JPH0352783B2 - - 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 melt 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 Patent Application Laid-open 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. Although it is possible to produce a composition that gives a molded product with suppressed surface condition 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 over 20℃, the gel content is 10% or less, and the solubility parameter is 9.0 to 11.0 (cal/
cc) 20 to 90% by weight (as solid content of the polymer) of an emulsion of a polymer [component polymer (A)] whose weight average molecular weight is ^1/2 and whose weight average molecular weight is 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. A 10 to 80% by weight emulsion 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 A polymer composition C obtained by separating the polymers after mixing them in an emulsion state (as the solid content of the combined solids) and a rubber component content of 2 to 50% by weight. , a rubber-containing styrene in which the monomers constituting the resin component are 40 to 90% by weight of styrene monomers, 5 to 50% by weight of nitrile monomers, and 0 to 40% by weight of other copolymerizable monomers. It is characterized by being mixed with 50 to 99.5% by weight of a system resin. The thermoplastic resin composition produced according to the method of the present invention has excellent environmental stress cracking resistance, and is less likely to cause defective molded products such as delamination and flow marks. Examples of vinyl monomers constituting the 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 allyrylate, 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, aliphatic 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 polymer composition C formed by mixing the component polymer (A) and the component polymer (B)
Since it is difficult to handle it as a powder or pellet, it is industrially disadvantageous, and it is also undesirable because it is mixed with a rubber-containing styrenic resin, greatly reducing its heat resistance. 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 . A thermoplastic resin obtained by mixing a rubber-containing styrenic resin with a polymer composition C obtained by mixing a (A) component polymer with a solubility parameter outside the range of the present invention with a (B) component polymer. The composition is undesirable because surface defects such as delamination and flow marks appear in the molded product. 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 each vinyl monomer constituting the copolymer consisting of m types of vinyl monomers and its weight fraction W _o . 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 obtained by mixing a polymer composition C consisting of a component polymer (A) having a molecular weight of less than 10 ⁵ with a component polymer (B) and a rubber-containing styrenic resin, Surface defects such as delamination and flow marks appear on the molded product, which is undesirable. In this specification, the weight average molecular weight based on polystyrene is the weight average molecular weight determined by gel permeation chromatography assuming that the component polymer (A) is polystyrene.
That is, using polystyrene, which has a narrow molecular weight distribution and a known molecular weight, as a standard substance, a calibration curve is created by determining the relationship between the outflow peak volume of the gel permeation chromatogram and the molecular weight. Next, the gel permeation chromatogram of the component polymer (A) is measured, the molecular weight is determined from the outflow volume using the calibration curve, and the weight average molecular weight is calculated according to a conventional method. The polymer component (A) of the present invention needs to have a gel content of 10% or less. The gel content in the present invention is calculated by accurately weighing approximately 1.0 g of component (A) polymer (S ₀
g), 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 the basket, and air-dried at room temperature (A) It is a value calculated by measuring the weight S ₁ g of the component polymer insoluble material and then calculating it according to the following formula. (S ₁ /S ₀ ) x 100 (%) ...[] A polymer composition C formed by mixing component (A) polymer with a gel content of more than 10% with component polymer (B), and rubber. A thermoplastic resin composition obtained by mixing with a styrene-based resin 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 component polymer (A) and the component polymer (B) are mixed, and the other reason is that emulsion polymerization allows for easy industrial production of high molecular weight polymers. 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 copolymerizable monomer. However, here, the specific example of the acrylic ester monomer is the same as the specific example of the acrylic ester monomer listed above as an example of the vinyl monomer constituting the component (A) polymer of the present invention. It is. 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, 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 are as follows. It is the same as the specific example listed above for the 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
In a thermoplastic resin composition obtained by mixing a polymer composition C obtained by mixing a component (B) polymer with a temperature exceeding 20°C with a component polymer (A) and a rubber-containing styrenic resin,
Environmental stress cracking resistance is poor and undesirable. 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. In a thermoplastic resin composition obtained by mixing a polymer composition C consisting of a component polymer (B) having a gel content of more than 70% with a component polymer (A), into a rubber-containing styrenic resin, , the environmental stress cracking resistance is poor and 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 8.4
(cal/cc) less than ^1/2 or more than 9.8 (cal/cc) ^1/2 , the polymer composition C formed by mixing the (B) component polymer with the (A) component polymer is The environmental stress cracking resistance of the thermoplastic resin composition obtained by mixing it with the styrenic resin contained therein is poor, 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 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. In the present invention, a polymer composition C is prepared by mixing 20 to 90% by weight of component polymer (A) and 10 to 80% by weight of component polymer (B) in an emulsion state. If the content of the polymer is less than 10% by weight, the thermoplastic resin composition obtained by mixing the polymer composition C and the rubber-containing styrenic resin will have poor environmental stress cracking resistance,
If it exceeds 80% by weight, surface defects such as delamination and flow marks will appear in molded articles made of the thermoplastic resin composition, which is not preferable. In the present invention, an emulsion of the polymer component (A) and an emulsion solution of the polymer component (B) are mixed in an emulsion state. When the (A) component polymer or (B) component polymer is manufactured by emulsion polymerization, the emulsion polymerization solution obtained by emulsion polymerization can be used as it is, but if it is manufactured by other polymerization methods. 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. Although there is no particular restriction on the particle size of the polymer in the emulsion of the component polymer (A) or the component polymer (B), 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 electron micrograph of the emulsion, and setting the fraction of the particle diameter where the particle diameter is d _i as f _i ,
Calculated according to the formula below. Σf _i d _i ³ /Σf _i d _i ² ...[] In particular, if the area average particle diameter of the component (B) polymer exceeds 5μ, the component (B) polymer may not be mixed with the component (A) polymer. Layer peeling phenomenon or flow marks may occur in a molded product of a thermoplastic resin composition obtained by mixing polymer composition C consisting of rubber with a rubber-containing styrenic resin. 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, amphoteric surfactants, Although any nonionic surfactant can be selected, anionic surfactants can be used most advantageously. There is no particular restriction on the method of mixing component (A) component polymer emulsion and (B) component polymer emulsion, and there is no particular restriction on the method of mixing component (A) component polymer emulsion and (B) component polymer emulsion.
Mixing can be carried out using equipment such as rotating vessel mixers, pipeline mixers, static mixers, and the like. There is no particular restriction on the method for separating the polymer composition C from the mixed emulsion of the (A) component polymer emulsion and (B) component polymer emulsion.
Precipitation of acids such as acetic acid, electrolytes such as sodium chloride, calcium chloride, aluminum chloride, sodium sulfate, magnesium sulfate, water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, carboxymethyl cellulose, etc. Examples include a method of adding an agent, a method of breaking the emulsion by freezing the emulsion, and a method of spraying the emulsion into a high-temperature gas. The polymer composition C separated from the mixture of the component (A) polymer emulsion and the (B) component polymer emulsion can be further supplied to a melt-kneading device for melt-kneading. Examples of melt-kneading devices that can be used include Banbury mixers, intensive mixers, mixtruders, co-kneaders, extruders, and rolls. In addition, special public service 59-
It is also possible to use the melt-kneading device with a dehydration mechanism disclosed in No. 37021, but when using this device, the emulsified liquid and precipitant are continuously supplied to the device for mixing and demulsification. It is also possible to perform dehydration, drying, and melt-kneading continuously in the same device. Monomers constituting the rubber component of the rubber-containing styrenic resin in the present invention include butadiene, isoprene, dimethylbutadiene, chloroprene,
Conjugated diene monomers such as cyclopentadiene,
Non-conjugated diene monomers such as 2,5-norbornadiene, 1,4-cyclohexadiene, 4-ethylidenenorbornene, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, etc. Nitrile monomers, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate, and olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene. etc., and homopolymerization or copolymerization of these is used. Furthermore, as a crosslinking monomer, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can also be used, but the polyfunctional vinyl monomers that can be used include divinylbenzene, ethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate, Examples include glycidyl methacrylate. The rubber component used in the rubber-containing styrene resin of the present invention needs to have a graft active site, and specifically, it is preferable to have a carbon-carbon double bond in the rubber molecule. . 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 rubber-containing styrenic resin does not need to be of one type, and may be a mixture of two or more types of rubber components that are separately polymerized. Monomers constituting the resin component of the rubber-containing styrenic resin in the present invention include styrene, α-
Styrenic monomers such as methylstyrene, vinyltoluene, and t-butylstyrene; nitrile monomers such as acrylonitrile and methacrylonitrile;
(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-cyclohexylmaleimide, N- Phenylmaleimide, N-toluylmaleimide, N-
Maleimide monomers such as xylylmaleimide are used, and they 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 rubber-containing styrenic resin obtained by graft polymerizing acrylonitrile, styrene and methyl methacrylate in the presence of polybutadiene,
- A resin component obtained by copolymerizing methylstyrene can be mixed. Specific examples of the rubber-containing styrenic resin of the present invention include ABS (acrylonitrile-butadiene-styrene) resin, heat-resistant ABS (acrylonitrile-butadiene-styrene) resin,
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 is 2 to 50% by weight, preferably 5 to 50% by weight.
It needs to be 40% by weight. When 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 is low;
If it exceeds 50% by weight, rigidity or heat resistance will decrease. Further, the resin components of the rubber-containing styrenic resin of the present invention include 40 to 90% by weight of styrene monomer, 5 to 50% by weight of nitrile monomer, and 0% of other copolymerizable monomers.
~40% by weight. 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 the present invention, a thermoplastic resin composition is produced by mixing 0.5 to 50% by weight of a polymer composition C and 50 to 99.5% by weight of a rubber-containing styrenic resin. More preferably, 2 to 40% by weight of the polymer composition C and 60 to 98% 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 cracking resistance,
If it exceeds 50% by weight, the composition will have poor rigidity, heat resistance, or impact resistance, which is not preferable. 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, a fixed container type mixing device such as a Henschel mixer, a rotating container type mixing device 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, co-kneader, extruder,
There are rolls etc. (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. In addition, all parts and percentages described in each example are based on weight. Example 1 and Comparative Example 1 [Production of component (A) - Production of A-1 to A-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
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 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). [Structure of component (B) - Manufacture 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 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 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 diacrylate [Production of polymer composition C] (A) 50 parts of component emulsion (of polymer as solids) and
50 parts of component (B) emulsion (as the solid content of the polymer) are mixed in an emulsion state, and then a polyethylene glycol-polypropylene glycol block copolymer (ethylene oxide polymerization fraction in the total molecule of 80%,
Polypropylene glycol molecular weight 1750 - Asahi Denka Kogyo Co., Ltd. Pluronic F-68) 0.7 parts 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 above-mentioned mixed emulsion was added thereto with 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. (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.

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【table】

【table】

【table】

【table】

【table】

[Manufacture of thermoplastic resin composition]

50% polybutadiene, 13% acrylonitrile,
30 parts ABS resin powder consisting of 37% styrene, 30% acrylonitrile, and AS resin powder consisting of 70% styrene (weight average molecular weight 1.1 based on polystyrene)
× ¹⁰⁵ ) 54 parts, and 0.2 part of 4,4'-isopropylidene bis[monophenyl-dialkyl ( _C12 - _C15 ) phosphorite] [MARK 1500, manufactured by Adeka Argus Chemical Co., Ltd.], mixed in a Henschel mixer with 16 parts of polymer composition C;
The pellets were supplied to VC-40 (single-screw extruder with vent) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets. Moldings were made using the obtained pellets and their physical properties were evaluated, and the results are shown in Table 5, Experiment Nos. 1 to 50.
It was shown to. In addition, the physical property measurement values of each example were determined by the following method. (1) Tensile yield point…ASTM D-638 (2) Izot impact strength…ASTM D-256 (3) Vikatsu softening temperature…JIS K-6870 (4) Chemical resistance (environmental stress cracking resistance) ASTM D- Give a 50mm deflection to a 638 type dumbbell, fix it on a jig, apply ethylene glycol monoethyl ether, and heat it at a temperature of 23℃.
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 Yacil manufactured by Kawaguchi Iron Works Co., Ltd.
1040S Mold; Alkyldes 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: The distance from the gate of the molded product to the free-flowing end and evaluation was measured. The larger the flow length is, the better the fluidity is evaluated.

【table】

【table】

【table】

【table】

[Table] 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 component (A) emulsion and the component (B) emulsion, although the glass transition temperature of component (A) is outside the range of the present invention. Thing C
Since the solid does not form a powder at room temperature but takes the form of a lump, for example, the process of dehydrating the precipitate, washing with water, drying,
Alternatively, operational disadvantages occurred during the mixing process with the 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 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 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, 10% of Pluronic F-68 used in Example 1 was added to 100 parts of the solid content of the polymer mixture.
7 parts of aqueous solution were added. The obtained mixed emulsion was subjected to precipitation treatment in the same manner as in Example 1 to obtain polymer compositions C-1 to C-8. Next, the ABS resin powder used in Example 1,
AS resin powder, and mark 1500 polymer composition C
-1 to C-8 in the following proportions to form pellets. ABS resin powder 30 parts AS resin powder 54 parts Mark 1500 0.2 parts Polymer composition C 16 parts The obtained pellets were evaluated for physical properties in the same manner as in Example 1, and the results are shown in Table 7.

【table】

[Table] As is clear from Comparative Example 2, if the content of component (B) in polymer composition C exceeds the lower limit of the range of the present invention, the visual stress cracking resistance is poor, and if it exceeds the upper limit, layered Peeling or flow marks become noticeable,
Both are undesirable. Example 3 and Comparative Example 3 50 parts of the A-1 emulsion (as 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. After mixing, 7 parts of a 10% aqueous solution of Pluronic F-68 were added. The obtained mixed emulsion was subjected to precipitation treatment in the same manner as in Example 1 to obtain a powder of polymer composition C. Next, the polymer composition C was fed to a VC-40 extruder manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets. Polymers D-1 to D-8 whose compositions are shown separately in Table 8
were mixed according to the formulation shown in Table 9 and fed to a VC-40 type extruder to produce rubber-containing styrenic resins E-1 to E.
-7 pellets were obtained. Note that D-1 and D-6 are the ABS resin and AS resin used in Example 1, respectively. Next, pellets of polymer composition C and pellets of rubber-containing styrenic resins E-1 to E-7 were displayed.
They were mixed at the ratio shown in 10 and fed to a VC-40 extruder and kneaded to obtain pellets. The physical properties of the obtained pellets were evaluated in the same manner as in Example 1, and the results are shown in Table 10. Note that spiral flow measurements were performed at a cylinder temperature of 280°C for experiment numbers 64, 65, 77, and 78, and 260°C for other samples.

【table】

【table】

【table】

【table】

[Table] Experiment numbers 59 to 70 in Table 10 are examples, and experiment numbers 71 to 78 are comparative examples. Comparing Experiment Nos. 59 to 65 and Experiment Nos. 72 to 78, it was found that 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 resulting composition It can be seen that the impact resistance is inferior. Example 4 and Comparative Example 4 Polymer composition C 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 pellets were evaluated in the same manner as in Example 1, and the results are shown in Table 11.

[Table] Experiment No. 83 is an example in which the amount of polymer composition C added exceeds the upper limit of the range of the present invention, and the thermoplastic resin composition obtained by mixing with the rubber-containing styrenic resin has high rigidity and heat resistance. It is unfavorable because of its poor properties and delamination properties. By the way, experiment number 71 of Comparative Example 3 shown in Table 10
Similarly to Experiment No. 83, this is an example in which the amount of the polymer composition added exceeds the upper limit of the range of the present invention, but the resulting thermoplastic resin composition has poor impact resistance, and is different from Experiment No. 83. behave differently. 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 Table 8D-1 80 parts of emulsion (as solid content of polymer)
and 20 parts of the B-3 emulsion prepared in Example 1 (as the solid content of the polymer) were mixed in an emulsion state, and poured into an aqueous solution of 5 parts of calcium chloride dihydrate.
It precipitated by stirring at ~95°C. 40 parts of the powder obtained by filtering the obtained slurry, washing with water, and drying, 60 parts of Table 8D-6 powder, mark
1500 mixed in a Henschel mixer with 0.2 parts;
The mixture was fed to a VC-40 extruder and made into pellets. Physical properties of the obtained pellets were evaluated according to Example 1, and the results showed that the tensile yield point was 410 Kg/cm ² , the Izot impact strength was 29 Kgcm/cm, the chemical resistance was >300 minutes, and the gloss was
88%, laminar peelability C, flow mark D, Vikatsu softening temperature 97°C, spiral flow (cylinder temperature 260°C) 36 cm, and was inferior to laminar peelability and flow mark. Comparative Example 6 Table 8D-1 emulsion 30 parts (as solid content of polymer), Table 8D-7 emulsion 62 parts (as solid content of polymer), and B-3 emulsion produced in Example 1 8 (as the solid content of the polymer) are mixed in an emulsion state,
It was poured into an aqueous solution of 5 parts of calcium chloride dihydrate and stirred at 105°C to precipitate. The resulting slurry was filtered, washed with water, and dried, and 100 parts of the resulting powder was mixed with 0.2 parts of Mark 1500 in a Henschel mixer and fed into a VC-40 extruder to form pellets. Physical properties of the obtained pellets were evaluated according to Example 1, and the results showed that the tensile yield point was 420 kg/cm ² , the Izot impact strength was 14 kg cm/cm, the chemical resistance was >300 minutes, and the gloss was
93%, laminar peelability D, Flow Mark D, Vikatsu softening temperature 110°C, spiral flow (cylinder temperature 280°C) 23 cm, and laminar peelability and flow mark were inferior. (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 molded 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 20 to 90% 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) ¹⁰
~80% by weight (as the solid content of the polymer) is mixed in an emulsion state, and then the polymer is separated to obtain a polymer composition C of 0.5 to 50% by weight and a rubber component content of 2%. ~50% by weight, and the monomers constituting the resin component are 40 to 90% by weight of styrene monomers, 5 to 50% by weight of nitrile monomers, and 0 to 40% by weight of other copolymerizable monomers. 50 to 99.5% by weight of a rubber-containing styrenic resin.