JP2556748B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a polycarbonate resin, a polyamide resin,
Rubber-reinforced styrene resin, α. The present invention relates to a thermoplastic resin composition which is composed of a β-unsaturated carboxylic acid modified copolymer and is excellent in chemical resistance and impact resistance (notched Izod).

<Prior Art> Polycarbonate resins are engineering plastics having excellent heat resistance and good mechanical properties, and are widely used in various fields. However, there are drawbacks that the molding temperature is high, the fluidity is poor, and the impact strength is highly dependent on the thickness. Therefore, in order to improve these drawbacks, it has been proposed to blend a polycarbonate resin with a styrene resin such as an ABS resin. (Japanese Patent Publication Sho 38-
15225, Japanese Examined Patent Publication No. 39-71, Japanese Examined Patent Publication No. 51-2454) However, none of the compositions has sufficient chemical resistance, which is important as a practical property of a molding material, and particularly as a molding method for a thermoplastic resin composition. In the most common injection molding, stress cracks due to chemicals due to residual strain of molded products are likely to occur.

<Means for Solving Problems> The inventors of the present invention have diligently studied improvement of the above-mentioned quality problems of the composition comprising a polycarbonate resin and a rubber-reinforced styrene resin, and as a result, a polycarbonate resin,
A thermoplastic resin composition having excellent chemical resistance and impact resistance (notched Izod) can be obtained by mixing a polyamide resin, a rubber-reinforced styrene resin and a specific carboxylic acid-modified copolymer in a specific ratio. Find out
The present invention has been reached.

That is, the present invention relates to an aromatic vinyl monomer 10 in the presence of (A) a polycarbonate resin, (B) a polyamide resin, and (C) a rubber-like polymer.
-90% by weight, vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer 10-90% by weight, and other copolymerizable vinyl-based monomer 0-40% by weight A rubber-reinforced styrene resin copolymerized with (D) 10 to 89.9% by weight of an aromatic vinyl monomer, 10 to 89.9% by weight of a cyanide vinyl monomer and / or a methacrylic acid ester monomer, α. β-unsaturated carboxylic acid 0.1
20% by weight and other copolymerizable vinyl monomer 0
Carboxylic acid-modified copolymer consisting of 39.9% by weight, (E) 10-90% by weight of aromatic vinyl-based monomer, 10-90% by weight of vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer , And a styrene resin comprising 0 to 40% by weight of another copolymerizable vinyl monomer, and the total amount of (A), (B), (C), (D) and (E) is 100% by weight. (A) 20 to 80 parts by weight, (B) 5
~ 60 parts by weight, (C) + (D) 75 to 10 parts by weight, (E) 0
50 parts by weight, and the rubbery polymer in the total composition is 5 to 40% by weight, α. The present invention provides a thermoplastic resin composition containing β-unsaturated carboxylic acid in a proportion of at least 0.01% by weight, which is excellent in chemical resistance and impact resistance.

 Hereinafter, the present invention will be described in detail.

Examples of the polycarbonate resin (A) include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally, a polymer of bisphenol such as 2.2-bis (4-oxyphenyl) alkane type, bis (4-oxyphenyl) ether type, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide type, or copolymer It is a combination, and a polymer or a copolymer using bisphenols substituted with halogen may be used depending on the purpose.

The molecular weight of the polycarbonate resin (A) is not particularly limited, but one having a viscosity average molecular weight of 10,000 to 100,000 is preferable.
The production method is also not particularly limited, and the phosgene method, transesterification method, etc. are used.

As the polyamide resin (B) used in the present invention,
Ethylenediamine, diaminobutane, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,3 and 1,4-bis (aminomethyl) cyclohexane, Aliphatic and alicyclic aromatic diamines such as bis (P-aminocyclohexyl) methane, metaxylylenediamine, and paraxylylenediamine and adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid Polyamides derived from aliphatic, alicyclic and aromatic dicarboxylic acids, polyamides obtained by ring-opening polymerization of lactams such as ξ-caprolactam and ω-dodecaractam, 6-aminocaproic acid,
Examples thereof include polyamides derived from 11-aminoundecanoic acid, 12-aminododecanoic acid and the like, copolyamides of these, and mixed polyamides.

Polycaproamide (nylon 6), polydodecaamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 6) in the sense that they are industrially manufactured inexpensively and in large quantities.
6), polyhexamethylene sebacamide (nylon 610),
And copolymers thereof, such as nylon 6/66 (“/”
Mark means copolymer), nylon 6/61
0, nylon 6/12, nylon 66/12, nylon 6/66/610/1
2 and their mixtures are useful. A bis (P-aminocyclohexyl) methane / terephthalic acid / isophthalic acid type polyamide is also useful.

There is no limitation on the degree of polymerization of the polyamide resin used, and the relative viscosity of concentrated sulfuric acid (polymer 1 g is 98% concentrated sulfuric acid 100 ml).
A polyamide which is dissolved in, and is measured at 25 ° C., and the same hereinafter) is within the range of 1.8 to 6.0 can be arbitrarily selected.

There is no limitation on the molecular structure of the polyamide resin, and any of linear polyamide, branched polyamide and the like may be used. A linear polyamide is produced by an ordinary method, but a branched polyamide is a branching agent having three or more functional groups capable of forming a polyamide in a raw material, such as bis (ω-aminohexyl) amine, diethylenetriamine, trimesic acid, and bislactam. Is added in a small amount to polymerize.

In Nylon-6, the ratio of the terminal amino group to the terminal carboxyl group is not particularly limited and any one can be used.

As a polymerization method, a melt polymerization, an interfacial polymerization, a solution polymerization, a bulk polymerization, a solid phase polymerization and a method combining these methods are used, and in general, the melt polymerization is most suitable. Further, particularly when the polyamide raw material is a lactam, a polymer may be obtained by anionic polymerization.

The rubber-reinforced styrene resin (C) in the present invention is 10 to 90% by weight of an aromatic vinyl monomer, a vinyl cyanide monomer and / or a methacrylic acid ester monomer in the presence of a rubbery polymer. It is produced by copolymerizing a monomer mixture consisting of 10 to 90% by weight of a polymer and 0 to 40% by weight of another copolymerizable vinyl monomer.

As the rubbery polymer, polybutadiene having a glass transition temperature of 0 ° C. or lower, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, acrylic ester copolymer, chlorinated polyethylene. Etc. are illustrated, and it can be used individually or in 2 or more types. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like. The particle size and gel content of the rubber-like polymer when produced by emulsion polymerization are not particularly limited, but the average particle size is 0.1 to 1 μm and the gel content is 0 to 95%.
It is desirable that

As the aromatic vinyl-based monomer, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene,
Dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, etc., as the methacrylic acid ester-based monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, etc., as the vinyl cyanide-based monomer. Examples of acrylonitrile, methacrylonyl, fumaronitrile, etc. can be used alone or in combination of two or more. Among them, styrene, α-methylstyrene,
Acrylonitrile and methyl methacrylate are preferred.

Other copolymerizable monomers include maleimide, N-
Examples include maleimide-based monomers such as phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide, and acrylic ester-based monomers such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, each of which may be used alone or It can be used in two or more kinds.

If the composition of the monomer is out of the above range, the compatibility between the rubber-reinforced styrene resin (C) and the carboxylic acid-modified copolymer (D) is poor, so that the impact strength when mixed with a polycarbonate resin or a polyamide resin is lowered. To do.

The ratio of the rubber-like polymer and the monomer is not particularly limited, but it is preferably 20 to 80% by weight of the rubbery polymer and 80 to 20% by weight of the monomer (total amount). The graft ratio is not particularly limited, but is preferably 20 to 100%. As the graft polymerization method, known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof may be used.

Carboxylic acid-modified copolymer (D) used in the present invention
Is 10 to 89.9% by weight of aromatic vinyl-based monomer, 10 to 89.9% by weight of vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer, and α. β-unsaturated carboxylic acid 0.1-2
0 wt% and other copolymerizable vinyl monomers 0-39.
It is a copolymer composed of 9% by weight. When the composition of the monomer is out of the above range, the compatibility with the styrene resin (E) is poor, which is not preferable.

Examples of the aromatic vinyl-based monomer, vinyl cyanide-based monomer, methacrylic acid ester-based monomer and other copolymerizable vinyl-based monomer that compose the carboxylic acid-modified copolymer (D) include Examples thereof include those exemplified in the above-mentioned rubber-reinforced styrenic resin (C), and each can be used alone or in combination of two or more, but styrene, α-methylstyrene, acrylonitrile and methylmethacrylate are preferable, and , Α. As β-unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Itaconic acid and anhydrides of dicarboxylic acids are exemplified, and they can be used alone or in combination of two or more. Of these, methacrylic acid and (anhydrous) maleic acid are particularly preferable.

Particularly preferred are 59.9 to 80% by weight of aromatic vinyl-based monomers, 19.9 to 40% by weight of vinyl cyanide-based monomers and / or methacrylic acid ester-based monomers, and α. The β-unsaturated carboxylic acid is 0.1 to 15% by weight.

As the method for producing the carboxylic acid-modified copolymer (D), known emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, or a combination thereof may be used. In addition, α. The method for adding the β-unsaturated carboxylic acid is also not particularly limited, and a method of adding the β-unsaturated carboxylic acid to the polymerization system by mixing with another monomer, a method of adding it as an aqueous solution, and the like are used.

The molecular weight is also not particularly limited, but the weight average molecular weight is preferably 10,000 to 1,000,000.

The styrene resin (E) in the present invention comprises 10 to 90% by weight of an aromatic vinyl monomer, 10 to 90% by weight of a vinyl cyanide monomer and / or a methacrylic acid ester monomer,
It is a resin composed of 0 to 40% by weight of another copolymerizable vinyl monomer. Aromatic vinyl-based monomers, vinyl cyanide-based monomers, methacrylic acid ester-based monomers and other copolymerizable vinyl-based monomers are exemplified in the section of rubber-reinforced styrene-based resin (C). Examples thereof include those mentioned above, which may be used alone or in admixture of two or more, and styrene, α-methylstyrene, acrylonitrile and methyl methacrylate are particularly preferable. The composition of the present invention comprises the above-mentioned polycarbonate resin (A), polyamide resin (B),
Assuming that the total amount of the rubber-reinforced styrene resin (C), the carboxylic acid-modified copolymer (D) and the styrene resin (E) is 100 parts by weight, (A) 20 to 80 parts by weight, (B) 5 to 60 parts by weight Parts, (C) + (D) 75-10 parts by weight and (E) 0-50 parts by weight.

Outside this range, the excellent chemical resistance and impact resistance aimed at by the present invention cannot be obtained.

Further, the content of the rubber-like polymer in the composition of the present invention is 5 to 40% by weight, and α. The β-unsaturated carboxylic acid content is at least 0.01% by weight. If the rubber-like polymer is less than 5% by weight, the impact strength will be poor, and if it exceeds 40% by weight, the moldability will be poor. If the β-unsaturated carboxylic acid is less than 0.01% by weight, the impact strength will decrease, which is not preferable.

There is no limitation on the mixing order of the polycarbonate resin (A), the polyamide resin (B), the rubber-reinforced styrene resin (C), the carboxylic acid-modified copolymer (D) and the styrene resin (E) and the state thereof. pellet,
Depending on the form of beads, powder, etc. (A), (B),
Simultaneous simultaneous mixing of the five components (C), (D) and (E),
An example is a method of premixing specific components and then mixing the remaining components. As a mixing method, a known method such as a Banbury mixer, a roll or an extruder can be adopted.

In addition, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants, glass fibers, metal fibers, carbon fibers, metal flakes, etc. may be added when necessary during mixing. Agents, reinforcing agents and fillers can be added. Further, a thermoplastic resin such as polyacetal, polyester, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can be appropriately blended.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The number of parts and the percentage are shown on a weight basis.

Further, various resins used in Examples and Comparative Examples were obtained by the following methods.

-Polycarbonate resin (A) -Caliber 300-10 manufactured by Sumitomo Nogatac-Polyamide resin (B) -B-1: Uchinichika nylon A-1030BRL manufactured by Unitika
(6-Nylon) B-2: Unitika's Uchinichika Nylon A-125 (66
-Nylon) -Rubber-reinforced styrene resin (C) -C-1: 12 parts of acrylonitrile by an emulsion polymerization method in the presence of 60 parts (solid content) of polybutadiene latex having an average particle diameter of 0.45 µ and a gel content of 83%. ABS graft copolymer latex (graft ratio 3
5%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.33) was prepared. The intrinsic viscosity was measured at 30 ° C. in dimethylformamide. (Unit: 100 ml / g, the same applies hereinafter.) C-2: An ABS graft copolymer latex composed of 50 parts of polybutadiene, 15 parts of acrylonitrile and 35 parts of styrene in the same manner as C-1 (graft ratio 55%, free acrylonitrile- A styrene copolymer with an intrinsic viscosity of 0.58) was produced.

C-3: In the presence of 50 parts (solid content) of cross-linked polybutyl acrylate latex having an average particle size of 0.3 μm, 15 parts of acrylonitrile and 35 parts of styrene were copolymerized by an emulsion polymerization method to form an AAS graft copolymer latex (graft Rate 50
%, Free acrylonitrile-styrene copolymer intrinsic viscosity 0.36) was produced.

C-4: AES graft copolymer consisting of 50 parts of ethylene-propylene-ethylidene norbornene copolymer (EPDM, iodine value 21, Mooney viscosity 75, propylene content 50%), acrylonitrile 15 parts and styrene 35 parts (graft ratio 52
%, The intrinsic viscosity of free acrylonitrile-styrene copolymer was 0.60) was produced by the solution polymerization method.

Graft copolymers C-1 to C-3 were each added with 1 part of Sumilizer NW and 2 parts of trinolylphenyl phosphite as an antioxidant per 100 parts of latex solid content, and then salting out with magnesium sulfate. It was separated and collected. The graft copolymer C-4 was separated and recovered after being precipitated in methanol.

-Carboxylic Acid Modified Copolymer (D) -D-1: Nitrogen-substituted reactor was charged with 120 parts of pure water and 0.3 part of potassium persulfate, and then heated to 65 ° C with stirring. Thereafter, 30 parts of acrylonitrile, 65 parts of styrene, 5 parts of methacrylic acid and 0.3 part of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecyl sulfonate were continuously added for 5 hours each, and then the polymerization system was added. Was heated to 70 ° C. and aged for 3 hours to complete the polymerization, to produce a copolymer having an intrinsic viscosity (in dimethylformamide, 30 ° C.) of 0.56.

D-2: In the same manner as D-1, 25 parts of acrylonitrile, 60 parts of styrene and 15 parts of methacrylic acid have an intrinsic viscosity of 0.65
Was produced.

D-3: In the same manner as D-1, 23 parts of acrylonitrile, 52 parts of styrene and 25 parts of methacrylic acid have an intrinsic viscosity of 0.68
Was produced.

Each carboxylic acid-modified copolymer was separated and recovered after salting out with calcium chloride.

-Styrenic resin (E) -Similar to D-1, acrylonitrile 30 parts, styrene
A copolymer having an intrinsic viscosity of 0.55 consisting of 70 parts was produced.

The styrene resin E was separated and recovered after salting out with magnesium sulfate.

Examples and Comparative Examples The above-mentioned polycarbonate resin (A), polyamide resin (B), rubber-reinforced styrene-based resin (C), carboxylic acid-modified copolymer (D) and styrene-based resin (E) are used as the first to first examples.
The mixture was mixed with the composition shown in Table 2, melt-mixed and granulated using a 40 mm twin-screw extruder. The granulation temperature is 250 ° C for the 6-nylon blend system and 2 for the 66-nylon blend system.
The temperature was set at 80 ° C.

The physical properties of the obtained resin composition were measured by the following methods, and the results are shown in Tables 1 and 2.

Impact strength (notched Izod): ASTM D-256 (23
℃) Chemical resistance: 150mm × 20mm × 3mm molded product is fixed to a jig with a single-sided stick, and after being bent for 30mm, it is exposed to various chemicals.
It was immersed for a time and the presence or absence of cracks was determined.

The test pieces for quality evaluation were molded by using a 3.5 ounce injection molding machine with the cylinder temperature set to 250 ° C. for the 6-nylon blend system and 280 ° C. for the 66-nylon blend system.

<Examples 1 to 3, Comparative Examples 1 to 3>: Shows the effect of polycarbonate.

<Examples 4 to 6, Comparative Examples 3 to 4>: The effects of polyamide are shown.

<Examples 7 to 8 and Comparative Examples 5 to 6>: The effects of the carboxylic acid-modified copolymer are shown.

<Examples 9 to 11>: The effect of the rubber-reinforced styrene resin is shown.

<Example 12>: Shows the influence of the type of polyamide.

<Examples 13 to 14, Comparative Examples 7 to 8>: Shows the influence of the amount of rubber.

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 55/02 LMF C08L 55/02 LMF 77/00 LQS 77/00 LQS LQU LQU

Claims (1)

(57) [Claims] 1. An aromatic vinyl monomer 10 in the presence of (A) a polycarbonate resin, (B) a polyamide resin (excluding polyether ester amide), and (C) a rubber-like polymer.
-90% by weight, vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer 10-90% by weight, and other copolymerizable vinyl-based monomer 0-40% by weight (D) 10-89.9% by weight of aromatic vinyl-based monomer, 10-89.9% by weight of vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer, α , Β-unsaturated carboxylic acid 0.1
20% by weight and other copolymerizable vinyl monomer 0
Carboxylic acid-modified copolymer consisting of 39.9% by weight, (E) 10-90% by weight of aromatic vinyl-based monomer, 10-90% by weight of vinyl cyanide-based monomer and / or methacrylic acid ester-based monomer And a styrene resin comprising 0 to 40% by weight of another copolymerizable vinyl monomer, and the total amount of (A), (B), (C), (D) and (E) is 100 parts by weight. (A) 20 to 80 parts by weight, (B) 5
~ 60 parts by weight, (C) + (D) 75 to 10 parts by weight, (E) 0
The rubber-like polymer is contained in an amount of 5 to 40% by weight and the α, β-unsaturated carboxylic acid is contained in an amount of at least 0.01% by weight in the total composition. A thermoplastic resin composition comprising: