JPH02199162A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. with excellent mechanical characteristics an moldability and a flame retardancy satisfying a specified standard by compounding a flame-retardant, a flame-retardant auxiliary and, in addition, polyetrafluoroethylene and an inorg. filler with a polycarbonate resin and a rubber-contg. thermoplastic resin. CONSTITUTION:100 pts.wt. (hereinbelow described as pts.) resin. compsn. consisting of 20-95wt.% (hereinbelow described as %) polycarbonate resin, 5-80% rubber-contg. thermoplastic resin obtd. by copolymerizing 2 or more vinyl monomers selected from (meth)acrylates, arom. monovinyl compd. and vinyl cyanide compd. in the presence of butadiene rubber, 0-50% thermoplastic resin obtd. by copolymerizing an arom. vinyl monomer and a vinyl cyanide monomer and 0-25% halogenated flame retardant and contg. 0.5-15% halogen atom is compounded with 1-15 pts. flame-retardant auxiliary, 0.02-2.0 pts. fibril-forming polytetrafluoroethylene and 3-100 pts. filler selected from glass beads, glass flakes, talc, diatomaceous earth, etc., to obtain a flame-retardant resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a flame-retardant resin composition. For more details,
The present invention relates to a resin composition having excellent flammability that satisfies UL standard 94-5V.

<Prior Art> Polycarbonate resins have various advantages such as excellent mechanical properties and thermal properties, and are therefore widely used in the industry. However, polycarbonate resin has the disadvantage of poor moldability, and blends with other thermoplastic resins, such as 70I, are being considered. Among them, ABS
Blends with resins are widely used in the automobile field, OA equipment field, electronic/electrical field, etc.

By the way, in recent years, flame retardant standards such as UL standards regarding the safety of thermoplastic resins have been strengthened year by year, so there is a strong demand for highly flame-retardant thermoplastic resins.

In particular, materials used for the exterior of electrical equipment such as OA housings are required to pass UL standard 94-5V.

Conventionally, in order to make polycarbonate resin and ABS resin blends flame retardant, flame retardants such as organic halogen compounds have been added, or metal oxides such as antimony trioxide have been added as flame retardant aids along with the flame retardant. It is being done.

However, even if flame retardants and flame retardant aids are added to the dormitory mat, the U
It was difficult to pass L94-5V.

<Object of the Invention> An object of the present invention is to provide a flame-retardant resin composition that has excellent mechanical properties and moldability and satisfies UL94-5V.

The inventors of the present invention have intensively investigated ways to pass tJL94-5V for blends of polycarbonate resin and ABS resin, and have added flame retardants and H combustion aids to polytetrafluorocarbons, which have the ability to form fibrils. The present invention was achieved by discovering that UL standard 94-5V can be satisfied by blending inorganic fillers such as fluoroethylene and talc.

<Structure of the Invention> The present invention provides a group consisting of a methacrylic acid ester, an acrylic acid ester, an aromatic monovinyl compound, and a vinyl cyanide compound in the presence of (A) a polycarbonate resin of 20 to 95 wt ω% (B) a butadiene rubber. Rubber-containing thermoplastic resin 5 copolymerized with at least two vinyl monomers selected from
~80% by weight (C) 0 to 50% by weight thermoplastic resin copolymerized with aromatic vinyl monomer and vinyl cyanide monomer (D) Halogen flame retardant 0 to 25% by weight, containing halogen atoms 065
(E) 1 to 15 parts by weight of a flame retardant aid (F) Polytetrafluoroethylene o, oi having fibril-forming ability to 100 parts by weight of the resin composition containing ~15% by weight (G) 3 to 100 parts by weight of at least one filler selected from the group consisting of glass beads, glass flakes, inorganic fibers with L/D≦10, talc, steel slag, silica, diatomaceous earth, mica, and calcium carbonate; Combined, LJL rules! The present invention relates to a resin composition having excellent flame retardancy that satisfies 894-5V.

The polycarbonate resin (A) used in the present invention is produced by reacting dihydric phenol and a carbonate precursor by a solution method or a melt method.

Representative examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1.1
-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane.

2.2-bis(4-hydroxy-3-methylphenyl)
Examples include propane, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, and the like. Preferred dihydric phenols are those based on bis(4-hydroxyphenyl)alkanes, particularly bisphenol A as the main raw material.

Further, carbonate precursors include carbonyl halides, carbonyl esters, haloformates, etc., specifically phosgene, diphenyl carbonate, 2
dihaloformates of hydric phenols and mixtures thereof. In producing a polycarbonate resin, the above dihydric phenols can be used alone or in combination of two or more.

Furthermore, two or more of the thus obtained polycarbonate resins may be used in combination.

The viscosity average molecular weight of the polycarbonate resin is generally from 10,000 to 100,000, preferably from 1,50,000 to 60,000.

When producing polycarbonate resins having these viscosity average molecular weights, an appropriate molecular weight regulator, a branching agent for improving processability, a catalyst for promoting the reaction, etc. may be added.

Specific examples of the rubber-containing thermoplastic resin (B) used in the present invention include ABS resin and MBS resin. In addition, examples of the butadiene rubber in this rubber-containing thermoplastic resin include polybutadiene,
Examples include polyisoprene, styrene-1-tadiene copolymer, and acrylonitrile-butadiene copolymer.

Examples of methacrylic esters and acrylic esters include methyl methacrylate, ethyl methacrylate,
Ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate.

Lower alkyl esters of methacrylic acid and acrylic acid, such as propyl acrylate and butyl acrylate, are preferred. Examples of aromatic monovinyl compounds include styrene and α-methylstyrene.

Examples include halogenated styrene and vinyltoluene. Furthermore, examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Rubber-containing thermoplastic resins can be processed by bulk polymerization, solution polymerization, suspension polymerization,
It may be produced by any polymerization method including emulsion polymerization, and the copolymerization method may be single-stage copolymerization or multi-stage copolymerization. Further, two or more types of copolymers may be used in combination.

The thermoplastic resin of component (C) used in the present invention is generally A
These are collectively called S resins. Aromatic vinyl monomer
Examples of the compound include styrene, α-methylstyrene, halogenated styrene, and vinyltoluene, with styrene and α-methylstyrene being particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile. In addition, vinyl monomers that can be copolymerized with these, such as methyl methacrylate,
Maleimide or the like may be copolymerized.

The flame retardant (D) used in the present invention is not particularly limited as long as it is a halogen compound commonly used as a flame retardant. Preferred specific examples include hexabromobenzene, pentabromotoluene, and biphenyl bromide.

Triphenyl chloride, diphenyl ether bromide, tetrachlorophthalic acid, tetrabromo phthalic anhydride.

Tribromophenol, dibromoalkyl diphenyl ether, tetrabromo-sphenol S.

Tetrachlorobisphenol A, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, tetrabromobisphenol sulfone, tetrabromobisphenol ether, polycarbonate oligomer of tetrabromobisphenol A Copolymerization of tetrabromobisphenol A and bisphenol In addition to polycarbonate oligomers, aromatic halogen compounds represented by the following formula can be mentioned.

m1 = integer of 1 to 5 n1 = integer of 1 to 5 Other specific examples of organic halogen compounds that can be used as flame retardants in the present invention include monochloropentabromocyclohexane, hexabromocyclododecane, perchloropentacyclodecane, and hexachloro. Alicyclic halogen compounds such as endomethylenetetrahydrophthalic anhydride, chlorinated paraffin, chlorinated polyethylene, tetrabromobutane, tris (β-chloroethyl) phosphate.

Examples include aliphatic halogen compounds such as tris(dichloropropyl)phosphate. Particularly preferred are bisphenol A halides, derivatives thereof, carbonate oligomers thereof, and copolymerized carbonate oligomers having the following structure m2 = 1 to 5, integer n2 = 1 to 5 integers (where X represents a halogen atom). These flame retardants may be used alone or
Two or more types may be combined.

The blending ratio of the above (A) to (D) components is 20% of the (A) component.
-95% by weight, preferably 30-90% by weight, 5-80% by weight of component (B), preferably 10-70% by weight, (C
) component is 0 to 50% by weight, component (0) is 0 to 25% by weight, and the total amount of halogen atoms in all components is 0.5 to 15% by weight. If component (A) is less than 20% by weight, that is, the total amount of components (B), (C), and (D) exceeds 80% by weight, mechanical properties and thermal properties will deteriorate; When the component exceeds 95% by weight, i.e. (B),
(C).

If the total content of component (D) is less than 5% by weight, the molding processability deteriorates, which is not suitable. Furthermore, if the total amount of halogen atoms in components (A) to (0) is less than 0.5% by weight, the following (E)
), component (F) and component (G) are added in sufficient amounts, sufficient flame retardancy cannot be obtained and the total amount of halogen atoms exceeds 15% by weight, or the amount of component (D) used is 2
Mechanical strength exceeds 5% by weight.

Thermal stability begins to decrease.

Furthermore, when adding component (C), it should be added in an amount of 50 or less with respect to the total amount of components (A) to (D).

If the weight exceeds 50, the mechanical properties and thermal properties will deteriorate. (D) Ingredient (A) depends on the amount used.
~(0) The total amount of halogen atoms in the component is 0.5 to 15
Adjust the weight percentage. Especially (A).

(B), (C) contains no halogen atoms, (D
) A preferred embodiment is one in which a predetermined amount of halogen atoms are contained only by the component.

The flame retardant aid (E) used in the present invention is not particularly limited as long as it promotes the above flame retardant effect, and examples include antimony compounds, borates, etc., with antimony compounds being particularly preferred. Antimony compounds include antimony trioxide, sodium antimonate, antimony metal, and antimony trichloride.

Antimony pentachloride, antimony antimony, antimony pentoxide, etc. can be used. Examples of borates include zinc borates such as zinc tetraborate, zinc metaborate, and basic zinc borate, barium orthoborate, barium metaborate, and barium diborate.

Barium borate such as barium tetraborate, lead borate.

Cadmium borate, magnesium borate, etc. can be used. These flame retardant aids may be used alone, or
Two or more types can also be used in combination.

The blending ratio of (E) flame retardant aid used in the present invention is (A
), 1 to 15 parts by weight, preferably 1 to 15 parts by weight, based on a total of 100 parts by weight of component (B), component (C) and component (D).
~10 parts by weight. If it is less than 1 part by weight, the effect of promoting flame retardancy will be insufficient, while if it exceeds 15 parts by weight, mechanical strength will decrease.

The polytetrafluoroethylene (CF) used in the present invention has fibril-forming ability and is classified as type 3 according to the A31M standard, and the object of the present invention cannot be achieved if it does not have fibril-forming ability.

The above-mentioned polytetrafluoroethylene having fibril-forming ability is available from Mitsui DuPont Fluorochemical ■, for example.
It is easily available commercially as Teflon 6J or as Polyflon from Daikin Chemical Industries.

The blending ratio of (F) polytetrafluoroethylene used in the present invention is from 0.01 to 100 parts by weight in total of component (A), component (B), component (C) and component (D).
A small amount of 2.0 parts by weight is sufficient, preferably 0.05 to 1,000 parts by weight.
It is 0 parts by weight. If it is less than 0.01 part by weight, it is insufficient to provide non-dripping properties during combustion, and it meets UL standard 94-5.
Unable to satisfy method A in V test, and 2.
If it exceeds 0 parts by weight, the viscosity of the resin increases significantly, making it undesirable as a molding material.

The filler (G) used in the present invention is glass beads.

Glass flakes, inorganic fibers with L/D≦10 (where D is the length and D is the diameter), talc, and steel slag.

Inorganic fillers such as silica, diatomaceous earth, mica, and calcium carbonate. Among them, glass beads, glass flakes, non-fibers, talc, steel slag, and silica are preferred, and glass beads, glass fiber powder, carbon fiber powder, whiskers, talc with an average particle size of 50 μm or less, and steel slag are particularly preferred. It is also preferable to treat these fillers with a silane coupling agent.

The blending ratio of the inorganic filler (G) used in the present invention is (
3 to 100 parts by weight based on a total of 100 parts by weight of component A), component (B), component (C) and component (D),
Preferably it is 5 to 50 parts by weight. If less than 3 parts by weight, U
It cannot satisfy the B method in the L standard 94-5V test, and if it exceeds 100 parts by weight, the mechanical strength will drop significantly.

The resin composition of the present invention can be produced by mixing the above-mentioned components using a mixer such as a tumbler V-type blender, a Nauta mixer, a Banbury mixer 1 kneading roll, or an extruder.

Polyester, as long as the purpose of the present invention is not impaired.
Other resins such as polyamide and polyphenylene ether, as well as the resin composition of the present invention, may contain various additives, such as stabilizers, mold release agents, ultraviolet absorbers, and dyeing agents, in amounts necessary to achieve their effects. There is no problem even if fees etc. are included.

The thus prepared flame-retardant resin composition can be easily molded by extrusion molding, injection molding, compression molding, etc., and can also be applied to blow molding, vacuum molding, etc.
It can be suitably used for housings of electronic/electrical products and OA equipment that require -94-5V, and as a material for various parts.

<Example> EXAMPLES The present invention will be specifically explained below with reference to Examples.

Examples 1 to 6 and Comparative Examples 1 to 3 Each component listed in Table 1 was mixed in a V-type blender at the blending ratio listed in the table, and then extruded to 30 mmφ (Nakata 2, V
SK-30) at a cylinder temperature of 260° C. to pelletize.

The obtained pellets were dried at 110°C for 5 hours, and then molded using an injection molding machine (Japan Steel Works ■, J-120SA) at a cylinder temperature of 260°C and a mold temperature of 80°C for 5°.

X1/2°'x3mm and 5"XI/2°'X2,5
A 111 m UL-94-5V A method combustion test piece was created.

Similarly, after drying the pellets at 110°C for 5 hours, they were molded using an injection molding machine (Japan Steel Works, J-120S^) at a cylinder temperature of 260°C and a mold temperature of 90°C.

U of X6°'x3mm and 6"X6°'x2.5u
L-94-5V B method combustion test pieces were created.

A UL standard 94-5V combustion test was conducted using the above two types of test pieces. Those that passed each combustion test are marked with an O, those that did not pass are marked with an X, and the results are listed in Table 1.
It was shown to.

The symbols in the table are as follows.

(A) PC: Polycarbonate resin, Yojin Kasei ■Panlite L-1250 (B) ABS: ABS resin, Daicel ■Sevian MB
5: MBS resin, Kanegafuchi Chemical Industry ■B-28(C)A
S: AS resin, Asahi Kasei Kogyo ■Tyril 767 (D) Flame retardant: Polycarbonate oligomer of tetrabromobisphenol A Large amount Kasei ■ FG-7000 (E) Flame retardant aid antimony ditrioxide.

Sumitomo Kinkuta Mine ■ (F) PTFE: Polytetrafluoroethylene, Mitsui DuPont Fluorochemical ■ Teflon 6J (G) Taruri Nippon Taruri ■, P-2 MF Nigarasu Powder, Nitto Boseki ■ L/D ~ 8 thing.

Claims (1)

[Scope of Claims] (A) 20 to 95% by weight of polycarbonate resin (B) selected from the group consisting of methacrylic ester, acrylic ester, aromatic monovinyl compound, and vinyl cyanide compound in the presence of butadiene rubber Rubber-containing thermoplastic resin copolymerized with at least two types of vinyl monomers 5
~80% by weight (C) 0 to 50% by weight thermoplastic resin made by copolymerizing aromatic vinyl monomers and vinyl cyanide monomers (D) Halogen flame retardant 0 to 25% by weight Consisting of halogen atoms (E) 1 to 15 parts by weight of a flame retardant aid (F) 0.01 to 2.0 parts of polytetrafluoroethylene having fibril-forming ability per 100 parts by weight of the resin composition containing 0.5 to 15% by weight Weight part (G) 3 to 100 weight parts of at least one filler selected from the group consisting of glass beads, glass flakes, inorganic fibers with L/D≦10, talc, steel slag, silica, diatomaceous earth, mica, and calcium carbonate. A flame-retardant resin composition comprising: