JPH0354984B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) 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 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 include () content of rubber components;
() Molecular weight of the resin component, () Composition of the resin component are known, and () increasing the content of the rubber component, () increasing the molecular weight of the resin component, respectively.
() Increase the absolute value of the difference between the solubility parameter of the resin component and the solubility parameter of the drug;
Alternatively, methods such as introducing bulky substituents into the polymer chains constituting the resin component to increase the dissolution viscosity of the resin component are known, but none of these methods have a practical effect on improving environmental stress cracking resistance. It was not good enough. By the way, the present inventors have reported that the environmental stress cracking resistance of the rubber-containing styrenic resin is dramatically improved by mixing an acrylic ester polymer with the rubber-containing styrenic resin. (Japanese Unexamined Patent Publication No. 179257/1983). 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 thought to be caused by the acrylic acid ester polymer particles dispersed in the rubber-containing styrene resin being flattened and deformed by shear stress during injection molding.
When a rubber-containing styrenic resin having a high melt viscosity is used, the occurrence of the above defective phenomenon is particularly remarkable. 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. ,
Moreover, although it is possible to produce a composition that provides a molded product with suppressed surface defects, the effect is unsatisfactory in practical terms. An object of the present invention is to provide a thermoplastic resin composition that improves the drawbacks of the prior art described above. (Means for Solving the Problems) To summarize the present invention, the present invention relates to a method for producing a thermoplastic resin composition, and includes: (A) a polymer of vinyl monomers and a glass thereof; The transition temperature is above 20℃, the gel content is below 10%, and the solubility parameter is 9.0-11.0 (cal/
cc) ^0.2 to 30% by weight (as solid content of the polymer) of an emulsion of a polymer [component polymer (A)] having a weight average molecular weight of 1/2 and a weight average molecular weight of 2 x 10 ⁵ or more based on polystyrene. (B) A homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers, whose glass transition temperature is 20°C or lower. An emulsion of 0.2 to 30% by weight of a polymer [component polymer (B)] with a gel content of 70% or less and a solubility parameter of 8.4 to 9.8 (cal/cc) ^1/2 (C) The content of the rubber component is 2 to 70% by weight, and the monomer constituting the resin component is 40% of the styrene monomer.
~90% by weight, 5 to 50% by weight of nitrile monomers, and 0 to 40% by weight of other copolymerizable monomers,
and 60 to 99.6% by weight of an emulsion of a rubber-containing styrenic resin [component polymer (C)] in which the weight average molecular weight of the resin component is less than 2 x 10 ⁵ based on polystyrene standards.
(as a solid content of the polymer) are mixed in an emulsion state, and then the polymer is separated. 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 aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, cyanostyrene, and chlorostyrene; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate,
Hexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, octadecyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate,
Acrylic acid ester monomers such as glycidyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate,
Methacrylic acid ester monomers such as decyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, methoxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate, amide monomers such as acrylamide and methacrylamide, acrylic acid, methacrylic acid, itaconic acid, etc. unsaturated carboxylic acid monomers, vinyl halide monomers such as vinyl chloride and vinylidene chloride, fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate, and vinyl octadecanoate;
Olefin monomers such as ethylene, propylene, 1-butene, isobutylene, 2-butene, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-
Maleimide monomers such as toluylmaleimide,
Acid anhydride monomers such as maleic anhydride, conjugated diene monomers such as butadiene, isoprene, chloroprene, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, decyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, cresyl vinyl ether , vinyl ether monomers such as glycidyl vinyl ether, vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone, and vinyl pyridine, but are not limited thereto. The vinyl monomer constituting the component polymer (A) of the present invention may be a polyfunctional vinyl monomer, and examples of the polyfunctional vinyl monomer include divinylbenzene, ethylene glycol di (meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 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, tetradecaethylene glycol di(meth)acrylate
Acrylate, eicosaethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, pentapropylene glycol di(meth)acrylate, nonapropylene glycol di(meth)acrylate, tetradecapropylene glycol di(meth)acrylate,
Examples include eicosapropylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate. Here, for example, ethylene glycol di(meth)acrylate means ethylene glycol diacrylate or ethylene glycol dimethacrylate. The component (A) polymer of the present invention has a glass transition temperature of 20
It is necessary to exceed ℃. A more preferable glass transition temperature is 30°C or higher. When the glass transition temperature of the component polymer (A) is 20°C or less, the thermoplastic resin composition obtained by mixing the component polymer (A) with the component polymer (B) and the component polymer (C) This is not preferred because heat resistance decreases. The (A) component polymer of the present invention has a molecular weight of 9.0 to 11.0 (cal/cc) ^1
/
It is necessary to have a solubility parameter in the range of ² , and the more preferable range is 9.5 to 10.5.
(cal/cc) ^1/2 . In a thermoplastic resin composition formed by mixing component (A) polymer with a solubility parameter outside the range of the present invention with component polymer (B) and component polymer (C), molded products may exhibit 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, 1975, published by J.Brandrup.
and EHImmergut (Eds.), Polymer Handbook No. 2
Using the solubility parameter values described on pages 337 to 359 of the edition, the solubility parameter δ _T of the copolymer is
It is calculated by the following formula [] from the solubility parameter δ _o of the homopolymer of the individual vinyl monomers constituting the copolymer consisting of m types of vinyl monomers and its weight fraction W _o . be. δ _T = _n 〓 ⁿ⁼¹ δ _o W _o ／ _n 〓 ⁿ⁼¹ W _o [(cal/cc) ^1/2 ] ...[] For example, the solubility parameters of butyl polyacrylate and ethyl polyacrylate are respectively 8.8
(cal/cc) ^1/2 , 9.4 (cal/cc) ^1/2 , butyl polyacrylate 70%, ethyl polyacrylate 30%
The solubility parameter of the copolymer consisting of wt% is
Calculated as 9.0 (cal/cc) ^1/2 . 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. Weight average molecular weight is 2 based on polystyrene
In a thermoplastic resin composition formed by mixing component (A) polymer with a molecular weight of less ^than This is not desirable as a defective phenomenon appears. 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 in the present invention is calculated by accurately weighing approximately 1.0 g of component (A) polymer (S ₀ g
Component (A) was placed in a basket made of 400 mesh stainless steel wire mesh, immersed in 100 g of methyl ethyl ketone, left at 5°C for 24 hours, pulled out of the basket, and air-dried at room temperature. The value is calculated by measuring the weight S ₁ g of the polymer insoluble material and then calculating it according to the following formula []. (S ₁ /S ₀ ) x 100 (%) ...[] Heat generated by mixing component (A) polymer with gel content exceeding 10% with component polymer (B) and component polymer (C) The plastic resin composition is not preferred because the molded product has poor gloss. There are no particular restrictions 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 can be applied. However, production by emulsion polymerization is industrially preferable. most advantageous. One reason is that in the present invention, it is in an emulsion state.
This is because the (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 can be manufactured. In producing the component (A) 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 component (A) 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, it is possible to create component (A) polymers that have a branched structure and a low gel content by using a chain transfer agent in combination. can. There are no particular restrictions on the chain transfer agents that can be used, such as octyl mercaptan, decyl mercaptan, dodecyl mercaptan, thioglycolic acid,
Ethyl thioglycolate, butyl thioglycolate, ethyl o-mercaptobenzoate, 1-naphthyl disulfide, sulfur compounds such as sulfur, halogen compounds such as carbon tetrabromide, hydrocarbons such as limonene and terpinolene, trinitrophenol , 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 component (A) polymer of the present invention. It is. Further, specific examples of copolymerizable monomers constituting component polymer (B) include acrylic acid among the monomers listed above as examples of vinyl monomers constituting component polymer (A). This is the same as the specific example except for the ester monomer. In addition, a polyfunctional vinyl monomer or a chain transfer agent may be used in the polymerization of component (B) of the present invention, and specific examples of the polyfunctional vinyl monomer and chain transfer agent are as follows. This is the same as the specific example listed above for component polymer (A). The component (B) polymer of the present invention has a glass transition temperature of 20
It is necessary that the temperature is below ℃. A more preferable glass transition temperature is 10°C or lower. glass transition temperature
When the temperature of (B) component polymer exceeds 20℃, (A) component polymer and (C) component polymer
Thermoplastic resin compositions formed by polymerization with component polymers have poor environmental stress cracking resistance and are not preferred. The component (B) polymer of the present invention needs to have a gel content of 70% or less. The method for measuring the gel content is the same as that for the component polymer (A), except that 100 g of toluene is used instead of 100 g of methyl ethyl ketone as the solvent, and is calculated according to the above-mentioned formula. A thermoplastic resin composition prepared by mixing component (B) polymer with a gel content of more than 70% with component polymer (A) and component polymer (C) has poor environmental stress cracking resistance. Undesirable. The (B) component polymer of the present invention has a molecular weight of 8.4 to 9.8 (cal/cc) ^1/
2
It is necessary to have a solubility parameter in the range of . A more preferable numerical range is 8.6 to 9.6.
(cal/cc) ^1/2 . The method for determining the solubility parameter is the same as that for the component polymer (A), and is calculated according to the above-mentioned formula []. (B) Solubility parameter of component polymer is less than 8.4 (cal/cc) ^1/2 or 9.8
(cal/cc) If it exceeds ^1/2 , 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. is poor 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 can be applied, but production by emulsion polymerization is industrially most advantageous. It is. When producing component (B) polymer, 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, which is the component polymer (C) of the present invention, include conjugated diene monomers such as butadiene, isoprene, dimethylbutadiene, chloroprene, and cyclopentadiene; -norbornadiene, 1,4-
Non-conjugated diene monomers such as cyclohexadiene and 4-ethylidenenorbornene, styrene monomers such as styrene, α-methylstyrene, and vinyltoluene, nitrile monomers such as acrylonitrile and methacrylonitrile, methyl methacrylate,
(meth)acrylic acid ester monomers such as ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, ethylene,
There are olefin monomers such as propylene, 1-butene, isobutylene, and 2-butene, and homopolymerization or copolymerization of these monomers is used. Additionally, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can also be used as a crosslinking monomer, but the polyfunctional vinyl monomers that can be used include divinylbenzene, ethylene glycol dimethacrylate, 1,
3-butylene glycol dimethacrylate, 1,
Examples include 4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate, 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. The method of polymerizing the monomer is not particularly limited, and known techniques such as emulsion polymerization and solution polymerization can be used. Further, 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-
These include maleimide monomers such as cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide, and N-xylylmaleimide.
It is used alone or as a copolymer, but it is essential to contain a styrene monomer and a nitrile monomer. The (C) component polymer used in the present invention is composed of a rubber component and a resin component as described above, and at the interface between the rubber component having a spherical structure and the resin component which is a continuous phase,
It is necessary that a graft structure 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 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, a rubber-containing styrenic resin emulsion obtained by graft polymerizing acrylonitrile, styrene, and methyl methacrylate in the presence of polybutadiene is mixed with a resin component emulsion obtained by copolymerizing acrylonitrile, styrene, and α-methylstyrene. (C) It can be a component polymer. Specific examples of the component (C) polymer of the present invention are as follows:
ABS (acrylonitrile-butadiene-styrene) resin, heat-resistant ABS (acrylonitrile-butadiene-styrene-α-ethylstyrene) 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 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) consists of 40 to 90% by weight of a styrene monomer, 5 to 50% by weight of a nitrile monomer, and 0 to 40% by weight of other copolymerizable monomers. There is a need. If the styrene monomer content is less than 40% by weight, fluidity will be low, and if it exceeds 90% by weight, impact resistance or rigidity will decrease. If the nitrile monomer content is less than 5% by weight, the impact resistance and rigidity will be low, and if it exceeds 50% by weight, the fluidity will be reduced. In addition, the weight average molecular weight of the resin component of the component polymer (C) must be less than 2×10 ⁵ based on polystyrene ^;
If it is more than that, the obtained thermoplastic resin composition has low fluidity, which is not preferable. 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, and a method in which a fine powder obtained by crushing a polymer is mixed and stirred with an emulsifier and water to form an emulsion. There are methods such as pulverizing the polymer in the presence of an emulsifier and water to obtain an emulsion, but the method is not limited to this method. There is no particular restriction on the particle size of the polymer in the emulsion of the (A) component polymer, (B) component polymer, or (C) 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 according to the following formula [] by taking an electron micrograph of the emulsion and setting f _i to be the fraction of the particle diameter where the particle diameter is d _i . Σf _i d _i ³ /Σf _i d _i ² ...[] In particular, when the area average particle diameter of the component polymer (B) exceeds 5μ, the component polymer (B) is mixed with the component polymer (A) and the component polymer (C). ) Layer peeling phenomenon or flow marks may occur in molded products of thermoplastic resin compositions mixed with the component polymer. 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, and (C)
The method of mixing with the component polymer emulsion is not particularly limited, and may be a fixed container type mixing device, a rotating container type mixing device,
Mixing can be carried out using equipment such as pipeline mixers, static mixers, etc. (A) Component polymer emulsion, (B) component polymer emulsion, and (C)
There are no particular restrictions on the method for separating the thermoplastic resin composition from the mixed emulsion with the component polymer emulsion. , adding precipitating agents such as electrolytes such as sodium sulfate and magnesium sulfate, polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymers, and water-soluble polymers such as carboxymethyl cellulose, and emulsification by freezing the emulsified liquid. Examples include a method of destroying the emulsion, and a method of spraying an emulsion into a high-temperature gas. (A) Component polymer emulsion, (B) component polymer emulsion, and (C)
The thermoplastic resin composition separated from the mixed liquid with the component polymer emulsion can be further supplied to a melt-kneading device for melt-kneading. Examples of melt-kneading equipment that can be used include Banbury mixer,
There are intensive mixers, mixtruders, co-kneaders, extra routers, rolls, etc.
It is also possible to use a melt kneading device with a dehydration mechanism disclosed in Japanese Patent Publication No. 59-37021, but when using this device, the emulsion and precipitating agent are continuously supplied to the device. It is also possible to perform mixing, demulsification, dehydration, drying, and melt-kneading continuously in the same device. In the present invention, the component polymer (A) is 0.2 to 30% by weight, the component polymer (B) is 0.2 to 30% by weight, and the component polymer (C) is 60 to 30% by weight.
99.6% by weight (both as polymer solids) are mixed. If the content of the component polymer (A) is less than 0.2% by weight, the molded product is a thermoplastic resin composition made by mixing the component polymer (A), the component polymer (B), and the component polymer (C). Surface defects such as delamination and flow marks appear, and if it exceeds 30% by weight, fluidity decreases, which is undesirable. In addition, the content of (B) component polymer is 0.2
If it is less than 30% by weight, the environmental stress cracking resistance of the thermoplastic resin composition is low, and if it exceeds 30% by weight, the rigidity and heat resistance are unfavorable. 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 can be used by mixing with a separately produced thermoplastic resin, if necessary. for example
It is known that rubber-containing styrenic resins, typified by ABS resins, can be used in combination with separately manufactured poly(acrylonitrile-styrene) resins, polyvinyl chloride resins, polycarbonate resins, etc. Therefore, even in the produced thermoplastic resin composition, these thermoplastic resins can be mixed arbitrarily. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present 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] 150 parts of pure water and 2 parts of potassium stearate were placed in an autoclave and heated to 50°C while stirring. Here, 0.005 part of ferrous sulfate heptahydrate,
Ethylenediaminetetraacetic acid tetrasodium dihydrate
An aqueous solution prepared by dissolving 0.01 part of sodium formaldehyde sulfoxylate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added. Next, 100% of the monomer mixture having the composition shown in Table 1 was added.
portions were added continuously over 4 hours. At the same time, an aqueous solution in which 0.05 part of potassium persulfate was dissolved in 25 parts of pure water was continuously added over 6 hours. After adding the monomer mixture, add 0.1 part of diisopropylbenzene hydroperoxide,
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 added thereto, and 100 parts of a monomer mixture having the composition shown in Table 1 was added continuously over a period of 4 hours. After the addition of the monomer mixture was completed, 0.1 part of lauroyl peroxide was added, and the mixture was further stirred at 70°C for 2 hours to complete the polymerization. Table 2 shows the properties of the obtained component (A). [Production of component (A) - Production of A-23] 175 parts of pure water and 2 parts of potassium stearate were placed in an autoclave and heated to 50°C while stirring. Here, 0.005 part of ferrous sulfate heptahydrate,
Ethylenediaminetetraacetic acid tetrasodium dihydrate
An aqueous solution prepared by dissolving 0.01 part of sodium formaldehyde sulfoxylate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added. Next, 100% of the monomer mixture having the composition shown in Table 1 was added.
A mixture of 0.2 parts of diisopropylbenzene hydroperoxide dissolved in 1 part of the solution was continuously added over 5 hours. After adding the monomer mixture, add 0.1 part of diisopropylbenzene hydroperoxide,
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 and 2 parts of sodium dodecylbenzenesulfonate were placed in an autoclave and heated to 65°C while stirring. Here, sulfuric acid No.
Iron heptahydrate 0.005 part, ethylenediaminetetraacetic acid 4
An aqueous solution prepared by dissolving 0.01 part of sodium dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added. Next, 100% of the monomer mixture having the composition shown in Table 3
20% of the total amount was poured into an autoclave, and 2.5 parts of a 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. Simultaneously with the start of polymerization, an aqueous solution of 0.05 parts of potassium persulfate dissolved in 20 parts of pure water was continuously added over 6 hours. 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 and 2 parts of sodium dodecylbenzenesulfonate were placed in an autoclave and heated to 65°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 3 was added continuously over a period of 4 hours. After adding the monomer mixture, add 0.1 part of diisopropylbenzene hydroperoxide,
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 component (C) - Production of C-1 and C-2] Made of stainless steel An autoclave was charged with 100 parts (as solid content) of polybutadiene rubber latex (area average particle diameter 400 mμ, gel content 92% using toluene as a solvent) and 200 parts pure water, and heated to 50°C while stirring. Here, 0.005 part of ferrous sulfate heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate dihydrate were added to 10 parts of pure water.
An aqueous solution dissolved in one portion was added. Next, a monomer mixture having the composition shown in Table 5 was continuously added over 4 hours. After adding the monomer mixture, add 0.1 part of diisopropylbenzene hydroperoxide,
The system was heated to 70°C and stirred for an additional 2 hours to complete the polymerization. [Production of component (C) - Production of C-3] In a stainless steel autoclave, add 150 parts of pure water, 1.2 parts of sodium dodecylbenzenesulfonate,
10 parts of acrylonitrile, 76 parts of α-methylstyrene
1 part, potassium persulfate 0.05 part, and t-dodecylmercaptan 0.4 part were added, and the mixture was stirred 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 addition, azobisisobutyronitrile 0.05
The system was heated to 85°C and stirred for 4 hours to complete the polymerization. [Production of component (C) - Production of C-4] Charge 100 parts of the polybutadiene rubber latex used in the production of C-1 (as solid content) and 200 parts of pure water into a stainless steel autoclave, and heat to 65°C while stirring. heated to. Here, potassium persulfate
0.2 part was added thereto, 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 910 differential scanning calorimeter and a 990 thermal analyzer, which are Dupont-type measuring instruments. It was measured. (2) Gel content The solid obtained by dropping the emulsion of component (A) or component (B) into methanol was dried. Approximately 1.0g
was precisely weighed, measured using the method described above, and calculated using the formula. However, the solvents used were different for components (A) and (B); methyl ethyl ketone was used for component (A), and toluene was used for component (B). (3) Solubility parameter The solubility parameter value [unit: (cal/cc) ^1/2 ] of each polymer used to calculate the solubility parameter in each example 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 Manufactured by Toyo Soda Kogyo Co., Ltd. Measurement was carried out using 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 apparatus is 6×10 ⁵ , and samples exceeding 6×10 ⁵ are marked as >6 in the relevant column of Table 2. The sample used was a solid obtained by precipitating the emulsion of component (A) with methanol.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[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-
An emulsion of 0.46 parts of butyl-4-hydroxyphenyl)propionate was added. The emulsion mixture was mixed with calcium chloride dihydrate 5
Pour 95 parts into an aqueous solution of 400 parts of pure water.
The thermoplastic resin composition was precipitated by stirring at ℃ for 5 minutes. The obtained slurry was filtered, washed with water, and dried in an atmosphere of 70°C to obtain a thermoplastic resin composition. 52 parts of the obtained thermoplastic resin composition, 48 parts of acrylonitrile-styrene suspension copolymer (acrylonitrile content 30%, weight average molecular weight based on polystyrene 1.12 x 10 ⁵ ), sorbitan ester of stearic acid (Riken Vitamin Co., Ltd.) Company manufactured Rikemar S-300) 1.5 parts, ethylene bisstearylamide
1.0 parts of VC- manufactured by Chuo Kikai Seisakusho Co., Ltd.
40 (single screw extruder with vent) to obtain pellets. Moldings were made using the obtained pellets and their physical properties were evaluated, and the results are summarized in Table 6. In addition, the physical property measurement values of each example were determined by the following method. (1) Tensile yield point…ASTM D-638 (2) Eye impact strength…ASTM D-256 (3) Vikatsu softening temperature…JIS K-6870 (4) Chemical resistance (environmental stress cracking resistance) ASTM D- 638 Type I dumbbells were given a 50mm deflection, fixed on a jig, coated with ethylene glycol monoethyl ether, and heated to a temperature of 23°C.
The time taken to break when left unused is expressed in minutes. In the table, >300 indicates no breakage after 300 minutes. (5) Glossy pellets IS-80CN- manufactured by Toshiba Machine Co., Ltd.
Injection molded using a V injection molding machine, 50 x 85 x 3
Create a plate-shaped molded product of mm. The gate shape is a tab gate. The incident angle of the obtained molded product was measured using a digital variable angle gloss meter model UGV-4D manufactured by Suga Test Instruments Co., Ltd.
The gloss value is measured at 60 degrees. (6) Layer peelability and flow mark A rectangular molded product of 20 x 80 x 3 mm is produced using an IS-80CN-V injection molding machine manufactured by Toshiba Machine Co., Ltd.
The gate is located at the center of one side with a length of 20 mm, and the gate shape is 2 mm in the length direction of the molded product and 1.5 mm in the thickness direction.
It is a 2 mm long edge gate with a rectangular cross section. The mold has four cavities. When the gate portion of the obtained molded product was manually folded, layer-like peeling occurred in the vicinity of 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 flow (fluidity) As an index of fluidity, the flow length of the resin when injection molded under certain conditions was measured according to the method below. Molding machine: Kawaguchi Churchill manufactured by Kawaguchi Iron Works Co., Ltd.
1040S Mold; Archimedean circle with a cross section obtained by bisecting an ellipse with a major axis of 5.0 mm and a minor axis of 4.6 mm along the major axis. Molding conditions: Injection pressure: 50 Kg/cm ² G cylinder temperature: 260°C or 280°C Mold temperature: 40°C Measurement method and evaluation: The distance from the gate to the free flowing end of the molded product was measured. The larger the flow length is, the better the fluidity is evaluated.

【table】

【table】

【table】

[Table] 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, and the glass transition temperature of component (A) falls within the range of the present invention. If the gel content of component (A) exceeds the range of the present invention, the gloss will be poor, and both are unfavorable. 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 cracking resistance will be poor, which is not preferable. Example 2 and Comparative Example 2 The A-1 emulsion, the B-3 emulsion, and the C-1 emulsion produced in Example 1 were mixed in an emulsion state at the ratio shown in Table 7 (the number of parts in the table (represents the number of parts as solid content). In addition, octadecyl-3
An emulsion of 0.5 part of -(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added. The emulsion mixture was mixed with calcium chloride dihydrate 5
Pour 95 parts into an aqueous solution of 400 parts of pure water.
The thermoplastic resin composition was precipitated by stirring at ℃ for 5 minutes. 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 1.12×10 ⁵ ) were blended in the proportions shown in Table 8. Furthermore, sorbitan ester of stearic acid (Rikemar S-300 manufactured by Riken Vitamin Co., Ltd.)
1.5 parts of ethylene bisstearylamide and 1.0 parts of ethylene bis stearylamide were blended and fed to VC-40 (single screw extruder with vent) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets. Moldings were made using the obtained pellets and their physical properties were evaluated, and the results are summarized in Table 8.

【table】

[Table] In Table 7 and Table 8, D-1 and D-2 are examples, D-
3 to D-7 are thermoplastic resin compositions of comparative examples. 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 The A-1 emulsion, B-3 emulsion, C-2 emulsion, and C-3 emulsion produced in Example 1 were all in an emulsion state at the ratios shown in Table 9. (The parts in the table represent the parts as solid content). Furthermore, octadecyl-3-(3,5-di-t-butyl-
An emulsion of 0.5 part of 4-hydroxyphenyl)propionate was added. The emulsion mixture was mixed with calcium chloride dihydrate 5
105 parts dissolved in 400 parts of pure water.
The thermoplastic resin composition was precipitated by stirring at ℃ for 5 minutes. The obtained slurry was filtered, washed with water, dried in an atmosphere of 70°C, and then fed to an extruder to obtain pellets. Moldings were made using the obtained pellets and their physical properties were evaluated, and the results are summarized in Table 9.

[Table] Experiment Nos. 59 to 61 are comparative examples, but if the A component polymer is not added, the layered peeling properties and flow marks are inferior, and if the B component polymer is not added, the environmental stress cracking resistance is inferior. I understand. Comparative Example 4 16 parts of A-1 emulsion prepared in Example 1, B-3
16 parts of the emulsion and 72 parts of the C-4 emulsion were mixed in the form of an emulsion (all parts are based on solid content). Further, an emulsion of 0.46 parts of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added thereto. The emulsion mixture was mixed with calcium chloride dihydrate 5
Pour 95 parts into an aqueous solution of 400 parts of pure water.
The thermoplastic resin composition was precipitated by stirring at ℃ for 5 minutes. The obtained slurry was filtered, washed with water, and dried in an atmosphere of 70°C to obtain a thermoplastic resin composition. 52 parts of the obtained thermoplastic resin composition, 48 parts of acrylonitrile-styrene suspension copolymer (acrylonitrile content 30%, weight average molecular weight based on polystyrene 1.12 x 10 ⁵ ), sorbitan ester of stearic acid (Riken Vitamin Co., Ltd.) Company manufactured Rikemar S-300) 1.5 parts, ethylene bisstearylamide
1.0 parts of VC- manufactured by Chuo Kikai Seisakusho Co., Ltd.
40 (single screw extruder with vent) to obtain pellets. A molded article was made using the obtained pellets and the physical properties were evaluated. As a result, the tensile yield point was 410 Kg/cm ² , the Izot impact strength was 41 Kgcm/cm, and the chemical resistance was >300 minutes.
Gloss 73%, layered peelability B, flow mark A, Vikatsu softening temperature 92℃, spiral flow (260℃)
It was 25 cm and had poor fluidity. (Effects of the Invention) As explained above, the thermoplastic resin composition produced according to the method of the present invention has excellent environmental stress cracking resistance, and the resulting formed product exhibits delamination and flow marks. This has the remarkable effect of preventing the occurrence of.

Claims (1)

[Scope of Claims] 1 (A) A polymer of vinyl monomers, whose glass transition temperature exceeds 20°C and whose gel content is 10%.
or less, and the solubility parameter is 9.0 to 11.0
(cal/cc) ^1/2 and a weight average molecular weight of 2×10 ⁵ or more based on polystyrene 0.2 to 30% by weight (as solid content of the polymer)
and (B) a homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers, whose glass transition temperature is 20°C An emulsion of a polymer having the following properties, a gel content of 70% or less, and a solubility parameter of 8.4 to 9.8 (cal/cc) ^1/2
(C) The content of the rubber component is 2 to 70% by weight (as solid content of the polymer), and the monomer constituting the resin component is 40% by weight of styrene monomer.
~90% by weight, 5 to 50% by weight of nitrile monomers, and 0 to 40% by weight of other copolymerizable monomers,
and 60 to 99.6% by weight (as solid content of the polymer) of a rubber-containing styrenic resin emulsion in which the weight average molecular weight of the resin component is less than 2 × 10 ⁵ based on polystyrene standards is mixed in an emulsion state, A method for producing a thermoplastic resin composition, which comprises separating a polymer.