JPH02153968A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent impact resistance, chemical resistance and weather resistance and suitable as a material for various industrial parts by compounding a polyamide, a rubber-reinforced styrene resin and a copolymer containing a tertiary ester of (meth)acrylic acid at specific ratios. CONSTITUTION:The objective composition is produced by compounding (A) 10-89.9 pts. wt. of a polyamide, (B) 10-60 pts. wt. of a graft copolymer produced by the graft-polymerization of monomers consisting of 40-100wt.% of aromatic vinyl monomer and 0-60wt.% of other copolymerizable vinyl monomer in the presence of a rubbery polymer, (C) 0-79.9 pts. wt. of a copolymer composed of 5-80wt.% of an aromatic vinyl monomer and 95-20wt.% of other copolymerizable vinyl monomer and (D) 0.1-30 pts. wt. of a copolymer composed of 0.1-30wt.% of a tertiary ester of (meth)acrylic acid, 0-60wt.% of an aromatic vinyl monomer, 99.9-40wt.% of a vinyl cyanide monomer and/or a primary of secondary ester of (meth)acrylic acid and 0-59.9wt.% of a copolymerizable vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent impact resistance and weather resistance.

<Conventional technology> Polyamide resin has excellent moldability, heat resistance, mechanical strength, chemical resistance, abrasion resistance, etc., so it is widely used in mechanical parts, electrical/electronic parts, automobile parts, etc. but,
There are problems such as a decrease in impact resistance in a dry state and dimensional changes due to moisture absorption.

On the other hand, typical rubber-reinforced styrene resins include acrylonitrile-butadiene-styrene copolymer (ABS resin), ABS resin in which the rubber component of ABS resin is replaced with ethylene-propylene rubber or acrylic rubber, and ABS resin.
AS resins are also widely used in automobile parts, electrical equipment parts, office equipment parts, etc., and although they have excellent impact resistance and dimensional stability, they have the problem of relatively poor chemical resistance.

Polyamide and ABS to improve these problems
It has been proposed to melt and mix resins (Japanese Patent Publication No. 1988)
-23476) is known to have poor compatibility between polyamide and ABS resin, resulting in molded products exhibiting delamination and resulting in only materials with low impact strength.

In order to improve the compatibility between polyamide and ABS resin, a carboxylic acid having reactivity or affinity with polyamide,
It has been proposed to introduce and modify functional groups such as amide groups into ABS resins (JP-A-54-11159, JP-A-58-32656, JP-A-58-93745, etc.), but it is difficult to improve impact strength and weather resistance. There is a problem that sexual improvement is not sufficient.

<Problems to be Solved by the Invention> As a result of intensive studies by the present inventors on improving the above-mentioned quality problems of compositions made of polyamide resin and rubber-reinforced styrene resin, the present inventors found that Impact resistance,
It was discovered that a material with excellent weather resistance as well as chemical resistance can be obtained, and the present invention was achieved.

<Means for Solving the Problems> That is, the present invention comprises: (8) polyamide, (4) aromatic vinyl monomer in the presence of a rubbery polymer;
A graft copolymer obtained by graft polymerization of a monomer consisting of ~100% by weight and 0 to 60% by weight of another copolymerizable vinyl monomer, 0 5 to 80% by weight of an aromatic vinyl monomer and 95 to 20% by weight of other copolymerizable vinyl monomers, and 0.1 to 30% by weight of tertiary ester of (meth)acrylic acid, and 0% of aromatic vinyl monomers. ~60% by weight, 99.9 to 40% by weight of vinyl cyanide monomer and/or primary or secondary nistyl monomer of (meth)acrylic acid, and other copolymerizable vinyl monomers 0-59.9% by weight
(A) 10-89.9 parts by weight, (3110-60 parts by weight), (C) 0-79. 9 parts by weight and 00.1~ The present invention will be described in detail below.

Polyamide 8 used in the present invention includes ethylenediamine, diaminobutane, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2.2
．． 4- and 2゜4.4-4-limethylhexamethylenediamine, 1.3- and 1.4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexyl)methane, metaxylylenediamine, paraxylylenediamine, etc. aliphatic, cycloaliphatic, aromatic diamines and adipic acid,
aliphatic, alicyclic, such as speric acid, sepacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid,
Polyamides derived from aromatic dicarboxylic acids, polyamides obtained by ring-opening polymerization of lactams such as ξ-caprolactam and ω-dodecalactam, and polyamides derived from 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Polyamides, copolyamides thereof, mixed polyamides, and the like can be mentioned.

Polycaproamide (nylon 6), polydodecaamide (nylon 12), polytetramethylene adipamide (nylon 46), and polyhexamethylene adipamide (nylon 6) are industrially produced at low cost and in large quantities.
6) Polyhexamethylene diamine (nylon 610)
, and copolymers thereof, such as nylon 6/66
('/' sign means copolymer), nylon 6/610, nylon 6/12, nylon 66/12
, nylon 6/66/610/12, and mixtures thereof are useful.

Also useful are bis(p-aminocyclohexyl)methane/terephthalic acid/isophthalic acid based polyamides.

Note that there is no limit to the degree of polymerization of the polyamide used;
Concentrated sulfuric acid relative viscosity (1 g of polymer is mixed with 98% concentrated sulfuric acid 100-
(measured at 25℃, the same applies hereafter) is 1.8 to 6.0
Any polyamide within the range can be selected.

There are no restrictions on the molecular structure of polyamide, and either linear polyamide, branched polyamide, etc. may be used. Linear polyamide is produced by conventional methods,
Branched polyamide is polymerized by adding a small amount of a branching agent having -8 or more functional groups capable of forming a polyamide, such as bis(ω-aminehexyl)amine, diethylenetriamine, trimesic acid, and bislactam, to the raw materials.

Furthermore, in nylon-6, there is no particular restriction on the ratio of terminal amino groups to terminal carboxyl groups, and any ratio can be used. Preferably it is 0.9 or less. (The terminal carboxyl group is measured with 0.08 N alkaline benzyl alcohol, and the terminal amino group is measured with 0.01 N hydrochloric acid.) Polymerization methods include melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and these methods. A combination of methods may be used, with melt polymerization being most suitable for the membrane. Further, particularly when the polyamide raw material is a lactam, the polymer may be obtained by anionic polymerization.

The graft copolymer (2) in the present invention is composed of 40 to 100% by weight of an aromatic vinyl monomer and 60 to 0% by weight of other copolymerizable vinyl monomers in the presence of a rubbery polymer. It is obtained by graft polymerization of a monomer mixture.

Rubbery polymers used in graft copolymers include:
? Diene rubbery polymers such as liptadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, acrylic rubbery polymer, chlorine Examples include non-diene rubber-like polymers such as chemically modified polyethylene, which can be used alone or in combination of two or more. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like.

There are no particular restrictions on the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, but the average particle size is 0.1 to 1 μm and the gel content is O to 9.
Preferably 5% monomethylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, t
-Butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, etc. are exemplified, and the hemers used alone or in combination of two or more are acrylonitrile, methacrylate, etc. Vinyl cyanide monomers such as lyl, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, etc.
meth) primary or secondary esters of acrylic acid, maleimide, N-phenylmaleimide, N-methylmaleimide, N
Maleimide compounds such as -cyclohexylmaleimide are exemplified and can be used alone or in combination of two or more.

There is no particular restriction on the ratio of the rubbery polymer and monomer mixture in graft polymerization, but the ratio of the rubbery polymer 20 to 8
Preference is given to 0% by weight and 80 to 20% by weight of the monomer mixture.

Furthermore, there is no particular restriction on the grafting rate of the graft copolymer, but it is preferably 20-100%.

If the amount of the aromatic vinyl monomer constituting the monomer is less than 40% by weight, the impact resistance will be poor, which is not preferable. Preferably, the content is 50 to 80% by weight of the aromatic vinyl monomer and 50 to 20% by weight of the other vinyl monomer.

As the graft polymerization method, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.

The copolymer 0 used in the present invention is a copolymer consisting of 5 to 80% by weight of an aromatic vinyl monomer and 95 to 20% by weight of other copolymerizable vinyl monomers.

If the aromatic vinyl monomer exceeds 80% by weight, the impact resistance will be poor, which is not preferable. Preferably, each of the monomers can be selected from one or more of the same monomers as those used in the graft copolymer. Although there is no particular restriction on the molecular weight of Copolymer 0, it is preferable that the weight average molecular weight is 10.000 to 1,000.000.

As a polymerization method for copolymer 0, known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these methods can be used.

Copolymer 0 used in the present invention refers to 0.1 to 30% by weight of tertiary ester of (meth)acrylic acid, 0 to 60% by weight of aromatic vinyl monomer, vinyl cyanide and/or (meth) ) Acrylic acid primary or secondary ester monomer 9
It is a copolymer consisting of 9.9 to 40% by weight and 0 to 60% by weight of other copolymerizable vinyl monomers.

If the tertiary ester of (meth)acrylic acid is less than 0.1% by weight, the impact resistance will be poor, and if it exceeds 30% by weight, the processability will be poor. If the amount of vinyl cyanide and/or (meth)acrylic acid ester monomer is less than 40%, weather resistance will be poor;
If it exceeds 9.9% by weight, impact resistance will be poor. Furthermore, if the amount of aromatic vinyl monomer or other vinyl monomer is 60% by weight, the impact resistance and weather resistance will be poor.

Preferably 0.1 tertiary nistyl (meth)acrylic acid
~20% by weight, aromatic vinyl monomer 0~55% by weight,
The content is 90 to 44.9% by weight of vinyl cyanide and/or the first or second ester monomer of (meth)acrylic acid, and 0 to 50% by weight of other copolymerizable vinyl monomers.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, and p-methylstyrene.
-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorstyrene,
Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, fumaronitrile, etc., and examples of primary or secondary esters of (meth)acrylic acid include methyl acrylate. Examples of other vinyl monomers include imide monomers such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Each type or two or more types can be used, and styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, N-phenylmaleimide, etc. are particularly preferred.

Examples of the tertiary ester of (meth)acrylic acid include t-butyl acrylate and t-butyl methacrylate, with t-butyl methacrylate being preferred.

Although there is no particular restriction on the molecular weight of the copolymer ◎, it is preferable that the weight average molecular weight is 10.000 to 1,000.000. As a polymerization method for copolymer 0, known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these methods can be used.

The thermoplastic resin composition of the present invention comprises the aforementioned polyamide 8,
It consists of graft copolymer ■, copolymer Ω and 0, and the composition ratio is (5), ■, (the total amount of Q and Ω is 10
■89.9 to IO parts by weight as 0 parts by weight, (13) 10
~60 parts by weight, (Q O~79.9 parts by weight, 00.1~
It is 30 parts by weight.

(8) If the composition ratio of ■, 0 and ◎ is outside the above range,
Only those with poor impact resistance and weather resistance have poor impact strength, and if the weight is 40% by weight, the rigidity and hardness will decrease, which is not preferable.

Preferably (A) 20 to 80 parts by weight, (8310 to 70 parts by weight)
parts by weight, (C) 0 to 30 parts by weight and 01 to 20 parts by weight, and the rubber content is 10 to 30% by weight.

There is no restriction on the mixing order of polyamide (8), graft copolymer ■, copolymer ◎, and copolymer 0, and the four components may be mixed at once or specific components may be premixed and then the remaining components may be mixed. be able to.

Furthermore, there are no restrictions on the mixing method, and known methods such as a Banbury mixer, roll, extruder, etc. can be employed.

In addition, when mixing, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers,
Additives such as metal flakes, reinforcing materials, fillers, etc. can be added. Also, polyacetal, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polymethyl methacrylate,
Thermoplastic resins such as polyvinyl chloride can also be blended as appropriate.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that all parts and percentages are expressed on a weight basis.

Reference Example 1 Production of Graft Copolymer (B-1) 15 parts of acrylonitrile and An ABS graft copolymer latex was prepared by copolymerizing 85 parts of styrene.

B-2 In the presence of 50 parts (solid content) of cross-linked polybutyl acrylate latex with an average particle diameter of 0.3 μm, 15 parts of acrylonitrile and 85 parts of styrene were copolymerized by emulsion polymerization to obtain an AAS graft copolymer latex. Created.

B-8 iodine value 15.8, Mooney viscosity 67, propylene content 50%, and 75 parts of EPDM containing ethylidene norbornene as the diene component were dissolved in 1000 parts of n-hexane and 650 parts of ethylene dichloride, and 75 parts of styrene was dissolved.
1 part, 25 parts of acrylonitrile, and 3 parts of benzoyl peroxide were added, and the mixture was polymerized at 67°C for 110 hours under a nitrogen atmosphere to prepare an AES graft copolymer solution.

Graft copolymers B-1 and B-2 were salted out using calcium chloride, separated and dried. Graft copolymer B
-8, the polymerization solution was poured into a large excess of methanol, and the precipitate was separated and recovered by drying.

When the amount of rubber contained in the graft copolymers B-1, B-2 and B-8 was measured by infrared spectroscopy, it was found to be about 50% in each case.

Reference Example 2 Production of Copolymer 0 After copolymerizing 30 parts of acrylonitrile and 70 parts of styrene by emulsion polymerization, the copolymer was salted out using calcium chloride and separated and recovered.

Reference Example 3 Production of Copolymer 0 D-1: By emulsion polymerization method, 30 parts of acrylonitrile,
15 parts of methyl methacrylate, 50 parts of styrene, t-
5 parts of butyl methacrylate were copolymerized.

D-2: In the same manner as D-1, 20 parts of acrylonitrile, 30 parts of methyl methacrylate, 40 parts of styrene, and 10 parts of t-butyl methacrylate were copolymerized.

D-8: In the same manner as D-1, 20 parts of acrylonitrile, 80 parts of methyl methacrylate, 30 parts of styrene, and 20 parts of t-butyl methacrylate were copolymerized.

D-4: Same as D-1, 10 parts of acrylonitrile, 7.5 parts of methyl methacrylate, 10 parts of styrene, t-
5 parts of butyl methacrylate was copolymerized.

Similar to D-52I)-1, methyl methacrylate 9
5 parts of t-butyl methacrylate were copolymerized.

D-6: Similarly to D-1, 30 parts of acrylonitrile, 65 parts of styrene, and 5 parts of t-butyl acrylate were copolymerized.

Incidentally, copolymers D-1 to D-6 were salted out using calcium chloride and separated and recovered.

Examples were mixed in the proportions shown in Table 1, and melt mixed and granulated at 250°C using a 40 m diameter twin screw extruder.

In addition, as polyamide, nylon 6 (concentrated sulfuric acid relative viscosity 2
．． 6) was used.

The physical properties of the obtained resin composition were measured by the following method,
The results are shown in Table 1.

0 Impact strength (notched isot) ASTM D-256 (A8°C) 0 Weather resistance test A molded article was molded and an accelerated test was conducted using a fade meter manufactured by Suga Test Instruments.

(Black panel temperature: 83°C) The above-mentioned test piece for quality evaluation was molded using a 3.5-ounce injection molding machine with the cylinder temperature set at 250°C.

<Example 1-3 and Comparative Examples 1-2> As shown in Table 1, examples using various graft copolymers are shown.

<Example 4-7 and Comparative Example 3> As shown in Table 1, the influence on the quality of copolymer (D) is shown.

<Example 8-9 and Comparative Example 4> As shown in Table 1, the influence of the amount of polyamide on quality is shown.

<Effects of the Invention> The thermoplastic resin composition of the present invention has excellent impact resistance and weather resistance, and has extremely high practical value as a material for various industrial parts.

Claims (1)

[Claims] (A) polyamide, (B) aromatic vinyl monomer 4 in the presence of a rubbery polymer.
A graft copolymer obtained by graft polymerization of a monomer consisting of 0 to 100% by weight and 0 to 60% by weight of another copolymerizable vinyl monomer, (C) aromatic vinyl monomer 5 to A copolymer consisting of 80% by weight and 95 to 20% by weight of other copolymerizable vinyl monomers, and (D) 0.1 to 30% of a tertiary ester of (meth)acrylic acid.
% by weight, 0 to 60% by weight of aromatic vinyl monomer, 99.9 to 40% by weight of vinyl cyanide monomer and/or first or second ester monomer of (meth)acrylic acid, and A copolymer consisting of 0 to 59.9% by weight of other copolymerizable vinyl monomers, and the total amount of (A), (B), (C) and (D) is 100%.
As parts by weight, (A) 10 to 89.9 parts by weight, (B) 1
A thermoplastic resin composition prepared by mixing 0 to 60 parts by weight, (C) 0 to 79.9 parts by weight, and (D) 0.1 to 30 parts by weight.