JPS6367818B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition in which the surface of a molded product is matte without reducing the mechanical properties and moldability of the rubber-modified thermoplastic resin composition. Rubber-modified thermoplastic resins have excellent impact resistance, moldability, and good surface gloss, and are therefore used for various purposes. However, depending on the intended use, it may be desirable to have a matte surface of the molded product without degrading other physical properties. Applications that require such matte finish include automobile interior parts, office and household electrical equipment parts, and the like. Conventional matting methods for molded products include titanium,
A well-known method is to add oxides or carbonates such as magnesium and calcium to rubber-reinforced resins, but this method has the disadvantage of greatly reducing the mechanical properties of the resin, especially the impact strength, and also makes it less matte. However, the drawback is that the gloss on the surface of the molded product does not disappear uniformly. Another well-known method is to remove the luster by adding a rubbery elastomer to rubber-reinforced resin.
This method reduces the mechanical properties of the resin, particularly its hardness and rigidity. Further, foreign matter appears on the surface of the molded product, significantly reducing the commercial value of the molded product. Furthermore, a method of adding a three-dimensional resin component using a crosslinking monomer is also known, but this method has drawbacks such as causing uneven gloss on the surface of the molded product and reducing moldability. The present inventors have developed a matte rubber-reinforced thermoplastic resin that improves the previously known technical problems mentioned above, such as a decrease in impact resistance, rigidity, moldability, etc., and the occurrence of uneven gloss. As a result of extensive research aimed at achieving this goal, the present invention has been achieved. According to the present invention, a rubber-modified aromatic vinyl thermoplastic resin containing 5 to 40% by weight of a rubbery polymer and 0.3 to 3% by weight of an ethylenically unsaturated carboxylic acid copolymerized with a monovalent, A thermoplastic with a matte surface for mold production, characterized in that at least one divalent or trivalent metal compound is blended in a molar ratio of 0.1 to 2 to the ethylenically unsaturated carboxylic acid in the resin. A resin composition is provided. In the present invention, the resin that is a component of the rubber-modified aromatic vinyl thermoplastic resin includes a vinyl aromatic compound (b), a vinyl cyanide compound (c) in the presence or absence of a rubbery polymer (a). ), an ethylenically unsaturated carboxylic acid (d), and optionally a compound (e) copolymerizable with these (e). As the rubbery polymer (a), diene rubbery polymers and non-diene rubbery polymers can be used.
Examples of diene-based rubbery polymers include polybutadiene, natural rubber, styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), polyisoprene, polychloroprene, and the like. These rubbery polymers are produced by emulsion polymerization, solution polymerization, etc. Polybutadiene, polyisoprene, SBR coupled with tin or lithium, and styrene-butadiene block copolymers can also be used. These rubbery polymers may be used alone or in combination
A mixture of two or more species can be used. On the other hand, examples of the non-diene rubbery polymer include ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, chlorinated polyethylene, and acrylic rubbery polymer.
These non-diene rubbery polymers may be used alone or in combination
Can be used in combination of more than one species. It is also possible to use a mixture of a diene rubbery polymer and a non-diene rubbery polymer. As the vinyl aromatic compound (b), styrene, α
-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, vinylnaphthalene The preferred monomers are styrene and α-methylstyrene. Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile. Examples of the ethylenically unsaturated carboxylic acid (d) include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, etc.
Preferred monomers are acrylic acid and methacrylic acid. Compounds (e) copolymerizable with the above monomers, such as vinyl compounds having an amide group, N-methylol compounds, ethylenically unsaturated carboxylic acid esters, and polyfunctional monomers, can be used. Examples of the compound having an amide group or the N-methylol compound include acrylamide, methacrylamide, and N-methylolacrylamide. Examples of ethylenically unsaturated carboxylic acid ester compounds include alkyl acrylates, alkyl methacrylates, and esters of ethylenically unsaturated carboxylic acids and hydroxyalkyl.
Examples of the alkyl acrylate include methyl acrylate and ethyl acrylate. Examples of the alkyl methacrylate include methyl methacrylate and ethyl methacrylate. Examples of the hydroxyalkyl ester of ethylenically unsaturated carboxylic acid include β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate. Examples of polyfunctional monomers include divinylbenzene. Preferred embodiments of the above resin in the present invention are listed below. (1) A vinyl aromatic compound (b), a vinyl cyanide compound (c), an ethylenically unsaturated carboxylic acid (d) and, if necessary, a compound copolymerizable with these in the presence of a rubbery polymer (a). A composition consisting of a graft copolymer (A) obtained by polymerizing a monomer mixture (f) consisting of (e); (2) a vinyl aromatic compound (b), a vinyl cyanide compound;
(c), a copolymer (A′) obtained by polymerizing a monomer mixture (f) consisting of an ethylenically unsaturated carboxylic acid (d) and, if necessary, a compound (e) that can be copolymerized with these. A composition consisting of a rubber-modified thermoplastic resin (B), or a composition consisting of the above (A'), (B) and a vinyl aromatic (co)polymer (C); (3) The above (A) is essential. (4) A composition comprising (A') as an essential component and at least one of (A'), (B) and (C); A composition consisting of at least one; Among these compositions, more preferable ones are
(2), (3), and (4), with (2) being particularly preferred. The graft copolymer (A) or copolymer (A') is prepared by emulsion polymerization, suspension polymerization, or solution polymerization of the monomer mixture (f) in the presence or absence of the rubbery polymer (a). , bulk polymerization, or a combination of these polymerization methods. In order to adjust the pH of the polymerization system, it is also possible to neutralize the ethylenically unsaturated carboxylic acid with a base and return it to the carboxylic acid with a mineral acid after polymerization. Further, as the rubber-modified thermoplastic resin (B) in the above embodiment, examples include acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, and methyl methacrylate. Copolymers containing (heat-resistant ABS resin), acrylonitrile-ethylene/α monoolefin-styrene copolymer (ABS resin), acrylonitrile-butyl acrylate-styrene copolymer (ASA resin), methyl methacrylate-butadiene-styrene copolymer Combined resin (MBS resin), rubber modified polystyrene (HIPS resin), mixed resin of polycarbonate resin and ABS resin or AES resin,
Flame-retardant resin that combines ABS resin with vinyl chloride resin, and flame-retardant resin that combines ABS resin with flame retardant.
Examples include ABS resin. Among the rubber-modified thermoplastic resins, those containing vinyl aromatic monomers and vinyl cyanide compound monomers are particularly preferred. The vinyl aromatic (co)polymer C is a polymer of the vinyl aromatic compound (b) alone, or a polymer of the vinyl aromatic compound (b), a vinyl cyanide compound (c), and the copolymerizable compound ( Examples include copolymers with at least one selected from e). According to the present invention, the resin may be monovalent, divalent or trivalent.
By adding at least one type of metal compound having a valence metal compound, an excellent matting effect on the surface of the molded product can be obtained, and a molded product with a good surface appearance and free from flow marks can be obtained. These metal compounds are found in the periodic table.
It is a compound that generates monovalent to trivalent metal ions of metals of the 1st, 1st, and 3rd groups, and includes, for example, hydroxides, oxides, salts, and alcoholates of these metals. As those metal ions
Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Ag ⁺ , Be ²⁺ , Mg ²⁺ ,
Examples include Ca ²⁺ , Zn ²⁺ , Ba ²⁺ , Al ³⁺ , Fe ²⁺ , and Fe ³⁺ . The above metal compound has a molar ratio of metal compound to ethylenically unsaturated carboxylic acid in the composition of 0.1 to
2, preferably in the range of 0.2 to 1.5. If the molar ratio of the metal compound is less than 0.1, the matting effect will not be sufficient, and if it exceeds 2.0, the impact resistance will decrease, which is not preferable. When a monovalent metal hydroxide, metal salt, or alcoholate is used as the metal compound, the matting effect is excellent. Further, when an oxide, hydroxide, or alcoholate is used as the divalent or trivalent metal compound, the matting effect is excellent and the surface appearance of the molded product is also good. Specific compounds for hydroxides, oxides, metal salts, and alcoholates are shown below. Zn(OH) ₂ , Al(OH) ₃ , KOH, Ca(OH) ₂ , Sn
(OH) ₂ , Fe(OH) ₂ , NaOH, Ba(OH) ₂ , Hg
Hydroxides such as (OH) ₂ ; ZnO, Al ₂ O ₃ , K ₂ O,
Oxides such as CaO, SnO, FeO, Na ₂ O, BaO, MgO; ZnCl ₂ , Zn(C ₂ H ₃ O ₂ ) ₂ , ZnSO ₄ , AlCl ₃ ,
Al ₂ (SO ₄ ) ₃ , KCl, KC ₂ H ₃ O ₂ , K ₂ SO ₄ , CaCl ₂ ,
Ca(C ₂ H ₃ O ₂ ) ₂ , CaSO ₄ , SnCl ₂ , SnSO ₄ , FeCl ₂ ,
Fe(C ₂ H ₃ O ₂ ) ₂ , FeSO ₄ , NaCl, NaC ₂ H ₃ O ₂ ,
Na ₂ SO ₄ , BaCl ₂ , Ba(C ₂ H ₃ O ₂ ), BaSO ₄ ,
Metal salts such as MgCl ₂ , Mg(C ₂ H ₃ O ₂ ) ₂ , MgSO ₄ , zinc stearate, celsium stearate, barium stearate, tin stearate, dibutyltin dilaurylate, dibutyltin distearate; sodium methylate , sodium ethylate, sodium phenolate, and other alcoholates. Preferably ZnO, Al ₂ O ₃ , K ₂ O, CaO, SnO,
These are oxides such as FeO, Na ₂ O, BaO, and MgO. There are no particular restrictions on the method of incorporating the metal compound into the resin composition, but generally there is a method of adding the metal compound directly to the resin, or a method of mixing the metal compound and the resin in advance to adjust the content of the metal compound. There is a method of making a high-performance resin composition and mixing this with a resin. Depending on the type of metal compound, it is also possible to react the ethylenically unsaturated carboxylic acid as a polymerizable component with the metal compound before polymerization in the production of the resin composition. In the present invention, the content of the rubbery polymer (a) in the resin is 5 to 40% by weight, preferably 5 to 30% by weight. The content of ethylenically unsaturated carboxylic acid in the resin is 0.3 to 3% by weight, preferably 0.3 to 3% by weight.
2% by weight, more preferably from 0.3 to less than 1% by weight, particularly preferably from 0.3 to 0.9% by weight. The content of the vinyl aromatic compound (b) in the resin is preferably 54.7 to 90% by weight, more preferably
The content of the vinyl cyanide compound (c) is preferably 4.7 to 40% by weight, more preferably 4.5 to 35% by weight, and the content of the other copolymerizable compound (e) is 20% by weight. % or less, more preferably 0 to 10% by weight. It is preferable that the vinyl aromatic content is 54.7% by weight or more because moldability is excellent and hardness is high. The rubbery polymer contributes to improving impact resistance, and if it is less than 5% by weight, impact resistance cannot be obtained;
If it exceeds % by weight, the hardness decreases and its applications are limited. If the content of the ethylenically unsaturated carboxylic acid monomer is less than 0.3% by weight, the matting effect will not be sufficient, and if it exceeds 3.0% by weight, uneven gloss will occur on the surface of the molded product, resulting in uneven gloss. This is not preferable because it becomes matte. The content of vinyl cyanide compounds contributes to improving impact resistance and chemical resistance, and if the content is low, it causes a decrease in impact resistance and chemical resistance, which is undesirable. On the other hand, if it is high, it causes a decrease in processability and color tone, which is not desirable. do not have. The content of the vinyl aromatic compound contributes to the moldability, and if the content is too low, the moldability deteriorates, while if it is too high, the amount of the vinyl cyanide compound monomer used decreases, resulting in the unfavorable behavior described above. The graft copolymer (A) preferably has a component ratio (wt%) of the rubbery polymer and monomer mixture (f) in the graft copolymer (A) of 5 to 60/95 to 40, more preferably 5-40/95-60. Also, composition ratio of monomer mixture (f) (total 100% by weight)
The ratio of vinyl aromatic compound (b)/vinyl cyanide compound (c)/ethylenic unsaturated carboxylic acid (d)/other copolymerizable compound (e) is 30-92.68/7-
40/0.32 to 30/0 to 25 are preferred, and more preferably 45 to 89.47/10 to 35/0.53 to 20/0 to 15. In addition, as the copolymer (A'), the (A')
The composition ratio of the monomer mixture (f) constituting is vinyl aromatic compound (b) / vinyl cyanide compound (c) / ethylenically unsaturated carboxylic acid (d) / other copolymerizable compound.
The ratio of (e) (total 100% by weight) is 30~92.6/7~
The ratio is preferably 40/0.4 to 30/0 to 25, more preferably 45 to 89.5/10 to 35/0.5 to 20/0 to 15. If the content of the ethylenically unsaturated carboxylic acid in (A) or (A') is too small, a sufficient matting effect cannot be obtained, and if it is too large, the miscibility with the rubber-modified thermoplastic resin decreases. In addition, the intrinsic viscosity [η] of the methyl ethyl ketone (MEK) soluble portion of the above copolymers (A) and (A′) (MEK30
C) is preferably 0.3 to 0.8 dl/g; if it is less than 0.3 dl/g, the matting effect will not be sufficient, and if it exceeds 0.8 dl/g, the matt state of the molded product will become uneven, which is not preferred. In the present invention, other resins such as polyphenylene oxide, vinyldene fluoride resin, nylon, polyacetal, etc. can be further blended with the resin composition containing the metal compound, and these have a matting effect, but especially The composition of the vinyl aromatic (co)polymer and the rubber-modified thermoplastic resin has excellent properties. That is, the resin composition according to the present invention can maintain its high impact strength and rigidity, and can obtain a good matting effect without causing uneven gloss on the surface of the molded product, and can be used as an internal part and interior material for automobiles. It can be used for household and business electrical equipment parts, etc. Further, the resin composition according to the present invention provides a good matte molded product not only by injection molding but also by extrusion molding, vacuum molding, etc., and has extremely high industrial utility value. Next, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited by the Examples unless the gist of the invention is exceeded. Example 1 20 parts of polybutadiene latex JSR#0700 (solid content 58%), 250 parts of water, 10 parts of potassium oleate
Add 0.2 parts of sodium pyrophosphate, 0.2 parts of dextrose, 0.004 parts of ferrous sulfate, and 0.4 parts of cumene hydroperoxide to the mixed solution. A mixture of each monomer shown in Table 1 (80 parts in total) and 0.3 part of t-dodecyl mercaptan was added dropwise to the reactor while stirring under a nitrogen stream. Note that the ethylenically unsaturated carboxylic acid was added after being neutralized with caustic potassium. The dropping time was 2 hours, and the polymerization temperature was 60°C. The resulting resin latex was coagulated with sulfuric acid, and at the same time the carboxylic acid salt was converted back to carboxylic acid. The resulting carboxylic acid-containing resin was dried, pelletized, and subjected to injection molding. The evaluation results are shown in Table 1. Table 1 shows that the resin composition of the present invention exhibits good impact resistance, matte properties, and appearance of molded products.

【table】

[Table] Example 2 - Method for producing copolymer - Add 300 parts of deionized water and 2 parts of sodium dodecylbenzenesulfonate to a reactor equipped with a stirrer, and add 1/3 of the monomers shown in Table 2. added. After thorough emulsification, when the reactor was heated to 65° C., 0.1 part of potassium persulfate was added. After 1 hour and 2 hours from this time, 1/3 of the monomers shown in Table 2 and 0.05 parts of potassium persulfate were added, and polymerization was carried out for a total of 3 hours. The resulting resin latex is coagulated to form a copolymer containing carboxylic acid.
(a), (b), (c), and (d) were produced. The copolymers shown in Table 2 were mixed with various rubber-reinforced resins as shown in Table 3, pelletized, injection molded, and evaluated. Each resin listed in Table 3 is as follows. ABS resin 1: Consists of 20 parts of polybutadiene rubber, 54 parts of styrene, and 26 parts of acrylonitrile.
ABS resin ABS resin 2: ABS resin consisting of 15 parts of polybutadiene rubber, 10 parts of styrene, 50 parts of α-methylstyrene, and 25 parts of acrylonitrile AES resin: EPT (manufactured by Japan EP Rubber Co., Ltd.)
JSREP-24) AES resin consisting of 30 parts, styrene 50 parts, and acrylonitrile 2 AAS resin; n-butyl acrylate polymer 25
AAS resin consisting of 50 parts of styrene, and 25 parts of acrylonitrile AS resin; Lightac 120PC (Mitsui Toatsu Chemical Co., Ltd.)
Polycarbonate resin; Novarex 7022
(Mitsubishi Kasei Corporation) The method for evaluating the prepared composition was the same as that described in Example 1. As can be seen from Table 3, each rubber-reinforced thermoplastic resin containing 0.3 to 3.0% by weight of ethylenically unsaturated carboxylic acid and adding a metal compound at a molar ratio of 0.1 to 2 to the unsaturated carboxylic acid was molded. The gloss of the surface of the product is reduced, and the surface is evenly matted without uneven gloss. On the other hand, if the amount of the metal compound added is small, a sufficient matting effect cannot be obtained, and if the amount is excessive, the impact strength will drop significantly.
Not suitable for practical use.

【table】

[Table] Example 3 The copolymer (a) in Table 2 was mixed with the following self-extinguishing resin, injection molded, and evaluated. Self-extinguishing resin (1): Mix 40 parts of ABS resin consisting of 25 parts of polybutadiene rubber, 55 parts of styrene, and 20 parts of acrylonitrile with 60 parts of vinyl chloride resin. Self-extinguishing resin (2): Mix 20 parts of polybutadiene rubber, 57 parts of styrene, 75 parts of ABS resin consisting of 23 parts of acrylonitrile, 21 parts of flame retardant (tetrabromobisphenol A), and 4 parts of antimony trioxide.

【table】 The blending amounts and evaluation results are shown in Table 4.

[Table] As can be seen from Table 4, the same effects described in Examples 1 and 2 can be obtained with self-extinguishing resins. Example 4 The same method as Example 1 was carried out except that the metal compounds shown in Table 5 were used. According to Table 5, the resin composition of the present invention has impact resistance,
It can be seen that both matte molded products exhibit excellent appearance properties.

【table】

[Table] * Magnesium stearate Example 5 The same method as Example 2 was carried out except that the metal compounds shown in Table 6 were used. Table 6 shows the evaluation results. From Table 6, the resin composition of the present invention has impact resistance,
It can be seen that both the matte properties and the appearance of the molded product are excellent.

[Table] *** Zinc stearate

Claims (1)

[Claims] 1. 0.3% of copolymerized ethylenically unsaturated carboxylic acid containing 5 to 40% by weight of a rubbery polymer.
At least one monovalent, divalent, or trivalent metal compound is added to a rubber-modified aromatic vinyl thermoplastic resin containing ~3% by weight at a molar ratio of 0.1 to 2 relative to the ethylenically unsaturated carboxylic acid in the resin. 1. A thermoplastic resin composition for producing molded products having a matte surface, characterized in that it is blended with: