JP2001323128A - Weather-resistant chemical-resistant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in weather resistance, chemical resistance and stain resistance. SOLUTION: The weather-resistant and chemical-resistant thermoplastic resin composition comprises (A) a rubber toughened thermoplastic resin formed by graft-polymerizing a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c), and, if necessary, other vinyl monomer, in the presence of a rubber (a) comprising a hydrogonated product of an ethylene-α-olefin copolymer rubber and/or a diene polymer, (B) a rubber toughened thermoplastic resin formed by graft-polymerizing the aforesaid monomer component in the presence of an acrylic rubber (d), (C) and (D) each a copolymer formed by copolymerizing the aforesaid monomer component in which the amount of the component (c) is in a respective specific range, and, if necessary, (E) at least one agent selected from the group consisting of talc, a weather-resistant agent and a lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent weather resistance, chemical resistance and stain resistance.

[0002]

2. Description of the Related Art A resin obtained by graft-polymerizing styrene and acrylonitrile using ethylene-α-olefin copolymer rubber, acrylic rubber or the like as a base rubber is AE.
S resin, also known as ASA resin, physical properties,
Because of their excellent chemical, mechanical and electrical properties, molded articles are obtained by various molding methods and used in a wide range of fields. The AES resin using the above-mentioned ethylene-α-olefin copolymer rubber as a base rubber has higher resistance to ultraviolet rays, oxygen and ozone and has much better weather resistance than the ABS resin using a conjugated diene rubber. It has been known. However, since the AES resin has poor chemical resistance, it is necessary to take measures such as reducing the amount of rubber, and as a result, the strength is reduced. On the other hand, an ASA resin using an acrylic rubber as a base rubber has almost no change due to exposure because rubber molecules are stable to ultraviolet rays and oxygen, and is excellent in weather resistance, but is liable to be delaminated.
There is a problem that the notched impact strength is not always high.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and provides a thermoplastic resin composition having excellent weather resistance, chemical resistance thermoplasticity, and excellent stain resistance. The purpose is to do.

[0004]

According to the present invention, there is provided (A) a rubber (a) comprising a hydrogenated product of an ethylene-α-olefin copolymer rubber and / or a diene polymer,
Rubber-reinforced thermoplastic resin obtained by graft-polymerizing a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c) and, if necessary, another vinyl monomer copolymerizable therewith. 5 to 40 parts by weight, (B) an aromatic vinyl compound (b), a vinyl cyanide compound (c) and optionally another vinyl compound copolymerizable therewith in the presence of an acrylic rubber (d) 5 to 40 parts by weight of a rubber-reinforced thermoplastic resin obtained by graft-polymerizing a monomer component comprising a monomer, (C) an aromatic vinyl compound (b), a vinyl cyanide compound (c), and if necessary, A monomer component comprising another vinyl monomer copolymerizable with the above, wherein the amount of component (c) in the monomer component is more than 35% by weight and 60% by weight or less 10 to 45% by weight of copolymer obtained by copolymerizing components And (D) a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c), and another vinyl monomer copolymerizable therewith, if necessary. (C) in body components
0 to 80 parts by weight of a copolymer obtained by copolymerizing a monomer component having a compounding amount of 10 to 35% by weight [however, (A)
+ (B) + (C) + (D) = 100 parts by weight] as a main component.
With respect to 100 parts by weight of the total amount of the above components (A) to (D),
Further, 0.01 to 20 parts by weight of (E) at least one selected from the group consisting of talc, weathering agent and lubricant may be blended. Next, the present invention relates to a multilayer molded article using the above weather-resistant and chemical-resistant thermoplastic resin composition as a surface material.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The rubber-reinforced thermoplastic resin (A) of the present invention is prepared by adding a rubber (a) comprising a hydrogenated product of an ethylene-α-olefin copolymer rubber and / or a diene polymer. And a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c) and, if necessary, another vinyl monomer copolymerizable therewith. (A) The ethylene-α-olefin copolymer rubber (a) used in the rubber-reinforced thermoplastic resin includes ethylene / α-olefin having 3 to 20 carbon atoms.
A copolymer rubber obtained by copolymerizing a monomer having a mixing ratio of non-conjugated diene = 5 to 95/95 to 5/0 to 30% by weight is preferable. Here, as the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, and the like, preferably propylene, 1-butene, 1-octene, and more preferably propylene. These α
-Olefins can be used alone or in combination of two or more. α ・ olefin has 3 to 2 carbon atoms
0, preferably 3 to 12, more preferably 3
８8. If the number of carbon atoms exceeds 20, the copolymerizability is extremely reduced, which is not preferable. The weight ratio of ethylene to α-olefin is preferably 5 to 95/95 to 5, more preferably 60 to 88/40 to 12, and particularly preferably 7 to
0 to 85/30 to 15.

Non-conjugated dienes which may be used in ethylene-α-olefin copolymer rubbers include alkenyl norbornenes, cyclic dienes, aliphatic dienes and the like, preferably 5-ethylidene-2. -Norbornene and dicyclopentadiene. These non-conjugated dienes can be used alone or in combination of two or more. The content of the non-conjugated diene in the ethylene-α-olefin copolymer rubber is 0 to 30% by weight, preferably 0 to 15% by weight. The amount of unsaturated groups in the copolymer rubber is preferably in the range of 0 to 40 in terms of iodine value.

To produce the ethylene-α-olefin copolymer rubber (a), either a heterogeneous catalyst or a homogeneous catalyst may be used. Examples of the heterogeneous catalyst include a vanadium-based catalyst obtained by combining a vanadium compound and an organoaluminum compound. Further, examples of the homogeneous catalyst include a metallocene catalyst. In particular, a metallocene-based catalyst is effective for producing the rubber using an α-olefin having 6 to 20 carbon atoms.

In order to exhibit the effects of the present invention, in addition to the rubber structure in which the rubber (a) to be used and the following (d) themselves are easily compatible with each other, it is necessary that the graft reaction proceeds uniformly during graft polymerization. Choosing organic peroxides and solvents,
The rubber (a) and the following (d) are dissolved in a uniform solution to initiate polymerization, or a solution obtained by melt-kneading in advance is dissolved in a solution to perform solution polymerization or bulk polymerization, or a re-emulsified product is emulsion-polymerized. Alternatively, the intended effect can be obtained by devising a polymerization method such as suspension polymerization.

The Mooney viscosity (ML 1 _{+ 4} , 100 ° C.) of the ethylene-α-olefin copolymer rubber (a) is as follows:
It is preferably 40 or less, more preferably 25 to 35. The Mooney viscosity can be adjusted by changing the type and amount of the molecular weight modifier, the monomer concentration, the reaction temperature, and the like. The ethylene-α-olefin copolymer rubber (a) has a content of a component having a weight average molecular weight of 1,000,000 or more in terms of polystyrene, preferably 10% by weight or less, more preferably 8% by weight or less. Such a copolymer rubber can be produced by changing the type and amount of the molecular weight regulator and the type and amount of the catalyst.
Further, ethylene-α-olefin copolymer rubber (a)
Has a glass transition temperature (Tg) of preferably -110 to-
40 ° C, more preferably -70 to -50 ° C, melting point (T
m) is preferably from 30 to 110 ° C, more preferably from 40 to 70 ° C.

On the other hand, hydrogenated diene polymers constituting the rubber (a) include hydrogenated styrene-butadiene (block) copolymer, hydrogenated butadiene-acrylonitrile copolymer, and butadiene- Examples include hydrogenated (meth) acrylates, hydrogenated styrene-butadiene random copolymers, and hydrogenated other butadiene (co) polymers.

(A) The average particle size of the rubber (a) dispersed in the rubber-reinforced thermoplastic resin is preferably 0.1 to 2 μm.
m, more preferably 0.2 to 1 μm.

The above rubbers (a) can be used alone or in combination of two or more. (A) The content of the rubber (a) in the rubber-reinforced thermoplastic resin is preferably 5 to 6
0% by weight, more preferably 5 to 35% by weight, particularly preferably 5 to 30% by weight. If it is less than 5% by weight,
Poor impact resistance. On the other hand, if it exceeds 60% by weight, the surface hardness is inferior.

Examples of the aromatic vinyl compound (b) to be graft-polymerized with the component (a) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-p-aminoethylstyrene, N, N
-Diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, vinylnaphthalene, etc., and especially styrene and α-methylstyrene. preferable. (A) The aromatic vinyl compound (b) used in the rubber-reinforced thermoplastic resin is usually contained in all the monomer components.
It is used in an amount of about 40 to 98% by weight, preferably about 50 to 95% by weight (provided that (b) + (c) + other vinyl monomers = 100% by weight, and so on).

Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile.
Preferably it is acrylonitrile. The vinyl cyanide compound (c) is used usually in an amount of about 2 to 60% by weight, preferably about 5 to 50% by weight, based on all the monomer components.

Further, other copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate,
Acrylates such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate;
Methacrylic esters such as butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate; maleic anhydride, itaconic anhydride, citraconic anhydride and the like Unsaturated acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α, such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
imide compounds of β-unsaturated dicarboxylic acids; epoxy group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether; unsaturated carboxylic acid amides such as acrylamide and methacrylamide;
Amino group-containing unsaturated compounds such as aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate and aminostyrene; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2- Butene, trans-4-hydroxy-2-
Butene, 3-hydroxy-2-methyl-1-propene,
Examples include a hydroxyl group-containing unsaturated compound such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and hydroxystyrene; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. The other copolymerizable vinyl monomer usually contains 5
0% by weight or less, preferably about 30% by weight or less. The monomers listed as the above monomer components can be used alone or as a mixture of two or more.

The rubber-reinforced thermoplastic resin (A) can be obtained by a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof.

In the solution polymerization method, a solvent is used. This solvent is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, and halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride. Are used. The amount of the solvent to be used is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of the rubbery polymer and the monomer component.

As the above-mentioned polymerization initiator, a general initiator suitable for a polymerization method is used. In the case of solution polymerization, for example, ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, hydroperoxide, etc. Organic peroxide is used as a polymerization initiator. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator used is
It is usually 0.05 to 2% by weight, preferably 0.2 to 0.8% by weight, based on the monomer component.

In the emulsion polymerization, a radical polymerization initiator, an emulsifier, a chain transfer agent and the like are used, and the monomer components can be added all at once or dividedly. Examples of the radical polymerization initiator include an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butylperoxylaurate, and sugar-containing iron pyrophosphate. Redox initiators in combination with reducing agents such as formulations, sulfoxylate formulations, and mixed formulations of sugar-containing iron pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisiso Butyronitrile, dimethyl-
Azo compounds such as 2,2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and preferably potassium persulfate and the like. Is a water-soluble initiator. The amount of the radical polymerization initiator to be used is generally 0.05-5 parts by weight, preferably 0.1-5 parts by weight, per 100 parts by weight of the monomer component used.
It is about 1 to 3 parts by weight.

Examples of emulsifiers include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate, sodium dialkali ester succinate, sodium or potassium salts of aliphatic carboxylic acids having 10 to 20 carbon atoms, and rosin acid. Anionic emulsifiers such as sodium salt or potassium salt, or nonionic emulsifiers such as polyoxyethylene alkyl ester and polyoxyethylene alkyl allyl ether. These may be used alone or in combination of two or more. Can also be used as a mixture. As the emulsifier, a method using a low critical micelle concentration is preferable. Here, as the critical micelle concentration, an emulsifier having a concentration of 30 mmol / L or less is preferable, and more preferably 15 mmol / L or less. The amount of the emulsifier used is based on the above monomer component 1
It is usually 0.5 to 5 parts by weight with respect to 00 parts by weight.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, and tetraethyl mercaptan. Thiuram sulfide, carbon tetrachloride, ethylene bromide,
Examples thereof include hydrocarbon salts such as pentaphenylethane, terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 1 part by weight based on 100 parts by weight of the monomer component.

In the polymerization of the component (A), 100 parts by weight of a monomer component may be used in combination with a radical polymerization initiator, an emulsifier, a chain transfer agent, etc., and if necessary, various electrolytes and a pH adjuster. On the other hand, water is usually used in an amount of 100 to 500 parts by weight and the above-mentioned radical polymerization initiator, emulsifier, chain transfer agent and the like in an amount within the above range, and the polymerization temperature is usually 40 to 1
Emulsion polymerization is carried out at a temperature of 00 ° C, preferably 50 to 90 ° C, and a polymerization time of 1 to 10 hours.

The component (A) used in the present invention is purified by coagulating a latex obtained by the above emulsion polymerization by a conventional method, washing the obtained powder with water, and drying. Here, examples of the coagulant include sodium chloride, calcium chloride, aluminum chloride, magnesium sulfate, ferrous sulfate, ferric sulfate, and ferric chloride.
Iron, aluminum sulfate, activated silica, calcium phosphate, sulfuric acid, acetic acid and the like.

The graft ratio of the rubber-reinforced thermoplastic resin (A) is not particularly limited, but is usually 5 to 200%, preferably 20 to 140%. Further, (A) the intrinsic viscosity [η] measured at 30 ° C. using methyl ethyl ketone as a solvent in the methyl ethyl ketone soluble portion of the rubber-reinforced thermoplastic resin is as follows:
Preferably 0.1 to 1.0 dl / g, more preferably 0.2 to 0.7 dl / g, particularly preferably 0.24 to dl / g.
0.6 dl / g. Here, the intrinsic viscosity [η] is
(A) A value obtained by dissolving 0.1 g of the component in 100 ml of methyl ethyl ketone and measuring with an Ubbelohde viscometer under a temperature condition of 30 ° C. The graft ratio and intrinsic viscosity of the component (A) can be controlled by changing the types and amounts of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, and the like. Also,
It can also be controlled by changing the method of adding the monomer component, the addition time, the polymerization time, the polymerization temperature, and the like.

The amount of the rubber-reinforced thermoplastic resin (A) used in the thermoplastic resin composition of the present invention is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 1 to 35 parts by weight.
0 to 30 parts by weight [however, (A) + (B) +
(C) + (D) = 100 parts by weight]. If less than 5 parts by weight,
Poor weather resistance. On the other hand, when it exceeds 40 parts by weight, the chemical resistance is poor.

Next, the rubber-reinforced thermoplastic resin (B) of the present invention can be copolymerized with the above-mentioned components (b) and (c) and, if necessary, in the presence of the acrylic rubber (d). It is obtained by graft-polymerizing a monomer component comprising another vinyl monomer. (B) The acrylic rubber (d) used in the rubber-reinforced thermoplastic resin is a polymer of an alkyl acrylate having 2 to 8 carbon atoms in the alkyl group,
Specific examples of the alkyl acrylate include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and the like. One type may be used alone, or two or more types may be used in combination. Preferred alkyl acrylates are n-butyl acrylate, i-butyl acrylate, and 2-ethylhexyl acrylate.
Some of the alkyl acrylates have a maximum of 20
Up to% by weight can be replaced by other copolymerizable monomers. Other monomers include vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ester, alkyl methacrylate, methacrylic acid, acrylic acid,
Styrene and the like.

It is preferred that the acrylic rubber (d) has a monomer type and a copolymerization amount selected so that the glass transition temperature is -10 ° C. or lower. Further, the acrylic rubber (d) is preferably copolymerized with a crosslinkable monomer as appropriate, and the amount of the crosslinkable monomer used is such that
Preferably 0 to 10% by weight, more preferably 0.01%
10 to 10% by weight, particularly preferably 0.1 to 5% by weight.

Suitable crosslinking monomers include mono- or polyethylene glycol diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate and tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate. Mono or polyethylene glycol dimethacrylate, such as triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate,
Examples thereof include di- or triallyl compounds such as divinylbenzene, diallyl phthalate, diallyl maleate, diallyl succinate, and triallyl triazine; allyl compounds such as allyl methacrylate and allyl acrylate; and conjugated diene compounds such as 1,3-butadiene. These can be used alone or in combination of two or more.

The acrylic rubber (d) is produced by a known polymerization method, but is preferably an emulsion polymerization method.
(B) The average particle size of the acrylic rubber (d) dispersed in the rubber-reinforced thermoplastic resin is preferably 0.07 to 1 μm.
m, more preferably 0.1 to 0.8 μm.
(B) Acrylic rubber in rubber-reinforced thermoplastic resin (d)
Is preferably 5 to 60% by weight, more preferably 5 to 50% by weight, particularly preferably 5 to 40% by weight. If it is less than 5% by weight, the chemical resistance is poor. On the other hand, 6
If it exceeds 0% by weight, the surface hardness is inferior.

As the aromatic vinyl compound (b) used for the component (B), all the aromatic vinyl compounds used for the component (A) can be used, and styrene is preferred. The vinyl cyanide compound (c) used for the component (B) is the same as that used for the component (A), and is preferably acrylonitrile. Further, as other copolymerizable vinyl monomers used for the component (B), those similar to the above-mentioned components (A) can be used. The monomers listed as the above monomer components may be used alone or as a mixture of two or more.
Mixtures of more than one species can be used. The proportion of the aromatic vinyl compound (b), the vinyl cyanide compound (c) and the other vinyl monomers among the monomer components used in the component (B) is also the same as that in the component (A). This is the same as the ratio of the monomer component.

The rubber-reinforced thermoplastic resin (B) can be obtained by a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof. Further, the graft ratio of the rubber-reinforced thermoplastic resin (B) is not particularly limited, but is usually 10 to 1
It is 50%, preferably 15 to 100%. Also,
(B) The intrinsic viscosity [η] measured at 30 ° C. using methyl ethyl ketone as a solvent in the methyl ethyl ketone soluble portion of the rubber reinforced thermoplastic resin is preferably 0.2 to 1.0 dl /.
g, more preferably 0.25 to 0.8 dl / g. The graft ratio and intrinsic viscosity of the component (B) can be controlled by changing the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, and the like. The control can also be performed by changing the method of adding the monomer component, the addition time, the polymerization time, the polymerization temperature, and the like.

The amount of the rubber-reinforced thermoplastic resin (B) used in the resin composition of the present invention is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, and more preferably 10 to 30 parts by weight. (A) + (B) + (C) + (D) =
100 parts by weight]. If it is less than 5 parts by weight, the chemical resistance is poor.
On the other hand, if it exceeds 40 parts by weight, the stain resistance is poor.

Next, the copolymer (C) of the present invention comprises (b)
Component (c) and, if necessary, a monomer component comprising another vinyl monomer copolymerizable therewith, and the amount of component (c) in the monomer component is 35. It is obtained by copolymerizing a monomer component of more than 60% by weight and not more than 60% by weight. The monomer components used in the copolymer (C) are the same as the components (b) and (c), and other vinyl monomers that can be copolymerized therewith, if necessary. (C) (c) in the monomer component used in the copolymer
The amount of the component is more than 35% by weight and not more than 60% by weight, preferably 36 to 60% by weight, more preferably 37 to 5% by weight.
0% by weight [however, (b) + (c) + other vinyl monomers = 100% by weight, and so on). If the compounding amount of the component (c) is 35% by weight or less, the chemical resistance is poor. On the other hand, if it exceeds 60% by weight, the thermal stability is poor. In addition,
(C) The above (b) in the monomer component used in the copolymer
The proportion of the components is usually 40% by weight or more and less than 65% by weight, preferably 40 to 64% by weight, more preferably 5% by weight.
0 to 63% by weight. The proportion of the other copolymerizable vinyl monomer in the monomer component used in the copolymer (C) is usually about 15% by weight or less, preferably about 10% by weight or less. .

The intrinsic viscosity [η] of the copolymer (C) of the present invention
But preferably 0.2 to 1.0 dl / g, more preferably 0.2 to 0.8 dl / g, and particularly preferably 0.25
0.8 dl / g. When the intrinsic viscosity is less than 0.2 dl / g, the chemical resistance is poor. On the other hand, when the intrinsic viscosity is more than 1.0 dl / g, poor dispersion of the copolymer (C) may occur, which may be undesirable.

The intrinsic viscosity of the copolymer (C) used in the present invention can be controlled by changing the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent and the like. Also,
It can be controlled by changing the method of adding the monomer component, the addition time, the polymerization time, the polymerization temperature, and the like. Here, as the polymerization method, a known polymerization method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, or a polymerization method combining these can be used, and preferably emulsion polymerization.

The amount of the copolymer (C) used in the resin composition of the present invention is 10 to 45 parts by weight, preferably 15 to 4 parts by weight.
0 parts by weight, more preferably 20 to 40 parts by weight [however, (A) + (B) + (C) + (D) = 100 parts by weight]. If the amount is less than 10 parts by weight, the chemical resistance is poor. on the other hand,
If it exceeds 45 parts by weight, the impact resistance is poor.

Next, the copolymer (D) of the present invention comprises (b)
Component, component (c) and, if necessary, a monomer component composed of another vinyl monomer copolymerizable therewith, wherein the amount of component (c) in the monomer component is 10 It is obtained by copolymerizing a monomer component of up to 35% by weight.
(D) The monomer component used in the copolymer is the above (b)
It is the same as the component, the component (c), and other vinyl monomers copolymerizable therewith as required. (D) The compounding amount of the component (c) in the monomer component used in the copolymer is as follows:
10 to 35% by weight, preferably 15 to 29% by weight, more preferably 15 to 28% by weight [however, (b)
+ (C) + the other vinyl monomer = 100% by weight, the same applies hereinafter). When the amount of the component (c) is less than 10% by weight,
Poor chemical resistance. On the other hand, if it exceeds 35% by weight, the moldability is poor. The proportion of the component (b) in the monomer component used in the copolymer (D) is 65 to 90% by weight,
Preferably 71-85% by weight, more preferably 72-85% by weight.
85% by weight. The proportion of the other copolymerizable vinyl monomer in the monomer component used in the copolymer (D) is 15% by weight or less, preferably about 10% by weight or less.

The intrinsic viscosity [η] of the copolymer (D) of the present invention
Is preferably 0.2 to 1.0 dl / g, more preferably 0.2 to 0.8 dl / g, particularly preferably 0.25 dl / g.
0.8 dl / g. When the intrinsic viscosity is less than 0.2 dl / g, the chemical resistance is poor. On the other hand, when the intrinsic viscosity is more than 1.0 dl / g, poor dispersion of the copolymer (D) may occur, which is not preferable.

(D) adjustment of the intrinsic viscosity [η] of the copolymer,
The polymerization method and the like are the same as those of the above-mentioned (C) copolymer. The amount of the (D) copolymer used in the resin composition of the present invention is:
0 to 80 parts by weight, preferably 10 to 65 parts by weight, more preferably 15 to 50 parts by weight [provided that (A) +
(B) + (C) + (D) = 100 parts by weight]. If it exceeds 80 parts by weight, the chemical resistance is poor.

The composition of the present invention further comprises (E) talc and 100 parts by weight of the total of the components (A) to (D).
At least one member selected from the group consisting of a weathering agent and a lubricant may be incorporated in an amount of 0.01 to 20 parts by weight. Talc is used as a filler, and the average particle size of talc is preferably 0.5 to 20 μm, more preferably 1 to 15 μm,
Particularly preferably, it is 1.3 to 13 μm. If the average particle size is less than 0.5 μm, agglomeration occurs during kneading and the appearance of the molded product is poor, while if it exceeds 20 μm, the physical properties such as impact resistance and the appearance of the molded product are impaired.

As the talc, those obtained by treating the surface with a silane coupling agent can be used. The amount of the silane coupling agent is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on talc. As the silane coupling agent, those having a functional group such as an epoxy group, an amino group, a vinyl group, and a hydroxyl group can be used. Among them, those having an epoxy group and an amino group are preferable. The amount of these talcs is determined according to (A) of the present invention.
The amount is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the total amount of the components (D). When the blending amount of talc is less than 0.5 part by weight, the effect of imparting rigidity by blending talc is small.
If it exceeds 0 parts by weight, the impact resistance and the appearance of the molded product are impaired.

Examples of the weathering agent include a benzotriazole-based ultraviolet absorber, a hindered amine-based light stabilizer and the like. Among them, as the benzotriazole-based ultraviolet absorber, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5
-Di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
-(3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-octylphenyl) benzotriazole and the like. Preferably, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5
-Di-t-butyl-2-hydroxyphenyl) benzotriazole.

Examples of hindered amine light stabilizers include, for example, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, N-N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6, -pentamethyl-4-
Piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like are used. Preferably, bis-
(2,2,6,6-tetramethyl-4-piperidyl) sebacate. The amount of the weathering agent used in the resin composition is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the total of the components (A) to (D). is there. If it is less than 0.01 part by weight, the effect of addition is insufficient. On the other hand, if it exceeds 10 parts by weight, no further effect can be obtained.

Further, as the lubricant, a known lubricant can be used. Specifically, compounds having a long-chain alkyl group and a functional group, such as ethylene and propylene,
-Olefin (co) polymers, silicone-containing polymers such as dimethylpolysiloxane, copolymers of α-olefins with functional group-containing unsaturated compounds, ethylene-based copolymers, propylene-based copolymers, ethylene-propylene copolymers Polymer,
Polymers obtained by adding a functional group-containing unsaturated compound to a polymer such as a silicone-containing polymer, polyethylene, polypropylene, an ethylene-propylene copolymer, and the like, and a polymer obtained by a method of adding a carboxyl group or the like. No.

The functional group of the unsaturated compound having a functional group includes a carboxyl group or a metal salt thereof, a hydroxyl group, an oxazoline group, an acid anhydride group, an ester group, an amino group, an amide group, an epoxy group, and an isocyanate group. , A urethane group, a urea group and the like. Preferred functional groups are a carboxyl group or a divalent metal salt thereof, an ester group, and an amide group. As a salt of a carboxyl group,
Sodium, potassium, lithium, calcium, magnesium, aluminum, zinc, barium, cadmium,
Metal salts such as manganese, cobalt, lead, and tin are exemplified. As the functional group-containing unsaturated compound, all those described above are used. Preferred are compounds having a long-chain alkyl group and a functional group, and ethylene-based copolymers.

The amount of the lubricant used in the resin composition is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, per 100 parts by weight of the above components (A) to (D).
Parts by weight. If it is less than 0.01 part by weight, the effect of addition is insufficient. On the other hand, if it exceeds 10 parts by weight, surging occurs during melt-kneading, and kneading cannot be performed.

The resin composition of the present invention contains a known coupling agent, antibacterial agent, fungicide, flame retardant, flame retardant auxiliary,
Additives such as antioxidants such as hindered phenol, phosphorus and sulfur, plasticizers, surfactants, coloring agents (pigments, dyes, etc.), ultraviolet absorbers, metal powders, antistatic agents, processing aids, etc. Can be blended. These additives are
It may be compounded at the time of kneading, or may be added externally. Further, a master batch in which these various additives are blended at a high concentration can be added.

The resin composition of the present invention can be blended with another (co) polymer according to the purpose. Other (co) polymers include, for example, ethylene, propylene,
Examples include α-olefin homopolymers such as butene-1, 3-methylbutene-1, 3-methylpentene-1, and 4-methylpentene-1, and copolymers thereof.
Representative examples include high-density, medium-density, low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, polyethylene such as ethylene-ethyl acrylate copolymer, and propylene alone. Examples thereof include polymers, polypropylenes such as propylene-ethylene-diene compound copolymers, polybutene-1, and poly-4-methylpentene-1. Of these, crystalline polyethylene and crystalline polypropylene are preferred.

As the crystalline polyethylene, commercially available high-density polyethylene, medium-density polyethylene, low-density polyethylene and linear low-density polyethylene having crystallinity can be used. Although the molecular weight of polyethylene is not particularly limited, the number average molecular weight is 1,000 to 20,
000 is preferred. Further, as the crystalline polypropylene, for example, a so-called propylene block copolymer composed of an isotactic propylene homopolymer having crystallinity and a copolymer part of an ethylene-propylene copolymer having a small ethylene unit content is used. A block copolymer of substantially crystalline propylene and ethylene, or each homopolymerized or copolymerized portion of the block copolymer, which is commercially available as a coalescence, further contains an α-olefin such as butene-1. Consisting of copolymerized ones,
Preferable examples include substantially crystalline propylene-ethylene-α-olefin copolymers.

The other (co) polymer includes a rubber-modified styrene resin other than the components of the resin composition of the present invention. Examples of the rubber-modified styrene resin include high impact polystyrene, ABS resin, ACS resin, and the like. These resins may be functional group-modified styrene resins modified with a small amount of functional groups. Among these, an ABS resin is preferable. Further, the other (co) polymers include polyvinyl chloride, polyphenylene ether, polycarbonate,
Examples include polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, and chlorinated polyethylene. These other (co) polymers can be used alone or in combination of two or more.

The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. A preferred production method is a method using an extruder and a Banbury mixer. When kneading each component, each component may be kneaded at once,
You may add and knead it several times. For kneading, kneading may be carried out in an extruder in a multi-stage addition manner, or kneading may be carried out using a Banbury mixer, a kneader, or the like, and then, pelletizing may be performed using an extruder.

The thermoplastic resin composition of the present invention may be formed by extrusion molding, injection molding, sheet extrusion molding, vacuum molding,
It can be formed by a molding method such as press molding, blow molding, foam molding, injection press, gas assist molding, calendering, inflation molding, or lamination molding. Among them, two-layer molding by coextrusion with a foamed ABS resin is preferable. Here, the foamed ABS resin is, for example, a resin obtained by blending a foaming agent with the ABS resin, and is used for foam molding. Commercially available ABS resins can be used. Examples of the foaming agent include azodicarbonamide (ADCA).

The molded article of the weather-resistant and chemical-resistant thermoplastic resin composition of the present invention obtained by the above-mentioned molding method can be used in the fields of OA / home appliances, vehicle / marine,
Housing-related fields such as furniture and building materials, sanitary fields,
It can be used in a wide range of fields such as toys and sports goods, and other miscellaneous goods. Above all, a two-layer molded product of the foamed ABS resin using the resin composition of the present invention as a surface material is excellent in weather resistance, and has excellent chemical resistance to shampoos, bath fragrances and the like, and hair dyes. Since it has excellent stain resistance, it can be suitably used as a window frame of a unit bath.

[0054]

EXAMPLES The present invention will now be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. In the examples,
Various measurement items followed the following.

Graft ratio A certain amount (x) of the rubber-reinforced thermoplastic resin is put into acetone, shaken with a shaker for 2 hours to dissolve the free copolymer, and then centrifuged. 23,000 solution
After centrifuging at 30 rpm for 30 minutes to obtain an insoluble content, it was dried at 120 ° C. for 1 hour using a vacuum dryer to obtain an insoluble content (y) and a free polymer. Calculated. Graft ratio (%) = [(yx × Rubber component ratio in rubber-reinforced thermoplastic resin) / (xx × Rubber component ratio in rubber-reinforced thermoplastic resin)] × 100

The limiting viscosity copolymer was completely dissolved in methyl ethyl ketone, and five points having different concentrations were prepared.
The intrinsic viscosity [η] was determined from the result of measuring the reduced viscosity η _SP / c at each concentration at ° C. Izod impact strength Measured according to ASTM D256 (1/4 cross section)
1/2 inch, notched). The unit is kg · cm / c
m. Fluidity (Melt Flow Rate) Measured according to ASTM D1238. Measurement temperature is 2
At 20 ° C., the load is 10 kg, and the unit is g / 10 minutes.

Exposure to a sunshine weather meter [WEL-6XS-DC, manufactured by Suga Test Instruments Co., Ltd.] using a weather-resistant carbon arc as a light source for 1,000 hours, and measuring Izod impact strength,
The retention (%) was calculated. Test conditions; Black panel temperature 63 ± 3 ° C Humidity in the chamber 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60 hours Izod impact strength ASTM D256

A molded article made of chemically resistant black blended pellets (blended resin: 100 parts, carbon black: 0.5 parts, calcium stearate: 0.3 parts) was immersed in JIS No. 6 kerosene (kerosene temperature: 80 ° C.) for one hour. After leaving, wipe off the surface and dry,
Evaluation was made by the following visual judgment. ；: No change and no decrease in gloss. C: Deterioration such as whitening and gloss reduction is observed.

Stain- resistant white blended pellets (blended resin 100 parts, titanium oxide 3
Parts, 0.3 parts of calcium stearate) were immersed in Vigen Hair Color 7G (manufactured by Hoyu Co., Ltd.), left for 24 hours, wiped off the surface, and dried.
Evaluation was made by the following visual judgment. ；: No discoloration Δ: Discoloration is slightly observed. X: Discoloration is clearly seen.

Reference Example 1 (Preparation of AES resin) AES-1: Ethylene-propylene copolymer rubber content was 30%,
Styrene-acrylonitrile component copolymer content of 70
%, An AES resin having a graft ratio of 50% and an acrylonitrile content of 35% in the above copolymer was used. AES-2: an ethylene-propylene-non-conjugated diene copolymer rubber content of 22%, a styrene-acrylonitrile component copolymer content of 78%, a graft ratio of 61%, and an acrylonitrile content in the above copolymer Used 30% AES resin.

Reference Example 2 (Preparation of ASA resin) ASA-1; butyl acrylate polymer rubber content: 31%
Styrene-acrylonitrile component copolymer content of 6
An ASA resin having 9%, a graft ratio of 50%, and an acrylonitrile content of 35% in the above copolymer was used.

Reference Example 3 (Preparation of AS resin) ASH-1: a copolymer of styrene and acrylonitrile, having an acrylonitrile content of 40% and an [η] of 0.1.
43 dl / g AS resin was used. ASL-1: a copolymer of styrene and acrylonitrile, having an acrylonitrile content of 31% and [η] of 0.1.
57 dl / g AS resin was used.

Reference Example 4 [Preparation of Component (E)] The following components were used as component (E). Talc: bulk density 0.9 to 1.3 ml / g Weathering agent: 2- (2-hydroxy-5-methylphenyl) benzotriazole (abbreviation: HMPBT) bis (2,2 ', 6,6'-tetramethyl- 4-piperidyl) sebacate (abbreviation: TMPS) Lubricant: magnesium stearate

Examples 1 to 4 and Comparative Examples 1 to 3 The above-mentioned components were mixed according to the formulation shown in Table 1, melt-kneaded using a twin-screw extruder, and extruded to obtain a pellet-shaped composition. . The obtained pellets are sufficiently dried, and a commercially available ABS resin [ABS150 manufactured by Techno Polymer Co., Ltd.]
A mixture of 0.5 part of azodicarbonamide (ADCA) as a foaming agent with respect to 100 parts was foamed and co-extruded at 180 ° C. using a co-extruder to obtain a sheet-like molded product. The weight ratio of the resin composition of the present invention to the ABS resin at a thickness of 5 mm of the sheet-like molded product was 1/9. Table 1 shows the evaluation results.

[0065]

[Table 1]

Table 1 shows that the thermoplastic resin composition of the present invention is excellent in weather resistance, chemical resistance and stain resistance. On the other hand, in Comparative Example 1, the amounts of the components (A) and (B) were small, so that the weather resistance and the chemical resistance were inferior. In Comparative Example 2, the amount of the component (A) was large. Comparative Example 3 is inferior in stain resistance because the amount of the component (B) used is large.

[0067]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in weather resistance, chemical resistance, and contamination resistance. -It can be used in a wide range of fields, such as the marine field, furniture and construction materials, and other housing-related fields, sanitary fields, toys and sports goods, and other miscellaneous goods. Above all, the two-layer molded article with the foamed ABS resin is excellent in weather resistance, and is excellent in chemical resistance to shampoos, bath fragrances and the like, and stain resistance to hair dyeing chemicals and the like. It can be suitably used as a window frame.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 5/3445 5/3445 C08L 25/02 C08L 25/02 33/18 33 / 18 51/06 51/06 101/00 101/00 (72) Inventor Hiroki Kashiwagi 1-18-1 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F term (reference) 4F071 AA02 AA22 AA34 AA77 AB30 AC12 AF02 AF55 AF57 AH03 AH07 AH12 AH19 BC07 4J002 BB035 BB045 BB125 BB165 BB205 BC06Y BC06Z BG10Y BG10Z BN06W BN12X BN13W CP035 DJ046 EU117 FD016 FD087 FD205 GC00 GL00 GN00 GQ00 A04A05 A04A04 A04A05 A04A04A04A04A04A04A04A04A04A04A04A04A04A04A04A05A

Claims (3)

[Claims] 1. An aromatic vinyl compound (b) and vinyl cyanide in the presence of (A) a rubber (a) comprising a hydrogenated product of an ethylene-α-olefin copolymer rubber and / or a diene polymer. 5 to 40 parts by weight of a rubber-reinforced thermoplastic resin obtained by graft-polymerizing a monomer component composed of the compound (c) and another vinyl monomer copolymerizable therewith if necessary; In the presence of the rubber (d), a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c) and, if necessary, another vinyl monomer copolymerizable therewith is grafted. 5 to 40 parts by weight of a rubber-reinforced thermoplastic resin obtained by polymerization, (C) an aromatic vinyl compound (b), a vinyl cyanide compound (c) and, if necessary, another vinyl monomer copolymerizable therewith. It is a monomer component composed of the body What copolymer 10 the amount of the component (c) in the monomer component is by copolymerizing a monomer component is less than 60 wt% greater than 35 wt%
And (D) a monomer component comprising an aromatic vinyl compound (b), a vinyl cyanide compound (c), and another vinyl monomer copolymerizable therewith, if necessary. A copolymer obtained by copolymerizing a monomer component in which the amount of the component (c) in the monomer component is 10 to 35% by weight [0 to 80 parts by weight [provided that (A) + (B ) + (C) + (D) = 100 parts by weight] as a main component. 2. The method according to claim 1, wherein at least one component selected from the group consisting of talc, a weathering agent and a lubricant is further added in an amount of 0.01 to 100 parts by weight of the total amount of the components (A) to (D).
A weather-resistant and chemical-resistant thermoplastic resin composition blended in an amount of up to 20 parts by weight. 3. A multilayer molded article comprising the weather-resistant and chemical-resistant thermoplastic resin composition according to claim 1 or 2 as a surface material.