JP2727695B2 - Matting agent, production method thereof, matting thermoplastic resin composition and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to automotive interior / exterior parts, home electric appliances,
It can be used in fields requiring heat resistance, impact strength, and matting properties as well as exterior parts such as OA equipment and construction materials such as gutters. The present invention relates to a matting agent, a matte thermoplastic resin composition, and a molded article.

(Prior Art) Thermoplastic resins are used in various applications because of their excellent workability and mechanical properties. The surface of a molded article made of these resins usually has good gloss, but on the other hand, there is also a demand for a molded article having a glossy surface.

In particular, when the molded article is used for interior and exterior parts of automobiles, it must be made low in gloss to prevent the visibility from being damaged by reflected light and to ensure safe driving.

Conventionally, methods for matting the surface of a molded article of a thermoplastic resin include (1) a method in which a mold surface is subjected to embossing, and (2)
A method of applying a matting paint on the surface of a molded article, (3) a method of mixing an inorganic filler such as talc, calcium carbonate, mica, etc. with a resin, (4) a method of mixing a crosslinked polymer with a thermoplastic resin, (5) There are known a method of adding a rubbery elastic material to a raw resin, and a method of (6) increasing the particle size of a rubber grafted by emulsion polymerization.

Among the above matting methods, the method (1) has the drawbacks that a sufficient matting effect cannot be obtained and that the surface of a molded article having a complicated shape cannot be embossed. The methods (2) have drawbacks such as the cost of the coating process and the problem of environmental pollution, and furthermore, the methods (3) and (4) have disadvantages such as deterioration of the resin surface due to the solvent and deterioration of physical properties. There are drawbacks in that the strength cannot be reduced, and the gloss of the molded article changes depending on molding conditions such as molding pressure and mold temperature, and uniform matting cannot be obtained. In addition, the methods (5) and (6) have drawbacks in that gloss unevenness easily occurs, a weld line based on the rubbery elastic body is generated, and the rigidity and hardness of the molded product are reduced. As described above, it has been extremely difficult to achieve both impact strength and matting properties with the conventional technology.

Also, in order to achieve the improvement in heat resistance required especially for parts for automobile interiors, it has been more difficult to maintain the impact strength of the same as general thermoplastic resins.

(Problems to be Solved by the Invention) The present invention relates to a matting agent capable of obtaining a molded article having low gloss on the surface of the molded article, no uneven gloss, and excellent heat resistance and impact resistance. And a matting thermoplastic resin composition and a molded article.

That is, the present invention relates to a graft copolymer based on a low cis polybutadiene rubber having a Mooney viscosity of 30 to 40, comprising a matting agent and another resin, Matting agent characterized in that at least 30% by volume of the rubber component particles are non-spherical rubber particles when a molded article in which rubber particles derived from the agent are dispersed in a matrix of another resin, and a method for producing the same And a matted thermoplastic resin composition and a molded article containing the matting agent.

First, the matting agent according to the present invention and a method for producing the same will be described.

The matting agent of the present invention is a graft copolymer containing a rubber component, and low cis polybutadiene having a Mooney viscosity of 30 to 40 is used as the rubber component. If the Mooney viscosity is greater than 40, the viscosity increases when dissolved in the monomer, making it difficult to stir or not exhibiting good solubility.
If it is less than 0, the matting effect is insufficient. The Mooney viscosity refers to the viscosity of rubber particles measured with a Mooney plastometer.

Rubber components such as high cis polybutadiene and styrene-butadiene-block copolymer do not achieve the desired matting properties and falling weight impact strength. When high cis polybutadiene is used, the matting property is good and is equivalent to low cis polybutadiene, but the falling weight impact strength is reduced. When a styrene-butadiene-block copolymer is used, the matting effect is insufficient. Such low cis polybutadiene is a known material, such as BR1241ST (manufactured by Nippon Zeon Co., Ltd.).

The matting agent of the present invention is obtained by blending a monomer as a graft component in the presence of the above rubber component and polymerizing it, but provides a good matting agent, impact resistance and the like. When the matting agent is melt-kneaded and molded, at least 3.0% by volume of the rubber component particles dispersed in the component matrix other than the rubber component must be non-spherical rubber particles. Here, in the present invention, that the rubber component particles are non-spherical means that the particles are other than spherical or elliptical spherical having a ratio of the major axis to the minor axis of 3 or less, or a shape similar thereto. In particular, if there are many fibrous (preferably those having the shape shown in FIG. 1) dispersed, good matting properties can be obtained, so that the rubber component has a fibrous shape near the surface layer of the molded product. Those that are dispersed are preferred.

The method for checking the shape of the rubber is not particularly limited. For example, a molded article molded as shown in FIG. 2 is made into an ultra-thin section in each of the xy plane, yz plane and zx plane (preferably a sample near the surface layer of the molded article, particularly within 40 μm from the surface layer). adjust, OsO ₄ stained and (OsO ₄ stained ultramicrotomy)
It can be determined by observing with a transmission electron microscope.

If the content of the non-spherical rubber particles is less than 30% by volume, good matting properties cannot be obtained, and impact resistance also decreases.

Matting with the above characteristics can be obtained by blending a monomer component in the presence of a specific rubber component and performing bulk suspension polymerization.

As the monomer component, it is preferable to use aromatic vinyl and vinyl cyanide from the viewpoint of moldability, impact resistance and chemical resistance. Styrene is a typical aromatic vinyl, but α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, etc. Is also used. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. The ratio of aromatic vinyl to vinyl cyanide is 50/50 for the former / the latter
9090/10, particularly preferably 60/408080/20 (all by weight). Here, when the amount of the aromatic vinyl is too small, the moldability tends to decrease, and when the amount is too large, the amount of vinyl cyanide decreases, so that the impact resistance and the chemical resistance tend to decrease. If necessary, a vinyl monomer copolymerizable therewith can be used. Examples of copolymerizable vinyl monomers include vinyl carboxylic acids such as acrylic acid and methacrylic acid, alkyl acrylates such as methyl acrylate and ethyl acrylate, and methacrylic acids such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Acid alkyl esters, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc., maleimide-based monomers, vinylamides such as acrylamide, methacrylamide Acid amide and the like.

The blending amount of the low cis polybutadiene during the production of the matting agent is in the range of 5 to 15% by weight (that is, 95 to 85% by weight of the monomer component) based on the total amount of the monomer component and the graft component of the rubber component. Is preferably within the above range. When the amount of the low cis polybutadiene is more than 15% by weight, the viscosity increases when dissolving in the monomer, uniform stirring cannot be performed, the dissolution time becomes longer, and the safety in bulk suspension polymerization is increased. May be deteriorated, resulting in defects such as the formation of rice cake and an increase in the amount of polymer adhered to the pot. If it is less than 5% by weight, the matting effect tends to be insufficient.

The matting agent in the present invention is produced by a bulk suspension polymerization method.
This is a very important management point for matting and impact resistance. That is, the low cis polybutadiene rubber as described above is dissolved in a monomer component, bulk polymerization is performed, and water containing a suspending agent is added when the polymerization rate of the monomer component reaches 1 to 15%. In addition, it is preferable to shift to suspension polymerization. If the degree of polymerization at this time is less than 1%, the matting properties are poor, and if it exceeds 15%, the surface becomes rough and welds tend to appear.
The matting agent produced by transitioning to suspension polymerization at a polymerization rate of 1 to 15% has the highest impact strength.

The polymerization rate can be determined by sampling a small amount of the reaction mixture from the polymerization system, measuring the weight, evaporating the volatile components with an infrared lamp or the like, and measuring and calculating the remaining nonvolatile components. In the examples described later, the polymerization rate was determined by this method.

The polymerization initiator used in the polymerization is not particularly limited, and a known radical polymerization initiator can be used. For example, lauroyl peroxide, benzoyl peroxide,
Diethylene glycol-bis (t-butylperoxycarbonate), diisopropylperoxycarbonate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylperoxybenzoate,
T-butyl perlaurate, dicumyl peroxide, t-peroxide
Organic peroxides such as butyl cumyl and di-t-butyl peroxide are exemplified. Also, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile can be used. These can be used alone or in combination as needed. The polymerization initiator, based on the total amount of the monomers,
It is preferred to use 0.01 to 10% by weight, especially 0.1 to 1% by weight.

The polymerization temperature may be selected at a temperature corresponding to the decomposition temperature of the polymerization initiator, but is generally preferably in the range of 50 to 150 ° C. In addition, if necessary, a suspension stabilizer, an antioxidant, a molecular weight regulator, a lubricant, a coloring agent, and the like can be used.

Suspension stabilizers are used in suspension polymerization, for example, water-soluble polymer compounds such as partially saponified polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, methyl cellulose, polyalkylene glycol, starch powder, Gelatin or the like can be used, and fine powder of a poorly water-soluble inorganic chemical, such as tribasic calcium phosphate, magnesium carbonate, or calcium carbonate, is also used in combination with various surfactants. These can be used alone or in combination as needed. Suspension stability is
It is preferable to use 0.01 to 5% by weight, especially 0.1 to 2% by weight, based on the total amount of the aqueous medium, because good suspension stability is exhibited.

In addition, since acrylonitrile-based monomers are water-soluble, they can be polymerized by adding water-soluble inorganic salts and water-soluble polymerization inhibitors for the purpose of reducing their solubility and preventing polymerization in the aqueous phase. it can.

The matting agent in the present invention has an acetone-soluble component having a weight average molecular weight of 100,000 to 60 in order to obtain particularly high impact properties.
It is preferably set to 10,000, especially 150,000 to 600,000. This adjustment can be performed by a known method using a molecular weight modifier or the like as necessary. If the weight average molecular weight is less than 100,000, the Izod impact strength tends to decrease. If it exceeds 600,000, the melt viscosity of the resin increases, the fluidity decreases, and the moldability tends to deteriorate. is there.

The weight-average molecular weight of the acetone-soluble component was determined by dissolving 2 g of the sample in 100 ml of acetone with stirring for 24 hours, separating the soluble and insoluble components with a centrifugal separator, and performing gel permeation chromatography on the soluble component. Measured by the E method,
It is converted using a standard polystyrene calibration curve.

As described above, in order to control the molecular weight of the matting agent, a molecular weight controlling agent can be used as needed during the bulk suspension polymerization. As the molecular weight regulator, for example, mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, various terpenes, and halogenated hydrocarbons such as chloroform and carbon tetrachloride are used. Can be. This molecular weight regulator need not always be used, and if used, a very small amount is preferably used, for example, a range of 0.3% by weight or less based on the monomer component.

The matting agent of the present invention obtained as described above can be used as it is for molding. It is contained as an essential component in the matte thermoplastic resin composition of the present invention.

 Next, the composition will be described.

The amount of the matting agent component in the composition is appropriately selected depending on the type of the polymer to be mixed and the desired degree of matting (glossiness), and is not particularly limited. It is preferable to contain 5% by weight or more of a matting agent from the viewpoint of giving a matting effect.

The other polymer components other than the matting agent to be mixed are not particularly limited, and various known copolymers can be used.

For example, the well-known acrylonitrile-
Butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-ethylene propylene diene
Styrene copolymer (AES resin), acrylonitrile-butyl acrylate-styrene copolymer (AAS resin), acrylonitrile-butyl acrylate-α-methylstyrene-styrene copolymer (heat-resistant AAS resin), acrylonitrile-butyl acrylate One or more copolymers such as -α-methylstyrene-N-phenylmaleimide (super heat-resistant AAS resin) can be used.

These copolymers are preferably less than 95% by weight, more preferably 70 to 30% by weight, in the matte thermoplastic resin composition. If it is more than 70% by weight, the light reflectance (glossiness) on the surface of the molded product tends to increase, and the matting tends to be insufficient. On the other hand, when the content is less than 30% by weight, the properties of the matting agent itself become strong, so that the surface becomes rough and the weld tends to come out easily. A particularly preferred range is 60 to 40% by weight.

The matting agent of the present invention can be mixed with polycarbonate to form a thermoplastic resin composition having excellent heat resistance.

Since the polycarbonate used in the present invention exhibits good heat resistance and impact strength, it has a number average molecular weight of about
8,000 to 200,000 is preferred, especially about 10,000 to 80,0
00 is preferred. In addition, the number average molecular weight can be measured by a gel permeation chromatography method. Further, those having an intrinsic viscosity of 0.4 to 1.0 dl / g when measured with a methylene chloride solvent at 25 ° C. are preferable. If the intrinsic viscosity is less than 0.4 dl / g, the mechanical strength tends to decrease, while if it exceeds 1.0 dl / g, the moldability tends to decrease.

The divalent phenols used as raw materials for this polycarbonate include 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, and 2,2-bis (4-hydroxy-3-methylphenyl). Propane, 4,4
-Bis (4-hydroxyphenyl) heptane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl)
There are propane, bis (3-chloro-4-hydroxyphenyl) methane and the like, which are used alone or in combination of two or more.

Examples of the method for producing the polycarbonate include a phosgene method in which phosgene is blown in the presence of a divalent phenol, an aqueous caustic solution and a solvent, and an ester produced by transesterifying a divalent phenol with a diester carbonate in the presence of a catalyst. There are known methods such as an exchange method, and the production method is not limited.

When mixing with polycarbonate, it is preferable to mix the above-mentioned matting agent component at 10 to 50% by weight and the polycarbonate at 50 to 90% by weight. If the matting agent is less than 10% by weight, the matting property of the composition tends to decrease, and if it exceeds 50% by weight, the heat resistance of the composition tends to decrease.

Further, the matting agent of the present invention can be mixed with a vinyl chloride resin to form a flame-retardant matte thermoplastic resin composition.

The vinyl chloride resin used in the present invention is generally known, and includes a homopolymer of vinyl chloride and a copolymer of vinyl chloride with another vinyl monomer such as ethylene. Here, in the case of a copolymer, the vinyl chloride content of the copolymer is preferably 90% by weight or more from the viewpoint of flame retardancy.

When mixing with the vinyl chloride resin, it is preferable to mix the matting agent component in an amount of 20 to 70% by weight and the vinyl chloride resin in an amount of 80 to 30% by weight.

Here, if the vinyl chloride resin content is less than 30% by weight, the flame retardancy is insufficient without being self-extinguishing, whereas if it exceeds 80% by weight, the impact resistance and heat deformation resistance tend to decrease. is there.

The matting agent and other copolymers can be mixed by a method in which beads, powders, or pellets of each component are melt-kneaded with a roll, screw, Banbury mixer, kneader, or the like. In such kneading or mixing,
If necessary, other resins, antioxidants, ultraviolet absorbers, flame retardants, pigments, glass fibers, plasticizers and the like can be added.

The resulting matte thermoplastic resin composition is molded by a known method and used as various molded articles.

The resulting molded article contains rubber particles derived from the matting agent component,
Since the rubber particles are dispersed in a matrix of another resin and 30% by volume or more of the rubber particles are the above-mentioned non-spherical rubber particles, the rubber particles have excellent impact resistance and matting properties.

(Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In the examples, “parts” and “%” are unless otherwise specified.
They represent "parts by weight" and "% by weight", respectively.

 The characteristic values in the examples were measured by the following methods.

Surface gloss: smooth surface of color plate obtained by molding (90
× 50 × 2 mm) was measured at an incident angle of 60 ° using a gloss meter VG-1B manufactured by Nippon Denshoku Industries Co., Ltd.

Izod impact: measured with a 1/8 "(inch) notch according to ASTM-D256.

Dropping weight impact (Dupont impact): Measured with a Dupont-type impact measuring instrument at a tip R of 1/4 "(inch) and a pedestal hole diameter of 1/2" (inch) per 1.5 mm of the color plate thin portion.

Heat distortion temperature (HDT): Heat resistance was measured at 1/2 ″ (inch) and about 18.56 kg / cm ² (264 psi) according to ASTM-D648.

MFR (Melt flow rate): 230 according to JIS K7210
The fluidity was measured at 10 ° C. and 10 kg.

Appearance The appearance of the obtained molded product was ignored, and the judgment was made according to the following criteria.

：: The surface is uniform and not rough at all.

Δ: It can be seen from staring that the surface is not uniform.

×: The surface is uneven and rough.

Tensile strength: Measured according to JIS K 7113 using a No. 1 test piece.

Elongation: Measured according to JIS K 7114 using a No. 1 test piece.

 Flame retardancy: The flame retardancy test was measured according to UL-94 standard.

Example 1 To an autoclave of 150, 16.4 kg of styrene, 95 g of t-dodecylmercaptan and 5.5 g of 2,6-di-t-butyl-4-methylphenol were charged, and low cis polybutadiene (trade name BR1241ST, manufactured by Zeon Corporation). Butadiene microstructure Vinyl: cis: trans = 11:37:52, Mooney viscosity 35) 3.55 kg was cut into small pieces and dispersed in a styrene monomer with stirring. Next, the temperature was raised to 80 ° C. and kept for 2 hours to completely dissolve the low cis-polybutadiene. Thereafter, the solution was cooled to 50 ° C., and 80 g of lauroyl peroxide and 89 g of diethylene glycol-bis (t-butylperoxycarbonate) (Kayaren O, trade name, manufactured by Gunpaku Nouri Co., Ltd.) were dissolved in 680 g of styrene monomer, and the solution was placed in a kettle. At the same time, 6.68 kg of acrylonitrile was charged and kept at 50 ° C. In this case, the polymerization rate was 1% / hour. 4
After a lapse of time, when the conversion reaches 4%, a 1.0% aqueous solution of polyvinyl alcohol (trade name: W-2, manufactured by Denki Kagaku KK)
4) 47.7 kg was added, and suspension polymerization was performed. The polymerization diagram is first at 80 ° C for 2 hours, then at 100 ° C for 2 hours,
The polymerization was continued at 10 ° C. for 3.5 hours to complete the reaction. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer beads were collected by a centrifugal separator and dried. The dried beads were pelletized with a 30 mm diameter extruder to obtain a low gloss resin (polishing agent). Using this pellet, a test piece was formed with an injection molding machine and evaluated. The molding machine uses KS-60B manufactured by Kanto Seiki Co., Ltd.
Cylinder temperature 260-260-240-200 (° C) was used as the standard temperature. Injection pressure is 400kg ・ f / cm ² , 600kg ・ f / cm ² , 800kg ・ f
The characteristics of the molded product obtained at an injection pressure which was molded at a pressure of / cm ² and did not cause a short shot were measured. Molding was performed at a medium injection speed and a constant mold temperature of 60 ° C.

In addition, the shape of the rubber particles in the molded article was determined by adjusting the specimen of the molded article in the xy, yz and zx planes by the OsO ₄ staining ultra-slicing method as shown in FIG. Photographs were taken at × 2 and measured (at the center of the test piece, at a depth of 40-50 μm from the surface layer).

In this example, the content of the non-spherical rubber particles was yz
The measurement was made based on the area of the non-spherical rubber particles in the photograph based on the plane.

FIGS. 3, 4 and 5 are photographs of the molded article manufactured in Example 1. FIG.

Example 2 The polymerization rate when shifting from bulk polymerization to suspension polymerization was 1.5
% (After 1.5 hours) in the same manner as in Example 1.

Example 3 In Example 1, the amount of lauroyl peroxide used was changed to 80 g.
To 120 g, the polymerization temperature (insulation temperature) at the start of polymerization is 50 ° C
From 55 to 55 ° C (polymerization rate was 3.3% / hour), and 4 hours after the start of bulk polymerization (when the conversion reached 13%), suspension polymerization was started. Other than that, it carried out similarly to Example 1.

Comparative Example 1 The conversion at the time of transition from bulk polymerization to suspension polymerization was 0.5
% (After 30 minutes), and the same procedure as in Example 1 was carried out.

Comparative Example 2 In Example 1, the amount of lauroyl peroxide used was 80 g.
To 120 g, the polymerization temperature (insulation temperature) at the start of polymerization is 50 ° C
From 60 to 60 ° C (polymerization rate was 5% / hour), and 3 hours and 40 minutes after the start of bulk polymerization (when the conversion reached 18%), the suspension polymerization was started. Other than that, it carried out similarly to Example 1.

Comparative Example 3 25% polymerization rate when shifting from bulk polymerization to suspension polymerization
(After 5 hours) The same procedure as in Comparative Example 2 was carried out. Table 1 shows the above results.

Comparative Examples 4 to 7 Synthesis and evaluation were performed in the same manner as in Example 1 except that the type of butadiene rubber was changed as shown in Table 2.

Note): The dissolution time is the time until the rubber component is completely dissolved. As a measuring method, the stirring of the yarn is stopped every hour, and the presence or absence of undissolved rubber floating on the surface is visually determined. The workability was evaluated as poor when the dissolution time was 5 hours or more and good when less than 5 hours.

Comparative Example 4 is an example using BR1242S (manufactured by ZEON Corporation, low cis polybutadiene), and has a large Mooney viscosity, poor dissolving workability, and low falling weight impact strength of the obtained resin. Comparative Examples 5 and 6 are examples using 1220SB and 1220SL (Hicis polybutadiene manufactured by Zeon Corporation), and also have the disadvantage that the falling weight impact strength is low. Comparative Example 7
This is an example in which S310 (manufactured by Nippon Zeon, styrene-butadiene copolymer rubber) is used. The surface gloss value is 94%, and there is no matting effect.

Examples 4 to 6 Although the rubber component in the matting agent of Example 1 was 13%,
This was changed to 5%, 10%, and 15%, and the other steps were the same as in Example 1.

Example 7 An acrylonitrile-butyl acrylate-styrene copolymer AAS (Vitax V, manufactured by Hitachi Chemical Co., Ltd.)
6700), the matting agent obtained in Example 1 was added at the ratio shown in Table 4 (units by weight, the same applies hereinafter), mixed with a Hensiel mixer, and pelletized with a 30 mm diameter extruder. An erased thermoplastic resin composition was obtained. Using this pellet,
A test piece was molded using an injection molding machine in the same manner as in Example 1.
The results were evaluated and the results are shown in Table 4.

Example 8 AES resin which is an acrylonitrile-ethylene propylene diene-styrene copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd.
# 110) was blended with the matting agent obtained in Example 1 at the ratio shown in Table 5, and evaluated in the same manner as in Example 7. The results are shown in Table 5.

Example 9 ABS resin which is an acrylonitrile-butadiene-styrene copolymer (manufactured by Sumitomo Nogatak Co., Ltd., Clara 2938)
In A), the matting agent obtained in Example 1 was blended in the proportions shown in Table 6 and evaluated in the same manner as in Example 7. The results are shown in Table 6.

Example 10 Super heat resistant acrylonitrile-butyl acrylate-α-methylstyrene-N-phenylmaleimide copolymer
AAS resin (Vitad VT2001, manufactured by Hitachi Chemical Co., Ltd.)
The matting agent obtained in Example 1 was mixed in the proportions shown in Table 7 and evaluated in the same manner as in Example 7. The results are shown in Table 7.

Example 11 A matting agent was prepared in the same manner as in Example 1 except that the conversion to the suspension polymerization was changed to 2% (after 2 hours), and 50 parts of the matting agent was added to 50 parts of Vitax V6700. It was blended and evaluated in the same manner as in Example 7, and the results are shown in Table 8.

Example 12 A matting agent was prepared in the same manner as in Example 3 except that the conversion to the suspension polymerization was changed to 10% (after 3 hours). 50 parts of the matting agent was added to 50 parts of Vitax V6700. Was evaluated in the same manner as in Example 7, and the results are shown in Table 8.

Comparative Example 8 In Example 1, a matting agent was produced by performing suspension polymerization from the beginning without performing bulk polymerization. This was mixed with 50 parts of Vitax V6700 and 50 parts, and evaluated in the same manner as in Example 7. The results are shown in Table 8.

Comparative Example 9 The same operation was performed as in Comparative Example 8, except that the matting agent used was that of Comparative Example 1.

Comparative Example 10 The same operation was performed as in Comparative Example 8, except that the matting agent used was Comparative Example 2.

Comparative Example 11 The same operation was performed as in Comparative Example 8, except that the matting agent used was Comparative Example 3.

Comparative Examples 12 to 15 As a matting agent, the ninth modified butadiene rubber was used.
The operation was performed in the same manner as in Comparative Example 8 except that the ones shown in the table were used.

Examples 13 to 15 As a matting agent, a low cis-butadiene rubber component (BR1241
ST) except that the one shown in Table 10 was used.
The same operation was performed as in Comparative Example 8.

Examples 16 to 22 The matting agent obtained in Example 1 and polycarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Iupilon S-1000, Mn about 1)
0.6d intrinsic viscosity measured with methylene chloride solvent at 0,000,25 ℃
l / g, with bisphenol A as the main raw material) were mixed at the ratio shown in Table 11 with a Henschel mixer and pelletized with an extruder having a diameter of 30 mm. Next, test pieces were molded using an injection molding machine using the pellets and evaluated. The results are shown in Table 11.

As is clear from Table 11, the balance between gloss and impact is particularly good when the matting agent is 10 to 50% by weight in the blend with polycarbonate.

Comparative Examples 16 to 19 Matting agents (comparative examples 4 to 7) in which the type of butadiene rubber was changed as shown in Table 12 and polycarbonate 70
And evaluated in the same manner as in Example 16.

Comparative Examples 20 to 22 The polymerization rates when shifting from bulk polymerization to suspension polymerization
30 parts of the matting agents of Comparative Examples 1 to 3 synthesized at 0.5%, 18% and 25% and 70 parts of polycarbonate were blended and evaluated in the same manner as in Example 16. The results are shown in Table 13.

Examples 23 to 24 Example 16 was repeated in which 30 parts of the matting agent of Examples 4 and 6 and 70 parts of polycarbonate were compounded by changing the compounding of the rubber component in the matting agent to 5% and 15%. Was evaluated in the same way as The results are shown in Table 14.

Examples 25 to 29 and Comparative Example 23 An ethylene-vinyl chloride copolymer (manufactured by Tosoh Corporation, Liuron E-430) as the vinyl chloride resin and the matting agent of Example 1 were used in the proportions shown in Table 15 to obtain the desired results. They were mixed with a shell mixer and pelletized with a 30 mm diameter extruder. Next, test pieces were molded using an injection molding machine using the pellets and evaluated.

From the above table, it can be seen that in the case of mixing with a vinyl chloride resin, the balance of each property is particularly well balanced when the matting agent is 20 to 70% by weight.

Comparative Examples 24 to 27 Forty parts of the matting agent (comparative examples 4 to 7) obtained by changing the type of butadiene rubber of Example 1 as shown in Table 16 and 60 parts of Liuron E-430 were blended. A comparison was made as in Example 25.

Comparative Examples 28 to 30 Each of the polymerization rates when shifting from bulk polymerization to suspension polymerization
Example 2 in which 40 parts of the matting agent of Comparative Examples 1 to 3 synthesized with changing to 0.5%, 18% and 25% and 60 parts of Liuron E-430 were blended.
Evaluation was made in the same manner as in 5. The results are shown in Table 17.

Examples 30, 31 40 parts of the matting agent of Examples 4 and 6 and 60 parts of Liuron E-430 were synthesized by changing the compounding of the rubber component in the matting agent to 5%, 15%. And evaluated in the same manner as in Example 25. The results are shown in Table 18.

Examples 32 to 33 and Comparative Example 31 Table 19 shows a vinyl chloride resin having a polymerization degree of 810 (manufactured by Tosoh Corporation, TH-800, vinyl chloride homopolymer) as the vinyl chloride resin and the matting agent of Example 1. It was blended at the indicated ratio and evaluated in the same manner as in Example 25.

Example 34 1150 kg of styrene, 47.5 g of t-dodecyl mecaptan (0.2% based on the monomer component) and 2,6
5.5 g of di-t-butyl-4-methylphenol was charged, and low cis polybutadiene (manufactured by Zeon Corporation, trade name BR1241ST, butadiene part microstructure, vinyl: cis:
Trans = 11: 37: 52, Mooney viscosity 35) 3.55 kg was cut into small pieces and dispersed in a styrene monomer with stirring.
Next, the temperature was raised to 80 ° C. and kept at this temperature for 2 hours to completely dissolve the low cis polybutadiene. Thereafter, the mixture was cooled to 50 ° C, and lauroyl peroxide (119 g, 0.5 g based on the monomer component)
%) And 89 g of diethylene glycol-bis (t-butylperoxycarbonate) (Kayaren O, manufactured by Gunpowder Nouri) are dissolved in 680 g of a styrene monomer and charged in a kettle, and 6.68 kg of acrylonitrile are charged at the same time, and 1.5 hours
The temperature was kept at 50 ° C. At this time, the polymerization rate was 5%.

Here, 47.7 kg of a 1.0% aqueous polyvinyl alcohol solution (trade name: W-24, manufactured by Denki Kagaku KK) was added, and suspension polymerization was carried out. The polymerization diagram is 80 ° C for 2 hours, 100 ° C for 2 hours, 1
A step of raising the temperature stepwise at 10 ° C. for 2 hours was employed. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer biz was recovered by a centrifugal separator and dried. The dried beads were pelletized with a 30 mm diameter extruder to obtain a low gloss resin (matting agent). A test piece is molded using an injection molding machine using this pellet.
evaluated.

The molding was performed using KS-60B manufactured by Kanto Seiki Co., Ltd.
The cylinder temperature of 260-260-240-220 ° C was used as the standard temperature. Injection pressure 400kg ・ f / cm ² , 600kg ・ f / cm ² , 80
Characteristics were measured on molded products obtained at an injection pressure of 0 kg · f / cm ^{2 and} which did not cause a short shot. The injection speed was set to medium speed, and the mold temperature was kept at 60 ° C.

The molecular weight of the acetone-soluble component was measured as follows. The resin components dissolved in acetone were measured by a gel order permeation chromatograph using a chromatograph manufactured by Uorders. The molecular weight was expressed in terms of standard polystyrene.

Examples 35 to 39 t-dodecyl mercaptan as a molecular weight modifier was added to
The evaluation was performed in the same manner as in Example 34 except that the amounts were changed to those shown in the table. Table 20 shows the results. As is clear from Table 20, Example 39 in which the acetone soluble molecular weight was 90,000 was used.
Although the MFR is good, the Izod impact tends to decrease.

Examples 40 to 43 Without using t-dodecyl mercaptan, the amount of lauroyl peroxide was 0.6%, 0.7%, 0.8%, 0.2%, based on the monomer component.
4%, and the other conditions were the same as in Example 34. The results are shown in Table 21. In Example 43, the molecular weight was too high and the MFR was small.

Examples 44 to 46 The rubber component in the matting agent of Example 34 was 13%.
This was changed to 5%, 10%, and 15%, and the other conditions were the same as in Example 34. The results are shown in Table 22.

Comparative Examples 32-34 In the synthesis of Example 34, the conversion was changed as shown in Table 23 at the time of transition from bulk polymerization to suspension polymerization, and synthesis was performed.

Comparative Examples 35 to 38 Evaluations were made in the same manner as in Example 34 except that the type of butadiene rubber was changed as shown in Table 24.

Example 47 The resin (matting agent) obtained in Example 34 and AAS which is an acrylonitrile-butyl acrylate-styrene copolymer
Second resin (Vitax V6810 manufactured by Hitachi Chemical Co., Ltd.)
The mixture was blended at the ratios shown in Table 5 and pelletized with an extruder having a diameter of 30 mm to obtain a low-gloss resin composition. Using this pellet, a test piece was molded using an injection molding machine and evaluated.

Example 48 Instead of the AAS resin of Example 47, an acrylonitrile-ethylene propylene diene-styrene copolymer AES resin (# 110 manufactured by Nippon Synthetic Rubber Co., Ltd.) was blended at the ratio shown in Table 26 and evaluated. .

Example 49 Instead of the AAS resin of Example 47, an acrylonitrile-butadiene-styrene copolymer ABS resin (Clara 2938A manufactured by Sumitomo Nogatak Co., Ltd.) was blended at the ratio shown in Table 27 and evaluated.

(Effect of the Invention) According to the present invention, Izod impact, mattability,
A matting agent balanced with physical properties such as DuPont impact can be obtained. Using this matting agent, heat resistance, impact resistance and low gloss of interior and exterior parts of automobiles and exterior parts of home electric appliances A matte thermoplastic resin composition and a molded article useful for a molded article requiring the following are obtained.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a preferable shape of a rubber component contained when the matting agent of the present invention is molded, and FIG. 2 is a perspective view of a plate of a molded article molded in the embodiment of the present invention. Fig. 3 and Fig. 3 show a sample prepared by the OsO ₄ stained ultra-thin section method using the xy plane 1 as a section in the molded article of Fig. 2.
FIG. 4 is an electron micrograph showing the particle structure at a magnification of 10000, FIG. 4 is a photograph similar to FIG. 3 with the yz plane 2 of FIG. 2 as a section, and FIG. 5 is a zx plane 3 of FIG. 3rd section
It is a photograph similar to a figure. Description of reference numerals 1 ... xy plane, 2 ... yz plane 3 ... zx plane

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location // C08F 279/02 C08F 279/02 (72) Inventor Masafumi Shitara 14 Goi south coast, Ichihara city, Chiba prefecture Address Hitachi Chemical Co., Ltd., Goi Plant (72) Inventor Kazura Yochi 4--13-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd., Ibaraki Research Laboratory (72) Inventor Jun Matsuzawa, Higashimachi 4, Hitachi City, Ibaraki Prefecture No. 13-1, Hitachi Chemical Co., Ltd. Ibaraki Research Laboratories (56) References JP-A-62-96511 (JP, A) JP-A-60-202143 (JP, A)

Claims (20)

(57) [Claims] 1. A matting agent comprising a graft copolymer based on a low cis polybutadiene rubber having a Mooney viscosity of 30 to 40, comprising a matting agent and another resin, and rubber particles derived from the matting agent. A matting agent characterized in that, when a molded article is dispersed in a matrix of another resin, 30% by volume or more of the rubber component particles are non-spherical rubber particles. 2. The matting agent according to claim 1, wherein the graft component of the graft copolymer contains aromatic vinyl and vinyl cyanide. 3. The graft copolymer according to claim 1, wherein the rubber component is 5 to 15% by weight and the graft component is 95 to 85% by weight.
Matting agent as described. 4. The matting agent according to claim 1, wherein the acetone-soluble component has a weight average molecular weight of 100,000 to 600,000. 5. The method for producing a matting agent according to claim 1, wherein a monomer component is blended in the presence of a low cis polybutadiene having a Mooney viscosity of 30 to 40, and bulk suspension polymerization is performed. 6. The process for producing a matting agent according to claim 5, wherein the polymerization rate of the monomer at the time of transition from bulk polymerization to suspension polymerization is 1 to 15%. 7. The method for producing a matting agent according to claim 5, wherein the polymerization is completed so that the acetone-soluble component has a weight average molecular weight of 100,000 to 600,000. 8. The method for producing a matting agent according to claim 5, wherein the monomer components to be blended are aromatic vinyl and vinyl cyanide. 9. The method according to claim 5, wherein 95 to 85% by weight of the monomer component is blended in the presence of 5 to 15% by weight of the low cis polybutadiene.
The method for producing a matting agent according to 6, 7, or 8. 10. A matting agent obtained by the production method according to claim 5. 11. A matting thermoplastic resin composition comprising the matting agent according to claim 1, 2, 3, or 10 and another polymer. 12. Other polymers include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-ethylenepropylenediene-styrene copolymer, acrylonitrile-butyl acrylate-styrene copolymer. 12. The matte thermoplastic resin according to claim 11, comprising a copolymer, acrylonitrile-butyl acrylate-α-methylstyrene-styrene and / or acrylonitrile-butyl acrylate-α-methylstyrene-N-phenylmaleimide copolymer. Composition. 13. The matte thermoplastic resin composition according to claim 11, which contains a matting agent in an amount of 5% by weight or more. 14. The matte thermoplastic resin composition according to claim 11, which comprises 30 to 70% by weight of a matting agent. 15. The heat-resistant matte thermoplastic resin composition according to claim 11, comprising polycarbonate as another polymer. 16. The heat-resistant matte thermoplastic resin composition according to claim 15, comprising a matting agent in an amount of 10 to 50% by weight. 17. The flame-retardant matte thermoplastic resin composition according to claim 11, further comprising a vinyl chloride resin as another polymer. 18. The flame-retardant matte thermoplastic resin composition according to claim 17, comprising 20 to 70% by weight of a matting agent. 19. A molded article obtained by molding the matting agent according to claim 1, 2, 3, 4 or 10, or the matting thermoplastic resin composition according to any one of claims 11 to 18. 20. The molding according to claim 19, wherein the matting agent-derived rubber particles are dispersed in a matrix of another polymer component, and at least 30% by volume of the rubber particles are non-spherical rubber particles. Goods.