JPS62158747A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To produce a thermoplastic resin compsn. having excellent environmental stress cracking resistance and giving moldings having improved surface profile by blending a specified polymer compsn. with a rubber-contg. styrene resin, CONSTITUTION:20-90% (by weight, the 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 9.0-11.0(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 a polymer which is a (co)polymer of an acrylic ester monomer and has a glass transition temp. of 20 deg.C or above, a gel content of 70% or below and a solubility parameter of 8.4-9.8(ccal/cc)<1/2> in the form of an emulsion. 0.5-50% polymer compsn. obtd. by separating the polymers from the emulsion mixture is mixed with 50-99.5% rubber-contg. styrene resin which has a rubber content of 2-50% and whose resin component is composed of 40-90% styrene monomer, 5-50% nitrile monomer and 0-40% other monomer.

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 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 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) 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 increasing the polymer chain constituting the resin component. Although there are known methods of increasing the melt viscosity of the resin component by introducing a bulky substituent into the resin, the effect of improving the 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).
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 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 caused serious damage to 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 stress during injection molding, and the appearance 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, 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 (ca Il / cc) "",
and an emulsion of a polymer [component polymer (A)] having a weight average molecular weight of 2×10 5 or more based on polystyrene 20 to 9
(B) Homopolymer or copolymer of acrylic ester monomer, or copolymer of acrylic ester monomer and other copolymerizable monomers. coalescence, and its 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 j!
/cc) 1/2 of the emulsion of the polymer [(B) component polymer] is mixed in an emulsion state with 10 to 80% by weight (as the solid content of the polymer), and then the polymer is separated. The resulting polymer composition C00 has a content of 5 to 50% by weight and a rubber component of 2 to 50% by weight, and the monomers constituting the resin component are 40 to 90% by weight of styrene monomers and nitrile monomers. It is characterized by mixing 50 to 99.5 weight % of a rubber-containing styrenic resin consisting of 5 to 50 weight % of monomers and 0 to 40 weight % of other copolymerizable monomers.

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 the vinyl monomers constituting the component polymer (A) of the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, t-7'tylstyrene, cyanostyrene, and chlorostyrene. , vinyl cyanide monomers such as acrylonitrile and methacrylate trile,
Acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, octadecyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, phenyl acrylate, methyl methacrylate, ethyl Methacrylic acid ester monomers such as methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, methoxyethyl acrylate, glycidyl methacrylate, and phenyl methacrylate; amides such as acrylamide and methacrylamide; monomers, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl chloride, vinyl halide monomers such as vinylidene chloride, vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate, Fatty acid vinyl ester monomers such as vinyl octadecanoate, olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
Maleimide monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-tolylmaleimide, acid anhydride monomers such as maleic anhydride, butadiene,
Conjugated diene 111 bodies such as isoprene and chloroprene, 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, methyl vinyl ketone, phenyl vinyl Examples include, but are not limited to, vinyl ketone monomers such as ketones, 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 gelicold di(meth)acrylate, l,4-butylene gelicold di(meth)acrylate, propylene glycol di(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, tri- Methylolpropane 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,
meth)acrylate, nonaethylene glycol di(meth)acrylate, tetradecaethylene glycol di(meth)acrylate, eicosaethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate
Acrylate, pentapropylene glycol di(meth)
Acrylate, nonapropylene glycol di(meth)acrylate, tetradepropylene glycol di(meth)acrylate, eicosabrobylene glycol di(meth)acrylate, 1,6-hexyldiol di(meth)acrylate, and the like. 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 as a powder or beret/), which is industrially disadvantageous. It is not preferable because it greatly reduces the performance.

The component (A) polymer of the present invention is 9.0 to 11.0 (ca.
A polymer composition C comprising a component polymer (A) having a solubility parameter in the range of 1/cc) which deviates from the scope of the present invention with a component polymer (B), and a rubber-containing styrene. Thermoplastic resin compositions obtained by mixing with thermoplastic resins are undesirable because surface defects such as delamination and flow marks appear in molded products.

In addition, the solubility parameter referred to in this specification refers to the solubility parameter as described by Brandrup (J) and Immergut (E, H, Immergut), published by John Wiley & Sons, New York City, 1975.
JA, Polymer Handbook (Polymer l1a
Using the solubility parameter values described in ndbook) 2nd edition IV-337 to ■359, the solubility parameter δ7 of the copolymer is determined by the individual vinyl monomers constituting the copolymer consisting of m types of vinyl monomers. It is calculated by the following formula (2) from the solubility parameter δ1 of the homopolymer of the body and its weight fraction W.

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are each 8.8 (cal
/cc) ””, 9.4 (ca 1 /cc)”
'', the solubility parameter of a copolymer consisting of 70% by weight of butyl polyacrylate and 30% by weight of ethyl polyacrylate is calculated as 9.0 (ca 1 /cc).

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. Heat obtained by mixing a rubber-containing styrenic resin with a polymer composition C obtained by mixing a component polymer (A) with a polymer component (B) having a weight average molecular weight of less than 2X10' based on polystyrene standards. Plastic 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 of the gel permeation chromatogram and the molecular weight. Next, measure the gel permeation chromatogram of the component polymer (A), determine the molecular weight from the outflow volume using the calibration curve, and calculate the weight average molecular weight 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 then placed in 100 g of methyl ethyl ketone. After leaving it at 5℃ for 24 hours, the basket was pulled up and air-dried at room temperature.
, and then calculated according to the following formula (■).

(S + /5o) A thermoplastic resin composition obtained by mixing it with a styrene resin 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
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 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 is used in combination to create a branched structure and a low gel content (A
) component polymers can be prepared.

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 0-mercaptobenzoate, 1-naphthyl disulfide, sulfur). Sulfur compounds such as, halogen compounds such as carbon tetrabromide, limonene,
Hydrocarbons such as terpinolene, trinitrophenol,
These include trinitrobenzene, which nitro compounds, and benzoquinone.

Next, the (B) component polymer of the present invention is a homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers. However, here, specific examples of acrylic ester monomers include the specific examples of acrylic ester monomers listed above as examples of vinyl monomers constituting the component (A) polymer of the present invention. The same is true. Further, specific examples of the copolymerizable monomers constituting the component polymer (B) include the monomers listed above as examples of the vinyl monomers constituting the component polymer (A).
This is the same as the specific example except for the acrylic acid 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:
The polymerization of component (A) is the same as in the above-mentioned specific example.

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 polymer (B) with a glass transition temperature exceeding 20° C. with a component polymer (A) and a rubber-containing styrenic 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
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 rubber-containing styrenic 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 to have a solubility parameter in the range of 1/cc). A more preferable numerical range is 8.
6 to 9.6 (cal/cc) ""-. 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 (2).

(B) Solubility parameter of component polymer is 8.4Cca
17cc)"" or less than 9.8 (cal/
cc) If it exceeds ``'', the (B) component polymer is converted into (A)
The thermoplastic resin composition obtained by mixing the polymer composition C mixed with the component polymer into a rubber-containing styrenic 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, (A) component polymer 20 to 90% by weight 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 rubber-containing styrenic resin with a rubber-containing styrene-based resin has poor environmental stress cracking resistance. Surface defects such as flow 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.

When the component polymer (A) or the component polymer (B) is produced by emulsion polymerization, the emulsion polymerization solution obtained by emulsion polymerization can be used as it is, but if it is produced by another polymerization method, In some cases, a step of emulsifying the obtained polymer is necessary.

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 size of the polymer in the emulsion of (A> component polymer or (B) component polymer), but it is preferable that the area average particle size is 5 μm or less.

Here, the area average particle diameter is calculated by taking an electronic w4@mirror photograph of the emulsion and setting fi to the fraction of the particle diameter where the particle diameter is d, according to the following formula (2).

Σfid13/Σf, d-... (1) In particular, if the area average particle diameter of the (B) component polymer exceeds 5μ, the (B)
Occurrence of layer peeling phenomenon or flow marks in a molded product of a thermoplastic resin composition obtained by mixing a polymer composition C formed by mixing a component polymer with a component polymer (A) into a rubber-containing styrenic resin. There are things to do.

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). , electrolytes such as sodium chloride, calcium chloride, aluminum chloride, sodium sulfate, and magnesium sulfate, and precipitating agents such as aqueous polymers such as polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymers, and carboxymethyl cellulose. Examples include a method of freezing the emulsion to break the emulsion, and a method of spraying the emulsion into a high-temperature gas.

The polymer composition C separated from the mixture of the component polymer emulsion (A) and the component polymer emulsion (B) 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 mixer, mixtruder, coneater, extruder, roll, 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.

Monomers constituting the rubber component of the rubber-containing styrenic resin in the present invention include conjugated diene monomers such as butadiene, isoprene, dimethylbutadiene, chloroprene, and cyclopentadiene, 2.5-norbornadiene, 1
．． Non-conjugated dienes such as 4-cyclohexadiene and 4-ethylidene norbornene, QL mer, styrene '1hjJ such as styrene, α-methylstyrene, and vinyltoluene.
Nitrile monomers such as Hfl, acrylonitrile, methacyclonitrile, methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate,
Examples include (meth)acrylic acid ester monomers such as octyl acrylate, olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene, and homopolymerization or copolymerization of these monomers is used.

Further, as a crosslinking monomer, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can also be used, and 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,
Examples include triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.

The rubber component used in the rubber-containing styrenic resin of the present invention is:
It is necessary to have a graft active site, and specifically, it is preferable to have a carbon-carbon double bond in the rubber molecule.

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 rubber-containing styrenic resin 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 rubber-containing styrenic resin in the present invention include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, acrylonitrile, metacyclonitrile, etc. Nitrile monomers, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, maleimide, N-methylmaleimide, N
-Ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N
-) There are maleimide monomers such as ruylmaleimide and N-xylylmaleimide, which are used alone or in copolymerization, but they must contain styrene monomers and nitrile monomers.

The rubber-containing styrenic resin used in the present invention is composed of a rubber component and a resin component as described above, and a graft structure is present at the interface between the rubber component that has a spherical structure and the resin component that is a continuous phase. It is necessary. 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 resin can also be produced by known graft polymerization techniques.

For example, in order to adjust the content of the rubber component contained in the rubber-containing styrenic resin, it is possible to mix a separately polymerized resin component with the rubber-containing styrenic resin; does not need to have the same composition as the resin component obtained by graft polymerization. For example, a resin component obtained by copolymerizing acrylonitrile, styrene, and α-methylstyrene can be mixed with a rubber-containing styrenic resin obtained by graft polymerizing acrylonitrile, styrene, and methyl methacrylate in the presence of polybutadiene.

Specific examples of the rubber-containing styrenic resin of the present invention are A
BS (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, MBAS (methyl methacrylate-butadiene-
Acrylonitrile-styrene) resin, etc.

The content of the rubber component contained in the rubber-containing styrenic resin of the present invention needs to be 2 to 50% by weight, preferably 5 to 40% 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 with polymer composition C will be low, and if it exceeds 50% by weight, the rigidity or heat resistance will be reduced.

Furthermore, the resin component of the rubber-containing styrenic resin of the present invention is
Styrenic monomer 40-90% by weight, nitrile monomer 5
-50% by weight, and 0-40% by weight of other copolymer monomers
It must consist of 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. Also, 5% by weight of nitrile monomer
If it is less than 50%, the impact resistance and rigidity will be low, and if it exceeds 50%, the fluidity will be decreased.

In the present invention, a thermoplastic resin composition is produced by mixing ~50% by weight of a polymer composition CO,S and 50~99.5% by weight of a rubber-containing styrenic resin. More preferably, 02 to 40% by weight of the polymer composition and 60 to 79% by weight of the rubber-containing styrenic resin are mixed. If the amount of polymer composition C added is less than 0.5% by weight, the resulting thermoplastic resin composition will have poor environmental stress resistance, and if it exceeds 50% by weight, the stiffness, heat resistance, Alternatively, it is undesirable due to poor impact resistance.

There is no particular restriction on the method of mixing the polymer composition C and the rubber-containing styrenic 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 V-type blender, and a tumbler.

An example of a method for mixing the polymer composition C and the rubber-containing styrenic resin is melt kneading. Specific examples of melt-kneading equipment used include Banbury mixer, intensive mixer, mixtruder, coneater,
There are extruders, rolls, etc.

(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 0.005 part, ethylenediamine 4
An aqueous solution prepared by dissolving 0.01 part of tetrasodium acetate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate 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-20-Production of 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 added thereto, and 100 parts of a monomer mixture having the composition shown in Table 1 was added continuously over 4 hours.

After the addition of the monomer 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.
0.01 part of iron heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 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] 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 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).・〔(
B) Component structure - Production of B-15 and B-27] K water 14
0 parts and 2 parts of sthorium dodecylbenzenesulfonate were placed in an autoclave and heated to 70° C. with 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 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 9PG; nonapropylene glycol dimethacrylate 9AG; nonaethylene glycol dimethacrylate [Production of polymer composition C] (A) 50 parts of component emulsion (of polymer ) and (as solids)
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 blotter copolymer (ethylene oxide weight fraction in the total molecule is 80%, polypropylene glycol molecular weight 1750-Asahi Denka Kogyo Co., Ltd. Pluronic F-68) 0.7 parts of a 10% aqueous solution 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 an atmosphere of 70°C to obtain a polymer composition C. .

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

il+ 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 99G 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 it was accurately weighed, measured using the method described above, and calculated using formula (2). However, the solvents used were different between the components (A) and (B); methyl ethyl ketone was used for the component (A), and toluene was used for the component (B).

(3) Solubility parameter Solubility parameter value of each polymer used for calculation of solubility parameter on each side [unit: (ca 1 /cc)
"") is as follows.

Polybutyl acrylate; 8.8 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 G M H-
Measurement was carried out using two type 6 columns arranged in a row. 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.

Table 4 Table 4 [Production of thermoplastic resin composition] 30 parts of BS resin powder consisting of 50% polybutadiene, 13% acrylonitrile, and 37% styrene, AS resin powder consisting of 30% acrylonitrile and 70% styrene (
Weight average molecular weight based on polystyrene 1. lX10')5
4 parts, and 4.4'-isopropylidene bis [monophenyl-dialkyl (C+z-C+s) phosphite] [7, manufactured by Deca Argus Chemical Co., Ltd., mark (M
A RK') 1500] 0.2 parts were mixed with 16 parts of polymer composition C in a Henschel mixer, and the mixture was fed to VC-40 (vented single-screw extrusion a) 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 50.

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

+11 Tensile yield point...ASTM D-638
(2) Izotsu impact strength...ASTM D-25
6 (3) Vicat softening temperature...JIS K-6
870 (4) Chemical resistance (environmental stress resistance) ASTM D-638 type ■ Give the dumbbell a 50fi deflection, fix it to a jig, apply ethylene glycol monoethyl ether, and leave it at a temperature of 23°C. The time required to reach rupture is expressed in minutes. 300 in the table indicates that no breakage occurred after 300 minutes. □(5
) The glossy pellets were injection molded using a 15-80CN-V injection molding machine manufactured by Toshiba Jm Machinery Co., Ltd. to form a 50×85×3
Create a flat plate-shaped crane. 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) Layered peeling mold and flow mark Toshiba Machine Co., Ltd. c! A short-sided molded product of 20 x 80 x 3 am was made using an AlS-80CN-■ injection molding machine. The gate is located in the center of one side of length 201R11,
The gate shape is 2 mm in the length direction of the molded product and 1 mm in the thickness direction.
It is an edge gate with a length of 2 dragons and a rectangular cross section with 5 fins. The mold has four cavities.

When the gate portion of the obtained molded product was brought close to the gate, layered peeling occurred near the gate, and the degree of peeling was compared with a standard sample and evaluated as follows.

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 Giro (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 Tekko Co., Ltd. Mold: Major axis: 5.0 mm, minor axis: 4.6 mm (7) Archimedean circle having a cross section obtained by bisecting an ellipse along the major axis.

Molding conditions: Injection pressure: 5 Q kg/cm" Q cylinder temperature: 260°C or 280°C Mold temperature: 40°C Measurement method: Free flow end from the gate of the molded product
The distance was measured. The larger the flow length is, the better the fluidity is evaluated.

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

Comparative Example 42 has a polymer composition obtained by mixing and precipitating the (A) component emulsion and (I3) 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 causes operational disadvantages, for example, during the dehydration of the precipitate, the water washing process, the drying process, or the mixing process with a rubber-containing styrenic resin.

In experiments other than Comparative Example 42, the solid of polymer composition C was powder-like, and no operational problems occurred.

As is clear from the comparative examples, when the weighted 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, heat resistance or operability during manufacturing will be poor, and if the gel content of component (A) deviates from the range of the present invention, gloss will be poor, both of which are undesirable. . 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-3 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, and the resulting mixed emulsion was subjected to precipitation treatment in the same manner as in Example 1. Polymer compositions C-1 to C-8 were obtained.

Next, the ABS resin powder, AS resin powder, and Mark 1500 used in Example 1 were mixed into a polymer composition C-1-C-
8 and the following ratio to make pellets.

Mark 1500 0.2 crystal type combined composition C 16 parts The obtained pellet was evaluated for physical properties in the same manner as in Application 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 resistance will be poor, and if it exceeds the upper limit, laminar peeling or flow marks 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) and 50 parts of the B-3 emulsion (as the solid content of the polymer) produced in Example 1 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 polymer composition C was supplied to a VC-40 extruder manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

Separately, polymers D-1 to D-8 whose compositions are shown in Table 8 are mixed in the formulation shown in Table 9, and fed to a VC-40 type extruder.
Berets of rubber-containing styrenic resins E-1 to E-7 were obtained.

In addition, D-1 and D-6 are the BSs used in Example 1, respectively.
resin and AS resin.

Next, pellets of polymer composition C and pellets of rubber-containing styrenic resins E-1 to B-7 were mixed in the proportions shown in Table 10, and the mixture was fed to a VC-40 extruder and kneaded to form pellets. I got it.

The physical properties of the obtained pellet were evaluated in the same manner as in Example 1, and the results are shown in Table 10.

Incidentally, the spiral flow was measured at a cylinder temperature of 280°C for experiment number 64, 65, 77, and 78, and 260°C for the other samples.

Experiment numbers 59 to 70 in Table 1O are examples, and experiment numbers 71 to 78 are comparative examples.

Comparing Experiment Nos. 59 to 65 and Experiment Nos. 72 to 78, the composition according to the production method of the present invention has excellent environmental stress cracking resistance regardless of the type of rubber-containing styrenic resin, and also exhibits no lamellar delamination. It can be seen that no phenomena or flow marks occur.

Furthermore, by comparing Experiment Nos. 66 to 72, it was found that when the blending ratio of polymer composition C and rubber-containing styrenic resin deviates from the range of the present invention, the environmental stress cracking resistance of the obtained composition It can be seen that the impact resistance is inferior.

Example 4 and Comparative Example 4 Polymer composition C1 used in Example 3 Table 8-D-1, D
-6 and Mark 1500 were mixed in the proportions shown in Table 11 and fed to a VC-40 extruder to obtain pellets.

The physical properties of the obtained pellet were evaluated in the same manner as in Example 1, and the results are shown in Table 11.

Table 11 Experiment No. 83 is an example in which the amount of polymer composition C added deviated from the upper limit of the range of the present invention, and the thermoplastic resin composition obtained by mixing with the rubber-containing styrenic resin had poor rigidity and heat resistance. Also, the layered peelability is poor, which is not preferable.

Incidentally, Experiment No. 71 of Comparative Example 3 shown in Table 10 is also an example in which the amount of the polymer composition added deviated from the upper limit of the range of the present invention, similar to Experiment No. 83, but the obtained thermoplastic resin The composition has poor impact resistance and behaves differently than Run No. 83. The physical property difference between Experiment No. 71 and Experiment No. 83 is based on the difference in the rubber content of the rubber-containing styrenic resin used.

Comparative Example 5 80 parts of Table 8 D-1 emulsion (as solid content of polymer) and 20 parts of emulsion B-3 produced in Example 1 (as solid content of polymer) were mixed in an emulsion state, Calcium chloride 2
It was poured into an aqueous solution containing 5 parts of aqueous salt and stirred at 90 to 95°C to precipitate.

The obtained slurry was filtered, washed with water, and 40 parts of the powder obtained was added to 60 parts of Table 8D-6 powder, mark 15,000.
2 parts were mixed in a Henschel mixer and fed into a VC-40 extruder to form pellets.

Physical properties of the obtained pellet were evaluated according to Example 1, and the tensile yield point was 410 kg/cm2, Izot impact strength was 29 kgcm/cm, chemical resistance was >300 minutes, gloss was 88%, layer peelability C, flow mark D, and Vika.・7
The softening temperature was 97° C., the spiral flow (cylinder temperature 260° C.) was 36 cm, and the layering was poor in release properties and flow marks.

Comparative Example 6 30 parts of Table 8D-1 emulsion (as solid content of polymer), 62 parts of Table 8D-7 emulsion (as solid content of polymer), and 8 parts of B-3 emulsion produced in Example 1 (as the solid content of the polymer) were mixed in an emulsion state, poured into an aqueous solution of 5 parts of calcium chloride dihydrate, and stirred at 105°C to precipitate.

The obtained slurry was filtered, washed with water, and 100 parts of the obtained powder was mixed with 15,000.2 parts of Mark in a Henschel mixer, and the mixture was fed to a VC-40 extruder to form pellets.

Physical properties of the obtained pellet were evaluated according to Example 1, and the tensile yield point was 420 kg/cm2, Izot impact strength was 14 kg cm/cyn, chemical resistance was >300 minutes, gloss was 93%, layer peelability D, and flow mark D1 Vikaso softening. The temperature was 110° C., the spiral flow (cylinder temperature 280° C.) was 23 cm, and the layer peelability and flow marks were 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 moldability, and also exhibits no layer flaking phenomenon in the molded product obtained. This has the remarkable effect of not generating flow marks.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment February 14, 1986 Director General of the Patent Office Michibe Uga 1. Indication of the case 1985 Patent Application No. 1539 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 Contents of the amendment in column 5 of the detailed description of the invention in the specification (11 Specification, page io, line 14) "1,6-hexyl"
is corrected to "l,6-hexane".

(2) Correct ``1'' on the bottom line of the 12th page of the specification to ``is''.

(3) "Solution polymer" on page 22, line 3 of the specification is corrected to "soluble polymer."

(4) “Melting and kneading” on page 22, line 17 of the specification is changed to “
I corrected it to ``Bath fused mixed wire''.

(5) "1 in cyanul" on page 24, line 2 of the specification is corrected to "isocyanur."

(6) "Comonomer" on page 27, line 10 of the specification is corrected to "copolymerizable".

(7) "60-79% by weight" in the first line of page 28 of the specification is corrected to "60-98% by weight."

(8) "Layered release mold" on page 46, line 17 of the specification is corrected to "layer release property."

(9) Specification pages 49, 50, 51 and 52
In Table 5 on page 1, "Distinction between applied examples and reference examples" is corrected to "Distinction between working examples and comparative examples."

(10) "Application Example 1" in the first line of page 55 of the specification is corrected to "Example 1."

(11) "Example composition" on page 58, line 13 of the specification is corrected to "polymer composition."

(12) In Table 8 on page 60 of the specification, "methyl methacrylate" is corrected to "methyl methacrylate."

(13) In Table 11 on page 65 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 9.0 to 11.0 (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.
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).
10 to 80% by weight of a polymer emulsion with ^1^/^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 2 to 50% by weight, and the monomer constituting the resin component is 40 to 40% by weight of the styrene monomer.
90% by weight of a rubber-containing styrenic resin consisting of 5-50% by weight of a nitrile monomer and 0-40% by weight of other copolymerizable monomers. A method for producing a thermoplastic resin composition.