JPH04309552A - 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, 0.1-40wt.% epoxidized vinylic copolymer, 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] As a result of extensive studies to achieve the above object, the present inventors have developed polycarbonate, thermoplastic polyester, epoxy group-containing vinyl copolymers, and impact-resistant materials used if necessary. The present inventors have discovered that the object can be achieved by blending a sex improver 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
) Epoxy group-containing vinyl copolymer 0.1 to 40%
and (D) a matting resin composition comprising 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 used in the present invention is 10 to 89.5%, preferably 20 to 80%. If the amount is less than 10%, impact resistance, heat deformation resistance,
Dimensional stability decreases, and on the other hand, if it exceeds 89.5%, chemical resistance and moldability 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 and polycyclohexane dimethylene terephthalate, with polyethylene terephthalate and polytetramethylene terephthalate being particularly preferred.

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. When the viscosity is less than 0.3, impact resistance and chemical resistance tend to decrease, while when it exceeds 2.0, moldability tends 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 vinyl copolymer, component (C), used in the present invention is a component used to produce a matte effect. Therefore, the epoxy equivalent weight is 100 to 200,000, and even 100
~50,000, preferably 100 ~20
,000 is more preferable.

The molecular weight of the epoxy group-containing vinyl copolymer is not particularly limited, but the number average molecular weight is 100
A range of 0 to 50,000, more preferably 1000 to 30,000 is preferred.

[0023] The epoxy group-containing vinyl copolymer is
0.1 to 75%, preferably 1.0 to 60%, of an epoxy group-containing vinyl monomer, and 25 to 99.9% of one or more vinyl monomers copolymerizable therewith; Preferably, it is a copolymer of 40 to 99%. If the epoxy group-containing vinyl monomer content is less than 0.1%, the matting effect will not be sufficient, and if it exceeds 75%, the impact resistance will deteriorate.
Molding processability etc. may deteriorate.

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

Examples of the copolymerizable vinyl monomers include vinyl cyanide monomers, aromatic vinyl monomers, and (meth)acrylic acid ester monomers. Examples of aromatic vinyl monomers include (meth)acrylic acid ester monomers such as styrene, α-methylstyrene, and chlorstyrene. Specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

There are no particular limitations on the type and proportion of vinyl monomers in the copolymerizable vinyl monomers, but vinyl cyanide monomers may be 0 to 30%, aromatic vinyl monomers may be 0 to 30%. 100%, (meth)acrylic acid ester monomer ratio is generally about 0 to 100%,
Vinyl cyanide monomer 0-30%, aromatic vinyl monomer 0-90%, (meth)acrylic acid ester monomer 10%
-100% is preferable from the viewpoint of matte effect and impact resistance. When the proportion of the vinyl cyanide monomer exceeds 30%, the molded product is likely to be colored and its impact resistance will be reduced.

The blending ratio of the epoxy group-containing vinyl copolymer in the resin composition of the present invention is from 0.1 to 40%, preferably from 0.5 to 30%, from the viewpoint of matting effect.

[0028] 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 is no particular limitation on the degree of polymerization of the polyolefin polymer, and one having a melt index of 0.05 to 50 g/10 minutes can usually be selected as desired.

[0032] 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.
C or lower, more preferably -40 C 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.

[0039] The ratio of the rubber-like elastic body to the vinyl compound used is 10/90 to 90/10, more preferably 3
0/70 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, if it exceeds 90/10, the effect of improving impact resistance tends to be insufficient.

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
It is preferable that the logarithmic viscosity (IV) at 1 is in the range of 0.3 to 2.0. When the viscosity is less than 0.3, impact resistance and chemical resistance tend to decrease, while when it exceeds 2.0, moldability tends 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.

[0046] The amount of the impact modifier as described above is as follows:
It is 0-40%, preferably 3-20%. The blending amount is 4
If it exceeds 0%, 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.

[0049] 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 8 and Comparative Examples 1 to 4 The following dried components (A) to (D) and PE as a stabilizer
P-36 (manufactured by Adeka Argus Co., Ltd.) was premixed in the proportions shown in Table 1, and each was melt-kneaded at 270°C using a twin-screw extruder to form pellets. Thereafter, test pieces were molded at 240 to 280°C 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 0.85, manufactured by Kanebo Co., Ltd.)
.

(C) Epoxy group-containing vinyl copolymer C-1: Bremmer CP-50S (copolymer of glycidyl methacrylate (50%) and styrene, number average molecular weight approximately 5500, manufactured by NOF Corporation) .

C-2: Bremmer CP-15 (copolymer of glycidyl methacrylate (15%), styrene and butyl methacrylate, number average molecular weight approximately 470
0, manufactured by Nippon Oil & Fats Co., Ltd.).

C-3: Bremmer CP-50M (copolymer of glycidyl methacrylate (50%) and methyl methacrylate, number average molecular weight approximately 6000, manufactured by NOF Corporation).

C-4: Blenmar CP-20S-A (
Copolymer of glycidyl methacrylate (20%) and acrylonitrile-styrene copolymer (80%), number average molecular weight approximately 3300, manufactured by NOF Corporation).

(D) Impact resistance imparting agent D-1: FW-20G (linear low density polyethylene, manufactured by Mitsubishi Kasei Corporation).

D-2: By emulsion polymerization, 40 parts of a rubber-like elastic body with an average particle diameter of 0.15 μm consisting of 67% butyl acrylate and 35% butadiene were added with 20% acrylonitrile, 30% methyl methacrylate, and 50% styrene.
A core obtained by graft copolymerizing 60 parts of a mixture consisting of %/
Shell-type graft polymer.

D-3: By the same method as D-2,
A core/shell made by graft copolymerizing 40 parts of a mixture of 15% acrylonitrile, 30% methyl methacrylate, and 55% styrene onto 60 parts of a rubber-like elastic material with an average particle diameter of 0.15 μm, which is made of 64% butyl acrylate and 36% butadiene. type graft polymer.

D-4: The proportion derived from dimethylene terephthalate and ethylene glycol produced by the method described in JP-A-2-92953 was 40%, and the proportion derived from bisphenol A-modified polyethylene glycol having a number average molecular weight of 1000. 60%, and the logarithmic viscosity (I
V) is a thermoplastic polyester elastomer of 0.70.

(Impact Resistance) Izod impact value was measured using a 1/4" thick notched test piece according to ASTM D-256.

(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 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, warpage, etc. are observed. △: Non-uniformity, flow marks, silveriness, burntness, warping, etc. are observed. ×: Significant non-uniformity, flow marks, silveriness, burntness, warpage, etc.

[0069]

[Table 1]

[0070]

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 (3)

[Claims] [Claim 1] (A) Polycarbonate 10-89
．． 5% by weight, (B) thermoplastic polyester 10-89
．． 5% by weight, (C) 0.1 to 40% by weight of an epoxy group-containing vinyl copolymer, and (D) 0 to 40% by weight of an impact modifier. [Claim 2] The epoxy group-containing vinyl copolymer is
The resin composition according to claim 1, which is a copolymer of 0.1 to 75% by weight of an epoxy group-containing vinyl monomer and 99.9 to 25% by weight of a copolymerizable vinyl monomer. 3. The resin composition according to claim 2, wherein 10 to 100% by weight of the copolymerizable vinyl monomers are (meth)acrylic acid ester monomers.