JPH0264152A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition outstanding in the appearance of the molded products therefrom and chemical resistance, thus suitable as a material for a variety of industrial parts by blending a polyamide with a specific styrene resin in specified proportion. CONSTITUTION:The objective composition comprising (A) 5-90 pts.wt. of a polyamide, 90-0 pts.wt. of (B) a graft copolymer prepared by copolymerization in the presence of a rubbery polymer, between B1: 10-100wt.% of an aromatic vinyl monomer and B2: 90-0wt.% of another vinyl monomer copolymerizable therewith and/or (C) a copolymer from C1: 10-100wt.% of the component B1 and C2: 90-0wt.% of the component B2, and 0.1-95 pts.wt. of (D) a graft copolymer prepared by copolymerization in the presence of a rubbery polymer, between D1: 10-99.9wt.% of the component B1, D2: 0.1-30wt.% of vinylpyridine and/or vinylpyrrolidone, and D3: 89.9-0wt.% of another vinyl monomer copolymerizable therewith and/or (E) a copolymer from E1: 10-99.9wt.% of the component B1, E2: 0.1-30wt.% of the component D2 and E3: 89.9-0wt.% of the component D3.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a composite thermoplastic resin composition of polyamide and styrene resin that has excellent molded product appearance and chemical resistance.

<Conventional technology> Polyamide resin has excellent moldability, heat resistance, mechanical strength, chemical resistance, abrasion resistance, etc., so it is used for mechanical parts, electrical and
Although it is widely used in electronic parts and automobile parts, it has problems such as a decrease in notched impact strength in dry conditions and dimensional changes due to moisture absorption. On the other hand, high-impact polystyrene (HIPS), which is a rubber-reinforced styrene resin, 7-crylonitrile-butadiene-styrene copolymer (ABS resin), and rubber components of ABS resin, ethylene-propylene rubber, and acrylic rubber have been substituted. ABS resin and AA
S resin is also widely used in automobile parts, electrical equipment parts, office equipment parts, etc., and although it has excellent impact resistance and dimensional stability, it has the problem of relatively poor chemical resistance.

Polyamide and A
It has been proposed to melt and mix styrene-based resins such as BS resin (Japanese Patent Publication No. 38-23476, etc.), but the compatibility between polyamide and styrene-based resin is poor, and molded products exhibit delamination, resulting in poor impact strength. It is known that only low materials can be obtained.

In order to improve the compatibility between polyamide and styrene resin, it has been proposed to introduce and modify functional groups such as carboxylic acid and amide groups that have reactivity or affinity with polyamide into ABS resin (Unexamined Japanese Patent Publication No. (1984-11159, JP-A-5832656, JP-A-58-93745, etc.), but impact strength and delamination are improved by introducing functional groups;
A problem arises in that flow marks occur on the surface of the molded product, spoiling its appearance.

<Problems to be Solved by the Invention> As a result of intensive study on improving the above-mentioned quality problems in polyamide-styrene resin compositions, the present inventors found that vinylpyridine and/or The inventors have discovered that by introducing vinylpyrrolidone and mixing it with polyamide in a specific ratio, a material with extremely excellent molded product appearance and chemical resistance can be obtained, and has thus arrived at the present invention.

Means for Solving the Problems> That is, the present invention comprises: (A) a polyamide; (B) a rubbery polymer (b-1); A monomer consisting of 90 to 0% by weight of another vinyl monomer copolymerizable with
), in the presence of (C) rubbery polymer (c-1), 90 to 99.9% by weight of an aromatic vinyl monomer, vinylpyridine and/or vinyl A graft copolymer obtained by copolymerizing a monomer (c-2) consisting of 0.1 to 30% by weight of pyrrolidone and 899 to 0% by weight of another vinyl monomer copolymerizable; (D) Aromatic Group vinyl monomer 90-100% by weight (
E) Aromatic vinyl monomer 90-99.9% by weight vinylpyridine and/or vinylpyrrolidone 0.1-99.9% by weight
Other vinyl monomers copolymerizable with 30% by weight89.9
A copolymer obtained by polymerizing ~0% by weight, (A), (B), (C), (D) and (
The total amount of E) is 100 parts by weight, (A) 5 to 90i
A molded product obtained by mixing 90 to 0 parts by weight of CB) and/or (D) and 0.1 to 95 parts by weight of (C) and/or (E) has excellent appearance and chemical resistance. The purpose is to provide materials that

Hereinafter, the present invention will be explained in detail.

The polyamide (A) used in the present invention includes ethylene diamine, diaminobutane, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2
, 2.4- and 2°4.4-)limethylhexamethylenediamine, l,3 and 1,4-bis(aminomethyl)cyclohexane, bis(P-aminocyclohexyl)
Aliphatic, alicyclic, and aromatic diamines such as methane, metaxylylene diamine, and paraxylylene diamine, and aliphatic and alicyclic diamines such as adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. , aromatic dicarboxylic acid; ε
- Polyamides obtained by ring-opening polymerization of lactams such as caprolactam and ω-dodecalactam, polyamides derived from 6-aminocaproic acid, 11-amineundecanoic acid, 12-niaminododecanoic acid, etc., copolyamides and mixed polyamides of these Examples include.

Polycaproamide (nylon 6), polydodecamide (nylon 12), polytetramethylene adipamide (nylon 46), and polyhexamethylene adipamide (nylon 6) are industrially produced at low cost and in large quantities.
6) Polyhexamethylene sebamide (nylon 610
), and copolymers thereof, such as nylon 6/6
6 (“/” means copolymer), nylon 6/610, nylon 6/12, nylon 66/1
2, 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 98% concentrated sulfuric acid Loom
/ and measured at 25°C, the same applies hereinafter) is 1.0 to 6.
Any polyamide within the range of 0 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 three or more functional groups capable of forming a polyamide, such as bis(ω-aminohexyl)amine, diethylenetriamine, trimesic acid, and bislactam, to the raw material. Polymerization methods include melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and combinations of these methods, with melt polymerization being generally the most suitable. Further, particularly when the polyamide raw material is a lactam, the polymer may be obtained by anionic polymerization.

The rubbery polymers used in the graft copolymer (B) in the present invention include diene rubbery polymers such as polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, and ethylene-propylene copolymers. , ethylene-propylene-nonconjugated diene copolymer, acrylic rubbery polymer, chlorinated polyethylene, and other non-diene rubbery polymers are exemplified, and one or more of them can be used. These rubbery polymers are produced by emulsion polymerization, solution polymerization, bulk polymerization, suspension 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 particle size is 0.1 to 1 μm and the gel content is 0 to 95%.
It is preferable that

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, and p-methylstyrene.
Examples include -methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromustyrene, dibromustyrene, vinylnaphthalene, etc., and one or more types can be used.

Other vinyl monomers that can be copolymerized with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile, methacrylatetrile, fumaronitrile, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2 - Methacrylic acid ester monomers such as ethylhexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate, acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, maleimide , N-phenylmaleimide, N-cyclohexylmaleimide and the like are exemplified, and one or more types of each can be used.

The graft copolymer CB) contains 90 to 100% by weight of an aromatic vinyl monomer and 90 to 0% by weight of other vinyl monomers that can be copolymerized in the presence of the rubbery polymer (b-1). It can be obtained by copolymerizing monomer (b-2) consisting of:

Rubber-like polymer (b-1) in graft copolymer CB)
) and the monomer (b-2>), although there is no particular restriction on the ratio, rubbery polymer (b 1 ) 20 to 80% by weight,
It is preferable that the monomer (b-2) is 80 to 20% by weight.

The composition of monomer (b-2) is preferably 30 to 100% by weight of aromatic vinyl monomers and 70 to 0% by weight of other vinyl monomers.

The graft copolymer (C) in the present invention is basically the same as the graft copolymer (B), except that it has been modified with vinylpyridine and/or vinylpyrrolidone.

The graft copolymer (C) contains 90 to 0% by weight of an aromatic vinyl monomer and 0.1 to 30% of vinylpyridine and/or vinylpyrrolidone in the presence of the rubbery polymer (CI).
It is obtained by copolymerizing a monomer (C-2) consisting of 899% to 0% by weight of another vinyl monomer.

Rubber-like polymer (C-1) in graft copolymer (C)
) and the monomer (C-2) is not particularly limited, but the rubbery polymer (C-1) is 20 to 80% by weight and the monomer (C-2) is 80 to 20% by weight. It is preferable that there be.

The composition of the monomer (C-2) is 30 to 99.9% by weight of aromatic vinyl monomer, 001 to 20% by weight of vinylpyridine and/or vinylpyrrolidone, and 0% of other vinyl monomer. ~69.9% by weight is preferred.

In addition, the rubber-like polymer (C-1), aromatic vinyl monomer, and other vinyl monomers used in the graft copolymer (C) are listed in the section of the graft copolymer (B). The same ones as those exemplified can be mentioned, and each can be used alone or in two or more kinds.

As vinylpyridine, 2-vinylpyridine, 4-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-vinylpyridine,
Examples include methyl-5-vinylpyridine, which can be used alone or in combination of two or more, with 2-vinylpyridine and/or 4-vinylpyridine being particularly preferred.

Examples of vinylpyrrolidone include ■-vinyl-2-pyrrolidone, 3-vinyl-2-pyrrolidone, 1-vinyl-3-methyl-2-pyrrolidone, and ■-vinyl-4-methyl-2-pyrrolidone.
Examples include pyrrolidone and 1-vinyl-5-methyl-2-pyrrolidone, which may be used alone or in combination of two or more, with 1-vinyl-2-pyrrolidone being particularly preferred.

In the present invention, the copolymer CD) refers to 90 to 100% by weight of an aromatic vinyl monomer, 90 to 0% by weight of other copolymerizable vinyl monomers, and 100% by weight of other copolymerizable vinyl monomers. A copolymer consisting of 85 to 0% by weight of a vinyl monomer is preferred.

The monomers used in the copolymer CD) are the same as those exemplified in the section of the graft copolymer CB), and each can be used alone or in two or more kinds.

Copolymer (E) in the present invention is basically the same as copolymer CD), except that it is modified with vinylpyridine and/or vinylpyrrolidone.

Copolymer (E) is an aromatic vinyl monomer of 90 to 99.9
It can be obtained by copolymerizing a monomer consisting of 0.1-30% by weight of vinylpyridine and/or vinylpyrrolidone and 89.9-0% by weight of other copolymerizable vinyl monomers. , especially aromatic vinyl monomers 15 to 99
．． 9% by weight, vinylpyridine and/or vinylpyrrolidone 20-0.1% by weight, other vinyl monomers 84.
Preference is given to copolymers consisting of 9 to 0% by weight.

The aromatic vinyl monomer and other copolymerizable vinyl monomers used in the copolymer (E) are the same as those exemplified in the section of the graft copolymer (B). Each can be used alone or in combination.

In addition, as vinylpyridine and vinylpyrrolidone, the same ones as those exemplified in the section of the graft copolymer (C) can be mentioned, and each can be used alone or in combination of two or more, but in particular, 2-vinylpyridine, 4-vinylpyridine, -vinylpyridine and/or l-vinyl-2-pyrrolidone are preferred.

In addition, the graft copolymers (B), (C) and the copolymer (D
) and (E) outside the ranges shown above, the appearance or chemical resistance of the molded product of the final composition will be degraded.

Graft copolymers (B), (C) and copolymers CD)
, (E) are known emulsion polymerization,
Suspension polymerization, solution polymerization, bulk polymerization, or a combination of these methods is used.

In the present invention, the mixed composition of polyamide (A), graft copolymer CB), graft copolymer (C), copolymer (D), and copolymer (E) is (A), (B).

When the total amount of (C), (D) and (E) is 100 parts by weight, (A) 5 to 90 parts by weight, preferably 10 to 8 parts by weight.
0 parts by weight, (B) and/or (D) 90-0 parts by weight, preferably 80-0 parts by weight, (C) and/or (E) 0.1-95 parts by weight, preferably 1
~80 parts by weight.

When the polyamide (A) is less than 5 parts by weight or exceeds 90 parts by weight, or the graft copolymer (C) and/or copolymer (E) exceeds 95 parts by weight, or less than O,t The thermoplastic resin composition of the present invention cannot achieve the extremely good balance between appearance and chemical resistance, which are the characteristics of the thermoplastic resin composition of the present invention.

There is no restriction on the mixing order of the polyamide (A), the graft copolymers CB), (C), and the copolymers (D), (E), and the following methods are exemplified.

After premixing the copolymer (E), the graft copolymer (B) and/or the copolymer CD) are mixed.

(3) After premixing the graft copolymer (C) and/or copolymer (E) and the graft copolymer (B) and/or copolymer CD), the polyamide (A) is mixed.

Also, there are no restrictions on the form of the mixture, such as latex, powder pellets, etc.

As a mixing method, a known method such as a Banbury mixer roll or an extruder can be employed.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these Examples.

〔polyamide〕

A-1: Nylon 6, concentrated sulfuric acid relative viscosity 2.6A-2; Nylon 6, 〃3.1 A-3: Nylon 66, 〃3. O [Reference example 13
Preparation of graft copolymer (B)-1: 50 parts (solid content) of polybutadiene latex (PBDE) with an average particle size of 0.4 μ and a gel content of 82% and 100 parts of pure water in a reactor purged with nitrogen. I prepared it. After adding 0.3 parts of potassium persulfate, the temperature was raised to 68°C, and a monomer solution consisting of 15 parts of acrylonitrile, 35 parts of styrene, and 0.25 parts of tertiary dodecyl mercaptan, 2.0 parts of potassium rosinate, and water were added. 20 parts of an aqueous emulsifier solution containing 0.05 part of sodium oxide were continuously added over 4.5 hours to each. Thereafter, the temperature of the polymerization system was raised to 70''C, and the polymerization was completed by aging for 3 hours.

B-2: Ethylene-propylene-ethylidene norbornene copolymer (EPDM, iodine number 211, Mooney viscosity 7
An AES graft copolymer consisting of 50 parts of propylene (50% propylene content), 15 parts of acrylonitrile, and 35 parts of styrene was prepared by a known solution polymerization method.

B-3: AAS graft copolymerization by copolymerizing 15 parts of acrylonitrile and 35 parts of styrene by emulsion polymerization in the presence of 50i (solid content) of cross-linked polybutyl acrylate latex (PBA) with an average particle size of 0.3 μm. Created a union.

[Reference Example 2] Creation of graft copolymer (C) C-1,
C-5: Graft copolymer (C) was prepared in the same manner as graft copolymer CB-1) except that the composition of the mixed monomers was changed as shown in Table 1.

Graft copolymers B-1, B-3, and C1 to C-5 were each treated with magnesium sulfate after adding 1 part of Sumilizer NW and 2 parts of yohytris nonylphenyl phosphite as an antioxidant per 100 parts of latex solid content. Salting out was carried out using , followed by separation and recovery. Graft copolymer B2
was precipitated into methanol, then separated and collected.

[Reference Example 3] Preparation of copolymer CD)-1: 120 parts of pure water and 0.3 parts of potassium persulfate were charged into a reactor purged with nitrogen, and the temperature was raised to 68°C while stirring. Then 30 parts of acrylonitrile, 7 parts of styrene
A mixed monomer solution consisting of 0 parts and 0.3 parts of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2.0 parts of potassium rosinate and 0.05 parts of sodium hydroxide were each continuously added over 5 hours. , then the polymerization system was heated to 70°C.
The temperature was raised to 1, and the polymerization was completed by aging for 3 hours. After salting out using calcium chloride, it was separated and collected.

[Reference Example 4] Preparation of copolymer (E) E-1 to E-6: Copolymer (D) was prepared in the same manner as copolymer (D) except that the composition of the mixed monomer was changed as shown in Table 2. Polymer (E)
It was created.

[Reference Example 5] Creation of maleic anhydride-modified copolymer (F) F-1: Using a modified copolymer (F) consisting of 60 parts of styrene, 35 parts of acrylonitrile, and 5 parts of maleic anhydride as an initiator, benzoyl peroxide , was created by a solution polymerization method using methyl ethyl ketone as a solvent.

E-1 to E-6 were separated and collected after salting out using calcium chloride. Maleic anhydride-modified copolymer F-1 was precipitated into methanol and then separated and recovered.

[Example] Polyamide (A), the graft copolymer and copolymer prepared in Reference Example were mixed at the blending ratio shown in Table 3, and 40
The mixture was melt-mixed and granulated using a twin-screw extruder with a blade diameter. In addition,
The granulation temperature is 250°C when using nylon 6.
When nylon 66 was used, the temperature was set at 280'C.

The physical properties of the obtained resin composition were measured by the following method,
The results are shown in Table 3.

0 Molded product appearance: 150sri+x 150mx 3.
18 molded products were molded, and their appearance (presence or absence of fluoromarks) was visually evaluated. In addition, the presence or absence of delamination was visually determined for the same molded product by a cross-cut test using an adhesive tape.

0 Chemical resistance: A molded product measuring 1501 m x 20 fi x 3 WM was fixed to a cantilever jig, subjected to a deflection of 3Q+n+, and then immersed in various chemicals for 24 hours to determine the presence or absence of cracks.

The above test pieces for quality evaluation were made using a 3.5-ounce injection molding machine, and the cylinder temperature was 250"C for the nylon 6 blend system and 2"C for the nylon 66 blend system.
Molding was carried out at a temperature of 80″C.

<Examples 1 to 9 and Comparative Examples 1 to 3> Table 3 shows the influence of vinylpyridine or vinylpyrrolidone on the quality.

<Examples 10 to 11 and Comparative Example 4> Table 3 shows the influence of the amount of polyamide (A) on quality.

<Examples 12 to 13> As shown in Table 3, examples using various graft copolymers CB) are shown.

<Examples 14-15 and Comparative Examples 5-6> As shown in Table 3, examples using various nylons are shown.

Table (1) PBDE...Polybutadiene Table *Maleic anhydride <Effects of the invention> The thermoplastic resin composition of the present invention has excellent chemical resistance and a good appearance of molded products, and is suitable for various industrial parts. It has extremely high practical value as a material for industrial use.

Claims (1)

Scope of Claims: (A) polyamide; (B) 90 to 0% of other vinyl monomer copolymerizable with 10 to 100% by weight of an aromatic vinyl monomer in the presence of a rubbery polymer; (C) In the presence of a rubbery polymer, 10 to 99.9% by weight of an aromatic vinyl monomer, vinylpyridine and/or A graft copolymer obtained by copolymerizing a monomer consisting of 0.1 to 30% by weight of vinylpyrrolidone and 89.9 to 0% by weight of another copolymerizable vinyl monomer, (D) aromatic vinyl A copolymer obtained by polymerizing 10 to 100% by weight of a vinyl monomer and 90 to 0% by weight of another copolymerizable vinyl monomer, (E) 10 to 99.9% of an aromatic vinyl monomer. Weight %, vinylpyridine and/or vinylpyrrolidone 0.1~
Other vinyl monomers copolymerizable with 30% by weight89.9
5 to 90 parts by weight of (A), with the total amount of (A), (B), (C), (D) and (E) being 100 parts by weight. Department, (B)
and/or (D) 90 to 0 parts by weight and (C) and/
or (E) a thermoplastic resin composition mixed in a proportion of 0.1 to 95 parts by weight.