JPH0674368B2 - Resin composition for molded articles having a textured surface - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a resin composition for a molded product having an embossed surface excellent in impact resistance, molding processability, chemical resistance and mold transferability. .

<Prior Art> Acrylonitrile-butadiene-styrene copolymer resin) has excellent impact resistance and molding processability, and is widely used as a molding resin. However, its chemical resistance and heat resistance are not sufficient, and its use is restricted under severe conditions.

Aromatic polyester resin (hereinafter abbreviated as polyester) has excellent mechanical properties, electrical properties, chemical resistance,
It has heat resistance, low hygroscopicity, workability, etc., and is widely used as an engineering plastic, but it has the drawback of poor impact resistance.

A blend with an ABS resin has been proposed to improve the impact resistance of polyester (for example, JP-A-49-97081, JP-A-56-14546, JP-A-57-117556, and JP-A-57-137350, JP-A-60-36558, JP-A-60-123550 and the like).

Also proposed is a blend of polyester with a graft copolymer obtained by graft-copolymerizing an α, β-unsaturated dicarboxylic acid anhydride or an unsaturated carbonamide with a rubber-like polymer together with other monomers (for example, JP-A-49-97081, JP-A-59-138256, JP-A-60-144349, JP-A-60-262847, JP-A-61-130366).

Further, a method of adding an epoxy resin to a mixture of polyester and a diene polymer has also been proposed (JP-A-59-59).
149951 publication).

<Problems to be Solved by the Invention> However, the above method has not yielded a composition that is sufficiently satisfactory in terms of total balance of compatibility, mechanical properties and fluidity.

For example, a mere blend of ABS resin and polyester has poor compatibility and remarkably low mechanical properties.

Further, in the case of a blend of the above-mentioned graft copolymer and polyester in which a monomer having a functional group having reactivity or affinity with polyester is graft-copolymerized with another monomer into a rubber-like polymer, impact resistance is Although it can be improved, the compatibility is poor and the surface condition of the molded product is poor, so that it is not practical.

Further, when an epoxy resin is added to a mixture of polyester and a diene polymer, the epoxy resin is localized and hardened, so that the fluidity is essentially deteriorated.

The object of the present invention is to provide a resin composition for a molded product having a textured surface having the chemical resistance of polyester, heat resistance and mold transferability, and having extremely high impact resistance, without impairing the molding processability of the ABS resin. To provide.

<Means for Solving Problems> That is, the present invention has the following configuration in order to solve the above problems.

(A) (a) Diene rubber 10 to 85 parts by weight, (b) (a) aromatic vinyl 50 to 90% by weight (b) vinyl cyanide 9 to 50% by weight (c) α, β-unsaturation From a graft copolymer obtained by graft copolymerizing 90 to 15 parts by weight of a monomer mixture consisting of 0.1 to 20% by weight of a carboxylic acid, or a copolymer obtained by copolymerizing the graft copolymer with the remaining monomer. A resin composition for moldings having a textured surface, which comprises 1 to 99 parts by weight of the graft copolymer composition and 99 to 1 parts by weight of the aromatic polyester resin (B).

The feature of the present invention is that a graft copolymer (composition) obtained by graft-copolymerizing three components of aromatic vinyl, vinyl cyanide and α, β-unsaturated carboxylic acid as a graft component of a diene rubber and polyester are essential. It is to blend. By including the above-mentioned three components in the graft component, the impact resistance of the resin composition for moldings having a textured surface is sufficiently high, the melt viscosity is not increased, and the compatibility and the mold transfer property are good. And the effect of exhibiting moldability is obtained.

Hereinafter, the present invention will be specifically described.

Graft copolymer or graft copolymer composition (A) in the present invention, the total of (a) and (b) is 100 parts by weight,
Diene rubber (a) 10-85 parts by weight, aromatic vinyl (a) 50-
90% by weight and vinyl cyanide (II) 9 to 50% by weight and α, β-
Unsaturated carboxylic acid (c) 0.1 to 20% by weight is 100% by weight
A monomer mixture (b) consisting of 15 to 90 parts by weight of a graft copolymer obtained by graft-copolymerizing the whole amount or a part of the monomer mixture is graft-copolymerized and the remaining It is a graft copolymer composition with a copolymer obtained by copolymerizing monomers.

The most important thing in the present invention is to add aromatic vinyl (a), vinyl cyanide (b) and α, β-unsaturated carboxylic acid (c) in the graft copolymer or the graft copolymer composition (A). It is to use a graft copolymer obtained by graft-copolymerizing the essential monomer mixture (b) with the diene rubber (a).

As the diene rubber (a) in the present invention, polybutadiene rubber, acrylonitrile-butadiene copolymer rubber,
There are styrene-butadiene copolymer rubber, polyisoprene rubber, etc. Among them, polybutadiene rubber, styrene-
Butadiene copolymer rubber and the like are preferable.

Examples of the aromatic vinyl (a) in the monomer mixture (b) in the present invention include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, etc., among them, styrene, α-methylstyrene, etc. preferable.

Vinyl cyanide (b) in the monomer mixture (b) in the present invention
Examples thereof include acrylonitrile and methacrylonitrile, and among them, acrylonitrile is preferable.

Examples of the α, β-unsaturated carboxylic acid (c) in the monomer mixture (b) in the present invention include acrylic acid and methacrylic acid, and these can be used in combination of two or more.

Further, (a), (b), with respect to the total 100 parts by weight of the monomer of (c)
It is also possible to graft-copolymerize another monomer which can be copolymerized within the range of 70 parts by weight or less.

As another copolymerizable monomer, methyl methacrylate,
Α, β-Unsaturated carboxylic acid esters such as ethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, α, β- such as maleic anhydride and itaconic anhydride
Unsaturated dicarboxylic acid anhydrides, N-phenylmaleimide,
Α such as N-methylmaleimide, Nt-butylmaleimide,
Examples thereof include imide compounds of β-unsaturated dicarboxylic acid.

The composition ratio of the diene rubber (a) in the graft copolymer or the graft copolymer composition (A) is 100 in total of (a) and (b).
10 to 85 parts by weight, preferably 12 to 80 parts by weight,
It is particularly preferably 15 to 70 parts by weight.

Further, aromatic vinyl (a), vinyl cyanide (b), α, β-unsaturated carboxylic acid in the monomer mixture (b) in the present invention
The composition ratio of (C) is such that (A) is 50 to 90% by weight, preferably 55 to
85% by weight, particularly preferably 57 to 82% by weight, (b) 9 to 50
% By weight, preferably 15-45% by weight, particularly preferably 18-
43% by weight.

(C) is used in the range of 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight
Used in the range of.

When (a) is less than 10 parts by weight based on the total of 100 parts by weight of (a) and (b) and 100% by weight of the total of (a), (b) and (c)
When (a) exceeds 90% by weight and (B) is less than 9% by weight, the resulting composition has low impact resistance, which is not preferable. In addition, (a) is 85 per 100 parts by weight of the total of (a) and (b).
When the amount is more than 50 parts by weight, and when (a) is less than 50% by weight and when (b) exceeds 50% by weight with respect to the total of 100% by weight of (a), (b) and (c), It is not practical because the resulting composition has poor moldability. Further, if (c) is less than 0.1% by weight, the resulting composition has low impact resistance, and if it exceeds 20% by weight.
A crosslinking reaction is likely to occur during the production of (A), which makes it difficult to obtain a product of constant quality, which is not practical.

The method for producing the graft copolymer or the graft copolymer composition (A) is not particularly limited, and ordinary methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization can be used. There is also no particular limitation on the charging method of the monomers, and they may be added all at once at the beginning, and in order to prevent the formation of the composition distribution of the copolymer, a part or all of the charged monomers are continuously charged or divided. Polymerization may be carried out while charging.

It is also possible to obtain the above composition by blending separately (grafted) copolymerized resins.

The aromatic polyester resin (B) used in the present invention is a polyester having an aromatic ring as a polymer chain unit, and is an aromatic dicarboxylic acid (or its ester-forming derivative).
And a diol (or an ester-forming derivative thereof) as a main component, which is a polymer or copolymer obtained by a polycondensation reaction.

The aromatic dicarboxylic acid as used herein includes terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,2'-biphenyldicarboxylic acid. acid,
3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4 ' -Diphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 '
-P-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like, and terephthalic acid is preferable.

You may use these aromatic dicarboxylic acid in mixture of 2 or more types. If the amount is small, a mixture of one or more of these aromatic dicarboxylic acids, adipic acid, azelaic acid, dodecanedioic acid, aliphatic dicarboxylic acids such as sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Can be used.

Further, as the diol component, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-
Aliphatic diols such as propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol and the like, and mixtures thereof can be mentioned. If it is a small amount, the molecular weight
One or more of 400 to 6,000 long chain diols, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate and the like. In addition, polyethylene isophthalate / terephthalate,
Copolyesters such as polybutylene terephthalate / isophthalate and polybutylene terephthalate / decane dicarboxylate may be mentioned. Of these, polybutylene terephthalate and polyethylene terephthalate having well-balanced mechanical properties and moldability can be preferably used.

The aromatic polyester used in the present invention is 0.5%
The o-chlorophenol solution having a relative viscosity of 1.15 to 3.0, particularly 1.3 to 2.5 is preferable. When the relative viscosity is less than 1.15, the impact strength of the obtained molded product is low, and when it is more than 3.0, the gloss of the molded product surface is poor and it is not practical.

In the resin composition for molded articles having a textured surface of the present invention,
The blending ratio of the graft copolymer or the graft copolymer composition (A) and the aromatic polyester (B) is 1 to 99 parts by weight of (A), preferably 2 to 94 parts by weight, particularly preferably 5 to 90 parts by weight. Parts, (B) is 99-1 parts by weight, preferably 94-2 parts by weight,
It is particularly preferably 90 to 5 parts by weight, and the total amount of (A) and (B) is 100 parts by weight. When (A) is less than 1 part by weight and (B) exceeds 99 parts by weight, the impact resistance of the composition is poor, and (A) exceeds 99 parts by weight and (B) is less than 1 part by weight. In that case, the chemical resistance of the composition is inferior, which is not preferable. Furthermore, when the weight of the diene rubber in the resin composition is 15% by weight or more, and particularly 15 to 25% by weight, the impact resistance of the resin composition is such that each of the graft copolymer composition and the aromatic polyester resin is independent. It will be dramatically improved compared to that. In this case, selecting polybutadiene terephthalate as the aromatic polyester has a particularly remarkable effect.

Α, β in the resin composition for molded articles having a textured surface of the present invention
-The content of unsaturated carboxylic acid residue is not particularly limited,
From the viewpoint of resin impact resistance and fluidity, it is usually 0.00165-19.
Molding having a copolymerization amount of α, β-unsaturated carboxylic acid in the graft copolymer or the graft copolymer composition (A) and a textured surface so as to be in the range of 8% by weight, particularly 0.01 to 10% by weight It is preferable to select the blending amount of the graft copolymer or the graft copolymer composition (A) in the product resin composition.

There is no particular limitation on the method for producing the resin composition for moldings having a textured surface of the present invention, and a generally known method can be adopted. That is, the graft copolymer or graft copolymer composition (A), polyester (B) pellets,
A method of melt-kneading in a single-screw or multi-screw extruder that has sufficient kneading capacity, and melt-kneading using a Banbury mixer or a rubber roll machine, after uniformly mixing the powder or the fine particles in a high-speed stirrer. Various methods such as a method can be adopted.

The resin composition for a molded article having a textured surface of the present invention is a graft copolymer or a graft copolymer composition (A), a polyester (B), and optionally polystyrene (PS) or styrene / acrylonitrile copolymer. Polymer (SAN), polymethylmethacrylate (PMMA), styrene / methylmethacrylate / acrylonitrile copolymer, α-methylstyrene /
Acrylonitrile copolymer, α-methylstyrene / styrene / acrylonitrile copolymer, α-methylstyrene / methyl methacrylate / acrylonitrile copolymer, P-
Methylstyrene / acrylonitrile copolymer, styrene
Vinyl-based polymers such as / N-phenylmaleimide copolymer
Methacrylic acid-butadiene-styrene terpolymer (MB
S) resin, AES resin, AAS resin, polycarbonate, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66) or other thermoplastic resin is appropriately mixed, polyethylene, polypropylene, ethylene / propylene copolymer , Ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / vinyl acetate copolymer and ethylene / butyl acrylate copolymer It is also possible to adjust to more desirable physical properties and characteristics by appropriately mixing a polyolefin rubber such as coalesced. Depending on the purpose, reinforcing materials and fillers such as pigments and dyes, glass fibers, metal fibers, metal flakes, carbon fibers, heat stabilizers, antioxidants, UV absorbers, light stabilizers, lubricants, plasticizers, electrostatic charge Inhibitors and flame retardants can be added.

In the present invention, (a), (b), the essential monomers of (c) can obtain substantially the same effect as the present invention by simply blending them as a copolymer without graft copolymerization. The vinyl-based monomer having an epoxy group (C)
It is possible to reduce the amount of copolymerization of the above, and it is possible to remarkably improve the moldability.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

ASTM with 1/2 ″ Izod impact strength as an evaluation of impact resistance
It was measured according to D256-56.

As an evaluation of molding processability, the melt viscosity was measured by a high flow tester at a resin temperature of 250 ° C to 280 ° C and a load of 50 kg.

As an evaluation of heat resistance, the Vicat softening temperature was measured according to ASTM-D1525.

For chemical resistance, the injection-molded square plate was immersed in methanol and gasoline at 23 ° C. for 24 hours, and the square plate surface was visually observed.

The mold transfer property was represented by ◯ when there was no board and by x when there was no board when the textured square plate was formed and the glossiness thereof was visually observed.

The following parts and% represent parts by weight and% by weight, respectively.

Reference Example 1 Graft copolymers A-1 to A-6 were produced according to the following formulation.

A-1: Polybutadiene latex (rubber particle size 0.25μ, gel content 80%) Styrene 70 in the presence of 60 parts (solid content conversion)
%, Acrylonitrile 20%, and methacrylic acid 10% 40 parts of a monomer mixture was emulsion polymerized. The obtained graft copolymer was coagulated with magnesium sulfate, washed, filtered and dried to prepare a powdery graft copolymer (A-1).

A-2: 60 parts of a monomer mixture consisting of 13% of methyl methacrylate, 70% of styrene, 15% of acrylonitrile and 2% of acrylic acid in the presence of 40 parts of the polybutadiene latex used in A-1 (in terms of solid content). After emulsion polymerization, a powdery graft copolymer (A-2) was prepared in the same manner as A-1.

A-3: Diene NF35A (manufactured by Asahi Kasei Corporation) 20 parts styrene 45
Part, α-methylstyrene 11 parts, acrylonitrile 20 parts,
After dissolving in 4 parts of methacrylic acid, bulk polymerization was carried out to prepare a graft copolymer (A-3).

A-4: 20 parts of Diene NF35A (manufactured by Asahi Kasei Corporation) and 50 parts of styrene
Parts, acrylonitrile 18 parts, methyl methacrylate 10 parts,
After dissolving in 2 parts of acrylic acid, bulk polymerization was carried out to prepare a graft copolymer (A-4).

A-5: 95% styrene, 5% methacrylic acid in the presence of 50 parts of polybutadiene latex used in A-1 (solid content conversion)
After emulsion-polymerizing 50 parts of the monomer mixture consisting of, a powdery graft copolymer (A-5) was prepared in the same manner as in A-1.

A-6: Styrene 75%, acrylonitrile in the presence of 60 parts (solid content equivalent) of the polybutadiene latex used in A-1.
After emulsion polymerization of 40 parts of a 25% monomer mixture, A-1
A powdery graft copolymer (A-6) was prepared in the same manner as in.

Examples 1 to 8 A-1 to A-4 produced in Reference Example 1 and PBT-1200L (polybutylene terephthalate manufactured by Toray Industries, Inc.) as polyester were mixed in a Henschel mixer at a mixing ratio shown in Table-1, respectively. Next, extrude with a 40 mmφ extruder at an extrusion temperature of 250 ° C., pelletize each, and then subject each pellet to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece and its physical properties. Was evaluated. The results are shown in Table-1.

Comparative Examples 1 to 4 A-1 to A-6 manufactured in Reference Example 1 and PBT-1200L (polybutylene terephthalate manufactured by Toray Industries, Inc.) as polyester were mixed in a Henschel mixer at the mixing ratios shown in Table-1, and then Extrusion temperature 250 ℃ by 40mmφ extruder
After being extruded and pelletized, each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and its physical properties were evaluated. These results are also shown in Table-1.

Examples 9 to 14 PET-J135 (polyethylene terephthalate manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester, and the extrusion temperature was 280.
The conditions were the same as those in Examples 1 to 6 except that the temperature was set to ° C.
Table 2 shows the measurement results of the blending ratio and the physical properties.

Comparative Examples 5 to 8 PET-J135 (polyethylene terephthalate manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester, and the extrusion temperature was 280.
The same conditions as in Comparative Examples 1 to 5 were used except that the molding temperature was 280 ° C. The results of measurement of blending ratio and properties are shown in the table.
2 shows.

The following is clear from the examples and comparative examples. That is, the products obtained by the present invention are all excellent in impact resistance, molding processability, chemical resistance and mold transferability. In contrast, the graft copolymer (A-6) that does not copolymerize α, β-unsaturated carboxylic acid has poor impact resistance,
The impact resistance of the graft copolymer (A-5) obtained by grafting only vinyl cyanide-free aromatic vinyl and α, β-unsaturated carboxylic acid as a graft component is insufficient,
High melt viscosity and poor moldability.

<Effects of the Invention> The resin composition for moldings having a textured surface of the present invention is a graft copolymer or graft copolymer obtained by graft-copolymerizing an aromatic vinyl and an α, β-unsaturated carboxylic acid with a diene rubber. Although the combined composition (A) and the aromatic polyester (B) are blended in a specific ratio, the compatibility of (A) and (B) is extremely good, especially due to the presence of an epoxy group. Furthermore, the resin composition for moldings having a textured surface of the present invention has impact resistance equivalent to ABS resin, molding processability and heat resistance of aromatic polyester, chemical resistance and mold transferability, and in addition, itself. Has a high gloss, it is possible to obtain a molded product having a desired appearance from low gloss to high gloss.

The resin composition for molded articles having a textured surface of the present invention is AB
Since it has the same molding processability, impact resistance, and heat resistance and chemical resistance of polyester as S resin, it can be used for molded products having various textured surfaces by taking advantage of these properties.

Claims (1)

[Claims] 1. A) (a) (a) diene rubber 10 to 85 parts by weight, (b) (a) aromatic vinyl 50 to 90% by weight (b) vinyl cyanide 9 to 50% by weight (c) α , A graft copolymer obtained by graft-copolymerizing 90 to 15 parts by weight of a monomer mixture consisting of 0.1 to 20% by weight of β-unsaturated carboxylic acid, or a copolymer of the graft copolymer and the remaining monomer. A resin composition for moldings having a textured surface, which comprises 1 to 99 parts by weight of a graft copolymer composition comprising a copolymer and 99 to 1 parts by weight of an aromatic polyester resin (B).