JPH0292947A - Flame retardant resin composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant resin composition, and more specifically, it is used in industrial applications that require flame retardancy such as electrical/electronic materials, automobile parts, household kitchen appliances, etc. The present invention relates to a resin composition suitable for molding household materials.

[Problems to be solved by conventional techniques and inventions] In recent years,
There are strict requirements for flame retardancy in the electric/electronic and automobile fields, and in particular, melt dripping of resin during combustion can cause fire spread, so prevention of melt dripping is strongly desired from a safety standpoint.

By the way, the inventor's group filed a patent application in 1983-492.
In the specification of No. 0, a flame-retardant resin composition mainly consisting of a styrenic polymer having a syndiotactic structure, a flame retardant and a flame retardant auxiliary agent is proposed. This flame-retardant resin composition has excellent flame retardancy (self-extinguishing properties) to some extent and is also heat resistant.

Although molded products with excellent mechanical strength can be obtained,
Among flame retardant properties, there was room for improvement in terms of prevention of resin melting and dripping.

The object of the present invention is to eliminate the above-mentioned conventional drawbacks, and in particular to provide a resin composition that can suppress melt dripping of resin during combustion, effectively prevent the spread of fire due to melt dripping, and has excellent mechanical properties. Our goal is to provide the following.

[Means to solve the problem]

That is, in the present invention, (A) 100 parts by weight of a styrene resin mainly having a syndiotactic structure, (B) 3 to 100 parts by weight of a flame retardant.
Weight part.

(C) 1 to 30 parts by weight of flame retardant aid and (D) 0.003 to 10 parts by weight of tetrafluoroethylene polymer
A flame retardant resin composition is provided in which the composition is blended in the following proportions: (E) 5 to 150 parts by weight of a thermoplastic resin and 5 parts by weight of a rubber-like elastic body;
The present invention provides a flame-retardant resin composition containing at least one of 1 to 100 parts by weight of an inorganic filler and 1 to 300 parts by weight of an inorganic filler.

The flame-retardant resin composition of the present invention includes the above (A) and (B).

(C) and (D) components or (A), (B), (
C) The main components are components (D) and (E).

Here, component (A) is a styrenic resin mainly having a syndiotactic structure. It has a three-dimensional structure in which side chain phenyl groups and substituted phenyl groups are alternately located in opposite directions with respect to the main chain, and its toughness is determined by nuclear magnetic resonance (C-NMR) method using carbon isotopes. method).l:lc
Cuticity measured by the NMR method is the proportion of a plurality of consecutive constituent units, for example, diat if there are two, and triat if there are three.

The case of 5 can be represented by a pentad, but
In the present invention, the styrenic polymer mainly having a syndiotactic structure is usually 75% or more, preferably 85% or more in terms of diad, or 30% or more, preferably 50% or more in pentad (racemic pentad). Polystyrene, poly(
Poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinylbenzoic M ester), mixtures thereof, or copolymers having these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene),
Examples include poly(tert-butylstyrene), and examples of poly(halogenated styrene) include poly(chlorostyrene).

Examples include poly(bromostyrene) and poly(fluorostyrene). Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly( m-chlorostyrene), poly(p-fluorostyrene), and copolymers of styrene and p-methylstyrene (Japanese Patent Application Laid-Open No. 62-187).
Publication No. 708).

The styrene resin used in the present invention is not particularly limited in molecular weight, but preferably has a weight average molecular weight of 10.000 or more, particularly 50.000 to 1,000.
0,000 is optimal. If the weight average molecular weight is less than 10.000, solvent resistance tends to be insufficient. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. This styrenic polymer mainly having a syndiotactic structure has a melting point of 160 to 310°C, and has much better heat resistance than conventional styrenic polymers having an atactic structure.

Such styrenic resins, which mainly have a syndiotactic structure, can be produced using styrenic monomers, for example, in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer corresponding to the above-mentioned styrenic polymer.

Next, in the present invention, a flame retardant is used as component (B).

Although various flame retardants can be mentioned here, halogen-based flame retardants and phosphorus-based flame retardants are particularly preferred. Examples of halogenated flame retardants include tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, tribromophenyl allyl ether, pentabromotoluene, pentabromophenol, tribromophenyl-2゜3-dibromo-propyl ether, tris (2
゜3-dibromo10biru) phosphate tris(2-
chloro-3-bromopropyl) phosphate, octabromodiphenyl ether, decabromodiphenyl ether, octabromo biphenyl.

Pentachloropentacyclodecane, hexabromocyclododecane, hexachlorobenzene, pentachlorotoluene, hexabromobiphenyl, decabromobiphenyl,
decabromobiphenyl oxide, tetrabromobutane,
Decabromodiphenyl ether, hexabromodiphenyl ether, ethylene-bis-(tetrabromophthalimide).

Bromination of tetrachlorobisphenol A, tetrabromobisphenol A, oligomers of tetrachlorobisphenol A or tetrabromobisphenol A, halogenated polycarbonate oligomers such as brominated polycarbonate oligomers, halogenated epoxy compounds, polychlorostyrene, polytribromostyrene, etc. Examples include polystyrene, poly(dibromophenylene oxide), and bis(tribromophenoxy)ethane.

On the other hand, examples of phosphorus-based flame retardants include ammonium phosphate, tricresyl phosphate triethyl phosphate, acidic phosphoric acid ester, triphenylphosphine oxide, and the like.

Among these flame retardants, polytribromostyrene, poly(dibromophenylene oxide), decabromodiphenyl ether, bis(tribromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, brominated Polycarbonate oligomers are preferred.

The above (B) component (flame retardant) includes the above (A) component and (B)
) It is blended in an amount of 3 to 100 parts by weight, preferably 5 to 90 parts by weight, based on a total of 100 parts by weight of the components.

If the blending ratio of component (B) is less than 3 parts by weight, the resulting resin composition will not have sufficient flame retardancy.

On the other hand, if it exceeds 100 parts by weight, the flame retardance will not improve in proportion to the proportion, and on the contrary, other mechanical properties will be impaired, which is not preferable.

In addition, in the present invention, together with the above-mentioned component (B), (
It is necessary to use a flame retardant aid as component C).

Even if only one of component (B) and component (C) is used, the desired effect cannot be obtained.

There are various flame retardant aids, such as antimony dioxide, antimony pentoxide, sodium antimonate, antimony metal, antimony trichloride, antimony pentachloride, and antimony trisulfide.

Examples include antimony flame retardant aids such as antimony trisulfide. In addition to these, zinc borate, barium metaborate, zirconium oxide, etc. can be mentioned.

Among these, antimony trioxide is particularly preferred as component (C).

Component (C) (flame retardant aid) is blended in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight of component (A).

If the blending ratio of component (C) is less than 1 part by weight, the effect as a flame retardant aid will not be sufficient.

On the other hand, even if the amount exceeds 30 parts by weight, the effect as a flame retardant aid will not improve in accordance with the proportion, and other physical properties may be impaired, which is not preferable.

Furthermore, a tetrafluoroethylene polymer is used as component (D) in the present invention. Specifically, the tetrafluoroethylene polymer includes a tetrafluoroethylene homopolymer (polytetrafluoroethylene), a copolymer of tetrafluoroethylene and hexafluoropropylene,
Further examples include tetrafluoroethylene copolymers containing a small amount of copolymerizable ethylenically unsaturated monomers. The tetrafluoroethylene polymer used contains 165 to 76% by weight of fluorine, preferably 70 to 76% by weight.

The above component (D) is blended in a proportion of 0.003 to 10 parts by weight, preferably 0.02 to 2 parts by weight, and more preferably 0.1 to 2 parts by weight per 100 parts by weight of the component (A). do. If the blending ratio of component (D) is less than 0.003 parts by weight, there is no effect of preventing melt dripping during combustion. On the other hand 10
Even if more than 1 part by weight is added, the effect of preventing melt dripping during combustion will not improve in accordance with the proportion, and on the contrary, other mechanical properties may be impaired, which is not preferable.

The flame retardant resin composition of the present invention basically comprises the above (A) to
It consists of component (D), and in some cases further contains (
One or more of thermoplastic resins, rubber elastic bodies, and inorganic fillers may be blended as component E).

As the thermoplastic resin that can be used as the component (E), various resins can be selected depending on the intended use of the composition, and there are no particular limitations as long as it is a thermoplastic resin other than the component (A).

For example, styrene polymers such as acute structure polystyrene, isotactic structure polystyrene, AS resin, and ABS resin, polyesters such as polyethylene terephthalate, polyethers such as polycarbonate, polyphenylene oxide, polysulfone, and polyethersulfone, and polyphenylene sulfide. (pp.
s).

Condensation polymers such as polyamide and polyoxymethylene,
Polyacrylic acid, polyacrylic ester.

Acrylic polymers such as polymethyl methacrylate, polyethylene, polypropylene, and polybutene.

Examples include polyolefins such as poly-4-methylpentene-1 and ethylene-propylene copolymers, halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride, or mixtures thereof.

Among these, polycarbonate, polyester, AB
S, polyether, etc. are preferred.

When the above thermoplastic resin is used as component (E) of the present invention, this thermoplastic resin is used in a proportion of 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of component (A). It is blended.

Here, if the blending ratio of the thermoplastic resin is less than 5 parts by weight, the effect of blending the thermoplastic resin is not seen;
If it exceeds 0 parts by weight, there will be no significant difference in the properties of the product itself, and no improvement in thermal properties can be expected.

Furthermore, various rubber-like elastic bodies can be used as the component (E), but the most preferable ones are:
It is a rubbery copolymer containing a styrene compound as one of its components. For example, styrene-butadiene copolymer rubber (SBR), rubber in which the butadiene portion of a styrene-butadiene block copolymer is partially or completely hydrogenated (
SEBS), styrene-isoprene block copolymer rubber.

A rubber made by partially or completely hydrogenating the isoprene portion of a styrene-isoprene block copolymer.

Alternatively, as described in Japanese Patent Application No. 63-121700, one or more monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, and polyfunctional monomers having conjugated diene type double bonds. Particulate elastomer obtained by polymerizing a vinyl monomer in the presence of a polymer obtained by polymerizing a polymer, such as acrylonitrile-styrene grafted butadiene rubber (ABS), 7-IJ lonitrile-butadiene grafted rubber Butadiene-butyl acrylate copolymer rubber (AABS), methyl methacrylate-styrene grafted butyl acrylate rubber (MAS), styrene-grafted butadiene rubber (S
B) Methyl methacrylate-styrene grafted butadiene rubber (MBS).

Examples include methyl methacrylate-styrene grafted butadiene-butyl acrylate copolymer rubber (MABS). Since these all have styrene units, they have good dispersibility in styrenic resins mainly having a syndiotactic structure, and as a result, the effect of improving physical properties is remarkable.

In addition to the above, examples of rubber-like elastic bodies include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber,
polysulfide rubber, thiokol rubber, acrylic rubber,
Examples include urethane rubber, silicone rubber, and epichlorohydrin rubber.

The rubber-like elastic body is blended in an amount of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, per 100 parts by weight of component (A). By blending this rubber-like elastic body, mechanical properties, particularly impact resistance, etc. are further improved. If the blending ratio is less than 5 parts by weight, impact strength and elongation will not be improved enough, and if it exceeds 100 parts by weight, rigidity and heat resistance will not be improved enough.

Furthermore, the inorganic filler that can be used as component (E) may be fibrous, granular, or powdery. Examples of the fibrous inorganic filler include glass fiber, carbon fiber, and alumina fiber, with glass fiber and carbon fiber being particularly preferred.

Here, the shapes of glass fibers include cross, mat,
There are bundle-cut, short fiber, and filament shapes.
Preferably, it has a convergent cut shape and a length of 0.05 wn
~13 m, with a fiber diameter of 5 to 20 μm, and is particularly preferably treated with silane. The carbon fiber is preferably polyacrylonitrile (PAN), and more preferably chopped carbon fiber. A fiber type bundle with a length of about 31 mm and a diameter of 7 to 15 μm is preferable.

On the other hand, talc is used as a granular and powdery inorganic filler.

Carbon black, graphite, titanium dioxide.

Silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate.

Examples include tin oxide, alumina, kaolin, silicon carbide, metal powder, and the like. Particularly preferred are talc, calcium carbonate, and mica. The preferred average particle size of talc is 0.3 to 20
It is preferably 0.6 to 10 μm, more preferably 0.6 to 10 μm. The preferred average particle size of calcium carbonate is 0.1-20μ
It is m. In addition, the preferred average particle size of mica is 40 to 2
It is 50 μm, more preferably 50 to 150 μm.

The inorganic filler is blended in an amount of 1 to 300 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts by weight of component (A). Here, if the blending ratio of the inorganic filler is less than 1 part by weight, a sufficient blending effect as a filler will not be recognized. On the other hand, if it exceeds 300 parts by weight, uniform dispersion may not be possible and the resulting composition may have poor mechanical strength.

As the component (E) of the present invention, at least one of the above-mentioned thermoplastic phase, rubber-like elasticity, and inorganic filler can be used, and not only one kind but also two or more kinds can be used in an appropriate combination. can.

The flame-retardant resin composition of the present invention consists of the above-mentioned components (A) to (D) and, if necessary, the component (E). Additives or other synthetic resins may be added as necessary. Here, the additive is, for example, a phosphite type.

Phosphoric acid ester-based antioxidants, benzotriazole-based and benzophenone-based ultraviolet absorbers, aliphatic carboxylic acid ester-based and paraffin-based external lubricants, commonly used nucleating agents, mold release agents, antistatic agents, 8 colorants, etc. Can be mentioned. Examples of other synthetic resins include polyethylene, polypropylene, polystyrene, AS resin, ABS resin, and polymethyl methacrylate.

The resin composition of the present invention is obtained by blending the above components (A) and (D), optionally component (E), and further various desired components as necessary, and kneading at an appropriate temperature, for example, 270 to 320°C. be able to. The blending and kneading at this time may be carried out by conventional methods. Specifically, a melt kneading method using a kneader, a mixing roll, an extruder, a Banbury mixer, a Henschel mixer, a kneading roll, or a solution blending method may be used.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Reference Example 1 (Production of polystyrene having a syndiotactic structure) To a reaction vessel, 21 toluene as a solvent, 5 mmol of tetraethoxytitanium as a catalyst component, and 500 mmol of methylaluminoxane as an aluminum atom were added.
Styrene 151 was added to this at 5°C, and a polymerization reaction was carried out for 4 hours.

After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component. It was then dried to obtain 2.5 kg of a styrene polymer (polystyrene). Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 97% by weight. The weight average molecular weight of this product is 400.000, and the number average molecular weight is 180.0.
00, and the melting point was 269°C. In addition, this polymer was analyzed by lcoC-NMR (i9 medium: 1.2-
Dichlorobenzene), absorption was observed at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in racemic pentad calculated from the peak area was 98%.

Example 1 100 parts by weight of the syndiotactic polystyrene obtained in Reference Example 1 was added with (2,6-di-t) as an antioxidant.
er t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name PEP-36: manufactured by Adeka Argus) 0.7 parts by weight and 2.6-diter
Add 0.1 part by weight of t-butyl-4-methylphenol (trade name: Sumilizer BHT, manufactured by Sumitomo Chemical ■), and further add 23 parts by weight of polytribromostyrene, 6 parts by weight of antimony trioxide (SbzOs), and polytetrafluoroethylene. After 0.3 parts by weight were mixed and triblended, the mixture was kneaded using a twin-screw kneading extruder to form tablets.

Using the obtained pellet, injection molding was carried out to 1/32
An inch-thick flammability test piece was prepared, and a flammability test was conducted based on the UL94 standard. The results of this flammability test are shown in Table 2 together with the results of impact strength and bending strength measurements.

Examples 2 to 8 and Comparative Examples 1 to 3 Test pieces were prepared in the same manner as in Example 1, except that the components (A) to (E) shown in Table 1 were blended in a predetermined ratio. A similar evaluation was conducted. The results are shown in Table 2.

(Left below) *2 *3 *4 Styrenic resin syndiotactic; Polystyrene flame retardant having a syndiotactic structure obtained in Reference Example 1 a: Polytrifluoromostyrene...manufactured by Nissho Ferro Co., Ltd., Pyrocheck 68 PBb2 Decabromodiphenyl ether...manufactured by Ethyl Corporation, 5AYT
EX 102C: Poly(dibromophenylene oxide)
...manufactured by Breitlake, GLCPO-64P tetrafluoro-engineered tyrene polymer polytetrafluoroethylene (manufactured by DuPont, product name:
Teflon) Thermoplastic resin PC: Polycarbonate (manufactured by Idemitsu Petrochemical ■, Idemitsu Polycarbonate) A 3000) GPPS: General-purpose polystyrene (manufactured by Idemitsu Petrochemical ■, Idemitsu Polystyrene US
-305) *5 Rubber-like elastic body SB: Styrene-grafted butadiene rubber (particle size 0.7
μm, manufactured by Mitsubishi Rayon Co., Ltd., prototype product name Metablane I
P-2) MAS: Methyl methacrylate-n-butyl acrylate-styrene copolymer (manufactured by Rohm & Haas, KM 330) *6 Inorganic filler GF Niglass fiber (manufactured by Asahi Fiber Co., Ltd.).

C3O3MA 429A, fiber length 3am.

Fiber diameter 13μm) Talc: Made by Asada Seifun■, talc FFR.

Average particle size: 0.6 μm (hereinafter referred to as blank space) [Effects of the invention] As described above, the resin composition of the present invention has excellent flame retardancy, and particularly suppresses melt dripping of the resin during combustion and prevents the spread of fire due to melt dripping. It can be effectively prevented.

Furthermore, the resin composition of the present invention has excellent mechanical properties.

Furthermore, the resin composition of the present invention, which contains at least one of a thermoplastic resin, a rubber-like elastomer, and an inorganic filler, has further improved mechanical properties while maintaining excellent flame retardancy. It is something.

Therefore, the resin composition of the present invention is flame retardant.

As an engineering plastic with excellent mechanical properties, it is used in electrical and electronic materials, automobile parts, home kitchen appliances, etc.
Particularly effective use is expected in applications requiring flame retardancy.

Procedural amendment (voluntary) December 28, 1989

Claims (2)

[Claims] (1) (A) 3 to 100 parts by weight of a flame retardant (B) 3 to 100 parts by weight of a flame retardant, (C) 1 to 30 parts by weight of a flame retardant aid, and (D) Tetra Fluoroethylene polymer 0.003-10
A flame-retardant resin composition that is blended in parts by weight. (2) (A) 3 to 100 parts by weight of a flame retardant, (C) 1 to 30 parts by weight of a flame retardant aid, (D) Tetra Fluoroethylene polymer 0.003-10
Parts by weight and (E) 5 to 150 parts by weight of thermoplastic resin, 5 parts by weight of rubber-like elastic body
A flame-retardant resin composition containing at least one of ~100 parts by weight and 1 to 300 parts by weight of an inorganic filler.