JPH0892327A - Thermoplastic resin, its production and resin composition containing the same - Google Patents

Abstract

PURPOSE: To obtain the subject resin excellent in chemical resistance and stress cracking resistance, etc., at a low temperature, not causing laminar release, excellent in appearance such as gloss or color tone and useful for electric refrigerator, etc., by carrying out graft polymerization of an aromatic vinyl monomer, etc., in the presence of a specific (meth)acrylic copolymer. CONSTITUTION: This method for producing a thermoplastic resin is to carry out graft polymerization of (B) a monomer mixture containing an aromatic vinyl monomer in the presence of (A) a (meth)acrylic copolymer obtained by carrying out radical polymerization of a monomer mixture containing (i) a (meth)acrylic acid alkyl ester having a 2-12C alkyl group and (ii) 0.1-10wt.% of a vinyl monomer having chloromethyl group. Furthermore, (iii) a mixture of other copolymerizable vinyl monomer with a polyfunctional vinyl monomer is preferably further used in the component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin, a method for producing the same, and a resin composition containing the same. More specifically, a specific (meth) acrylic copolymer that exhibits excellent chemical resistance, resistance to stress cracking at low temperatures, and the appearance of molded products such as gloss and color tone and that does not cause delamination. The present invention relates to a thermoplastic resin obtained by graft-polymerizing a styrene-based monomer in the presence of, a method for producing the same, and a thermoplastic resin composition containing the thermoplastic resin and a styrene-based resin of a different type.

[0002]

BACKGROUND OF THE INVENTION Styrenic resins are used as general-purpose resins because they are inexpensive and have good moldability. For example, in the presence of a rubbery polymer such as a conjugated diene polymer latex, a resin composition such as an ABS resin obtained by polymerizing a monomer mixture such as styrene or acrylonitrile, which is a hard resin component, As a molding material with excellent impact resistance and chemical resistance, it is used in various applications including housings for electrical products. However, A
Molded articles made of the BS resin composition are restricted in use because when they are brought into contact with chemicals under stress, cracks may occur on the surface of the molded articles and they may break in extreme cases.

In order to obtain a resin material excellent in these properties, a method of increasing the content ratio of an acrylonitrile component in an ABS resin (for example, Japanese Patent Laid-Open No. 47-5594), an ABS resin containing acrylic rubber / styrene / acrylonitrile Method of mixing polymer (ASA resin) (Japanese Examined Patent Publication No. 54-40285, Japanese Examined Patent Publication No. 63-428460)
JP-B-63-22222), a method of mixing an acrylic acid ester-based polymer with an ABS resin (JP-B-63-22222), and a method of mixing two types of characteristic graft polymers (JP-B-SHO). 57-22064 and JP-A-2-175745) have been proposed.

However, these techniques are meaningful because they provide solutions to existing problems, but as far as the present inventors know, they are not completely satisfactory. That is, among the proposed methods, JP-A-47-5594 and JP-B-54-402.
58, JP-B-63-22222, JP-B-6
In JP-A 3-28460, a defective phenomenon may be observed in the surface condition of the injection-molded product, for example, a defective surface appearance called a flow mark, or a surface peeling phenomenon,
In addition, a surface appearance defect called die band may be observed on the surface of the extruded product, which reduces the commercial value of the product and may cause a problem in use.

Further, the ones proposed in Japanese Examined Patent Publication No. 57-22064 and Japanese Unexamined Patent Publication No. 2-175745 have insufficient chemical resistance, and in the field where more chemical resistance is required, the same is true. There was a problem in use. The appearance of the molded product, the delamination phenomenon, and the like can be improved by crosslinking the acrylate polymer, but the chemical resistance could not be improved.

An example of use under more severe conditions is the use of the inner box of an electric refrigerator. Due to the recent problem of ozone layer depletion, CFC-141b, which has a strong chemical attack on styrene-based resins, has been used as the freon, which is a foaming agent used to form the heat insulation layer of electric refrigerators. There has been a demand for a material having excellent chemical resistance and stress cracking resistance at low temperatures, and at the same time, a molded article having excellent gloss and color tone can be obtained.

[0007]

The object of the present invention is to provide excellent chemical resistance, stress cracking resistance at low temperatures, etc.
It is an object of the present invention to provide a thermoplastic resin that does not cause delamination and can give a molded article excellent in appearance such as gloss and color tone, a method for producing the same, and a resin composition containing the thermoplastic resin.

[0008]

In order to solve the above-mentioned problems, in the invention described in claim 1, a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms is provided. In the presence of a (meth) acrylic copolymer obtained by radical polymerization of a monomer mixture containing 0.01 to 10% by weight of a vinyl monomer having a chloromethyl group. Means are taken to obtain a thermoplastic resin by graft-polymerizing a monomer mixture containing a vinyl monomer. In the invention according to claim 3, a thermoplastic resin is produced by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of a (meth) acrylic copolymer. In this regard, as the (meth) acrylic copolymer, a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, and 0.01 to
A (meth) acrylic copolymer obtained by radical polymerization of a monomer mixture containing 10% by weight of a vinyl monomer having a chloromethyl group is used. is there. Further, in the invention according to claim 4, a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms and a vinyl having 0.01 to 10% by weight of a chloromethyl group relative to the alkyl ester A heat for graft-polymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of a (meth) acrylic copolymer obtained by radically polymerizing a monomer mixture containing a monomer. The means of mainly containing the plastic resin (A) and the styrene resin (B) different from the thermoplastic resin (A) is taken.

[Detailed Description of the Invention] The present invention will be described in detail below. [1] Thermoplastic resin (A) The invention according to claim 1 of the present invention is a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, and 0.01 to 10 relative thereto. A monomer mixture containing, by weight, a vinyl monomer having a chloromethyl group,
A thermoplastic resin (A) obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of a (meth) acrylic copolymer obtained by radical polymerization.

(1) (Meth) acrylic Copolymer The (meth) acrylic copolymer which constitutes the thermoplastic resin (A) functions as a rubber substrate in the case of graft polymerization, Alkyl group has 2 to 1 carbon atoms
Two (meth) acrylic acid alkyl esters and a vinyl monomer having a chloromethyl group are essential. Specific examples of the acrylic acid alkyl ester include ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and dodecyl acrylate. Of these, an ester compound of a monohydric alcohol having 4 to 8 carbon atoms and acrylic acid is particularly preferable.

Specific examples of the methacrylic acid alkyl ester include ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and dodecyl methacrylate. Can be mentioned. Of these, an ester compound of a monohydric alcohol having 6 to 12 carbon atoms and methacrylic acid is particularly preferable. These ester compounds may be one kind or a mixture of two or more kinds.

The vinyl monomer having a chloromethyl group is
A monomer having a vinyl group such as vinyl ether, allyl ether, (meth) acryloyloxy, vinyl ester, allyl ester and styryl, and also having a chloromethyl group such as chloromethylalkyl, chloroacetyl and chlorobenzyl. Good. These monomers are
Further, it may have a functional group such as a hydroxyl group or an alkoxyl group. Specific examples thereof include chloromethylstyrene, chloroethyl vinyl ether, chloromethyl allyl ether, vinyl chloroacetate, allyl chloroacetate, and 3-chloro-2-hydroxypropyl methacrylate.

The (meth) acrylic copolymer essentially comprises the above-mentioned two kinds of components, but may contain other copolymerizable monomers and polyfunctional vinyl monomers, if necessary. . Specific examples of other copolymerizable monomers include styrene and
Aromatic vinyl monomers such as α-methylstyrene and t-butylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic amide, methacryloamide, vinylidene chloride, alkyl (having 1 carbon atom).
To about 6) vinyl ether and the like. These other copolymerizable monomers may be one kind or a mixture of two or more kinds.

The polyfunctional vinyl monomer has a function of crosslinking a (meth) acrylic copolymer and is a monomer having two or more vinyl groups in one molecule of the monomer. Specific examples of polyfunctional vinyl monomers include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, methacrylates of polyhydric alcohols such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate, and acrylates. , Diallyl malate, diallyl fumarate, triallyl isocyanurate, allyl methacrylate, allyl acrylate and the like. These polyfunctional vinyl monomers may be one kind or a mixture of two or more kinds.

The (meth) acrylic copolymer has a ratio of the vinyl monomer having a chloromethyl group of 0.01 to 10
It is necessary to select in the range of weight%. When the proportion of this monomer is less than 0.01% by weight, the number of graft base points is small and gloss and delamination cannot be sufficiently improved, while the proportion of this monomer is 10% by weight. If it exceeds, not only is the effect of including this monomer saturated, but also the cost is high, so neither is preferable. When another copolymerizable monomer is used, it can be selected in a range of up to 30% by weight, and when a polyfunctional vinyl monomer is used, it can be selected in a range of 3% by weight or less. .

The (meth) acrylic copolymer is preferably produced by the following procedure. The polymerization vessel is charged with a part or all of a monomer mixture of a (meth) acrylic acid alkyl ester monomer and a vinyl monomer having a chloromethyl group, and if necessary, a polymerization initiator, a molecular weight modifier, Another copolymerizable monomer and / or a polyfunctional vinyl monomer are allowed to coexist and polymerization is performed by a known polymerization method. Examples of the polymerization method include an emulsion polymerization method, an emulsion-suspension polymerization method, a solution polymerization method, a bulk polymerization method, and a bulk-suspension polymerization method. Among them, the emulsion polymerization method is preferable because it is easy to control the particle size, the particle structure, the reaction temperature, and the like. The method of charging the above-mentioned monomer, polymerization initiator, molecular weight modifier and the like into a polymerization vessel may be any of batch charging, divided charging, continuous charging and the like. When the monomer mixture is post-charged, the proportion of the monomer mixture can be changed in the initial, middle and late stages. As the polymerization initiator, there are used organic and inorganic peroxides known as radical polymerization initiators, and so-called redox type initiators obtained by combining these with a reducing agent. When the copolymer is produced by the emulsion polymerization method, conventionally used emulsifiers can be used without particular limitation.

The (meth) acrylic copolymer preferably has a weight average particle diameter of 0.05 to 0.50 μm. When it is less than 0.05 μm, the impact resistance of the finally obtained resin composition is poor and the moldability is not excellent, which is not preferable. When it exceeds 0.50 μm, the appearance of the molded article obtained from the resin composition is not excellent, which is not preferable.
Particularly preferred in the above range is 0.10 to 0.40 μm.
When using a polyfunctional vinyl monomer,
The effects of improving impact resistance, moldability, appearance of molded products, etc. are particularly remarkable. The weight average particle size of the (meth) acrylic copolymer is based on the value measured by "N4S" manufactured by Coulter Co., USA.

(2) Graft Polymerization The thermoplastic resin (A) is obtained by graft polymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of the (meth) acrylic copolymer. To be The monomer mixture containing an aromatic vinyl monomer is meant to include a mixture of an aromatic vinyl monomer alone and a monomer copolymerizable therewith. As a specific example of the aromatic vinyl monomer, styrene is representative, and in addition, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear halogenated styrene, lower alkoxystyrene, Examples include trifluoromethylstyrene. The present invention is not limited to these examples. As the monomer copolymerizable with the aromatic vinyl monomer, acrylonitrile, vinyl cyanide monomer such as methacrylonitrile, acrylic acid,
Acrylic acid lower alkyl ester, methacrylic acid lower alkyl ester and the like can be mentioned. The lower alkyl preferably has 1 to 10 carbon atoms. The copolymerizable monomer may be one kind or a mixture of two or more kinds. The monomer mixture contains an aromatic vinyl monomer as a main component, and a copolymerizable monomer can be used up to about 50% by weight.

In the graft polymerization, the above (meth)
20 parts of a monomer mixture containing an aromatic vinyl monomer was added to 100 parts by weight (based on the solid content) of the acrylic copolymer.
It is preferable to select in the range of up to 900 parts by weight. When the amount of the monomer mixture is too small, a molded product having an excellent appearance cannot be obtained from the finally obtained resin composition, and when it is too large, sufficient chemical resistance cannot be exhibited. Within the above range, 100 to
A range of 550 is especially preferred.

Graft polymerization is carried out by known methods such as bulk polymerization method, bulk-suspension polymerization method, emulsion polymerization method, emulsion-suspension polymerization method and solution polymerization method. Among them, the emulsion polymerization method is preferable because it is easy to adjust the reaction temperature and the operability of polymerization. When carrying out the graft polymerization, a polymerization initiator, a molecular weight modifier and the like can be used if necessary. The method of charging the monomer mixture, the polymerization initiator, the molecular weight modifier and the like into the polymerization vessel may be batch charging,
Either divided preparation or continuous preparation may be used. When the monomer mixture is post-charged, the proportion of the monomer mixture may be different in the initial, middle and late stages. The polymerization initiator is
In addition to organic and inorganic peroxides known as radical polymerization initiators, so-called redox type initiators in which these are combined with a reducing agent are used. When the copolymer is produced by the emulsion polymerization method, conventionally used emulsifiers can be used without particular limitation.

When the graft polymerization is carried out according to the above procedure, a graft polymer is obtained by grafting a part of the monomer mixture containing the aromatic vinyl monomer on the (meth) acrylic copolymer of the rubber substrate. A thermoplastic resin (A) comprising a mixture with a copolymer obtained from a monomer mixture containing an aromatic vinyl monomer is obtained. The latter copolymer becomes a non-grafted hard resin component which is a continuous layer of the thermoplastic resin (A).

[2] Thermoplastic Resin (B) Since the above-mentioned thermoplastic resin (A) can be used as a molding material by itself, it can be directly used as a molding material depending on the application. However, since a vinyl monomer having a chloromethyl group is expensive, it is disadvantageous to use a monomer having a high content of this monomer component as it is as a molding material. Usually, a styrene resin (B) different from the thermoplastic resin (A) is mixed with the thermoplastic resin (A) having a high vinyl monomer content having a chloromethyl group, and the mixture is used as a molding material.

As the styrene resin (B) different from the thermoplastic resin (A), polystyrene, high impact polystyrene, AS resin (acrylonitrile-styrene copolymer), SMA resin (styrene-maleic anhydride copolymer) are used. ), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic acid ester-styrene copolymer), AES resin (acrylonitrile-EPDM-styrene copolymer),
Heat resistant ABS resin (acrylonitrile-butadiene-styrene-α-methylstyrene copolymer), super heat resistant AB
Examples thereof include S resin (acrylonitrile-butadiene-styrene-phenylmaleimide copolymer) and MABS resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer). These may be one kind or a mixture of two or more kinds.

The blending amounts of the thermoplastic resin (A) and the styrene resin (B) differ depending on the use of the resin composition, but usually 100 parts by weight of the thermoplastic resin (A) are used.
The styrene resin (B) is selected in the range of 1 to 300 parts by weight. These thermoplastics include powders, beads, flakes,
Or, those having a pellet form, two or more kinds, a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader,
The desired thermoplastic resin composition can be obtained by a kneader such as a two-roll mill. Further, in some cases, a method of mixing two or more of these copolymers that have been polymerized, while still undried, precipitating, washing, drying and kneading can be adopted.

The thermoplastic resin composition comprising the thermoplastic resin (A) and the styrene resin (B) may be added to the thermoplastic resin (A) or the styrene resin as needed, as long as the object of the present invention is not impaired. Thermoplastic resin other than resin (B), inorganic filler, metal powder, reinforcing material, plasticizer, compatibilizer, heat stabilizer, antioxidant, ultraviolet absorber, dye, pigment, antistatic agent, lubricant, Various resin additives such as flame retardants can be added in appropriate combination.

The thermoplastic resin composition according to the present invention has excellent chemical resistance, resistance to stress cracking at low temperature, gloss, color tone, molding appearance and excellent delamination resistance. Especially chemical resistance, applications requiring stress cracking resistance at low temperature, for example, as electric parts such as inner box materials of electric refrigerators and various industrial parts,
Can be used. Applicable molding methods include various known molding methods such as an injection molding method, an extrusion molding method, a compression molding method, a hollow molding method, and a differential pressure molding method.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following description examples as long as the gist thereof is not exceeded. In addition,
In the following examples, "part" means part by weight, and the physical properties of the thermoplastic resin composition were measured by the following methods.

(1) Average particle size of rubber component: Measured with "N4S" manufactured by Coulter Co., USA. It means the weight average particle diameter, and the unit is μm. (2) Tensile strength It was measured according to JIS K7113. Unit: Kg / cm ² (3) Izod impact strength Measured according to JIS K7110. Unit: Kg-cm /
cm (4) Appearance A test piece (thickness 2.5 mm, width 75 mm,
The length of 160 mm) was manufactured and the presence or absence of flow marks was visually observed on the surface of this test piece. The judgment result was displayed as follows. ⊚: Almost no flow mark is recognized. ○: Flow mark is not recognized. Δ: Some flow marks are recognized. X: Flow marks are considerably recognized.

(5) Gloss For the same type of test piece as used in the above (4) appearance test,
Using a variable angle gloss meter (VGS-300A type) manufactured by Nippon Denshoku Industries Co., Ltd.
The gloss value was measured at 10 points at an incident angle of 60 degrees, and the average value was calculated. (6) Yellowness For the same type of test piece used in (4) Appearance test,
S & M Color Computer Model SM manufactured by Suga Test Instruments Co., Ltd.
4 was used to measure the yellowness index (YI). (7) Chemical resistance Test pieces manufactured by compression molding (thickness 2 mm, width 35
mm, length 230 mm) by a bending foam method at a temperature of 23 ° C. under an atmosphere of HCFC-141b.
The critical strain value in which cracking occurred when left for 7 hours was measured to determine the chemical resistance. The judgment result was displayed as follows. A: The critical strain value exceeds 0.8% and the chemical resistance is extremely good. ◯: The critical strain value is 0.8 to 0.6%, and the chemical resistance is good. Δ: The critical strain value is 0.6 to 0.4%, and the chemical resistance is slightly poor. X: The critical strain value is less than 0.4% and the chemical resistance is poor.

(8) Low-temperature whitening occurrence strain value A dumbbell-shaped test piece having a length of 115 mm, a wide width portion of 30 mm, a narrow width portion of 10 mm, a thickness of 1 mm, and a narrow width portion of 50 mm was formed by a compression molding method. did. HCFC-141b was used as a foaming agent on one side of the narrow portion of this test piece to perform in-sit
A rigid polyurethane foam was adhered by a foaming method to a width of 10 mm, a thickness of 10 mm and a length of 50 mm. This test piece was fixed to a jig at a temperature of 23 ° C. while being loaded with tensile strain, cooled to −20 ° C., and maintained at this temperature for 17 hours, after which the surface of the test piece to which the rigid polyurethane foam was adhered The back side was visually observed for the presence of crazes or cracks. The smaller the number, the easier the low temperature whitening is, and the larger the number, the less the low temperature whitening is.

(9) Layered peelability By injection molding method, thickness 2 mm, width 30 mm, length 90 mm
Then, a molded product having a gate at the center of one end in the length direction was manufactured. With respect to the molded product, the gate portion was manually folded, and the state of the folded portion was visually observed to determine the layered peelability. The judgment result was displayed as follows. ⊚: Does not peel at all. ◯: Almost no peeling. Δ: A little peeled off. X: It peels considerably.

Production of thermoplastic resin (A) 1. Production of (meth) acrylic copolymer A1-1 In a glass flask having a capacity of 5 liters, equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device, 151 parts of deionized water and higher fatty acid Soap (18 carbon atoms
2 parts of a sodium salt of a fatty acid containing as a main component and 1 part of sodium hydrogen carbonate are charged, and while stirring under a nitrogen stream,
The internal temperature was raised to 75 ° C. 0.135 parts of potassium persulfate was added to the flask, and after 5 minutes, 100 parts of butyl acrylate (BA) and chloromethylstyrene (CMS).
Of the monomer mixture containing 5 parts, 4 parts were charged. After a few minutes, heat was generated and it was confirmed that the polymerization had started. 20 minutes after the initial charging of the monomer mixture, continuous charging of the remaining monomer mixture was started, and the continuous charging was completed over 3 hours. On the way, 1 part of fatty acid soap was charged 2 hours after the first addition of the monomer mixture, and 0.015 parts of potassium persulfate was additionally charged 2 hours and 30 minutes later. After the continuous charging of the monomer mixture was completed, the internal temperature was raised to 80 ° C., and the polymerization reaction was carried out at this temperature for another hour. The rubbery latex (A
1-1) had a solid content concentration of 39.5% by weight and an average particle diameter of 0.08 μm.

A1-2 In the example described in A1-1, the monomer mixture was mixed with BA10.
Polymerization reaction was carried out by the same procedure as in the same example except that 0 part and CMS were changed to 1 part. The obtained rubbery latex (A1-2) had a solid content concentration of 39.2% by weight and an average particle diameter of 0.08 μm.

A1-3 In the example described in A1-1, the monomer mixture was mixed with BA10.
The polymerization reaction was carried out by the same procedure as in the same example except that the content was changed to 0 part and CMS 0.3 part. The obtained rubbery latex (A1-3) had a solid content concentration of 39.2% by weight and an average particle diameter of 0.08 μm.

A1-4 In the example described in A1-1, the monomer mixture was mixed with BA10.
The polymerization reaction was carried out by the same procedure as in the example except that the content was changed to 0 part and CMS 0.03 part. The obtained rubbery latex (A1-4) had a solid content concentration of 39.2% by weight,
The average particle diameter was 0.08 μm.

A1-5 In the example described in A1-1, the monomer mixture was mixed with BA10.
The polymerization reaction was performed by the same procedure as in the same example except that the content was changed to 0 part and CMS 0.001 part. The obtained rubber-like latex (A1-5) had a solid content concentration of 39.2% by weight and an average particle diameter of 0.08 μm.

A1-6 In the example described in A1-1, the monomer mixture was mixed with BA10.
Polymerization reaction was carried out by the same procedure as in the same example except that 0 parts, 1 part of CMS, and 0.4 parts of ethylene glycol dimethacrylate (EGDM) were changed. The obtained rubbery latex (A1-6) had a solid content concentration of 39.5% by weight,
The average particle diameter was 0.08 μm.

A1-7 In the example described in A1-1, the monomer mixture was mixed with BA10.
0 part, CMS 1.0 part, t-dodecyl mercaptan (T
DM) was changed to 0.4 part, and the polymerization reaction was carried out by the same procedure as in the same example. The obtained rubbery latex (A1-7) had a solid content concentration of 38.6% by weight and an average particle diameter of 0.08 μm.

A1-8 In the example described in A1-1, the monomer mixture was mixed with BA95.
Parts, methyl methacrylate (MMA) 5 parts, CMS 1.
The polymerization reaction was performed by the same procedure as in the same example except that the content was changed to 0 part. The obtained rubbery latex (A1-
8) has a solid content concentration of 39.4% by weight and an average particle size of 0.
It was 09 μm.

A1-9 In the example described in A1-1, the monomer mixture was mixed with BA10.
Polymerization reaction was carried out by the same procedure as in the same example except that 0 parts and 0.3 parts of chlorovinyl acetate (CAV) were used.
The obtained rubber-like latex (A1-9) had a solid content concentration of 39.2% by weight and an average particle diameter of 0.08 μm.

A1-10 In the example described in A1-1, the monomer mixture was mixed with BA10.
0 part, chloroethyl vinyl ether (CEVE) 0.3
Polymerization reaction was carried out by the same procedure as in the same example except that parts were changed. The obtained rubbery latex (A1-1
0) has a solid content concentration of 39.2% by weight and an average particle size of 0.
It was 08 μm.

A1-11 In the example described in A1-1, the monomer mixture was mixed with BA10.
The polymerization reaction was carried out in the same procedure as in the same example except that 0 part of the vinyl monomer having a chloromethyl group was not used. The obtained rubbery latex (A1-11) is
Solid content concentration 39.2% by weight, average particle size 0.08 μm
Met. (Meth) acrylic copolymers A1-1 to A1
The production examples of -11 are summarized in Table-1.

[0043]

[Table 1]

2. Production of thermoplastic resin (A) A-1 A (meth) acrylic copolymer latex A1 was placed in a glass autoclave with a capacity of 5 liters equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary agent charging device. −
1 as solid content 100 parts, sodium pyrophosphate 1.0
Parts, glucose 0.25 parts, ferrous sulfate 0.01 parts and deionized water 258 parts (including latex water) were charged, and the internal temperature was raised to 70 ° C. while stirring under a nitrogen stream. . When the internal temperature reached 70 ° C, styrene (St)
154 parts, acrylonitrile (AN) 66 parts and TD
A monomer mixture containing 0.2 part of M and an aqueous solution in which 1.8 parts of disproportionated potassium rosinate soap and 0.5 part of cumene hydroperoxide were dissolved in 48 parts of deionized water, respectively, for 3 hours and 30 minutes. It took a long time to prepare continuously. After the continuous charging was completed, the reaction was continued for another 30 minutes at the same temperature, and the internal temperature was cooled to complete the reaction. To the obtained graft polymer latex, after adding 2.5 parts of a total amount of a phenol type and a phosphorus type antioxidant, this latex was added to a magnesium sulfate aqueous solution heated to 95 ° C. with stirring, Solidified. The solidified product was washed with water and dried to obtain a white powdery thermoplastic resin (A-1).

A-2 to A-11 In the examples described in A-1, the (meth) acrylic copolymer latex was replaced with A1-2 to A1 as shown in Table-2.
A graft reaction was carried out by the same procedure as in the same example except that -11 was used to obtain a thermoplastic resin. The obtained white powdery thermoplastic resins are referred to as A-2 to A-11, respectively.

A-12 In the example described in A-1, the monomer mixture to be reacted with the (meth) acrylic copolymer latex (A1-1) is composed of St630 parts, AN270 parts and TDM0.20 part. A graft reaction was carried out in the same procedure as in the same example except that the mixture was replaced with a mixture to obtain a thermoplastic resin. The white powdery thermoplastic resin thus obtained is referred to as A-12.

A-13 In the example described in A-1, the monomer mixture to be reacted with the (meth) acrylic copolymer latex (A1-1) comprises St 14 parts, AN 6 parts and TDM 0.20 part. A graft reaction was carried out in the same procedure as in the same example except that the mixture was replaced with a mixture to obtain a thermoplastic resin. The white powdery thermoplastic resin thus obtained is referred to as A-13.

A-14 In the example described in A-1, the monomer mixture to be reacted with the (meth) acrylic copolymer latex (A1-1) is composed of St 7 parts, AN 3 parts and TDM 0.20 part. A graft reaction was carried out in the same procedure as in the same example except that the mixture was replaced with a mixture to obtain a thermoplastic resin. The white powdery thermoplastic resin thus obtained is referred to as A-14. Table 2 collectively shows production examples of the thermoplastic resin (A).

[0049]

[Table 2]

Production of Styrenic Resin (B) B-1 (1) Production of Rubbery Polymer SUS autoclave with a capacity of 5 liters equipped with a stirrer, heating / cooling device, thermometer, and raw material / auxiliary charging device. 150 parts of deionized water, 4.0 parts of higher fatty acid soap (sodium salt of fatty acid having 18 carbons as a main component),
After adding 0.075 part of sodium hydroxide and replacing with nitrogen, the internal temperature was raised to 68 ° C. while stirring. Separately prepared 1,3-butadiene (B
D) 20% of a monomer mixture consisting of 90 parts, St 10 parts and 0.3 part TDM was charged, and 0.135 part of potassium persulfate was added. After a few minutes, heat was generated and it was confirmed that the polymerization had started. One hour after the addition of potassium persulfate, the remaining monomer mixture was continuously charged over 5 hours. After the continuous charging was completed, the internal temperature was raised to 80 ° C., and the polymerization reaction was carried out at this temperature for another hour. The obtained conjugated diene rubbery (SBR) latex has a solid content concentration of 3
The content was 9.5% by weight, the average particle diameter was 0.08 μm, and the gel content was 95.0%.

(2) Production of Graft Copolymer The particle size of the above conjugated diene rubbery latex was enlarged with acetic anhydride to have an average particle size of 0.25 μm and 0.65 μm. In a reaction vessel having a capacity of 5 liters equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device, 100 parts (80 of 0.25 μm 80) of the conjugated diene rubbery latex as a solid content. Parts, a mixture of 20 parts of 0.65 μm) and 347 parts of deionized water (including water in the latex).
Was charged, and the internal temperature was raised to 70 ° C. with stirring under a nitrogen stream. When the internal temperature reached 60 ° C during heating, 1.0 part of sodium pyrophosphate and 0.8 of dextrose
Part, 0.01 parts of ferrous sulfate were dissolved in 20 parts of deionized water to prepare an aqueous solution.

When the internal temperature reaches 70 ° C., St70
Part, 30 parts of AN and 1.1 parts of TDM, and 1.8 parts of disproportionated potassium rosinate soap in 35 parts of deionized water, 0.37 parts of potassium hydroxide and 0.5 parts of cumene hydroperoxide. An aqueous solution in which parts were dissolved was continuously charged for 2 hours and 30 minutes. After the continuous charging was completed, the reaction was continued for another 30 minutes at the same temperature, and the internal temperature was cooled to complete the reaction. To the obtained graft polymer latex, 5 parts by total of a phenol-based and phosphorus-based antioxidant was added, and then this latex was added to a magnesium sulfate aqueous solution heated to 95 ° C. with stirring,
Solidified. The solidified product was washed with water and dried to obtain a white powdery thermoplastic resin (B-1).

B-2 (1) Production of rubbery polymer In a glass flask having a capacity of 5 liters equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device, 151 parts of deionized water, Higher fatty acid soap (18 carbon atoms
2 parts of a fatty acid sodium salt containing as a main component) and 1 part of sodium hydrogencarbonate were charged, and the internal temperature was raised to 75 ° C. with stirring under a nitrogen stream. 0.135 parts of potassium persulfate was added to the same autoclave, and after 5 minutes, BA
95 parts, AN 5 parts and allyl methacrylate (AM
4 parts of a monomer mixture containing 0.5 parts of A) was charged. After a few minutes, heat was generated and it was confirmed that the polymerization had started.
20 minutes after the initial charging of the monomer mixture, continuous charging of the remaining monomer mixture was started, and the continuous charging was completed over 3 hours. On the way, 1 part of fatty acid soap was charged 2 hours after the first monomer mixture was added, and 0.015 parts of potassium persulfate was additionally charged 2 hours and 30 minutes after the addition. After the continuous charging of the monomer mixture was completed, the internal temperature was raised to 80 ° C., and the polymerization reaction was further carried out at this temperature for 1 hour. The obtained rubber-like (AR) latex had a solid content concentration of 39.5% by weight and an average particle diameter of 0.08 μm.

(2) Preparation of Graft Copolymer The particle size of the above acrylic rubbery (hereinafter referred to as AR) latex was enlarged by acetic anhydride to have an average particle size of 0.15 μm. In a reaction vessel having a capacity of 5 liters equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device, 100 parts of the AR latex as a solid content, 1 part of sodium hydrogen carbonate, and 274 deionized water were added. Part (including water in latex) was charged, and the internal temperature was raised to 80 ° C. while stirring under a nitrogen stream. When the internal temperature reached 70 ° C during heating, AMA
0.5 part was added. When the internal temperature reaches 80 ° C, St
An aqueous solution prepared by dissolving 70 parts, 30 parts of AN, and 0.2 part of TDM in a monomer mixture, and 0.5 parts of potassium persulfate and 1.8 parts of disproportionated potassium rosinate soap in 45 parts of deionized water. And were continuously charged over 3 hours and 30 minutes. After the continuous charging was completed, the reaction was continued for another 30 minutes at the same temperature, and the internal temperature was cooled to complete the reaction. To the obtained graft polymer latex, 5 parts by weight of a total of phenol-based and phosphorus-based antioxidants were added, and then the latex was added to a magnesium sulfate aqueous solution heated to 95 ° C with stirring to coagulate. It was The solidified product was washed with water and dried to obtain a white powdery thermoplastic resin (B-2).

B-3 An autoclave having a capacity of 2 liters equipped with an anchor type stirring device, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device is provided with St394 parts, EPDM (Moonie viscosity ML _{1 + 4).}
(100 ° C.) 45, iodine value 25, DM is ethylidene norbornene (100 parts), and n-heptane 71 parts were charged, and after nitrogen substitution, the internal temperature was adjusted to 50 ° C. and 2 hours, 1 hour
The EPDM was completely dissolved in St by stirring at 00 rpm. Then, with stirring, AN was added at a rate of 3 parts / min for a total of 18
Diter-butyl peroxide 0.3 after charging 4 parts
57 parts, ter-butyl peracetate 0.093 parts, and tapinolene 0.357 parts were charged, and the temperature was raised to 97 ° C.
Bulk polymerization was carried out at this temperature for 7 hours and 20 minutes. About 30 minutes before the end of the bulk polymerization, a monomer solution in which 1.07 parts of diter-butyl peroxide and 0.357 parts of tapinolene were dissolved in 36 parts of St was charged into an autoclave. The average particle size of EPDM at the end of the bulk polymerization was 1.6 μm.

An autoclave with a capacity of 3 liters equipped with a backward stirring blade, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device was charged with 790 parts of deionized water in which 1.8 parts of the suspending agent was dissolved. The internal temperature was raised to 100 ° C., the atmosphere was replaced with nitrogen, and then the mixture was agitated at 500 rpm and waited. The syrup obtained in the bulk polymerization step was charged into this autoclave, the atmosphere was replaced with nitrogen, the internal temperature was raised to 130 ° C., suspension polymerization was carried out for 2 hours while stirring in the same manner, and 150 minutes was taken over 30 minutes. The temperature was raised to 0 ° C., and stripping was performed for 1 hour while maintaining the internal temperature of the autoclave at this temperature. The obtained polymer was washed with water and dried at 100 ° C. to obtain 920 g of a bead-shaped graft copolymer (B-3).

Table 3 collectively shows a production example of the styrene resin (B).

[Table 3]

Examples 1 to 13 Thermoplastic resin (A), styrene resin (B) and AS resin for dilution (SAN-L, manufactured by Monsanto Kasei Co.) were used in the proportions shown in Tables 4 to 6. As a resin raw material, 0.4 parts of magnesium stearate and n-octadecyl-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate (Ciba-Geigy, Irganox
1076) 0.2 parts, 9,10-dihydro-9-oxa-1
0.2 parts of 0-phosphophenanthrene-10-oxide (manufactured by Sanko Co., HCA) and 4.0 parts of titanium oxide were respectively weighed and blended, uniformly mixed with a blender, kneaded with a Banbury mixer, and pelletized. . The obtained pellets were subjected to various evaluation tests such as physical property measurement, appearance, gloss, yellowness, chemical resistance, low temperature whitening occurrence strain value, and layered peelability by injection molding. The results of the evaluation test are shown in Table-4 to Table-
6 is shown.

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

Comparative Examples 1 to 5 A thermoplastic resin (A), a styrene resin (B) and a diluting AS resin (SAN-L) were used as resin raw materials in the proportions shown in Table 7 in the same manner as in the examples. The same amount of each additive was blended and pelletized by the same procedure as in the example. Various evaluation tests were performed on the obtained pellets in the same procedure as in the examples. The results of the evaluation test
It shows in Table-7.

[0063]

[Table 7]

The following is clear from Tables 4 to 7. (1) The thermoplastic resin composition containing the thermoplastic resin (A) according to the present invention is less likely to cause flow marks, is excellent in the appearance of molded articles such as gloss and yellowness, and is also resistant to stress cracking at low temperatures. In addition to being excellent and hardly causing delamination, it also has excellent chemical resistance and does not deteriorate in physical properties such as tensile strength and impact resistance (see Examples 1 to 13). (2) On the other hand, when a monomer having a chloromethyl group at the terminal is not included (Comparative Examples 1 to 3) or when it is extremely small (Comparative Example 4), the appearance of the molded article ( (Including flow mark / die band, gloss, yellowness, etc.), stress cracking resistance at low temperature, chemical resistance, delamination, etc. are not well balanced. (3) When the amount of the styrene-based monomer to be grafted on the (meth) acrylic copolymer is small during the production of the thermoplastic resin (A), the finally obtained thermoplastic resin composition has a molded article appearance. (Including flow mark, gloss, yellowness, etc.),
The stress cracking resistance at low temperature, chemical resistance, delamination, etc. are not well balanced (Comparative Example 5).

[0065]

INDUSTRIAL APPLICABILITY The present invention has the following special advantageous effects and its industrial utility value is extremely large. 1. The thermoplastic resin composition according to the present invention does not cause delamination of the molded product when it is a molded product, has chemical resistance, is excellent in stress cracking properties at low temperatures, is used for manufacturing inner boxes of electric refrigerators, and other industrial materials. Suitable for use in 2. The molded product obtained from the thermoplastic resin composition according to the present invention is less likely to cause flow marks and die bands, is excellent in appearance of the molded product such as gloss and yellowness, and does not deteriorate in physical properties such as tensile strength and impact resistance.

Claims (4)

[Claims] 1. A (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, and an alkyl group (meth) acrylic acid having a carbon number of 0.
In the presence of a (meth) acrylic copolymer obtained by radical polymerization of a monomer mixture containing 01 to 10% by weight of a vinyl monomer having a chloromethyl group,
A thermoplastic resin which is obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer. 2. A (meth) acrylic copolymer, wherein the alkyl group has a carbon number of 2 to 12 (meth) acrylic acid alkyl ester, a vinyl monomer having a chloromethyl group, and another copolymerizable vinyl. The thermoplastic resin according to claim 1, which is a copolymer of a monomer and a polyfunctional vinyl monomer mixture. 3. In producing a thermoplastic resin by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of a (meth) acrylic copolymer, the above-mentioned (meth) acrylic is used. As a system copolymer, a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms and a vinyl monomer having a chloromethyl group in an amount of 0.01 to 10% by weight based on the same A method for producing a thermoplastic resin, comprising using a (meth) acrylic copolymer obtained by radically polymerizing the monomer mixture described above. 4. A (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, and an alkyl group of 0.
Aromatic vinyl monomer in the presence of (meth) acrylic copolymer obtained by radical polymerization of a monomer mixture containing 01 to 10% by weight of a vinyl monomer having a chloromethyl group A thermoplastic resin composition mainly containing a thermoplastic resin (A) for graft-polymerizing a monomer mixture containing styrene and a styrene resin (B) different from the thermoplastic resin (A). Stuff.