JPS60197713A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in impact resistance, rigidity and moldability and capable of providing a molding having a matted surface, a prepared by adding a univalent to trivalent metal compound to a specified, rubber- modified aromatic thermoplastic resin composition. CONSTITUTION:A rubber-modified aromatic vinyl thermoplastic resin composition is obtained by copolymerizing 0.3-3wt% ethylenically unsaturated carboxylic acid (e.g., acrylic acid) with 54.7-90wt% vinyl aromatic compound (e.g., styrene), 4.7-40wt% vinyl cyanide compound (e.g., acrylonitrile), and 0-20wt% other copolymerizable compounds (e.g., acrylamide) in the presence of 5-40wt% rubbery polymer (e.g., polybutadiene). This composition is mixed with a univalent to trivalent metal compound (e.g., zinc stearate) in an amount to provide a molar ratio to the ethylenically unsaturated carboxylic acid of 0.1-2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition with a matte surface of a molded product without reducing the mechanical properties and moldability of the rubber-modified thermoplastic resin composition. Plastic 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.

The conventional method for matting molded products is titanium.

A well-known method is to add oxides or carbonates such as magnesium and calcium to gum-strengthening resins, but this method has the disadvantage that it greatly reduces the mechanical properties of the resin, especially the impact strength, and it also reduces gloss. Although it can be erased, it has the disadvantage that the gloss on the surface of the molded product does not disappear uniformly.

Furthermore, a method of removing luster by adding a shim-like elastic body to a rubber-reinforced resin is well known, but 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 crosslinkable monomer is also known, but this method has disadvantages such as causing uneven gloss on the surface of the molded product and reducing moldability. The inventors have developed a matte comb-reinforced thermoplastic resin that has improved the previously known technical problems mentioned above, such as a decrease in impact resistance, rigidity, moldability, etc., and the occurrence of uneven gloss. The present invention was achieved as a result of extensive research aimed at developing the following.

According to the invention, the rubber-like polymer contains 5-40% by weight and the ethylenically unsaturated carboxylic acid. 4110.3 to 31% of a copolymerized aromatic vinyl thermoplastic resin composition, at least 18i of a monovalent, divalent, or trivalent metal compound is added to the ethylenic inorganic resin composition. The above resin composition is characterized in that it is blended in a molar ratio of 0.1 to 20 with respect to saturated carboxylic acid.

In the present invention, the resin composition that is a constituent component of the rubber-modified aromatic vinyl thermoplastic/resin composition includes a vinyl aromatic compound axis), vinyl Cyanide (C).

It contains a copolymer obtained by polymerizing a monomeric thermometallic material (f) consisting of ethylenically unsaturated carunic acid (d) and, if necessary, a compound (-) which can be co-merged with these.

As the rubbery polymer (&), diene rubbery polymers and non-diene rubbery polymers can be used.

As a diene-based rubbery polymer, polycitadiene is used.

Natural copolymer, styrene-butadiene copolymer (8BB)
.

Acrylonitrile-butadiene copolymer (NBR).

Examples include polyisograin/polychlorograin.

These rubber-like polymers are produced by emulsion polymerization, solution polymerization, etc., and are also made of polytutadiene, polyiso! Styrene, SBR, styrene-butadiene block copolymers, etc. can also be used. These gummy polymers can be used alone or in a mixture of 2s or more.

On the other hand, examples of the non-diene rubbery polymer include ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, and chlorinated polyethylene.

Examples include acrylic-based polymers. These non-diene rubber-like aggregates can be used alone or in combination of two or more. It is also possible to use a mixture of a diene rubber-like polymer and a non-diene rubber-like polymer.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-ethylstyrene, methyl-
α-Methylstyrene, dimethylstyrene, chlorstyrene, dichlorostyrene.

Bromstyrene, N-bromstyrene, vinylnaphthalene, etc. are mentioned, but preferred monomers are styrene, α-
It is methylstyrene.

As the vinyl cyanide compound (c), acrylonitrile,
Examples include methacrylate trile.

Examples of ethylenically unsaturated carboxylic acid (d) include acrylic ridge, methacrylic acid, ethacrylic acid, and itacon #! , maleic acid, fumaric acid, etc., but preferred monomers are acrylic acid and methacrylic acid. Compounds (e) copolymerizable with the above monomers, such as vinyl compounds having amide i, N- Methylolated metals, ethylenically unsaturated carboxylic acid esters, and polyfunctional monomers can be used.

Examples of the compound having an amide group or N-methylol compound include acrylamide, methacrylamide,
Examples include N-methylol acrylamide. Examples of the ethylenically unsaturated cargenic acid ester compound include alkyl acrylates, alkyl methacrylates, and esters of ethylenically unsaturated cargen acid and hydroxyalkyl, and examples of the alkyl acrylates include methyl acrylate and ethyl acrylate. Examples of the alkyl methacrylate include methyl methacrylate and ethyl methacrylate. As the hydroxyalkyl enether of ethylenically unsaturated H carbic acid, for example, β-
These include hydroxyethyl acrylate, β-hydroxyethyl methacrylate, and the like. Examples of the polyfunctional monomer include divinylbenzene. Preferred embodiments of the resin composition of the present invention are listed below.

(1) A vinyl aromatic compound (b) a vinyl cyanide compound ('), an ethylenically unsaturated carunic acid (d) and a must! in the presence of a mucous polymer (a). A composition consisting of a graft copolymer (A) obtained by polymerizing a monomer mixture (f) consisting of a compound (,) copolymerizable with these according to the composition (2) a vinyl aromatic compound (b), A copolymer obtained by polymerizing a monomer mixture (f) consisting of a vinyl cyanide compound (C), an ethylenically unsaturated carboxylic acid (d), and, if necessary, a compound copolymerizable with these (.) (A composition consisting of a rubber-modified thermoplastic resin (B), or the above (A)
U, (B) and vinyl aromatic system (both)! Combination (composition consisting of q; (3J) with the above (A) as an essential component, and (A')
*A composition comprising at least one of (B) and (C); (4) A composition comprising the above (A') as an essential component and at least one of (M) and (B); Among these compositions, (2) is more preferred.

(3) and (4)), particularly preferred is (2).

The graft copolymer (A) or copolymer (A')
The monomer mixture (f) may be subjected to yoke polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these in the presence or absence of the rubbery polymer (a). It is something that can be done.

In order to adjust the - content of the polymerization system, it is also possible to neutralize ethylenically unsaturated carboxylic acid with a base, and then return it to carboxylic acid with a mineral acid after polymerization.

Furthermore, the thermoplastic resin (B) modified in the above embodiments
For example, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-butadiene-styrene-α-methylstyrene copolymer and a copolymer containing methyl methacrylate therein (heat-resistant ABS resin), acrylonitrile-butadiene-styrene-α-methylstyrene copolymer (heat-resistant ABS resin), Ethylene/α monoolefin-styrene copolymer (ABS resin), acrylonitrile-rutyl acrylic-to-styrene copolymer (A8A resin), methyl methacrylate-butadiene-styrene copolymer CMBS resin), cam-modified polystyrene ( HIPS resin), polycarbonate resin and ABS
Resin or mixed resin with ABS resin.

A flame-retardant resin that combines ABS resin with vinyl chloride resin,
and flame-retardant ABS resin, which is a mixture of ABS resin with a flame retardant. Among the rubber-modified thermoplastic resins, those containing vinyl aromatic monomers and vinyl cyanide compound monomers are particularly preferred.

The vinyl aromatic compound (C) is a polymer of the vinyl aromatic compound (b) alone, or a polymer of the vinyl aromatic compound (b) and a vinyl cyan compound (,) and the copolymerizable compound. Examples include copolymers with at least one selected from (.).

According to the invention, by adding at least 1 m of a monovalent, divalent or trivalent metal compound to the resin composition,
An excellent matting effect on the surface of the molded product can be obtained, and a molded product with a good surface appearance and no 70-marks etc. can be obtained.

These metal compounds are number 1 on the periodic table. Part ■.

Compounds that generate monovalent to trivalent metal ions of metals of Groups 1, 2, and V, such as hydroxides, chlorides, salts, and alcolades of these metals.

These metal ions include Li'', Na'', K0, Cm'', Ag10, Be'', and Mg''.

Ca”, Zn”, Ba”, AL”, Fe”,
Examples include Fe.

The above metal compound is blended in a composition with a molar ratio of metal compound to ethylenically unsaturated carboxylic acid in the range of 0.1 to 2, preferably 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 (47, but if it exceeds 2.0, the impact resistance will decrease, which is not preferred).

The aforementioned metal compound is a hydroxide of a monovalent metal.

When metal salts and alcolades are used, they have an excellent matting effect.

Also, examples of divalent and trivalent metal compounds include oxides.

When a hydroxide or an alcoholic acid is used, the matting effect is excellent and the surface appearance of the molded product is also good.

Specific compounds for hydroxides, oxides, metal salts, and alcolades are shown below.

Zn(OH), , At(OH)s, KOH, Ca
(OH)2. an(OH),.

Fe(OH)2, NaOH, Ba(OH)g,
Hydroxides such as Hg(OH)2; ZnO? A40
B 11c20. sCaO* SnO+ FeO.

Ni, 0, BaO, MgO, & any oxide; Zn
Cl2.

zn(c2Hso2)2, ZnSO4@AACA
s, A4(804)3 eKCt, xc2n, o□
s K2SO3s CaCt2* C1(C2H502
)z*CaSO4,5nCtz, 5n804,
FeCl2. F@(C2HsO,).

Fe3O4, NaC1, NaC2H3O,, Na, 80
4, BaCl2゜Ba(C2H,O□), Ba
804. MgCl2. Mg(C2H502)2.

Mg804. Zinc stearate, celsium stearate, barium stearate, tin stearate.

Metal salts such as noptyltin di-urirate and dibutyltin distearate; sodium methylate.

There are alcoholades such as sodium ethylate and sodium phenolate.

Preferably ZnO, AL, OB, K, O, Ca0
, 8nO.

These are oxides such as FeO, Na2O, BaO, and MgO.

As a method for incorporating a metal compound into a resin composition,
Although not particularly limited to fllJ, in general, there is a method of directly adding a metal compound to a resin, or a method of mixing a metal compound and a resin in advance to form a resin composition with a high content of metal compound, and then adding this and the resin. There are methods of mixing.Depending on the type of metal compound, it is also possible to react the ethylenically unsaturated carboxyl acid, which is a polymerizable component, with the metal compound before polymerization in the production of the resin composition.

In the present invention, the content of the slimy polymer (a) in the composition is 5 to 40% by weight, preferably 5 to 30% by weight.

The content of ethylenically unsaturated carboxylic acid in the composition is from 0.3 to 3 parts by weight, preferably from 0.3 to 2 parts by weight, and more preferably from 0.3 to less than 1 part by weight. Particularly preferred is 0.3 to 0.911.

The content of the vinyl aromatic compound (b) in the above composition is preferably 54.7 to 90% by weight, more preferably 5% to 90% by weight.
9.5 to 90% by weight, vinyl cyanide compound (0)
The content of the copolymerizable compound (·) is preferably 4.7 to 40'M, more preferably 4.5 to 35% by weight, and the content of the copolymerizable compound (.) is preferably 20% by weight or less, more preferably is 0 to 10% by weight.

Rubbery polymers contribute to improving impact resistance, and if the amount is less than 5x, impact resistance cannot be obtained, while if it exceeds 40% by weight, the hardness decreases and its applications are limited. - The content of ethylenically unsaturated carunic acid monomer is 0.
If the weight is less than 3, the matting effect will not be sufficient;
．． If it exceeds 0 weight, uneven gloss will occur on the surface of the molded product, resulting in an uneven matte state, which is not preferable.

The content of vinyl cyanide compounds contributes to the improvement of impact resistance and chemical resistance, and if the content is low, it is undesirable as it causes a decrease in impact resistance and chemical resistance. It is undesirable to cause a decrease in

The content of the vinyl aromatic compound contributes to the moldability, and if the content is too low, the moldability deteriorates, and if the content is too high, the unfavorable behavior shown above will occur unless the amount of vinyl cyanide compound monomer used is small.

As the graft copolymer (A), the component ratio (MIL) of the rubbery polymer and monomer mixture (f) in the graft copolymer (A),
Kes) is preferably 5-60/95-40, more preferably 5-40,795-60.

Also, the composition ratio of the monomer mixture (f) (total 100% by weight)
The ratio of vinyl aromatic compound color)/vinyl cyanide compound (C)/ethylenic unsaturated carboxylic acid (d)/other copolymerizable compound (.) is 30 to 92.68/7.
-4010.32-3010-25 is preferred, more preferably 45-89.47/10-3570.53-2
070-15.

Further, as for the copolymer (A'), the composition ratio of the monomer mixture (f) constituting the copolymer (A') is vinyl aromatic compound (b)/vinyl cyanide compound (C)/ethylenic compound. Unsaturated carboxylic acid (d)/other copolymerizable compounds (
, ) ratio (total 100 weight ratio) is 30 to 92.6/7
-4010.4-3070-25 is preferred, more preferably 45-89.5/10-3510.5-2070
~15.

If the content of ethylenically unsaturated carboxylic acid in the above (A) or (A') is too small, a sufficient matting effect cannot be obtained,
On the other hand, if the amount 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-mentioned comonomer (A) l (A') (MEK
30°C) is preferably 0.3 to 0.8 dl/I, and 0
．． If it is less than 3 dt/I, the matting effect will not be sufficient, and if it exceeds 0.8 dl/I, the matte state of the molded product will become uneven, which is not preferable.

In the present invention, other resins such as polyphenylene oxide, vinylidene fluoride resin, nylon, polyacetal, etc. can be further blended with the resin composition containing the metal compound. A composition containing an aromatic (co)polymer and a 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.

Furthermore, the resin composition according to the present invention can be used not only for injection molding, but also for injection molding.
It also provides good matte molded products in extrusion molding, vacuum molding, etc., and has extremely great industrial 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 as long as the gist thereof is not exceeded.

Example 1 20 parts of Polytutadiene Latex JAR 0700 (
solid content 58%), water 250 parts, potassium oleate 10
0.2 parts of sodium pyrophosphate to the mixed solution.

Add 0.2 parts of dextrose, 0.004 parts of ferrous sulfate, and 0.4 parts of cumene hydroperoxide.

To this, each monomer shown in Table 1 (total 80 parts) and t-P
A mixture of 0.3 parts of decyl mercaptan was added dropwise to the reactor with stirring under a nitrogen stream. Note that the ethylenically unsaturated carboxylic acid was neutralized with caustic potassium before being added. The dropwise addition 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 calgenate was converted back to calcaric acid. The obtained carnic acid-containing resin was dried, pelletized, and subjected to injection molding. The evaluation results are shown in Table 1.

From Table 1, it can be seen that the resin composition of the present invention exhibits good impact resistance, matte properties, and appearance of molded products.

(1) Impact resistance S A8TM (D2fS6-54T)
Notched Izot 23°C (2) Surface gloss; Molded product (150 x 170 cm, thickness 3 - ) is molded into a digital variable angle gloss meter UGV manufactured by Suga Test Instruments Co., Ltd.
-4D was used to measure reflected light at an incident angle of 60°. (3) Surface appearance: 150mm using an 8oz injection molding machine.
A molded product of ×150-thickness of 30 pieces was molded, and its surface appearance was visually evaluated. O is uniform with no uneven surface gloss, Δ
indicates that the surface has slight uneven gloss and roughness, and x indicates that the surface has significant uneven gloss and roughness. Example 2 Method for producing one copolymer - 300 parts of deionized water and dodecylbenzene sulfone in a reactor equipped with a stirrer. 2 parts of sodium chloride were added and the monomeric IA shown in Table 92 was added. After sufficient emulsification, when the reactor was heated to 65°C, potassium persulfate was added to 0.
．． 1 part was added. One or two hours after this time, the second
1/3 of the monomers shown in the table and 0.05 part of potassium persulfate were added, and polymerization was carried out for a total of 3 hours. The resulting resin latex was coagulated to produce carganic acid-containing copolymers (a), (b), f→, and ni).

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 has the following formula.

ABS resin-1; ABS resin consisting of 20 parts of polyzotazoene rubber, 54 parts of styrene, and 26 parts of acrylonitrile Mu B8 resin AES resin; 30 parts of EPT (Layerbi-24 manufactured by Japan EP Rubber Co., Ltd.), 5 parts of styrene
ABS resin AA8 resin consisting of 0 parts and 20 parts of acrylonitrile; AA8 resin consisting of 25 parts of n-butyl acrylate polymer, 50 parts of styrene, and 25 parts of acrylonitrile
Resin S resin; 2 Itatsuku 120PC (manufactured by Mitsui Toatsu Chemical Co., Ltd.) Isucarnate resin; Nopare, Kusu 7022 (manufactured by Mitsubishi Kasei (E)) The method for evaluating the prepared composition was described in Example 1. This is the same method as above.

31st! As can be seen, each gym contains 0.3 to 3.0 weight of ethylenically unsaturated caronic acid and 0.1 to 2 of the metal compound is added in a molar ratio to the unsaturated caronic acid. Reinforced thermoplastic resins reduce the surface gloss of molded products,
Moreover, there is no uneven gloss on the surface, and the surface is matted uniformly. On the other hand, if the amount of the metal compound added is small, a sufficient matting effect cannot be obtained, and if it is in excess, the impact resistance strength is significantly reduced, making it unsuitable for practical use.

21st! ! Example 3 Copolymer 0) in Table 2 was mixed with the following self-extinguishing resin and injection molded for evaluation.

Self-extinguishing resin (1); 5 parts of solid polybutadiene, 5 parts of styrene.

40 parts of ABS resin consisting of 20 parts of acrylonitrile and 60 parts of vinyl chloride resin are mixed.Self-extinguishing resin (2): 75 parts of ABS resin consisting of 2120 parts of polybutadiene and 23 parts of 5711° styrene.

Mix 2195 flame retardant (NATO 2F Lomobisphenolum) and 4 parts of antipropylene trioxide.

Procedural amendment June 15, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 1984-84362, Title of the invention: Thermoplastic resin composition3, Person making the amendment: Relationship with the case Patent applicant name (417) Japan Synthetic Rubber Co., Ltd. 4, Agent address 40 Toranomon, 5-13-1 Toranomon, Minato-ku, Tokyo, Mori Building The Detailed Description of the Invention column will be amended as follows.

1) 15! The first line from the bottom of page 24 of the specification [...
Insert the following statement next to "The same effect can be obtained."

[Example-4 Example-4 except that the metallized structure shown in No. 5 ml was used]
Table 5 shows the impact resistance of the resin composition of the present invention.

It can be seen that the appearance of the matte molded product is excellent and exhibits round properties.

In Table 6 Magnesium stearate Example-5 #I6 Except for using the winter 1 umbrella compound shown in table:
Performed in the same manner as Example-2. 61st! ! 6g61 whose evaluation results were shown in! [Y] The resin composition wire of the present invention has impact resistance against various resins.

It is clear that the matte properties and the appearance of the molded product are both excellent.

Claims (1)

[Claims] Contains 5-40% by weight of a rubbery polymer and contains ethylenically unsaturated calcium. At least i'm of a monovalent, divalent or trivalent metal compound is added to a rubber-modified aromatic vinyl thermoplastic resin composition copolymerized with 0.3 to 3% by weight of phosphoric acid. The above resin composition, characterized in that ethylenically unsaturated calcium is blended in a molar ratio of 0.1 to 2 with respect to phosphoric acid.