JPH072886B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent environmental stress crack resistance and improved layered peeling property.

[Conventional technology]

When the rubber-containing styrene resin is brought into contact with a chemical under stress, a crack is generated, and in a remarkable case, a phenomenon of breaking is observed. This phenomenon is called environmental stress crack phenomenon,
As is well known, it is remarkably observed in chemicals such as alcohols, carboxylic acids, esters, alkanes and alkenes, which have low solubility in resins.

The environmental stress cracking phenomenon is such that even when no external force is applied to the resin molded product, the distortion during molding that remains inside the molded product
Since it is generated by being opened by contact with a chemical, it greatly limits the use of the rubber-containing styrene resin.

The rubber component content and the resin component molecular weight are known as factors that affect the environmental stress crackability of rubber-containing styrenic resins. Increase the rubber component content or increase the resin component molecular weight. The higher the stress, the better the environmental stress crackability, but the effect was not practically sufficient.

Recently, the present inventors have found that the environmental stress cracking property of the rubber-containing styrene-based resin is dramatically improved by mixing the acrylic acid ester-based polymer with the rubber-containing styrene-based resin (special feature: (Kaisho 58-179257).

However, although the composition of the invention has a remarkable effect of improving the environmental stress cracking property, a mica-like layered delamination phenomenon may be observed in an injection-molded product, and improvement has been required. The layered delamination phenomenon is remarkable in a molded product injection-molded under a high shear rate condition, and is remarkable in the vicinity of the gate.

The layered peeling phenomenon occurs when the acrylic ester polymer particles dispersed in the rubber-containing styrene resin are coagulated and enlarged, and are flatly deformed due to shear stress during injection molding. It is effective to copolymerize a polyfunctional vinyl monomer during the polymerization of the acrylic acid ester polymer for the purpose of preventing flat deformation of the acrylic acid ester polymer particles.

[Problems to be solved by the invention]

However, for example, an acrylic acid ester-based polymer obtained by copolymerizing a polyfunctional vinyl monomer such as divinylbenzene or ethylene glycol dimethacrylate has a high gel content although the layered peeling phenomenon is improved. However, the effect of improving the environmental stress cracking resistance of the rubber-containing styrene resin is insufficient. Therefore, by using a polyfunctional vinyl monomer and a chain transfer agent in combination to produce an acrylate polymer having a low gel content and a branched structure, the layered delamination phenomenon and environmental stress resistance can be improved. It is possible to balance the crackability, but the effect was unsatisfactory in practice.

An object of the present invention is to provide a thermoplastic resin composition that has improved the above-mentioned drawbacks of the prior art.

[Means for solving problems]

Briefly describing the present invention, the present invention relates to a thermoplastic resin composition, which comprises a dispersed phase composed of a rubber component, an aromatic vinyl monomer residue and a glass transition temperature.
100 parts by weight of a rubber-containing styrenic resin (A) containing a continuous phase composed of a resin component having a temperature higher than 20 ° C. and a covalent bond product of a rubber component and a resin component at the interface between the dispersed phase and the continuous phase; Acrylic acid ester monomer residue 50-99.9% by weight,
The following general formula I: [Wherein R ₁ is H or CH ₃ group, R ₂ is the same or different, and is H or C
H ₃ group, R ₃ is CmH ₂ m ₊₁ group (m is an integer of 0 or more) or Group (n is an integer of 0 or more), l represents an integer of 2 or more] from 0.1 to 20% by weight of the monomer residue and from 0 to 50% by weight of the other copolymerizable monomer residue Thus, the solubility parameter is 8.4 to 9.8 (cal / cc) ^1/2 , the glass transition temperature is 20 ° C or lower, and the gel content is 70% by weight or less (B) 1 to 50% by weight And a polymer having no aromatic vinyl monomer residue and a glass transition temperature of 20 ° C.
Polymer (C) 0 having a higher gel content of 10% or less and a solubility parameter of 9.0 to 11.0 (cal / cc) ^1/2
It is characterized by containing ˜50 parts by weight.

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has excellent resistance to environmental stress cracking, and is unlikely to exhibit a layered peeling phenomenon.

[Rubber-containing styrene resin (A) component]

The rubber-containing styrene resin as the component (A) of the present invention is
Consist of a rubber component and a resin component having a glass transition temperature of more than 20 ° C, and a covalent bond between the rubber component and the resin component is present at the interface between the rubber component as the dispersion layer and the resin component as the continuous layer. Is characterized by.

As the monomer constituting the rubber component of the rubber-containing styrene resin which is the component (A) in the present invention, butadiene,
Isoprene, dimethylbutadiene, chloroprene, conjugated diene monomers such as cyclopentadiene, 2,5-norbornadiene, 1,4-cyclohexadiene, non-conjugated diene monomers such as 4-ethylidene norbornene, styrene,
Aromatic vinyl monomers such as α-methylstyrene and vinyltoluene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and (meth) acryl such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate and octyl acrylate. There are acid ester monomers and olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene, and those obtained by homopolymerization or copolymerization are used. Further, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer as a crosslinking monomer can also be used, but as the polyfunctional vinyl monomer that can be used, 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, Glycidyl methacrylate and the like.

The rubber component contained in the component (A) of the present invention is required to have a graft active point, and specifically, it is preferable to have a carbon-carbon double bond in the rubber molecule. .

The method for polymerizing the monomer is not particularly limited, emulsion polymerization,
Known techniques such as solution polymerization can be used.

Also, the rubber component of component (A) does not have to be one type,
It may be a mixture of two or more rubber components separately polymerized.

Examples of the monomer that constitutes the resin component of the rubber-containing styrene resin that is the component (A) in the present invention include styrene and α
-Aromatic vinyl monomers such as methylstyrene, vinyltoluene and t-butylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate and octyl acrylate (Meth) acrylic acid ester monomer, maleimide, N
-Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-
There are maleimide-based monomers such as phenylmaleimide, N-toluylmaleimide, and N-xylylmaleimide, which are used alone or as a copolymer, but it is essential to contain an aromatic vinyl monomer. The aromatic vinyl monomer is preferably contained in the resin component of component A in an amount of 50% by weight or more.

The component (A) used in the present invention is composed of a rubber component and a resin component. At the interface between the rubber component which is a dispersed phase and the resin component which is a continuous phase, a rubber component and a resin component called a graft structure are provided. It is necessary that the covalently bound product is intervened. It is known that such a structure is achieved by a so-called graft polymerization method in which a part or all of the monomers constituting the resin component are polymerized in the presence of the rubber component, but the component (A) of the present invention is known. Can also be produced by a known graft polymerization technique.

The glass transition temperature of the resin component (A) must exceed 20 ° C. If the glass transition temperature of the resin component of component (A) is
When the temperature is 20 ° C. or lower, the thermoplastic resin composition which is the object of the present invention obtained by mixing the component (A) has low heat resistance or rigidity, which is not preferable.

The rubber-containing styrenic resin as the component (A) is composed of the rubber component and the resin component as described above, and the proportion thereof is preferably 2 to 70% by weight of the rubber component and 30 to 98% by weight of the resin component. The graft ratio represented by the following formula II is 5 to 20.
It is preferably 0%.

The rubber-containing styrene-based resin may be made of not only one kind but also two or more kinds of resins. For example, two or more kinds of resins grafted with a rubber component can be used. Further, it is preferable as an industrial production method to mix the separately-polymerized resin component with the rubber-containing styrene resin having a relatively high concentration of the rubber component. Here, the separately polymerized resin component is a polymer of a separately polymerized vinyl-based monomer, and the vinyl-based monomer is exemplified as a monomer constituting the resin component of component (A) described above. It refers to the monomer group. However, it should be noted here that the separately polymerized resin component does not necessarily have the same composition as the resin component obtained by graft polymerization. For example, a resin component obtained by copolymerizing acrylonitrile, styrene and α-methylstyrene with a rubber-containing styrene resin obtained by graft-polymerizing acrylonitrile, styrene and methyl methacrylate in the presence of polybutadiene can be mixed.

The separately-polymerized resin component mixed with the rubber-containing styrene-based resin needs to have a glass transition temperature of more than 20 ° C., but if the glass transition temperature is 20 ° C. or less, it is the object of the present invention. The heat resistance or rigidity of the plastic resin composition is low, which is not preferable.

Specific examples of the component (A) of the present invention include high-impact polystyrene (butadiene-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, and heat resistance.
ABS (acrylonitrile-butadiene-styrene-α-
Methyl styrene) resin, AAS (acrylonitrile-acrylic acid ester-styrene) resin, AES (acrylonitrile-ethylene-propylene-styrene) resin, MBAS
(Methyl methacrylate-butadiene-acrylonitrile-styrene) resin and the like.

[About component (B) polymer]

The copolymer which is the component (B) of the present invention comprises an acrylic acid ester monomer residue, a monomer residue represented by the general formula I and optionally other copolymerizable monomer residues. Composed.

Examples of the acrylate monomer used as a raw material for producing the copolymer as the component (B) of the present invention include:
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, phenyl acrylate and glycidyl acrylate.

On the other hand, examples of other copolymerizable monomers include styrene and α
-Aromatic vinyl monomers such as methyl styrene and t-butyl styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methacrylic acid ester monomers such as methyl methacrylate, butyl methacrylate and glycidyl methacrylate, ethylene, propylene,
Examples thereof include olefin monomers such as 1-butene, isobutylene and 2-butene, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and phenyl vinyl ether.

Further, the monomer represented by the general formula I is (meth) in a broad sense.
It is included in the acrylic acid ester monomer, but since it has a unique mechanism of action, it was distinguished from the (meth) acrylic acid ester monomer and added as an essential requirement item. Specific examples of the monomer represented by the general formula I include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, and phenoxy polyethylene. Glycol mono (meth) acrylate, phenoxy polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, etc. . Here, for example, polyethylene glycol mono (meth) acrylate means polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate. The average degree of polymerization of the polyethylene glycol residue or the polypropylene glycol residue of the above monomer group, in other words, the value of l in the general formula I is 2
It is preferably in the range of 100 to 100, more preferably in the range of 2 to 20.

The effect of incorporating the monomer residue represented by the general formula I into the component (B) polymer is that the environmental stress crack resistance of the thermoplastic resin composition comprising the component (A) and the component (B) is impaired. The layered peelability is improved.

The component (B) polymer has an acrylic acid ester monomer residue of 50
~ 99.9% by weight, monomer residue 0.1-2 represented by the general formula I
It is composed of 0% by weight and 0 to 50% by weight of other copolymerizable monomer residues, but when the acrylic acid ester monomer residue is less than 50% by weight, the components (A) and (B) are Inferior environmental stress crack resistance of the thermoplastic resin composition comprising, and if the monomer residue represented by the general formula I is less than 0.1% by weight, the layered peeling property of the thermoplastic resin composition is inferior, If it exceeds 20% by weight, not only the effect is saturated but also the environmental stress crack resistance is deteriorated, which is not preferable. If a more preferable embodiment of the composition of the component (B) polymer is shown,
(B) Acrylic acid ester monomer residue in component polymer 60
% To 99% by weight, 1 to 10% by weight of the monomer residue represented by the general formula I, and 0 to 40% by weight of the other copolymerizable monomer residue.

Further, in the component (B) polymer of the present invention, a polyfunctional vinyl monomer may be copolymerized in addition to the above-mentioned monofunctional vinyl monomer. Examples of polyfunctional vinyl monomers that can be used are 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, polyethylene glycol di (meth)
Examples thereof include acrylate, polypropylene glycol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, and vinyl (meth) acrylate.

Component (B) of the present invention should have a solubility parameter of 8.4~9.8 (cal / cc) ^1/2, more preferable numerical range is 8.6~9.6 (cal / cc) ^1/2 . Solubility parameter as used herein means New York City John
Published by Wiley End Sons in 1975, Brand Wrap (J. Brandrup) and Inmargut (EHImmergut)
Ed., Polymer Handbook Second Edition
Using the solubility parameter values described on pages IV-337 to IV359, the solubility parameter δ _T of the copolymer is determined by the homopolymer of individual vinyl monomers constituting the copolymer composed of m kinds of vinyl monomers. It is calculated by the following formula III from the solubility parameter δn of the above and its weight fraction Wn.

For example, the solubility parameters of polybutyl acrylate and ethyl polyacrylate are 8.8 (cal / cc) ^1/2 ,
Assuming 9.4 (cal / cc) ^1/2 , the solubility parameter of a copolymer consisting of 70% by weight of polybutyl acrylate and 30% by weight of polyethyl acrylate is calculated as 9.0 (cal / cc) ^1/2 .

When the solubility parameter of the component (B) is less than 8.4 or exceeds 9.8, the resin composition of the present invention has low environmental stress crack resistance, which is not preferable.

The component (B) of the present invention needs to have a glass transition temperature of 20 ° C or lower, preferably 10 ° C or lower. When the glass transition temperature exceeds 20 ° C., the environmental stress crack resistance of the resin composition of the present invention becomes low, which is not preferable.

Further, the component (B) of the present invention is required to have a gel content of 70% by weight or less. The gel content referred to in the present specification means that about 1.0 g of the component (B) is precisely weighed (S ₀ g), put in a basket made of 400 mesh stainless wire gauze, and put in 100 g of toluene. The mixture is left in 5 ° C. for 24 hours, then the basket is pulled up and air-dried at room temperature to measure the weight S ₁ g of the component (B) insoluble matter, and then the value calculated according to the following formula IV.

(S ₁ / S ₀ ) × 100 (%) …… [IV] When the gel content of the component (B) exceeds 70% by weight, the environmental stress crack resistance of the resin composition of the present invention becomes low, which is preferable. Absent.

The method for polymerizing the component (B) of the present invention is not particularly limited, but the production by the emulsion polymerization method is industrially most advantageous, and known techniques relating to the emulsion polymerization method can be arbitrarily applied.

As an embodiment of the emulsion polymerization method of the component (B), an acrylic acid ester monomer, a monomer represented by the general formula I, and, if necessary, other copolymerizable monomer are prepared as a homogeneous solution in the polymerization system. Emulsion polymerization by adding them all at once or continuously (homogeneous polymerization method), emulsion (co) polymerization of at least a part of the monomer represented by the general formula I There is a method (e.g., a heterogeneous polymerization method) in which the emulsion polymerization is carried out by adding it to the polymerization system during or after completion of

It is possible to use a chain transfer agent for the purpose of controlling the molecular weight of the component (B) polymer. In particular, in the case of copolymerizing a polyfunctional vinyl monomer, it is possible to produce a component (B) polymer having a branched structure and a low gel content by using a chain transfer agent together. However, the component (B) thus produced exerts a favorable effect on improving the layered peelability.

The chain transfer agent that can be used is not particularly limited, and examples thereof include octyl mercaptan, decyl mercaptan, dodecyl mercaptan, thioglycolic acid, ethyl thioglycolate, butyl thioglycolate, ethyl o-mercaptobenzoate, 1-naphthyl disulfide, and sulfur. Sulfur compounds, halogen compounds such as carbon tetrabromide, hydrocarbons such as linemon and terpinolene, nitro compounds such as trinitrophenol and trinitrobenzene, and benzoquinone.

The resin composition of the present invention is essentially a mixture of 1 to 50 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). The polymer containing no monomer residue may be added in an amount of 0 to 50 parts by weight based on 100 parts by weight of the component (A).

The component (C) polymer may be a homopolymer of one type of monomer or a copolymer of two or more types of monomers.
Examples of vinyl-based monomers constituting the component polymer, acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, Octadecyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate,
Acrylic ester monomers such as glycidyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, methoxyethyl methacrylate, glycidyl methacrylate, phenyl Methacrylate ester monomers such as methacrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, vinyl halides such as vinyl chloride and vinylidene chloride Monomer, vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate, vinyl octadecanoate Fatty acid vinyl ester monomers such as Le, ethylene, propylene, 1-butene, isobutylene, olefin monomers such as 2-butene, maleimide, N- methyl maleimide, N- ethylmaleimide, N
-Propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide and other maleimide monomers, maleic anhydride and other acid anhydride monomers, butadiene, isoprene, chloroprene and other conjugated diene monomers , Vinyl vinyl monomer such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, decyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, cresyl vinyl ether, glycidyl vinyl ether, vinyl ketone monomer such as methyl vinyl ketone, phenyl vinyl ketone, vinyl Pyridine, etc., but not limited to this.

Further, the vinyl-based monomer constituting the component (C) polymer may be a polyfunctional vinyl monomer. Examples of the polyfunctional vinyl monomer include divinylbenzene and 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) There are acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and the like.

The glass transition temperature of the component (C) polymer of the present invention must exceed 20 ° C. A more preferable glass transition temperature is 30 ° C or higher. When the glass transition temperature of the component (C) polymer is 20 ° C. or lower, the polymer composition (D) obtained by mixing the component (B) polymer and the component (C) polymer is formed into powder or pellets. When the composition is industrially produced because it is difficult to handle, for example, in the method of mixing with the component (A) described below, there are disadvantages and the heat resistance of the composition is improved by mixing with the rubber-containing styrene resin. It is not preferable because it greatly decreases.

The component (C) polymer of the present invention is 8.0 to 11.0 (cal / cc) ^1/2
It is necessary to have a solubility parameter in the range of, and a more preferable range is 8.5 to 10.5 (cal / cc) ^1/2 . A polymer composition D obtained by mixing a component (C) polymer having a solubility parameter outside the range of the present invention with a component (B) polymer was obtained by mixing the composition with a rubber-containing styrene resin. Layered peeling phenomenon and surface defects such as flow marks appear on the molded product of the composition, which is not preferable.

The component (C) polymer of the present invention needs to have a gel content of 10% or less. Here, the gel content means a value calculated according to the above-mentioned formula VI by the same measuring method as the gel content of the component (B) polymer except that 100 g of methyl ethyl ketone is used instead of 100 g of toluene. Say.
When the gel content of the component (C) polymer exceeds 10%, a molded article of a composition obtained by mixing the component (C) polymer and the component (B) polymer with a rubber-containing styrene resin is obtained. Unsatisfactory due to poor gloss

The method for producing the component (C) polymer is not particularly limited, and known techniques such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization can be arbitrarily applied, but the production by emulsion polymerization is industrially most advantageous. Is.

In producing the component (C) polymer, the selection of the monomers is
The glass transition temperature, gel content, and solubility parameter of the obtained component (C) polymer are arbitrary as long as they satisfy the requirements of the present invention.

[Mixing of components (A), (B) and (C)]

In the present invention, 100 parts by weight of the component (A), 1 to 50 parts by weight of the component (B), preferably 2 to 40 parts by weight, and further 0 to the component (C).
Although 50 parts by weight is mixed, if the content of the component (B) is less than 1 part by weight, the effect of improving the environmental stress cracking property is insufficient.
If the amount is more than parts by weight, not only the effect is saturated, but also the rigidity is lowered, which is not preferable.

In order to mix the component (A), the component (B) and the component (C) in the present invention, a known mixing technique is applied, and both components in an emulsified state, a particle state or a molten state are blended and melted. The desired mixture can be easily obtained by kneading. When the component (B) and the component (C) are produced by an emulsion polymerization method, the polymer latex is blended with the component (A) in an emulsion state, a particle state or a molten state,
Melt kneading can be performed through the dehydration step or simultaneously with the dehydration step. Examples of the melt-kneading device include a Banbury mixer, an intensive mixer, a mixed trader, a cokneader, an extruder and a roll. Also,
The manufacturing method disclosed in JP-A-56-131656 can also be applied.

If a more preferable production method of the thermoplastic resin composition of the present invention is presented, 10 to 80% by weight of the emulsion of the component (B) polymer (as the solid content of the polymer) and the emulsion of the component (C) polymer are used. Obtained by separating the polymer after mixing 20 to 90% by weight (as the solid content of the polymer) of a part of the emulsion and / or the resin component constituting the component (A) in the emulsion state. A method of mixing the polymer composition (D) with the component (A) can be mentioned.

[About Polymer Composition D]

Therefore, the polymer composition D is prepared by mixing 20 to 90% by weight of the component (C) polymer and / or the resin component (A) and 10 to 80% by weight of the component (B) polymer in an emulsified liquid state. However, if the content of the component (B) polymer is less than 10% by weight, the composition obtained by mixing the polymer composition and the rubber-containing styrene resin is inferior in environmental stress crack resistance. When it exceeds 80% by weight, a layered delamination phenomenon occurs in a molded article composed of the composition,
Surface defects such as flow marks appear, which is not preferable.

In the method, the emulsion of the component (C) polymer and / or the emulsion of the resin component constituting the component (A) and the emulsion of the component (B) polymer are mixed in an emulsion state. According to the method, since the component (B) is uniformly dispersed, and a polymer containing the component (B) in a high concentration can be handled as a powder, the component (B) is contained in the component (A). The object of uniform dispersion can be industrially advantageously achieved. When the component (C) polymer, the resin component (A) or the component (B) polymer is produced by emulsion polymerization, the emulsion polymerization liquid obtained by emulsion polymerization can be used as it is, When it is produced by various polymerization methods, a step of emulsifying the obtained polymer is necessary.

The emulsification method of the polymer is not particularly limited, and known techniques can be arbitrarily applied. For example, a method of mixing and stirring a polymer solution with an emulsifier and water to form an emulsion and then removing the solvent, a method of mixing and stirring fine powder obtained by pulverizing the polymer with an emulsifier to form an emulsion, a polymer. However, the method is not limited to this.

The particle diameter of the polymer in the emulsion of the component (C), the resin component of the component (A), or the emulsion of the component (B) is not particularly limited, but the area average particle diameter is preferably 5 μm or less. Here, the area average particle diameter is calculated according to the following formula V, where an electron micrograph of the emulsion is taken, and the fraction of the particle diameter at which the particle diameter is di is fi.

Σfidi ³ / fidi ² ...... [V] In particular, when the area average particle diameter of the component (B) polymer exceeds 5 μ, the component (B) polymer is converted into the component (C) polymer and / or the component (A). Polymer composition D formed by mixing with resin component
May be mixed with a rubber-containing styrenic resin, and a layered peeling phenomenon or a flow mark may occur in a molded product of the composition.

The type of the emulsifier used for emulsion polymerization of the component (C) polymer, the component (A) resin component or the component (B) polymer, or the emulsification of the polymer is not particularly limited, and an anionic surfactant,
The cationic surfactant, the amphoteric surfactant and the nonionic surfactant can be arbitrarily selected, but the anionic surfactant can be most advantageously used.

The mixing method of the component (C) polymer emulsion and / or the resin component emulsion of the component (A) and the component (B) polymer emulsion is not particularly limited, and is a fixed container type mixing device or a rotary container type mixing device. Mixing can be carried out using a device such as a pipeline mixer or a static mixer.

There is no particular limitation on the method for separating the polymer composition D from the mixed emulsion of the component (C) polymer emulsion and / or the component (A) resin component emulsion and the (B) component polymer emulsion. In the emulsion, hydrochloric acid, sulfuric acid, phosphoric acid, acids such as acetic acid, sodium chloride, calcium chloride, ammonium chloride, sodium sulfate, electrolytes such as magnesium sulfate, polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, Examples thereof include a method of adding a precipitant such as a water-soluble polymer such as carboxymethyl cellulose, a method of freezing an emulsion and breaking the emulsion, a method of spraying the emulsion in a high temperature gas, and the like.

The polymer composition D separated from the mixture of the component (C) component polymer emulsion and / or the component (A) resin component emulsion and the component (B) polymer emulsion is placed in a melt-kneader. It can be supplied and melt-kneaded. Examples of melt-kneading devices that can be used include Banbury mixers, intensive mixers, mixed extruders, co-kneaders, extruders, and rolls. In addition, Japanese Examined Japanese Patent Publication Sho 59-37021
Although it is also possible to use a melt-kneading device having a dehydration mechanism disclosed in No. 6, in the case of using the device, an emulsion and a precipitating agent are continuously supplied to the device, mixing, emulsion destruction, It is also possible to continuously perform dehydration, drying, and melt-kneading in the same device.

The method for mixing the polymer composition D and the rubber-containing styrene resin is not particularly limited, and the desired thermoplastic resin composition can be produced by mixing both components in powder or pellet form. Examples of the mixing device include a fixed container type mixing device such as a Henschel mixer, and a rotating container type mixing device such as a V-type blender and a tumbler, but are not limited thereto.

As a method for mixing the polymer composition D and the rubber-containing styrene resin, melt kneading can be exemplified. Specific examples of the melt-kneading device to be used include Banbury mixer, intensive mixer, mixed extruder, co-kneader,
There are extruders and rolls.

Furthermore, in the present invention, it is possible to add additives other than the above, for example, pigments, dyes, stabilizers, dispersants, reinforcing materials, fillers, lubricants and the like.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

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

Example 1 and Comparative Example 1 [Production of Component (A)] (1) A-1, A-2, A-3, A-5 Corresponding monomers in the presence of the rubber latex shown in Table 1. Was added to produce an emulsion polymerization method.

(2) The monomers shown in Table 1 were added to a toluene solution of A-4 EPDM rubber to prepare a solution by a polymerization method.

(3) A-6, A-7, A-8 Produced by emulsion polymerization of the monomers shown in Table 1.

[Production of component (B) -excluding B-17 and B-18] 120 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate are charged in an autoclave at 65 ° C with stirring.
Heated to. Here, 0.005 parts of ferrous sulfate heptahydrate, 0.015 parts of ethylenediamine tetraacetic acid tetrasodium dihydrate, and sodium formaldehyde sulfoxylate-2
An aqueous solution prepared by dissolving 0.3 parts of water salt in 10 parts of pure water was added.

Next, 20% of 100 parts of the monomer mixture having the composition shown in Table 2
Was poured into an autoclave and 2.5 parts of a 0.2% aqueous solution of potassium persulfate was added to initiate polymerization.

Simultaneously with the start of the polymerization, the remaining amount of the monomer mixture solution was continuously added over 4 hours. Simultaneously with the start of polymerization, an aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 20 parts of pure water was continuously added over 6 hours. After completing the addition of the potassium persulfate solution,
The contents of the autoclave were cooled to complete the polymerization.

Table 3 shows the properties of the obtained component (B).

[Manufacture of component (B) -manufacture of B-17 and B-18] 140 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate were charged into an autoclave and stirred at 70 ° C.
Heated to.

An aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 10 parts of pure water was added thereto, and the monomer mixture solution having the composition shown in Table 2 was further added.
0 part was continuously added in 4 hours.

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

Table 3 shows the properties of the obtained component (B).

The abbreviations of the monomers represented by the general formula I (monomers I) used in Table 2 are as follows.

4EM: Tetraethylene glycol monomethacrylate M4EM: Methoxytetraethylene glycol monomethacrylate M4EA: Methoxytetraethylene glycol monoacrylate M8EM: Methoxyoctaethylene glycol monomethacrylate M8PM: Methoxyoctapropylene glycol monomethacrylate M20EM: Methoxyeicosa ethylene glycol monomethacrylate P4EM: Phenoxytetraethylene glycol monomethacrylate [Production of component (B) -Production of B-19 120 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate are charged into an autoclave and stirred at 65 ° C.
Heated to. Here, 0.005 parts of ferrous sulfate heptahydrate, 0.015 parts of ethylenediamine tetraacetic acid tetrasodium dihydrate, and sodium formaldehyde sulfoxylate-2
An aqueous solution prepared by dissolving 0.3 parts of water salt in 10 parts of pure water was added.

Then, 20% of a monomer mixture consisting of 70 parts of n-butyl acrylate, 30 parts of methyl methacrylate, 0.1 part of t-dodecyl mercaptan and 0.5 part of ethylene glycol dimethacrylate was poured into an autoclave and potassium persulfate was added.
Polymerization was initiated by adding 2.5 parts of 0.2% aqueous solution.

Simultaneously with the start of the polymerization, the remaining amount of the monomer mixture solution was continuously added over 4 hours. Simultaneously with the start of polymerization, an aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 20 parts of pure water was continuously added over 6 hours.

After continuously adding the remaining amount of the monomer mixture, 5 parts of methoxytetraethylene glycol monomethacrylate was added. The polymerization rate of the monomer in the system immediately before the addition of methoxytetraethylene glycol monomethacrylate was 88%.

After the addition of the aqueous potassium persulfate solution was completed, the contents of the autoclave were cooled to complete the polymerization.

The component (B) thus obtained is called B-19, and its properties are shown in Table 3.
Shown in.

[Production of component (C)] 150 parts of pure water and 2 parts of potassium stearate were charged into an autoclave and heated to 50 ° C while stirring. 0.005 parts of ferrous sulfate heptahydrate, ethylenediamine 4
0.01 parts of sodium tetrahydrate / dihydrate and 0.3 parts of sodium formaldehyde sulfoxylate / dihydrate in 1 part of pure water
An aqueous solution dissolved in 0 part was added.

Then, 100 parts of the monomer mixture having the composition shown in Table 4 was continuously added over 4 hours. At the same time, an aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 25 parts of pure water was continuously added over 6 hours.

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

Table 5 shows the properties of the obtained component (C).

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

(1) Glass transition temperature The solid obtained by dropping the component (B) or the component (C) emulsion in methanol is dried and a DuPont-type measuring instrument is used.
It was measured using a 0 differential scanning calorimeter and a 990 thermal analyzer.

(2) Gel content The solid obtained by dropping the component (B) or (C) component emulsion into methanol was dried. Weigh about 1.0 g of it,
It was measured by the method described above and calculated by the formula IV. However,
The solvent used is different between the component (B) and the component (C),
Methyl ethyl ketone was used as the component (C), and toluene was used as the component (B).

(3) Solubility Parameter The solubility parameter value [unit (cal / cc ^1/2 ]) of each polymer used for calculating the solubility parameter in each example is as follows.

Butyl polyacrylate; 8.8 ethyl polyacrylate; 9.4 polymethyl methacrylate; 9.5 polyacrylonitrile; 12.5 polystyrene; 9.1 Further, the solubility parameter of the homopolymer of the monomer represented by the general formula I is not known, It was calculated by using Hoy's group molar attraction constants described on page 339 of Polymer Handbook, cited above, assuming the density of the homopolymer to be 1.0.

Poly (tetraethylene glycol monomethacrylate); 8.8 Poly (methoxytetraethylene glycol monomethacrylate); 8.5 Poly (methoxytetraethylene glycol monomethacrylate); 8.5 Poly (methoxyoctaethylene glycol monomethacrylate); 8.5 Poly (methoxyoctapropylene glycol) Monomethacrylate); 8.3 Poly (methoxyeicosa ethylene glycol monomethacrylate); 8.6 Poly (phenoxytetraethylene glycol monomethacrylate); 8.5 [Production of polymer composition D] 50 parts of component (B) emulsion (solid of polymer) (As the solid content) and 50 parts of the component (C) emulsion (as the solid content of the polymer) are mixed in the emulsion state, and the polyethylene glycol-polypropylene glycol block copolymer (weight of ethylene oxide in the total molecule) is mixed. 80%, polypropylene glycol molecular weight 1750-Pluronic F manufactured by Asahi Denka Co., Ltd.
-68) 0.7 parts of 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 mixed emulsion was added thereto with stirring to deposit.

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

[Production of thermoplastic resin composition]

Table 1 A-1 resin powder 34 parts, A-6 resin powder 50 parts, polymer composition D solid [see Table 6 for the details of the components (B) and (C)] 16 parts sorbitan monostearate 4 parts, And 4,
4'-isopropylidene bis [monophenyl - di - alkyl (C ₁₂ ~C ₁₅₎ phosphite] [Adeka Argus Chemical Co., Mark (MARK) 1500] 0.2 parts were mixed in a Henschel mixer, CHUO Machine Manufacturing VC-
40 (single screw extruder with vent) was fed to obtain pellets.

A molded product was prepared using the obtained pellets and the physical properties were evaluated. The results are shown in Table 6, Experiment Nos. 1-26.

The measured physical properties of each example were obtained by the following methods.

(1) Tensile yield point ... ASTM D-638 (2) Izod impact strength ... ASTM D-256 (3) Vicat softening temperature ... JIS K-6870 (4) Chemical resistance (environmental stress crack resistance) ASTM D- The 638 type 1 dumbbell was given a deflection of 50 mm, fixed to a jig, coated with ethylene glycol monoethyl ether, and the time until breakage was expressed in minutes when left at 23 ° C at a temperature. In the table,> 300 indicates that no fracture occurs after 300 minutes.

(5) Gloss Pellets are injection-molded using an IS-80CN-V injection molding machine manufactured by Toshiba Machine Co., Ltd. to prepare a 50 × 85 × 3 mm flat plate molded product. The gate shape is a tab gate.

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

(6) Layered peeling property and flow mark 20 × 80 × with IS-80CN-V injection molding machine manufactured by Toshiba Machine Co., Ltd.
Create a 3 mm strip shaped product. Gecht is located in the center of the piece with a length of 20 mm, the gate shape is 2 mm in the length direction of the molded product,
It is an edge gate with a length of 2 mm and a rectangular cross section with a thickness of 1.5 mm. The mold has four cavities.

When the gate portion of the obtained molded product was manually broken, layer-like peeling might occur near the gate, and the degree of peeling was evaluated in the following manner in comparison with a standard sample.

Further, a fan-shaped flow mark may be generated in the vicinity of the gate of the obtained molded product. Some of the flow marks were compared with the standard sample, and the same evaluation as the layered peeling was performed as follows.

A: Not recognized at all B: Little recognized C: Quite recognized D: Remarkably recognized In addition, Rank AB indicates that it is located between Rank A and Rank B.

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

Molding machine: Kawaguchi Ironworks Co., Ltd. Kawaguchi Churchill 1040S Mold: Archimedean circle having a cross section obtained by halving an ellipse with a major axis of 5.0 mm and a minor axis of 4.6 mm along the major axis.

Molding condition: Injection pressure: 50 kg / cm ² G Cylinder temperature: 250 ° C. or 280 ° C. Mold temperature: 40 ° C. Measuring method and evaluation: The distance from the gate part of the molded product to less than free flow was measured. The larger the flow length, the better the flowability.

Numbers 1 to 20 are examples, and numbers 21 to 26 are comparative examples.

In Experiment No. 25, the glass transition temperature of the component (C) deviates from the scope of the present invention, but the polymer composition obtained by mixing and precipitating the component (C) emulsion and the component (B) emulsion Since the solid of the substance D does not become a powder at room temperature but has a lump form, an operational disadvantage is caused, for example, in the dehydration process of the precipitate, the washing process, the drying process, or the mixing process with the rubber-containing styrene meter resin.

In the experiments other than the experiment No. 25, the solid of the polymer composition D was in the form of powder and no operational trouble occurred.

As is clear from the comparative examples, when the glass transition temperature of the component (C) deviates from the range of the present invention, heat resistance or operability during production is poor, and the gel content of the component (C) falls within the range of the present invention. If it deviates, it is inferior in gloss and both are not preferable. Further, if the solubility parameter, gel content or glass transition temperature of the component (B) deviates from the scope of the present invention, the environmental stress crack resistance becomes poor and a layered structure is obtained unless the monomer represented by the general formula I is copolymerized. Peelability is inferior, which is not preferable.

Example 2 and Comparative Example 2 The B-2 emulsion and the C-1 emulsion produced in Example 1 were mixed in the emulsion state at the ratios shown in Table 7 (the parts in the table are solid contents of the polymer). Represents the department as). Further, 7 parts of a 10% aqueous solution of Pluronic F-68 used in Example 1 was added to 100 parts of the solid content of the polymer mixture.

The obtained mixed liquid emulsion was subjected to a precipitation treatment in the same manner as in Example 1 to obtain polymer compositions D-1 to D-5.

Then, the ABS resin powder (A-1) used in Example 1, A
S resin powder (A-6), sorbitan stearate, and mark 1500 were blended with polymer compositions D-1 to D-5 in the following proportions to form pellets.

ABS resin powder (A-1) 34 parts AS resin powder (A-6) 50 parts Sorbitan stearate 4 parts Mark 1500 0.2 parts Polymer composition D 16 parts Physical properties of the obtained pellets were evaluated in the same manner as in Example 1. The results are shown in Table 8.

As is clear from Comparative Example 2, (B) in the polymer composition D
If the component content deviates from the lower limit of the range of the present invention, the environmental stress crack resistance is inferior, and if it deviates from the upper limit, the layered peeling property or the flow mark becomes remarkable, both of which are not preferable.

Example 3 and Comparative Example 3 50 parts of B-2 emulsion (as polymer solids) and 50 parts of C-1 emulsion (as polymer solids) prepared in Example 1.
And are mixed in an emulsion state, and then Pluronic F-68 10
% Aqueous solution was added 7 parts.

The obtained mixed emulsion was subjected to a precipitation treatment in the same manner as in Example 1 to obtain a polymer composition D powder.

Then, the polymer composition D was supplied to a VC-40 type extruder manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

Separately, the component (A) having the composition shown in Table 1 was mixed with the composition shown in Table 10 and supplied to a VC-40 type extruder to obtain pellets of the rubber-containing styrenic resins E-1 to E-7. It was

Then, the pellets of the polymer composition D and the pellets of the rubber-containing styrenic resins E-1 to E-7 were mixed at the ratio shown in Table 11, and were supplied to a VC-40 type extruder and kneaded to form pellets. Got

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

The spiral flow measurement was carried out at a cylinder temperature of 280 ° C. for experiment numbers 37, 38, 50 and 51 and 260 ° C. for other samples.

Experiment numbers 32-43 in Table 11 are examples, and experiment numbers 44-51.
Is a comparative example.

Comparing Experiment Nos. 32 to 38 with Experiment Nos. 45 to 51, the composition according to the production method of the present invention was excellent in the environmental stress crack resistance regardless of the type of the rubber-containing styrene resin, and had a layered peeling property. It can be seen that the phenomenon or flow mark does not occur.

Further, by comparing Experiment Nos. 39 to 45, when the compounding ratio of the polymer composition D and the rubber-containing styrene resin deviates from the scope of the present invention, the environmental stress crack resistance or the resistance to resistance of the obtained composition is increased. It can be seen that it is inferior in impact resistance.

Example 4 and Comparative Example 4 80 parts of an ABS resin emulsion obtained by graft-polymerizing 42 parts of styrene and 18 parts of acrylonitrile in the presence of 40 parts of polybutadiene latex (as solid content of polymer),
After mixing 20 parts of B-2 or B-16 emulsion (as a solid content of the polymer) in an emulsion state, the mixed emulsion is poured into an aqueous solution containing 6 parts of calcium chloride, and the mixture is heated at 95 ° C. A polymer slurry was obtained by stirring.

40 parts of the powder obtained by filtering, washing and drying the slurry was mixed with 60 parts of A-6 powder used in Example 1, 2 parts of ethylenebisstearylamide and 0.2 part of Mark 1500 in a Henschel mixer, and the extruder was used. To obtain pellets.

Physical properties were evaluated using the pellets, and the results are shown in Table 12.
Summarized in.

Comparing Example 4 with Comparative Example 4, it can be seen that the layered peelability is improved by copolymerizing the monomer represented by the general formula I with the component (B).

〔The invention's effect〕

As described above, the thermoplastic resin composition provided by the present invention is excellent in environmental stress crack resistance and has a remarkable effect that the layered delamination phenomenon does not occur in the obtained molded product. .

Claims (2)

[Claims] 1. A dispersed phase comprising a rubber component, and a continuous phase comprising a resin component containing an aromatic vinyl monomer residue and having a glass transition temperature higher than 20 ° C., and the dispersed phase and the continuous phase. 100 parts by weight of a rubber-containing styrenic resin (A) containing a covalent bond of a rubber component and a resin component at the interface, 50 to 99.9% by weight of an acrylic acid ester monomer residue, the following general formula I: [Wherein R ₁ is H or CH ₃ group, R ₂ is the same or different, and is H or C
H ₃ group, R ₃ is CmH ₂ m ₊₁ group (m is an integer of 0 or more) or Group (n is an integer of 0 or more), l represents an integer of 2 or more] from 0.1 to 20% by weight of the monomer residue and from 0 to 50% by weight of the other copolymerizable monomer residue Thus, the solubility parameter is 8.4 to 9.8 (cal / cc) ^1/2 , the glass transition temperature is 20 ° C or lower, and the gel content is 70% by weight or less (B) 1 to 50% by weight And a polymer having no aromatic vinyl monomer residue and a glass transition temperature of 20 ° C.
Polymer (C) 0 having a higher gel content of 10% or less and a solubility parameter of 9.0 to 11.0 (cal / cc) ^1/2
A thermoplastic resin composition containing 50 to 50 parts by weight. 2. A dispersed phase comprising a rubber component and a continuous phase comprising a resin component containing an aromatic vinyl monomer residue and having a glass transition temperature higher than 20 ° C., and the dispersed phase and the continuous phase. 100 parts by weight of a rubber-containing styrenic resin (A) containing a covalent bond of a rubber component and a resin component at the interface, 50 to 99.9% by weight of an acrylic acid ester monomer residue, the following general formula I: [Wherein R ₁ is H or CH ₃ group, R ₂ is the same or different, and is H or C
H ₃ group, R ₃ is CmH ₂ m ₊₁ group (m is an integer of 0 or more) or Group (n is an integer of 0 or more), l represents an integer of 2 or more] from 0.1 to 20% by weight of the monomer residue and from 0 to 50% by weight of the other copolymerizable monomer residue Thus, the solubility parameter is 8.4 to 9.8 (cal / cc) ^1/2 , the glass transition temperature is 20 ° C or lower, and the gel content is 70% by weight or less. And a polymer having no aromatic vinyl monomer residue and a glass transition temperature of 20 ° C.
Polymer (C) 0 having a higher gel content of 10% or less and a solubility parameter of 9.0 to 11.0 (cal / cc) ^1/2
In producing a thermoplastic resin composition containing 50 to 50 parts by weight, 10 to 80% by weight of the emulsion of the component (B) polymer (as the solid content of the polymer) and the emulsion of the component (C) polymer and And / or a partial emulsion of the resin component constituting the component (A) 20 to 90
A thermoplastic resin composition, characterized in that a polymer composition D obtained by separating the polymer by mixing in an emulsion state by weight% (as the solid content of the polymer) is mixed with the component (A). Manufacturing method.