JPH11181227A - Acrylonitrile-butadiene-styrene resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ABS resin composition having highly improved solvent resistance and good impact resistance, and to provide a method for producing the same. SOLUTION: This acrylonitrile-butadiene-styrene resin composition comprises (A) 30-95 wt. % of an acrylonitrile-butadiene-styrene resin (ABS resin), (B) 70-5 wt.% of a styrenic polymer having a melting point of <=255 deg.C and mainly having a syndiotactic structure, and, if necessary, further (C) an inorganic filler in an amount of 5-200 pts.wt. per 100 pts.wt. of the total amount of the components (A) and (B). The characteristic of the method for producing the resin composition comprises controlling the temperature of the resins to the melting point of the component B to 270 deg.C, when the components of the resin composition are kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to acrylonitrile
More specifically, the butadiene / styrene resin composition (hereinafter, may be referred to as “ABS resin composition”) is more specifically an ABS resin, and a specific styrene polymer mainly having a syndiotactic structure, The present invention relates to an ABS resin composition containing an inorganic filler as required and a method for producing the same.

[0002]

2. Description of the Related Art ABS resins exhibit excellent solvent resistance and impact resistance, but are not always satisfactory in terms of solvent resistance to specific solvents such as surfactants, cosmetics, machine oils and alcohols. Instead, the range applicable as a material was limited. In order to improve such solvent resistance, blending of a crystalline resin such as polyamide or polyethylene terephthalate with an ABS resin has been carried out. However, these resins are essentially incompatible with the ABS resin and have a simple structure. However, there is a problem that the physical properties are reduced only by blending with the styrene. In addition, a problem has arisen that blending these resins causes a decrease in hydrolysis resistance.

On the other hand, in order to improve the heat resistance of the ABS resin, a styrene resin having a syndiotactic structure (hereinafter referred to as “SPS”) is mainly used as the ABS resin.
It may be called. ) Are disclosed (JP-A-62-257950, JP-A-1-1-1).
No. 82344), however, the solvent resistance and impact resistance of the molded product were not sufficiently satisfactory.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and has improved solvent resistance.
Another object of the present invention is to provide an ABS resin composition having good impact resistance and a method for producing the same.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies and found that an ABS resin having a specific melting point has a specific melting point.
By simply blending S, it was found that the impact resistance was hardly reduced and the solvent resistance could be improved. Further, it has been found that the heat resistance and the elastic modulus can be further improved by adding an inorganic filler in a predetermined ratio to the above composition. Furthermore, it has been found that the resin composition according to the present invention can be efficiently produced by setting the temperature at which the components of the resin composition are kneaded in a specific range. The present invention has been completed based on such findings.

That is, the present invention provides the following resin composition. (1) (A) 30 to 95% by weight of an acrylonitrile / butadiene / styrene resin (ABS resin); (B) 70 to 5% by weight of a styrene polymer having a melting point of 255 ° C. or less and having a mainly syndiotactic structure. An acrylonitrile-butadiene-styrene resin composition comprising: (2) (A) 30 to 95% by weight of an acrylonitrile / butadiene / styrene resin (ABS resin), (B) 70 to 5% by weight of a styrene polymer having a melting point of 255 ° C. or less and mainly having a syndiotactic structure. And (A)
Acrylonitrile / butadiene / styrene resin composition containing 5-200 parts by weight of an inorganic filler (C) based on 100 parts by weight of the total of the component and the component (B). (3) In the above (1) or (2) In the acrylonitrile-butadiene-styrene resin composition described above, the resin temperature at the time of kneading each component is set to a value not lower than the melting point of the component (B), at least 27.
(1) or (2), wherein the temperature is set to 0 ° C. or lower.
The method for producing an acrylonitrile / butadiene / styrene-based resin composition according to the above.

[0007]

Embodiments of the present invention will be described below. 1. Contents of each component constituting the ABS-based resin composition (1) Acrylonitrile / butadiene / styrene-based resin (ABS-based resin) The ABS-based resin as the component (A) is each monomer of acrylonitrile and styrene and optionally a rubber component. A method of mixing butadiene rubber or nitrile rubber with an acrylonitrile / styrene copolymer, and graft copolymerization of acrylonitrile and styrene with polybutadiene (bulk / suspension polymerization, emulsification / bulk polymerization, emulsification Synthetic method, solution polymerization method), a method of terpolymerizing acrylonitrile, butadiene and styrene monomers, and a method of blending these. In the present invention, the method of preparing the ABS resin is not particularly limited, and various methods may be used as appropriate.

The styrene content, acrylonitrile content and rubber content in the ABS resin are not particularly limited, but usually, styrene / acrylonitrile = 95 / 5-5.
0/50 and a rubber content of about 0 to 50% are used. As the rubber component, in addition to polybutadiene, butadiene-acrylonitrile copolymer (NBR), styrene-butadiene copolymer (SBR), acrylic rubber (A
Various types of rubbers such as R), ethylene-propylene copolymer (EPR), chlorinated polyethylene (CPE) and the like are used. It is also possible to use a copolymer of another monomer depending on the purpose. As other monomers, methyl methacrylate, α-methylstyrene, N-phenylmaleimide and the like are appropriately used. (2) Styrene-based polymer having syndiotactic structure (B) In the styrene-based polymer having a syndiotactic polystyrene structure as the component (B), a syndiotactic structure means a stereochemical structure having a syndiotactic structure. ,
That is, it has a steric structure in which phenyl groups, which are side chains, are alternately located in opposite directions to the main chain formed from carbon-carbon bonds, and its tacticity is determined by nuclear magnetic resonance (13C) -NMR). 13
The tacticity measured by the C-NMR method can be represented by the abundance ratio of a plurality of continuous structural units, for example, dyad for two, triad for three, and pentad for five. The styrenic polymer having a syndiotactic structure referred to in the present invention is usually 75% or more, preferably 85% or more in racemic diad, or 30% or more in racemic pentad,
Polystyrene, poly (alkylstyrene), poly (alkyl) having preferably 50% or more syndiotacticity
Halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxystyrene), poly (vinyl benzoate), hydrogenated polymers thereof, mixtures thereof, or copolymers containing these as main components I do. Here, poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), poly (phenylstyrene), poly (vinylnaphthalene) , Poly (vinylstyrene), and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Further, as poly (halogenated alkylstyrene), poly (chloromethylstyrene) and the like, and as poly (alkoxystyrene),
Poly (methoxystyrene), poly (ethoxystyrene)
and so on.

Among these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (p-chlorostyrene). Styrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units.

The styrenic polymer having such a syndiotactic structure is prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. Can be produced by polymerizing a series monomer (a monomer corresponding to the styrene polymer).
-187708). Further, poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912 and hydrogenated polymers thereof can be obtained by the method described in JP-A-1-178505.

The component (B) in the present invention has a melting point of 255 ° C.
It is necessary to use the following SPS. 255 ° C
Although there is no particular limitation as long as it is the following, for example, a copolymer of styrene having a syndiotactic structure and a substituted styrene, a styrene polymer having a low syndiotacticity, and a styrene polymer having a syndiotactic structure, polyphenylene ether is used. Blended materials and the like are used. Of these, styrene-alkylstyrene copolymers such as styrene-p-methylstyrene copolymer and styrene-t-butylstyrene copolymer are particularly preferably used.

The molecular weight is not particularly limited, but has a weight average molecular weight of 10,000 or more, preferably 50,000.
0 or more. Further, the molecular weight distribution is not limited in its width, and various molecular weight distributions can be applied. Here, if the weight average molecular weight is less than 10,000, the thermal and mechanical properties of the obtained composition or molded article are undesirably reduced.

These styrenic polymers having a syndiotactic structure may be used alone or
Two or more can be used in combination. (3) Inorganic Filler The inorganic filler of the component (C) may be fibrous, granular or powdery. Examples of the fibrous filler include glass fiber, carbon fiber, and whisker. Cloth, mat,
There are bundle cut, short fiber, filament, whisker, etc., but in the case of bundle cut, the length is 0.05 mm to 50 mm.
mm and a fiber diameter of 5 to 20 μm are preferred.

On the other hand, as the granular or powdery filler, for example, talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, Oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, glass beads and the like can be mentioned.

Among the various fillers as described above, especially glass fillers such as glass powder, glass flake,
Glass beads, glass filaments, glass fibers, glass lobing, and glass mats are preferred. Also,
These fillers are preferably surface-treated.
The coupling agent used for the surface treatment is used for improving the adhesiveness between the filler and the resin,
Any one of conventionally known ones such as a so-called silane coupling agent and a titanium coupling agent can be selected and used. Above all, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And aminosilane, epoxysilane and isopropyl tri (N-amidoethyl, aminoethyl) titanate.

As the film former, a conventionally known one can be used. Among them, urethane type, epoxy type, polyether type and the like are preferably used. In addition, these inorganic fillers can be used alone or in combination of two or more. (4) Other Additives In the resin composition of the present invention, a nucleating agent, a plasticizer, a release agent, an antioxidant, in addition to the above components (A) to (C), as long as the object of the present invention is not impaired. , A flame retardant, a flame retardant auxiliary, a rubber-like elastic body, a thermoplastic resin, and additives such as a pigment and an antistatic agent. Each of these can be used alone or in combination of two or more.

Nucleating agent A nucleating agent can be added to promote the crystallization of SPS and further increase the solvent resistance. Examples of the nucleating agent include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate), metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate, and talc. And phthalocyanine derivatives and the like can be arbitrarily selected and used.

Plasticizer The plasticizer is arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalate ester, polystyrene oligomer, polyethylene wax, mineral oil and silicone oil. Can be used.

Release Agent The release agent can be arbitrarily selected from known materials such as polyethylene wax, silicone oil, long-chain carboxylic acid, and metal salt of long-chain carboxylic acid. Antioxidant As the antioxidant, any known antioxidant such as phosphorus-based, phenol-based, and sulfur-based can be used.

Flame retardants and flame retardant assistants Examples of the flame retardant include brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether, brominated diphenylalkane, and brominated diphenyl ether. Any known compound such as a brominated aromatic compound can be used. Further, as the flame retardant auxiliary, any one of antimony compounds such as antimony trioxide and other known ones can be arbitrarily selected and used.

Rubbery Elastic Body In order to improve the impact resistance, a rubber component can be blended according to the purpose. Specific examples of the rubber-like elastic body include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SB
S), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-
Styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEP)
S) or ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate -Styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core shell rubber (ABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate- Core-shell type particulate elastic material such as siloxane-containing core-shell rubber such as butyl acrylate-siloxane, Like rubber, and the like. Among them, SBR, SEB, SBS, SEBS, SI
R, SEP, SIS, SEPS, core shell rubber, EP
M, EPDM, or rubber modified from these is preferably used.

Thermoplastic resin As the thermoplastic resin, linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene,
Isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene,
Cyclic polyolefin, polyolefin resin including poly-4-methylpentene, polystyrene, HIP
Polystyrene resins including S, polycarbonate resins, polyester resins including polyethylene terephthalate, polybutylene terephthalate, polyamide resins including polyamide 6, polyamide 6,6, and polyarylene sulfide resins; Can be selected for use. 2. Mixing ratio of each component constituting the ABS resin composition (1) Regarding the mixing ratio of the above components (A) and (B), (A) acrylonitrile / butadiene / styrene resin (ABS resin) is 30 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 85% by weight, and (B) 70 to 5% by weight, preferably 50 to 10% by weight of a styrenic polymer (SPS) mainly having a syndiotactic structure. %, More preferably 40 to 15% by weight. (B) If the SPS is less than 5% by weight, the effect of solvent resistance may not be exhibited. (B) S
If the content of PS exceeds 70% by weight, the properties of ABS may be lost and the impact resistance may be reduced. (2) About the compounding ratio of the (C) inorganic filler,
5 to 100 parts by weight of the total of the components (A) and (B)
It is 200 parts by weight, preferably 10 to 100 parts by weight.
When the amount is less than 5 parts by weight, the effect of blending the inorganic filler is not exhibited, and when the amount is more than 200 parts by weight, dispersibility may be deteriorated, and molding may be difficult. 3. Method for Preparing ABS-Based Resin Composition According to the Present Invention The method for preparing the ABS-based resin composition according to the present invention is not particularly limited, and can be prepared by a known method. For example, the components and various additives are melt-kneaded using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. The resin composition of the present invention can be obtained. SPS may be added at the time of producing ABS by blending or graft blending.
Any method can be selected, such as a method of melt-kneading ABS or a method of melt-kneading ABS and SPS appropriately selected according to the purpose.

The resin temperature at the time of melt-kneading is not lower than the melting point of SPS and not higher than 270 ° C., preferably not lower than the melting point of SPS and not higher than 265 ° C.
The temperature is preferably 260 ° C. or lower. When the melting point is lower than the melting point of the SPS, the dispersion state of the SPS is deteriorated, and the effect of improving the solvent resistance may be reduced, and the impact resistance may be reduced. May cause. 4. Molding method using the ABS resin composition according to the present invention The molding method is not particularly limited, and molding can be performed by a known method such as injection molding or extrusion molding.

The resin temperature during molding is not particularly limited, but is preferably 200 to 270 ° C., and more preferably 220 to 270 ° C.
Set to 60 ° C. If the temperature is lower than 200 ° C., the fluidity may be inferior. If the temperature exceeds 270 ° C., deterioration of the ABS may occur, which is not preferable. The mold temperature during molding is 3
0-100 ° C is preferably used. If the temperature is lower than 30 ° C., the surface appearance of the molded product may be inferior. 5. Use of ABS-based resin composition according to the present invention The ABS-based resin composition according to the present invention can be used for various uses, and is not particularly limited. Applications for automotive parts include, for example, console boxes, speaker boxes, instrument panels, wheel caps,
A radiator cover, an air spoiler, an outer plate, and the like can be cited. The use for electric / electronic parts includes, for example, a battery case, and the use for industrial structural materials includes a housing and a chassis. For home appliances, for example, door caps, air conditioner covers,
Fans, etc., various machine parts, extruded sheets and films, extruded and thermoformed containers and trays, extruded and drawn uniaxial and biaxially drawn films,
It is also suitably used for sheet and spinning fibrous molded products.

[0025]

〔Evaluation methods〕

-Impact strength (with notch): JIS K 7110
Sought in accordance with. -Solvent resistance (1) Stress cracking The solvent cracking was measured using a surfactant (manufactured by Kao Corporation, trade name: Basmagiclin) or isopropanol. The specific method is as follows. The test piece was fixed to the curved part using a 0.8% bending strain jig, and the solvent was dripped so that the solvent could soak into the entire gauze spread over the curved part of the test piece. For 1 hour.
Thereafter, the change in appearance was visually determined. The case where no change in appearance was observed was evaluated as ◎, the case where almost no change was observed was evaluated as ○, the case where slight craze occurred was evaluated as Δ, and the case where cracks occurred or fractured was evaluated as x. (2) Immersion test Brake fluid (Apollo Service Co., Ltd., trade name: AXCE)
The appearance change when immersed in LA BF3) at 80 ° C. for 1 hour was visually judged. A case where no change in appearance was observed was marked as ◎, and a case where almost no change was observed was marked as 、,
The case where it was slightly recognized was rated as Δ, and the case where it was considerably recognized was rated as x.

The appearance change when immersed in Freon 141B at room temperature for 1 hour was visually judged. The determination of the appearance change is the same as above. [Raw materials used] (A) Component-ABS resin: Acrylonitrile / butadiene / styrene resin (manufactured by Sumika ABS Latex Co., Ltd., trade name: CLASTIC GA-704) (B) component In the following, the weight average molecular weight and The molecular weight distribution is 1,
The measurement was performed by gel permeation (GPC) at 130 ° C. using 2,4-trichlorobenzene as a solvent. The melting point was determined from the peak position at a heating rate of 20 ° C./min by differential thermal analysis (DSC). Each SPS was manufactured by a known method described in JP-A Nos. 62-104818 and 62-187708. SPS1: Styrene-p-methylstyrene copolymer (p-methylstyrene content: 12 mol%) Weight average molecular weight Mw = 180,000, Mw / Mn = 2.3 Melting point 240 ° C. SPS2: Styrene-p-methyl Styrene copolymer (p-methylstyrene content: 12 mol%) Weight average molecular weight Mw = 300,000, Mw / Mn = 2.5 Melting point 240 ° C. SPS3: Styrene-p-methylstyrene copolymer (p-methyl) (Styrene content: 7 mol%) Weight average molecular weight Mw = 300,000, Mw / Mn = 2.5 Melting point 253 ° C. SPS4: Styrene homopolymer Weight average molecular weight Mw = 300,000, Mw / Mn = 2.5 Melting point 270 ° C (C) component ・ GF: Glass fiber (Asahi Fiberglass Co., Ltd., trade name: FT712) (D) Other components ・ SEBS: SEBS Ib rubber-like elastic body (manufactured by Shell Co., trade name: Clayton G1651) SBS: SBS type rubber-like elastic body (manufactured by Shell Co., trade name: Clayton D1101) [Example 1] Acrylonitrile-butadiene. Styrene resin (manufactured by Sumika ABS Latex Co., Ltd., trade name: CLLASTIC GA-704) 90
% By weight, 10% by weight of SPS-1 syndiotactic polystyrene as the component (B), and 100 parts by weight of the total of the components (A) and (B), (2,6-di-t) as an antioxidant. -Butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36 manufactured by Asahi Denka Co., Ltd.) 0.1 part by weight, tetrakis (methylene-
3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl)) propionate (Made by Adeka Argus)
ARKAO60) Add 0.1 part by weight of Henschel mixer
, And melt-kneaded with a twin-screw extruder to form pellets. At this time, the resin temperature was 255 ° C. Using the obtained pellets, resin temperature 260 ° C,
Injection molding was performed at a mold temperature of 60 ° C. to obtain an Izod test piece and a bending test piece. Using the obtained test pieces, Izod impact strength and solvent resistance were measured. The results are shown in Table 1.

[0027]

[Table 1]

[Examples 2 to 17, Comparative Examples 1 to 17]
As shown in Table 1, the components (A), (B) and (C)
The procedure was performed in the same manner as in Example 1 except that the composition and the composition ratio were used and the resin temperature was changed. The results are shown in Tables 1 and 2.

[0029]

[Table 2]

[0030]

According to the present invention, it is possible to obtain a molded article having high solvent resistance, excellent impact resistance, and excellent physical properties irrespective of the molding method. The acrylonitrile-butadiene-styrene resin composition of the present invention is, for example, various molded products by injection molding,
It is effectively used in the production of extruded sheets and films, containers and trays by extrusion and thermoforming, uniaxial and biaxially oriented films and sheets by extrusion and stretching, and fibrous molded articles by spinning.

Claims (3)

[Claims] (A) Acrylonitrile butadiene.
Styrene resin (ABS resin) 30 to 95% by weight,
(B) An acrylonitrile-butadiene-styrene resin composition mainly comprising 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a melting point of 255 ° C. or lower. (A) acrylonitrile butadiene.
Styrene resin (ABS resin) 30 to 95% by weight,
(B) 70 to 5% by weight of a styrene polymer having a syndiotactic structure having a melting point of 255 ° C. or lower,
An acrylonitrile-butadiene-styrene resin composition further comprising 5 to 200 parts by weight of an inorganic filler (C) based on 100 parts by weight of the total of the components (A) and (B). 3. The acrylonitrile-butadiene-styrene resin composition according to claim 1 or 2, wherein the resin temperature at the time of kneading each component is equal to or higher than the melting point of the component (B).
The method for producing an acrylonitrile-butadiene-styrene resin composition according to claim 1, wherein the temperature is 70 ° C. or lower.