JPH0358379B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a matte thermoplastic resin composition. So-called ABS resins are made by graft polymerizing vinyl monomers such as styrene monomers to rubbery polymers such as synthetic rubber and natural rubber.
Styrenic rubber-modified thermoplastic resins such as AES resins, or flame-retardant styrenic rubbers blended with halogen compounds, antimony compounds, and halogen-containing resins such as polyvinyl chloride resins to impart flame retardancy to these thermoplastic resins. Modified thermoplastic resins have excellent processability and physical properties, and are relatively inexpensive, so they are used for various purposes. Molded products made of these resins are generally glossy, but recently, so-called so-called molded products that maintain impact resistance and other resin properties and have a non-glossy surface are being used for automobile interior parts and exterior parts of household electrical equipment. There are applications where matte properties are desired. In general, methods for matting thermoplastic resin molded products include (1) blending inorganic materials with the resin, (2) surface treatment such as squeezing or matting on the surface of the molded product, and (3) solid Alternatively, a method of blending a latex-like rubbery polymer with a resin is known. However, in method (1) above, the impact resistance and formability are significantly reduced due to the blending of a large amount of inorganic materials, and in method (2) above, a sufficient matting effect cannot be obtained and matting occurs during vacuum forming. In addition, matte coating is costly and has poor productivity. moreover
In method (3), the weight resistance of the rubber and the compatibility with the resin were poor, and it was difficult to satisfy both the matte effect and the excellent properties of the resin such as impact resistance and processability. Based on the above background, the present inventors conducted intensive studies and arrived at the present invention with the aim of efficiently producing a resin with excellent matte properties with almost no deterioration in the physical properties and processability of the resin. . According to the present invention, (A) rubber modification heat obtained by copolymerization of at least one compound selected from vinyl cyanide compounds, acrylic esters and methacrylic esters and an aromatic vinyl compound in the presence of a rubbery polymer; A mixture of 40 to 97% by weight of a copolymer consisting of a plastic resin, or the above-mentioned rubbery polymer or rubber-modified thermoplastic resin and the above-mentioned monomer, and (B) an aromatic vinyl compound, a vinyl cyanide compound, and a copolymer thereof. A copolymer obtained by polymerizing a monomer mixture consisting of a polymerizable polyfunctional compound and, if necessary, another polymerizable vinyl compound, using an organic hydroperoxide as an initiator. Type flow tester (200℃,
30Kg/cm ² , 1φ x 2mm nozzle)
A matte thermoplastic resin composition comprising 60 to 3% by weight of a copolymer having a copolymer of 10×10 ^-3 cm ³ /sec or less is provided. The resin composition of the present invention is (A) a rubber-modified thermoplastic resin.
Consisting of 40-97% by weight, preferably 40-95%, more preferably 50-95% and (B) copolymer 60-3%, preferably 60-5%, more preferably 50-5% by weight . If the proportion of the polymer (B) is less than 3%, a sufficient matting effect cannot be obtained, while if it exceeds 60%, only a resin with low impact resistance and poor moldability is obtained. The rubber-modified thermoplastic resin used in the present invention contains at least one compound selected from a vinyl cyanide compound and a (meth)acrylic acid ester compound and an aromatic vinyl compound as a rubber-like polymer, and if necessary, these compounds. It is obtained by graft polymerizing a monomer consisting of a compound copolymerizable with. Polymer blends of rubbery polymers and copolymers of the above monomers may also be used. Rubber polymers include diene rubber polymers such as polybutadiene, natural rubber, styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), polyisoprene, polychloroprene, and ethylene-propylene copolymer. combination, ethylene-propylene-nonconjugated diene copolymer, chlorinated polyethylene,
Examples include non-diene rubbery polymers such as acrylic rubbery polymers. These rubbery polymers are produced by emulsion polymerization or solution polymerization, and polybutadiene, polyisoprene, SBR coupled with tin or lithium, and styrene-butadiene block copolymers can also be used. These rubbery polymers can be used alone or in combination of two or more. It is also possible to use a mixture of a diene rubbery polymer and a non-diene rubbery polymer. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile; examples of (meth)acrylic acid ester compounds include alkyl acrylates, alkyl methacrylates, and hydroxyalkyl esters of ethylenically unsaturated carboxylic acids; examples of alkyl acrylates include methyl acrylate; , ethyl acrylate,
Examples of the alkyl methacrylate include butyl acrylate and the like, and examples of the alkyl methacrylate include methyl methacrylate and ethyl methacrylate. Among them, methyl methacrylate is preferred. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and halogenated styrene, among which styrene is preferred. The content of the aromatic vinyl compound is preferably 20-95%, preferably 25-90%, and more preferably 30-85% by weight based on the total amount of the above monomers.
It is. A typical rubber-modified thermoplastic resin is acrylonitrile-butadiene-styrene resin (so-called
ABS resin), acrylonitrile-ethylene propylene-styrene resin (so-called AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-
Acrylonitrile methacrylate-butyl acrylate-butadiene-styrene resin (AAS resin)
Examples include. The rubber content of the above-mentioned rubber-modified thermoplastic resin is preferably in the range of 5 to 70% by weight in terms of physical properties. Further, the rubber-modified thermoplastic resin (A) of the present invention also includes a blend-type thermoplastic resin of a copolymer composed of the monomer component of (A) and a rubber-modified thermoplastic resin. Next, among the monomers constituting the copolymer (B), aromatic vinyl compounds and cyanide vinyl compounds are exemplified as monomer components in the rubber modified resin (A). Vinyl compounds are used. In addition, as a functional compound, two or more non-conjugated divinyl compounds represented by divinylbenzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, etc.
Preferably, a compound having two copolymerizable double bonds can be used. Examples of polyvalent acrylate compounds that can be used in the present invention include the following compounds. Examples of diacrylate compounds include polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-acryloxy, propyloxyphenyl)propane, 2,2'-bis(4-acryloxy, diethoxyphenyl)propane, and triacrylate compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, and tetraacrylate. The compound is tetramethylolmethanetetraacrylate, and the dimethacrylate compound is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate. Methacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-methacryloxydiethoxyphenyl)propane trimethacrylate compounds Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate The following methods can be used to add the polyfunctional monomer. (1) A method in which it is added to the reaction system together with a vinyl aromatic compound and a vinyl cyanide compound, either once or in batches. (2) A method of adding it to the reaction system together with a vinyl aromatic compound and a vinyl cyanide compound by adding it in batches at least once and adding it continuously. (3) A method in which a vinyl aromatic compound and a vinyl cyanide compound are added continuously to the reaction system. (4) A method in which a functional monomer is added when the vinyl aromatic compound and vinyl cyanide compound reach a polymerization conversion rate of 50 to 90%. The preferred content of the polyfunctional monomer in the crosslinked copolymer (B) resin is 0.006 to 1.5 mol%, more preferably
It is 0.01-1.2 mol%. When used within this range,
A crosslinked resin is obtained that provides a balance between matte effect and processability. However, if a large amount of the molecular weight regulator is used in a region where the amount of polyfunctional monomer used is small, a resin that does not have an acetonation-soluble (transparent) crosslinked structure may be obtained. When such a resin is used, a sufficient matting effect cannot be obtained. Other copolymerizable vinyl compounds that may be used as needed include alkyl acrylate,
Examples include alkyl methacrylates and hydroxyalkyl esters of ethylenically unsaturated carboxylic acids. The copolymer (B) is obtained by emulsion polymerization using an organic hydroperoxide as an initiator. A sufficient matting effect is not achieved when initiators other than organic hydroperoxides are used. By using the emulsion polymerization method, a polymer with stable quality can be easily obtained industrially and has an excellent matting effect. Preferred examples of the organic hydroperoxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, paramenthane hydroperoxide, and di-t-butyl hydroperoxide. One type or two or more types can be used. The crosslinked copolymer (B) resin of the present invention is preferably a resin that does not completely dissolve in acetone. If it is not completely dissolved, the state is 1 in acetone at room temperature.
A state in which some or all of the liquid does not dissolve. When part or all of the resin in acetone is not dissolved, the acetone resin solution becomes cloudy, so it can be determined, for example, whether the resin is crosslinked or not based on the cloudiness of the 5% acetone solution. If a copolymer that is soluble in acetone is used, the matting effect aimed at by the present invention cannot be sufficiently achieved. In addition, the copolymer (B) has a Q value of 200℃ and 30Kg/
cm ² , 10×10 ^-3 cm ³ /sec under 1φ×2mm nozzle conditions
It is preferably 5×10 ⁻³ cm ³ /sec or less.
Here, the Q value is an index of the fluidity of the resin, and if the Q value exceeds 10×10 ^-3 cm ³ /sec, a sufficient matting effect cannot be obtained. The composition of the present invention may contain one or more flame retardants such as organic halogen compounds, flame retardant synergistic agents, and halogen-containing resins. Specifically, the organic halogen compounds include, for example, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), and tetrabromobisphenol A-bis(2,3-dibromopropyl ether).
Tetrabromobisphenol A derivatives such as, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, bis(tribromophenoxy)ethane, hexabromocyclododecane, etc. can be used. Further, for example, monobromophenol, tribromophenol, pentabromophenol, tribromocresol, dibromopropylphenol, tetrabromobisphenol S, cyanuric chloride, etc. can be polymerized or combined with one or more selected from the group of the above-mentioned halogen compounds. Oligomeric halogen compounds obtained by copolymerization with halogen compounds can be used. As the flame retardant synergistic agent, one or more of antimony trioxide, borax, barium metaphosate, zirconium oxide, etc. can be used. These flame retardants are added in appropriate amounts depending on the type of resin and flame retardant.
In order to obtain sufficient flame retardancy, it is preferable to use an amount such that the amount is V- or higher according to Underwriters Laboratories Standard UL-94. Flame retardants may be added to component (A) and/or component (B) in advance, or may be added to a mixture of components (A) and (B). When using the thermoplastic composition of the present invention, other commonly added antioxidants, ultraviolet absorbers,
A lubricant, an antistatic agent, a filler, etc. can be added. The compositions of the present invention may also include synthetic rubbers, e.g.
Diene-based (co)polymers such as NBR, SBR, BR, 1,2-polybutadiene, inorganic fillers, etc. can be blended, and even better effects of the present invention can be obtained. It is also possible to blend other styrene resins. The composition of the present invention can be molded into various molded products such as home appliance parts and automobile parts by injection molding, extrusion molding, etc. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded. Parts in the examples are parts by weight. The measurement and evaluation methods used in Examples and Comparative Examples are shown below. (1) Solubility of acetone: After shaking 1 g of sample and 20 c.c. of acetone in a shaker for 24 hours, the cloudy state was visually observed. (2) Impact strength: ASTM D256 test piece 1/2″ x 1/4″ x 5/2″ notched piece (3) Heat distortion temperature: ASTM D-648 test piece 1/2″ x 1/2″ x 5 ″ Load 18.6Kg/cm ² (4) Fluidity: Temperature set at 240℃ using an injection molding machine with a capacity of 50z
The flow length of the resin was measured when molded at 220°C (Example 9 only). Molded product thickness: 2mm Injection pressure: 70Kg/cm ² (gauge pressure) Mold temperature: 50℃ (5) Surface gloss: Test piece: 55 x 80 x 1.6mm Mold temperature: 50℃ Gloss meter: Automatic measurement color difference meter AV-CH-G (manufactured by Suga Test Instruments Co., Ltd.) Incident angle, reflection angle: 45° (6) Surface appearance: Visual evaluation of the surface appearance of a 55 x 80 x 1.6 mm flat plate molded product was tested. ○: Good with no uneven gloss or flow marks △: Some uneven gloss or flow marks ×: Significant uneven gloss or flow marks (7) Flame retardancy: UL94 V test test piece 1/8″×1 /2″×5″ (8) Koka type flow: Measurement temperature: 200℃ Nozzle: 1mmφ×2mm Load: 30Kg/cm ² Manufacturing method of resin used in Examples and Comparative Examples Rubber-modified thermoplastic resin (A) (1) Production of resins A-(1) to A-(6) Resins were produced by the following method using the rubber components and monomer components shown in Table 1. Nitrogen-substituted reaction In a container, add polybutadiene latex (see Table 1) 2.0 parts of potassium rosinate Sodium ethylenediaminetetraacetate 0.045 (〃) Sodium formaldehyde sulfoxylate 0.03 (〃) Ferrous sulfate 0.05 (〃) Ion exchange water 150 (〃) and stir. At a polymerization temperature of 60°C, a monomer mixture of 0.3 (parts) of t-dodecyl mercaptan and 0.4 (parts) of cumene hydroperoxide (see Table 1) was added dropwise over 3 hours to carry out graft polymerization. Conversion of monomers The obtained latex was coagulated with sulfuric acid, the resin content was filtered, washed with water, dehydrated, and dried to form powdered rubber-modified thermoplastic resins A-(1) to A-(6). ) was obtained.

[Table] (2) Production of resin A-(7) After purging the interior of a stainless steel reactor equipped with a paddle-type stirring blade with nitrogen, the iodine value was 15, the Mooney viscosity was 65, the propylene content was 43% by weight, and the diene component was EPDM containing 5-ethylidene-2-norbornene (manufactured by Japan EP Rubber Co., Ltd.)
JSR EP-24) 18 parts, 57 parts of styrene, 25 parts of acrylonitrile, and 110 parts of toluene were prepared.
Stir at ℃ until the rubber is completely dissolved.
After adding 0.1 part of dodecyl mercaptan, 0.2 part of dibenzoyl peroxide, 0.2 part of t-butylperoxy-1-propyl carbonate, and 0.1 part of dicumyl peroxide, the temperature was raised at a stirring speed of 100 rpm, and the temperature was raised to 80°C. time,
Polymerization was further carried out at 100°C for 3 hours and at 125°C for 3 hours, totaling 9 hours. After distilling off unreacted monomers and solvent by steam distillation, it is pulverized and dried (A-
7) was obtained. Method for producing thermoplastic resin (B) (1) Production of thermoplastic resins B-(1) to (7) Using the monomer components, polyfunctional monomer, and molecular weight modifier shown in Table 2, the following conditions were used. The company produced resin. First, 1.0 (parts) of potassium oleate and 180 (parts) of ion-exchanged water were charged into a reactor, the atmosphere was purged with nitrogen, and the temperature was raised to 60°C. As components for imparting catalyst activity after heating up: Sodium formaldehyde sulfoxylate 0.045 (parts) Iron sulfate 0.006 (〃) Sodium ethylenediaminetetraacetate
After adding 0.07 (〃) 10 (〃) of ion-exchanged water and further adding the initiator shown in Table-2, a mixture of monomer components, polyfunctional monomer components, and molecular weight modifier components shown in Table-2 was prepared. was added dropwise over 2 hours at a polymerization temperature of 60°C, and after the addition was completed, the mixture was further stirred for 1 hour. The polymerization conversion rate was 94% or more. The obtained latex was coagulated with dilute sulfuric acid, and the resin content was filtered, washed with water, dehydrated, and dried to obtain resins B-(1) to (7). Note that the surface gloss of B-(1) was 15%. (2) Method for producing thermoplastic resin B-(8) In B-(1), no catalyst activation component is used, and 1.0 part of potassium persulfate is used instead of cumene hydroperoxide as an initiator. B-(8) was produced under the same conditions as B-(1) except that B-(8) was used. (3) Method for producing thermoplastic resin B-(9) 0.1 part of benzoyl peroxide was used in place of citric hydroperoxide in B-(1). B-(9) under exactly the same conditions as B-(1) except for
was manufactured.

[Table] Examples and Comparative Examples The blended compositions shown in Table 3 were pelletized using a 50 m/m vented extruder, and then injection molded with the results shown in Table 3. Examples are compositions made of various rubber-modified thermoplastic resins of the present invention and various thermoplastic resins (B),
A composition having the physical properties targeted by the present invention has been obtained. On the other hand, in Comparative Example 1, even though the Q value of the thermoplastic resin (B) is within the range of the present invention, the resin does not use a polyfunctional monomer and is soluble in acetone, which is outside the range of the present invention, and the matting effect is not achieved. I can't get it. Comparative Example 2 is an example using a thermoplastic resin whose Q value is outside the range of the constituent requirements of the present invention, but the matteness is not sufficient. In Comparative Example 3, even if a polyfunctional monomer is used in the polymerization of the thermoplastic resin (B), a matting effect cannot be obtained because the resin does not have a crosslinked structure and is soluble in acetone. Comparative Example 4 is an example in which potassium persulfate, which is outside the scope of the present invention, was used as an initiator in the polymerization of the thermoplastic resin (B). A sufficient matting effect cannot be obtained. Comparative Example 5 is an example in which the blending ratio of the thermoplastic resin (B) was outside the range of the present invention, but the impact strength and fluidity were greatly reduced, and the surface of the molded product was rough, making it unsuitable for practical use. Comparative Example 6 shows a case where the blending ratio of the thermoplastic resin (B) is smaller than the lower limit of the range of the present invention. A sufficient matting effect cannot be obtained. Comparative Example 7 is a crosslinked AS polymerized using benzoyl peroxide, which is an organic peroxide having a structure other than the hydroperoxide of the present invention.
However, it did not have the same matting effect as the one using hydroperoxide.

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Claims (1)

[Scope of Claims] 1 (A) Rubber modification obtained by copolymerization of at least one compound selected from vinyl cyanide compounds, acrylic esters, and methacrylic esters and an aromatic vinyl compound in the presence of a rubbery polymer. 40 to 97% by weight of a thermoplastic resin, or a mixture of the above-mentioned rubber-modified thermoplastic resin and a copolymer consisting of the above-mentioned monomers, and (B) an aromatic vinyl compound, a vinyl cyanide compound, and a polymer copolymerizable with these. A copolymer having a crosslinked structure obtained by polymerizing a monomer mixture consisting of a functional compound and, if necessary, another polymerizable vinyl compound, using an organic hydroperoxide as an initiator, and A matte thermoplastic resin consisting of 60 to 3% by weight of a copolymer with a Q value of 10 x 10 ^-3 cm ³ /sec or less as measured by a flow tester (200°C, 30Kg/cm ² , 1φ x 2mm nozzle) Composition.