JPS62158748A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To produce the titled compsn. having excellent environmental stress cracking resistance and giving moldings having improved surface profile, by mixing a specified polymer compsn. with a high-impact polystyrene resin. CONSTITUTION:20-90% (by weight, to same applies hereinbelow, on a solid basis) emulsion (A) of a vinyl polymer having a glass transition temp. of higher than 20 deg.C, a gel content of 10% or below, a solubility parameter of 8.0-10.0(cal/cc)<1/2> and a weight-average MW of 2X10<5> or above in terms of PS is mixed with 10-80% (on a solid basis) emulsion (B) of an acrylic ester (co)polymer having a glass transition temp. of 20 deg.C or below, a gel content of 70% or below and a solubility parameter of 8.4-9.8(cal/cc)<1/2> in then form of an emulsion. 0.5-50% polymer compsn. C obtd. by separating the polymers from the emulsion mixture is mixed with 50-99.5% high-impact polystyrene resin which has a rubber content of 1-20% and wherein at least 90% of monomers constituting the resin component is a styrene monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a thermoplastic resin composition that has excellent environmental stress formability and improved surface condition of molded products.

(Prior Art) When a rubber-containing styrenic resin comes into contact with a chemical under stress, it is observed that cracks occur and, in severe cases, breakage occurs. This phenomenon is called environmental stress cracking phenomenon.
Alkanes, alkenes, which do not have high solubility in resins,
It is well known that this phenomenon is significantly observed with chemicals such as alcohols, carboxylic acids, and esters.

Environmental stress cracking occurs even when no external force is applied to the resin molded product, when the distortion remaining inside the molded product during the engraving process is released by contact with chemicals. This imposes many restrictions on the uses of styrenic resins.

Factors that affect the environmental stress cracking properties of rubber-containing styrenic resins are i) the content of the rubber component, ii) the molecular weight of the resin component, and iii) the composition of the resin component.
Respectively, i) increasing the content of the rubber component, ii) increasing the molecular weight of the resin component, iii) increasing the absolute value of the difference between the solubility parameter of the resin component and the solubility parameter of the drug, or constituting the resin component. Although methods such as introducing bulky substituents into polymer chains to increase the melt viscosity of resin components are known, the effect of improving environmental stress cracking resistance is insufficient for practical use. Ta.

By the way, the present inventors have discovered that by mixing an acrylic ester polymer with a rubber-containing styrene resin,
It has been reported that the environmental stress cracking resistance of rubber-containing styrenic resins is dramatically improved (Japanese Patent Laid-Open No. 58-179).
No. 257).

However, although the composition of the invention has a remarkable effect of improving environmental stress cracking resistance, poor phenomena are sometimes observed in the surface condition of injection molded products, and improvements have been required.

That is, when the composition of the invention is subjected to injection molding, a mica-like layer (a separation phenomenon) may be observed near the gate of the molded product, or an abnormal surface called a flow mark may be observed near the gate. This caused serious damage to the design of the molded product.

These poor surface conditions are caused by the fact that acrylic ester polymer particles containing rubber particles are dispersed in styrene resin.
It is thought that this occurs due to flattening deformation due to shear output during injection molding, and the occurrence of the defective phenomenon is particularly noticeable when using a rubber-containing styrene resin with a high melt viscosity.

In order to prevent flattening of the acrylic ester polymer particles, it is effective to copolymerize a polyfunctional vinyl monomer during polymerization of the acrylic ester polymer.

(Problems to be Solved by the Invention) However, in the case of acrylic ester polymers obtained by copolymerizing polyfunctional vinyl monomers such as divinylbenzene and ethylene glycol dimethacrylate, poor surface conditions may occur. Although improvements have been achieved, the gel content is high and the effect of improving the environmental stress cracking properties of rubber-containing styrenic resins is insufficient. Therefore, by using a polyfunctional vinyl monomer and a chain transfer agent together to produce an acrylic ester polymer with a low gel content and a branched structure, it has excellent environmental stress cracking resistance. Although it is possible to produce a composition that gives a molded product with suppressed surface defects, the effect is unsatisfactory in practical terms.

An object of the present invention is to provide a thermoplastic resin composition that improves the drawbacks of the prior art described above.

(Means for Solving the Problems) To summarize the present invention, the present invention relates to a method for producing a thermoplastic resin composition, and (8) a polymer of vinyl monomers, the glass The transition temperature is above 20°C, the gel content is below 10%, and the solubility parameter is 8.
．． 0 to 10.0 (cal/cc)'' and a weight average molecular weight based on polystyrene of 2 x 105 or more [(A) component polymer] emulsion of 20 to 90% by weight
(as the solid content of the polymer) and (B) a homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers. , whose glass transition temperature is 2
0°C or lower, the gel content is 70% or lower, and the solubility parameter is 8.4 to 9.8 (ca 1!
/cc) "" is obtained by mixing 10 to 80% by weight (in solid content of the polymer) of an emulsion of a polymer [component polymer (B)] in an emulsion state, and then separating the polymer. A polymer composition C0.5 to 50% by weight, a rubber component content of 1 to 20% by weight, and 90% by weight or more of the monomers constituting the resin component are styrene monomers. It is characterized in that it is mixed with 50 to 99.5% by weight of impact polystyrene resin.

The thermoplastic resin composition produced according to the method of the present invention has excellent environmental stress cracking resistance, and is less likely to cause defective molded products such as delamination and flow marks.

Examples of vinyl monomers constituting the polymer that is component (A) of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, cyanostyrene,
Aromatic vinyl monomers such as chlorstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylate trile, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, octadecyl acrylate, hydroxyethyl Acrylic acid ester monomers such as acrylate, methoxyethyl acrylate, glycidyl acrylate, phenyl acrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, Methacrylic acid ester monomers such as methoxyethyl methacrylate, glycidyl methacrylate and phenyl methacrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, vinyl chloride , vinyl halide monomers such as vinylidene chloride, fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate, vinyl octadecanoate, ethylene, propylene, 1-butene, isobutylene, 2- Olefin monomers such as butene, maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, maleic anhydride Acid anhydride monomers such as butadiene, isoprene, chloroprene and other conjugated diene monomers, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, decyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, talesyl vinyl ether, glycidyl vinyl ether, etc. Examples include, but are not limited to, vinyl ether monomers, vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone, and vinyl pyridine.

The vinyl monomer constituting the component polymer (A) of the present invention may be a polyfunctional vinyl monomer, and examples of the polyfunctional vinyl monomer include divinylbenzene, ethylene glycol di (meth)acrylate, 1,3-butylene glycol di(meth)acrylate, l,4-butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triallyl cyanurate,
Triallyl incyanurate, trimethylolpropane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(
meth)acrylate, pentaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate
Acrylate, Tetradecaethylene glycol di(meth)acrylate, Eicosaethylene glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, Bentapropylene glycol di(meth)acrylate, Nonapropylene glycol di(meth)acrylate, Tetra Decabrobylene glycol di(meth)
Acrylate, eicosapropylene glycol di(meth)acrylate, 1,6-hexyldiol di(meth)
There are acrylates, etc. Here, for example, ethylene glycol di(meth)acrylate means ethylene glycol diacrylate or ethylene glycol dimethacrylate.

The (A) component polymer of the present invention has a glass transition temperature of 20°C.
It is necessary to exceed the A more preferable glass transition temperature is 30°C or higher. When the glass transition temperature of the (A) component polymer is 20°C or less, the (A) component polymer and (B)
It is difficult to handle the polymer composition C in the form of powder or pellets, which is industrially disadvantageous. It is not preferable because it causes a large decrease.

The component (A) polymer of the present invention is 8.0 to 10.0 (ca.
17cc) It is necessary to have a solubility parameter in the range of ``'', and the more preferable range is 8,6~
9.4 (ca 1 /cc) "". A thermoplastic resin obtained by mixing a high-impact polystyrene resin with a polymer composition C obtained by mixing a component polymer (A) with a solubility parameter outside the range of the present invention with a component polymer (B). In the case of compositions, it is undesirable for the molded product to have a layered structure (surface defect phenomena such as separation phenomenon and flow marks appear).

In addition, Honmei! The solubility parameter referred to in Book II is a
Published in 2013, by Brandrup (J) and Immergut (E, H, Immergut).
Pigeon, Polymer Handbook (Polymer 1lan)
dbook) 2nd Edition IV-337~■359 Using the solubility parameter values listed in It is calculated by the following formula I from the solubility parameter 67 of the homopolymer and its weight fraction W, 1.

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are each 8.8 (ca 17
cc) ””, 9.4 (ca 1 /cc) ””
Then, the solubility parameter of a copolymer consisting of 701 iit% of butyl polyacrylate and 30% by weight of ethyl polyacrylate is 9.0 (cal/cc).
It is calculated as follows.

The component (A) polymer of the present invention needs to have a weight average molecular weight of 2×10 5 or more based on polystyrene. A polymer composition C obtained by mixing a component polymer (A) having a weight average molecular weight of less than 2X10' based on polystyrene standards with a component polymer (B) and a high impact polystyrene resin. Thermoplastic resin compositions are undesirable because surface defects such as delamination and flow marks appear in molded products.

In this specification, the weight average molecular weight based on polystyrene is the weight average molecular weight determined by gel permeation chromatography assuming that the component polymer (A) is polystyrene. That is, using polystyrene, which has a narrow molecular weight distribution and a known molecular weight, as a standard substance, a calibration curve is created by determining the relationship between the outflow peak volume MJ of the gel permeation chromatogram and the molecular weight.

Next, the gel permeation chromatogram of the component polymer (A) is measured, the molecular weight is determined from the outflow volume using the calibration curve, and the weight average molecular weight is calculated according to a conventional method.

The polymer component (A) of the present invention needs to have a gel content of 10% or less. In the present invention, the gel content means that approximately 1.0 g of component polymer (A) is accurately weighed (Sag), placed in a container made of 40Q mesh stainless steel wire mesh, and placed in 100 g of methyl ethyl ketone. The weight of the insoluble polymer component (A) after leaving it for 24 hours at 5°C, pulling it up, and air-drying it at room temperature, S + g, is the value calculated according to the following formula (■). .

(Sl /56) A thermoplastic resin composition obtained by mixing with a thermoplastic resin is not preferable because the molded product has poor gloss.

There are no particular restrictions on the method for producing component (A) polymer of the present invention, including emulsion polymerization,! Although any known technique such as Q-turbidity polymerization, solution polymerization, or bulk polymerization can be applied, production by emulsion polymerization is industrially most advantageous.

One reason is that in the present invention, (A
This is because the polymer component () and the polymer component (B) are mixed, and the other reason is that emulsion polymerization allows industrially easy production of high molecular weight polymers.

In producing the (A) component polymer of the present invention, the vinyl monomer is selected so that the glass transition temperature, gel content, solubility parameter, and weight average molecular weight of the obtained (A) component polymer are in accordance with the present invention. It is particularly preferable that the component polymer (A) is polystyrene in order to improve layered peelability, although it is optional as long as it satisfies the above requirements.

It is possible to use a chain transfer agent for the purpose of controlling the molecular weight of the component polymer (A). In particular, when copolymerizing polyfunctional vinyl monomers, a chain transfer agent is used in combination to create a branched structure and a low gel content (A
) component polymers can be produced.

There are no particular limitations on the chain transfer agents that can be used (e.g., octylmercaptan, decylmercaptan, dodecylmercaptan, thioglycolic acid, ethyl thioglycolate, butyl thioglycolate, ethyl O-mercaptobenzoate, 1-naphthyl disulfide, sulfur). Sulfur compounds such as, halogen compounds such as carbon tetrabromide, limonene,
Hydrocarbons such as terpinolene, trinitrophenol,
Examples include nitro compounds such as trobenzene, and henzoquinone.

Next, the component CB) polymer of the present invention is a homopolymer or copolymer of an acrylic ester monomer, or a copolymer of an acrylic ester monomer and another copolymerizable monomer. However, here, the specific example of the acrylic ester monomer is the same as the specific example of the acrylic ester monomer listed above as an example of the vinyl monomer constituting the (A) component polymer of the present invention. be. Specific examples of the copolymerizable monomers constituting the component polymer (B) include acrylic acid among the monomers listed above as examples of vinyl monomers constituting the component polymer (A). This is the same as the specific example except for the ester monomer.

In addition, the (B) component polymer of the present invention may use a polyfunctional vinyl monomer or a chain transfer agent during its polymerization, and specific examples of the polyfunctional vinyl monomer and chain transfer agent include:
Each is the same as the specific example listed above for component (A) polymer.

The (B) component polymer of the present invention has a glass transition temperature of 20°C.
It is necessary that the following is true. A more preferable glass transition temperature is 10°C or lower. A thermoplastic resin composition obtained by mixing a polymer composition C obtained by mixing a component (B) polymer with a glass transition temperature exceeding 20° C. with a component polymer (A) and a high impact polystyrene resin. In this case, the environmental stress cracking resistance is poor and it is not preferable.

The component (B) polymer of the present invention needs to have a gel content of 70% or less. To measure the gel content, replace the solvent with 100 g of methyl ethyl ketone and use LOOG
It is the same as that of the component polymer (A) except that toluene is used, and it is calculated according to the above-mentioned formula (2). In a thermoplastic resin composition obtained by mixing a polymer composition C obtained by mixing a (B) component polymer with a gel content of more than 70% with a (A) component polymer, into a high impact polystyrene resin, , the environmental stress cracking resistance is poor and undesirable.

The component (B) polymer of the present invention is 8.4 to 9.8 (ca.
It is necessary that the solubility parameter is in the range of 8.6 to 9.6 (ca I!/cc)''2. The method for determining the solubility parameter is the same as that for the component polymer (A), and is calculated according to the above-mentioned formula r.

(B) The solubility parameter of the component polymer is 8.4 (ca
1/cc) less than 9.8 (ca 1
/cc) If it exceeds ``'', the (B) component polymer will be
The thermoplastic resin composition obtained by mixing the polymer composition C mixed with the component polymer A) with a high-impact polystyrene resin has poor environmental stress cracking resistance, which is not preferable.

There are no particular restrictions on the method for producing component polymer (B), and any known techniques such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be applied, but production by emulsion polymerization is industrially most advantageous. It is.

When producing component polymer (B), the selection of acrylic ester monomer or copolymerizable monomer is determined based on the glass transition temperature, gel content, and The solubility parameter is arbitrary as long as it satisfies the provisions of the present invention.

In the present invention, 20 to 90% by weight of (A) component polymer and (B)
10 to 80% by weight of the component polymer (B) are mixed in an emulsion state to form a polymer composition C. However, if the content of the component polymer (B) is less than 10% by weight, the polymer composition Thing C
A thermoplastic resin composition prepared by mixing a high-impact polystyrene resin and a high-impact polystyrene resin has poor environmental stress moldability. Surface defects such as marks appear, which is undesirable.

In the present invention, an emulsion of the (A) component polymer and an emulsion of the (B) component polymer are mixed in an emulsion state.

(A) component polymer or (B) component polymer is emulsion polymerized! ! i! If it is left over, the emulsion polymerization solution obtained by emulsion polymerization can be used as it is, but if it is manufactured by other polymerization methods, a step of emulsifying the obtained polymer is required. .

There is no particular restriction on the method of emulsifying the polymer, and any known technique can be applied. For example, a method in which a polymer solution is mixed and stirred with an emulsifier and water to form an emulsion and then the solvent is removed; a fine powder obtained by crushing a polymer is mixed and stirred together with an emulsifier and water to form an emulsion; Methods include, but are not limited to, pulverizing a polymer in the presence of an emulsifier and water to obtain an emulsion.

Although there is no particular restriction on the particle diameter of the polymer in the emulsion of the component polymer (A) or the component polymer (B), it is preferable that the area average particle diameter is 5 μm or less.

Here, the area average particle diameter is calculated according to the following formula (2) by taking an electron micrograph of the emulsion and setting the fraction of the particle diameter where the particle diameter is dA as fl.

Σf, d,”/Σf, d−... (n[) especially (B)
When the area average particle diameter of the component polymer exceeds 5μ, the (B
A molded product of a thermoplastic resin composition obtained by mixing a polymer composition C obtained by mixing a component polymer with a component polymer (A) with a high-impact polystyrene resin exhibits delamination phenomena or flow marks. This may occur.

There is no particular restriction on the type of emulsifier used for emulsion polymerization of component polymer (A) or component polymer (B) or for emulsification of the polymer, including anionic surfactants, cationic surfactants,
The surfactant may be arbitrarily selected from amphoteric surfactants and nonionic surfactants, but anionic surfactants can be used most advantageously.

There are no particular restrictions on the method of mixing component (A) component polymer emulsion and (B) component polymer emulsion, and devices such as a fixed container type mixing device, a rotating container type mixing device, a pipeline mixer, a static mixer, etc. are used. Mixing can be done by

There is no particular restriction on the method for separating the polymer composition C from the mixed emulsion of the component polymer emulsion (A) and the component polymer emulsion (B). acids, electrolytes such as sodium chloride, calcium chloride, aluminum chloride, sodium sulfate, and magnesium sulfate, precipitating agents such as polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymers, and aqueous polymers such as carboxymethyl cellulose. Examples include a method of adding, a method of breaking the emulsion by freezing the emulsion, and a method of spraying the emulsion into a high-temperature gas.

The polymer composition C separated from the mixture of the (A) component polymer emulsion and the (B) component polymer emulsion can be further supplied to a melt-kneading device for melt-kneading. Examples of melt-kneading equipment that can be used include Banbury mixer.
, intensive mixers, mixtruders, co-kneaders, extruders, rolls, etc. It is also possible to use a melt-kneading device with a dehydration mechanism disclosed in Japanese Patent Publication No. 59-37021, but when using this device, the emulsion and precipitating agent must be continuously supplied to the device. It is also possible to continuously perform mixing, demulsification, dehydration, drying, and melt-kneading in the same device.

The high impact polystyrene resin of the present invention refers to a rubber-containing styrenic resin comprising a rubber component, a resin component, and a covalent bond of the rubber component and the resin component. Examples of rubber components include polybutadiene, polyisoprene,
Polychloroprene, poly(butadiene-styrene),
Conjugated diene rubbers such as poly(butadiene-acrylonitrile), poly(butadiene-styrene-methyl methacrylate), poly(ethylene-propylene-4-
Examples include ethylene propylene rubbers such as poly(ethylene-propylene-dicyclopentadiene) and poly(ethylene-propylene-2,5-norbornadiene). In addition, monomers constituting the resin component include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, nitrile monomers such as acrylonitrile and methacrylate, methyl methacrylate, and ethyl styrene. Acrylate, (meth)acrylic acid ester monomers such as butyl acrylate, hexyl acrylate, octyl acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-)ruyl Examples include maleimide monomers such as maleimide, maleic anhydride, etc., but 90% by weight or more of the monomers constituting the resin component must be styrene monomers.

There are no particular restrictions on the method for producing the high-impact polystyrene resin, and any known techniques such as bulk polymerization, bulk-suspension polymerization, suspension polymerization, solution polymerization, and emulsion polymerization may be applied.

For example, it is possible to mix a separately polymerized resin component with a high impact polystyrene resin in order to adjust the rubber component contained in the high impact polystyrene resin. It does not need to have the same composition as the resin component obtained by polymerizing impact polystyrene resin. For example, high impact polystyrene obtained by polymerizing styrene in the presence of polybutadiene can be mixed with poly(styrene-maleic anhydride) obtained by separate polymerization.

A covalent bond between a rubber component and a resin component, which is one of the essential structural units of high-impact polystyrene resin, can be produced by a so-called graft polymerization method, but in the present invention, any known graft polymerization technique can be applied. .

It is necessary that the rubber component content of the high impact polystyrene resin is 1 to 20% by weight.

If the rubber component content is less than 1% by weight, the impact resistance of the thermoplastic resin composition obtained by mixing with polymer composition C will be low;
If it exceeds 0% by weight, the rigidity will decrease.

In the present invention, a thermoplastic resin composition is produced by mixing a polymer composition CO, 5 to 50% by weight, and 50 to 99.5% by weight of an impact polystyrene resin. More preferably, 02 to 40% by weight of the polymer composition and 60 to 99% by weight of the high impact polystyrene resin are mixed.

If the amount of polymer composition C added is less than 0.5% by weight, the environmental stress resistance of the resulting thermoplastic resin composition will be poor;
If it exceeds % weight, the composition will deteriorate in rigidity, heat resistance, or impact resistance, which is not preferable.

There are no particular limitations on the method of mixing polymer composition C and high impact polystyrene resin, and the desired thermoplastic resin composition can be produced by mixing both components in powder or pellet form. Examples of the mixing device include, but are not limited to, fixed container type mixing devices such as a Henschel mixer, rotating container type mixing devices such as a type blender, and a tumbler.

An example of a method for mixing the polymer composition C and the high impact polystyrene resin is melt kneading.

Specific examples of the melt-kneading apparatus used include a Banbury mixer, intensive mixer, mixtruder, coney goo, extra goo, and roll.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

In addition, all parts and percentages described in each example are based on weight.

Example 1 and Comparative Example 1 [Production of component (A) - Production of A-1 to A-15] Pure water 1
50 parts of potassium stearate and 2 parts of potassium stearate were placed in an autoclave and heated to 50°C while stirring. Here, 0.005 part of ferrous sulfate heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate dihydrate.
An aqueous solution prepared by dissolving 1 part in 10 parts of pure water was added.

Next, 100 parts of the monomer mixture having the composition shown in Table 1 was added to 4
It was added continuously over time. At the same time, potassium persulfate 0.
An aqueous solution of 0.05 parts dissolved in 25 parts of pure water was continuously added over 6 hours.

After the addition of the monomer mixture was completed, 0.1 part of diisopropylbenzene hydroperoxide was added, and the system was heated to 70° C. and stirred for an additional 2 hours to complete the polymerization.

Table 2 shows the properties of the obtained component (A).

[Production of component (A)-A-16 to A-17] 175 parts of pure water and 2 parts of potassium stearate were placed in an autoclave and heated to 70°C while stirring.

An aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 10 parts of pure water was added thereto, and 100 parts of a monomer mixture having the composition shown in Table 1 was added continuously over a period of 4 hours.

After the addition of the monomer mixture was completed, 0.1 part of lauroyl peroxide was added, and the mixture was further stirred at 70° C. for 2 hours to complete the polymerization.

Table 2 shows the properties of the obtained component (A).

[Production of component (A) - Production of A-18] 175 parts of pure water,
Charge 2 parts of potassium stearate into an autoclave,
The mixture was heated to 50° C. with stirring. Here, sulfuric acid No.
0.01 part of iron heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate dihydrate are added to 1 part of pure water.
0 parts of an aqueous solution was added.

Next, a mixture of 0.2 parts of diisopropylbenzene hydroperoxide dissolved in 100 parts of the monomer mixture having the composition shown in Table 1 was continuously added over 5 hours.

After the addition of the monomer mixture was completed, 0.1 part of diisopropylbenzene hydroperoxide was added, and the system was heated to 70° C. and stirred for an additional 2 hours to complete the polymerization.

Table 2 shows the properties of the obtained component (A).

[Structure of component (B) - excluding B-15 and B-27] Pure water 12 (1, sodium dodecylbenzenesulfonate 2
Place the sample in an autoclave and heat to 65°C while stirring.
heated to. Here, 0.005 part of ferrous sulfate heptahydrate, 0.0 part of ethylenediaminetetraacetic acid tetrasodium dihydrate
An aqueous solution prepared by dissolving 1 part of sodium formaldehyde sulfoxylate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added.

Next, 2 parts of 100 parts of the monomer mixture having the composition shown in Table 3 was added.
Pour 0% into the autoclave and add 0.2% potassium persulfate.
% aqueous solution was added to initiate polymerization.

Simultaneously with the start of polymerization, the remaining amount of the monomer mixture was continuously added over 4 hours. In addition, at the same time as the start of polymerization, 6 parts of an aqueous solution of 0.05 parts of potassium persulfate dissolved in 20 parts of pure water was added.
It was added continuously over time. After the addition of the potassium persulfate solution was completed, the contents of the autoclave were cooled to terminate the polymerization.

Table 4 shows the properties of the obtained component (B).

[Structure of component (B) - Production of B-15 and B-27] Pure water 141, sodium dodecylbenzenesulfonate 2
Place the sample in an autoclave and heat to 70°C while stirring.
heated to.

An aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 10 parts of pure water was added thereto, and 100 parts of a monomer mixture having the composition shown in Table 3 was added continuously over a period of 4 hours.

After addition of the jut mixture liquid, 0.1 part of diisopropylbenzene hydroperoxide was added, and the temperature was further heated to 70°C.
The mixture was stirred for 2 hours to complete the polymerization.

Table 4 shows the properties of the obtained component (B).

In addition, the abbreviations of the long chain bifunctional monomers used in Table 3 are as follows.

9G; Nonaethylene glycol dimethacrylate 14G; Tetradecaethylene glycol dimethacrylate 9PC; Nonapropylene glycol dimethacrylate 9ACi Nonaethylene glycol dimethacrylate [Production of polymer composition C] (A) Component emulsion 50 parts (polymer solids ) and (
B) 50 parts of component emulsion (as the solid content of the polymer) are mixed in an emulsion state, and further a polyethylene glycol-polypropylene glycol block copolymer (ethylene oxide weight fraction in the total molecule is 80%, polypropylene glycol molecular weight 1750-0.7 part of a 10% aqueous solution of Pluroni F-68 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added.

An aqueous solution prepared by dissolving 5 parts of calcium chloride dihydrate in 400 parts of pure water was heated to 80 to 95°C, and the mixed emulsion was poured into the solution while stirring to precipitate.

The obtained slurry was filtered, washed with water, and dried in a 70°C atmosphere to obtain a polymer composition C.

In addition, each physical property value was calculated|required by the following method.

(1) Glass transition temperature The solid obtained by dropping the emulsion of component (A) or component (B) into methanol is dried and measured using a DuPont type measuring device.
It was measured using a 10 differential scanning calorimeter and a 990 thermal analyzer.

(2) Gel content The solid obtained by dropping the emulsion of component (A) or component (B) into methanol was dried. Approximately 1.0 g of the weight was accurately weighed, measured using the method described above, and calculated using formula (2). However, the solvents used are different for components (A) and (B),
Methyl ethyl ketone was used as the component (A), and toluene was used as the component (B).

(3) Solubility parameter The solubility parameter value of each polymer used to calculate the solubility parameter on each side [unit: (ca1/cc) section'
z] is as follows.

Polybutyl acrylate: 868 Polyethyl acrylate; 9.4 Polymethyl methacrylate
;9.5 polyacrylonitrile;12.5 polystyrene;9. 1 polyvinyltoluene; 8,9 poly(t-butylstyrene); 7.
9 (4) Weight average molecular weight The weight average molecular weight was measured using HLC-802A gel permeation chromatography manufactured by Toyo Soda Kogyo Co., Ltd., with two GMH-6 columns manufactured by the same company lined up. A refractometer was used as a detector, and tetrahydrofuran was used as a solvent.

The upper limit of weight average molecular weight measurement using this device is 6X
105, and for samples exceeding 6X10', see Table 2.
Write 〉6 in the relevant column.

The sample used was a solid obtained by precipitating the emulsion of component (A) with methanol.

Table 4 Table 4 [Manufacture of thermoplastic resin composition] 90 parts of high impact polystyrene resin pellets consisting of 7% polybutadiene and 93% polystyrene, the weight average molecular weight of the polystyrene being 2.15 x 10'), and a polymer composition. The mixture was mixed with 10 parts of C powder and fed to VC-40 (single-screw extruder with vent) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

Moldings were made using the obtained pellets and their physical properties were evaluated, and the results are shown in Table 5 Experiment Nos. 1 to 45.

Note that the physical property measurements on each side were determined by the following method.

(1) Tensile yield point...ASTM D-638
(2) Izotsu impact strength...ASTM D-25
6(3) Vicat softening temperature...JIS 687
0 (4) Gloss...JIS Z-8741 (5) Chemical resistance (environmental stress resistance) ASTM 'D-638 type ■ Give a 20 degree deflection to the dumbbell and fix it on a jig and use niethylene glycol monomer. The time taken to break when ethyl ether is applied and left at a temperature of 23°C is expressed in minutes. In the table, >180 indicates that no breakage occurred after 180 minutes.

(6) N-shaped peel tuning and flow mark 2 with Toshiba Machine Co., Ltd. 1s-80CN-V injection molding machine
0 x 80 x 3 am rectangular molding to create a product. The gate is located at the center of one side of 20mm in length, and the gate shape is an edge gate with a length of 2mm having a rectangular cross section of 2mm in the length direction of the molded product and 185mm in the thickness direction. The mold has four cavities.

When the gate portion of the obtained molded product was folded flat, layered peeling occurred near the gate, and the degree of peeling was evaluated as follows by comparing with a standard sample.

A: Not observed at all B: Slightly observed C: Significantly observed D: Significantly observed Experimental numbers 1 to 38 are examples, and numbers 39 to 45 are comparative examples.

Comparative Example 39 has a polymer composition obtained by mixing and precipitating the (A) component emulsion and (B) component emulsion, although the glass transition temperature of the (A) component is outside the range of the present invention. Since the solid product C does not turn into powder at room temperature but takes on the form of a lump, it poses operational disadvantages, for example, in the dehydration of the precipitate, the water washing process, the drying process, or the mixing process with rubber-containing styrenic resin.

In experiments other than Comparative Example 39, the solid of polymer composition C was powder-like, and no operational problems occurred.

As is clear from the comparative examples, when the weight average molecular weight or solubility parameter of component (A) deviates from the range of the present invention, the delamination phenomenon becomes noticeable, and when the glass transition temperature of component (A) deviates from the range of the present invention. Heat resistance and operability during production are poor, and if the gel content of component (A) is outside the range of the present invention, gloss is poor, both of which are not preferred. Furthermore, if the solubility parameter, gel content, or glass transition temperature of component (B) deviates from the range of the present invention, the environmental stress resistance will be poor, which is not preferable.

Example 2 and Comparative Example 2 Emulsion A-1 and emulsion B-1 produced in Example 1 were mixed in the emulsion state at the ratio shown in Table 6 (the parts in the table indicate the solid content of the polymer). ).

Furthermore, 7 parts of the 10% aqueous solution of Pluronic F-68 used in Example 1 was added to 100 parts of the solid content of the polymer mixture.

The obtained mixed emulsion was subjected to precipitation treatment in the same manner as in Example 1 to obtain polymer compositions C-1 to C-7.

Next, 90 parts of the high impact polystyrene resin pellets used in Example 1 and polymer compositions C-1 to G-7 were added.
The mixture was mixed with 10 parts of powder and fed to a VC-40 extruder to obtain pellets.

Using the obtained pellets, physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 7.

As is clear from Comparative Example 2, (B) in polymer composition C
If the component content exceeds the lower limit of the range of the present invention, the environmental stress cracking resistance of the fabric will be poor, and if it exceeds the upper limit, the layered peeling phenomenon will become noticeable, both of which are undesirable.

Example 3 and Comparative Example 3 50 parts of the A-1 emulsion (as the solid content of the polymer) produced in Example 1 and 50 parts of the B-1 emulsion (as the solid content of the polymer) were mixed in an emulsion state. Mix and then add Pluronic F-6
7 parts of a 10% aqueous solution of No. 8 were added.

The obtained mixed emulsion was subjected to precipitation treatment in the same manner as in Example 1 to obtain powder of Example Composition C.

Next, the powder of the polymer composition C was fed to a VC-40 extruder to obtain pellets.

Table 8 shows the obtained pellets of polymer composition C and the high impact polystyrene resin pellets used in Example 1.
They were mixed in the proportions shown in (1) and fed to a C-40 type extruder to obtain thermoplastic resin composition pellets.

The physical properties of the obtained pellets were evaluated in the same manner as in Example 1, and the results are shown in Table 8.

As is clear from Comparative Example 3, when the amount of polymer composition C added exceeds the lower limit of the range of the present invention, the resulting thermoplastic resin composition has poor environmental stress cracking resistance, and when it exceeds the upper limit, heat resistance deteriorates. This is undesirable as it reduces performance.

(Effects of the Invention) As explained above, the thermoplastic resin composition produced according to the method of the present invention has excellent environmental stress cracking resistance, and the delamination phenomenon of the obtained molded product is significantly suppressed. This has a remarkable effect.

Patent Applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendment February 14, 1985 Director General of the Patent Office Michibe Uga 1. Indication of the case 1985 Patent Application No. 1540 2. Name of the invention Process for producing thermoplastic resin composition 3. Relationship with the case of the person making the amendment Patent applicant address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo 4. Detailed explanation of the invention in the specification subject to the amendment 5. Contents of the amendment <17 Specification page 10 Correct "1,6-hexyl" in line 11 to "l,6-hexane".

Correct ``to be more than that'' to ``to be more than that.''

(3) Solution polymer” on page 22, line 4 of the specification
Soluble polymer” is corrected.

(4) “Melting and kneading” on page 22, line 18 of the specification is changed to “
"Melt kneading" is corrected.

(5) Replace “t-buti” on page 23, line 14 of the specification with “
T-buchi,” he corrected.

(6) "99% by weight" on page 25, line 17 of the specification is corrected to "98% by volume."

(7) 110' on page 40, line 4 of the specification) Replace J with "105"
” he corrected.

(8) In the specification, page 41, line 5, "layered peelable" is corrected to "layered peelable".

(9) In Table 5 on pages 42, 43, and 44 of the specification, "distinction between applied examples and reference examples" is corrected to "distinction between working examples and comparative examples."

Claims (1)

[Scope of Claims] (A) A polymer of vinyl monomers, whose glass transition temperature exceeds 20°C and whose gel content is 10% or less,
The solubility parameter is 8.0-10.0 (cal/cc
)^1^/^2 and a weight average molecular weight based on polystyrene of 2 x 10^5 or more emulsion 20
~90% by weight (as the solid content of the polymer); and (B) a homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers. It is a polymer whose glass transition temperature is 2.
0°C or less, gel content is 70% or less, and solubility parameter is 8.4 to 9.8 (cal/cc)
10 to 80% by weight of a polymer emulsion with ^l^/^2 (
Polymer composition C0.5 to 5 obtained by mixing (as solid content of the polymer) in an emulsion state and then separating the polymer.
0% by weight, the content of the rubber component is 1 to 20% by weight, and 90% by weight or more of the monomers constituting the resin component are styrene monomers.
A method for producing a thermoplastic resin composition, the method comprising mixing 0 to 99.5% by weight of a thermoplastic resin composition.