JPS60161412A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful in a field of exterior automotive trim, having improved adhesivity of urethane coating compound, obtained by blending specific components such as a rubber-like polymer, an aromatic vinyl compound, a vinyl cyanide compound, etc. in a specified blending ratio. CONSTITUTION:(A) 5-40wt% rubber-like polymer (e.g., polybutadiene, etc.) is blended with (B) 35-90wt% aromatic vinyl compound (preferably styrene, etc.), (C) 3-45wt% vinyl cyanide compound (e.g., acrylonitrile, etc.), (D) 0.1-10wt% one or more of a compound (preferably dimethylaminoethyl methacrylate, etc.) shown by the formula I (R is H, or CH3; R1 and R2 are 1-8C alkyl; X is 1-4C alkylene) and a compound [preferably beta-hydroxypropyl(meth)acrylate, etc.] shown by the formula II (R3 is 1-6C hydroxy alkyl), and (E) 0-50wt% another vinyl compound (e.g., methyl methacrylate, etc.), to give the desired composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber-modified aromatic vinyl thermoplastic resin composition, and particularly to improving the adhesion of a urethane paint to a thermoplastic resin composition.

PUM-modified thermoplastic resin compositions are widely used as molding materials, particularly in the exterior field of automobiles and motorcycles. In this field, it is common practice to apply paint to the entire or partial surface of a molded article for the purpose of improving surface performance or for decoration. In this field, the use of urethane paints has been increasing in recent years from the viewpoint of coating film performance.

However, with the paint made by Urethane Paint Co., Ltd., it takes about a week for the paint film to completely cure, and the paint film is not fully cured immediately after drying, so if it is exposed to a strong impact. In some cases, the paint film may peel off, or when a molded product is coated and dried and subjected to impact during handling, the paint film may peel off, resulting in a defective product.

Further, depending on the type of thermoplastic resin composition, even if the urethane coating film is cured, the adhesion may be weak, and urethane coating may not be possible.

An object of the present invention is to provide a Bum-modified aromatic vinyl thermoplastic resin composition that has improved adhesion of urethane paint to molded articles.

According to the present invention, a rubber-modified aromatic vinyl thermoplastic resin composition is provided, wherein the polymer-forming components in the resin composition include (a) 5 to 40% by weight of a rubbery polymer.

(b) 35 to 90 layers of aromatic vinyl compound.

(C) 3 to 45% by weight of vinyl cyanide compound.

(d) The following general formula % formula % (wherein R is H or CH, , R, and R2 have 1 to 8 carbon atoms.
0.1 to 10 weight/kg of at least one compound selected from
A rubber-modified aromatic vinyl thermoplastic resin composition is provided, which comprises O to 50% by weight of other vinyl compounds.

As the mucilage polymer used in the DEM-modified aromatic vinyl thermoplastic resin composition of the present invention, diene-based rubbery polymers and non-diene-based mume-like polymers can be used.

Examples of diene-based rubbery polymers include polybutadiene, natural rubber, styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), polyimprene, polychlorogrene, and the like. These rubber-like polymers are sieved by emulsion polymerization, solution polymerization, etc., and are also treated with tin or lithium, such as polybutadiene, polyisoprene, SBR, and styrene-butadiene block copolymers. can be used. These nine comb-like violet combinations may be present singly or in pairs.
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-zolo♂ylene-nonconjugated diene copolymer, and chlorinated polyethylene.

These non-diene rubbery polymers, including acrylic 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.

The key to the rubbery polymer in the thermoplastic resin composition of the present invention is 5.
The amount is in the range of 10 to 30% by weight, preferably 10 to 30% by weight. If the content is less than 5%, the impact resistance will not be improved, and if it exceeds 40 inches, the hardness will decrease.

Examples of the aromatic vinyl compound (b) include styrene, α-methylstyrene, O-methylstyrene, m-methylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, p-methylstyrene, α-etherstyrene. , methyl-α-methylstyrene, dimethylstyrene, vinylnaphthalene, etc. Preferred monomers include styrene, α-methylstyrene, p-
-Methylstyrene.

Vinyl cyanide compounds (,) include acrylonitrile,
Methacrylonitrile etc. can be used.

The content of the above aromatic vinyl compound (b) is 35 to 90
It is a heavy-duty piece, preferably 60 to 90 pieces.

If it is less than 35%, moldability decreases, while if it exceeds 90%, impact resistance and chemical resistance decrease.

Moreover, the word density of the above vinyl cyanide compound (c) is 3 to
45% by weight, preferably 10-40% by weight 3%
If it is less than 45%, impact resistance and chemical resistance will decrease, while if it exceeds 45%, moldability and one color tone will decrease.

Furthermore, as the polymer component (d) used in the present invention, the compound represented by the general formula (wherein R, R, and R2 are the same as those described above) is specifically, for example, tsumedelamino. Ethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, methylethylaminoethyl methacrylate, dibutylaminoethyl methacrylate, diptylaminopropyl methacrylate.

Diethylamine butyl methacrylate, zohexylaminoethyl methacrylate, dioctylaminoethyl methacrylate, etc. are used.

Among these, preferred are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, methylethylaminoethyl methacrylate, and the like.

In addition, as the above component (d), in the hydroxyalkyl (meth)acrylate represented by the general formula % (in which R and R3 are as defined above), the alkyl group may include ethyl, propyl, zotyl, cyclohexyl, etc. preferred are ethyl and propyl.

Examples of specific compounds include β-hydroxyethyl acrylate, β-hydroxyzorobyl acrylate, β-
Hydroxyethyl methacrylate, β-hydroxy′
f112 pill methacrylate.

Examples include β-hydroxyisobutyl acrylate, β-hydroxy n-zoteracrylate, and γ-hydroxy n-butyl acrylate.

Among these, particularly preferred are β-hydroxypropyl (meth)acrylate or β-hydroxyethyl (meth)acrylate.

The content of the functional (meth)acrylate of the component (d) is 0.11 to 10% by weight, preferably 0.3 to 5% by weight,
More preferably, it is 0.3 to 3 times. Content is 0
．． If it is less than 1 weight, the effect of improving the adhesion of the urethane coating film will not be sufficient, while if it is more than 10 weight, the thermal stability and impact strength will decrease, which is not preferable.

VC required as a polymer forming component in the resin composition of the present invention
Depending on the component (b), (0) i (d) and other vinyl compounds (,) copolymerizable may be contained in an amount of 0 to 50% by weight, such as, for example, methyl acrylate.

, ethyl acrylate, butyl acrylate.

amyl acrylate, hexyl acrylate, olfk
Acrylic acid alkyl esters such as acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Methacrylic acid alkyl esters such as amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate and the like are used.

Although the resin composition of the present invention is not particularly limited, it can be produced by the following method.

(1) in the presence of the mucous polymer (,), component (b),
(Thermoplastic resin composition A) obtained by graft copolymerizing components (e), (d) and optionally the component (@).

(2) Component (d) and component (b)', (c) and (
It is obtained by blending copolymer B obtained by copolymerizing at least one component selected from e) and rubber-modified thermoplastic resin C (resin composition D).

(3) The above composition A and/or D and component (b)
).

It is obtained by blending with a (co)polymer obtained by polymerizing at least one selected from (C), (d), and (,).

The above-mentioned (co)polymers can be obtained by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or combinations thereof.

Examples of the rubber-modified thermoplastic resin (C) include acrylonitrile-tutadiene-styrene copolymer (ABS
Tree III, acrylonitrile-citadiene-styrene-α-methylstyrene copolymer and a copolymer containing methyl methacrylate-r (heat-resistant ABS resin i+1)
1), acrylonitrile-dtyrene-alpha monoolefin-styrene A polymer (aEs resin), acrylonitrile-butyl acrylate-styrene copolymer (AA8 resin), methyl methacrylate-tutadiene-stereno copolymer,
1 coalescence (MBS resin), rubber modified polystyrene (urp
s8M).

Polycarbonate resin and AB8 packaging IIITo or A1
Mixed resins with 8 resins can be used.

A more useful thermoplastic resin composition can be obtained by adding commonly used dispersants, lubricants, stabilizers, colorants, etc. to the composition of the present invention.

The thermoplastic composition of the present invention is also suitable for coating with acrylic paints in addition to urethane paints.

The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

In addition, parts by weight in Examples are shown.

Examples 1 to 6; Comparative Examples 1 to 3 A mixed solution of polybutadiene 2, 20 parts of camphorax (J8R 0700), 250 parts of water, and 1.0 part of potassium oleate was added with 0.2 part of sodium birophosphate and dextrose.

-Add 0.2 part of ferrous sulfate, 0.004 part of ferrous sulfate, and 0.4 part of cumene hydro/4-O Φ side.

A mixture of a total of 80 parts of each monomer shown in Table 1 and 0.3 part of t-dodecylmercaptaf was added dropwise to the reactor with stirring under a nitrogen stream. The dropping time was 2 hours and polymerization fa
& was 60°C. The obtained latex was coagulated and dried, then pelletized and subjected to injection molding. The evaluation results are shown in Table 1.

It can be seen from Table 1 that the composition of the present invention has good film adhesion.

On the other hand, if the amount of dialkylaminoether methacrylate and/or dialkylaminoethyl acrylate is small, the adhesion of the coating film will be insufficient (), while if it is too large, the thermal stability will be reduced.

Examples 7-10; Comparison? lJ 4-5 200 parts of water and 1 part of potassium oleate in a reactor with a stirrer
．． Add 0 parts of the mixed solution and add 22.29 parts of styrene.

7.04 parts of acrylonitrile and 4 parts of diethylaminoethyl methacrylate were added, followed by 0.2 part of t-dodecylmercaptan, and when the reactor was heated to 60°C, 0.05 part of potassium persulfate was added.

One hour and two hours after this time, the same amounts of monomer, t-dodecyl mercaptan, and potassium persulfate as initially added were added to carry out polymerization. The obtained latex was coagulated to obtain copolymer (1).

As shown in the second variation, the 51° C. copolymer (1) was mixed with various thermomodified resins, pelletized, and injection molded for evaluation.

The mu-modified resins used were as follows.

AB841111-1: JFIRABS 12 (Japan Synthetic f A (a) #1 AES tree rIiI: JSR
AE8110(#)AA8#: Pitax 6100
A (manufactured by Hitachi Chemical Co., Ltd.) The evaluation method was the same as that described in Example 1.

From Table 2, it can be seen that the composition of the present invention has good coating adhesion.

On the other hand, it can be seen that if the amount of diethylaminoethyl methacrylate is too small, the improvement in coating film adhesion is insufficient, and if it is too large, the gloss retention rate decreases.

) Fruits 111-15; Comparative Examples 6-8 Polytsutatsune Latex (JARsu0700) 2
0 parts, 250 parts of water, and 1.0 parts of potassium oleate.

Add 0.2 parts of sodium birophosphate to a mixed solution of 1.5 parts of KOH.

Dextrose 0.2 parts, ferrous sulfate 0.004 parts.

Add 0.4 part of cumene hydroperoxide.

A mixture of a total of 80 parts of each monomer shown in Table 3 and 0.3 s of t-dodecylmercaptan was added dropwise to the reactor while stirring under a nitrogen stream. The dropping time was 2 hours and the polymerization temperature was 6
It was 0°C. The obtained latex was vertically dried, pelletized, and subjected to injection molding. The evaluation results are shown in Table 3.

Table 3 shows that the composition of the present invention exhibits good coating film adhesion.

On the other hand, it can be seen that when the amount of hydroΦ dialkyl (meth)acrylate is small, the c11 film density is insufficient, and on the other hand, when it is too large, the impact strength is reduced.

Examples 16 to 19; Comparative Examples 9 to 10 200 parts of water and 1 part of potassium oleate in a reactor equipped with a stirrer
．． Add a mixture of 0 parts and 1.5 parts of KOH to 22 parts of styrene.
．． 29 parts of acrylonitrile, 7.04 parts of acrylonitrile, 4 parts of hydroxyzolobyl methacrylate, 0.2 part of 1-dodecylmercaptaf, and when the reactor was heated to 60°C, 0.05 part of potassium persulfate was added. added. One hour and two hours later, the same amounts of the monomer, t-dodecylmercagutan, and potassium persulfate as initially added were added and polymerized.

The obtained latex was coagulated and dried to obtain a copolymer (2).

As shown in Table 4, the copolymer (2) was mixed with various rubber-modified resins, pelletized, and injection molded for evaluation. The fat is as described in Examples 7 to 10.

The monovalent method is the same as that described in Example 1.

Claims (1)

[Scope of Claims] A modified aromatic vinyl thermoplastic resin composition, wherein the polymer-forming component in the resin composition is (,) 5 to 40% by weight of a rubbery polymer. (b) 35 to 90 qb by weight of an aromatic vinyl compound. (,) 3 to 45 weight of vinyl cyanide compound. (d) The following general formula (wherein R is H or CR2, R, and R2 have 1 to B carbon atoms)
R5 is a hydroxyalkyl group having 1 to 6 carbon atoms, X is an alkylene group having 1 to 4 carbon atoms) in an amount of 0.1 to 10% by weight, and A rubber-modified aromatic vinyl thermoplastic resin composition comprising O to 50% by weight of a vinyl compound.