JPH09151297A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin compsn. improved in flowability, impact strength, and mold-staining properties by compounding a specific resin component with a polyphosphate compd., a halogenated epoxy resin, and a fluororesin. SOLUTION: This flame-retardant resin compsn. is obtd. by compounding 100 pts.wt. resin component comprising 10-90wt.% polycarbonate and 90-10wt.% styrenic resin with 1-30pts.wt. polyphosphate compd. represented by formula I, II, III, or IV, 1-30 pts.wt. halogenated epoxy resin represented by formula V, and 0.05-5 pts.wt. fluororesin. The styrenic resin comprises 0-90wt.% copolymer formed from 50-90wt.% arom. vinyl (α), 10-40wt.% vinyl cyanide (β), 0-40wt.% alkyl (meth)acrylate (γ), and 0-40wt.% N-substd. maleimimde and 100-10wt.% graft copolymer formed by grafting 90-5wt.% monomer mixture comprising monomer α, monomer β, monomer γ, and another copolymerizable monomer (δ) and satisfying the table onto 10-95wt.% rubbery polymer having a glass transition point of 20 deg.C of lower.

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 having excellent fluidity, and more specifically, it is made of polycarbonate and styrene resin and has excellent fluidity, impact resistance and mold stain resistance. Also relates to an excellent flame-retardant resin composition.

[0002]

2. Description of the Related Art A mixture of polycarbonate and styrene resin is widely used for mechanical, electric and electronic parts because it is excellent in impact resistance, heat resistance and moldability. In recent years, demands for OA equipment and home appliance parts have been increasing, and flame retardancy is inevitable for that purpose.

Usually, a halogen-based flame retardant is used to make a synthetic resin flame-retardant. However, most resin compositions containing only a halogen-based flame retardant have poor moldability and impair the appearance of a molded article. Occurs.

To make a mixture of a polycarbonate and a styrene resin flame-retardant, a brominated polycarbonate oligomer or a monophosphoric acid ester compound is added. Poor, and in the latter case gas is generated during molding, which not only impairs the appearance of the molded body, but many resin compositions containing only a phosphorus compound contain polycarbonate in order to maintain flame retardancy. The amount may be relatively high, the moldability may be poor, and the appearance of the molded product may be impaired.

[0005]

In view of the above points, the present invention is a mixture of a polycarbonate and a styrene resin, which has excellent fluidity, good moldability, impact resistance and mold stain resistance. It is intended to provide an excellent flame-retardant resin composition.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above objects, the present inventors have found that a specific condensed phosphorus compound and a halogenated epoxy resin are used in combination with a mixture of a polycarbonate and a styrene resin. It was found that a resin composition excellent in flame retardancy, fluidity, impact resistance, and mold contamination can be obtained by the addition, and the present invention has been completed.

That is, the present invention provides the following components (A) to (E).
1 to 30 parts by weight of the component (C) with respect to 100 parts by weight of the resin component containing 10 to 90 parts by weight of the component (A) and 90 to 10 parts by weight of the component (B). A flame-retardant resin composition in which (D) is 1 to 30 parts by weight and component (E) is 0.05 to 5 parts by weight. (A) Polycarbonate, (B) 0 to 90% by weight of the following component (Ba) and the component (B
b) 100 to 10% by weight of a styrene resin, (Ba) a copolymer of the following components (Ba1) to (Ba4) (Ba1) aromatic vinyl 50 to 90% by weight (Ba2) vinyl cyanide 10 -40% by weight (Ba3) Alkyl methacrylate and / or alkyl acrylate 0-40% by weight (Ba4) N-substituted maleimide 0-40% by weight (Bb) Ingredient (Bb1) 10-95% by weight (Bb2) Graft copolymer obtained by grafting 90 to 5% by weight (Bb1) Rubber-like polymer having a glass transition point Tg ≦ 20 ° C. (Bb2) Constituting the following components (α) to (δ) Satisfactory Monomer Mixture (α) Aromatic Vinyl (β) Vinyl Cyanide (γ) Alkyl Methacrylate and / or Alkyl Acrylate (δ) Other Copolymerizable Vinyl Formula (I): 10 ≦ β + γ / 4 ≦ 40 δ = 100−β−γ−α β ≧ 0, γ ≧ 0 0 ≦ α ≦ 90, 0 = δ ≦ 20, where α, β, γ, and δ are The weight ratio (%) is shown. ] (C) The following general formulas [I] to [IV]:

Embedded image [In the formula, R _{1 to} R ₈ are each a hydrogen atom or a carbon number 1
To 3 are shown, and n shows the integer of 1-5. ]
One or more compounds selected from the group consisting of resorcin polyphosphate compounds, hydroquinone polyphosphate compounds, 4,4′-bisphenol polyphosphate compounds, and bisphenol A polyphosphate compounds represented by: (D) The following formula [V]

Embedded image A halogenated epoxy resin represented by: (E) a fluororesin.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate (A) used in the present invention is preferably a thermoplastic aromatic polycarbonate, more preferably an aromatic polycarbonate produced by reacting a dihydric phenol compound with phosgene or a carbonic acid diester. As the above dihydric phenol compound,
Bisphenols are preferred, especially 2,2-bis (4-
Hydroxyphenyl) propane, so-called bisphenol A, is preferred. It is also possible to substitute a fixed amount or a total amount of bisphenol A with another phenol compound. As divalent phenol compounds other than bisphenol A,
Examples thereof include compounds such as hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl) ketone. It may be a homopolymer composed of these dihydric phenol compounds, a copolymer composed of two or more kinds, or a blend thereof. Further, a phosphorus compound can be used for copolymerization or end capping in order to enhance flame retardancy.

Styrene resin (B) used in the present invention
Is the following component (Ba) 0 to 90% by weight and component (Bb)
It consists of 100 to 10% by weight. (Ba) Copolymer consisting of the following components (Ba1) to (Ba4) (Ba1) Aromatic vinyl 50 to 90% by weight (Ba2) Vinyl cyanide 10 to 40% by weight (Ba3) Alkyl methacrylate and / or alkyl acrylate 0-40% by weight (Ba4) N-substituted maleimide 0-40% by weight (Bb) Graft copolymer obtained by grafting 90-5% by weight of the component (Bb2) on 10-95% by weight of the following component (Bb1). (Bb1) Rubber-like polymer having a glass transition point Tg ≦ 20 ° C. (Bb2) A monomer mixture composed of the following components (α) to (δ) and satisfying the following formula group (I): (α) Aromatic vinyl (β) ) Vinyl cyanide (γ) Alkyl methacrylate and / or alkyl acrylate (δ) Other copolymerizable vinyl Formula group (I): 10 ≦ β + γ / 4 ≦ 40 δ = 100-β-γ- αβ ≧ 0, γ ≧ 0 0 ≦ α ≦ 90, 0 = δ ≦ 20, [wherein α, β, γ, and δ represent weight ratios (%), respectively. ]

The styrene resin (B) is preferably 30 to 80% by weight of the following component (Ba) and the component (B).
b) 70 to 20% by weight. (Ba) Copolymer consisting of the following components (Ba1) to (Ba4) (Ba1) Aromatic vinyl 65 to 85% by weight (Ba2) Vinyl cyanide 15 to 35% by weight (Ba3) Alkyl methacrylate and / or alkyl acrylate 0 to 35% by weight (Ba4) N-substituted maleimide 0 to 30% by weight (Bb) 40 to 90% by weight of the following component (Bb1) and 60 to 10% by weight of the component (Bb2) graft copolymer (Bb1) Rubber-like polymer having a glass transition point Tg ≦ 0 ° C. (Bb2) A monomer mixture composed of the following components (α) to (δ) and satisfying the following formula group (I): (α) Aromatic vinyl (β) ) Vinyl cyanide (γ) Alkyl methacrylate and / or alkyl acrylate (δ) Other copolymerizable vinyl Formula group (I): 10 ≦ β + γ / 4 ≦ 40 δ = 100-β-γ- αβ ≧ 0, γ ≧ 0 0 ≦ α ≦ 90, 0 = δ ≦ 20, [wherein α, β, γ, and δ represent weight ratios (%), respectively. ]

Styrene resin (B) used in the present invention
If the composition is out of the above range, impact resistance or fluidity tends to decrease.

(Ba in the styrene resin (B)
The aromatic vinyls of 1) and (α) include styrene and α-
Methyl styrene, p-methyl styrene, chlorostyrene, etc. are illustrated.

Examples of vinyl cyanide of (Ba2) and (β) include acrylonitrile and methacrylonitrile.

Examples of the alkyl methacrylate and alkyl acrylate of (Ba3) and (γ) include methyl methacrylate or methyl acrylate, ethyl methacrylate or ethyl acrylate, propyl methacrylate or propyl acrylate, butyl methacrylate or butyl acrylate, glycidyl silacrylate or glycidyl. Examples thereof include silacrylate, 2-hydroxyethylmethacrylate or 2-hydroxyacrylate, 2-ethylhexylmethacrylate or 2-ethylhexylacrylate.

Examples of the N-substituted maleimide of (Ba4) include N-phenylmaleimide, N-methylmaleimide,
N-ethylmaleimide, N-propylmaleimide, N-
Isopropyl maleimide, N-butyl maleimide, N-
Examples thereof include isobutyl maleimide, N-tert-butyl maleimide, N-cyclohexyl maleimide and the like.

Other copolymerizable vinyls include acrylic acid, methacrylic acid, and a graft copolymer (Bb).
Examples of the component (δ) in the above include the N-substituted maleimides described above. The above-mentioned aromatic vinyl, vinyl cyanide, alkyl methacrylate, alkyl acrylate, and other copolymerizable vinyl may be used alone or in combination.
Used in combination of more than one species.

The copolymer (Ba) has a reduced viscosity of the methyl ethyl ketone-soluble portion of 3 in a dimethylformamide solution.
Copolymers in the range of 0.20 to 1.20 dL / g at 0 ° C are preferred. If the reduced viscosity is less than 0.20 dL / g, the impact strength tends to decrease, and if it exceeds 1.20 dL / g, the fluidity tends to decrease.

Examples of the rubber-like polymer in the graft copolymer (Bb) include polybutadiene rubber, styrene-butadiene copolymer rubber (SBR), diene rubber such as acrylonitrile-butadiene rubber (NBR), and polyacrylic acid. Acrylic rubbers such as butyl and polyolefin rubbers such as ethylene-propylene-diene terpolymer rubber (EPDM) are exemplified, and these are used alone or in combination of two or more. T of rubbery polymer
When g exceeds 20 ° C., the impact resistance decreases.

The composition of the polycarbonate (A) and the styrene resin (B) is 90 to 10 parts by weight with respect to 10 to 90 parts by weight of the component (A). Component (A) is 1
If it is less than 0 parts by weight, impact resistance and flame retardancy are lowered, and if it exceeds 90 parts by weight, moldability is lowered.

The polyphosphate (C) used in the present invention is represented by the following general formulas [I] to [IV]:

Embedded image [In the formula, R _{1 to} R ₈ are each a hydrogen atom or a carbon number 1
To 3 are shown, and n shows the integer of 1-5. ]
Is a compound selected from one or more selected from the group consisting of resorcin polyphosphate compound, hydroquinone polyphosphate compound, 4,4′-bisphenol polyphosphate compound and bisphenol A polyphosphate compound. Tetra (2,6-xylyl) resorcindipolyphosphate is particularly preferable in terms of workability during pellet production and coloring of natural pellets.

The compounding amount of the polyphosphate (C) is 1
-30 parts by weight, and 5 in order to effectively show flame retardancy.
-20 parts by weight is preferred. If the blending amount is lower than 1 part by weight, the effect of flame retarding the resin is not exhibited, and if it exceeds 30 parts by weight, the heat resistance tends to be lowered.

The halogenated epoxy resin (D) used in the present invention has the following formula [V]:

[Chemical 6] And a halogen compound having a weight average molecular weight of 500 to 60,000 and a bromine atom and / or chlorine atom content of 33 to 60%. From the viewpoint of fluidity and impact resistance, the weight average molecular weight is preferably 1400 to 10,000. The amount of the halogenated epoxy resin (D) is 1 to 30 parts by weight, and preferably 5 to 20 parts by weight in order to effectively exhibit flame retardancy. If the blending amount is less than 1 part by weight, the effect of flame retarding the resin is not exhibited, and if it exceeds 30 parts by weight, the impact strength tends to be lowered.

The fluororesin (E) used in the present invention is
It is added to prevent dripping during resin combustion, and is preferably finely dispersed in the resin in the form of fibrils. Examples of the fluororesin used in the present invention include polytetrafluoroethylene, polyfluorovinyl, and polyfluorovinylidene. Among these fluororesins, polytetrafluoroethylene is particularly preferable.
Further, in polytetrafluoroethylene, a large number of particles are aggregated to form secondary particles, so that the particle size is 0.2 μm to 0.5 μm.
It is preferable that the primary particles have a size of μm, and it is desirable that a large number of these particles are aggregated to form secondary particles having a size of 300 μm to 600 μm. Those exceeding these particle ranges tend to be unable to prevent dripping during combustion.
The number of parts used is 0.05 to 5 parts by weight, and 0.05
If it is less than 5 parts by weight, it is insufficient to prevent the dripping of the resin during combustion, and if it exceeds 5 parts by weight, the impact resistance decreases, which is not preferable.

The flame-retardant resin composition of the present invention comprises a polycarbonate (A), a styrene resin (B), a polyphosphate (C), a halogenated epoxy resin (D), and a fluororesin (E), which are extruded from an extruder. It can be manufactured by melt-kneading with a kneader or the like.

The flame-retardant resin composition of the present invention contains not only antioxidants and heat stabilizers that are generally well known, but also ultraviolet (UV) absorbers, pigments, antistatic agents, and other additives as required. A flame retardant, a flame retardant aid, etc. may be used alone or in combination of two or more. Further, it is possible to use a phenolic antioxidant, a phosphite stabilizer, a benzophenone-based or a benzotriazole-based UV absorber used for polycarbonate and styrene resins. The flame-retardant resin composition of the present invention can also be used by blending a small amount of a flame-retardant auxiliary agent such as an antimony compound depending on the degree of necessity of flame retardancy. Further, in order to improve mechanical properties such as elastic modulus and heat resistance, reinforcing fibers such as glass fiber and carbon fiber, and fillers such as mica, talc, clay and glass beads are used alone or in combination of two or more kinds. You can also do it. Further, when impact resistance is insufficient, a generally known elastomer can be added.

[0026]

EXAMPLES The present invention will now be described in detail with reference to specific examples, but these examples do not limit the present invention. In the examples, "part" means part by weight and "%" means% by weight.

(1) Synthesis of Styrene Resin (B) (a) Production of Styrene Copolymer (Ba) A reaction vessel equipped with a stirrer and a cooler was charged with the following substances in a nitrogen stream. Water 200 parts Sodium dioctyl sulfosuccinate 3 parts Ferrous sulfate 0.0025 parts Ethylenediaminetetraacetic acid sodium 0.01 part While stirring the reaction vessel, the temperature was raised to 60 ° C under a nitrogen stream. After reaching 60 ° C., the amount of vinyl monomer mixture (I) shown in Table 1 was charged, and after sufficiently stirring, the amount of vinyl monomer mixture (II) shown in Table 1 was continuously added in 6 hours. Dropped.

[0028]

[Table 1]

After the completion of dropping, the mixture was further stirred at 60 ° C. for 1 hour to complete the polymerization, and the styrene copolymer (Ba-i,
Ba-ii) was produced.

(B) Production of Graft Copolymer (Bb) A reaction vessel equipped with a stirrer and a cooler was charged with the following substances in a nitrogen stream. Water 250 parts Sodium formaldehyde sulfoxynate 0.3 parts Ferrous sulfate 0.0025 parts Sodium ethylenediamine tetraacetate 0.01 parts Polybutadiene (Tg = -75 ° C) 70 parts 60 ° C under a nitrogen stream while stirring the reactor. The temperature was raised to. After reaching 60 ° C., the compounds shown in Table 2 were continuously added dropwise over 4 hours.

[0031]

[Table 2]

After completion of the dropping, the mixture was further stirred at 60 ° C. for 1 hour to complete the polymerization, and the graft copolymer (Bb-i),
(Bb-ii) was produced. The polybutadiene used was latex-like with an average particle size of 0.25 μm and a gel content of 90%.

Styrene-based polymers (Ba-i), (Ba-
ii) The graft copolymer (Bb-i) or (Bb-ii) is mixed in the latex obtained by mixing each in the same amount so that the polybutadiene content in the latex state is 25%, and the phenolic antioxidant is added. After adding, the mixed latex is coagulated with calcium chloride, dehydrated, washed with water and dried,
Styrene resins (B-i) and (B-ii) were obtained.

Examples 1 to 6 Polycarbonate (A) (Taflon FN2500A manufactured by Idemitsu Petrochemical Co., Ltd.) and the styrene resin (B-
i) and (B-ii), and the following polyphosphate (C1),
(C2), (C3):

Embedded image And brominated epoxy resin (D1) (manufactured by Dainippon Ink and Chemicals, Inc., end cap EC20: molecular weight = 200)
0, bromine content = 56%), (D2) (manufactured by Tohto Kasei Co., Ltd., YPB43D: molecular weight = 55000, bromine content = 53%), polytetrafluoroethylene (E) (manufactured by Daikin Industries, Ltd., Polyflon PTFE) F10
4), and 1 part of oxidized polyethylene wax, antioxidant AO-20 (manufactured by Asahi Denka Co., Ltd.) 0.5 part, PE
0.5 parts of P24G (manufactured by Asahi Denka Kogyo Co., Ltd.) and 0.4 parts of UV absorber TINUVIN 234 (manufactured by Nippon Ciba-Geigy Co., Ltd.) were blended in the composition shown in the example of Table 3,
The mixture was stirred with a super mixer (Kawata SMV-75) and extruded with a twin-screw extruder. Only the polyphosphate (C3) was added from the middle of the cylinder of the twin-screw extruder to obtain a flame-retardant thermoplastic resin composition.

Comparative Examples 1 to 5 The formulations of the comparative examples shown in Table 3 were used in the same manner as in the examples.
A flame-retardant thermoplastic resin composition was obtained.

Physical properties of the resin compositions obtained in the above Examples and Comparative Examples were tested, and the results are shown in Table 3.

[0037]

[Table 3]

The flame retardancy was evaluated according to the vertical combustion test method (UL-94) of Underwriters Laboratories, Inc. (UL test) in the United States. The test piece was evaluated at a thickness of 1/16 inch.

The fluidity is determined by the spiral mold (spiral shape, 3
(mm thickness), comparative evaluation was performed by the length of the molded body at a resin temperature of 250 ° C.

The heat distortion resistance was evaluated by HDT under a load of 18.6 kg / cm ² based on ASTM D648.

The mold contamination is determined by the molding machine (FANUC: FA
S-150B) hot runner mold (2 point gate,
Using a small article molding and a resin temperature of 250 ° C.), the degree of contamination of the mold after 20 shots of short shot molding was visually evaluated. In the evaluation, ○ is thin (thin) cloudy at the tip of the molded product, Δ is cloudy near the molded product tip (middle thick), and × is cloudy at the entire molded product (thick cloud at the tip) , XX, the traces on the entire molded body were uniformly clouded (contamination was severe on the whole).

[0042]

As described above, the flame retardant resin composition of the present invention is excellent in flame retardancy, fluidity and heat resistance. Further, the mold is less contaminated, and there is no appearance defect such as bleeding on the surface of the molding.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 25/00 LEA C08L 25/00 LEA LEC LEC 63/00 NJM 63/00 NJM 69/00 LPP 69 / 00 LPP LPQ LPQ // (C08L 55/02 25:00 69:00 63:00 27:12)

Claims (3)

[Claims] 1. A composition comprising the following components (A) to (E), wherein the component (A) is 10 to 90 parts by weight and the component (B) is 90:
10 to 10 parts by weight of the resin component, 1 to 30 parts by weight of the component (C), 1 to 30 parts by weight of the component (D), and 0.05 to 5 parts by weight of the component (E). A flame-retardant resin composition. (A) Polycarbonate, (B) 0 to 90% by weight of the following component (Ba) and the component (B
b) 100 to 10% by weight of a styrene resin, (Ba) a copolymer of the following components (Ba1) to (Ba4) (Ba1) aromatic vinyl 50 to 90% by weight (Ba2) vinyl cyanide 10 -40% by weight (Ba3) Alkyl methacrylate and / or alkyl acrylate 0-40% by weight (Ba4) N-substituted maleimide 0-40% by weight (Bb) Ingredient (Bb1) 10-95% by weight (Bb2) A graft copolymer obtained by grafting 90 to 5% by weight, (Bb1) a rubber-like polymer having a glass transition point Tg ≦ 20 ° C. (Bb2) consisting of the following components (α) to (δ), and the following formula group (I): (Α) Aromatic vinyl (β) Vinyl cyanide (γ) Alkyl methacrylate and / or alkyl acrylate (δ) Other copolymerizable vinyl Group (I): 10 ≦ β + γ / 4 ≦ 40 δ = 100−β−γ−α β ≧ 0, γ ≧ 0 0 ≦ α ≦ 90, 0 = δ ≦ 20, where α, β, γ, δ Indicates the weight ratio (%). (C) The following general formulas [I] to [IV]: [In the formula, R _{1 to} R ₈ are each a hydrogen atom or a carbon number 1
To 3 are shown, and n shows the integer of 1-5. )
One or more compounds selected from the group consisting of resorcin polyphosphate compounds, hydroquinone polyphosphate compounds, 4,4′-bisphenol polyphosphate compounds, and bisphenol A polyphosphate compounds represented by: (D) The following formula [V] A halogenated epoxy resin represented by: (E) a fluororesin. 2. The flame-retardant resin composition according to claim 1, wherein the polyphosphate compound as the component (C) is tetra (2,6-xylyl) resorcindiphosphate. 3. The flame-retardant resin composition according to claim 1 or 2, wherein the fluororesin as the component (E) is polytetrafluoroethylene.