JPH0326745A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in resistance to impact and chemicals, molding processability, weld strength and appearance when molded, comprising a specific rubber-reinforced polymer, a polyamide polymer and a specific vinyl copolymer at specified proportion. CONSTITUTION:The objective composition comprising (A) 10-80 (pref. 14 -75) wt.% of a rubber-reinforced polymer 5-200 (pref. 10-150)% in graft rate, prepared by graft copolymerization, in the presence of A1: 5-85wt.% of a rubbery polymer, between A2: 10-70wt.% of an aromatic vinyl compound and A3: 5-50wt.% of a maleimide monomer and/or (meth)acrylic alkyl ester, (B) 10-89 (pref. 20-80) wt.% of a polyamide polymer (e. g. nylon-6) and (C) 1-70 (pref. 5-60) wt.% of a vinyl copolymer from (1) a unsaturated compound having at least one functional group selected from carboxyl, acid anhydride and epoxy groups and (2) an aromatic vinyl compound.

Description

[Detailed description of the invention] ,. INDUSTRIAL APPLICATION FIELD The present invention relates to a thermoplastic resin composite sole having excellent impact resistance, shaping workability, chemical resistance, welt strength, and a high-gloss, imposing appearance. b. Conventional technology Polyamide resins such as nylon-6, nylon-66, nylon-12, and nylon 4.6 have various excellent properties, and these properties are used in many fields such as plastic products and films. It is used in

However, polyamide resin has the drawback of not having very good impact resistance, especially when notched, which has been an obstacle to expanding its use in a wider range of applications. .

Therefore, in order to improve impact resistance, many methods have been proposed for blending rubber or the like, but although these methods can improve impact resistance to some extent, they are not sufficient in terms of weld strength and molded appearance.

C. Problems to be Solved by the Invention As described above, it is not possible to sufficiently improve the weld strength and shape appearance of polyamide resin using conventional methods.
Solving this problem was an issue.

As a result of extensive studies, the present inventors found that a rubber-reinforced polymer obtained by graft polymerizing an aromatic vinyl, a maleimide monomer, a methacrylic acid ester, etc. to a rubber body, a polyamide-based polymer, and a specific functional It has been discovered that a composite material made of a vinyl copolymer copolymerized with an unsaturated compound containing groups has excellent impact resistance, moldability, chemical resistance, weld strength, and dignified appearance. , arrived at the present invention.

d. Means for Solving the Problems The present invention provides (^) 10 to 70% by weight of aromatic vinyl, a maleimide monomer and/or (meth)acrylic in the presence of 5 to 85% by weight of a rubbery polymer. Rubber-reinforced polymer obtained by graft polymerization of 5 to 501i weight % of a monomer consisting of an acid alkyl ester IO to 80 weight %, (B)
Polyamide polymer IQ ~ 89% by weight, (C
) A vinyl copolymer consisting of an unsaturated compound having at least one functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group, and aromatic vinyl, or a monomer copolymerizable with these and other monomers. The object of the present invention is to provide a thermoplastic resin composition characterized by comprising 1 to 70% by weight.

The above (A) rubber reinforced polymer is composed of 10 to 70% by weight of aromatic vinyl, a maleimide monomer and/or a (meth)acrylic acid alkyl ester in the presence of 5 to 85% by weight of a rubbery polymer. This is a graft polymer obtained by graft polymerizing 5 to 50% by weight of monomers (hereinafter referred to as graft polymer (A)).

As the rubbery polymer in the graft polymer (A), copolymers of ethylene and α-olefin such as ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, etc. Copolymerization; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methacrylate and ethylene-butyl acrylate; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; ethylene-propylene-ethylidene norbornene copolymers; Ethylene-propylene-nonconjugated diene terpolymers such as ethylene-propylene-hexadiene copolymers: polybutadiene, isoprene, styrene, random copolymers and block copolymers of butadiene, and hydrogenated products of the block copolymers, Diene rubbers such as acrylonitrile-butadiene copolymer and butadiene-isoprene copolymer; butylene-isoprene copolymer, etc.
It can be used in one species or in combination of two or more.

Among these rubbery polymers, diene rubber, ethylene-propylene rubber,
Ethylene-propylene-nonconjugated diene terpolymer,
It is a hydrogenated product of styrene-butadiene copolymer. More preferred are polyptadiene and styrene-butadiene copolymers, and the styrene content in the styrene-butadiene copolymer is preferably 50% by weight or less from the viewpoint of impact resistance.

The blending ratio of the rubbery polymer in the graft polymer (A) is 5
-85% by weight, preferably 10-75% by weight. If it is less than 5% by weight, impact resistance and weld strength will be low.
, if it exceeds 85%, the formability is poor.

Aromatic vinyls include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dipromstyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and 0-methyl. Examples include styrene, p-methylstyrene, dimethylstyrene, etc., and these may be used alone or in combination of two or more. Preferred vinyl aromatics are styrene and/or alpha-methylstyrene. The content of aromatic vinyl in the graft polymer (A) is 10 to 70% by weight, preferably 15 to 70% by weight. If it is less than 10% by weight, impact resistance will be poor, and if it exceeds 70% by weight, moldability will be reduced.

For example, maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, N
-cyclohexylmaleimide, etc., preferably N-phenylmaleimide, N-0-chlorophenylmaleimide, N-cyclohexylmaleimide, etc.
These maleimide monomers may be used alone or in combination of two or more.

Examples of (meth)acrylic acid alkyl esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and probyl acrylate; and methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and probyl methacrylate.

The maleic monomer and/or in the graft polymer (A)
Alternatively, the content of the (meth)acrylic acid alkyl ester is 5 to 50% by weight, preferably 10 to 50% by weight. If it is less than 5% by weight, the heat resistance will be low, and if it exceeds 50% by weight, the shapeability will be decreased.

The graft polymer (A) may be copolymerized with an unsaturated compound having a carboxy group, an acid anhydride group, an epoxy group, etc., vinyl cyanide, etc., which will be described later, within a range that does not impair the purpose of the present invention.

The graft polymer (A) has a graft copolymer structure in which a monomer component is graft copolymerized to a rubbery polymer, or a copolymer of the graft copolymer and a monomer, depending on the polymerization conditions. I can do things with a structure.

The preferable graft ratio of the graft polymer (A) is 5 to 20
The content is 0% by weight, more preferably 10 to 150% by weight, and within this range, an even more excellent thermoplastic resin composition, which is the object of the present invention, can be obtained.

Further, the content of the rubbery polymer in the entire thermoplastic resin composition is preferably 5 to 40% by weight, more preferably 6 to 4% by weight.
0% by weight, particularly preferably 8-35% by weight. If it is too small, the impact resistance will not be sufficient, and if it is too large, the formability will be reduced.

The method for producing the graft polymer (^) is not particularly limited, and for example, known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.

(B) The polyamide ξ-do polymer (hereinafter referred to as boria ξ-do polymer (B)) which is the tc component of the present invention is not particularly limited, and includes, for example, ethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine. , Dodecame Chirenjia-kun, 2, 3.4 and 2, 4, 4,
monotrimethylhexamethylene diamine, 1,3 and 1,4-bis(aminomethyl)cyclohexane, bis(
Aliphatic, alicyclic, aromatic diamines such as p-aminosyldiamine, p-xylylene diamine, p-xylylene diamine, adipic acid, speric acid, sehacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Polyamides derived from aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids; polyamides obtained by ring-opening polymerization of lactams such as ε-cabulactam and ω-dodecalactam; 6-aminocaproic acid; Polyamides derived from 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc., and copolymerized polyamides thereof,
Nylon-6 (polycaproamide), nylon-66 (polyhexamethylene adipamide), and nylon-6, which are mixed boria ξ-does and are industrially produced at low cost and in large quantities.
12 (polydodecamide), nylon-610 (polyhexamethylene sebacamide), nylon-4.6, and mixtures of these copolymers are useful.

The method of polymerizing the polyamide polymer (B) is not particularly limited, and conventionally known melt polymerization, solid phase polymerization, and a combination thereof can be employed.

Furthermore, the degree of polymerization of the boria ξ-d polymer (B) is not particularly limited, and usually the relative viscosity (1 g of the polymer is 98% H.SO4
100d and measured at 25°C) within the range of 1.8 to 6.0 can be arbitrarily used. However, if one with a relative viscosity in the range of 2 to 5 is used, a product with an excellent balance between impact resistance and formability can be obtained. The molecular structure of the polyazide polymer (B) is not particularly limited either, and it may be either a linear polyamide or a branched polyamide.

The vinyl copolymer (C) tc component of the present invention (hereinafter referred to as vinyl copolymer (C)) contains at least one functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group. These are copolymers of the unsaturated compound contained therein and aromatic vinyl, and/or copolymers of the functional group-containing unsaturated compound, aromatic vinyl, and other copolymerizable monomers.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred. These may be used in one type or in combination of two or more types.

Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrophthalic anhydride, with maleic anhydride being preferred. . These may be used alone or in combination of two or more.

Examples of the unsaturated compound containing an epoxy group 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-1-butene, 3,4-epoxy-1-pentene, 3,
4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide,
Examples include P-glycidylstyrene. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, p-t-7′-methylstyrene, and the like.

Other copolymerizable monomers include vinyl cyanide such as acrylonitrile, methacrylonitrile, alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, and propylene acrylate; methyl methacrylate, ethyl mequaacrylate, propylene methacrylate, etc. methacrylic acid alkyl esters, and these can be used alone or in combination of two or more. Preferred are vinyl cyanide, (meth)acrylic acid alkyl esters, and more preferred are vinyl cyanide.

The method for producing the vinyl copolymer (C) is not particularly limited, and conventionally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used.

The content of the functional group-containing unsaturated compound in the vinyl copolymer (C) is usually 0.1 to 8% by weight, preferably 0.2 to 7% by weight based on the tc content of the copolymer (C). %, more preferably 0.3 to 7% by weight. If it is less than 0.1% by weight, the impact resistance will be low, and if it is too much, the impact resistance, shapeability,
Poor appearance and weld strength.

The content of aromatic vinyl in the vinyl copolymer (C) is
Preferably 30 to 99.9% by weight, more preferably 5
0 to 9968% by weight, and other copolymerizable monomers (
The content of (hereinafter referred to as other monomers) is preferably 0 to 0.
62% by weight, more preferably 0 to 42% by weight.

In order to obtain the effect of copolymerization of other monomers, the content of other monomers is preferably 5 to 2% by weight, and the content of aromatic vinyl is preferably 30 to 94.9% by weight. weight%
It is.

In the thermoplastic resin composition of the present invention, the blending ratio of the graft polymer (A), the polyamide polymer (B), and the vinyl copolymer (C) is 10 to 80% by weight,
Preferably 12 to 80% by weight, more preferably 14 to 80% by weight
75% by weight, (B) 10-89% by weight, preferably 1
5 to 86 M% by weight, more preferably 20 to 80% by weight, and (C) is 1 to 70% by weight, preferably 2 to 65% by weight.
% by weight, more preferably 5 to 60% by weight, and (A
), (B) and (C) at a ratio such that the total amount is 100% by weight.

(A) is 10! ! less than f amount% or (B) is 89% by weight
If (C) exceeds 1% by weight, or if (C) is less than 1% by weight, the resulting resin composition will have poor impact resistance.

If (A) exceeds 80% by weight or (B) is less than 10% by weight, chemical resistance will be poor, and if (C) exceeds 70% by weight, moldability and molded appearance will be poor.

The content of the above unsaturated compound in the resin composition of the present invention is:
The vinyl copolymer (C) was adjusted to be 0.02 to 4% based on the miscibility of the rubber-reinforced styrene copolymer and the polyamide polymer, the molding processability of the resulting resin composite sole, and the molded appearance.
It is preferable to select a blending amount of .

In the composition of the present invention, common methods are used to mix components (A) to (C). For example, after mixing each component in a mixer, the mixture is melt-kneaded and granulated in an extruder at 220 to 320'C. Even more simply, each precept can be directly melted and kneaded in a preforming machine to be formed.

The M precepts of the present invention include antioxidants, such as 2,6-di-L
-Petyl-4-medylphenol, 2(1-methylcyclohexyl)-4.6-dimethylphenol, 2.2-
Methylene-bis-(4-ethyl-6-t-7'thylphenol), tris(dinonylphenyl) phosphite; UV absorbers, such as p-t-butylphenyl salicylate, 2,2'-monodihydroxy-4-methoxy Benzphenone, 2(2'-hydroxy-4'-m
-octoxyphenyl)henzotriazole: lubricants such as paraffin wax, stearic acid, hydrogenated oil, stearamide, methylene bisstearamide, m-butyl stearate, ketone wax, octyl alcohol,
Hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, IsLI
．． }, tricresyl phosphate, tris(dichloroprovir) phosphate, chlorinated paraffins, tetrabutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as stearamide propyl dimethyl-β-hydroxyethyl, ammonium trate; coloring. agents such as titanium oxide, carbon black;
Fillers such as calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers; pigments, etc. can be added as required.

e. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. "Part F" in each example indicates "part by weight."

A: Goof 8 ^1 ~ A-4's indigo tea, 200 parts of raw manufactured water, 1.5 parts of sodium oleate, ferrous sulfate (
FeSO4' 7H*0) 0.002 parts, ethylenediaminetetraacetic acid 2Na salt 0.005
part, 0.2 part of sodium formaldehyde sulfoxylate, 0.2 part of tripotassium phosphate, 57 parts of putadiene, 23 parts of styrene, 1.0 part of divinylbenzene and 0.1 part of diisopropylbenzene hydroperoxide, Pour into a polymerization container equipped with a stirrer, polymerize at 50°C for 10 hours, and confirm that the polymerization conversion rate is 95% or more.
2, 20 parts of butadiene and 0.05 part of diisopropylbenzene hydroperoxide were added, and polymerization was further carried out for 7 hours to obtain a rubber latex (polymerization conversion rate of 99%) with an average particle size of 500.

180 parts of the obtained rubber latex (solid content: 60 parts), 60 parts of water, 0.002 part of sulfuric acid, 0.004 part of ethylenediaminetetraacetic acid 2Na salt, 0.1 sodium formaldehyde sulfoxylate. 20 parts of methyl methacrylate, 20 parts of styrene and 0.1 part of cumene hydroperoxide were added continuously at 70°C over a period of 3 hours, and the polymerization was continued for an additional hour. , a graft copolymer latex was obtained. The obtained graft polymer Latinx was acid-digested with sulfuric acid, filtered and dried to obtain a white powder.

The composition was 60 parts of rubber, 1.20 parts of methyl methacrylate, and 20 parts of styrene.

】Σ■” Sen 1-Ken polybutadiene rubber (manufactured by Japan Synthetic Rubber, JSR BR
After dissolving 40 parts of OI) in 20 parts of methyl methacrylate and 40 parts of styrene, the mixture was subjected to bulk polymerization to produce a rubber-reinforced styrenic copolymer (A-2).

"L" raw ethylene-propylene rubber (manufactured by Japan Synthetic Rubber, JSR
EPDMOI) (30 parts) was dissolved in 50 parts of styrene and 20 parts of methyl methacrylate, and then subjected to bulk polymerization to produce a rubber-reinforced styrenic copolymer (A-3).

(A-
It was manufactured in the same manner as in 1).

B: Nylon-6 (Capron 8202, manufactured by Allied) was used as the polyamide Δ polyamide ξ polymer.

Bead-shaped vinyl polymers ((C-1 to c-7)) were produced by suspension polymerization according to the combination shown in Table 1.

Table 1 Examples 1 to 11, Comparative Examples 1 to 9 Each component (^) ([1) (C) shown in Table 2 was added to 40
Pellets were prepared by melt-kneading at a temperature of 250°C using an m/1 extruder. Using this pellet, JIS K721
The melt flow index (MFR: measurement conditions: 240°C, }Okg) was measured in accordance with 0. In addition, the above pellets were molded using a 5oz injection molding machine (Toshiba 1s-8
A test piece was prepared by molding at a molding temperature of 260°C using Izod impact strength (ASTM D256, ×
"23°C with notch" (abbreviated as Izod Inρ) was measured.

In addition, the glossiness of the test piece (ASTM D5
23, 23°C) was measured.

Furthermore, the test piece (178″ x l/2″ x 5″) had a strain rate of 1
% constant strain is applied, and dioctyl phthalate is applied to the deflected part.
(abbreviated as DOP), apply brake fluid, and
The time taken to break after being left at ℃ was measured and used as an index of chemical resistance.

(◎ indicates that there is no breakage or cracking for 200 hours or more. ○ indicates that there is no breakage or crack for 100 hours or more).

Tensile strength (Tw) was measured using a test piece molded using a mold with a weld line in the center of an ASTM No. 1 dumbbell.
was measured, and then the tensile strength (To) was measured using a test piece that had been shaped in a mold with no weld lines.

From the obtained tensile strength (Tw.To), the weld strength retention rate was determined according to the following formula.

As is clear from the results shown in Table 2, Examples 1 to 1l
Thus, a thermoplastic resin composition, which is the object of the present invention, is obtained, which is excellent in impact resistance, moldability, chemical resistance, and weld strength, and has a high gloss appearance.

On the other hand, in Comparative Examples 1 to 9, the desired effects of the present invention cannot be obtained.

That is, in Comparative Example 1, the amount of component (A) is less than the range of the present invention, and the Izod Imp and weld strength are inferior.

Comparative Example 2 is a case in which the amount of (A) precipitate exceeds the range of the present invention, and the chemical resistance and precipitability are poor.

Comparative Example 3 is a case in which the amount of rubber in the entire composition exceeds the range of the present invention, and the moldability is poor.

In Comparative Example 4, the amount of component (B) was less than the range of the present invention,
Poor chemical resistance.

In Comparative Example 5, the amount of rubber in the entire assembly was less than the range of the present invention, (
B) This is a case where the component exceeds the scope of the present invention, and Izod
Imp and weld strength are poor.

Comparative Example 6 is a case in which the amount of component (C) exceeds the range of the present invention, and the moldability and shaped appearance are poor.

Comparative Example 7 is (C) where the amount of carboxyl group-containing unsaturated compound in tc exceeds the range of the present invention (as shown in Table 1, C-5 has a high content of methacrylic acid). , Izod lap, is inferior in shape, appearance and weld strength.

Comparative Example 8 is a case in which the amount of the functional group-containing unsaturated compound in the entire composition exceeds the range of the present invention, and the Izod Imp, moldability, molded appearance, and weld strength are inferior.

Comparative example 9 is a case where (C) precepts are not included, and Izod
Imp and weld strength are poor.

f. Effects of the Invention In the shaping industry that uses thermoplastic resins, the performance required of shaped products is becoming more complex and sophisticated due to the diversification of applications for shaped products. In other words, there is a need for products with even better impact resistance, shaping workability, chemical resistance, and weld strength than in the past, but conventional polyamide resins and their compositions are insufficient to meet these demands. I couldn't respond.

However, the composition of the present invention has poor impact resistance, moldability,
It is a molding material that has high chemical resistance and weld strength, improves the shortcomings of conventional boria resins and their composites, and satisfies the demands of the molding industry, and its industrial value is big.

Claims (1)

[Scope of Claims] (A) Consisting of 10 to 70% by weight of aromatic vinyl, maleimide monomer and/or (meth)acrylic acid alkyl ester in the presence of 5 to 85% by weight of a rubbery polymer. 10-80% by weight of a rubber-reinforced polymer obtained by graft polymerization of 5-50% by weight of a monomer, (B) 10-89% by weight of a polyamide polymer, (C) a carboxyl group, an acid anhydride group, and an epoxy group. 1 to 70% by weight of a vinyl-based copolymer consisting of an unsaturated compound having at least one functional group selected from the group consisting of aromatic vinyl, or a monomer copolymerizable with these and other copolymerizable monomers. Characteristic thermoplastic resin composition.