JPH10147702A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin compsn. excellent in impact resistance and slidability. SOLUTION: (D) Phosphoric ester flame retardant (5-20 pts.wt.), (E) 0.1-5 pts.wt. polyorganosiloxane graft copolymer are incorporated into 100 pts.wt. basic resin compsn. comprising (A) 40 to 95% (by wt.) aromatic polycarbonate resin, (B) 5 to 60% rubber-contg. graft copolymer obtd. by graft-polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, another copolymerizable monomer in the presence of a rubbery polymer, and (C) 50% or less rigid copolymer obtd. by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, another coplymerizable monomer. By this constitution, a flame-retardant resin compsn. having an excellent flame- retarding effect, and a high impact resistance and slidability can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and more particularly, to a flame-retardant resin composition having excellent flame retardancy, good impact resistance and good slidability.

[0002]

2. Description of the Related Art A resin composition containing an aromatic polycarbonate resin and an ABS resin has excellent physical properties such as strength characteristics, impact resistance, heat resistance and dimensional stability. Widely used as materials.

However, the flame retardancy of this resin composition is insufficient, and various improvements have been made for the purpose of improving the flame retardancy. For example, JP-A-64-22958 discloses a method for imparting flame retardancy by adding an organic halogen compound as a flame retardant and antimony trioxide as a flame retardant aid. However, the addition of such an organic halogen compound lowers the fluidity during molding; causes thermal decomposition to generate hydrogen halide, corrodes the mold; and deteriorates or colors the resin itself. In addition, there is a problem that the working environment is deteriorated. That is, a resin composition containing a halogen compound is harmful to the environment because it may generate harmful dioxins during combustion.

[0004] For this reason, it has been studied to incorporate a flame retardant other than the organic halogen compound.

[0005] Flame retardants other than organic halogen compounds include inorganic compound flame retardants such as aluminum hydroxide and magnesium hydroxide. However, these compounds have a significantly lower flame retardant effect than the above-mentioned organic halogen compounds. For this reason, in order to obtain a sufficient flame-retardant effect, it is necessary to add a large amount, and there is a disadvantage that the original characteristic of the resin is impaired by the large addition.

As a flame-retardant resin composition which does not use an organic halogen compound and which solves such a problem, JP-A-4-29
No. 8554 discloses a flame-retardant resin composition in which a resin composition comprising an aromatic polycarbonate and an ABS resin is blended with a phosphate ester and a polyorganosiloxane, so that a molded article thinner than 2.8 mm can pass UL94 SVA and CSA. Has been proposed.

[0007]

In recent years, there has been an increasing demand for cost reduction and weight reduction of various devices, and in response to such demands, housing materials, enclosure materials, etc. of OA devices have tended to become thinner. is there. Also, in particular,
It is required that the components of the paper feeding unit and the paper discharging unit of the printer have even better slidability.

Accordingly, a flame-retardant resin composition which satisfies such demands, has higher impact resistance and slidability, and further has excellent flame retardancy without using an organic halogen compound. The development of is desired.

The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a flame-retardant resin composition excellent in impact resistance and slidability, and free of an organic halogen compound. Aim.

[0010]

The flame-retardant resin composition of the present invention comprises (A) 40 to 95% by weight of an aromatic polycarbonate resin and (B) an aromatic vinyl monomer in the presence of a rubbery polymer. 5 to 60% by weight of a rubber-containing graft copolymer obtained by graft-polymerizing a copolymer, a vinyl cyanide monomer and another copolymerizable monomer used as required, and (C) an aromatic vinyl monomer A base resin composition comprising a monomer, a vinyl cyanide monomer and 50% by weight or less of a hard copolymer obtained by copolymerizing other copolymerizable monomers used as required.
(D) 5 to 20 parts by weight of a phosphate ester-based flame retardant and (E) 0.1 to 10 parts by weight of a polyorganosiloxane graft copolymer are mixed with 100 parts by weight of the base resin composition. It is characterized by being.

According to the present invention, a predetermined amount of a phosphate ester-based flame retardant is added to a base resin composition having a predetermined component composition,
Flame-retardant resin that has excellent flame-retardant effects without using organic halogen compounds, and has high impact resistance and good slidability by blending with a polyorganosiloxane graft copolymer. A composition can be obtained.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the flame-retardant resin composition of the present invention will be described below in detail.

The aromatic polycarbonate resin (A) used in the present invention includes, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
5-dimethylphenyl) propane, 2,2-bis (4-
Obtained from bis (hydroxyaryl) alkanes such as hydroxy-3,5-dichlorophenyl) propane and bis (4-hydroxyphenyl) phenylmethane and carbonates such as phosgene (phosgene method) or diaryl carbonate (ester exchange method). Bis (hydroxyaryl) alkane-based polycarbonate resin and the like can be mentioned. These may be used alone or in combination of two or more.

Specific examples of the rubber-containing graft copolymer (B) used in the present invention include ABS resin, AES resin,
AAS resin and the like can be exemplified.

The rubber component in the rubber-containing graft copolymer (B) includes polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, ethylene-propylene-non-conjugated diene copolymer rubber (EPDM) and the like. One or more of these can be used. In addition, as a diolefin contained in EPDM, dicyclopentadiene, 1,4-hexadiene,
1,4-heptadiene, 1,5-cyclooctadiene,
6-methyl-1,5-heptadiene, 11-ethyl-
1,11-tridecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 2,5-
Examples include norbornadiene, 2-methyl-2,5-norbornadiene, methyltetrahydroindene, and limonene.

The aromatic vinyl monomer component used for producing the rubber-containing graft copolymer (B) includes, for example, styrene, α-methylstyrene, o-, m- or p-methylstyrene.
-Methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like, preferably styrene and α-methylstyrene , One or more of these can be used. Examples of the vinyl cyanide monomer component include acrylonitrile and methacrylonitrile, and one or more of these can be used.

In the production of the rubber-containing graft copolymer (B) used in the present invention, in addition to the above-mentioned aromatic vinyl monomer component and vinyl cyanide monomer component, a monomer which can be copolymerized therewith is used. The body can be used as long as the object of the present invention is not impaired. Examples of such a copolymerizable monomer include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl (meth) acrylate (“(meth) acrylate” is “acrylate and / or methacrylate”). Α, β-unsaturated carboxylic esters such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate and 2-ethylhexyl methacrylate; maleic anhydride Α, β- such as acid and itaconic anhydride
Unsaturated dicarboxylic anhydrides; α, β such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide
-Imide compounds of unsaturated dicarboxylic acids, and the like, and one or more of these monomers can be used.

The method for producing the rubber-containing graft copolymer (B) is not particularly limited, and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are used. There are no particular restrictions on the mixing ratio of the rubbery polymer component, the aromatic vinyl monomer component, the vinyl cyanide monomer component and other copolymerizable monomer components used as necessary. Each component is appropriately blended depending on the use. It is also possible to obtain a rubber-containing graft copolymer (B) by blending separately copolymerized resins.

Generally, the mixing ratio of each component of the rubber-containing graft copolymer (B) is as follows.

Formulation of rubber-containing graft copolymer (B)
%) Rubbery polymer component: 30 to 70 Aromatic vinyl monomer component: 18 to 56 Vinyl cyanide monomer component: 9 to 28 Other copolymerizable monomer component: 0 to 56 The hard copolymer (C) used in (1) is a copolymer containing an aromatic vinyl monomer component, a vinyl cyanide monomer component, and other copolymerizable monomer components used as needed. . Specific examples of these components include those described above in relation to the rubber-containing graft copolymer (B), and the composition ratio thereof is not particularly limited, and is appropriately selected depending on the application. Examples of preferred hard copolymers include SAN resin, styrene-acrylonitrile-α-methylstyrene copolymer, styrene-acrylonitrile-
And N-phenylmaleimide copolymer. The method for producing the hard copolymer (C) is not particularly limited, and a generally known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization is used.

Generally, the mixing ratio of each component of the hard copolymer (C) is as follows.

Hard copolymer (C) blend (% by weight) Aromatic vinyl monomer component: 60 to 80 Vinyl cyanide monomer component: 20 to 40 Other copolymerizable monomer components: 0 to 0 50 A basic resin composition comprising the aromatic polycarbonate resin (A), the rubber-containing graft copolymer (B) and the hard copolymer (C) according to the present invention is known. The composition ratio of the base resin composition is influenced by the rubber content in the rubber-containing graft copolymer (B), but the mechanical properties, thermal properties and fluidity of the obtained resin composition, for example, Strength properties, impact resistance, high rigidity, dimensional stability, heat resistance,
In order to maintain fluidity and the like within a desired range, the aromatic polycarbonate resin (A) component is added to the base resin composition in an amount of 40%.
And the rubber-containing graft copolymer (B) is used in an amount of 5 to 60% by weight, preferably 10 to 20% by weight of the base resin composition. The hard copolymer (C) component is used in an amount of 50% by weight or less, preferably 15% by weight or less of the base resin composition.

As the phosphate ester flame retardant (D) used in the present invention, there can be mentioned a compound represented by the following general formula (I).

[0024]

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In the above general formula (I), the number of carbon atoms of the hydrocarbon group of R ^{a to} R ^c is preferably 2 to 16, particularly preferably 6 to 10. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aralkyl group, an unsubstituted aryl group, and a substituted aryl group, and the substituted aryl group includes an alkaryl group, a cycloalkaryl group, and an aryl-substituted group. Alkaryl groups and aryl-substituted aryl groups. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, neopentyl, 3,5,5-trimethylhexyl,
3-methylhexyl, 2-ethylhexyl and 2,5
5-trimethylhexyl. Examples of cycloalkyl groups include cyclohexyl. Examples of aralkyl groups include benzyl and phenethyl. Examples of unsubstituted aryl groups include phenyl and naphthyl. Examples of alkaryl groups include o-, p- and m-tolyl, 2,6- and 2,4-dimethylphenyl, trimethylphenyl, o-, p- and m-isopropylphenyl, nonylphenyl, pt-
Butylphenyl, 2,4-diisopropylphenyl and triisopropylphenyl. Examples of cycloalkaryl groups include o-cyclohexylphenyl. Examples of aryl-substituted alkaryl groups include p
-Benzylphenyl and p-phenethylphenyl. Examples of aryl-substituted aryl groups include diphenyl.

In the above formula (I), R ^a , R ^b and R ^c are preferably an aryl group or an alkaryl group, and particularly, phenyl, o-, p- and m-tolyl,
Preferred are 2,6-dimethylphenyl and 2,4-diisopropylphenyl.

Specific examples of the phosphate ester flame retardant (D) used in the present invention include the following.

Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (Dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-
Dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctylphosphate, alkoxy as substituents such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate and the like. Preferably, triphenyl phosphate and various bisphosphates are used.

The polyorganosiloxane graft copolymer (E) used in the present invention is obtained by graft copolymerizing a polyorganosiloxane represented by the following general formula (II) with a polyolefin resin.

[0030]

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In the above formula (II), specific examples of R ^{1 to} R ⁸ include, in the case of an aromatic hydrocarbon group, an aryl group such as phenyl, xylyl and tolyl; a halogenated aryl group such as chlorophenyl; Aralkyl groups such as ethyl and benzyl; in the case of aliphatic hydrocarbon groups, alkyl groups such as methyl, ethyl and propyl; alkenyl groups such as vinyl, propenyl and butenyl; cyanoalkyl groups such as cyanoethyl and cyanobutyl; And in the case of an alicyclic hydrocarbon group, cyclohexyl and the like. R ^{1 to} R ⁸ may be the same or different from each other. R ^{1 to} R
⁸ is preferably selected from methyl, phenyl and vinyl.

The polyorganosiloxane represented by the above formula (II) has a reactive functional group such as an epoxy group, an amino group, a carboxylic acid group, a carboxylic ester group, a mercapto group, a hydroxyl group, etc. added to a part thereof. You may use it.
Further, a vinyl group-containing polyorganosiloxane to which an unsaturated group is added may be used.

Examples of the thermoplastic resin for graft copolymerization of such a polyorganosiloxane include polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-
An acrylonitrile copolymer can be used.

The polyorganosiloxane graft copolymer (E) is obtained by kneading 30 to 70% by weight of the above polyorganosiloxane and 70 to 30% by weight of the above thermoplastic resin in the presence or absence of an organic oxide. Can be manufactured.

As the polyorganosiloxane graft copolymer (E), specifically, R ¹ in the above formula (II)
And 60 wt% vinyl functional group containing polyorganosiloxane containing partially unsaturated vinyl groups to R ^8, ethylene -
Polyorganosiloxane graft copolymer "S" obtained by graft copolymerization with 40% by weight of vinyl acetate copolymer
P-110 "(trade name, manufactured by Dow Corning Asia Limited) can be used.

According to the present invention, the combined use of the phosphate ester-based flame retardant (D) and the polyorganosiloxane graft copolymer (E) achieves an excellent flame retarding effect by an excellent synergistic effect, and a polyorganosiloxane. By the graft copolymer (E), good properties such as impact resistance and slidability are obtained, and heat resistance is also good. In order to obtain such a synergistic effect of each component without impairing the physical properties of the base resin composition, in the present invention, the phosphoric ester-based flame retardant (D): 5 with respect to 100 parts by weight of the base resin composition. To 20 parts by weight, preferably 9 to 15 parts by weight Polyorganosiloxane graft copolymer (E):
1 to 5 parts by weight, preferably 0.5 to 4 parts by weight is blended.

If the amount of the polyorganosiloxane graft copolymer (E) is less than 0.1 part by weight, the flame retardancy of UL94 standard V-2 or more cannot be obtained, and if it exceeds 5 parts by weight, the rigidity is reduced, and Flammability also worsens.

In the present invention, a fluorinated hydrocarbon obtained by polymerizing tetrafluoroethylene as a main component, for example, polytetrafluoroethylene, may be further blended as an anti-dripping agent. In this case, the compounding amount of the polytetrafluoroethylene is 0.01 to 2 parts by weight, particularly 0.05 to 1.0 part by weight based on 100 parts by weight of the base resin composition.
It is preferred to use parts by weight.

In addition to the above components, the flame-retardant resin composition of the present invention may be used at the time of production (at the time of mixing) or at the time of molding, as long as the physical properties are not impaired. It is possible to add additives such as pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidant deterioration inhibitors, weathering agents, lubricants, mold release agents, plasticizers, antistatic agents and the like. it can.

The method for producing such a flame-retardant resin composition of the present invention is not particularly limited, and it can be produced using a commonly used method and apparatus. A commonly used method is a melt mixing method, and examples of the apparatus include an extruder, a Banbury mixer, a roller,
Kneaders and the like can be mentioned. This production may be either a batch system or a continuous system, and the mixing order of the components is not particularly limited, as long as all the components are completely mixed.

[0041]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.

The aromatic polycarbonate resin (A), rubber-containing graft copolymer (B), hard copolymer (C), phosphate ester flame retardant (D), The organosiloxane graft copolymer (E) is as follows: (A) Aromatic polycarbonate resin: Panlite L-1
250 (manufactured by Teijin Chemicals Ltd.)) (Aromatic polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane and phosgene (B) Rubber-containing graft copolymer: Graft copolymer B- 1: ABS resin by emulsion polymerization 50% by weight of polybutadiene 35% by weight of styrene 15% by weight of acrylonitrile Graft copolymer B-2: AAS resin by emulsion polymerization 50% by weight of acrylate rubber 50% by weight of styrene 15% by weight of acrylonitrile (C) Hard copolymer: SAN resin by suspension polymerization 74% by weight of styrene 26% by weight of acrylonitrile (D) Phosphate ester flame retardant: Triphenyl phosphate (TPP) Product name "CR733S" manufactured by Daihachi Chemical Co., Ltd. An aromatic phosphoric acid oligomer of the formula (wherein n is one or more Number))

[0043]

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(E) Polyorganosiloxane graft copolymer: trade name "SP-110" manufactured by Dow Corning Asia Co., Ltd. Examples 1 to 8, Comparative Examples 1 to 5 The mixture was mixed with a Henschel mixer and kneaded into pellets with an extruder. The obtained pellet was injection molded at 260 ° C. to obtain a molded product. The physical properties and flame retardancy of the obtained molded article were evaluated by the following test methods, and the results are shown in Tables 2 and 3.

Izod impact strength (Kg · cm / c
m): Measured according to ASTM D256 with a thickness of 1/8 inch and notch. Flexural modulus (Kg / cm ² ): ASTM D 79
0 was measured. Heat distortion temperature (° C.): Measured according to ASTM D 648-56. Dynamic friction coefficient (-): Measured in accordance with JIS K7218-A method. Test conditions Material: Polyquinmethylene Test load: 1.5 kg Test speed: 100 mm / sec Flame retardancy: Thickness of 1 according to UL94 standard test method
Tests were performed at / 10, 1/12 and 1/16 inch.
Based on the test results of the test materials (sample number of evaluation of V: 5, sample number of evaluation of HB: 3), UL-94 V-
The rating was 0, V-1, V-2, or HB. The outline of the criteria for each grade is as follows.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

As is clear from Tables 2 and 3, the flame-retardant resin compositions of the present invention (Examples 1 to 8) have good impact strength, flexural modulus, heat deformation temperature and various physical properties of slidability. The test pieces of all thicknesses of 1/10 ", 1/12" and 1/16 "exhibited excellent flame retardancy.

On the other hand, resin compositions outside the scope of the present invention (Comparative Examples 1 to 5) are inferior in flame retardancy and / or other physical properties. In particular, in Comparative Examples 1 and 5 in which the polyorganosiloxane graft copolymer was not blended, and in Comparative Examples 2 and 4 in which the blended amount of the polyorganosiloxane graft copolymer was large, the flexural modulus was low and the flame retardancy was low. Poor characteristics. In addition, when the polyorganosiloxane graft copolymer of Comparative Example 3 was blended with polymethylphenyl silicone instead of the polyorganosiloxane graft copolymer, sufficient flame retardancy was not obtained.

[0051]

As described in detail above, the flame-retardant resin composition of the present invention is excellent in strength characteristics such as impact resistance and rigidity, flame retardancy, slidability, fluidity, thermal stability and the like. In particular, since it is extremely excellent in impact resistance, slidability and flame retardancy, even in a thin-walled molded product, its properties are sufficiently exhibited.
It can sufficiently respond to demands for housing materials and enclosure materials of equipment, and is industrially very useful.
Further, since an organic halogen compound is not used as a flame retardant, it is very useful from the viewpoint of environmental problems.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25:12 83:04) (C08L 55/02 69:00 25:12 83:04)

Claims (1)

[Claims] (A) Aromatic polycarbonate resin 40
(B) graft polymerization of an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable monomers used as needed with the presence of a rubber polymer. 5 to 60% by weight of a rubber-containing graft copolymer comprising:
(C) a base containing 50% by weight or less of a hard copolymer obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomers used as required. (D) 5 to 20 parts by weight of a phosphoric ester-based flame retardant, and (E) polyorganosiloxane graft copolymer 0.1 with respect to 100 parts by weight of the base resin composition.
To 5 parts by weight.