JPH04309553A - Matte finishing resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which is excellent in moldability and gives a matte finished molded article excellent in resistance to heat distortion, impact, chemicals, and weathering. CONSTITUTION:The title compsn. comprises 10-89.5wt.% polycarbonate, 10-89.5wt.% thermoplastic polyester, 0.5-40wt.% epoxidized ABS resin, and 0-40wt.% impact modifier.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is suitable for use in automobile parts, electric/electronic parts, miscellaneous goods, etc., and has good moldability, matte finish, heat deformation resistance, impact resistance, and chemical resistance. The present invention relates to a resin composition that provides molded products with excellent properties such as durability and weather resistance.

0002

[Prior Art/Problems to be Solved by the Invention] Polycarbonate has conventionally been known as a resin that has the highest impact resistance among engineering plastics and has good resistance to heat deformation. It is used in various fields. However, it has drawbacks such as insufficient chemical resistance and moldability, and thickness dependence of impact strength.

On the other hand, thermoplastic polyester has excellent chemical resistance and moldability, but has drawbacks such as poor impact resistance and dimensional stability.

[0004] Various resin compositions have therefore been disclosed in order to take advantage of the characteristics of each of these resins and compensate for their deficiencies. For example, Tokuko Sho 36-140
No. 35, Special Publication No. 39-20434, Special Publication No. 55-94
No. 35, Special Publication No. 62-37671, Special Publication No. 62-3
No. 4792, JP-A-62-13378, JP-A-62-
295951 and Japanese Unexamined Patent Publication No. 63-83158.

However, the resin compositions described above cannot simultaneously satisfy the impact resistance, heat deformation resistance, chemical resistance, weather resistance, rigidity, etc. required for automobile parts, and there is a need for improvement. desired.

[0006]Furthermore, when used in automobile interior parts, etc., it is desired that the surface reflectance of the molded product be suppressed and that the molded product be matte, from the viewpoints of luxury, comfort, and safety.

[0007] As a method of suppressing the surface reflectance and obtaining a matte molded product, there is a method of blending additives such as inorganic fillers and rubber into the resin composition, but in this method,
Although the luster disappears, the surface becomes uneven, impact resistance,
Heat deformation resistance, rigidity, etc. deteriorate, making it impossible to obtain a material with a satisfactory balance of physical properties.

[0008]Also, attempts have been made to make the surface matte by improving the texture of the mold, but it is difficult to obtain a sufficient effect, and maintenance and management of the mold requires a large amount of cost, which is not preferable.

[0009] Furthermore, there is a method using matte coating,
This increases cost and is not desirable.

The present invention has been made in order to simultaneously solve a wide variety of required performances that cannot be achieved using such conventional resin compositions.

[0011]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have made extensive studies and have found that polycarbonate, thermoplastic polyester, epoxy group-containing ABS resin, and impact resistance improved materials used if necessary. The inventors have discovered that the objective can be achieved by blending the agents in a predetermined ratio, and have completed the present invention.

[0012] That is, the present invention comprises (A) polycarbonate 10 to 89.5% (wt%,
(Same below), (B) 10-89.5% thermoplastic polyester, (C
) A matting resin composition comprising 0.5 to 40% of an epoxy group-containing ABS resin and (D) 0 to 40% of an impact modifier.

[0013]

EXAMPLES The polycarbonate component (A) used in the present invention is a polycarbonate derived from dihydric phenol, and is usually obtained by the reaction of dihydric phenol and phosgene or dihydric phenol and carbonic acid diester.

[0014] Although there are no particular limitations on dihydric phenol,
Bisphenol A is particularly preferred from the economic point of view.

The molecular weight of the polycarbonate is preferably in the range of 10,000 to 60,000 in terms of viscosity average molecular weight. When the molecular weight is less than 10,000, impact resistance, chemical resistance, etc. tend to decrease, and when it exceeds 60,000, moldability tends to decrease.

The amount of polycarbonate in the composition of the present invention is 10 to 89.5%, preferably 20 to 80%.
It is. If the amount is less than 10%, impact resistance, heat deformation resistance, dimensional stability, etc. will decrease, while if it exceeds 89.5%, chemical resistance, moldability, etc. will decrease.

The thermoplastic polyester as component (B) used in the present invention is a polymer or copolymer obtained from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.

Specific examples of thermoplastic polyester include:
For example, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate,
Examples include polycyclohexane dimethylene terephthalate, but polyethylene terephthalate and polytetramethylene terephthalate are particularly preferred in terms of impact resistance, heat deformation resistance, and economical efficiency.

The solution viscosity of the thermoplastic polyester is phenol/tetrachloroethane=1/1 (weight ratio)
The logarithmic viscosity (IV) at 25° C. and a concentration of 0.5 g/dl in a mixed solvent is preferably in the range of 0.3 to 2.0 g/dl. When the viscosity is less than 0.3 g/dl, impact resistance, chemical resistance, etc. tend to decrease, while when it exceeds 2.0 g/dl, moldability etc. tend to decrease.

[0020] The blending amount of thermoplastic polyester in the composition of the present invention is 10 to 89.5%, preferably 20 to 89.5%.
It is 0%. If the amount is less than 10%, chemical resistance, molding processability, etc. will decrease, while if it exceeds 89.5%, impact resistance, heat deformation resistance, etc. will decrease.

The epoxy group-containing ABS resin used in the present invention as component (C) is a component used for matting. Therefore, the epoxy equivalent is 300
~140,000 is preferred, and 1,000 ~
More preferably, it is 70,000.

The epoxy group-containing ABS resin is composed of a vinyl cyanide monomer, an aromatic vinyl monomer, a rubbery elastic material, and an epoxy group-containing vinyl monomer. Specifically, it is made of a component obtained by graft copolymerizing a rubber-like elastic body with a cyanide vinyl monomer, an aromatic vinyl monomer, and an epoxy group-containing vinyl monomer, or if necessary, a cyanide vinyl monomer is used. A component made by copolymerizing a monomer, an aromatic vinyl monomer, and optionally an epoxy group-containing vinyl monomer may be mixed.

The proportions of each component in the epoxy group-containing ABS resin are vinyl cyanide monomer 3 to 30%;
Furthermore, 6 to 30%, aromatic vinyl monomer 6 to 80%,
Furthermore, the range of components is 13 to 60%, epoxy group-containing vinyl monomer 0.1 to 45%, further 0.2 to 30%, rubber-like elastic material 5 to 90%, and further 20 to 80%. is preferred. The ratio of the vinyl cyanide monomer is 3
If it is less than 30%, the impact resistance, chemical resistance, etc. of the molded article will tend to decrease, and if it exceeds 30%, the molded article will tend to be colored or its impact resistance will decrease. If the amount of the aromatic vinyl monomer is less than 6%, molding processability tends to decrease, and if it exceeds 80%, the chemical resistance, impact resistance, etc. of the molded product tend to decrease. Furthermore, if the amount of the epoxy group-containing vinyl monomer is less than 0.1%, the matting effect will not be sufficient, and if it exceeds 45%, impact resistance, moldability, etc. will tend to deteriorate. Furthermore, if the content of the rubber-like elastic body is less than 5%, impact resistance tends to decrease, and if it exceeds 90%, heat deformation resistance, rigidity, etc. tend to decrease.

The solution viscosity of the methyl ethyl ketone soluble component of the epoxy group-containing ABS resin is 0.0 in terms of logarithmic viscosity.
2 to 1.5 g/dl (N,N'-dimethylformamide solution, 30°C), and even 0.4 to 1.0
A range of g/dl is preferred. The viscosity is 0.2 g/dl
If it is less than 1.5 g, impact resistance, chemical resistance, etc. will decrease.
If it exceeds /dl, moldability etc. tend to deteriorate.

Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, etc. Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, methylstyrene, chlorostyrene, etc. can be given.

The rubber-like elastic body preferably has a glass transition temperature of 0°C or lower, more preferably -40°C or lower. Examples of rubber-like elastic materials include polybutadiene, butadiene-styrene copolymer, and butadiene-styrene copolymer.
Acrylonitrile copolymer, butadiene-butyl acrylate copolymer, polybutyl acrylate, ethylene-
Examples include propylene copolymer and ethylene-propylene-diene copolymer.

There are no particular limitations on the average particle diameter or gel content of the rubber-like elastic body, but the average particle diameter is 0.0
A gel content in the range of 5 to 2.0 μm is preferred from the viewpoint of matte properties and impact resistance, and a gel content of 10 to 90% is preferred from the viewpoint of impact resistance.

Specific examples of the epoxy group-containing vinyl monomer include glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconate, glycidyl styrenecarboxylate, and 3,4-epoxy-1-butene. .

The method for producing the epoxy group-containing ABS resin is not particularly limited, and any method such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be employed.

Epoxy group-containing A in the composition of the present invention
The content of the BS resin is 0.5 to 40%, preferably 3 to 30%. If the blending amount is less than 0.5%, the matting effect will be insufficient, and if it exceeds 40%, the heat deformation resistance,
Molding processability tends to decrease.

[0031] If necessary, an impact modifier may be added to the resin composition of the present invention.

Specific examples of the impact modifier include, but are not limited to, polyolefin polymers, core/shell type graft copolymers, and polyester elastomers.

Specific examples of the polyolefin polymer include linear low density polyethylene, low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-
Examples include homopolymers and copolymers such as diene copolymers.

There are no particular limitations on the degree of polymerization of the polyolefin polymer, and those having a melt index of 0.05 to 50 g/10 minutes can usually be arbitrarily selected and used.

[0035] The core/shell type graft copolymer is
It is made by graft polymerizing a vinyl compound onto a rubber-like elastic body.

The rubber-like elastic body used for producing the core/shell type graft copolymer has a glass transition temperature of 0.
℃ or lower, more preferably -40℃ or lower.

Specific examples of the rubber-like elastic body include polybutadiene, butadiene-styrene copolymer,
Diene rubbers such as butadiene-butyl acrylate copolymers, acrylic rubbers such as butyl polyacrylate and 2-ethylhexyl polyacrylate, olefins such as ethylene-propylene copolymers and ethylene-propylene-diene copolymers. Examples include rubbers such as
From the viewpoint of weather resistance and impact resistance, butadiene-butyl acrylate copolymer is preferred.

The proportion of butyl acrylate in the butadiene-butyl acrylate copolymer is preferably 50 to 70%. If the proportion of butyl acrylate is less than 50%, good weather resistance cannot be obtained, while if it exceeds 70%, impact resistance, especially low-temperature impact resistance, tends to decrease.

There are no particular limitations on the average particle diameter or gel content of the rubber-like elastic body, but the average particle diameter is 0.0.
The thickness is preferably in the range of 5 to 2.0 μm, and the gel content is preferably in the range of 10 to 90%.

The vinyl compound used for producing the core/shell type graft copolymer is one or more monomers selected from aromatic vinyl compounds, vinyl cyanide compounds, acrylic esters, and methacrylic esters. is used.

Styrene is preferably used as the aromatic vinyl compound, acrylonitrile as the vinyl cyanide compound, butyl acrylate as the acrylic ester, and methyl methacrylate as the methacrylic ester.

[0042] The ratio of the rubber-like elastic body to the vinyl compound used is 10/90 to 90/10, more preferably 2
0/80 to 80/20 is preferable. If the ratio of the rubber-like elastic body is less than 10/90, impact resistance may decrease. On the other hand, when it exceeds 90/10, heat resistance tends to decrease.

The polyester elastomer is a copolymer consisting of aromatic dicarboxylic acid or its ester-forming derivative, diol or its ester-forming derivative, and polyether having a number average molecular weight of 700 to 3,000, and is derived from polyether. The ratio of ingredients is 5-70
% range is preferred. When the proportion is less than 5%, impact resistance tends to decrease, and when it exceeds 70%, heat resistance tends to decrease.

Furthermore, the solution viscosity of the polyester elastomer is phenol/tetrachloroethane=1/
1 (weight ratio) in mixed solvent, 25°C, concentration 0.5 g/d
The logarithmic viscosity (IV) at l is 0.3 to 2.0 g
/dl is preferable. The viscosity is 0.3 g
If it is less than 2.0 g/dl, impact resistance, chemical resistance, etc. tend to decrease, while if it exceeds 2.0 g/dl, moldability, etc. tend to decrease.

Specific examples of aromatic dicarboxylic acids or ester-forming derivatives thereof used in the polyester elastomer include terephthalic acid, isophthalic acid, and ester-forming derivatives thereof.

Specific examples of diols or their ester-forming derivatives include ethylene glycol, propylene glycol, tetramethylene glycol, and ester-forming derivatives thereof.

Specific examples of the polyether include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, 2,2-bis(p-hydroxyphenyl)propane (bisphenol A ) with ethylene oxide added to bisphenol A-modified polyethylene glycol. Specific examples of polyethers that can be further used include those exemplified in JP-A-2-92953.

As mentioned above, the number average molecular weight of the polyether is 700 to 3000, more preferably 800 to 3000.
A range of 2000 is preferred. When the number average molecular weight is less than 700, heat resistance tends to decrease, while when it exceeds 3000, thermal stability tends to decrease.

The impact resistance modifiers mentioned above may be used alone or in combination of two or more.

[0050] The blending amount of the impact modifier is 0 to 40
%, preferably 1 to 20%. If the blending amount exceeds 40%, rigidity, heat deformation resistance, etc. will decrease.

The resin composition of the present invention further contains stabilizers such as phosphite and phenol stabilizers, light stabilizers, flame retardants, plasticizers, lubricants, mold release agents, ultraviolet absorbers, antistatic agents, dyes, Fillers such as pigments, glass fibers, talc, and mica can be added.

The resin composition of the present invention can be produced by any method. For example, it can be produced by mixing using a blender, super mixer, etc., or kneading using a single screw or multi-screw extruder.

[0053] The mixing and kneading described above consists of (A) component, (B)
Ingredients, (C) Ingredients and optionally used (D)
The components may be mixed all at once, or some of the components may be mixed and kneaded first, and then the remaining components may be mixed and kneaded.

The resin composition of the present invention thus obtained can be molded by known methods such as injection molding and extrusion molding, and can be used to manufacture automobile parts, electrical/electronic parts, miscellaneous goods, etc. be done.

The composition of the present invention will be specifically explained below using Examples and Comparative Examples.

Examples 1 to 5 and Comparative Examples 1 to 4 The following dried components (A) to (D) and the phosphite stabilizer PEP-36 (manufactured by Adeka Argus Co., Ltd.) are shown in Table 1. Premix at 270 °C in the proportion of 2
The mixture was melt-kneaded and pelletized using a screw extruder. Thereafter, test pieces were molded using an injection molding machine, and their properties were evaluated using the methods described below. The results are shown in Table 1.

(A) Polycarbonate Panlite L-
1250 (viscosity average molecular weight approximately 25,000, manufactured by Teijin Kasei Ltd.).

(B) Polyethylene terephthalate resin EFG-85A (IV approximately 0.85, manufactured by Kanebo Co., Ltd.).

(C) Epoxy group-containing ABS resin emulsion polymerization method, average particle diameter 0.30 μm, gel content 83%
(a) A mixture of 6% acrylonitrile, 21% styrene, and 3% glycidyl methacrylate was graft copolymerized with 70% (solid content) of latex butadiene-butyl acrylate (butadiene content 35%).
. Acrylonitrile 30%, styrene 7% by emulsion polymerization method
0% mixture was copolymerized (b). Both were blended in latex form at a ratio of a:b = 1:3 (weight ratio, solid content), salted with calcium chloride, washed with water, filtered, and dried. The logarithmic viscosity of the methyl ethyl ketone soluble portion of the obtained product was 0.60 g/dl, and the composition was almost the same as the charging ratio.

(D) Impact resistance imparting agent Polyethylene (FW-20G, manufactured by Mitsubishi Kasei Corporation).

(Impact resistance) Using a 1/4" thick notched test piece according to ASTM D-256, at 23°C.
Measure the Izod impact value.

(Falling ball strength) 150 mm x 150 mm
Measurement was carried out at -30°C using a 3 mm flat test piece, and the evaluation was based on the half-break height x the weight of the ball.

(Heat deformation resistance) Measured according to ASTM D-648 at a thickness of 1/4'' and a load of 4.6 kg/cm2.

(Flexural modulus) Measured at 23° C. using a 1/4″ thick test piece according to ASTM D-790.

(Surface gloss) 60 degree reflectance was measured according to JIS K 7105.

(Appearance of molded product) A box-shaped molded product weighing approximately 100 g was molded using a 5-ounce injection molding machine at a cylinder temperature of 280°C and a mold temperature of 70°C, and was visually observed and evaluated according to the following criteria. . ○: Hardly any non-uniformity, flow marks, silveriness, burntness, warping, etc. are observed. △: Non-uniformity, flow marks, silveriness, burntness, warping, etc. are observed. ×: Significant non-uniformity, flow marks, silveriness, burntness, warpage, etc.

(Spiral flow value) Using a 3.5 oz injection molding machine, the cylinder temperature was 280°C, the injection pressure was 100 Kg/cm2 (gauge), and the mold temperature was 70°C.
Using a spiral mold with a gate of 3 mm x 3 mm, width of 4 mm, and thickness of 3 mm, the flow length was evaluated.

[0068]

[Table 1]

[0069]

Effects of the Invention: When a molded article is manufactured using the composition of the present invention, a molded article that has good impact resistance, heat deformation resistance, flexural modulus, weather resistance, and chemical resistance, and is matte. available.

Claims (1)

[Claims] [Claim 1] (A) Polycarbonate 10-89
．． 5% by weight, (B) thermoplastic polyester 10-89
．． 5% by weight, (C) epoxy group-containing ABS resin 0
．． 5 to 40% by weight and (D) impact modifier 0 to
A matting resin composition consisting of 40% by weight.