (A-2) is selected from the group consisting of: a) A polymer containing (a) an aromatic vinyl unimer component (unimer) as its structural component; b) a copolymer containing (a) an aromatic vinyl single-mer component and (b) a vinyl cyanide single-mer component as its structural components; c) Copolymers containing (a) aromatic vinyl single-mer components, (b) vinyl cyanide single-mer components, and (c) rubber polymers as their structural components; d) aromatic polyesters; e) polyphenylene ether; f) polyetherimide; and g) polyphenylene sulfide. 3. The flame retardant composition of claim 1, wherein said thermoplastic resin (A-2) is selected from: ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-benzene ethylene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer) and AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer). 4. The flame retardant composition of claim 1, wherein the silicone resin (B) contains at least two siloxane units selected from the group consisting of: a) a siloxane unit (T unit) represented by RSiO1.5, b) a siloxane unit (D unit) represented by R2SiO1.0, c) a siloxane unit (M unit) represented by R3SiO0.5 and d) siloxane units represented by SiO2.0 (Q units), wherein R represents a monovalent unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms. 5. The flame retardant composition of claim 4, wherein said silicone resin (B) is a) a silicone resin composed of T units and M units or b) a composition of siloxane units represented by T units, M units and Q units of silicone. 6. The flame retardant composition of claim 4, wherein said silicone resin has a molecular weight of about 1,000-50,000. 7. The flame retardant composition according to claim 5, wherein in the monovalent hydrocarbon group R contained in the above-mentioned silicone resin (B), the proportion of aryl groups is at least 20 mol%. 8. The flame retardant composition of claim 1, wherein the phosphate ester compound (C) is bisphenol A-tetraphenyl diphosphate or bisphenol A tetrahydroxycresyl diphosphate. 9. The flame retardant composition of claim 1, wherein the epoxy stabilizer (D) is 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate or two-(3 , 4-epoxycyclohexyl) adipate. 10. The flame retardant composition according to claim 1, further comprising an anti-dripping agent (E). 11. The flame retardant composition of claim 10, wherein the anti-drip agent (E) is relative to the polycarbonate family resin (A-1) of 100 parts by weight or the polycarbonate family resin (A-1) of a total amount of 100 parts by weight 1) and thermoplastic resin (A-2) are present in an amount of about 0.01-10 parts by weight. 12. A method of preparing a flame retardant composition, said method comprising combining and mixing the following ingredients: a) polycarbonate (A-1); b) a thermoplastic resin other than polycarbonate (A-2); c) a silicone resin (B); d) a phosphate compound (C) represented by the following formula: Wherein, each of R ¹ , R ² , R ³ and R ⁴ represents a C ₁ -C ₃₀ hydrocarbon; X represents a C ₁ -C ₃₀ divalent organic group that may contain an oxygen atom and/or a nitrogen atom; and m represents integers from 0-5; and e) an epoxy stabilizer (D), Wherein the weight ratio (A-1:A-2) of the polycarbonate resin (A-1) to the thermoplastic resin (A-2) is in the range of 99:1-1:99, The silicone resin (B) is present in an amount of 0.1-15 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2), The phosphate ester compound (C) exists in an amount of 1-30 parts by weight relative to the total amount of 100 parts by weight of polycarbonate resin (A-1) and thermoplastic resin (A-2), and The epoxy stabilizer (D) is present in an amount of 0.01-10 parts by weight relative to the total amount of 100 parts by weight of the polycarbonate resin (A-1) and the thermoplastic resin (A-2). 13. The method of claim 12, further comprising the step of reducing the composition to form a particulate form.