JPH03111444A - Rubber-reinforced resin and thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a rubber-reinforced resin improved in transparency, heat resistance, etc., by copolymerizing a specified compound with at least one compound selected from among an aromatic vinyl, a vinyl cyanide and a (meth) acrylic ester and a copolymerizable monomer in the presence of a rubberlike polymer. CONSTITUTION:20-97wt.% monomer mixture comprising 1-90wt.% compound of the formula (wherein R is H or a methyl; and (n)=0-8), e.g. tricyclo[5.2.1.0<2>,<6>]dec-8-yl methacrylate, 10-99wt.% at least one member selected from among an aromatic vinyl, a vinyl cyanide and a (meth-acrylic ester and 0-80wt.% copolymerizable monomer is copolymerized in the presence of 3-80wt.% rubberlike polymer, desirably a latex of a mean particle diameter <=0.3mu (e.g. polybutadiene latex), by using, if necessary, an emulsifier, an electrolyte, a polymerization modifier, a polymerization initiator, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a rubber reinforced resin having excellent heat resistance, impact resistance and transparency, and a thermoplastic resin composition thereof.

b. Conventional technology Until now, as a method for obtaining thermoplastic resins with excellent heat resistance and impact resistance, α
- A method of mixing a terpolymer consisting of methyl styrene, methyl methacrylate, and acrylonitrile (Japanese Patent Publication No. 70143/1983), or a method of mixing a polycarbonate resin and a diene rubber (Japanese Patent Publication No. 38/1982).
No. 5225) and the like have been proposed.

However, with these methods, it is difficult to balance physical properties such as heat resistance, impact resistance, and flow processability, and the surface gloss is also unsatisfactory.

In particular, in the case of a mixture of polycarbonate and diene rubber, there are problems such as a marked decrease in flow processability, so there is a need for a material that has good heat resistance, impact resistance, flow processability, and surface gloss. It was getting worse.

Furthermore, vinyl chloride resins have many excellent properties such as physical strength 1, transparency, chemical resistance, weather resistance, and flame retardancy, and are used in a wide range of applications.

However, vinyl chloride resin has the disadvantage of low heat resistance, and is used in heat-resistant bottles, housings for home appliances, and office automation equipment.
There is a problem in that it is unsuitable as a constituent material for equipment exteriors and automobile interior parts.

As a means to solve this problem, a graft copolymer obtained by grafting styrene, methyl methacrylate, and acrylonitrile onto a conjugated diene-based rubbery polymer and a copolymer of α-methylstyrene, methyl methacrylate, and acrylonitrile was used. A method of blending with resin (Japanese Patent Publication No. 48-18101), a method of blending α-methylstyrene, methyl methacrylate, acrylonitrile copolymer with a conjugated diene rubber-like polymer of 0.1 to 0°3μ, styrene, methyl methacrylate, A method of blending a graft copolymer obtained by graft polymerizing acrylonitrile with vinyl chloride resin (
Special Publication No. 57-42094) etc. have been developed.

However, the modifiers disclosed in the above-mentioned Japanese Patent Publication No. 48-18101 and Japanese Patent Publication No. 57-42094 have the disadvantage that the improvement in heat resistance is insufficient, and even if the heat resistance is improved, the transparency is reduced. Therefore, it is not a modifier that fully satisfies heat resistance and transparency, and there is room for further investigation, and improvements have been desired.

In addition, in Japanese Patent Publication No. 48-33978, a copolymer of the compound represented by the formula (1) of the present invention (hereinafter abbreviated as DMB) and methyl methacrylate was mixed with a vinyl chloride resin to improve heat resistance. Although an improved vinyl chloride resin composition has been obtained, in order to also improve impact resistance, a diene rubber-like polymer with an average particle size of 0.3 μ or less is added to the vinyl chloride resin composition, and methyl methacrylate, Graft copolymer obtained by graft copolymerizing aromatic vinyl and vinyl cyanide (
It has been found that when the DMB-methacrylic acid copolymer and the graft copolymer (MBS resin for transparency) are mixed, the transparency decreases due to poor compatibility between the DMB-methacrylic acid copolymer and the graft copolymer (MBS resin for transparency).

Therefore, it has been a long-standing problem to develop a modifier that has excellent transparency while maintaining impact resistance and heat resistance, and great efforts have been made to solve this problem.

C6 Problems to be Solved by the Invention An object of the present invention is to provide a thermoplastic resin composition with an excellent balance of physical properties including heat resistance, impact resistance, flow processability, and surface gloss.

Further, by blending the resin with a vinyl chloride resin, a vinyl chloride resin composition having excellent heat resistance, impact resistance, and transparency is provided.

Means for solving the d0 problem The present invention provides (1) in the presence of 3 to 80% by weight of a rubbery polymer, (a) 1 to 90% by weight of a compound represented by the following general formula (1) (n =0 to 8) [In the formula, R is hydrogen or a methyl group] (b) 10 to 99% by weight of at least one selected from aromatic vinyl, vinyl cyanide, and (meth)acrylic acid ester (c) Others A rubber reinforced resin obtained by copolymerizing 20 to 97% by weight of monomers selected from 0 to 80% by weight of copolymerizable monomers.

(2) (A) (a) Compounds 1 to 9 represented by the following general formula (1)
0% (n=0-8) [In the formula, R is hydrogen or methyl group] (b) At least one selected from aromatic vinyl, vinyl cyanide, (meth)acrylic acid ester 10-99
(c) 3 to 80 parts by weight of a copolymer obtained by polymerizing a monomer consisting of 0 to 80 parts by weight of other copolymerizable monomers (B) 0 to 80 parts by weight of a rubber-modified styrenic resin , and (C) at least one copolymer selected from aromatic vinyl, vinyl cyanide, and (meth)acrylate 0
A thermoplastic resin composition containing ~80 parts by weight of (A), (B) and (C) such that the total is 100 parts by weight.

and the rubber-reinforced resin and/or (
The present invention provides a thermoplastic resin composition comprising 20 to 80% by weight of the thermoplastic resin composition of 2) and 20 to 80% by weight of a vinyl chloride resin.

The present invention will be specifically explained below.

Claim (Description of the rubber reinforced resin of the month) As a representative example of the rubbery polymer used in the present invention,
Natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), acrylonitrile-butadiene rubber (NB
R), diene-based synthetic rubber such as chloroprene rubber (CR), non-diene-based rubber such as ethylene-propylene rubber (EPR), ethylene-propylene-nonconjugated diene rubber (EPDM), acrylic rubber (ACM, ANM), fluororubber, etc. Synthetic rubber, a block copolymer consisting of at least one polystyrene block and at least one polybutadiene block or a hydrogenated product thereof, a hydrogenated product of a random copolymer of styrene and butadiene, at least one polystyrene block and a block copolymer consisting of at least one styrene and butadiene random copolymer block, or a hydrogenated product thereof.

Preferred are SBR, BRSEPR, block copolymers, or hydrogenated products thereof, and are preferred from the viewpoint of physical properties and industrial production. More preferably, a latex with an average particle size of 0.3μ or less of a polymer mainly composed of butadiene is transparent. Preferable from a gender perspective.

The rubbery polymer is 3 to 80% by weight, preferably 30 to 70% by weight.
% by weight is required. If the proportion of the rubbery polymer is less than 3% by weight, the resulting composition will have poor impact resistance, and if it exceeds 80% by weight, the resulting composition will have poor gloss, which is not preferred.

Preferably, the compound represented by the general formula (1) is tricyclo[5,2,1゜02.6]-dec-8-yl methacrylate (hereinafter referred to as tricyclodecyl methacrylate) and tricyclo(acrylate). 5, 2, 1, 0
2.6]-dec-8-yl (hereinafter referred to as tricyclodecyl acrylate).

The amount of the compound represented by general formula (1) is 1 to 90% by weight, preferably 2 to 80% by weight, more preferably 3 to 70% by weight, particularly preferably 5 to 65% by weight. If the compound represented by formula (1) is less than 1% by weight, heat resistance and surface gloss will be insufficient, and if it exceeds 90% by weight, moldability and thermal stability will deteriorate, which is not preferred.

The aromatic vinyl compound of component (b) includes styrene,
α-methylstyrene, methylstyrene, p-methylstyrene, dichlorostyrene, vinylxylene, monochlorostyrene, monobromstyrene, dibromstyrene, p
-Tertiary-butylstyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc. Among these, styrene and α-methylstyrene are most preferred.

Examples of the vinyl cyanide compound as component (b) include acrylonitrile and methacrylonitrile. Particularly preferred is acrylonitrile.

(b) Component (meth)acrylic acid ester monomer is:
For example, methyl acrylate, ethyl acrylate, 2-
Ethylhexyl acrylate, lauryl acrylate,
Examples include acrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and glycidyl acrylate, with methyl acrylate being preferred.

Also, methyl methacrylate, ethyl methacrylate,
Examples include methacrylic acid esters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and glycidyl methacrylate, with methyl methacrylate being particularly preferred.

Preferred component (b) is an aromatic vinyl compound, (
A monomer consisting of at least two types selected from meth)acrylic acid ester and vinyl cyanide compound, and particularly preferably a monomer containing 5 to 80% by weight of (meth)acrylic acid ester in component (b). , is preferable from the viewpoint of transparency.

10 to 99% by weight, preferably 15 to 90% by weight of at least one or two or more selected from aromatic vinyl, vinyl cyanide, (meth)acrylic acid ester,
It is more preferably used in an amount of 20 to 80% by weight, particularly preferably 30 to 70% by weight. If it is less than 10% by weight, moldability will be poor, and if it exceeds 99% by weight, heat resistance will be insufficient, which is not preferable.

Other copolymerizable monomers of component (C) include ethylene, propylene, butylene, α-olefins such as 4-methylpentene-1, vinyl halides such as vinyl fluoride and vinyl bromide, and vinyl acetate. , vinyl propionate,
Organic acid vinyl such as vinyl stearate, vinyl ether such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, Maleimide monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, N-(P-bromophenyl)maleimide, N-(P-chlorophenyl)maleimide, N-cyclohexylmaleimide, vinylidene chloride, vinylidene fluoride, etc. Examples include vinylidene halides, vinyl methyl ketone, vinyl pyridine, isobutylene, and 1,1-chlorofluoroethylene.

Depending on the purpose of use, these are type 1 or 2 weight - 1
- is preferably used in an amount of 0 to 80% by weight.

Depending on the polymerization conditions, the rubber reinforced resin can be made of a graft copolymer in which all of the monomer components are grafted onto a rubber-like polymer, or a graft copolymer in which a part of monomer is grafted onto a rubber-like polymer. It consists of a polymer and a copolymer copolymerized without grafting.

Grafting ratio of graft copolymer in rubber reinforced resin (*)
is preferably 5 to 200% by weight, more preferably 1
The content is from 0 to 150% by weight, and within this range, an even more excellent rubber-reinforced resin, which is the object of the present invention, can be obtained.

Rubber-like monomer (1 quantity) In the production of rubber-reinforced resin, commonly used emulsifiers, electrolytes, polymerization regulators, polymerization initiators, etc. can be used.

Examples of emulsifiers include alkali metal salts of rosin acids, alkali metal salts of fatty acids, alkali metal salts of aliphatic alcohol sulfates, and alkali metal salts of alkylarylsulfonic acids. Examples of electrolytes include sulfuric acid, phosphoric acid, hydrochloric acid, Examples include various alkali metals such as carbonic acid.

Furthermore, as polymerization regulators, mercaptans, terpenes, halides, etc. can be added as necessary, and as polymerization initiators, persulfates, organic/X hydroperoxides, or organic hydroperoxides can be added. A redox catalyst based on a combination of agents can be suitably used.

As the graft copolymerization method, various widely known graft copolymerization methods can be applied.

For example, the method of adding monomers to be graft copolymerized in the presence of a diene-based rubbery polymer may be any method such as bulk addition polymerization, continuous addition polymerization, or multistage polymerization. It is preferable to graft-copolymerize the mixture by dividing it into a part mainly composed of methacrylic acid methyl ester and a part mainly composed of a monovinyl aromatic monomer.

Alternatively, a method in which a small amount of dilute acetic acid is added prior to graft copolymerization to enlarge the particles of the diene-based rubbery polymer latex and then graft copolymerization is performed, or sodium chloride or potassium chloride is added to the diene-based rubbery polymer. However, the preferred average particle diameter of the graft copolymer latex is 0.03 to 0. .3μ, and a more preferable average particle diameter is 0.05 to 0.2μ.

The most preferred method of graft copolymerization is to add an electrolyte to a diene-based rubbery polymer, first add a monomer containing DMB and methyl methacrylate as main components, and coagulate and enlarge latex particles while performing graft copolymerization. This is a method in which a monomer whose main component is a monovinyl aromatic monomer is then added to complete the graft copolymerization.

Incidentally, after the above-mentioned graft copolymerization is completed, an antioxidant such as 2°6-ditertiary-butyl-4-methylphenol can be added.

Description of the thermoplastic resin composition of claim (2)Claim (2)
Components (a), (b), and (C) are each included in claim (1).
), and can be used as is.

The content of component (a) is 1 to 90% by weight, preferably 2 to 80% by weight, more preferably 3 to 70% by weight, particularly preferably 5 to 65% by weight. If component (a) is less than 1% by weight, heat resistance and surface gloss will be insufficient, and if it exceeds 90% by weight, moldability and thermal stability will deteriorate, which is not preferred.

(b) One type of component 10 to 99% by weight, preferably 15 to 99% by weight
It is 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight. (b) component is 10
If it is less than 99% by weight, moldability will be poor;
If it exceeds , heat resistance is insufficient.

Component (c) is used in an amount of 0 to 80% by weight depending on the purpose.

(A) The copolymer includes the above-mentioned (a), (b) and (C).
The monomer component consisting of
Obtained by polymerization such as solution polymerization.

The rubber-modified styrenic resin (B) is a polymer containing as an essential component an aromatic vinyl compound modified with the rubbery polymer of claim (1), preferably in the presence of the rubbery polymer. It is obtained by copolymerizing monomers containing aromatic vinyl as an essential component, and is composed of a graft copolymer or a copolymer of a graft copolymer and a non-grafted monomer.

The monomers to be copolymerized are preferably at least two selected from aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid esters.

As the rubber-modified styrenic resin, preferably acrylonitrile-butadiene-styrene resin (ABS resin),
Acrylonitrile-ethylene propylene-styrene resin (AES resin), methyl methacnolate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABMS resin), acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), and those using a hydrogenated diene rubber instead of the rubbery polymer of the above ABS resin or MBS resin.

Component (c) includes, for example, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer,
Styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-α-methylstyrene-methyl methacrylate copolymer, styrene-α-methylstyrene-acrylonitrile-methyl methacrylate copolymer, polystyrene , polychlorostyrene, polyα-methylstyrene, etc., and these may be used alone or in combination of two or more.

The polymerization method for component (C) is the same as the polymerization method for component (A).

The thermoplastic resin composition of claim (2) comprises (A) component 3 to
80 parts by weight, preferably 5 to 65 parts by weight, 0 component (B)
~80 parts by weight, preferably 5 to 60 parts by weight, 0 to 80 parts by weight, preferably 5 to 60 parts by weight of component (C),
, (B) and (C) in a total amount of 100 parts by weight, it has good flow processability and has an excellent balance of physical properties of heat resistance, impact resistance, and transparency. The thermoplastic resin composition 2) is obtained.

Claim (3) Description of thermoplastic resin composition The thermoplastic resin composition of claim (3) comprises the rubber reinforced resin of claim (1) and/or the thermoplastic resin composition 20 to 20 of claim (2).
80% by weight, preferably 30-60% by weight, vinyl chloride resin 20-80% by weight, preferably 40-70% by weight
This thermoplastic resin composition has heat resistance,
Excellent impact resistance and transparency.

The rubber reinforced resin (a) of claim (1) and the resin composition (b) of claim (2) may be mixed with the vinyl chloride resin (c) as they are, but usually they are coagulated and dried. Powdered.

In this case, the rubber reinforced resin (a) and the resin composition (b) are
The rubber reinforcing resin and the resin composition may be coagulated and dried separately to form a powder, or the rubber reinforcing resin and the resin composition may be mixed in advance and then coagulated so that the desired physical properties are obtained when mixed with the vinyl chloride resin (c). - May be made into powder after drying. Usually, the rubber reinforced resin (a) and the resin composition (b) are separately coagulated and dried to form a powder.

As the vinyl chloride resin (c), polyvinyl chloride, 7
A copolymer of 0% by weight or more of vinyl chloride monomer and less than 30% by weight of a copolymerizable monomer such as vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid, methacrylic acid, ethylene, or chlorinated Polyvinyl chloride etc. can be used.

The vinyl chloride resin (c), the rubber reinforced resin (a), and the resin composition (b) are mixed in powder form, and can be mixed using, for example, a ribbon blender or Henschel type mixer, or a known kneading machine, molding machine, For example, it can be mixed using a mixing roll, a Banbury mixer 1 extruder, or a blow molding machine.
It can also be molded.

If necessary, commonly used stabilizers, pigments,
Fillers, plasticizers, lubricants, acrylic processing aids, etc. may also be added.

Here, the rubber reinforced resin of claim (1) and (2) (A
) In the production of the copolymer, the following emulsifiers, molecular weight regulators, and polymerization initiators can be used.

Examples of emulsifiers include anionic surfactants, nonionic surfactants, and amphoteric surfactants, preferably rosinate salts such as potassium rosinate and sodium rosinate,
Sodium and potassium salts of fatty acids such as potassium oleate, potassium laurate, sodium laurate, sodium stearate, and potassium stearate and sulfuric acid ester salts of fatty alcohols such as sodium lauryl sulfate, as well as sodium dodecylbenzenesulfonate, etc. Examples include alkylarylsulfonic acid.

As molecular ff1g moderating agents, mercaptans such as n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-hexadecylmercaptan, n-tetradecylmercaptan, t-tetradecylmercaptan, terpinolene, dipentene, t- Terpenes consisting of terpinene and small amounts of other cyclic terpenes, tetraethylthiuram sulfide, carbon tetrachloride,
Examples include hydrocarbons such as ethylene bromide and pentaphenylethane, or acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, and the like. These molecular weight modifiers may be used alone or in combination.
More than one species can be used in combination. The method of use may be one-time addition, divided addition, or continuous addition.

As a polymerization initiator, cumene hydroperoxide,
Representative examples include sugar-containing pyrophosphate formulations, sulfoxylate formulations, and mixed formulations of sugar-containing pyrophosphate formulations/sulfoxylate formulations of organic hydroperoxides such as diisopropylbenzene hydroperoxide and para-menthane hydroperoxide. A redox initiator in combination with a reducing agent, persulfates such as potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, etc. can be optionally used. . Particularly preferably, an oxidizing agent of organic hydroperoxides represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide and a sugar-containing pyrophosphoric acid formulation,
Combinations with reducing agents are typified by sulfoxylate formulations, sugar-containing pyrophosphoric acid formulations/sulfoxylate mixture formulations, etc.

The composition of the present invention may also contain antioxidants, such as 2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,
6-dimethylphenol, 2,2'-methylene-bis-
(4-ethyl-6t-butylphenol), dilaurylthiodipropionate, 4,4'-thiobis-(6-t
-butyl-3-methylphenol), tris(di-nonylphenyl) phosphite, wax, etc. As ultraviolet absorbers, for example, pt-butylphenyl salicylate, 2,2'-dihydroxy-4methoxybenzophenone, 2 - (2'-Hydroxy-4'-〇-octoxyphenyl)benzotriazole, etc., lubricants such as paraffin wax, stearic acid, hydrogenated oil,
stearamide, n-butyl stearate, methylene bis stearamide, ethylene bis stearamide, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, flame retardants such as antimony oxide, aluminum hydroxide,
Zinc oxalate, tricresyl phosphate, tris(dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A, etc., as antistatic agents, e.g. stearamidopropyl dimethyl-β-hydroxy Coloring agents such as ethyl ammonium nitrate, titanium oxide, carbon black, etc., fillers such as calcium carbonate, clay, silica, glass fiber, glass beads, carbon fiber, etc., or pigments, etc., as necessary. One or two weighing amounts -L can be added.

e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention.

In addition, in the following implementation, the following graft copolymers were produced in the production of the rubber reinforced resin according to claim (1), in which parts and % are characterized by weight parts and weight %, respectively.

In addition, as a compound of general formula (1) in the claims,
Tricyclodecyl methacrylate.

[Production example ■〈Graft copolymer (A-1) to (A-5)
>] Charge the batch components shown in Table 1 into a reactor equipped with a jacket and a stirrer, replace the air inside with nitrogen while stirring the mixture at 20 rpm, and then replace the jacket with nitrogen at 70 rpm.
℃, and when the internal temperature reaches 40℃, an aqueous solution prepared by dissolving 0.3 parts of sodium birophosphate, 0.35 parts of dextrose, and 0.01 parts of ferrous sulfate in 10 parts of water and cumene hydroper. 0.1 part of oxide was added and reacted.

One hour after starting the reaction, the incremental components shown in Table 1 were added continuously over 3 hours, and the reaction was continued for 1 hour while stirring.

2,2'-methylene-bis-(4-ethyl-6-t) was added to the obtained graft copolymer latex as an antiaging agent.
-butylphenol) is added, sulfuric acid (2 parts per 100 parts of polymer) is added to coagulate, and this is separated, washed with water, dehydrated, and dried to obtain graft copolymers (A-1) -
(A-5) was obtained.

(A) Production of copolymer of claim (2) The following copolymers were produced.

[Production Example ■ Copolymers (B-1) to (B-5)> The components shown in Table 2 were charged into a reactor equipped with a co-jacket and a stirrer, and the mixture was stirred at 20 Orpm while the inside was purged with nitrogen. After replacing the air, the jacket was controlled at 70°C, and when the internal temperature reached 50°C, 0.3 parts of sodium pyrophosphate and 0.3 parts of dextrose were added to 10 parts of water.
5 parts of ferrous sulfate, an aqueous solution containing 0.01 part of ferrous sulfate, and 0.1 part of cumene hydroperoxide were added and reacted for 3 hours.

Sulfuric acid (2 parts per 100 parts of polymer) was added to the obtained copolymer latex to solidify it, which was separated, washed with water, dehydrated,
After drying, copolymers (B-1) to (B-5) were obtained.

[Examples 1 to 7, Comparative Examples 1 to 5, Graft copolymers (A-1) to (A
-5), copolymers (B-1) to (B
-5), a styrene-acrylonitrile copolymer resin (AS240) manufactured by JSR, and a rubber-modified styrene resin (ABS grafted body, 140 parts of rubber ff, graft ratio 75%, bonded Acrylonitrile content = 25%, [η] = 0.40) and α-methylstyrene-acrylonitrile copolymer produced by the method of Production Example ① (α-methylstyrene copolymerization amount 72°5%).
, [ηconi 0.30) were mixed using a Henschel mixer according to the formulation shown in Table 3, and then using a screw extruder, the cylinder temperature was 210 to 270°C and the die temperature was 26°C.
The mixture was melt-kneaded at 0°C and pelletized.

After sufficiently drying the obtained pellet-shaped thermoplastic resin composition in a blow dryer, a test piece was prepared using an injection molding machine.
Impact resistance, heat resistance, and surface gloss were evaluated using the following evaluation methods, and processability was evaluated using the pellets after drying.Table 3
Physical property results were obtained.

Evaluation method> - Izot impact strength: Measured with a 1/4' thickness notch according to ASTM D256.

- Heating deformation temperature: according to ASTM D648, load 18. 6 kg/cr1, measured without annealing.

-Surface gloss: Measured according to ASTM D523.

- Melt flow rate: Measured at 220°C and a load of 10 kg according to JIS K7210.

As is clear from comparing Examples 1 to 7 and Comparative Examples 1 to 5 in Table 3, the resin composition of the present invention has good heat resistance, impact resistance,
It can be seen that the resin has excellent fluidity and surface gloss.

In Comparative Example 1, the copolymerization amount of tricyclodecyl methacrylate in the graft copolymer was less than 1%, which was outside the range of the present invention, and therefore the heat distortion temperature and surface gloss were insufficient.

In Comparative Example 2, the amount of copolymerized tricyclodecyl methacrylate in the graft copolymer was outside the range of the present invention, so the Izot impact strength, surface gloss, and melt flow rate were significantly reduced.

In Comparative Example 3, the copolymerized amount of tricyclodecyl methacrylate in the matrix was less than 1%, which was outside the range of the present invention, and therefore the heat distortion temperature and surface gloss were insufficient.

In Comparative Example 4, the amount of copolymerized tricyclodecyl methacrylate in the matrix was outside the range of the present invention, so the isot impact strength, surface gloss, and melt flow rate were significantly reduced.

Comparative Example 5 is a heat-resistant resin composition copolymerized with α-methylstyrene, but compared to this resin, the resin composition of the present invention has a very good balance of physical properties among heat resistance, melt flow rate, and Izot impact strength. It can be seen that this is an excellent heat-resistant resin with good properties.

Below is a blank space [Manufacturing Example ■〈Graft copolymers for blending with vinyl chloride resin (A-6) to (A-10)> In order to obtain a co-vinyl chloride resin composition, vinyl chloride resin (c) A graft copolymer (A-6) for blending with was produced.

(1) Production of diene rubber polymer 150 parts of deionized water, 4 parts of potassium stearate, 1 part of potassium sulfate, 75 parts of 1,3-butadiene, 2 parts of styrene
5 parts, 0.2 parts of t-shalidedecyl mercaptan, 0.06 parts of para-menthane hydroperoxide, and 0.01 parts of ferrous sulfate, 2 parts of ethylenediaminetetraacetic acid.
-0.025 parts of sodium and 0.04 parts of sodium formaldehyde sulfoxylate were charged into an autoclave purged with nitrogen, and polymerized at 8°C for 12 hours with stirring. Polymerization was terminated at a polymerization conversion rate of 95%. Next, steam was blown into the obtained diene-based rubbery polymer latex to remove unreacted monomers. The average particle size of the obtained diene-based rubbery polymer latex was measured using a laser particle size analyzer manufactured by Otsuka Electronics, and it was found to be 0.
It was 07μ.

(2) Production of graft copolymer (a) In an autoclave purged with nitrogen, 65 parts solids of the diene rubber latex produced in (1) above and 150 parts deionized water (diene rubber polymer latex) were placed in a nitrogen-purged autoclave. (including water in the combined latex) and 0.5 part of potassium sulfate.
The temperature was raised to 80°C.

Next, 15 parts of methyl methacrylate, 5 parts of tricyclodecyl methacrylate, 0.1 part of diisopropylbenzene hydroperoxide, and 0.04 part of sodium formaldehyde sulfoxylate were continuously added over 4 hours.

After the continuous addition was completed, graft polymerization was continued for another hour.

Next, 15 parts of styrene, 0.1 part of diisopropylbenzene hydroperoxide, and 0.04 part of sodium formaldehyde sulfoxylate were continuously added over 4 hours. After the continuous addition was completed, graft polymerization was further carried out for 1 hour to complete the polymerization. The polymerization conversion rate was 98%, and the average particle diameter of the graft copolymer latex was 0.23μ. Then, after adding 1 part of butylated hydroxytoluene,
After coagulating with a 0.5% sulfuric acid aqueous solution, it was washed with warm water and subjected to a drying process to obtain a white powder.

In the same manner, the graft copolymer (a) was prepared in Table-4.
(A-7) to (A-10) were manufactured with the compositions shown below.

[Production Example ■ Copolymer for blending with vinyl chloride resin (B
-6)>] In order to obtain a vinyl chloride resin composition, a copolymer (B-6) for blending with the vinyl chloride resin (c) was produced under the following conditions.

(1) Production of copolymer (B-6) 250 parts of deionized water, 3.0 parts of sodium dodecylbenzenesulfonate, 40 parts of tricyclodecyl methacrylate,
35 parts of styrene, 25 parts of methyl methacrylate, 0.5 part of t-dodecyl mercaptan, 0.1 part of diisopropylbenzene hydroperoxide, and 0.1 part of ferrous sulfate.
0.003 parts, 0.1 part of ethylenediaminetetraacetate-2-sodium, and 0.2 parts of sodium formaldehyde sulfoxylate were charged into an autoclave purged with nitrogen.
Polymerization was carried out at 65° C. with stirring. The polymerization conversion rate after 3 hours was 98%. Next, after coagulating with a 0.5% sulfuric acid aqueous solution, it was washed with warm water and subjected to a drying process to obtain a white powder.

In the same manner, copolymers (B) (B-7) to (B-9) were produced with the compositions shown in Table 5.

Production of vinyl chloride resin composition and evaluation of its physical properties Polyvinyl chloride resin with a degree of homogeneity of 700, graft copolymer (a) produced in Production Example ■, copolymer produced in Production Example ■ (B), and A mixture of 2 parts of octyltin mercaptide stabilizer and 2 parts of butylene glycol moncinate was charged into a Henschel mixer with the composition shown in Table 6, heated to 120°C with stirring, and then cooled to 50°C. . Next, the obtained mixture was kneaded for 6 minutes with a roll at 165°C, and then pressure-molded for 8 minutes with a press at 185°C, and a test piece for an Izod impact test with a thickness of 6.35 mm and a test piece with a thickness of 1.6 mm were formed. Transparent plate and thickness 6.35
A test piece for measuring heat deformation temperature of mm was prepared.

The following method was used as a test method for evaluating physical properties.

・Charpy impact test is ASTM-D256, with U notch, 23℃ ・Total light transmittance and haze value are JIS K674 ・Heat distortion temperature is ASTM-D648.4.6kg/load The physical property evaluation is Table 6 Shown below.

The following margin [Examples 8 to 11, Comparative Examples 6 to 10] As is clear from the results shown in Table 6, Examples 8 to 11
The vinyl chloride resin composition obtained is within the scope of the present invention in the production of the graft copolymer (a) and copolymer (b) and blending with the vinyl chloride resin,
All resin compositions have excellent heat resistance, transparency, and impact resistance.

Comparative Example 6 is 1 in which the copolymerized amount of tricyclodecyl methacrylate in the graft copolymer (a) is outside the range of the present invention.
%, the compatibility with the copolymer (b) decreases, and impact resistance and transparency decrease.

In Comparative Example 7, the copolymerization amount of tricyclodecyl methacrylate in the graft copolymer (a) was 90%, which was outside the range of the present invention.
impact resistance is significantly reduced.

In Comparative Example 8, the copolymerized amount of tricyclodecyl methacrylate in the copolymer was less than 1%, which was outside the scope of the present invention, and therefore the heat resistance and transparency were reduced.

In Comparative Example 9, the copolymerized amount of tricyclodecyl methacrylate in the copolymer (b) exceeds 90%, which is outside the range of the present invention, and therefore the impact resistance and transparency are reduced.

Comparative Example 10 is an example in which α-methylstyrene was used instead of tricyclodecyl methacrylate in the copolymer (b), but although heat resistance was obtained, good impact resistance and transparency were not obtained. It has not been done.

f0 Effects of the Invention As detailed above, the thermoplastic resin composition obtained by the present invention can be used in various processing fields by injection molding, extrusion molding, vacuum molding, profile molding, foam molding, etc.

It is also possible to perform brightening treatments such as plating, vacuum deposition, and sputtering, and it is also possible to paint.

The various molded products obtained by these methods are useful for applications such as exterior and interior parts of automobiles, various electrical and electronic related parts, and housings by utilizing their excellent properties.

Claims (3)

[Claims] (1) In the presence of 3 to 80% by weight of a rubbery polymer, (a)
1 to 90% by weight of a compound represented by the following general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (1) (n = 0 to 8) [In the formula, R is hydrogen or a methyl group] ( b) 10 to 99% by weight of at least one selected from aromatic vinyl, vinyl cyanide, and (meth)acrylic acid ester; and (c) 0 to 80% by weight of other copolymerizable monomers. A rubber-reinforced resin obtained by copolymerizing 20 to 97% by weight of a polymer. (2) (A) (a) Compounds 1 to 9 represented by the following general formula (1)
0% by weight ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (n=0-8) [In the formula, R is hydrogen or methyl group] (b) Aromatic vinyl, vinyl cyanide, (meth) 3-80% by weight of a copolymer obtained by polymerizing a monomer consisting of 10-99% by weight of at least one selected from acrylic esters, and (c) 0-80% by weight of other copolymerizable monomers. Part (B) 0 to 80 parts by weight of a rubber-modified styrenic resin, and (C) at least one copolymer selected from aromatic vinyl, vinyl cyanide, and (meth)acrylic acid ester.
A thermoplastic resin composition containing ~80 parts by weight of (A), (B) and (C) such that the total is 100 parts by weight. (3) A thermoplastic resin composition comprising 20 to 80% by weight of the rubber reinforced resin of claim (1) and/or the thermoplastic resin composition of claim (2), and 20 to 80% by weight of a vinyl chloride resin.