JPH03265648A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a polymer alloy improved in weatherability, impact strength, heat resistance, etc., by compounding a specific rubber-reinforced resin, an arom. polyester resin, and a copolymer of functional monomers. CONSTITUTION:95-40 pts.wt. at least one monomer selected from the group consisting of an arom. vinyl compd., a vinyl cyanide compd., a (meth)acrylic ester compd., and other copolymerizable monomers (provided that the sum of the hydrogenated diene polymer and the monomer is 100 pts.wt.) is graft copolymerized in the presence of 5-60 pts.wt. hydrogenated diene polymer obtd. by hydrogenating a diene polymer comprising 0-60wt.% arom. vinyl compd. and 100-40wt.% conjugated diene to give a rubber-reinforced resin. 10-90 pts.wt. said resin is compounded with 90-10 pts.wt. arom. polyester resin and 0.1-30 pts.wt. (based on 100 pts.wt. in total of the reinforced resin and the polyester resin) copolymer obtd. by copolymerizing a monomer component contg. at least one functional monomer selected from the group consisting of an epoxidized monomer, a carboxylated monomer, an amidated monomer, a hydroxylated monomer, and a dicarboxylic anhydride monomer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a rubber-reinforced resin obtained by graft copolymerizing a specific monomer component and an aromatic polyester resin or By blending polyamide resin and a copolymer (compatibilizer) made by (co)polymerizing a functional group-containing monomer as the main ingredients, the product has impact resistance, chemical resistance, and significantly improved weather resistance and molded appearance. The present invention relates to a thermoplastic resin composition with excellent heat resistance.

[Conventional technology]

In recent years, rubber-reinforced resins made by graft copolymerizing monomers such as aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid ester compounds to conjugated diene-based rubbery polymers such as polybutadiene, as well as polycarbonate and polyphenylene, have been developed. Research is being conducted on polymer alloys containing general-purpose engineering plastics such as ether and polyamide.

This polymer alloy has many features compared to those used alone as graft polymers or engineered plastics (engineering plastics) alone.In particular, impact strength can be greatly improved by reinforcing it with rubbery polymers, so it can be used in various applications. Overlaid with rubber reinforced polymer alloy. The rubber used here is a conjugated diene-based rubbery polymer represented by polybutadiene, which has low resistance to ultraviolet rays, oxygen, ozone, etc., and may have poor weather resistance such as reduced strength and surface gloss. Are known.

In addition, some of the engineering plastics that are used for alloys have a high glass transition temperature, and the temperature during blending or molding is high, resulting in crosslinking of the unsaturated bonds in the conjugated diene part, resulting in a decrease in impact strength and thermal stability. There is also a problem.

In order to solve these problems, we developed a rubbery polymer containing ethylene-propylene rubber (E
PM], ethylene-propylene-diene rubber (EPDM
], or acrylic rubber using acrylic acid ester. However,
When EPM or EPDM is used, thermal stability and weather resistance can be improved, but compared to diene-based rubbery polymers, the colorability with colorants such as pigments and dyes is poor, and the molded appearance of the weld part is poor. There are problems such as:

This is because the refractive index of EPM and EPDM is lower than that of diene-based rubbery polymers, so the difference in refractive index with the graft resins usually used, such as aromatic vinyl compounds and vinyl cyanide compounds, becomes large, resulting in scattered light. This is because the crosslink density is low due to the increased strength and because there are fewer or very few unsaturated bonds compared to conjugated diene-based rubbery polymers, which causes significant distortion of the rubber particles during injection molding and extrusion molding. be. A rubbery polymer using a monomer with a refractive index close to that of EPDM also has a small degree of improvement for the same reason.

On the other hand, when acrylic rubber is used as a rubbery polymer, the glass transition temperature of this rubber is higher than that of conjugated diene rubber, EPM, or EPDM. It is known that the impact strength of

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned problems of the prior art, and improves weather resistance, molded appearance, impact resistance including impact strength in a low temperature range, chemical resistance, and heat resistance including thermal stability. The purpose of the present invention is to provide a significantly improved polymer alloy consisting of a rubber-reinforced resin and a general-purpose engineering plastic.

[Means to solve the problem]

The present invention is directed to (a) a hydrogenated diene polymer (1) obtained by hydrogenating a diene polymer that is a polymer of 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene;
60% by weight (hereinafter referred to as "hydrogenated diene polymer (1)")
In the presence of, an aromatic vinyl compound (a), a vinyl cyanide compound (b), a (meth)acrylic acid ester compound (
At least one monomer component (■) selected from the group of c) and other monomers copolymerizable with it (d) (hereinafter referred to as "
A rubber-reinforced resin (hereinafter referred to as "(a) rubber-reinforced resin" or " (a) component") 10 to 90% by weight, (h
) Aromatic polyester resin (hereinafter sometimes referred to as "(h) Ffc content") 10 to 90% by weight [However, (a) +
(h) = 100% by weight], and (c) epoxy group-containing monomer (e), carboxyl group-containing monomer (f), amide group-containing monomer (chain, hydroxyl group-containing monomer (h
], and at least one functional group-containing monomer component selected from the group of dicarboxylic anhydride group-containing monomer (i)
III) (hereinafter referred to as "functional group-containing monomer component (III)"), a copolymer (IV) obtained by copolymerizing a monomer containing the above-mentioned (a) component and (h) component (total amount of 100 weight) The present invention provides a thermoplastic resin composition (hereinafter sometimes referred to as "first group acid compound") in which the weight deficit is 0.1 to 30 parts by weight per part.

The present invention also provides (a)' hydrogenated diene polymer (1) 5
Monomer component (I1) 94-20 in the presence of ~60% by weight
Weight% and functional group-containing monomer component (D1) from 1 to 20
Weight% [where (1) + (If) + (II1) =
100% by weight] is graft copolymerized with rubber reinforced resin (
(hereinafter referred to as "(a)' rubber reinforced resin" or "(a)'component")) 10 to 90% by weight, (h) aromatic polyester resin 90 to 10% by weight [however, (a)'+(h)=
100% by weight], and (c) copolymer (IV) (
A thermoplastic resin composition (hereinafter sometimes referred to as "second acid group") comprising 0 to 30 parts by weight of component (b)' and component (h) based on 100 parts by weight of the total amount. It is.

Furthermore, the present invention provides (a) 5 to 95% by weight of rubber reinforced resin.
, (h)' polyamide resin (hereinafter sometimes referred to as "(h)'component") 95 to 5% by weight [However, (a) + (h)
)′=100% by weight], and (c) copolymer (IV)
A thermoplastic resin composition containing 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of component (a) and component (h)' (hereinafter sometimes referred to as "third group acid compound") It provides:

Furthermore, the present invention provides (a)' rubber reinforced resin 5-95
% by weight, (h)' polyamide resin 95 to 5% by weight (however, (a)' + (h)' = 100% by weight), and (c) copolymer (TV) with (i)' component and ( h) A thermoplastic resin composition containing 0 to 30 parts by weight based on 100 parts by weight of the total amount of components (hereinafter referred to as "4th group acid compound",
The composite acid compound to the fourth component compound may be collectively referred to simply as a "thermoplastic resin composition."

The thermoplastic resin composition of the present invention essentially consists of (a) a rubber-reinforced resin, (h) an aromatic polyester resin and/or (h) a 'boriatonic resin, and (c) a copolymer (
IV) is the main component.

Hereinafter, the thermoplastic resin composition of the present invention will be explained separately into the first to fourth compositions.

First, to explain the first set paraboloid of the present invention, this first set paraboloid mainly contains (a) rubber reinforced resin, (h) aromatic polyester resin, and (c) copolymer (IV). do.

The hydrogenated polymer (1) constituting (a) Ili of the first group acid is 0 to 60% by weight of an aromatic vinyl compound.
It is obtained by hydrogenating a diene-based polymer which is a polymer of 100 to 40% by weight of conjugated diene and conjugated diene. The diene polymer before hydrogenation may be a conjugated diene homopolymer, a Pronk copolymer or random copolymer consisting of an aromatic vinyl compound and a conjugated diene, or a mixture thereof.

Here, as the aromatic vinyl compound used for the hydrogenated diene polymer (1), styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monochlorostyrene, Bromstyrene, dibromstyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1. l-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene,
Examples include N,N-diethyl-p-aminoethylstyrene and vinylpyridine, with styrene and α-methylstyrene being particularly preferred.

Further, as the conjugated diene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1.
3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-
Examples include octadiene, 3-butyl-1,3-octadiene, chlorobrene, etc., but in order to obtain a hydrogenated diene polymer (1) that is industrially usable and has excellent physical properties,
1,3-7'tadiene, isoprene, and 1,3-pentadiene are preferred, and 1,3-butadiene is more preferred.

The content of aromatic vinyl compounds in the diene polymer is 6
It is 0% by weight or less, preferably 40% by weight or less, and 40 to 5% by weight when the aromatic vinyl compound is an essential component. If it exceeds 60% by weight, the hydrogenated diene polymer will take on resinous properties and its impact resistance will decrease.

The diene polymer has a 1.2-
The content of vinyl binders such as 13,4- is preferably 10% by weight or more, more preferably 20 to 80% by weight, particularly preferably 30 to 60% by weight. This ratio is 1
If it is less than 0% by weight, the obtained hydrogenated diene polymer will take on resinous properties and the impact resistance of the finally obtained thermoplastic resin composition will decrease, which is not preferable.

The diene polymer used in the present invention before hydrogenation is a block copolymer or a random copolymer, such as A; vinyl aromatic polymer block B; conjugated diene polymer block A/B, vinyl aromatic Random copolymer block C of a group compound/conjugated diene: A tapered block consisting of a copolymer of a conjugated diene and a vinyl aromatic compound, and in which the vinyl aromatic compound gradually increases, and has the following structure. can be mentioned.

■A-B ■A-B-A ■A-B-C ■A B+ Bt (Here, the vinyl bond amount of B is preferably 20% or more, and the vinyl bond amount of Bz is less than 20%). B ■A/B ■A-A/B ■A-A/B-C ■A-A/B-A ■B, -B, -Bt (Here, B, , B are the same as above) @ C-B @C-B-C ■C-A/B-C @)C-A-B The ratio of vinyl aromatic compound/conjugated diene in these block copolymers or random copolymers is the weight ratio and preferably 5-60/95-4o, more preferably 1
0-50/90-5o.

Here, if the content of the vinyl aromatic compound exceeds 60% by weight, the composition becomes resinous and the impact resistance of the resulting composition decreases.

Further, the amount of bonded metal in the total monomers of the vinyl aromatic compound in block A and tapered block C is preferably 3 to 25
% by weight, more preferably 5 to 20% by weight; if it is less than 3% by weight, the coloring properties of the resulting composition will decrease;
If it exceeds 5% by weight, the composition becomes resinous and the impact resistance of the resulting composition decreases.

Furthermore, the amount of vinyl bond in the conjugated diene moiety in the block copolymer or random copolymer is preferably 15
-65% by weight, more preferably 20-60% by weight, particularly preferably 25-50% by weight; if it is less than 15% by weight, the structure after hydrogenation will be close to that of polyethylene, and when it is made into a resin composite acid product, impact The strength will decrease, while 6
If it exceeds 5% by weight, it loses its rubbery properties after hydrogenation, resulting in a decrease in impact strength, which is not preferable.

In addition, as the block copolymer or random copolymer, the low-temperature properties of the resulting composition are preferably used, preferably the ones listed in (1) to (2) above, more preferably those listed in (1) to (2), particularly preferably those listed in (1) to (3). A product with excellent fatigue properties can be obtained.

In addition, other preferable examples include the above-mentioned ■, [phase] and ■~■
Examples include those whose ends are coupled with a coupling agent.

Furthermore, in the hydrogenated diene polymer (1) used in the present invention, at least 50%, preferably 65% or more, more preferably 80% or more of the double bonds in the conjugated diene moiety are hydrogenated and saturated. If it is less than 50%, the heat resistance, weather resistance, and ozone resistance will be poor.

Furthermore, the hydrogenated diene polymer (1) of the present invention preferably has a number average molecular weight of 10.000 to 1.000,000.
, preferably from 30,000 to 700,000, more preferably from 50,000 to 500,000; if it is less than 10,000, the impact strength of the resulting composition will be low;
If it exceeds 00.000, colorability, fluidity, and processability will deteriorate, leading to deterioration in surface appearance.

Furthermore, the ratio of weight average molecular weight to number average molecular weight (Mw/
Mn) is 10 or less, preferably 7 or less, more preferably 5 or less; if it exceeds 10, coloring properties, weld appearance, etc. will deteriorate, and the effect of using the hydrogenated diene copolymer (1) will be lost. .

The hydrogenated diene polymer (1) used in the present invention is prepared by placing blocks A1, B1, A/B, or tapered blocks C in an organic solvent with living anions using an organic alkali metal compound as an initiator. After obtaining a copolymer or random copolymer, the block copolymer and/or random copolymer is further hydrogenated.

Examples of the organic solvent include pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane,
Hydrocarbon solvents such as benzene and xylene are used.

As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable.

As this organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyllithium, n-propyllithium, isopropyllithium, and n-propyllithium.
-butyl lithium, 5ec-butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl lithium, isoprenyl dilithium, etc., and the amount of 0.02 to 0.2 N parts per 100 parts by weight of monomers is exemplified. used in quantity.

At this time, Lewis bases such as ethers, azines, etc., specifically diethyl ether, tetrahydrofuran, propyl ether, butyl ether,
Higher ethers, ether derivatives of polyethylene glycol such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine; It is used together with the organic solvent.

Furthermore, the polymerization reaction is usually carried out at -30°C to 150°C.

Further, the polymerization may be carried out at a controlled constant temperature or may be carried out at an elevated temperature without heat removal.

Any method may be used to form a block copolymer, but generally, block A or block B is first polymerized in the organic solvent using a polymerization initiator such as the alkali metal compound, and then block B Alternatively, block A is polymerized.

There is no limitation as to whether block A or block B is polymerized first. Further, the boundary between block A and block B does not necessarily need to be clearly distinguished. Furthermore, in order to obtain an A-B-C block copolymer or an A-B-A block copolymer, block A is polymerized by adding an aromatic vinyl compound using an organolithium initiator in an organic solvent. Then, a conjugated diene or a conjugated diene and an aromatic vinyl compound are added to form a block B, and a conjugated diene and an aromatic vinyl compound or an aromatic vinyl compound are further added to polymerize a tapered block C or a block A. Bye.

In this case, a method may be employed in which the tapered block C1 or block A is first polymerized, then block B, and then block A is polymerized.

Moreover, in order to obtain a random copolymer, an aromatic vinyl compound and a conjugated diene compound may be simultaneously polymerized using an organolithium initiator in an organic solvent.

The block copolymer or random copolymer thus obtained may be a copolymer in which the polymer molecular chain is extended or branched by adding a coupling agent.

Examples of coupling agents in this case include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1.2-dibromoethane, 1.4 -Chloromethylbenzene, bis(trichlorosilyl)ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2.4
-benzene triisocyanate and the like.

The amount of the vinyl aromatic compound in the block copolymer or random copolymer is adjusted by the amount of monomer supplied during polymerization at each stage, and the amount of the vinyl aromatic compound in the conjugated diene is controlled by the amount of the vinyl aromatic compound in the block copolymer or random copolymer. Adjustments can be made by varying the ingredients of the agent.

Further, the number average molecular weight and melt flow rate are controlled by the amount of a polymerization initiator, such as n-butyllithium.

The hydrogenated diene polymer (1) of the present invention can be obtained by dissolving the block copolymer or random copolymer obtained in this manner in an inert solvent and dissolving the block copolymer or random copolymer at 20 to 150°C and 11 to 10°C.
It is carried out in the presence of a hydrogenation catalyst under pressurized hydrogen at 0 kg/ci.

Inert solvents used in hydrogenation include hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, or polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, tetrahydrofuran.

Hydrogenation catalysts include dicyclopentadienyl titanium halide, nickel organic carboxylate, nickel organic carboxylate and organic metal compounds of Groups 1 to 2 of the periodic table, carbon, silica, and diatomaceous earth. Nickel, platinum, palladium, ruthenium supported by
Rhenium, rhodium metal catalysts, cobalt, nickel, rhodium, ruthenium complexes, lithium aluminum hydride, p-toluenesulfonyl hydrazide,
Furthermore, Zr-Ti-Fe-V-Cr alloy, Zr-Ti
Examples include hydrogen storage alloys such as -Nb-Fe-V-C1 alloy and LaNi5 alloy.

The hydrogenation rate of the double bond in the conjugated diene moiety of the hydrogenated diene polymer (1) of the present invention can be determined by changing the hydrogenation catalyst, the amount of hydrogenation compound added, or the hydrogen pressure and reaction time during the hydrogenation reaction. It is adjusted by

Catalyst residues are removed from the hydrogenated polymer solution,
By adding a phenol-based or amine-based anti-aging agent, the hydrogenated diene-based polymer (1) can be easily isolated from the polymer solution. Isolation of hydrogenated diene polymer (1) is as follows:
For example, a method of adding acetone or alcohol to a polymer solution to precipitate it, a method of adding a polymer solution to boiling water with stirring,
This can be done by adding a solvent and removing the solvent by distillation.

The aromatic vinyl compound (a) in the monomer component (II) to be graft copolymerized to this hydrogenated diene polymer (1) is the aromatic vinyl compound (a) used in the production of the hydrogenated diene polymer (1). Examples include those similar to the group vinyl compounds.

Furthermore, the vinyl cyanide compound (
Examples of c) include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound (b).

Furthermore, as the (meth)acrylic acid ester compound (c) in the monomer component (If), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl Acrylic acid alkyl esters such as acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate , cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, and other methacrylic acid alkyl esters, with methyl methacrylate being particularly preferred.

Furthermore, other copolymerizable monomers (d) in the monomer component (I1) include acrylic acid, methacrylic acid, maleimide, N-methylmaleimide, N-butylmaleimide, N-( p-methylphenyl)maleimide,
Examples include imide compounds of α,β-unsaturated dicarboxylic acids such as N-phenylmaleimide and N-cyclohexylmaleimide. One or more of these copolymerizable monomers (a) may be used as long as they do not interfere with the rubber-reinforced resin (a) that is the object of the present invention.

By using the aromatic vinyl compound (a) among the above monomer components (If), a composition with improved moldability can be obtained.

In addition, when (b) vinyl cyanide compound is used, a composition with even better impact resistance, chemical resistance, and paintability can be obtained, and (meth)acrylic acid alkyl ester compound (c
), a composition with even better weather resistance can be obtained,
Moreover, when a large amount of the component (c) is used, a composition with excellent transparency can be obtained. Furthermore, it is preferable to copolymerize with another copolymerizable monomer (d), since the compatibility with general-purpose engineering plastics such as polyester resins and polyamide resins used in the present invention can be improved.

Preferred examples of the monomer component (I1) include styrene and vinyl cyanide compounds (as the aromatic vinyl compound (a)).
(c) is acrylonitrile, and (meth)acrylic acid alkyl ester (c) is methyl methacrylate.

Further, specific examples of combinations of monomer components (II) are illustrated below.

■Styrene-acrylonitrile ■Styrene-methyl methacrylate ■Styrene-acrylonitrile-methyl methacrylate Heat resistance can be imparted by replacing part or all of the styrene with α-methylstyrene. Furthermore, flame retardancy can be imparted by replacing part or all of styrene with halogenated styrene.

Furthermore, in the above-mentioned combination, when methyl methacrylate is used in combination, the transparency of the rubber-reinforced resin obtained (a) is improved, and it comes to have much better coloring properties.

The proportion of the above monomer component (If) is 0 to 100% by weight, preferably 2 to 98% by weight of the aromatic vinyl compound (a).
, vinyl cyanide compound (b) 0 to 70% by weight, preferably 2 to 65% by weight, (meth)acrylic acid ester compound (c) 0 to 100% by weight, preferably 2 to 98% by weight, copolymerized with these. Possible other monomers (d) 0-30
% by weight, preferably 0 to 20% by weight [however, (a)+
(b)+(c)+(d)=100% by weight).

(a) The content of the hydrogenated diene polymer (1) in producing the rubber reinforced resin in the present invention can be arbitrarily selected depending on the purpose, but the impact resistance of the resulting composition, moldability, etc. In order to satisfy the properties, the range is 5 to 60% by weight, preferably 10 to 55% by weight. If the hydrogenated diene polymer (1) is less than 5% by weight, a composition with insufficient impact resistance will be obtained, while if it exceeds 60% by weight, moldability will deteriorate, which is undesirable. Therefore, the content of the graft monomer component that becomes the matrix resin is the remaining content.

The graft ratio of (a) the rubber reinforced resin is preferably 20 to 90%, more preferably 25 to 85%, particularly preferably 30 to 80%. Here, the graft ratio refers to the ratio of the copolymer component directly graft-bonded to the rubber with respect to the amount of rubber in the graft polymer. This grafting rate can be controlled by the amount of polymerization initiator, polymerization temperature, etc.
%, as exemplified in JP-A No. 51-9183, impact strength is sufficient even without substantial grafting, but chemical resistance is markedly reduced, and coloring and welding The appearance of the molding, such as the external appearance, also deteriorates.

Furthermore, the intrinsic viscosity (η) of the methyl ethyl ketone soluble portion of the resin portion of the rubber reinforced resin (a) of the present invention (measured at 30°C) is 0.2 dl/g or more, preferably 0.22 to 1.
5d1/g, more preferably 0.24-1.2dl/
It is g.

Furthermore, (a) the particle size of the rubber reinforced resin is usually 0.0
5 to 1.0 am, preferably 0.05 to 0.75 μm,
More preferably, it is 0.07 to 0.60 μm, particularly preferably 0.08 to 0.5 μm. In order to improve the impact strength of ordinary general-purpose engineering plastics, the particle size is mostly 0.5 μm or more, but in the hydrogenated diene copolymer (1) used in the present invention,
Impact strength can be improved within a range where the particle size is small.

This particle size can be adjusted by adjusting the stirring speed during polymerization.

(a) Rubber reinforced resin used in the present invention is emulsion polymerized,
Manufactured by solution polymerization, suspension polymerization, etc.

On the other hand, the aromatic polyester resin used in the present invention includes, for example, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, polypentamethylene terephthalate, polyhexamethylene terephthalate, and polyethylene terephthalate is particularly preferred. preferable.

On the other hand, the copolymer (IV) (c) used in the present invention serves to make the rubber-reinforced resin (i) compatible with the aromatic polyester (i) which is a general-purpose engineering plastic.

The copolymer (IV) of (c) is composed of an epoxy group-containing monomer (e), a carboxyl group-containing monomer (f), an amino group-containing monomer (g), and a hydroxyl group-containing monomer ( h) and at least one functional group-containing monomer component (II1) selected from the group of dicarboxylic anhydride group-containing monomers (i).
) and/or a rubbery modified vinyl polymer.

These functional group-containing monomer components (II[) are, for (h) aromatic polyester resin, an epoxy group-containing monomer (e), a carboxyl group-containing monomer (f], and a dicarboxylic acid The anhydride group-containing monomer (i) is also a carboxyl group-containing monomer (f), the amino group-containing monomer (
g], the hydroxyl group-containing monomer and the dicarboxylic anhydride group-containing monomer (i) each serve as copolymerizable monomer components that improve compatibility.

Here, the epoxy group-containing monomer (e) is a compound having in its molecule an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound, and an epoxy group. Examples of the epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3.4- Epoxybutene, 3,4-epoxy-3-methyl-■-butene, 3,4-epoxy-1-pentene,
Examples thereof include 3.4-epoxy-3-methylpentene, 5.6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer (f) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred.

These compounds can be used alone or in combination of two or more.

Furthermore, as the amino group-containing monomer (g), the following general formula (wherein R1 is a hydrogen atom, a methyl group or an ethyl group,
z is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and 2 carbon atoms.
Vinyl type having at least one type of amino group or substituted amino group represented by ~12 alkanoyl groups, phenyl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, or derivatives thereof) It is a monomer.

Specific examples of the amino group-containing unsaturated compound include allylamine, aminoethyl methacrylate, aminopropyl methacrylate, and aminostyrene, which are particularly preferably used because they can be obtained economically on an industrial scale. These compounds can be used alone or in combination of two or more.

Furthermore, the hydroxyl group-containing monomer (h) is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples include alcohols with double bonds,
Alcohols having a triple bond, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, esters of the unsaturated carboxylic acids with unsubstituted trihydric alcohols,
Examples include esters with unsubstituted tetrahydric alcohols and esters with unsubstituted pentahydric or higher alcohols.

As a specific example of these hydroxyl group-containing monomers (h), it is preferable to use 2-hydroxyethyl methacrylate. These hydroxyl group-containing unsaturated compounds can be used alone or in combination of two or more.

Furthermore, examples of the dicarboxylic anhydride group-containing monomer (i) include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl anphosuccinic acid, and tetrahydrophthalic anhydride, preferably. Maleic anhydride.

These compounds can be used alone or in combination of two or more.

The base materials for producing the copolymer (IV) of (c) include: ■ a rubbery polymer, ■ a graft layer of a graft copolymer,
Alternatively, (2) non-grafted vinyl polymers may be mentioned, but (3) is preferred among these.

Specifically, the component (c) obtained in this way is as follows:
Conventional acrylonitrile-butadiene-styrene resin (
ABS resin], acrylonitrile-ethylene propylene-styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin, acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), rubber modified polystyrene (high impact polystyrene; HI PS), acrylonitrile-styrene resin (AS resin), methyl methacrylate-styrene resin (MS resin), methyl methacrylate-styrene-acrylonitrile resin, and other copolymer resins. During production, a part of the monomer in the copolymer resin or in the vinyl polymer to be mixed with the copolymer resin is replaced with the functional group-containing monomer component (II1) and polymerized. It is obtained by

At this time, the functional group-containing monomer component (I[1
) is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight.

In addition, component (c) consists of monomers (a) to (d) of component (i).
) and at least one monomer of component (e)
) to (i) may be copolymerized with at least one monomer.

Component (c) used in the present invention is produced by emulsion polymerization, solution polymerization, suspension polymerization, etc.

Further, at this time, as the polymerization initiator, molecular weight regulator, emulsifier, dispersant, solvent, etc. used in the polymerization, those normally used in these polymerization methods can be used as they are.

The first composition of the present invention comprises the above-mentioned (a) rubber reinforced resin, (h
) aromatic polyester resin and (c) copolymer (IV
) is the main component, but the blending ratio of component (a) and (h) tc is 10 to 90% by weight, preferably 15 to 88% by weight, more preferably 20 to 86% by weight of component (a).
, (h) component 90-10% by weight, preferably 85-12%
% by weight, more preferably 80 to 14% by weight [however,
(a)+(h)=100% by weight].

If component (a) is less than 10% by weight, the resulting composition will have low impact strength, while if it exceeds 90% by weight, moldability will be poor and chemical resistance will be insufficient. Undesirable.

The blending amount of component (c) is 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, per 100 parts by weight of component (a) and (h).

(c) Even compositions obtained by blending only components (a) and (h) without blending 1 minute have excellent mechanical strength represented by impact resistance, but ( c) By incorporating the tc component, better mechanical properties and molded appearance can be obtained.

On the other hand, the blending amount of component (c) is (a) + component (h) 100
If it exceeds 30 parts by weight, weather resistance, impact resistance, etc. will deteriorate, which is not preferable.

The first composition of the present invention comprises the above-mentioned (a) rubber reinforced resin, (h
) aromatic polyester resin and (c) copolymer (IV
) using a conventional mixing method.

For example, after mixing each component with a mixer, they are melt-kneaded and granulated using an extruder at 200 to 280°C.

Furthermore, each component can be easily melted and kneaded directly in a molding machine to be molded.

Next, in the second &u bottom material of the present invention, the monomer component (II) is used as a monomer component to be subjected to graft copolymerization during the production of the rubber reinforced resin (a) of the first composition. In addition to (c) a functional group-containing monomer component (II1) similar to that used in the production of copolymer (IV), (a)' rubber-reinforced resin is used.

(a) The hydrogenated diene polymer ()) which is a component of the rubber reinforced resin is 5 to 60% by weight, preferably 10 to 55% by weight, and the monomer component (11) is 94 to 20% by weight. % by weight, preferably 92 to 23% by weight, monomer component (II1) is 1
-20% by weight, preferably 3-17% by weight [However, (
1) +(I1) +(Ilr)=100% by weight].

(b)'Functional group-containing monomer component (II
By graft copolymerizing 1), a composition having excellent mechanical properties and molded appearance can be obtained.

Furthermore, in this second composition, since component (a)' is blended, copolymer (iv) (c) does not need to be used.

The other configurations and effects of the second composition are the same as those of the first paraboloid.

Next, the third composition of the present invention comprises (a) rubber reinforced resin, (
h) A composition mainly composed of a 'boria-based resin and (c) a copolymer (■), in which (h) an aromatic polyester resin of the first composition is replaced by (h)' It uses resin.

This (h)′ polyamide resin includes nylon 4,6
, nylon 6, nylon 6.6, nylon 6.10, nylon 11, nylon 12, etc., and those having a melting point of 250°C or lower are particularly preferred; from this point of view, nylon 6
is preferred. These (h)' polyamide resins can be used alone or in combination of two or more.

The blending ratio of (a) rubber reinforced resin and (h)' polyamide resin is 5 to 95% by weight of component (a), preferably 8 to 9% by weight.
2% by weight, more preferably 10-90% by weight, (h)
' component 95 to 5% by weight, preferably 92 to 8% by weight, more preferably 90 to IO% by weight [However, (a) + (
h)'=100% by weight].

Here, if component (a) is less than 5% by weight, the impact strength of the polyamide resin cannot be improved;
If the amount exceeds 100%, the abrasion resistance and chemical resistance of the resulting composition cannot be improved.

The third composition of the present invention comprises (a) rubber reinforced resin, (h)
Since it contains a polyamide resin and (c) copolymer (IV), it has excellent weather resistance, abrasion resistance, and chemical resistance, and in particular, weather resistance and molded appearance are significantly improved. That is, in the third composition of the present invention, (a) when there is a large amount of rubber-reinforced resin, the disadvantages of the rubber-reinforced resin, such as heat resistance, chemical resistance, and abrasion resistance, can be improved; (a) When the amount of rubber-reinforced resin is small, it improves moldability and impact resistance, which are disadvantages of polyamide as an engineering plastic, and at the same time greatly improves molding appearance such as weather resistance, colorability, and the appearance of welded parts. can do.

The other structures and effects are the same as those of the first composition except for the essential function of (h)' polyamide resin.

Next, the 4m-th acid of the present invention is (a)' rubber reinforced resin [
Functional group-containing monomer component (III
) as a graft monomer] and (h
)' Polyamide resin and (c) Copolymer (IV) It is a composition in which component (a) of the third composition is replaced with component (a)' of the second composition. be.

Furthermore, in this fourth composition, since the component (a)' is blended, the copolymer (c) (c) does not need to be used.

The other configurations and effects of the fourth composition are the same as those of the second and third compositions.

The composition of the present invention comprises the above (a) and/or (a)'
component, (h) and/or (h)' component, and (
The thermoplastic resin composition of the present invention contains component c) as the main component, but other thermoplastic polymers such as vinyl chloride resin, polyolefin resin, polycarbonate,
It can contain about 50% by weight or less of various common synthetic resins such as polyphenylene ether, polyglutarimide, styrene-butadiene block copolymer, or elastomer.

Moreover, various compounding agents can be added to the composition of the present invention.

Examples of these compounding agents include 2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-cyphthylphenol, and 2,2-methylene-bis-(4- Ethyl 6-t-butylphenol]
, 4,4'-thiobis-(6-1-butyl-3-methylphenol), dilaurylthiodipropionate, tris(di-nonylphenyl)phosphite, wax, and other antioxidants; p-t-butyl phenyl salicylate,
2. UV absorbers such as 2'-dihydroxy-4-methoxyhensiphenone, 2-(2'-hydroxy-4'-n-octoxyphenyl)benzotriazole; paraffin wax, stearic acid, hydrogenated oil, stearamide, Lubricants such as methylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; antimony oxide, ammonium hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) Flame retardants such as phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, and tetrabromobisphenol A; Antistatic agents such as stearamidopropyl dimethyl-β-hydroxyethylammonium nitrate; Colorants such as titanium oxide and carbon black. agents; fillers such as calcium carbonate, clay, silica, glass fibers, glass spheres, and carbon fiber; pigments; and the like.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, parts and percentages are based on weight unless otherwise specified.

In addition, various physical property test methods in Examples were measured according to the following procedures.

90% of the rubber-modified thermoplastic resin pellets of Toyosumi Examples and Comparative Examples
Molded with a 7ON injection molding machine (220-250″C),
The physical properties of the obtained test piece were measured.

Among the measurements of this physical property, the melt flow rate is
Measured according to K7210.

The Izot impact strength is based on ASTM D256 (cross section 1
/4 x 1/2 inch, with a notch).

The heat distortion temperature was measured according to ASTM D64B.

The rubber-modified thermoplastic resin pellets of Examples and Comparative Examples were colored using the following formulation through an extruder, and the resulting colored pellets were molded to obtain a color tone evaluation plate.

Regarding black coloring properties, the brightness was measured using a color difference meter.
It was expressed as a Munsell color table value (the larger the value, the worse the coloring property).

For other coloring formulations, saturation was determined visually.

[Black formulation] (Part) Resin
100 carbon black
0.5 Calcium stearate
0.3 [Red combination prescription]
(Part) Resin 100
Red iron 1.0 Calcium stearate 0. 5 [Blue formulation] (Part) Resin
100 ultramarine blue
1.0 Calcium stearate 0
．． 5 Color saturation judgment: ◎: Quite vivid, ○: Vivid, ×;
It was determined that the image was not vivid.

Weld 1 The rubber-modified thermoplastic resin pellets of Examples and Comparative Examples were molded using a mold in which a weld portion was formed, and the presence or absence of a weld line was visually confirmed.

The evaluation was as follows: ◎: Hardly observed, ○: Slightly observed, ×: Clearly observed.

A weather resistance test was conducted under the following conditions using the same test piece as used for the physical property measurement.

Test conditions: Testing machine = Sunshine Weather-Ometer (Suga Test Machine)
manufactured by WE-6xS-DC) Black panel temperature = 63 ± 3°C Humidity in tank = 60 ± 5% RH Rainfall cycle = 18/120 minutes Carbon exchange cycle = 60 minutes Measurement method = ASTM D256 (cross section 1/8 x 1/ 2 inches) ■ ASTM D523 weather resistance evaluation was performed by measuring Izot impact strength, glossiness, or mechanical properties using the methods described above.
It is expressed as the retention rate after 00 hours.

In addition, changes in color tone were investigated and expressed as color difference ΔE from the initial color tone.

Examples 1 to 17, Comparative Examples 1 to 15 [Hydrogenated diene polymer a] of diene Ia to b After charging 2,500 g of degassed and dehydrated cyclohexane and 75 g of styrene into an autoclave with an internal volume of 51, 9.8 g of tetrahydrofuran and 0.2 g of n-butyllithium were added to carry out isothermal polymerization at a polymerization temperature of 50''C (first stage polymerization).

After the polymerization conversion rate reached almost 100%, 1.
350 g of 3-butadiene was added and polymerization was carried out at a temperature of 70°C (second stage polymerization).

After the polymerization conversion rate reached approximately 100%, 75 g of 1°3-butadiene was added and adiabatic polymerization was carried out (third stage polymerization).

Sampling was performed every 5 minutes during the polymerization, and the styrene content and the microstructure of 1,3-butadiene in the produced polymer were measured at any time.

After the polymerization conversion rate reached almost 100%, the reaction solution was
"C, cooled to 0.6 g of n-butyllithium, 2.6
Add 0.6 g of -t-butyl-p-cresol, 0.28 g of bis(cyclopentadienyl)titanium dichloride and 1.1 g of diethylaluminium chloride,
The reaction was carried out for 1 hour while maintaining the pressure at 10 kg/d with hydrogen gas.

The reaction solution was cooled to room temperature, and the solvent was removed by steam stripping, followed by drying with a roll at 120° C. to obtain hydrogenated diene polymer a.

Table 1 shows the molecular properties of the obtained hydrogenated diene polymer a.

[Hydrogenated diene polymer b]

By appropriately changing the monomer composition, polymerization aid, and polymerization conditions so as to obtain the polymer structural characteristics shown in Table 1,
The hydrogenated diene polymers shown in Table 1 were obtained. Note that commercially available butadiene rubber and EPDM are also shown in Table 1.

Table 1 Rubber 27 to 11' [Rubber reinforced resin a] Hydrogenated base rubber shown in Table 1 as a homogeneous solution in a stainless steel autoclave with an internal volume of 10 f equipped with a ribbon-type stirring blade. 30 parts of diene polymer a,
A mixture of 49 parts of styrene, 120 parts of toluene, and 0.1 part of t-dodecyl mercaptan was charged, heated while stirring, and heated to 50°C with 21 parts of acrylonitrile, 0.5 parts of benzoyl peroxide, and 0.5 parts of dicumyl peroxide. After adding 0.1 part of oxide and further raising the temperature to 80°C, stir at 1100 r while controlling the temperature to be constant at 80°C.
The polymerization reaction was carried out at p.

After the start of the reaction, the temperature was raised to 120° C. over 1 hour from 6 hours, and the reaction was continued for another 2 hours to complete the polymerization. The polymerization conversion rate was 97%.

After cooling this to 100°C, 0.2 part of 2,2'methylenebis(4-methyl-6-t-butylphenol) was added, and the reaction mixture was taken out from the autoclave and unreacted monomers were removed by steam distillation. After distilling off the solvent and finely pulverizing, the volatile matter was substantially distilled off using a 40 mmφ vented extruder (220°C, 700 mmHg vacuum), and the polymer was made into pellets to form the rubber-reinforced resin atom of the present invention. I got it.

The composition of this rubber reinforced resin A is shown in Table 2.

[Rubber reinforced resin 1-1]

Rubber reinforced resins I to I were obtained using the rubber components and monomer components shown in Table 2, but in the same manner as in the production of rubber reinforced resin A.

Table 2 also shows the polymerization time and polymerization conversion rate.

(Margins below) Table 2 Table 2 (Continued) Ox person Using a glass separable flask with an internal volume of 10 f, A-C.
Add 250 parts of ion-exchanged water, 10 parts of styrene, 6.67 parts of acrylonitrile, 13.34 parts of methyl methacrylate, 3.334 parts of methacrylic acid, and 2.5 parts of sodium dodecylbenzenesulfonate, replace with nitrogen, and heat at 60°.
0.6 parts of potassium persulfate and 0.3 parts of sodium acid sulfite were added, and polymerization was carried out for 2 hours while controlling the internal temperature at 60"C.

Thereafter, the same amounts of styrene, acrylonitrile, and methacrylic acid as above were charged, and polymerization was repeated twice at 80°C for 2 hours to obtain a copolymer with a polymerization conversion rate of 98%.

A 2% aqueous potassium chloride solution was added to this for salting out, followed by heating and drying to obtain a resin powder.

A copolymer powder having the composition shown in Table 3 was obtained in a similar manner.

In the rubber reinforced resin and copolymer obtained as shown in Table 3,
Aromatic polyester resin or polyamide resin as the fourth
They were blended in the proportions shown in the table, mixed using a Henschel mixer, and melt-kneaded at 240°C to produce pellets. Using this pellet, various physical properties were measured. The results are also shown in Table 4.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention is a rubber that has excellent weather resistance and molded appearance, and has significantly improved impact resistance including impact strength in a low temperature range, chemical resistance, and heat resistance including thermal stability. It is possible to provide a polymer alloy of reinforced resin and engineering plastic, which is extremely useful industrially.

Claims (4)

[Claims] (1) (A) Hydrogenated diene polymer obtained by hydrogenating a diene polymer of 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene (1) In the presence of 5 to 60% by weight at least one selected from the group consisting of an aromatic vinyl compound (a), a vinyl cyanide compound (b), a (meth)acrylic acid ester compound (c), and another monomer copolymerizable therewith (d). 10-90% by weight of a rubber reinforced resin obtained by graft copolymerizing 95-40% by weight of one type of monomer component (II) [however, (I) + (II) = 100% by weight], (b) aromatic Polyester resin 90-10% by weight [However,
(a) + (b) = 100% by weight], and (c) epoxy group-containing monomer (e), carboxyl group-containing monomer (
f), at least one functional group-containing monomer selected from the group of amide group-containing monomers (g), hydroxyl group-containing monomers (h), and dicarboxylic anhydride group-containing monomers (i); The copolymer (IV) obtained by copolymerizing the monomer containing the monomer component (III) was prepared by adding the total amount of the components (a) and (b) to 10
A thermoplastic resin composition containing 0.1 to 30 parts by weight relative to 0 parts by weight. (2) (a)' The hydrogenated diene polymer according to claim 1 (
1) Monomer component (II) 94-94% in the presence of 5-60% by weight
20% by weight and functional group-containing monomer component (III) 1-2
0% by weight [However, (I) + (II) + (III) = 100
% by weight] is graft copolymerized with rubber reinforced resin 10 to 9
0% by weight, (b) 90 to 10% by weight of the aromatic polyester resin according to claim 1 [provided that (a)′+(b)=10
0% by weight], and (c) the copolymer according to claim 1 (
A thermoplastic resin composition containing 0 to 30 parts by weight of IV) based on 100 parts by weight of the total amount of components (a)' and (b). (3) (a) 5 to 95% by weight of the rubber reinforced resin according to claim 1; (b) 95 to 5% by weight of the polyamide resin;
(a) + (b)' = 100% by weight], and (c) the copolymer (IV) according to claim 1, based on 100 parts by weight of the total amount of components (a) and (b)'. A thermoplastic resin composition containing 0.1 to 30 parts by weight. (4) (a)' 5 to 95% by weight of the rubber reinforced resin according to claim 2, (b)' 95 to 5% by weight of the polyamide resin [however, (a)' + (b)' = 100% by weight], and (c)
A thermoplastic resin composition comprising 0 to 30 parts by weight of the copolymer (IV) according to claim 1, based on 100 parts by weight of the total amount of components (a)' and (b)'.