JPH09132684A - Chemical-resistant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemical-resistant thermoplastic resin composition excellent in mechanical characteristics, moldability and color stability when melted by blending a specified rubber-containing graft polymer, a vinyl cyanide base copolymer, and a (meth)acrylic acid polymer and/or an aromatic polyester polymer. SOLUTION: This composition consists of 10-40 pts.wt. graft polymer (A) (having a graft ratio of at least 15%) obtained by the graft polymerization of 5-80 pts.wt. diene rubber having a weight-mean particle diameter of 0.1-2.0μm with 95-20 pts.wt. mixture of 45-85wt.% aromatic vinyl compound and/or α,β-unsaturated carboxylic acid ester compound, 15-55wt.% vinyl cyanide compound and 0-40wt.% other copolymerizable vinyl monomer, 10-80 pts.wt. copolymer (B) of an aromatic vinyl compound, an α,β-unsaturated carboxylic acid ester compound, a vinyl cyanide compound, etc., and 10-50 pts.wt. (meth)acrylic acid polymer (C) and/or aromatic polyester polymer (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to chemical resistance, in particular, stress crack resistance does not occur in a molded product when it comes into contact with a chemical liquid, excellent stress crack resistance, and a balance of mechanical properties and molding processability. And a chemical resistant thermoplastic resin composition excellent in stability of color tone when melted, and a resin molded product from the composition.

[0002]

2. Description of the Related Art Acrylonitrile is added to a diene rubber component.
A so-called ABS resin containing a graft copolymer obtained by copolymerizing a vinyl cyanide compound such as methacrylonitrile and an aromatic vinyl compound component such as styrene and α-methylstyrene, has high impact resistance, mechanical strength, and Due to its excellent molding processability, it is widely used for OA equipment and home appliances as a quasi-engineering plastic having intermediate properties between general-purpose resins and engineering plastics.

However, rubber-reinforced styrenic resins represented by ABS resins are known to be inferior in chemical resistance to other crystalline polymers and engineering plastics, such as alcohols and hydrocarbons. Chemicals such as compounds and esters, synthetic detergents, and chemicals such as CFCs, gasoline, kerosene, brake oil, and vinyl chloride plasticizers cause crazes and cracks, and are used in home appliances, miscellaneous goods fields, automobile fields, etc. Use is restricted in. In addition, ABS resin is widely used for parts of a heat insulating structure such as an inner box and a door member of a refrigerator, miscellaneous goods such as a pachinko tray, and sanitary uses such as a toilet and a kitchen. As the foaming agent for the rigid urethane foam used as the heat insulating material in the heat insulating structure, the specified CFC-11 has been used, but due to the ozone problem, it is being replaced by CFC alternative-141b or cyclopentane. -14
1b and cyclopentane are more
The BS resin is severely attacked, and crazes and cracks occur in the molded product under a stressed state. In general merchandise and sanitary applications, household or commercial detergents are used for cleaning the members, and these detergents also cause crazes and cracks in molded articles, causing a problem of significantly impairing commercial value. As a means for improving such a problem, plating or coating on the surface of a resin molded product, or a method of sticking a film or the like to prevent contact with chemicals is known, but the manufacturing process is complicated, and processing is performed. It is not advantageous in terms of cost increase and deterioration over time.

Regarding the ABS resin, a method for increasing the content ratio of the vinyl cyanide-based monomer component in the resin composition is known, and some so-called high nitrile content thermoplastic resin compositions have been proposed. . For example, from the viewpoint of merely improving chemical resistance and mechanical properties, a resin composition in which the graft ratio of the graft copolymer is specified (Japanese Patent Laid-Open No. 4-258).
No. 619, JP-A-5-78428), from the viewpoint of having chemical resistance and excellent thermal stability, a high nitrile-containing thermoplastic resin composition containing a methacrylic acid ester as an essential component as a matrix component ( JP-A-4-126
756).

However, in the above-mentioned conventional high nitrile-containing thermoplastic resin composition, a certain degree of chemical resistance improving effect is recognized by increasing the content ratio of the vinyl cyanide monomer component in the resin composition. However, there is a problem such as a decrease in heat coloring property and fluidity at the time of molding, and a fundamental problem has not been solved yet. It is known that the thermal coloring property in these high nitrile-containing thermoplastic resin compositions, so-called deterioration of color tone, is caused by the molecular structure in which nitrile groups are adjacent to each other (56, Modern Plastics Internati
onal, April, 1990), but it was difficult to control the molecular structure. However, the present inventors have found such a control method (Japanese Patent Application No. 6-264241), and have a thermoplastic resin composition having excellent chemical resistance containing the high nitrile-containing vinyl copolymer as a constituent component (Japanese Patent Application No. 6-264241). No. 6-314618). Further, as a means for improving chemical resistance, a method of blending a crystalline resin such as polybutylene terephthalate, polyamide or polypropylene having excellent chemical resistance (Japanese Patent Publication No. 7-21096, JP-A-6-31309).
No. 1, JP-A-6-329852, etc.) have been proposed, but when a crystalline resin is blended, the molding shrinkage rate becomes large, and the mold used in the conventional styrene resin cannot be used. In addition, the compatibility with the ABS resin is insufficient, and the mechanical properties cannot be satisfied.

Further, Japanese Patent Publication No. 55-50063 discloses that
A technique of blending an ethylene / (meth) acrylic acid ester / carbon monoxide terpolymer with a thermoplastic resin to obtain an effect as a plasticizer is disclosed. On the other hand,
No. 287653 is blended with ABS resin, and JP-A No. 5-125253 is described with α-methylstyrene modified ABS.
JP-A-6-116469 discloses a technique of improving impact resistance by blending with a resin, and further by blending with a maleimide resin. However, the ethylene /
No technique has been disclosed for blending a terpolymer of (meth) acrylic acid ester / carbon monoxide to improve chemical resistance.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide chemical resistance, particularly stress crack resistance which does not cause stress cracks in a molded product when it comes into contact with a chemical solution, excellent mechanical properties and molding. It is an object of the present invention to provide a chemical resistant thermoplastic resin composition having excellent balance of processability and excellent color stability during melting.

The inventors of the present invention have conducted extensive studies as a result of achieving the above object. As a result, a rubber-containing graft copolymer having a rubber particle diameter and a graft ratio within a specific range, and a vinyl cyanide-based copolymer having a specific structure. By combining the polymer with a (meth) acrylic acid ester-based polymer and / or an aromatic polyester-based polymer, the chemical resistance, mechanical properties and molding processability are excellently balanced, and the color tone is stable when melted. It has been found that a chemically resistant thermoplastic resin composition having excellent properties is obtained, and the present invention has been accomplished.

[0009]

The above-mentioned object of the present invention is to add an aromatic vinyl compound to 5 to 80 parts by weight of a diene rubber (A-1) having a weight average particle diameter of 0.1 to 2.0 μm. (A) and / or α, β-unsaturated carboxylic acid ester compound (B) 45 to 85% by weight, vinyl cyanide compound (C) 15 to 55% by weight, other copolymerizable vinyl-based monomer ( D) 10 to 40 parts by weight of a graft copolymer (A) having a graft ratio of 15 to 100% by graft polymerization of 95 to 20 parts by weight of a monomer mixture (A-2) consisting of 0 to 40% by weight. Parts and aromatic vinyl compounds (a)
And / or α, β-unsaturated carboxylic acid ester compound (b) 45 to 75% by weight, vinyl cyanide compound (c) 25 to 55% by weight, other copolymerizable vinyl monomer (d) 0 10 to 80 parts by weight of a copolymer (B) obtained by copolymerizing a monomer mixture of 40 to 40% by weight, and a (meth) acrylic acid ester-based polymer (C) and an aromatic polyester-based polymer (D). 10 to 50 parts by weight of one or more polymers selected from the above, and the ratio of the triple sequence of the vinyl cyanide compound in the copolymer (B) is 10 parts by weight in the copolymer (B). % Or less, and can be achieved by a chemical resistant thermoplastic resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The diene rubber (A
Examples of -1) include polybutadiene and styrene-
Butadiene copolymers, acrylonitrile-butadiene copolymers, styrene-butadiene block copolymers, butyl acrylate-butadiene copolymers, polyisoprene rubber and the like can be mentioned, among which polybutadiene and styrene-butadiene copolymer rubbers are preferred. .

As the aromatic vinyl compound (a) in the monomer mixture (A-2) and the copolymer (B) monomer mixture in the present invention, styrene, α-methylstyrene,
Examples thereof include p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-dichlorostyrene, but styrene and α-methylstyrene are particularly preferable. One or more of these can be used.

Examples of the α, β-unsaturated carboxylic acid ester compound (b) include methyl (meth) acrylate and (meth)
Ethyl acrylate, n-propyl (meth) acrylate,
N-butyl (meth) acrylate, t- (meth) acrylate
-Butyl, n-hexyl (meth) acrylate, (meth)
Examples thereof include cyclohexyl acrylate, chloromethyl (meth) acrylate, and 2-chloroethyl (meth) acrylate, with methyl methacrylate being preferred.

Examples of the vinyl cyanide compound (C) include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferred.

Other copolymerizable vinyl monomers (d) include maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, unsaturated dicarboxylic acids such as maleic acid, Examples thereof include unsaturated dicarboxylic acid anhydrides such as maleic anhydride, and copolymerizable vinyl compounds represented by unsaturated amide compounds such as acrylamide. These may be used alone or in combination of two or more.

The weight average particle diameter of the diene rubber (A-1) in the graft copolymer (A) is 0.1 to 2.0 μm.
Is required, and preferably 0.2 to 1.5 μ
m. When the weight average particle diameter is out of the range of 0.1 to 2.0 μm, the chemical resistance and mechanical properties aimed by the present invention are not exhibited. The content of the diene rubber (A-1) is 5 to 80 parts by weight, preferably 10 to 60 parts by weight, with the total amount being 100 parts by weight.

Aromatic vinyl compound (a) and / or α, β-unsaturated carboxylic acid ester compound (b), vinyl cyanide compound (c) in the monomer mixture (A-2),
The composition ratio of the other copolymerizable vinyl-based monomer (c) is such that (a) and / or (b) is 45 to 85% by weight,
It is preferably 50 to 80% by weight, (C) is 15 to 55% by weight, preferably 20 to 50% by weight, and (D) is 0 to 40% by weight. Aromatic vinyl compound (a) and / or α, β-unsaturated carboxylic acid ester compound (b), vinyl cyanide compound (c), and other copolymerizable vinyl-based monomer in the copolymer (B) Each composition ratio of the body (C) is
(A) and / or (B) is 45 to 75% by weight, preferably 50 to 70% by weight, and (C) is 25 to 55% by weight,
Preferably 20 to 50% by weight, (D) 0 to 20% by weight
It is. The monomer composition may be the same or may be different as long as the mechanical properties are not impaired. Among the monomer mixture of the copolymer (B), a vinyl cyanide compound is an important monomer, and if the total amount of the monomer mixture is less than 25% by weight based on 100% by weight, the chemical liquid is less than 25% by weight. If it comes into contact with the molded product, crazes and cracks are likely to occur in the molded product, which is not preferable. On the other hand, if it exceeds 55% by weight, not only the effect of improving the chemical resistance gradually decreases but also there are drawbacks such as thermal coloring during molding and markedly lowering of fluidity.

The graft ratio in the graft copolymer (A) must be 15 to 100%, preferably 20 to 70%. If the graft ratio is out of the range of 15 to 100%, not only the chemical resistance is not exhibited, but also the mechanical properties are significantly deteriorated.

The method for producing the graft copolymer (A) may be any of polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization, and is not particularly limited. There are no particular restrictions on the method of charging the monomer, the initiator and the chain transfer agent, and a part or the whole of the charged monomer is continuously charged in order to suppress the generation of the initial composition or the distribution of the composition of the copolymer. The polymerization may be carried out while charging the target or divided.

In the present invention, the triple sequence of vinyl cyanide compound in the copolymer (B) is a segment of the copolymer represented by the formula (1), and the copolymer is exposed to high temperature. In such a state, the intramolecular reduction reaction represented by the formula (2) proceeds, so that it is presumed that coloring occurs.

[0020]

Embedded image

Embedded image The chemical resistant thermoplastic resin composition of the present invention relates to the copolymer (B) which is a constituent component, and the proportion of the triple sequence of the vinyl cyanide compound which inhibits the thermal discoloration preventive property is 10% by weight.
Since it is as small as the following, it is excellent in thermal discoloration preventive property during melt-kneading and molding. The more preferable ratio of the triple sequence of the vinyl cyanide compound is less than 8% by weight, and if the ratio exceeds 10% by weight, the thermal discoloration preventive property at the time of melt kneading or molding is deteriorated, which is not preferable. The proportion of such a triple sequence of a vinyl cyanide compound is 10% by weight.
The copolymer (B) controlled below can be produced by controlling the ratio of the vinyl cyanide-based monomer component in the residual monomer to carry out the polymerization. The polymerization method is preferably aqueous suspension polymerization, but is not particularly limited to this method.

Examples of the suspension stabilizer used in the aqueous suspension polymerization include inorganic suspension stabilizers such as clay, barium sulfate, and magnesium hydroxide, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, and methyl methacrylate / acrylamide. Examples thereof include organic suspension stabilizers such as polymers. Among them, organic suspension stabilizers are preferable because they are excellent in preventing thermal discoloration during melting, and methyl methacrylate / acrylamide copolymers are more preferable. Further, the total amount of water charged as a dispersion medium relative to 100 parts by weight of the total charged monomers is 80 from the viewpoint of maintaining good dispersibility of the monomers in water and dissolving and transferring a large amount of the vinyl cyanide-based monomer into water. To 350 parts by weight, and more preferably 100 to 200 parts by weight for controlling the vinyl cyanide-based monomer component ratio in the residual monomer.

The polymerization initiator used in the aqueous suspension polymerization is 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (2,4,4-trimethylvaleronitrile). And organic peroxides such as t-butylperoxide, t-butylperoxyneodecanate, t-butylperoxyneoxexanoate, and t-butylperoxypivalate. One kind or two or more kinds can be used in combination, and among them, an azonitrile compound is preferable. The chain transfer agent used here is not particularly limited, but alkyl mercaptans are preferable.

There are no particular restrictions on the method of charging the above-mentioned aqueous suspension polymerization monomer, initiator and chain transfer agent, and initial charging at once or in order to suppress formation of the composition distribution of the copolymer, A part or the whole may be polymerized continuously or while being charged separately.

In the present invention, in order to obtain the copolymer (B), the amount of residual monomer in the polymerization system from the start to the end of the polymerization is controlled in order to control the ratio of the triple sequence of the vinyl cyanide monomer. 95% of vinyl cyanide monomer component in the body
It is preferable to control the amount to be below and to set the ratio of the vinyl cyanide-based monomer component in the residual monomer from the initiation of polymerization to the point of time when the polymerization rate is 10% to 70% by weight or more and 95% by weight or less. The ratio of the vinyl cyanide-based monomer component in the residual monomer from the start of the polymerization to the point where at least a polymerization rate of 10% has passed is 7
If it is 0% by weight or less, it becomes difficult to maintain chemical resistance. Chemical resistance, which is an advantage of the resin composition of the present invention,
Regarding the copolymer (B) which is the matrix component,
A high content ratio of vinyl cyanide-based monomer component produced by maintaining the ratio of vinyl cyanide-based monomer component in the residual monomer to 70% by weight or more from the start of polymerization until the point of 10% of the polymerization rate, This is because it is developed by the high nitrile copolymer component. The high nitrile copolymer component described here is a component which is obtained by dissolving the copolymer (B) in methyl ethyl ketone and then depositing it by dropping cyclohexane. The ratio of vinyl cyanide monomer component of the deposit is FT It can be quantified by IR analysis. The ratio of the vinyl cyanide-based monomer component in the residual monomer is the amount of the polymerization initiator, the addition of the polymerization inhibitor, or the vinyl cyanide-based monomer removed from the polymerization system of the vinyl cyanide-based monomer by stripping. It can be controlled by adding a monomer other than the monomer component into the polymerization system during the polymerization.

The (meth) acrylic acid ester polymer (C) in the present invention has a carbon number of 1 to 1 in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.
Polymers obtained by polymerizing 20 acrylic acid alkyl esters, methacrylic acid alkyl esters, etc., or copolymers obtained by copolymerizing two or more kinds of these, and other monomers that can be copolymerized as necessary. Body, for example, α-olefins such as ethylene and propylene, aromatic vinyl,
Examples thereof include copolymers with vinyl cyanide, methacrylic acid ester, methacrylic acid, acrylic acid, butadiene, silicon, carbon monoxide and the like. Of these, homopolymers or copolymers using alkyl acrylate are preferable. Acrylic acid alkyl ester-based polymer,
Those cross-linked by copolymerization with a cross-linking agent having a plurality of ethylenic double bonds in the molecule, a graft copolymer in which a vinyl-based monomer is graft-polymerized to an alkyl acrylate polymer, ethylene / ( The meth) acrylate / carbon monoxide terpolymer is particularly preferred. In this ethylene / (meth) acrylic acid ester / carbon monoxide terpolymer, the acrylic group of the (meth) acrylic acid ester is linear or branched, and its carbon number is 1-18. Preferably, methyl group, ethyl group, n-
Examples thereof include a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group, and those having 2 to 8 carbon atoms are more preferable. The composition ratio of the copolymer (C) is such that ethylene is 10 to 85% by weight, and more preferably 40 to 80% by weight.
% By weight, 10 to 50% by weight of (meth) acrylic acid ester, more preferably 15 to 40% by weight, carbon monoxide 5
-40% by weight, more preferably 5-20% by weight,
If necessary, it can be copolymerized with other copolymerizable monomers.

The aromatic polyester polymer (D) of the present invention is a polymer, copolymer or block copolymer obtained by a polycondensation reaction containing dicarboxylic acid and diol as main components. As the dicarboxylic acid, terephthalic acid,
Isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4
′ -Biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1, 2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,
6-anthracene dicarboxylic acid, 4,4'-p-ta-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, cyclohexanedicarboxylic acid, and the like, among which, Terephthalic acid is preferred. These dicarboxylic acids may be used as a mixture of two or more kinds.

As the diol component, ethylene glycol, propylene glycol, butylene glycol
, Hexylene glycol, neopentyl glycol,
2-Methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol and the like can be mentioned. If it is a small amount, one or more kinds of long chain diol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-polypropylene glycol, polytetramethylene glycol, etc. are copolymerized. May be.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethyl terephthalate, polyester hard segment and polyether. Examples thereof include polyester-ether block polymers having a soft segment. Among them, polybutylene terephthalate and polyester-ether block polymers are preferable, but not limited thereto.

One or more selected from the graft copolymer (A), the copolymer (B), the (meth) acrylic acid ester polymer (C) and / or the aromatic polyester polymer (D). Polymer weight ratio (A) / (B) /
(C) and / or (D) is 10-40 / 10-80
If the component (A) exceeds 40, the rigidity and fluidity will be deteriorated, and if it is less than 10, the impact resistance will be deteriorated. Also,
If the component (B) exceeds 80, impact resistance and heat discoloration-preventing property are deteriorated, and if it is less than 10, chemical resistance and fluidity are deteriorated, which is not preferable. further,
If the amount of the component (C) and / or the component (D) is less than 10, chemical resistance is not exhibited, while if it exceeds 50, the rigidity and fluidity are deteriorated, and further delamination occurs, which is not preferable.

The chemical resistant thermoplastic resin composition and molded article of the present invention are preferably used for applications requiring chemical resistance. The liquid medicine effective in the present invention is preferably an organic compound, which is a drug containing a hydrocarbon, a halogenated hydrocarbon, an ester compound, an ether compound and an alcohol compound. Furthermore, it is a drug containing a hydrocarbon having 4 to 20 carbon atoms, CFCs, gasoline, kerosene, brake oil, a plasticizer for polyvinyl chloride (eg dialkyl phthalate, alkyl phthalate) and detergent. is there.

In order to improve the chemical resistance of the chemical resistant thermoplastic resin composition and the molded article of the present invention, 24 at 23 ° C.
It is necessary that the critical strain for cracking after contact with the chemical solution for 0.5 hour is 0.5% or more, preferably 0.7% or more, more preferably 1.0% or more, and if less than 0.5%,
The effect of improving chemical resistance is small.

The applications of these molded articles are electricity,
There are no particular restrictions on electronic parts, automobiles, machinery, sundries, chemical plants, aviation and space parts, materials and the like, but the features of the molded article of the present invention make it effective for applications requiring chemical resistance.
Among them, it can be used as a structural part of electric / electronic product housings and refrigerators, miscellaneous goods such as saucers for pachinko machines, sanitary applications such as toilets and kitchens, and interior / exterior materials for automobiles.

In the chemical resistant thermoplastic resin composition of the present invention, vinyl chloride, polyolefin such as polyethylene and polypropylene, nylon 6, nylon 6,
The performance as a molding resin can be improved by adding polyamide such as nylon 66, polycarbonate, and various elastomers. In addition, if necessary, antioxidants such as hindered phenols, sulfur-containing organic compounds and phosphorus-containing organic compounds, heat stabilizers such as phenols and acrylates, benzotriazoles, benzophenones, salicylates, etc. Various stabilizers such as UV absorbers, organic nickel-based, hindered amine-based light stabilizers, etc., metal salts of higher fatty acids, lubricants such as higher fatty acid amides, plasticizers such as phthalate esters, phosphate esters, etc. Bromodiphenyl ether, tetrabromobisphenol-A,
It is also possible to add halogen-containing compounds such as brominated epoxy oligomers and brominated polycarbonate oligomers, phosphorus compounds, flame retardants / flame retardants such as antimony trioxide, carbon black, titanium oxide, pigments and dyes. Further, reinforcing agents and fillers such as glass fibers, glass flakes, glass beads, carbon fibers, and metal fibers can also be added. Regarding the method for producing the thermoplastic resin composition of the present invention, various methods such as melt kneading with a Banbury mixer, rolls, and a single-screw or multi-screw extruder can be adopted.

The chemical resistant thermoplastic resin composition obtained as described above is a known method currently used for molding thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas assist molding. It can be molded by, and is not particularly limited.

In order to explain the present invention more specifically, examples and comparative examples will be described below, but these examples do not limit the present invention. Here, unless otherwise specified, "%" represents% by weight and "parts" represents parts by weight. The method for analyzing the resin properties of the chemical resistant thermoplastic resin composition will be described below. For general properties such as mechanical strength and heat resistance, test pieces were molded by injection molding and measured according to the following test methods.

Rubber particle size: Sodium alginate method Graft ratio: Graft copolymer Acetone was added to a predetermined amount (m) and refluxed for 3 hours. p. m
After centrifugation at (10000 G) for 40 minutes, the insoluble matter was filtered, the insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated by the following formula (3). L in (Formula 3) is the rubber content of the graft copolymer.

[0037]

(Equation 1) Quantification of triplicate sequence of vinyl cyanide monomer in copolymer (B): α-carbon signal shift of vinyl cyanide monomer appearing in 13 C-NMR is slightly different due to difference of adjacent monomer species. Therefore, the ratio of the triplicate sequence was quantified from the signal integral value. Device: JE0L JNM-GSX400 type Observation frequency: 100.5 MHz Solvent: DMSO-d6 Concentration: 445 mg / 2.5 mL Chemical shift reference: Me4Si temperature: 110 ° C Observation width: 20000 Hz Data point: 32K flip angle: 90 ° (21 μs ) Pulse delay time: 5.0s Number of integrations: 7400 or 8400 Decoupling: gated decoupling
(Without NOE)

Quantification of unreacted monomer, vinyl cyanide copolymerization amount and polymerization rate in the polymerization system relating to the polymerization of the copolymer (B): Gas chromatograph (GC manufactured by Shimadzu Corporation)
-14A type). The vinyl cyanide copolymerization amount and the polymerization rate were calculated by the following formulas (4) and (5).

[0039]

(Equation 2)

(Equation 3) Determination of high nitrile copolymerization component ratio in copolymer (B):
After dissolving 1 g of the copolymer (B) in 40 g of methyl ethyl ketone, 20 g of cyclohexane is continuously added dropwise. After stirring well at 5 ° C., the mixture was allowed to stand at room temperature for 12 hours, further heated at 30 ° C. in a constant temperature bath, and the precipitated copolymerization component was centrifuged, and the content ratio was quantified from the dry weight.

Quantification of the ratio of vinyl cyanide-based monomer component in the high nitrile copolymerization component: The copolymer component subjected to the above-mentioned treatment is hot-press molded into a film of about 30 μm, which is subjected to FT-IR analysis. And 2260 cm ^-1 and 160
It quantified using the calibration curve shown in Formula (6) from the ratio of the baseline height of the absorbance peak generated at 0 cm ^-1 .

[0041]

(Equation 4) Flexural modulus: ASTM D790 (23 ° C) Load deflection temperature: ASTM D648 (1/4 inch, load stress 18.56 kg / cm ² ) AZ0D Impact strength: ASTM D256 (23 ° C, with 1/2 inch notch) MFR ( Melt flow rate): ISO 1133 (2
20 ° C., 10 kg / load) Yellowing degree (YI value): in accordance with JIS K7103,
An injection-molded square plate (120 x 100 x 3 mm) was measured for tristimulus values X, Y, Z with a colorimetric color difference meter (ND-100 type) manufactured by Nippon Denshoku Industries Co., Ltd. Y. I. Values were calculated.

[0042]

(Equation 5) Chemical resistance test: Injection-molded strip-shaped test pieces (126 x 1
(2.6 x 1.5 mm) along the 1/4 elliptical jig shown in Fig. 1 and fix it, and then apply the chemical solution to the surface of the test piece, or in the case of a highly volatile chemical solution, add 250 ml of the chemical solution. The jig was introduced into a desiccator having a diameter of 300 mm. 2
After standing for 24 hours in an environment of 3 ° C., the presence or absence of crazes and cracks was confirmed, and the critical strain (%) was calculated from the formula (8).

[0043]

(Equation 6)

[0044]

[Reference example]

(A) Graft copolymer A ₁ : 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.001 part of ferrous sulfate in a reactor substituted with nitrogen. A fixed amount of polybutadiene latex was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. Using the time point when the internal temperature reached 65 ° C. as the polymerization initiation point, the predetermined amounts of the monomer and t-dodecyl mercaptan mixture shown in Table 1 were continuously added over 5 hours.
At the same time, in parallel, an aqueous solution of cumene hydroperoxide and potassium oleate shown in Table 1 was continuously added over 7 hours to complete the reaction. 2,2'-methylenebis (4-methyl-6-t) was added to the obtained latex.
-Butylphenol) was added to 100 parts of latex solids, and the latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to obtain a powder-like graft. A copolymer was obtained.
The graft ratio of this graft copolymer was 45%. A ₂ to A _8: In the same manner as A _1, to obtain a graft copolymer at the composition ratio shown in Table 1.

(B) Copolymer B ₁ : 0.05 part of methyl methacrylate / acrylamide copolymer was dissolved in 165 parts of pure water and stirred in a reactor,
The system was replaced with nitrogen. Certain monomers shown in Table 2 and t-dodecyl mercaptan, 2,2'-azobis (2,2
4-dimethylvaleronitrile), 2,2'-azobisisobutylnitrile mixed solution is added with stirring, and 5
The temperature was raised to 8 ° C. to initiate polymerization. Fifteen minutes after the start of the polymerization, the monomers shown in Table 2 were added intermittently over 110 minutes.
During this time, the reaction temperature rose from 58 ° C to 65 ° C. After the intermittent addition of styrene to the reaction system was completed, the temperature was raised to 100 ° C. over 50 minutes to complete the reaction. After cooling the reactor, the polymer was separated from the slurry, washed and dried to obtain a bead-shaped copolymer. The final polymerization rate was 95%, and the ratio of the vinyl cyanide-based monomer component in the residual monomer after the completion of the polymerization was 90%.

Copolymers having the composition ratios shown in Table 2 were obtained in the same manner as B _{2 to} B ₄ : B ₁ . Table 3 shows changes over time (in terms of polymerization rate) of the vinyl cyanide-based monomer component ratio in the residual monomers in the polymerization system from the initiation of polymerization of the copolymer to the completion of the polymerization.
Shown in Further, various characteristic values of the copolymer are also shown in Table 2.

(C) (Meth) acrylic ester type copolymer C ₁ : 97% ethyl acrylate, 3% divinylbenzene
After emulsion polymerization of the monomer mixture consisting of, sulfuric acid was added, and subsequently sodium polyacrylate was added to solidify. After neutralization with caustic soda, washing, filtration and drying were carried out to obtain a powdery ethyl acrylate polymer. C _2: ethyl acrylate to emulsion polymerization, to complete the reaction. Subsequently, 50 parts of a monomer mixture consisting of 60% styrene and 40% acrylonitrile was emulsion polymerized in the presence of 50 parts of the latex (calculated as solid content). The obtained polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery polymer composition. C ₃ : "Elvalloy" manufactured by Mitsui DuPont Polychemicals
EP4051

(D) Aromatic polyester polymer D ₁ : Toray polybutylene terephthalate "PBT"
1200S D _2: Toray DuPont polyester - ether block copolymer "Hytrel" 4057

[0049]

Examples 1 to 30, Comparative Examples 1 to 13 Graft copolymer (A), copolymer (B), (meth) acrylic acid ester copolymer (C) and / or aromatic compound described in Reference Example After blending the polyester polymer (D) in the proportions shown in Tables 4 to 6, a 40 mmφ single-screw extruder (cylinder set temperature is 23
Melt kneading at (° C.) to obtain a resin pellet. Injection molding machine IS-50A manufactured by Toshiba Machine Co., Ltd.
(Cylinder setting temperature is 23 ° C.), a test piece was molded, various properties were evaluated, and the results are shown in Tables 7 to 12. According to Examples 1 to 30, the chemical resistant thermoplastic resin composition in the range defined by the present invention has an excellent balance of chemical resistance, mechanical properties, moldability and color stability during melting. ◎ In contrast, Comparative Examples 1 to 1
In the present invention, 3 is the blending ratio of the graft copolymer (A), the copolymer (B), the (meth) acrylic acid ester polymer (C) and / or the aromatic polyester polymer (D). Since it is out of the range, Comparative Examples 1 to 3 and 7 to 12
Has low chemical resistance, and Comparative Examples 7 to 12 also have low impact resistance. Comparative Examples 4 to 6 have good chemical resistance, Comparative Examples 4 to 5 have low fluidity, heat resistance and rigidity, and Comparative Example 6 has good chemical resistance but low heat resistance and colorability.

[0050]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[0051]

Industrial Applicability The chemical resistant thermoplastic resin composition of the present invention or a molded article made of the composition is a rubber-containing graft copolymer having a rubber particle diameter and a graft ratio within a specific range, and a cyan having a specific structure. Vinyl chloride copolymer,
Characterized by combining with a (meth) acrylic acid ester-based polymer and / or an aromatic polyester-based polymer, which has an excellent balance of chemical resistance, mechanical properties, molding processability, and color tone stability during resin melting. ing. The chemical-resistant thermoplastic resin composition of the present invention or a molded article thereof is used for various applications by making use of the above-mentioned characteristics, but it is used for electric refrigerators, household appliances that come into contact with detergents, sanitary applications, and commercial games. Suitable for equipment use.

[Brief description of the drawings]

FIG. 1 shows a schematic view of a 1/4 elliptical jig used for a chemical resistance test.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 33/06 LJC C08L 33/06 LJC LJD LJD LJE LJE 55/02 LME 55/02 LME LMF LMF 67/02 LNZ 67/02 LNZ 73/00 LQQ 73/00 LQQ

Claims (14)

[Claims] 1. An aromatic vinyl compound (a) and / or α, β-unsaturated in 5 to 80 parts by weight of a diene rubber (A-1) having a weight average particle diameter of 0.1 to 2.0 μm. A single amount consisting of 45 to 85% by weight of a carboxylic acid ester compound (B), 15 to 55% by weight of a vinyl cyanide compound (C), and 0 to 40% by weight of another copolymerizable vinyl monomer (D). 95 to 20 parts by weight of the polymer mixture (A-2) is graft-polymerized, and 10 to 40 parts by weight of the graft copolymer (A) having a graft ratio of 15 to 100%, the aromatic vinyl compound (a) and / Or an α, β-unsaturated carboxylic acid ester compound (b) 45 to 75% by weight,
Copolymer (B) 10 obtained by copolymerizing a monomer mixture containing 25 to 55% by weight of a vinyl cyanide compound (C) and 0 to 40% by weight of another copolymerizable vinyl monomer (D).
To 80 parts by weight and 10 to 50 parts by weight of one or more polymers selected from the group consisting of (meth) acrylic acid ester-based polymers (C) and aromatic polyester-based polymers (D), A chemical resistant thermoplastic resin composition, wherein the proportion of triple sequences of the vinyl cyanide compound in the copolymer (B) is 10% by weight or less in the copolymer (B). 2. The component (C) has an alkyl group having 1 to 10 carbon atoms.
Polymer (C1) and / or polymer (C1) obtained by polymerizing 20 (meth) acrylic acid alkyl ester
From the group consisting of aromatic vinyl compound (a), α, β-unsaturated carboxylic acid ester compound (b), vinyl cyanide compound (c), and other copolymerizable vinyl-based monomer (d) A polymer (C2) obtained by polymerizing at least one selected monomer.
The chemically resistant thermoplastic resin composition described. 3. The component (C) is a copolymer (C3) comprising ethylene / (meth) acrylic acid ester / carbon monoxide and the components (C1) and / or (C2) according to claim 2. The chemical-resistant thermoplastic resin composition according to claim 1 or claim 2. 4. The component (D) is polybutylene terephthalate.
(D1) and / or polyester-ether block copolymer (D2), The chemical-resistant thermoplastic resin composition according to claim 1. 5. The component (C) is the component (C) according to claim 2.
The chemical resistant thermoplastic resin composition according to claim 1, which is 1) and / or (C2), and component (D) is polybutylene terephthalate (D1). 6. The component (C) is the component (C) according to claim 2.
The chemical resistant thermoplastic resin composition according to claim 1, which is 1) and / or (C2) and the component (D) is a polyester-ether block copolymer (D2). 7. The component (C) is the component (C) according to claim 2.
3. The chemical resistant thermoplastic resin composition according to claim 1, which is 3) and the component (D) is a polybutylene terephthalate (D1) and / or a polyester-ether block copolymer (D2). . 8. The component (C) is the component (C) according to claim 3.
3) and the component (C1) and / or (C) according to claim 2.
The chemical resistant thermoplastic resin composition according to claim 1, which is 2) and the component (D) is polybutylene terephthalate (D1). 9. The component (C) is the component (C) according to claim 3.
3) and the component (C1) and / or (C) according to claim 2.
The chemical-resistant thermoplastic resin composition according to claim 1, which is 2) and the component (D) is a polyester-ether block copolymer (D2). 10. The component (C) is the component (C) according to claim 3.
3) and the component (C1) and / or (C) according to claim 2.
The chemical resistant thermoplastic resin composition according to claim 1, which is 2) and the component (D) is a polybutylene terephthalate (D1) and a polyester-ether block copolymer (D2). 11. The chemical resistant thermoplastic resin composition according to any one of claims 1 to 10, wherein a critical strain for crack generation after contact with a chemical solution at 23 ° C. for 24 hours is 0.5% or more. . 12. The chemical resistance according to claim 11, wherein the chemical liquid contains one selected from a hydrocarbon, a halogenated hydrocarbon, an ester compound, an ether compound and an alcohol compound. Thermoplastic resin composition. 13. The chemical solution contains one selected from hydrocarbons having 4 to 20 carbon atoms, freons, gasoline, kerosene, brake oil, polyvinyl chloride plasticizer and detergent. Item 11. A chemical resistant thermoplastic resin composition according to item 11. 14. A resin molded product obtained by molding the chemical resistant thermoplastic resin composition according to claim 1.