JPS62277458A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved environmental stress cracking resistance and improved surface state of molded article, by blending emulsion of specific vinyl monomer polymer with emulsion of acrylic acid ester monomer polymer, etc. CONSTITUTION:(A) 0.2-30wt% (calculated as solid content of polymer) emulsion of a polymer of vinyl monomer, which has >=20 deg.C glass transition temperature, <=10% gel content, 9-11(cal/cc)<1/2> and >=2X10<5> weight-average molecular weight is blended with (B) 0.2-30wt% (co)polymer of acrylic acid ester, which has <=20 deg.C glass transition temperature, <=70% gel content and 8.4-9.8 solubility parameter and (C) 60-99.6wt% emulsion of rubber-containing styrenic resin consisting of a resin component, which has 2-70wt% rubber component content, comprises 40-90wt% styrenic monomer, 5-50wt% nitrile monomer, etc., and has <2X10<5> weight-average molecular weight and the polymers are separated.

Description

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

(Prior Art) When rubber-containing styrenic resin 2 comes into contact with chemicals under stress, it is observed that cracks occur and, in severe cases, breakage occurs. This phenomenon is called an environmental stress cracking phenomenon, and it is well known that it is significantly observed with chemicals such as alkanes, alkenes, alcohols, carboxylic acids, and esters that do not have high solubility in resins.

Environmental stress cracking occurs even when no external force is applied to the resin molded product, when distortions during molding that remain inside the molded product are released by contact with chemicals; therefore, rubber-containing styrene This places significant restrictions on the uses of these resins.

Factors that influence 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. ii) Increase the molecular weight of the resin component; iii) Increase the absolute value of the difference between the solubility parameter of the resin component and the solubility parameter of the drug; or Methods such as introducing bulky substituents to increase the melt viscosity of resin components are known, but the effect of improving environmental stress cracking resistance has not been sufficient for practical use.

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).
Publication No. 257).

However, although the compositions of the above-mentioned inventions have a remarkable effect of improving the 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 layered peeling 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 can seriously damage the design of the molded product.

These poor surface conditions are caused by the acrylic ester polymer particles dispersed in the rubber-containing styrene resin.
It is thought that this occurs due to flattening deformation due to shear center force during injection molding, and the occurrence of the defective phenomenon is particularly noticeable when using a rubber-containing styrenic 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 made, 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, which includes (A) a polymer of vinyl monomers, and a glass The transition temperature is above 20°C, the gel content is below 10%, and the solubility parameter is 9.
．． 0 to 11.0 (cal/cc) "",
and an emulsion of a polymer [component polymer (A)] having a weight average molecular weight of 2X105 or more based on polystyrene, from 0.2 to
30% by weight (as the solid content of the polymer); (B) a homopolymer or copolymer of an acrylic ester monomer, or a copolymer of an acrylic ester monomer and another copolymerizable monomer; coalescence, and its glass transition temperature is 2
0°C or less, the gel content is 70% or less, and the solubility parameter is 8, 4 to 9.8 (cal
/cc) Emulsification of a polymer [(B) component polymer]? FI 0.2 to 30% by weight (as solid content of the polymer); (C) The content of the rubber component is 2 to 70% by weight, and the monomer constituting the resin component is styrene monomer 40%. ~90% by weight, 5 to 50% by weight of nitrile monomer, and 0 to 40% by weight of other copolymerizable monomers, and the weight average molecular weight of the resin component is less than 2X10' based on polystyrene. An emulsion of styrenic resin [(C) component polymer] containing 60 to 99.6% by weight (as solid content of the polymer),
It is characterized in that the polymers are separated after being mixed in an emulsified state.

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 component polymer (A) of the present invention include styrene, α-methylstyrene, vinyltoluene, aromatic vinyl mitomers such as butylstyrene, cyanostyrene, and chlorostyrene, and acrylonitrile. , vinyl cyanide single plates such as trimethacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate,
Acrylic acid ester monomers such as octadecyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, cricidyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate,
Methacrylic acid ester monomers such as cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, methoxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate, amide monomers such as acrylamide and methacrylamide, acrylic acid , unsaturated carboxylic acid monomers such as methacrylic acid and itaconic acid, vinyl halide monomers such as vinyl chloride and vinylidene chloride, fatty acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate and vinyl octadecanoate. Vinyl ester monomers, olefin monomers such as ethylene, propylene, 1-butene, isobutylene, 2-butene, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
Maleimide monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-toluylmaleimide, acid anhydride monomers such as maleic anhydride, butadiene,
Conjugated dienes such as isoprene and chloroprene tJ-m
vinyl ether monomers such as 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, vinyl ketone monomers such as methyl vinyl ketone, phenyl vinyl ketone, Examples include, but are not limited to, vinylpyridine.

The vinyl monomer constituting the component polymer (A) of the present invention may be a polyfunctional vinyl monomer. Examples of polyfunctional vinyl monomers include divinylbenzene, ethylene glycol di (meth)acrylate, 1.3-butylene glycol di(meth)acrylate, 1.4-butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triallyl cyanurate,
Triallyl isocyanurate, 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, pentapropylene glycol di(meth)acrylate, nonapropylene glycol di(meth)acrylate, Tetradepropylene glycol di(meth)
Acrylate, eicosapropylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)
There are acrylates, etc. Here, for example, ethylene glycol di(meth)acrylate means ethylene gelyl 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 is
This is not preferred because the heat resistance of the thermoplastic resin composition formed by mixing the component polymer () and the component polymer (C) decreases.

The component (A) polymer of the present invention is 9.0 to 11.0 (ca.
It is necessary to have a solubility parameter in the range of l/cc) ``'', and a more preferable range is 9,
5 to 10.5 (cal/cc).

In a thermoplastic resin composition formed by mixing the (A) component polymer with the solubility parameter outside the range of the present invention with the (B) component polymer and the (C) component polymer, the molded product may suffer from layer delamination phenomenon or flow. Surface defects such as marks appear, which is undesirable.

In addition, the solubility parameter referred to in this specification refers to the solubility parameter published by John Wiley & Sons, New York City, 1975, Brandrup (J, Brandrup) and Inmergut (E, 'A, b++merguL) 1.
4. Polymer Hand
Using the solubility parameter values listed on pages 337 to 359 of the second edition of the book), the six solubility parameters of the copolymer are determined by the individual vinyl monomers constituting the copolymer consisting of m types of vinyl monomers. From the solubility parameter δ of the polymer homopolymer and its weight fraction W7, the following formula CI)
It is calculated by.

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are each 8.8 (cal
/ (() + yz, 9.4 (ca j2 /c
c) "" means 70% by weight of butyl polyacrylate
The solubility parameter of the copolymer consisting of 30% by weight of polyethyl acrylate is 9. O(cal/cc)
It is calculated as "".

The component (A) polymer of the present invention needs to have a weight average molecular weight of 2×10′ or more based on polystyrene.

In a thermoplastic resin composition formed by mixing a component polymer (A) with a weight average molecular weight of less than 2X10' based on polystyrene standards with a component polymer (B) and a component polymer (C), a layered peeling phenomenon occurs in the formed product. , surface defects such as flow marks appear, which is undesirable.

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 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. The gel content as used in the present invention means that approximately 1.0 g of component polymer (A) (accurately weighed as Sog) is placed in a cage made of 400 mesh stainless steel wire gauze and placed in 100 g of methyl ethyl ketone. The weight of the insoluble polymer component (A) after being left to stand at 5°C for 24 hours, pulling up the basket, and air drying at room temperature Sr g
is measured and then calculated according to the following formula (II).

(S, /So) The plastic resin composition is not preferred because the molded product has poor gloss.

There are no particular limitations on the method for producing the component polymer (A) of the present invention, 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 preferable. most advantageous.

One reason is that in the present invention, (A
) component polymer, (B) component polymer, and (C) component polymer are mixed. Another reason is that emulsion polymerization makes it easy to industrially produce high molecular weight polymers. This is because it is wet.

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 optional as long as it satisfies the provisions of.

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 can be used in combination to form a polyfunctional vinyl monomer with a branched structure and a low gel content (
A) A component polymer can be produced.

There are no particular limitations on the chain transfer agents that can be used, and examples include octylmercaptan, decylmercaptan, dodecylmercaptan, thioglycolic acid, ethyl thioglycolate, butyl thioglycolate, ethyl 0-mercaptobenzoate, 1-naphthyl disulfide, sulfur, and the like. sulfur compounds, halogen compounds such as carbon tetrabromide, limonene,
Hydrocarbons such as terpinolene, trinitrophenol,
These include nitro compounds such as trinitrobenzene and benzoquinone.

Next, the component (B) 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 copolymer 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. It is. 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). Same as the specific example except for the ester monomer.
0 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 polymerizing a component (B) polymer with a glass transition temperature exceeding 20°C with a component polymer (A) and a component polymer (C) has poor environmental stress cracking resistance. Undesirable.

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 100g of methyl ethyl ketone,
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). A thermoplastic resin composition prepared by mixing a component (B) polymer with a gel content of more than 70% with a component polymer (A) and a component polymer (C) has poor environmental stress cracking resistance. Undesirable.

The component (B) polymer of the present invention is 8.4 to 9.8 (ca.
It is necessary to have a solubility parameter in the range of 8.6 to 9.6 (cal/cc)'.The method for determining the solubility parameter is ( A) It is the same as that of the component polymer, and is calculated according to the above-mentioned formula (1).

(B) The solubility parameter of the component polymer is 8.4 (ca
7! / cc) ''' or less than 9.8 (c
a 1 /cc) exceeds ``'', the environmental stress cracking resistance of the thermoplastic resin composition formed by mixing the (B) component polymer with the (A) component polymer and the (C) component polymer decreases. It is inferior and undesirable.

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.

Monomers constituting the rubber component of the rubber-containing styrenic resin that is the component polymer (C) of the present invention include butadiene,
Conjugated diene monomers such as isoprene, dimethylbutadiene, chlorobrene, and cyclopentadiene; non-conjugated diene monomers such as 2.5-norbornadiene, 1.4-cyclohexadiene, and 4-ethylidenenorbornene; styrene, α- Styrenic monomers such as methylstyrene and vinyltoluene, nitrile monomers such as 7-crylonitrile and methacrylonitrile, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate. There are olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene, and those obtained by homopolymerization or copolymerization of these monomers are used. Furthermore, as a crosslinking monomer, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can also be used, but the polyfunctional vinyl monomers that can be used include divinylbenzene, ethylene glycol dimethacrylate, 1° 3-butylene glycol dimethacrylate, 1゜4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate, Examples include glycidyl methacrylate.

In the present invention, the rubber component used for the component polymer (C) must have a graft active site, and specifically, it must have a carbon-carbon double bond in the rubber molecule. preferable.

There are no particular restrictions on the method of polymerizing the monomers, including emulsion polymerization,
Known techniques such as solution polymerization can be used.

Furthermore, the rubber component of the component polymer (C) does not need to be of one type, and may be a mixture of two or more separately polymerized rubber components.

Monomers constituting the resin component of the component polymer (C) in the present invention include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, acrylonitrile, methacrylonitrile, etc. Nitrile monomers, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- Maleimide monomers such as cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide, and N-xylylmaleimide are used alone or in copolymerization, but styrene monomers and nitrile monomers must be included.

The (C) component polymer used in the present invention is composed of a rubber component and a resin component as described above, but a graft structure is present at the interface between the rubber component having a spherical structure and the resin component which is a continuous phase. It is necessary to be present. It is known that such a structure can be achieved by a so-called graft polymerization method in which part or all of the monomers constituting the resin component are polymerized in the presence of a rubber component. The polymer can also be produced by known graft polymerization techniques.

The resin component of the component polymer (C) can be produced by the above-mentioned graft polymerization method, but if necessary, a separately polymerized resin component can also be mixed with the polymer obtained by craft polymerization. At this time, the separately polymerized resin component does not need to have the same composition as the resin component obtained by graft polymerization.

For example, acrylonitrile is added to a rubber-containing styrenic resin emulsion obtained by graft polymerizing acrylonitrile, styrene, and methyl methacrylate in the presence of polybutadiene.
A resin component emulsion obtained by copolymerizing styrene and α-methylstyrene can be mixed to obtain the component (C) polymer.

Specific examples of the component (C) polymer of the present invention include ABS
(acrylonitrile-butadiene-styrene) resin, heat-resistant ABS (acrylonitrile-butadiene-styrene-α-methylstyrene) resin, AAS (acrylonitrile-acrylic acid ester-styrene) resin, AES
(acrylonitrile-EPDM-styrene) resin, M
Examples include BAS (methyl methacrylate-butadiene-acrylonitrile-styrene) resin.

The content of the rubber component contained in the component (C) polymer of the present invention needs to be 2 to 70% by weight, preferably 5 to 65% by weight. If the content of the rubber component is less than 2% by weight, the impact resistance of the thermoplastic resin composition obtained by mixing the (A) component polymer, (B) component polymer, and (C) component polymer will be low. , if it exceeds 70% by weight, the rigidity or heat resistance will decrease.

Furthermore, the resin component of the component polymer (C) contains 40 to 90% by weight of a styrene monomer, 2) 5 to 50% by weight of an IJ monomer, and 0 to 40% by weight of other copolymerizable monomers. % by weight. If the styrene monomer content is less than 40% by weight, the fluidity will be low (and if it exceeds 90% by weight, the impact resistance or rigidity will decrease. If the nitrile monomer content is less than 5% by weight, the impact resistance or rigidity will be low. , if it exceeds 50% by weight, fluidity decreases.

In addition, the weight average molecular weight of the resin component of the component polymer (C) must be less than 2x10' based on polystyrene standards, but if the weight average molecular weight of the resin component is 2x10S or more, the obtained thermoplastic resin The fluidity of the composition is low (unpreferable).The weight average molecular weight based on polystyrene herein is determined by the same measuring method as the weight average molecular weight of the component (A) polymer described above.

In the present invention, an emulsion of a component polymer (A), an emulsion of a component polymer (B), and an emulsion of a component polymer (C) are mixed in an emulsion state. When the (A) component polymer, (B) component polymer, or (C) component polymer is produced by emulsion polymerization, the emulsion polymerization solution obtained by emulsion polymerization can be used as it is, but other When produced by a polymerization method, 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.

There is no particular restriction on the particle diameter of the polymer in the emulsion of the component polymer (A), the component polymer (B), or the component polymer (C), although it is preferable that the area average particle diameter is 5 μm or less. Here, the area average particle diameter is calculated by taking an electron micrograph of the emulsion, dividing the particle diameter by d, and dividing the fraction of the particle diameter by f.
Calculated according to the following formula (T[I].

Σf,d,” /Σf,d,Z ・(I[[]
In particular, when the area average particle diameter of the component polymer (B) exceeds 5μ, the component polymer (B) is combined with the component polymer (A) and the component polymer (C).
Layering (separation phenomenon or flow marks) may occur in molded products of thermoplastic resin compositions mixed with component polymers.

There are no particular restrictions on the type of emulsifier used for emulsion polymerization of (A) component polymer, (B) component polymer, or (C) component polymer, or for emulsification of the polymer, including anionic surfactants and cationic surfactants. , amphoteric surfactants, and nonionic surfactants, but anionic surfactants can be used most advantageously.

(A) component polymer emulsion, (B) component polymer emulsion (
There is no particular restriction on the method of mixing component C) with the polymer emulsion;
Mixing can be carried out using devices such as fixed container mixers, rotating container mixers, pipeline mixers, static mixers, and the like.

(A) component polymer emulsion, (B) component polymer emulsion (
C) Component The method for separating the thermoplastic resin composition from the mixed emulsion with the polymer emulsion is not particularly limited. Electrolytes such as aluminum chloride, sodium sulfate, magnesium sulfate, polyvinyl alcohol,
Methods of adding precipitating agents such as polyethylene glycol, polyethylene glycol-polypropylene glycol bloc copolymer, water-soluble polymers such as carboxymethyl cellulose, methods of breaking the emulsion by freezing the emulsion, and spraying the emulsion into high-temperature gas. For example, how to do this.

(A) component polymer emulsion, (B) component polymer emulsion (
The thermoplastic resin composition separated from the mixture with the component C) polymer emulsion can be further supplied to a melt-kneading device for melt-kneading. Melting and kneading equipment that can be used include:
Examples include Banbury mixer, intensive mixer, mixtor-9'-, coneater, extorter, and roll. Also, special public service No. 59-37021
It is also possible to use the melt-kneading device with a dehydration mechanism disclosed in the above publication, but when using this device, the emulsion and the precipitating agent are continuously supplied to the device to mix, mix, and mix.
It is also possible to continuously perform demulsification, dehydration, drying, and melt-kneading in the same device.

In the present invention, (A) component polymer 0.2 to 30% by weight B
) component polymer 0.2 to 30% by weight, and (C) component polymer 60 to 99.6% by weight (both as solid content of the polymer)
Mix. (A) Content of component polymer is 0.2% by weight
(A) component polymer, (B) component polymer, and (
Surface defects such as delamination and flow marks appear in the molded product of the thermoplastic resin composition prepared by mixing component C) with the component polymer, and if it exceeds 30% by weight, the fluidity decreases, which is undesirable. Furthermore, if the content of the component polymer (B) is less than 0.2% by weight, the environmental stress cracking resistance of the thermoplastic resin composition will be low, and if it exceeds 30% by weight, the rigidity and heat resistance will be poor, which is not preferable. Furthermore, if the content of component (C) polymer is less than 60% by weight, impact resistance will be poor, and if it exceeds 99.6% by weight, environmental stress cracking resistance will be poor, which is not preferred.

The thermoplastic resin composition produced according to the method of the present invention is
If necessary, it can be used by mixing with a separately manufactured thermoplastic resin. For example, rubber-containing styrenic resins such as ABS resins are manufactured separately from poly(
It is known to be used in combination with acrylonitrile-styrene (acrylonitrile-styrene) resin, polyvinyl chloride resin, polycarbonate resin, etc., and even in the thermoplastic resin composition produced according to the method of the present invention, mixing of these thermoplastic resins is optional. It can be done.

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

Note that 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-19] 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,
Ferrous sulfate heptahydrate o, oos part, ethylenediamine 4
0.01 part of tetrasodium acetate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate were dissolved in 10 parts of pure water. j? I focused on the night.

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) - Production of A-20 to A-22] 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 poured into the solution, 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 iX-mer mixture was completed, 0.1 part of lauroyl peroxide was added, and the polymerization was completed at 70'C for 2 hours.

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

[Production of component (A) - Production of A-23] 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.
Add 0.005 part of iron heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate dihydrate 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 a 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').

[Production of component (B) - excluding B-15 and B-27] 120 parts of pure water, 2 parts of sodium dodecylbenzenesulfonate
Place the sample in an autoclave and heat to 65°C while stirring.
heated to. Here, ferrous sulfate heptahydrate o, oos part, ethylenediaminetetraacetic acid tetrasodium dihydrate 0.0
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 of 100 parts of the i-mer 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).

[Production of component (B) - Production of B-15 and B-27] 140 parts of pure water, 2 parts of sodium dodecylbenzenesulfonate
Place the sample in an autoclave and heat to 65°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 the addition of the monomer mixture was completed, 0.1 part of diisopropylbenzene hydroperoxide was added, and the mixture was further stirred at 70° C. 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 9AGi Nonaethylene glycol diacrylate [Production of component (C) - Production of C-1 and C-2] Stainless steel autoclave Polybutadiene rubber latex (
Area average particle diameter 400 mμ, gel content 92% using toluene as a solvent) 100 parts (as solid content) and 200 parts pure water
The mixture was heated to 50° C. with stirring. Here, 0.01 part of ferrous sulfate heptahydrate, oos part, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.01 part of sodium formaldehyde sulfoxylate dihydrate.
An aqueous solution prepared by dissolving 3 parts in 10 parts of pure water was added.

Next, a monomer mixture having the composition shown in Table 5 was continuously added over 4 hours.

After addition of the monomer mixture, 0.1 part of diisopropylbenzene hydroperoxide was added and the system was heated to 70"C.
The temperature was raised to 1, and the polymerization was completed after a further 2 hours.

[Production of component (C) - Production of C-3] In a stainless steel autoclave, 150 parts of pure water, 1.2 parts of sodium dodecylbenzenesulfonate, 10 parts of acrylonitrile, 76 parts of α-methylstyrene, and 0.0 parts of potassium persulfate were added. 0.05 parts of L-dodecyl mercaptan and 0.4 parts of L-dodecyl mercaptan were added, and the mixture was dried at 70°C.

Simultaneously with the start of the reaction, 14 parts of acrylonitrile and 25 parts of a 0.2% aqueous solution of potassium persulfate were continuously added over 8 hours.

After the addition was completed, 0.05 part of azobisisobutyronitrile was added, and the system was heated to 85° C. and stirred for 4 hours to complete the polymerization.

[Manufacture of component (C) - Manufacture of 〇-4] In a stainless steel autoclave, 100 parts of polybutadiene rubber Latin lath (as solid content) used for the production of Cl and 200 parts of pure water were charged, and heated to 65°C while stirring. heated to. To this, 0.2 part of potassium persulfate was added, and then a monomer mixture having the composition shown in Table 5 was continuously added over 4 hours.

After the addition of the monomer mixture was completed, the mixture was further stirred at 65° C. for 2 hours to complete the polymerization.

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 [units are (cal/cc)]
””) Ha below 0) Pass T: Al.

Polybutyl acrylate; 8.8 Polyethyl acrylate; 9.4 Polymethyl methacrylate
;9.5 polyacrylonitrile ;12.5 polystyrene ;9.1 polyvinyltoluene :8.9 poly(L-butylstyrene)
7.9 (4) Weight average molecular weight Measured using Toyo Soda Kogyo Co., Ltd.'s HLC-802A gel permeation chromatography using two GMH-6 columns manufactured by the same company in series. 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
10', 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.

[Manufacture of thermoplastic resin composition]

(A) component polymer 16 parts (as solid content), (B) component polymer 16 parts (solid content), and C-1 polymer 72 parts
(as solid content) were mixed in an emulsion state. Furthermore, octadecyl-3-(3,5-di-t-butyl-4-
An emulsion of 0.46 parts of hydroxyphenyl)propionate was added.

The emulsion mixture was poured into an aqueous solution containing 5 parts of calcium chloride dihydrate dissolved in 400 parts of pure water, and stirred at 95°C for 5 minutes to precipitate a thermoplastic resin composition.

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

Acrylonitrile-styrene suspension copolymer (acrylonitrile content: 3) was added to 52 parts of the obtained thermoplastic resin composition.
0%, weight average molecular weight based on polystyrene 1.12X1
0') 48 parts, sorbitan ester of stearic acid (IJ '7mar S-300 manufactured by Riken Vitamin Co., Ltd.) 1
．． 5 parts of ethylene bis stearylamide and 1.0 part of ethylene bis stearylamide were blended and fed to VC-40 (vented single screw extruder) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

A molded article was made using the obtained pellets and the physical properties were evaluated, and the results are summarized in Table 6.

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

(1) Tensile yield point...ASTM D-638 (2
) Akishift impact strength...ASTM D-25
6 (3) Bikaft softening temperature...JIS K-6
870 (4) Chemical resistance (environmental stress resistance) ASTM D-638 Type I dumbbells were given 50 degrees of deflection, fixed in a jig, coated with ethylene glycol monoethyl ether, and left at a temperature of 23°C. The time required to reach rupture is expressed in minutes. 〉300 in the table is
Indicates that no breakage occurred after 300 minutes.

(5) Injection mold the glossy pellets using a Toshiba Machine Co., Ltd. l5-80CN-V injection molding machine to form a 5° x 85 x 3 m
1 flat plate-shaped molded product is prepared. The gate shape is a tab gate.

The gloss value of the obtained molded product was measured using a digital variable angle gloss meter model UGV-4D manufactured by Suga Test Instruments Co., Ltd. at an incident angle of 60 degrees.

(6) Layer peelability and flow mark 2 with Toshiba Machine Co., Ltd. 1s-80CN-V injection molding machine
A rectangular molded product of 0 x 80 x 3 ml is prepared. The gate was located at the center of one side with a length of 20 s*, and the gate shape was an edge gate with a length of 2 mm and a rectangular cross section of 2 mm in the length direction of the molded product and 1.5 mm in the thickness direction. The mold has four cavities.

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

In addition, fan-shaped flow marks may occur near the gate of the obtained molded product, and the degree of flow marks was compared with a standard sample and evaluated as described below in the same manner as for delamination.

A: Not recognized at all B: Slightly recognized C: Significantly recognized D: Significantly recognized Note that rank AB indicates that it is located between rank A and rank B.

(7) Spiral flow (fluidity) As an index of fluidity, the flow length of the resin when injection molded under certain conditions was measured according to the following method.

Molding machine: Kawaguchi Churchill 040S manufactured by Kawaguchi Iron Works Co., Ltd. Mold: Long axis 5. Otm, an Archimedean circle with a cross section obtained by dividing an ellipse with a minor axis of 4.61 into three equal parts along the major axis.

Molding conditions: Injection pressure 50 kg/cm'' Q cylinder temperature: 260°C or 280°C Mold temperature: 40°C Measurement method and evaluation: The distance from the gate of the molded product to the free flowing end was measured.

The larger the flow length, the more The quality is evaluated as good.

Numbers 1 to 41 are Examples, and numbers 42 to 50 are Comparative Examples.

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, delamination phenomena or flow marks become noticeable.
If the glass transition temperature of component (A) deviates from the range of the present invention, the heat resistance will be poor, and if the gel content of component (A) deviates from the range of the present invention, the gloss will be poor, both of which are not preferred. Also(
If the solubility parameter, gel content or glass transition temperature of component B) deviates from the range of the present invention, the resistance to environmental stress will be poor and this is not preferred.

Example 2 and Comparative Example 2 A-1 emulsion, B-3 emulsion and c produced in Example 1
-i emulsions were mixed in the emulsion state at the proportions shown in Table 7 (the parts in the table represent the parts as solid content). Further, an emulsion of 0.5 part of octadecyl-3-(3,5-di-L-butyl-4-hydroxyphenyl)propionate was added thereto.

The emulsion mixture was poured into an aqueous solution of 5 parts of calcium chloride dihydrate dissolved in 400 parts of pure water, and stirred at 95°C for 5 minutes to precipitate a thermoplastic resin composition.

The obtained slurry was filtered, washed with water, and dried in an atmosphere of 70°C to obtain thermoplastic resin compositions D-1 to D-7.

The obtained thermoplastic resin composition and an acrylonitrile-styrene suspension copolymer (AS resin) (acrylonitrile content 30%, weight average molecular weight based on polystyrene 1.1)
2X105) in the ratio shown in Table 8, and further added 1.5 parts of sorbitan stearic acid (Rikemar S-300 manufactured by Riken Vitamin Co., Ltd.) and 1.0 part of ethylene bis stearylamide. The pellets were supplied to VC-40 (vented axle extruder) 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 summarized in Table 8.

In Table 7 and Table 8, D-1 and D-2 are Examples, D-3 to D-
7 is a thermoplastic resin composition of a comparative example.

As is clear from the comparative examples, when the amount of the component A polymer added exceeds the lower limit of the range of the present invention, delamination or flow marks are noticeable, and when it exceeds the upper limit, fluidity decreases. Furthermore, if the amount of the component B polymer added exceeds the lower limit of the range of the present invention, the environmental stress cracking resistance will be poor, and if it exceeds the upper limit, the rigidity or heat resistance will be poor.

Example 3 and Comparative Example 3 A-1 emulsion, B-3 emulsion, and C- manufactured in Example 1
Emulsion 2 and Emulsion C-3 were mixed together in the form of an emulsion in the proportions shown in Table 9 (the numbers in the table represent the number of parts as solid content). In addition, octadecyl-3-(3,5
An emulsion of 0.5 part of -di-t-butyl-4-hydroxyphenyl)propionate was added.

The emulsion mixture was poured into an aqueous solution containing 5 parts of calcium chloride dihydrate dissolved in 400 parts of pure water, and stirred at 105°C for 5 minutes to precipitate a thermoplastic resin composition.

The obtained slurry was filtered, washed with water, dried in an atmosphere of 70°C, and then supplied to an extruder to obtain pellets.

A molded article was made using the obtained pellets and the physical properties were evaluated, and the results are summarized in Table 9.

Experiments Nos. 59 to 61 are comparative examples, and it can be seen that if the A-component polymer is not added, the laminar peelability and flow marks are poor, and if the 18-component polymer is not added, the environmental stress cracking resistance is poor.

Comparative Example 4 16 parts of the A-1 emulsion, 16 parts of the B-3 emulsion, and 72 parts of the C-4 emulsion produced in Example 1 were mixed in an emulsion state (all parts are based on solid content). ), to which was further added an emulsion of 0.46 parts of octadecyl-3-(3°5-',;-t-7'thyl-4-hydroxyphenyl)propionate.

The emulsion mixture was poured into an aqueous solution of 5 parts of calcium chloride dihydrate dissolved in 400 parts of pure water and stirred at 95°C for 5 minutes to precipitate a thermoplastic resin composition.

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

Acrylonitrile-styrene Qi copolymer (acrylonitrile content: 3) was added to 52 parts of the obtained thermoplastic resin composition.
0%, weight average molecular weight based on polystyrene 1.12XI
O5), 1.5 parts of sorbitan ester of stearic acid (Rikemar S-300, manufactured by Riken Vitamin Co., Ltd.), and 1.0 part of ethylene bisstearylamide, and VC-40 (vented) manufactured by Chuo Kikai Seisakusho Co., Ltd. Pellets were obtained by (A feeding) in uniaxial extrusion m).

A molded article was made using the obtained pellet and the physical properties were evaluated. As a result, the tensile yield point was 410 kg/cm2, the Izod impact strength was 41 kgcm/cm, and the chemical resistance was 300 minutes.
Gloss 73%, layered peelability B2 flow mark A, Vicat softening temperature 92°C, spiral flow (260°C) 25
cm, and the fluidity was poor.

- (Effects of the Invention) As explained above, the thermoplastic resin composition produced according to the method of the present invention has excellent environmental stress resistance and moldability, and the resulting formed product does not exhibit layer peeling phenomenon or flow marks. This has the remarkable effect of not causing this.

Patent Applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendment Written on June 20, 1986 by Mr. Michibe Uga, Commissioner of the Patent Office ■, Case Description 1986 Patent Application No. 120146 2, Name of Invention Thermoplastic Resin Composition Method of manufacturing a product 3, Relationship with the case of the person making the amendment Address of the patent applicant ■100 Column 5 of the detailed description of the invention in the specification, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo, Contents of the amendment (1) Specification "Glycidyl acrylate" in the first line of page 8 of the book has been corrected to "glycidyl acrylate."

(2) In Table 3 on page 40 of the specification, the number "0" for acrylonitrile (parts) for sample N11B-22 is corrected to "6".

(3) “Akishift impact strength” on page 40, line 9 of the specification
is corrected to "eye shift impact strength".

(4) Mei 111, No. 48i (7) Table 6 (1) Naka, Sei” JNn 12 (D 7.

- Correct mark evaluation rAJ to rBJ.

(5) Table 6 on page 48 of the specification (1), Experiment IV&l
13 flow mark evaluation rBJ is corrected to rAJ.

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 9.0 to 11.0 (cal/cc
)^1^/^2, and the weight average molecular weight based on polystyrene is 2 x 10^5 or more.
(B) a homopolymer or copolymer of acrylic ester monomers, or acrylic ester monomers and other copolymerizable monomers; It is a copolymer whose glass transition temperature is 2.
The temperature is 0°C or less, the gel content is 70% or less, and the solubility parameter is 8.4 to 9.8 (cal/cc).
Emulsion of polymer with ^1^/^2 0.2 to 30% by weight
(as the solid content of the polymer) and (C) the content of the rubber component is 2 to 70% by weight, and the monomers constituting the resin component are styrene monomers of 40 to 90% by weight, and nitrile monomers of 40 to 90% by weight. body 5
~50% by weight, and 0-40% by weight of other copolymerizable monomers
An emulsion of a rubber-containing styrenic resin consisting of 60 to 99.6% by weight (as solid content of the polymer) of which the weight average molecular weight of the resin component is less than 2 x 10^5 based on polystyrene. 1. A method for producing a thermoplastic resin composition, which comprises separating the polymers after mixing in a state.