JPS62151441A - Polymer composition - Google Patents

Abstract

PURPOSE:The titled composition which is added to a rubber-containing styrenic resin to improved environmental stress cracking resistance, etc., obtained by blending an emulsified solution of a specific polymer of vinyl monomer with an emulsified solution of a (co)polymer of an acrylic acid ester and separating the polymers. CONSTITUTION:(A) 20-90wt% (calculated as solid content of polymer) emulsified solution of a polymer of a vinyl monomer, having >=20 deg.C glass transition temperature, <=10% gel content, 8-11(cal/cc)<1/2> solubility parameter and >=2X10<5> weight-average molecular weight of polystyrene base is blended with (B) 10-80wt% emulsified solution of a (co)polymer of an acrylic ester nomomer, having <=20 deg.C glass transition temperature, <=70% gel content and 8.4-9.8(cal/cc)<1/2> solubility parameter and the polymers are separated.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polymer composition that provides a thermoplastic resin composition that has excellent environmental stress cracking resistance and also has an improved surface condition of molded articles.

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

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

Factors that influence the environmental stress cracking properties of rubber-containing styrenic resins are 1) the content of the rubber component, 1) the molecular weight of the resin component, and iii) the composition of the nail fat component, respectively. ) Increasing the content of the rubber component, 11) Increasing the molecular weight of the resin component, iii)! The melt viscosity of the resin component can be increased by increasing the absolute value of the difference between the solubility parameter of the fat component and the solubility parameter of the drug, or by introducing bulky substituents into the polymer chains that make up the resin component. Although the methods are known, the effect of improving environmental stress cracking resistance is insufficient for practical use.

By the way, the present inventors have discovered that by mixing an acrylic ester polymer with a rubber-containing styrene resin,
It has been reported that the environmental stress cracking resistance of rubber-containing styrenic resins is dramatically improved (Japanese Patent Laid-Open No. 58-179).
No. 257).

However, although the composition of the invention has a remarkable effect of improving environmental stress cracking resistance, poor phenomena are sometimes observed in the surface condition of injection molded products, and improvements have been required.

That is, when the composition of the invention is subjected to injection molding, a mica-like layered peeling phenomenon may be observed near the gate of the molded product, or an abnormal surface called a flow mark may be observed near the gate. This caused serious damage to the design of the molded product.

These poor surface conditions are caused by the acrylic ester polymer particles dispersed in the rubber-containing styrene resin.
It is thought that this occurs due to flattening deformation due to shear core force during injection molding, and the appearance of the defective phenomenon is particularly noticeable when using a rubber-containing styrene resin with a high melt viscosity.

In order to prevent flattening of the acrylic ester polymer particles, it is effective to copolymerize a polyfunctional vinyl monomer during polymerization of the acrylic ester polymer.

(Problems to be Solved by the Invention) However, in the case of acrylic ester polymers obtained by copolymerizing polyfunctional vinyl monomers such as divinylbenzene and ethylene glycol dimethacrylate, poor surface conditions may occur. Although improvements have been achieved, the gel content is high and the effect of improving the environmental stress cracking properties of rubber-containing styrenic resins is insufficient. Therefore, by using a polyfunctional vinyl monomer and a chain transfer agent together to produce an acrylic ester polymer with a low gel content and a branched structure, it has excellent environmental stress cracking resistance. Although it is possible to produce a composition that gives a molded product with suppressed surface defects, the effect is unsatisfactory in practical terms.

An object of the present invention is to provide a thermoplastic resin composition that improves the drawbacks of the prior art described above.

(Means for Solving the Problems) To summarize the present invention, the present invention relates to a polymer composition, (A> a polymer of vinyl monomers, the glass transition temperature of which is 20 ℃, the gel content is 10% or less, and the solubility parameter is 8.0-11.0 (ca f
! /cc) "" and the weight average molecular type based on polystyrene is 2 x 10' or more [(A
20 to 90% by weight (in solid content of the polymer) of an emulsion of (B) a homopolymer or copolymer of an acrylic ester monomer, or a single acrylic ester and others. A copolymer of copolymerizable monomers, whose glass transition temperature is 20°C or less, and whose gel content is 70% or less,
and the solubility parameter is 8, 4 to 9.8 (ca 1
/cc) "10 to 80% by weight (as the solid content of the polymer) of the emulsion of the polymer 2 [component polymer (B)] is mixed in an emulsion state, and then the polymer is separated. It is characterized by being a polymer composition.

The polymer composition of the present invention, when mixed with a rubber-containing styrenic resin, improves its environmental stress cracking resistance, and is less likely to cause defects in molded products such as delamination and flow marks.

Examples of vinyl monomers constituting the (A> component polymer of the present invention) include aromatic vinyl 1it bodies such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, cyanostyrene, and chlorostyrene; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, tenru acrylate, octadecyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, Acrylic acid ester monomers such as cidyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl acrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl acrylate, hydroquine ethyl methacrylate, methquin ethyl methacrylate, Methacrylic acid ester monomers such as glycidyl methacrylate and phenyl methacrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, and itaconic acid, vinyl chloride, vinylidene chloride, etc. vinyl halides, fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate, and vinyl octadecanoate, olefins such as ethylene, propylene, 1-butene, imbutylene, and 2-butene. Monomer, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
Maleimide monomers such as N-cyclohexynelumaleimide, N-phenylmaleimide, N-tolylmaleimide, acid anhydride monomers such as maleic anhydride, butadiene,
Conjugated diene II forms such as isoprene and chloroprene, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl Vinyl ketone monomers such as vinyl ketone and phenyl vinyl ketone, vinyl pyridine, etc. (but not limited to these).

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 incyanurate, trimethylolpropane tri(meth)acrylate, allyl(meth)acrylate, vinyl methacrylate, 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, Tetrade Ethylene glycol di(meth)acrylate, Eicosaethylene glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, Pentapropylene glycol di(meth)acrylate, Nonapropylene glycol di(meth)acrylate, Tetrade Power propylene glycol di(meth)
Acrylate, eicosapropylene glycol di(meth)acrylate, 1,6-hexyl diol di(meth)
There are acrylates, etc. Here, for example, ethylene glycol di(meth)acrylate means ethylene glycol diacrylate or ethylene glycol dimethacrylate.

The (A) component polymer of the present invention has a glass transition temperature of 20°C.
It is necessary to exceed the A more preferable glass transition temperature is 30°C or higher. When the glass transition temperature of the (A) component polymer is 20°C or less, the (A) component polymer and (B)
It is industrially disadvantageous because it is difficult to handle the polymer composition formed by mixing the component polymers as a fence or pellets, and it is also difficult to handle the polymer composition formed by mixing the component polymers with the rubber-containing styrenic resin.
This is not preferable because it greatly reduces its heat resistance.

The (Δ) component polymer of the present invention is 8.0 to 11,0 (ca
It is necessary to have a solubility parameter in the range of 1/CC) 1/2, and a more preferable range is 8.5 to 1/2.
O,5 (ca e /cc) ''.In a polymer composition formed by mixing component polymer (A) with a polymer component (B) whose solubility haramometer is outside the range of the present invention, Surface defects such as delamination and flow marks appear in molded products of the composition obtained by mixing the composition with a rubber-containing styrene resin, which is undesirable.

In addition, the solubility parameter referred to in this specification refers to the solubility parameter described by Brandrup (J) and HlImmergut (ε), published by John Wiley & Sons, New York City, 1975.
Group, Polymer Handbook (Polymer) Ian
dbook) 2nd edition ■-337 to ■359 pages, the solubility parameter δ of the copolymer is determined by the individual vinyl monomers constituting the copolymer consisting of m types of vinyl monomers. solubility parameter δ of the polymer homopolymer. It is calculated from the following formula (2) and its weight fraction W, .

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are each 8.8 (can
/cc) "2.9.4. (ca R/cc) "2
Then, the solubility parameter of a copolymer consisting of 70% by weight of butyl polyacrylate and 30% by weight of ethyl polyacrylate is calculated to be 9.0 (ca f!/cc).

The component (A) polymer of the present invention needs to have a weight average molecular weight of 2 x 105 or more based on polystyrene. When the weight average molecular weight of the component polymer (A) is less than 2 x 105 based on polystyrene standards, the polymer composition obtained by mixing the component polymer (Δ) with the component polymer (B) is a rubber-containing styrene polymer. Surface defects such as delamination and flow marks appear in molded products of the composition obtained by mixing the composition with the system fat, which is undesirable.

In this specification, the weight average molecular weight based on polystyrene is the weight ratio/average molecular weight determined by gel permeation chromatography, assuming that the component polymer (A>) is polystyrene. 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 (Δ) component polymer is measured, the molecular weight is determined from the outflow volume using the calibration curve, and the weight average molecular weight is calculated according to a conventional method.

The polymer component (A) of the present invention needs to have a gel content of 10% or less. The gel content as used in the present invention refers to approximately 1.0 g of (A) component polymer (accurately weighed as Sog), placed in a cage made of 400 mesh stainless wire mesh, and added to 100 g of methyl ethyl ketone. The weight of (A>component polymer insoluble matter, ls+g) is measured, and then calculated according to the following formula H.

(S, /So) X100 (%) ... [■]
<If the gel content of component polymer A) exceeds 10%, a polymer composition obtained by mixing component polymer (A) with component polymer (B) may be mixed with rubber-containing styrenic resin. The resulting molded product has poor gloss, which is undesirable.

There is no particular restriction on the method for producing the component polymer (A) of the present invention, and any known technique such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be applied, but production by emulsion polymerization is industrially preferable. most advantageous.

One reason is that in the present invention, in the emulsion state (Δ
This is because the component polymer () and the component (B) polymer are mixed, and another reason is that emulsion polymerization allows industrially easy production of high molecular weight polymers.

In producing the (A) component polymer of the present invention, the vinyl monomer is selected so that the glass transition temperature, gel content, solubility parameter, and weight average molecular weight of the obtained (Δ) component polymer are in accordance with the present invention. It is optional as long as it satisfies the provisions of.

It is possible to use a chain transfer agent for the purpose of controlling the molecular weight of the component polymer (A). In particular, when copolymerizing polyfunctional vinyl monomers, a chain transfer agent is used in combination to create a branched structure and a low gel content (A
> component polymers can be produced.

There are no particular restrictions on the chain transfer agent that can be used, and examples include sulfur compounds such as octylmercaptandodenlumerbutane, thioglycolic acid, ethyl thioglycolate, butyl thioglycolate, ethyl mercaptobenzoate, l-naphthyl disulfide, and sulfur. , halogen compounds such as carbon tetrabromide, hydrocarbons such as limonene and terpinolene, nitro compounds such as trinitrophenol and trinitrobenzene,
Examples include pentuquinone.

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, specific examples of the acrylic ester monomer include the acrylic ester monomer (
This is similar to this example. Further, specific examples of the copolymerizable monomers constituting the component polymer (B) include the monomers listed above as examples of the vinyl spinning wheel bodies constituting the component polymer (A).
This is the same as the specific example except for the acrylic acid ester monomer.

Further, the (B) 5i-minute polymer of the present invention may use a polyfunctional vinyl monomer or a chain transfer agent during its polymerization, and specific examples of the polyfunctional vinyl monomer and chain transfer agent include: Each is the same as the specific example listed above for component (A) polymer.

The (B) component polymer of the present invention has a glass transition temperature of 20°C.
It is necessary that the following is true. A more preferable glass transition temperature is 10°C or lower. If the glass transition temperature of the (B) component polymer exceeds 20°C, the (B) component polymer
A composition obtained by mixing a polymer composition mixed with a component polymer with a rubber-containing styrenic fat has poor environmental stress cracking resistance, which is not preferable.

The component (B) polymer of the present invention needs to have a gel content of 70% or less. To measure the gel content, replace the solvent with 100g of methyl ethyl ketone,
It is the same as that of the component polymer (A) except that toluene is used, and it is calculated according to the above-mentioned formula (2). A composition obtained by mixing a polymer composition obtained by mixing a (B) component polymer having a gel content of more than 70% with a component polymer (A) in an emulsified liquid state, and mixing a rubber component with a styrene resin. When used as a material, the environmental stress cracking resistance is poor and undesirable.

The component (B) polymer of the present invention is 8.4 to 9.8 (ca.
It is necessary to have a solubility parameter in the range of R/cc). A more preferable numerical range is 8.
．． 6-9. 6 (cal/cc) ”2.

The method for determining the solubility parameter is the same as that for the component polymer (A), and is calculated according to Formula I above.

(B) The solubility parameter of the component polymer is 8.4 (ca
f! /cc) ”' or less than 9.8 (caβ/
cc) If the amount exceeds 1/2, the (B) component polymer is converted into (A)
A composition obtained by mixing a polymer composition formed by mixing the component polymer with a rubber-containing styrenic resin has poor environmental stress cracking resistance, which is not preferable.

There are no particular restrictions on the method for producing component polymer (B), and any known techniques such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be applied, but production by emulsion polymerization is industrially most advantageous. It is.

When producing component polymer (B), the selection of acrylic ester monomer or copolymerizable monomer is determined based on the glass transition temperature, gel content, and The solubility parameter is arbitrary as long as it satisfies the provisions of the present invention.

In the present invention, 20 to 90% by weight of (A) component polymer and (B)
10 to 80% by weight of the component polymer (B) are mixed in an emulsion state to form a polymer composition, but if the content of the component polymer (B) is less than 10% by weight, the polymer composition A composition prepared by mixing a rubber-containing styrenic fat with a rubber-containing styrenic fat has poor environmental stress cracking resistance, and when the amount exceeds 80% by weight, surface defects such as delamination phenomenon and flow marks may occur in molded products made of the composition. Unfavorable phenomena occur.

In the present invention, an emulsion of the (A>component polymer) and an emulsion of the (B) component polymer are mixed in an emulsion state.

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

There is no particular restriction on the method of emulsifying the polymer, and any known technique can be applied. For example, a method in which a polymer solution is mixed and stirred with an emulsifier and water to form an emulsion and then the solvent is removed; a fine powder obtained by crushing a polymer is mixed and stirred together with an emulsifier and water to form an emulsion; Methods include, but are not limited to, pulverizing a polymer in the presence of an emulsifier and water to obtain an emulsion.

Although there is no particular restriction on the particle size of the polymer in the emulsion of component (A) or component (B), it is preferable that the area average particle size is 5 μm or less. Here, the area average particle diameter is calculated according to the following formula (2) by taking an electron micrograph of the emulsion and setting the fraction of the particle diameter where the particle diameter is dl as fl.

Σf, d, 3/Σf, d,'... [II[] In particular, when the area average particle diameter of the (B) component polymer exceeds 5μ, the (B) component polymer is replaced with the (A) component polymer. Layer peeling phenomenon or flow marks may occur in a molded product obtained by mixing a polymer composition obtained by mixing 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,
The surfactant may be arbitrarily selected from amphoteric surfactants and nonionic surfactants, but anionic surfactants can be used most advantageously.

There are no particular restrictions on the method of mixing component (A) component polymer emulsion and (B) component polymer emulsion, and devices such as a fixed container type mixing device, a rotating container type mixing device, a pipeline mixer, a static mixer, etc. are used. Mixing can be done by

There is no particular restriction on the method for separating the polymer composition from the mixed emulsion of the component polymer emulsion (A) and the component polymer emulsion (B). acid,
Sodium chloride, calcium chloride, aluminum chloride,
Methods of adding precipitating agents such as electrolytes such as sodium sulfate and magnesium sulfate, polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymers, and aqueous polymers such as carboxin methyl cellulose, and emulsification by freezing the emulsified liquid. Examples include a method of destroying the emulsion and a method of spraying an emulsion into a high-temperature gas.

The polymer composition separated from the mixture of the (A) component polymer emulsion and the (B) component polymer emulsion can be further supplied to a melt-kneading device for melt-kneading. Melting and kneading equipment that can be used include Totoeva, Banbury mixer,
There are intensive mixers, mix routers, co-kneaders, extruders, rolls, etc. It is also possible to use a melt-kneading device with a dehydration mechanism disclosed in Japanese Patent Publication No. 59-37021, but when using this device, the emulsion and precipitating agent must be continuously supplied to the device. It is also possible to continuously perform mixing, demulsification, dehydration, drying, and melt-kneading in the same device.

The polymer composition of the present invention is particularly useful practically when used in combination with a rubber-containing styrenic resin. The absolute value Δ5P=IsPΔ−5PMI of the difference between the parameter SPA and the solubility parameter SPM of the resin component of the rubber-containing styrenic resin to be mixed is 1. O(ca (
i /ccν/2 or less, more preferably 0.5 (ca
It is preferable that it is 12 /ccv/2 or less. ΔSP
is 1. If O (ca R/cc) exceeds 2, the thermoplastic resin molded product obtained by mixing the polymer composition of the present invention and the rubber-containing styrenic resin may show surface delamination phenomena or flow marks. Defect phenomena may appear.

For example, if the rubber-containing styrenic resin is a high-impact polystyrene resin manufactured by polymerizing styrene in the presence of polybucundiene, the resin component of the rubber-containing styrenic resin is polystyrene, and SPM=9.1 (
caβ/c c ) l/2, so SPA
is preferably 8.1 to 10.1 (ca R/CC).

The rubber-containing styrenic resin mixed with the polymer composition of the present invention refers to a layer of thermoplastic resin consisting of a rubber component, a resin component, and a covalent bond of the rubber component and the resin component. The essential constituent units of the components are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, cyanostyrene, and chlorostyrene. Specifically, high-impact polystyrene (butadiene-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, and heat-resistant BS
(acrylonitrile-butadiene-styrene-α-methylstyrene) resin, AAS (acrylonitrile-acrylic acid ester-styrene) resin, AES (acrylonitrile-EPDM-styrene) resin, MBAS (methyl methacrylate-butadiene-acrylonitrile-
Styrene) resin, etc.

Furthermore, it is known that a rubber-containing styrene-based sealant is used in combination with a different type of sealant such as a polycarbonate-based resin or a polyvinyl chloride (styrene-based sealant). (Rubber-containing styrene resin mixed with sealant can be used.

When mixing a rubber-containing styrene type (sealing resin) into the polymer composition of the present invention, after mixing the (A> component polymer and the (B) component polymer in an emulsion state, )
A mixture of the component polymer and the (B) component polymer is separated, and a rubber-containing styrenic resin is mixed into the separated polymer composition. Examples of embodiments of mixing the polymer composition and the rubber-containing styrenic resin include, for example, mixing the dried polymer composition of the present invention and the rubber-containing styrenic resin, or mixing the undried polymer composition separated from the emulsion. For example, there is a method of introducing the polymer composition of the present invention together with a rubber-containing styrenic resin into a melt-kneading apparatus, kneading and drying.

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

All parts and percentages listed in each example are based on heavy machinery standards.

Example 1 and Comparative Example 1 [Production of (Δ) component-Production of A-1 to A-19] Pure water 1
50 parts of potassium stearate and 2 parts of potassium stearate were placed in an autoclave and heated to 50° C. while stirring. Here,
Ferrous sulfate heptahydrate 0.005 part, ethylenediamine 4
0.01 parts of tetrasodium acetate dihydrate and 0.3 parts of IJ formaldehyde sulfoxylate dihydrate
An aqueous solution prepared by dissolving 1 part in 10 parts of pure water was added.

Next, 100 parts of the monomer mixture having the composition shown in Table 1 was added to 4
It was added continuously over time. At the same time, potassium persulfate 0.
An aqueous solution of 0.05 parts dissolved in 25 parts of pure water was continuously added over 6 hours.

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

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

[Production of component (A) - 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 inch of potassium persulfate in 10 parts of pure water was added thereto, and 100 parts of a monomer mixture having the composition shown in Table 1 was added continuously over 4 hours.

After the addition of the monomer mixture was completed, 0.1 part of lauroyl peroxide was added, and the 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,
Charge 2 parts of potassium stearate into an autoclave,
The mixture was heated to 50° C. with stirring. Here, sulfuric acid No.
0.005 part of iron heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate! , and 0.3 parts of sodium formaldehyde sulfoxylate dihydrate in 1 part of pure water.
An aqueous solution of 01 was added.

Next, a mixture of 0.2 parts of diisopropylbenzene hydroperoxide dissolved in 100 parts of a monomer mixture having the composition shown in Table 1 was continuously added over 5 hours.

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

The properties of the obtained (A>component) are shown in Table 2.

[Structure of component (B) - excluding B-15 and B-27] 120 parts of pure water, 2 parts of sodium dodecylbenzenesulfonate
Place the sample in an autoclave and heat to 65°C while stirring.
heated to. Here, 0.005 part of ferrous sulfate heptahydrate, 0.0 part of ethylenediaminetetraacetic acid tetrasodium dihydrate
An aqueous solution prepared by dissolving 1 part of sodium formaldehyde sulfoxylate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added.

Next, 2 parts of 100 parts of the monomer mixture having the composition shown in Table 3 was added.
Pour 0% into the autoclave and add 0.2% potassium persulfate.
% aqueous solution was added to initiate polymerization.

Simultaneously with the start of polymerization, the remaining amount of the monomer mixture was continuously added over 4 hours. In addition, at the same time as the start of polymerization, 6 parts of an aqueous solution of 0.05 parts of potassium persulfate dissolved in 20 parts of pure water was added.
It was added continuously over time. After the addition of the potassium persulfate solution was completed, the contents of the autoclave were cooled to terminate the polymerization.

Table 4 shows the properties of the obtained component (B).

[Structure of component (B) - Production of B-15 and B-27] 140 parts of pure water, 2 parts of sodium dodecylbenzenesulfonate
Place the sample in an autoclave and heat to 70°C while stirring.
heated to.

An aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 10 parts of pure water was added thereto, and 100 parts of a monomer mixture having the composition shown in Table 3 was added continuously over a period of 4 hours.

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

Table 4 shows the properties of the obtained component (B).

The abbreviations of the long chain bifunctional monobonds used in Table 3 are as follows.

9G: Nonaethylene glycol dimethacrylate 14G; Tetradecaethylene glycol dimethacrylate 9PG; Nonapropylene glycol dimethacrylate 9ΔG; Nonaethylene glycol diacrylate [mixture of component (to 1) and component (B)] (A > component emulsion 50 (as the solid content of the polymer) and 50 parts of the emulsion of component (B) (as the solid content of the polymer) are mixed in the form of an emulsion, and then the polyethylene glycol-polypropylene glycol blotta copolymer is added to the total molecule. The weight fraction of ethylene oxide was 80%, and 0.7 part of a 10% aqueous solution of polypropylene glycol molecules 1175 (Pluronic F-68' manufactured by Asahi Denka Kogyo Co., Ltd.) was added.

An aqueous solution prepared by dissolving 5 parts of calcium chloride dihydrate in 400 parts of pure water was heated to 80 to 95°C, and the mixed emulsion was poured into the solution while stirring to precipitate.

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

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

(1) Glass transition temperature The solid obtained by dropping the emulsion of component (A) or component (B) into methanol is dried and measured using a DuPont type measuring device.
It was measured using a 10 differential scanning calorimeter and a 990 thermal analyzer.

(2) Gel content The emulsion of component (A) or component (B) was dropped into methanol, and the solid was dried after 1 fathom. Approximately 1.0 g of the weight was accurately weighed, measured using the method described above, and calculated using formula (2). However, the solvents used for component (A) and (B) were different; methyl ethyl ketone was used for component (A) III, and toluene was used for component (B).

(3) Solubility parameter The solubility parameter value C unit of each polymer used to calculate the solubility parameter on each side is (cal / cc)
”') is as follows.

Polybutyl acrylate; 8,8 polyethyl acrylate; 9.4 polymethyl methacrylate
;9.5 polyacrylonitrile ;12.5
Polystyrene; 9.1 Polyvinyltoluene; 8.9 Poly(t-butylstyrene);
7.9 (4) Weight average molecule l Manufactured by Toyo Soda Kogyo Co., Ltd.) (For LC-802A gel permeation chromatography, manufactured by the same company) 4H-6
Measurement was carried out using two type columns 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 when using a wooden neck is 6
X I Q', and samples exceeding 6X105 correspond to Table 2 (6 is written on the leap line).

The sample was obtained by precipitating the emulsion of component (A) with methanol.
etc. A solid was used.

Table 4 Table 4 Application example 1 and reference example 1 30 parts of HeBS resin powder consisting of 50% polybutadiene, 13% acrylonitrile, and 37% styrene, Astit resin powder consisting of 30% acrylonitrile, and 70% styrene (weight average molecular weight based on polystyrene) 1.lX105
) 54 parts, and 0.2 parts of 4,4'-isopropylidene bis[monophenyl-dialkyl<C,2-C15) phosphite] [manufactured by Adeka Argus Chemical Co., Ltd., mark (MΔRK) 1500]. , Example 1 or Comparative Example 10 was mixed with 16 parts of the polymer composition in a Henschel mixer, and mixed with VC-40 manufactured by Chuo Kijo Seisakusho Co., Ltd.
(Vented insect cob extruder) to produce pellets of 1st grade.

Molded products were prepared using the pellets prepared in the above manner, and their physical properties were evaluated, and the results are shown in Table 5, Experiment Nos. 1 to 49.

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

(1) Tensile yield point...ΔSTM ll-638 (2
) Izot impact strength...ΔSTM D-25
6 (3) Vicat softening temperature...JIS K-6
870(4) Chemical resistance (environmental stress cracking resistance) ΔST
MD-638 Type I dumbbell is given a deflection of 50 mm, fixed to a jig, coated with ethylene glycol monoethyl ether, and left at a temperature of 123°C. The time until breakage is expressed in minutes. >300 in the table means 30
Indicates that it does not break after 0 minutes.

(5) The glossy pellets were injection molded using an IS-80CN-V injection molding machine manufactured by Toshiba Machine Co., Ltd. to a size of 50 x 35 x 3 m.
A flat molded product of m is created. The gate shape is a tab gate.

The resulting molded product was subjected to a single gloss measurement using a digital variable angle gloss meter model UGV-4D manufactured by Suga Test Instruments Co., Ltd. at an incident angle of 60 degrees.

(6) A rectangular molded product of 20 x 80 x 3 n+n+ is produced using a layered peeling machine and a Flowmark IS-80CN-V injection molding machine manufactured by Toshiba Machinery Co., Ltd. The gate is located in the center of one side with a length of 20 mm.
The gate shape is 2mm in the length direction of the molded product and 1.5mm in the thickness direction.
It is an ezodigate with a length of 2 mm and a rectangular cross section of mm. The mold has four cavities.

When the gate portion of the obtained molded product was folded in half, the area around the gate sometimes showed layered peeling, and the degree of peeling was evaluated as follows in comparison with a standard sample.

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

Δ: Not observed at all B: Slightly observed C: Significantly observed D: Significantly observed Rank ΔB indicates that it is located between rank A and rank B.

Numbers 1 to 41 are application examples, and numbers 42 to 49 are reference examples.

Reference Example 42 is a polymer composition obtained by mixing and precipitating the (A) component emulsion and (B) component emulsion, although the glass transition temperature of the (A) component is outside the range of the present invention. Since the solid material does not form a powder at room temperature but takes the form of a lump, it poses operational disadvantages, for example, in the dehydration of the precipitate, the washing process, the drying process, or the mixing process with a rubber-containing styrenic resin.

In experiments other than Reference Example 42, the polymer composition solids had a powder-like appearance, and no operational problems occurred.

As is clear from the reference examples, when the weight average molecular structure or solubility parameter of component (A) deviates from the range of the present invention, delamination phenomena or flow marks become noticeable.
If the glass transition temperature of component (A) deviates from the range of the present invention, heat resistance or operability during manufacturing will be poor, and if the gel content of component (A) deviates from the range of the present invention, gloss will be poor, both of which are undesirable. . Furthermore, if the solubility parameter, gel content, or glass transition temperature of component (B) deviates from the range of the present invention, the environmental stress cracking resistance will be poor, which is not preferable.

Example 2 and Comparative Example 2 The A-1 emulsion and the B-3 emulsion produced in Example 1 were mixed in the emulsion state at the proportions shown in Table 6. The parts in the table indicate the polymer solids. ).

Furthermore, 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 emulsion was subjected to precipitation treatment in the same manner as in Example 1 to obtain polymer compositions A-H.

Application Example 2 and Reference Example 2 The polymer composition prepared in Example 2 or Comparative Example 2 was
It was mixed with the AB S resin powder, AS resin powder, and Mark 1500 used in Application Example 1 to form pellets.

ABS resin powder, A S +M resin powder, mark 1500
, and Example 2 or Comparative Example 2 (Table 7 shows the blending ratios of the polymer compositions).

The physical properties of the obtained pellets were evaluated in the same manner as in Application Example 1, and the results are shown in Table 7.

Table 6 As is clear from Reference Example 2, if the content of component (B) in the polymer composition exceeds the lower limit of the range of the present invention, the environmental stress cracking resistance will be poor, and if it exceeds the upper limit, the delamination property or Flow marks become noticeable, both of which are unfavorable.

Example 3 50 parts of the A-1 emulsion produced in Example 1 (as the solid content of the polymer) and 50 parts of the B-3 emulsion (as the solid content of the polymer) were mixed in an emulsion state, and further Pluronic F-6
7 parts of a 10% aqueous solution of No. 8 were added.

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

Next, the polymer composition was fed to a VC-40 extruder manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

Application Example 3 and Reference Example 3 Polymers C-1 to C-8 whose compositions are shown in Table 8 are mixed in the formulation shown in Table 9, and fed to a VC-40 extruder to produce a rubber-containing styrenic tH = D-i to D-9 pellets were obtained.

In addition, C-1 and C-6 are the ABS used in Application Example 1, respectively.
resin and AS resin.

Moreover, PvC described in Table 9 is polyvinyl chloride with an average degree of polymerization of 500, and PC is bisphenol A type polycarbonate with an average degree of polymerization of 200.

Rubber-containing styrenic resins D-1 to D-9 (D in Table 10)
The pellets of the polymer composition obtained in Example 3 (denoted as AB component in Table 1O) were mixed in the proportions shown in Table 10, and the mixture was fed to a VC-40 extruder. Pellets were obtained by kneading.

A molded article was made from the obtained pellets, and the physical properties were evaluated in the same manner as in Application Example 1, and the results are shown in Table 1O.

Experiment numbers 58 to 66 in Table 10 are examples of blending the polymer composition of the present invention, and experiment numbers 67 to 75 are examples of non-blended polymer compositions.

As is clear from Table 1O, the polymer composition of the present invention can be added to various rubber-containing styrenic oils to improve their living environment stress cracking resistance, and does not cause delamination or flow marks. I understand that.

Reference Example 4 80 parts of Table 80-1 emulsion (as the solid content of the polymer) and 20 parts of the B-3 emulsion produced in Example 1 (as the solid content of the example) were mixed in an emulsion state, Calcium chloride 2
It was poured into an aqueous solution containing 5 parts of aqueous salt and stirred at 90 to 95°C to precipitate.

40 parts of the powder obtained by filtering the obtained slurry, washing with water, and drying was added to Table 80-6 60 parts of powder, mark 1500 0
．． Mix in a Henschel mixer with 2 parts of VC-49
It was fed into a die extruder to form pellets.

When the physical properties of the obtained pellets were evaluated according to Application Example 1, the tensile yield point was 410 kg/cut, the Izot impact strength was 29 kgcm/cm, and the chemical resistance was 300 minutes.
The gloss was 88%, the layered peelability was C, and the Flowmark D1 Vicat softening strength was 97°C, which was inferior to the layered peelability and Flowmark.

Reference Example 5 Table 80-1 emulsion 30 parts (as solid content of polymer), Table 8C-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) were mixed in an emulsion state, poured into an aqueous solution of 5 parts of calcium chloride dihydrate, and stirred at 105°C to precipitate.

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

Physical properties of the obtained pellets were evaluated in accordance with Application Example 1: tensile yield point: 420 kg/cnf, Izod impact strength: 14 kgcm/cm, chemical resistance: 300 minutes, gloss: 93%, layer peelability: D1, flow mark: D, The Vicat softening strength was 110°C, and the layer peelability and flow marks were poor.

Example 4 50 parts of the A-18 emulsion produced in Example 1 (as the solid content of the polymer) and 50 parts of the B-3 emulsion (as the solid content of the polymer) were mixed in an emulsion state, and further Pluronic F-
7 parts of a 10% aqueous solution of 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 a polymer composition.

Application Example 4 and Reference Example 6 Table 11 shows a high-impact polystyrene resin consisting of 7% polybutadiene and 93% polystyrene, and the weight average molecular weight of the polystyrene is 2.15 x 105, and the polymer composition produced in Example 4. VC
-40 type extruder to obtain pellets.

A molded article was made using the obtained pellets and the physical properties were evaluated, and the results are shown in Table 11. However, the chemical resistance was observed for 180 minutes with a deflection of 20 mm. Table 11
Among them, >180 indicates no breakage after 180 minutes.

Table 11 As is clear from Table 11, the polymer composition of the present invention can also be suitably used for high-impact polystyrene resin.

(Effects of the Invention) As explained above, the polymer composition of the present invention is added to a comb-containing styrenic resin to improve its environmental stress cracking resistance, and the resulting molded product has no layer delamination. Alternatively, it has the remarkable effect of not generating flow marks.

Patent Applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendments January 28, 1985 Director General of the Patent Office Ubuya Michibe Indication of Case 1985 Patent Application No. 292193 2 Name of Invention Polymer Composition 3 Amendment Relation to the case of a person who does “Even if it comes”
Even if it is,” he corrected.

Correct it to "1,6-hexane".

(3) In the specification, page 16, line 13, ``koto-necessary'' is corrected to ``shi-koto-necessary''.

(4) "R-liquid polymer" on page 21, line 10 of the specification is replaced with "
Correct it to "Polymer J".

(5) On page 22, line 14 of the specification, "and is preferable" is corrected to "and is preferably J."

(6) "Mixed" in line 6 of page 23 of the specification is corrected to "mixed".

(7) "Ethylene glycol methacrylate" in Table 1 on pages 33 and 34 of the specification is corrected to "1 ethylene glycol no methacrylate."

(8) Sample No. 16 B in Table 3 on page 37 of the specification
The value of styrene (parts) in No.9 [6J is corrected to 'OJi'.

(10) “Acid impact strength” in Table 7 on page 51 of the specification
is corrected to "Izotsu impact strength".

(11) [Methyl methacrylate] in Table 8 of Specification No. 54if is corrected to "methyl methacrylate."

(12) "Acid impact strength -1" in Table 1o in picture 56 of the specification has been corrected to "Izot impact strength", and the value of Izot impact strength of Experiment/i662 in the same table r 8.8 J
r 8. Correct O.J.

(13) "Acid impact strength" in Table 1o of detailed program 5700 is corrected to "Izot impact strength".

(14) “Correct the body environment j to 1 environment resistance J” on page 58, line 5 of Ming #1 tatami mat.

Claims (1)

[Scope of Claims] (A) A polymer of vinyl monomers, whose glass transition temperature exceeds 20°C and whose gel content is 10% or less,
The solubility parameter is 8.0 to 11.0 (cal/cc
)^1^/^2 and a weight average molecular weight based on polystyrene of 2 x 10^5 or more emulsion 20
~90% by weight (as the solid content of the polymer); and (B) a homopolymer or copolymer of acrylic ester monomers, or a copolymer of acrylic ester monomers and other copolymerizable monomers. It is a polymer whose glass transition temperature is 2.
The temperature is 0°C or less, the gel content is 70% or less, and the solubility parameter is 8.4 to 9.8 (cal/cc).
10 to 80% by weight of a polymer emulsion with ^1^/^2 (
A polymer composition obtained by mixing (as a solid content of a polymer) in an emulsion state and then separating the polymer.