JPH0834901A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Objective] To provide a thermoplastic resin composition excellent in impact resistance, rigidity, surface appearance of a molded article and chemical resistance. . [Structure] (A) 100 parts by weight of a rubber-modified styrene resin obtained by polymerizing an aromatic vinyl compound and a vinyl cyan compound in the presence of a rubbery polymer (a), and (C) a non-polar α-olefin ( A (co) polymer and a vinyl-based (co) polymer comprising at least one vinyl monomer,
A resin composition comprising 0.1 to 30 parts by weight of a multi-phase structure thermoplastic resin having a particle diameter of the dispersed resin of 0.001 to 10 μm, wherein vinyl in the methyl ethyl ketone soluble part of the component (A) is used. The cyan compound amount is 27 to 45% by weight, and the melt flow rate ratio of the component (A) and the component (C) is 0.
2-20, The thermoplastic resin composition characterized by the above-mentioned.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition excellent in impact resistance, rigidity, surface appearance of molded articles and chemical resistance.

2. Description of the Related Art Styrenic resins such as ABS resins are used in a wide range of fields because of their excellent impact resistance, rigidity and surface appearance of molded products, but they are not sufficiently resistant to chemicals and are used. There was a limitation in usage.

SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems of the prior art, and is a heat that can be used in a wide range of applications having excellent impact resistance, rigidity, surface appearance of molded articles and chemical resistance. An object is to provide a plastic resin composition.

[0002]

The present invention is directed to (A) an aromatic vinyl compound, a vinylcyanide compound in the presence of a rubbery polymer (a), and optionally another vinyl monomer which is copolymerizable therewith. Resin material comprising 5 to 100% by weight of a rubber-modified styrene resin obtained by polymerizing a monomer, (B) an aromatic vinyl compound, a vinyl cyan compound and, if necessary, another vinyl monomer copolymerizable therewith. Polymer 0-95% by weight
And (C) with respect to 100 parts by weight of (A) + (B)
A non-polar α-olefin (co) polymer and a vinyl-based (co) polymer composed of at least one vinyl monomer, one (co) polymer of which is contained in the other (co) polymer. Are dispersed, and the particle size of the dispersed resin is 0.001 to
A resin composition comprising 0.1 to 30 parts by weight of a thermoplastic resin having a size of 10 μm, wherein the amount of vinyl cyan compound in the methyl ethyl ketone soluble part of the components (A) + (B) is 2
7-45% by weight, and melt flow rate of (A) + (B) component and (C) component (220 ° C., 10 kg load measurement)
The present invention provides a thermoplastic resin composition characterized in that the ratio is (C) / (A) + (B) = 0.2 to 20. Examples of the rubbery polymer (a) used as the component (A) of the present invention include polybutadiene, polyisoprene, butyl rubber, styrene-butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer. Coalesce, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, polyisoprene, Styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, AB type, ABA type, taper type, radial teleblock type structure And the like are included. Further, the hydrogenated butadiene-based polymer is, in addition to the above block copolymer, a hydride of a block of a styrene block and a styrene-butadiene random copolymer, and a 1,2-vinyl bond content in polybutadiene of 20% by weight. % Of blocks and polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight, such as hydrides of polymers.

In 100 parts by weight of the component (A), the rubbery polymer is 5 to 80 parts by weight, preferably 10 to 70 parts by weight. If it is less than 5 parts by weight, the impact resistance is poor and exceeds 80 parts by weight. And rigidity and surface appearance of molded products are poor. Examples of the aromatic vinyl compound used in the component (A) include styrene and t-
Butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, 1,1-diphenyl styrene, bromo styrene, vinyl pyridine, vinyl xylene, fluorostyrene, ethyl styrene and the like are mentioned, and styrene and α-methyl threthin are particularly preferable. .
As the vinyl cyanide compound used in the component (A),
There are acrylonitrile, methacrylonitrile, etc. 1
They may be used alone or as a mixture of two or more. Other vinyl monomers copolymerizable with the aromatic vinyl compound used here include (meth) acrylic acid alkyl esters, maleimide compounds, unsaturated acids, acid anhydride group-containing unsaturated compounds, and epoxy groups. There are unsaturated compounds containing compounds, unsaturated compounds containing hydroxyl groups, unsaturated compounds containing amino groups and unsaturated compounds containing oxazoline groups, and these are used alone or in combination of two or more.

Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate,
Acrylic esters such as hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl Methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid ester such as benzyl methacrylate and the like, and these are one kind or two.
Used in seeds and above. Examples of the maleimide compound include maleimide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide. Used alone or in combination of two or more. Examples of unsaturated acids include acrylic acid, methacrylic acid, and maleic acid. Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, citraconic anhydride, and itaconic anhydride. Examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether. Examples of the amino group-containing unsaturated compound include acrylic amine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, acrylamide, and methacrylamide. As the hydroxyl group-containing unsaturated compound, hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene,
Examples include trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate. As the oxazoline group-containing unsaturated compound,
Examples include vinyl oxazoline.

The amount of the above-mentioned monomer or monomer mixture is 95 to 20 parts by weight, preferably 90 to 30 parts by weight, per 100 parts by weight of the component (A). The impact resistance is poor, and if it is less than 20 parts by weight, the rigidity and the surface appearance of the molded product are poor. The preferable combinations of the monomer components assembled in the presence of the component (a) are listed below. 1) Aromatic vinyl compound / vinyl cyanide compound 2) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester 3) Aromatic vinyl compound / vinyl cyanide compound / maleimide monomer 4) Aromatic Vinyl compound / vinyl cyanide compound / acid anhydride monomer 5) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester / acid anhydride monomer

The aromatic vinyl compound, vinyl cyan compound, and other vinyl monomer copolymerizable with these used in the resinous polymer of the component (B) of the present invention are:
All of the above are used. The component (C) is composed of a nonpolar α-olefin (co) polymer and a vinyl (co) polymer composed of at least one vinyl monomer, and one (co) polymer of the other (co) polymer It is dispersed in the polymer, and the particle size of the dispersed resin is 0.001 to 10 μm.
Is a thermoplastic resin. The thermoplastic resin used in the component (C) of the present invention is a multi-phase structure thermoplastic resin due to its dispersed structure. As the non-polar α-olefin monomer in the multi-phase structure thermoplastic resin used in the present invention,
Examples include ethylene, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1. Of these, ethylene is preferred. The polar vinyl-based monomer is a monomer having a non-polar α-olefin monomer and a copolymerizable vinyl group, such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride. Α, β-unsaturated carboxylic acids such as itaconic acid and metal salts thereof, methyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic acid 2
-Α, β-unsaturated carboxylic acid esters such as ethylhexyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate. , Vinyl stearate,
Examples thereof include vinyl ester monomers such as triral vinyl acetate. Specific examples of the copolymer composed of a non-polar α-olefin monomer and a polar vinyl-based monomer include ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer. Polymer,
Ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl methacrylate copolymer, ethylene-2-ethylhexyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene -Ethyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, ethylene vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer and the like can be mentioned. Copolymers composed of these non-polar α-olefins and polar vinyl monomers can also be used as a mixture. The vinyl-based (co) polymer in the thermoplastic resin having a multiphase structure used in the present invention means vinyl such as styrene, nucleus-substituted styrene, for example, methylstyrene, dimethylstyrene, α-substituted styrene, for example, α-methylstyrene. Aromatic monomer; alkyl ester of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, (meth) acrylic acid ester of (meth) acrylic acid such as methyl-, ethyl-, propyl-, isopropyl-, butyl- Monomer; (meth) acrylic acid hydroxyalkyl ester monomer such as 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate; vinyl cyanide such as acrylonitrile or methacrylonitrile. Monomer;
Vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers such as acrylamide and methacrylamide; (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, etc. It is a (co) polymer obtained by polymerizing one or more vinyl monomers such as unsaturated carboxylic acids and their derivatives such as amides, imides, esters and anhydrides. Among these, (meth) acrylic acid ester is preferable. The term "multiphase thermoplastic resin" as used in the present invention means that a different component, vinyl (co) polymer or olefin polymer, is uniformly dispersed in an olefin polymer or vinyl (co) polymer matrix. What you are doing. The particle size of the dispersed polymer is usually 0.001 to 10 μm, preferably 0.005 to 7 μm.
m, and more preferably 0.01 to 5 μm. When the dispersed resin particle size is less than 0.001 μm or 10 μm
When it exceeds m, the mechanical strength of the obtained composition decreases, which is not preferable. The number average degree of polymerization of the vinyl (co) polymer in the thermoplastic resin of the multiphase structure of the present invention is preferably 5 to 10,000, and more preferably 10 to 5,000. The multiphase thermoplastic resin of the present invention preferably contains the olefin polymer in an amount of 5 to 95% by weight, preferably 20 to 90% by weight, in order to achieve the object of the present invention.

The grafting method for producing the component (C) of the present invention may be any of the well-known methods such as the chain transfer method and the ionizing radiation irradiation method, but the most preferable one is JP-A This is the method described in JP-A-64-48856. In the component (C) of the present invention, the amount of the vinyl (co) polymer grafted on the olefin polymer, that is, the graft ratio is preferably at least 1% by weight or more. The thermoplastic resin having a multi-phase structure may be used alone or in combination of two or more. The amount of component (A) used in the thermoplastic resin composition of the present invention is 5-10.
It is 0% by weight, preferably 10 to 90% by weight, more preferably 20 to 85% by weight, particularly preferably 30 to 75% by weight. If the amount used is less than 5% by weight, impact resistance is poor. The amount of component (B) used is 0 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 85% by weight,
It is particularly preferably 15 to 80% by weight. If the amount used exceeds 95% by weight, impact resistance is poor. The amount of component (C) used is 0.1 to 3 with respect to 100 parts by weight of (A) + (B).
0 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, particularly preferably 0.4 to 3 parts by weight.
Parts by weight. If the amount used is less than 0.1 parts by weight, there is no effect of improving the chemical resistance, and if the amount used exceeds 30% by weight, impact resistance, rigidity and surface appearance of the molded product are poor. In the thermoplastic resin composition of the present invention, the amount of the vinyl cyan compound in the methyl ethyl ketone soluble part of the components (A) + (B) is 27 to 45% by weight, preferably 27 to 40% by weight, particularly preferably 28 to 35% by weight. If the content of the vinyl cyan compound is less than 27% by weight, there is no effect of improving the chemical resistance, and if it exceeds 45% by weight, the impact resistance is lowered. Furthermore, the intrinsic viscosity of the methyl ethyl ketone soluble part of the components (A) + (B) (using methyl ethyl ketone as a solvent
The range of 0.45 to 1.0 is preferable for achieving the object of the present invention. The melt flow rate (220 ° C., 10 kg load measurement ratio) of the components (A) + (B) and the component (C) in the thermoplastic resin composition of the present invention is (C) /
(A) + (B) = 0.2 to 20. Preferably 0.
It is 3-18, more preferably 0.4-15.
When (C) / (A) + (B) is outside this range, the effect of improving chemical resistance is small.

The thermoplastic resin composition of the present invention includes glass fiber, carbon fiber, metal fiber, metal flake, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flake, milled fiber, kaolin. Fillers such as barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. These fillers are added to 100 parts by weight of the composition of the present invention.
Usually, it is used in the range of 5 to 150 parts by weight. Further, the composition of the present invention is blended with additives such as known flame retardants, coupling agents, light stabilizers, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils and foaming agents. be able to. Further, by adding an antibacterial agent such as silver or a silver compound or a commercially available antifungal agent to the composition of the present invention, excellent antibacterial agent and antifungal property can be imparted. The amount of the antibacterial agent and antifungal agent to be compounded is 0.01 to 30.
%, Preferably 0.05 to 20% by weight. Further, the composition of the present invention contains other polymer such as polyamide, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, fluorine resin, styrene-vinyl acetate copolymer depending on the required performance. , Polycarbonate, polyphenylene ether, polyamide elastomer, polyester elastomer, polyethylene, polypropylene, HIPS, P
MMA etc. can be blended appropriately.

The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system. The thermoplastic resin composition of the present invention thus obtained is molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, etc. be able to. Various molded products obtained by the above-mentioned molding method utilize OA due to their excellent properties.
-It can be used for various parts, housings, chassis, etc. in the fields of home appliances, electric and electronic fields, sundries, sanitary fields, automobile fields, etc.

[0010]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various evaluations in the examples,
It is a value measured as follows. Impact resistance Izod impact strength was measured according to ASTM D256. The flexural modulus in accordance with rigidity ASTM D790 were measured. Surface appearance of molded product The surface of the flat plate injection-molded product was visually evaluated according to the following evaluation criteria. ◯: Smooth and good appearance Δ: Flow mark is visible or smoothness is slightly inferior. X: The surface has large irregularities and the appearance is poor. The critical strain for a chemical-resistant toilet detergent (Johnson Endback: Johnson End Johnson) was measured. 225 mm x 40 created by injection molding on a 1/4 oval jig
mm, 1.6 mm thick flat plate is fixed, chemicals are applied, and 2
After being left to stand at 3 ° C. for 72 hours, the test piece was observed and the minimum strain (critical strain) in which cracks occurred was determined. Melt flow rate (A) + (B) component pelletized, and (C) component melt flow rate in accordance with ASTM test method D1238, set temperature 220 ℃, load 10kg melt flow rate g / 10min Was measured. The rubbery polymers (a) -1, (a) -2, and (a) -3 shown in Table 1 were used as the rubbery polymer used for the (A) rubber-modified styrene resin of the present invention.

[0011]

[Table 1]

Of the graft polymers (A) -1 to (A) -5
Preparation A graft polymer obtained by graft-polymerizing various monomers in the presence of the rubbery polymers (a) -1 to (a) -3 was obtained. The compositions of these polymers are shown in Table 2. (A) -1,
(A) -2, (A) -5 are emulsion polymerization, (A) -3,
(A) -4 was obtained by solution polymerization.

[0013]

[Table 2]

Resinous polymer (component (B) of the present invention)
(B) -1 to B-3 The following polymers were obtained by solution polymerization. (B) -1: Styrene / acrylonitrile = 70/30
% (B) -2: Styrene / acrylonitrile = 76/24
% Preparation of component (C) of the present invention The component (C) of the present invention was obtained by the following production method. Pure water was put into a stainless steel autoclave, and polyvinyl alcohol was added and dissolved as a suspending agent. Polypropylene or polyethylene was put in this and stirred to disperse. Separately, benzoyl peroxide as a radical polymerization initiator, t-butylperoxymethacryloyloxyethyl carbonate as a radically polymerizable organic peroxide, and styrene and acrylonitrile as vinyl monomers are dissolved, and this solution is put into the autoclave. It was stirred. Next, the autoclave was heated to 60 to 65 ° C. and stirred for 2 hours to impregnate polypropylene or polyethylene with a vinyl monomer containing a radical polymerization initiator and a radically polymerizable organic peroxide. Then, the total amount of the impregnated vinyl monomer, radically polymerizable organic peroxide and radical polymerization initiator is 10% of the initial amount.
After confirming that the temperature is above, set the temperature to 80-85.
C. and maintained at that temperature for 7 hours to complete the polymerization,
It was washed with water and dried to obtain a grafted precursor. Then, this grafted precursor was extruded at 200 ° C. by a single-screw extruder to obtain a multiphase thermoplastic resin of the component (C) of the present invention. When this thermoplastic resin having a multiphase structure was observed with a scanning electron microscope, it was found that a spherical resin having a particle size of 0.3 to 0.4 μm was uniformly dispersed. By changing the non-polar α-olefin polymer species and the molecular weight by the above method, (C) -1 to (C) -9 having the compositions shown in Table 3 were obtained.

[0015]

[Table 3]

Examples 1 to 11 and Comparative Examples 1 to 6 The above various aggregates were mixed at the compounding ratios shown in Table 4 and melt-kneaded at a barrel setting temperature of 220 ° C. in a twin-screw extruder to form pellets. After sufficiently drying the pellets, a test piece was prepared using an injection molding machine at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C., and evaluated by the evaluation method described above. The evaluation results are shown in Table 4.

[0017]

[Table 4]

The following is clear from the examples and comparative examples. All of Examples 1 to 11 obtained by the present invention are excellent in impact resistance, rigidity, surface appearance of molded articles and chemical resistance. Comparative Example 1 is an example in which the amount of the component (A) is out of the range and the impact resistance is poor. Comparative Example 2 is an example in which the amount of the component (C) is small outside the range, and the chemical resistance is poor. Comparative Example 3 is an example in which the amount of the component (C) is out of the range, and the impact resistance, rigidity, and surface appearance of the molded product are poor. Comparative Example 4
This is an example in which the amount of the vinyl cyan compound in the methyl ethyl ketone soluble part of the components (A) + (B) is too small and the chemical resistance is poor. This is an example in which the amount of vinyl cyan compound is out of the range, and the impact resistance is poor. In Comparative Example 5, the melt flow rates of the (A) + (B) component and the (C) component (220 ° C., 10 k
This is an example where the g load measurement ratio is small outside the range, and the chemical resistance is poor. Comparative Example 6 is an example in which the melt flow rate (220 ° C., 10 kg load measurement) ratio of the components (A) + (B) and the component (C) is large outside the range, and the chemical resistance is poor.

[0019]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is used in a range of excellent impact resistance, rigidity, surface appearance of molded articles and chemical resistance, for example, various parts for interior and exterior of automobiles, OA, etc.
It can be used for various parts such as home appliances, electric / electronics, miscellaneous goods, and sanitary fields, housings, chassis, etc.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeki Furuyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A rubber obtained by polymerizing (A) an aromatic vinyl compound, a vinyl cyan compound and, if necessary, another vinyl monomer copolymerizable therewith in the presence of the rubbery polymer (a). Modified styrenic resin 5-100% by weight, (B)
0 to 95% by weight of a resinous polymer composed of an aromatic vinyl compound, a vinylcyanide compound and, if necessary, another vinyl monomer copolymerizable therewith, relative to 100 parts by weight of (A) + (B). , (C) a non-polar α-olefin (co) polymer and a vinyl-based (co) polymer comprising at least one vinyl monomer, one (co) polymer of which is the other (co) polymer Thermoplastic resin having a particle size of 0.001 to 10 μm dispersed in the coalescence
A resin composition containing 30 to 30 parts by weight,
The amount of the vinyl cyanide compound in the methyl ethyl ketone soluble part of the components (A) + (B) is 27 to 45% by weight, and (A) +
Melt flow rate of component (B) and component (C) (220
℃, 10kg load measurement) ratio is (C) / (A) + (B) =
The thermoplastic resin composition is 0.2 to 20.