JP2003020384A - Matte resin composition, and matte resin molding having uniform matte surface, obtained by molding it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a matte resin composition having good physical property balance between the impact resistance and the rigidity, and a matte resin molding having a uniform matte surface, obtained by molding it. SOLUTION: The matte resin composition consists of 70-99 wt.% of a rubber- toughened styrene resin (A) consisting of 70-90 wt.% continuous phase component comprising a copolymer of an aromatic vinyl and vinyl cyanide, or an aromatic vinyl, vinyl cyanide and other monomer copolymerizable therewith and 10-30 wt.% disperse phase component comprising a rubbery polymer component grafted with the above-mentioned monomers, occluding the copolymer and having a weight-mean particle diameter of 1-20 μm; and 1-30 wt.% of a matting agent (B) having a mean particle diameter of 1-90 μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a matte resin composition having an excellent balance of impact resistance and rigidity, and further excellent moldability, and a matte having a uniform matte surface formed by molding the matte resin composition. Resin molded article.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resins represented by ABS resin (acrylonitrile-butadiene-styrene resin) are excellent in impact resistance, molding processability, heat resistance and the like, and are therefore home electric appliances housings and automobile parts. It is used in a wide range of fields. By the way, in recent years, in the field of these parts for automobiles, parts for home electric appliances, etc., in order to obtain a matte calm texture from the viewpoint of its safety or with the intention of increasing the sense of luxury, There is a demand for a resin material which has a matte property with suppressed gloss. Conventionally, as a method for obtaining these matte parts whose gloss is suppressed, (1) a method of subjecting a mold surface to a texture treatment, (2) a method of matte coating, (3) a method of blending an inorganic filler, ( 4) A method of blending a crosslinked polymer and (5) a method of blending a rubber component have been used. However, when these methods are used alone, sufficient matting properties are not exhibited, and there are various problems as described below.
That is, in the method (1), it is difficult to repair and manage the mold, and it is difficult to impart a certain level of mattness because the glossy state depends on the molding conditions. Further, it has a drawback that the surface of a molded product having a complicated shape cannot be textured. The method (2) has drawbacks such as high cost of the coating process, environmental pollution, and deterioration of physical properties due to deterioration of the resin surface by the solvent. (3)
In methods (4) and (4), there is a problem in that physical properties, particularly impact resistance, deteriorate, and the gloss of the molded product changes depending on the molding conditions such as molding pressure and mold temperature, and uniform matte properties cannot be obtained. Had the drawback of. In the method (5), uneven gloss is likely to occur, flow marks and weld lines based on the rubber component are generated, and when the rubber component is increased, heat distortion resistance, rigidity, and moldability are deteriorated. Therefore,
There has been a demand for a material having a good balance of impact resistance, rigidity, and moldability, and further having stable matte properties.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and has a good balance of physical properties of impact resistance and rigidity, and a matte resin composition excellent in molding processability. An object of the present invention is to provide an article and a matte resin molded article having a uniform matt surface formed by molding the article.

[0004]

Means for Solving the Problems As a result of intensive studies on the solution of the above-mentioned problems, the inventors of the present invention have controlled the content of the rubber-like polymer component of the rubber-reinforced styrene resin and the size of its dispersed particles, Furthermore, by adding a matting agent in a specific ratio, the physical properties of impact resistance and rigidity are well balanced, and the matting resin composition is excellent in molding processability, and a matte surface having a uniform matting surface formed by molding the matting resin composition. The inventors have found that an erasable resin molded product can be obtained and reached the present invention.

That is, the present invention provides [1] an aromatic vinyl-based monomer and a vinyl cyanide-based monomer, or an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and these monomers. From 70 to 90% by weight of a continuous phase component consisting of a copolymer with another monomer copolymerizable with, and a rubbery polymer component grafted with the monomer and occluded the copolymer. Rubber-reinforced styrenic resin (A) 70 which comprises 10 to 30% by weight of the dispersed phase component, and the dispersed phase component consisting of the rubbery polymer component has a weight average particle diameter of 1 to 20 μm.
, 99% by weight and 1 to 30% by weight of a matting agent (B) having an average particle size of 1 to 90 μm,
[2] The rubber-reinforced styrene resin (A) has a continuous phase component of 70 to 85% by weight, a dispersed phase component of 15 to 30% by weight, and a dispersed phase component of 3 to 20 μm in weight average particle diameter [ [1] The matte resin composition according to [1] or [2], wherein the matte agent (B) is an inorganic filler, [4] [1] to [3] ] A matte resin molded article having a uniform matte surface formed by molding the resin composition according to any one of [5] JIS- of the resin molded article
A matte resin molded article having a uniform matt surface according to [4], which has a 45 ° specular gloss value of 20% or less according to K7105.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The matte resin composition in the present invention is
Aromatic vinyl-based monomers and vinyl cyanide-based monomers, or aromatic vinyl-based monomers, vinyl cyanide-based monomers and other monomers copolymerizable with these monomers 70 to 90% by weight of a continuous phase component consisting of a copolymer, and 10 to 30% by weight of a dispersed phase component consisting of a rubber-like polymer component grafted with the above-mentioned monomer and occluding the above-mentioned copolymer, The dispersed phase component consisting of the rubber-like polymer component is 1
70 to 99% by weight of a rubber-reinforced styrene resin (A) having a weight average particle diameter of ˜20 μm and an average particle diameter of 1 to 90 μm
The matting agent (B) of 1 to 30% by weight.

In the rubber-reinforced styrene resin (A), the dispersed phase component consisting of the rubber-like polymer component is 10% by weight.
If the amount is less than 90% by weight (continuous phase component exceeds 90% by weight), the impact resistance is poor, which is not preferable. On the other hand, if the dispersed phase component exceeds 30% by weight (continuous phase component is less than 70% by weight), the heat distortion resistance and the rigidity are lowered, and the moldability is deteriorated, which is not preferable. The disperse phase component is preferably 15 to 30% by weight (continuous phase component is 70 to 85% by weight). Further, if the weight average particle size of the dispersed phase component is less than 1 μm, a resin composition having a sufficient matte property cannot be obtained, which is not preferable. However, the weight average particle size of the dispersed phase component is 20 μm
Since it is difficult to form larger particles, the upper limit is about 20 μm. The weight average particle diameter of the dispersed phase component is preferably 3 to 20 μm.

The rubber-like polymer constituting the rubber-reinforced styrene resin (A) used in the present invention is not particularly limited as long as it is a polymer showing a rubber-like property at room temperature. For example, polybutadiene, isoprene- Butadiene copolymer, styrene-butadiene random copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer and the like are used, Polybutadiene and styrene-butadiene copolymer are preferably used.

Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, One or more of halogenated styrene, ethyl styrene, p-isopropyl styrene, pt-butyl styrene, 2,4-dimethyl styrene, divinyl benzene and the like are used, and particularly styrene, α-methyl styrene, p-
Methylstyrene is preferred. Of these, styrene is the most versatile and inexpensive, and the use of α-methylstyrene or p-methylstyrene improves the heat resistance of the resin.

As the vinyl cyanide-based monomer used in the present invention, one or more kinds of acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like are used, and acrylonitrile is particularly preferable.

Further, in the present invention, other monomers copolymerizable with the above aromatic vinyl-based monomer and vinyl cyanide-based monomer, if necessary, such as methyl (meth) acrylate, ( Unsaturated carboxylic acid alkyl ester monomers such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide It is also possible to use maleimide-based monomers such as, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

Aromatic vinyl monomers and vinyl cyanide monomers constituting the rubber-reinforced styrene resin (A) in the present invention, or aromatic vinyl monomers, vinyl cyanide monomers and Other monomers copolymerizable with these monomers and rubber-like polymers can be obtained by a known solution polymerization method, bulk polymerization method or a method in which these are arbitrarily combined.

The matting agent (B) used in the present invention is preferably an inorganic filler. Specific examples are at least one compound selected from spherical or plate-shaped inorganic fillers such as calcium carbonate, mica, talc, silica, clay, (hollow) glass beads, and glass flakes. Further, if the average particle size of the matting agent (B) is 1 μm or less, the effect as a matting agent is poor, and if it exceeds 90 μm, the appearance of the molded product is rough and the product value is poor. It is not preferable because it is not possible.

When the amount of the matting agent (B) used in the matting resin composition is less than 1% by weight, sufficient rigidity and matting properties cannot be obtained, which is not preferable. On the other hand, if the amount used exceeds 30% by weight, impact resistance is lowered and molding processability is deteriorated, which is not preferable.

The method of mixing the matte resin composition comprising the rubber-reinforced styrenic resin (A) and the matting agent (B) used in the present invention is not particularly limited, and commonly used rolls, screws, kneaders, A Banbury mixer, plastomill, extruder or the like can be used. Also, there is no particular limitation on the processing method for obtaining a molded product,
Injection molding, T-die sheet processing, inflation molding,
It can be molded by a method such as powder slush molding.

In such mixing or processing molding,
Depending on the purpose, conventional additives such as lubricants, dyes and pigments, antistatic agents, antioxidants, ultraviolet absorbers, stabilizers and flame retardants may be added in conventional amounts.

The molded article obtained from the matte resin composition of the present invention preferably has a 45 ° specular gloss value of 20% or less according to JIS-K7105.

[0019]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The analysis and physical property evaluation of the resin composition were performed by the following methods.

Weight average particle diameter of rubber-like polymer : An ultrathin section of the resin composition dyed with osmic acid was photographed with a transmission electron microscope, and the particle diameter of 500 to 700 rubber-like polymer particles in the photograph was measured. The weight average particle diameter is obtained by averaging according to the following formula I (Equation 1). However, n is the number of rubber-like polymer particles having a particle diameter D.

[0021]

[Equation 1] Average particle size of rubber-like polymer = ΣnD4 / ΣnD3 ... I

Molding processability : Melt flow rate was measured according to ASTM D-1238 (200 ° C. × 5 k).
g load, unit g / 10 min). Rigidity : The flexural modulus was measured according to ASTM D-790 (23 ° C, unit MPa). Impact resistance : Notched Izod impact strength was measured according to ASTM D-256 (23 ° C, unit J /
m). Matting property : (1) Specular gloss at an incident angle of 45 degrees was measured according to JIS-K7105. (Unit:%) (2) Appearance of molded product: The appearance of the surface of the molded product whose matteness was evaluated was visually observed and judged according to the following two criteria.・ Gate part flow mark (○: good, △: flow mark is slightly conspicuous, ×: flow mark is conspicuous) ・ Gloss unevenness (○: surface is uniform and not rough at all, △: surface is non-uniform when staring X: Surface is uneven and rough)

Matting agent (B) B-1: talc [average particle size: 3 to 11 μm] (UPN HS-T compressed fine powder talc manufactured by Hayashi Chemical Co., Ltd.) B-i: calcium carbonate [average particle size: 0.04 μm] ]
(Shiraishi CC manufactured by Shiraishi Industry Co., Ltd.)

[0024]

Example 1 A plug flow tower type reaction vessel having a volume of 15 liters ("New Polymer Manufacturing Process" (Industrial Research Society, Koji Saeki / Shinzo Omi), page 185, Mitsui described in FIG. 7.5 (b) C1 divided into 10 stages by the same type of reactor as the Toatsu type
/C0=0.955. A thermoplastic resin was produced by using a continuous polymerization apparatus in which two 10-liter complete mixing tanks were connected in series to each other. The plug flow tower type reaction tank constitutes the particle forming step, the first complete mixing tank which is the second reactor constitutes the particle diameter adjusting step, and the third reactor constitutes the post-polymerization step. 59 parts by weight of styrene, 19.8 parts by weight of acrylonitrile, 25 parts by weight of ethylbenzene, 21.2 parts by weight of Asaprene BR730A manufactured by Asahi Kasei Corporation, 0.3 parts by weight of t-dodecyl mercaptan, 1, 1 in a plug flow tower type reaction tank.
A raw material consisting of 0.04 parts by weight of bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was prepared, and 10 kg of this raw material was placed in a three-stage stirred polymerization tank array reactor.
/ H was continuously fed to polymerize the monomer. Three
The polymerization liquid was introduced into the separation and recovery process consisting of a preheater and a decompression chamber from the tank at the stage. The resin discharged from the recovery step was subjected to an extrusion step to obtain an ABS resin composition as granular pellets. The weight average particle size of the rubber-like dispersed phase component of the obtained resin is 6.0 μm.
Met. ABS resin composition 85 thus produced
A matting resin composition was obtained by kneading 15 parts by weight of the matting agent B-1 with parts by weight with an extruder. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0025]

Example 2 Polymerization was carried out in the same manner as in Example 1 to obtain A
95 parts by weight of the BS resin composition and 5 parts by weight of the matting agent B-1 were kneaded with an extruder to obtain a matting resin composition. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0026]

EXAMPLE 3 In Example 1, the raw material was styrene 67.
5 parts by weight, acrylonitrile 22.5 parts by weight, ethylbenzene 25 parts by weight, Asaprene BR730A manufactured by Asahi Kasei Corporation
10 parts by weight, 0.35 parts by weight of t-dodecyl mercaptan, 1,1-bis (t-butylperoxy) 3, 3, 5
Polymerization was carried out in the same manner as in Example 1 except that the raw material consisted of 0.04 parts by weight of trimethylcyclohexane.
An ABS resin composition was obtained. At this time, the weight average particle diameter of the rubber-like dispersed phase component of the obtained resin was 1.2 μm.
90 parts by weight of the ABS resin composition thus produced and 10 parts by weight of the matting agent B-1 were kneaded with an extruder to obtain a matting resin composition. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0027]

Comparative Example 1 In Example 1, the raw materials were 59 parts by weight of styrene, 19.8 parts by weight of acrylonitrile, 25 parts by weight of ethylbenzene, and 21.2 parts of NS310S manufactured by Zeon Corporation.
Parts by weight, t-dodecyl mercaptan 0.4 parts by weight, 1,
Polymerization was carried out in the same manner as in Example 1 except that the raw material was changed to 0.04 parts by weight of 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane to obtain an ABS resin composition. . At this time, the weight average particle diameter of the rubber-like dispersed phase component of the obtained resin was 10 μm. 5 parts by weight of the matting agent B-1 and 95 parts by weight of the ABS resin composition thus produced were kneaded by an extruder to obtain a matting resin composition. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0028]

Comparative Example 2 AB obtained by carrying out polymerization in the same manner as in Example 1
2 parts of polybutadiene rubber to 80 parts by weight of S resin composition
0 part by weight (solid content) was kneaded with an extruder to obtain an ABS resin composition. The rubber-like dispersed phase component of the obtained resin had a weight average particle diameter of 5.0 μm. A produced in this way
Matting agent B-1 was added to 5 parts by weight of the BS resin composition.
The mixture was kneaded with 1 part by weight in an extruder to obtain a matte resin composition. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0029]

Comparative Example 3 Emulsion graft polymerization was carried out at a ratio of 20 parts by weight of polybutadiene latex (solid content), 40 parts by weight of styrene and 40 parts by weight of acrylonitrile. The obtained graft polymer latex was coagulated with dilute sulfuric acid, washed, filtered, and dried. The weight average particle diameter of the rubber-like dispersed phase component of the obtained resin was 0.6 μm. 5 parts by weight of the matting agent B-1 and 95 parts by weight of the ABS resin composition thus produced were kneaded by an extruder to obtain a matting resin composition. Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0030]

Comparative Example 4 Polymerization was carried out in the same manner as in Example 1 to obtain an ABS resin composition. Table 1 shows the measurement results of the physical properties and the like.

[0031]

Comparative Example 5 Polymerization was carried out in the same manner as in Example 1 to obtain A.
60 parts by weight of the BS resin composition and 40 parts by weight of the matting agent B-1 were kneaded with an extruder to obtain a matting resin composition.
Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0032]

Comparative Example 6 Polymerization was carried out in the same manner as in Example 3 to obtain A
90 parts by weight of the BS resin composition and 10 parts by weight of the matting agent B-2 were kneaded with an extruder to obtain a matting resin composition.
Table 1 shows the measurement results of the physical properties and the like of the obtained resin.

[0033]

[Table 1]

[0034]

The matte resin composition of the present invention is
It has a good balance of impact resistance and rigidity, and also has excellent moldability. Further, a molded product using the same has a uniform matte surface.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA12X AA22X AA34X AA77                       AB21 AB26 AB28 AD07 AE22                       AF32Y BA01 BC01 BC07                 4J002 BN15 DE236 DJ016 DJ036                       DJ046 DJ056 DL006 FA016                       FA086 FD206

Claims (5)

[Claims] 1. An aromatic vinyl-based monomer and a vinyl cyanide-based monomer, or an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, and another copolymerizable with these monomers. 70 to 90% by weight of continuous phase component consisting of copolymer with monomer
And a dispersed phase component 10 comprising a rubber-like polymer component grafted with the above-mentioned monomer and occluded with the above-mentioned copolymer.
70 to 99% by weight of rubber-reinforced styrenic resin (A) having a weight average particle diameter of 1 to 20 μm and an average particle diameter of 1 to 90 μm. A matting resin composition comprising 1 to 30% by weight of the matting agent (B). 2. The rubber-reinforced styrene resin (A) has a continuous phase component of 70 to 85% by weight, a dispersed phase component of 15 to 30% by weight, and a dispersed phase component of 3 to 20 μm in weight average particle diameter. The matte resin composition according to claim 1. 3. The matte resin composition according to claim 1, wherein the matte agent (B) is an inorganic filler. 4. A matte resin molded article having a uniform matt surface formed by molding the resin composition according to claim 1. 5. The resin molded article according to JIS-K7105 45.
The matte resin molded article having a uniform matte surface according to claim 4, which has a degree of specular gloss of 20% or less.