JPH08120036A - Thermoplastic resin, its production, and resin composition containing the same - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin which is excellent in resistance to stress cracking at a low temp. and gives a molding which does not undergo interlayer separation by successively subjecting specific monomer mixtures to graft polymn. in the presence of a specific copolymer. CONSTITUTION: A monomer mixture comprising a 2-12C alkyl ester of (meth) acrylic acid (e.g. butyl acrylate) and 0-10wt.% chloromethylated vinyl monomer is subjected to graft polymn. in the presence of a copolymer obtd. by polymerizing a monomer component comprising an arom. vinyl monomer (e.g. styrene) and 0.05-10wt.% chloromethylated vinyl monomer (e.g. chloromethylstyrene). Then, in the presence of the resultant graft copolymer, an arom. vinyl monomer is subjected to graft polymn.

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 graft copolymer that has excellent chemical resistance, stress cracking resistance at low temperature, and excellent appearance such as gloss and color tone of molded products and does not cause delamination. Thermoplastic resin (A) composed of
It relates to a method for producing the same and a thermoplastic resin composition (C) containing this thermoplastic resin and a styrene resin (B) 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 an acrylic rubber / styrene / acrylonitrile Method of mixing copolymer (ASA resin) (Japanese Patent Publication No. 54-40258, Japanese Patent Publication No. 63-28460)
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 defect phenomenon appearing on the surface of an injection-molded product, for example, a surface appearance defect called a flow mark or a surface peeling phenomenon may be observed, and a die band is formed on the surface of an extrusion-molded product. In some cases, the surface appearance was said to be poor, which reduced the commercial value and caused problems 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, a foaming agent used when forming a heat insulating layer of an electric refrigerator, was changed to HCFC-141b, which has a strong chemical attack on styrene-based resins. 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 problems, in the invention described in claim 1, an aromatic vinyl monomer and a vinyl monomer having 0.05 to 10% by weight of a chloromethyl group are used. (Meth) acrylic acid having 2 to 12 carbon atoms in the alkyl group in the presence of the first step of polymerizing the monomer mixture (I) containing a monomer and the copolymer obtained in the first step. The second step of graft-polymerizing a monomer mixture (II) containing an alkyl ester monomer and a vinyl monomer having a chloromethyl group in an amount of 0 to 10% by weight, and the copolymer obtained in the second step Monomer mixture containing aromatic vinyl monomer in the presence of
A means of using (III) as a thermoplastic resin obtained by the third step of graft polymerization is taken.

Further, in the invention described in claim 3,
In producing a thermoplastic resin, a first step of polymerizing a monomer mixture (I) containing an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group of 0.05 to 10% by weight, In the presence of the copolymer obtained in the first step, a vinyl having a (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 to 12 carbon atoms and 0 to 10% by weight of a chloromethyl group. Second step of graft-polymerizing a monomer mixture containing a monomer (II), in the presence of the copolymer obtained in the second step, a monomer mixture containing an aromatic vinyl monomer (II
The production method comprises a third step of graft-polymerizing I).

Further, in the invention described in claim 6, a thermoplastic resin comprising the thermoplastic resin (A) according to claim 1 and a styrene resin (B) different from the thermoplastic resin (A). A resin composition is used.

[Detailed Description of the Invention] The present invention is described in detail below. [1] Thermoplastic Resin (A) The thermoplastic resin (A) polymerizes a monomer mixture (I) containing an aromatic vinyl monomer and a vinyl monomer having a specific amount of chloromethyl group. 1st step, in the presence of the copolymer obtained in the 1st step, a specific (meth) acrylic acid alkyl ester monomer, a monomer containing a specific amount of a vinyl monomer having a chloromethyl group Second step of graft-polymerizing the mixture (II), the third step of graft-polymerizing a monomer mixture (III) containing an aromatic vinyl monomer in the presence of the copolymer obtained in the second step , Was obtained by.

(1) First Step In the first step, a copolymer serving as a base of the thermoplastic resin (A) is manufactured. Monomer mixture polymerized in the first step (I)
Requires an aromatic vinyl monomer and a vinyl monomer having 0.05 to 10% by weight of a chloromethyl group. 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.

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 monomer mixture (I) contains, in addition to the above-mentioned two essential components, an alkyl group having 1 to 4 carbon atoms (meth).
An alkyl acrylate, another vinyl monomer copolymerizable therewith, and a polyfunctional vinyl monomer may be included. Specific examples of the acrylic acid alkyl ester whose alkyl group has 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, and n-.
Butyl acrylate, i-butyl acrylate, etc. are mentioned. Of these, particularly preferred are methyl acrylate and ethyl acrylate. Specific examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate and the like. Of these, particularly preferred are methyl methacrylate and ethyl methacrylate.

Other copolymerizable vinyl monomers include:
Examples thereof include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. 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. The monomers that can be contained in the monomer mixture (I) may be one kind or a mixture of two or more kinds.

To prepare the thermoplastic resin (A), the monomer mixture (I) is used as the aromatic vinyl monomer 20 to 99.95.
Weight%, vinyl monomer having chloromethyl group 0.05
10% by weight, 0 to 70% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms, and 0 to another vinyl monomer copolymerizable therewith.
It is preferable to select in the range of 50% by weight. Monomer mixture
The proportion of each monomer component constituting (I) is compatible with the use of the thermoplastic resin (A), the type of the other styrene resin (B) mixed with the thermoplastic resin (A), and particularly with each other. It is preferable to select within the range.

When the amount of the aromatic vinyl monomer in the monomer mixture (I) is less than 20% by weight, the compatibility with other styrene resins (B) cannot be obtained, and the graft base point is provided. A vinyl monomer having a chloromethyl group at 0.
The aromatic vinyl monomer cannot exceed 99.95% by weight because it must be contained in an amount of 05% by weight or more. The aromatic vinyl monomer is particularly preferably 6 in the above range.
It is 0 to 80% by weight.

The proportion of the vinyl monomer having a chloromethyl group in the monomer mixture (I) is 0.05 to 10% by weight.
It is necessary to choose within the range. The ratio of this monomer is 0.05
If it is less than wt%, sufficient graft base points cannot be introduced into the resulting copolymer, and effects such as chemical resistance as the thermoplastic resin (A) cannot be sufficiently exhibited. On the other hand, when the proportion of this monomer exceeds 10% by weight, the thermoplastic resin (A) and the styrene resin (B) described later are used.
The thermoplastic resin composition (C) obtained by mixing with the above not only affects the color tone and thermal stability, but also has a large graft ratio and is poor in chemical resistance, and is also disadvantageous from an economical point of view. . The ratio of the vinyl monomer having a chloromethyl group is particularly preferably 0.1 to 5% by weight in the above range.

The (meth) acrylic acid alkyl ester in the monomer mixture (I) is preferably selected in the range of 0 to 70% by weight. As other copolymerizable vinyl monomer,
When a vinyl cyanide monomer is used, it is preferably selected in the range of 0 to 50% by weight. When the amount of the vinyl cyanide monomer exceeds 50% by weight, not only the moldability of the thermoplastic resin (A) and the thermoplastic resin composition (C) is significantly lowered but also the thermal stability is deteriorated, which is preferable. Absent.
The preferable range of vinyl cyanide monomer is 40% by weight.
It is the following.

The first step is preferably performed by the following procedure. First, a polymerization vessel is charged with a part or all of a mixture of an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group, and if necessary, a polymerization initiator, a molecular weight modifier, and other copolymerizability. Polymerization is carried out by a known polymerization method in the presence of a monomer, a polyfunctional vinyl monomer and the like. Examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, an emulsion-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 the polymerization vessel may be batch charging, divided charging, continuous charging or 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. 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.

(1) Second Step In the second step, the monomer mixture (II) containing a (meth) acrylic acid alkyl ester monomer as a main component is added to the copolymer of the substrate obtained in the first step. This is the step of grafting. The monomer mixture (II) polymerized in the second step comprises 70 to 100% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 to 12 carbon atoms and a vinyl monomer having a chloromethyl group. It comprises 0 to 10% by weight of a monomer, 0 to 30% by weight of another vinyl monomer copolymerizable therewith, and 0 to 1% by weight of a polyfunctional vinyl monomer.

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

Specific examples of the vinyl monomer having a chloromethyl group may be the same as those described in the monomer mixture (I). Specific examples of other vinyl monomers copolymerizable with these include styrene, α-methylstyrene, and t.
-Aromatic vinyl monomers such as butyl styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic amide, methacryloamide, vinylidene chloride, alkyl (about 1 to 6 carbon atoms) vinyl ether, and the like. . These other copolymerizable monomers may be one kind or a mixture of two or more kinds. Specific examples of the polyfunctional vinyl monomer may be the same as those described in the monomer mixture (I).

The (meth) acrylic acid alkyl ester in the monomer mixture (II) is in the range of 70 to 100% by weight. If it is less than 70% by weight, it is difficult to obtain the chemical resistance and the stress cracking resistance at low temperature of the thermoplastic resin (A) and the thermoplastic resin composition (C), so that it will be described later in the thermoplastic resin (A). There are restrictions when the styrene resin (B) is mixed and used. In the above range, 80 to 100% by weight is preferable. Therefore, the range of use of the other vinyl monomer is 30% by weight or less, particularly preferably 20% by weight or less.

The polyfunctional vinyl monomer which can be contained in the monomer mixture (II) is in the range of 0 to 1% by weight.
If it exceeds 1% by weight, a large amount of gel is generated, and although the molding processability and appearance of the thermoplastic resin (A) are improved, the chemical resistance and the stress cracking resistance at low temperatures are significantly reduced. However, the thermoplastic resin composition (C) having a good physical property balance cannot be obtained. The polyfunctional vinyl monomer is
It is preferably 0.2% by weight or less.

The amount of the monomer mixture (II) to be grafted on the base copolymer obtained in the first step is determined by the amount of the base copolymer 1
It is preferable to select in the range of 2 to 200 parts by weight with respect to 00 parts by weight. If it is less than 2 parts by weight, the proportion of the acrylic resin in the thermoplastic resin (A) and the thermoplastic resin composition (C) will be small, so that chemical resistance and stress cracking resistance at low temperatures are sufficient. It is not preferable.
On the other hand, if it exceeds 200 parts by weight, a large amount of the free acrylic copolymer that is not grafted to the base copolymer is produced, resulting in poor compatibility with the styrene resin (B) described later, which is not preferable. The amount of the monomer mixture (II) is particularly preferably 50 to 150 parts by weight within the above range.

The second step is preferably performed by the following procedure. First, a polymerization vessel is charged with the copolymer of the substrate obtained in the first step, a part or all of the monomer mixture (II) is charged, and if necessary, a polymerization initiator, a molecular weight modifier, etc. Are allowed to coexist, and polymerization is performed by a known polymerization method. Examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, an emulsion-bulk polymerization method, and a bulk-suspension polymerization method. Among them, the emulsion polymerization method makes it easy to control the particle size, particle structure, reaction temperature, etc.
It is suitable. The method of charging the above-mentioned monomer, polymerization initiator, molecular weight modifier and the like into the polymerization vessel, the type of the polymerization initiator, the type of radical polymerization initiator, the charging method and the like can be the same as in the case of the first step.

(1) Third Step In the third step, a step of grafting the monomer mixture (III) containing an aromatic vinyl monomer as a main component to the graft copolymer mixture obtained in the second step Is. The monomer mixture (III) polymerized in the third step is the aromatic vinyl monomer 20.
To 100% by weight, 0 to 70% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms, and 0 to another vinyl monomer copolymerizable therewith.
50% by weight.

Specific examples of the aromatic vinyl monomer, the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms, and other vinyl monomers copolymerizable therewith include: It may be the same kind as described in the monomer mixture (I). The amount of the aromatic vinyl monomer in the monomer mixture (III) is in the range of 20 to 100% by weight. Two
If it is less than 0% by weight, the compatibility with the styrene resin (B) is poor and it is not preferable. The aromatic vinyl monomer is particularly preferably in the range of 60 to 80% by weight. The (meth) acrylic acid alkyl ester monomer is selected from 0 to 70% by weight, and particularly preferably 50% by weight or less. When a vinyl cyanide monomer is used as another copolymerizable vinyl monomer, it is preferably selected in the range of 0 to 50% by weight. When the amount of the vinyl cyanide monomer exceeds 50% by weight, not only the moldability of the thermoplastic resin (A) and the thermoplastic resin composition (C) is significantly lowered but also the thermal stability is deteriorated, which is preferable. Absent. The preferred range for vinyl cyanide monomer is 40% by weight or less.

The amount of the monomer mixture (III) to be further grafted on the graft copolymer obtained in the second step is the same as that of the acrylic graft copolymer obtained in the second step (obtained in the first step). 30 excluding 100 parts by weight (excluding copolymer)
It is preferable to select in the range of up to 300 parts by weight. If the amount of the monomer mixture (III) is less than 30 parts by weight, the amount of grafted thermoplastic resin (A) obtained in the third step is not sufficient, and if it exceeds 300 parts by weight, chemical resistance is high. However, the improvement effects such as stress cracking resistance at low temperature are saturated, but the productivity is decreased and the proportion of the acrylic copolymer is decreased, resulting in a thermoplastic resin composition with the styrene resin (B) described below. It is not preferable because there is a restriction when the product (C) is used. The amount of the monomer mixture (III) is particularly preferably selected from the range of 50 to 200 parts by weight.

The third step is preferably performed by the following procedure. First, a polymerization vessel is charged with the graft copolymer obtained in the second step, a part or all of the above-mentioned monomer mixture (III) is charged, and if necessary, a polymerization initiator, a molecular weight modifier, etc. Coexist and polymerize by a known polymerization method. Examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, an emulsion-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 the polymerization vessel, the type of the polymerization initiator, the type of radical polymerization initiator, the charging method and the like can be the same as in the case of the first step.

When the graft polymerization is carried out according to the above-mentioned procedure, a hard copolymer containing an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group has a carbon number of 2 to 2 in the alkyl group.
A graft polymer obtained by graft-polymerizing a monomer mixture (II) containing 12 (meth) acrylic acid ester as a main component, and a monomer mixture (I containing an aromatic vinyl monomer as a main component)
II) grafted ternary graft polymer, a copolymer of the monomer mixture (I), a copolymer of the monomer mixture (II), and a copolymer of the monomer mixture (III) A mixed thermoplastic resin (A) is obtained.

[2] Styrenic Resin (B) Since the above-mentioned thermoplastic resin (A) can be used as a molding material by itself, it can be used as it is 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.

Examples of the styrene resin (B) different from the thermoplastic resin (A) include polystyrene, high impact polystyrene, AS resin (acrylonitrile-styrene copolymer), SMA resin (styrene-maleic anhydride copolymer). ), 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 styrenic resin (B) vary 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 (C) comprising the thermoplastic resin (A) and the styrene-based resin (B) may be added to the thermoplastic resin (A), if necessary, within a range not impairing the object of the present invention. Thermoplastic resin other than styrene resin (B),
Various resin additives such as inorganic fillers, metal powders, reinforcing materials, plasticizers, compatibilizers, heat stabilizers, antioxidants, UV absorbers, dyes, pigments, antistatic agents, lubricants, flame retardants, etc. It can be added in 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.

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. 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 latex particles It was measured by "N4" 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) Flow mark Test piece (thickness 2.5mm, width 75mm,
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.

[0041]

[Table 1] ⊚: Flow marks are hardly recognized. ○: Flow mark is not recognized. Δ: Some flow marks are recognized. X: Flow marks are considerably recognized.

(5) Gloss With respect to the same type of test piece as used in the above (4) flow mark test, a variable angle gloss meter (VGS-3000A manufactured by Nippon Denshoku Industries Co., Ltd.
Type), the gloss value was measured at 10 points at an incident angle of 60 degrees, and the average value was displayed.

(6) Chemical resistance A test piece (thickness: 2 mm, width: 35) manufactured by the compression molding method.
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.

[0044]

[Table 2] ⊚: 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.

(7) 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.

(8) Delamination property 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.

[0047]

[Table 3] A: No peeling occurs. ◯: Almost no peeling. Δ: A little peeled off. X: It peels considerably.

Production of Thermoplastic Resin (A) First Step [Production Example 1-1] In a glass flask having a capacity of 3 liters, equipped with a stirrer, a heating / cooling device, a condenser, a thermometer, and a raw material / auxiliary charging device. , 1.4 l of deionized water, 20 g of higher fatty acid soap (sodium salt of fatty acid mainly having 18 carbon atoms), 10 g of sodium hydrogencarbonate,
The internal temperature was raised to 75 ° C. while stirring under a nitrogen stream.
The flask was charged with 1.35 g of potassium persulfate (KPS) and allowed to stand for 5 minutes, after which styrene (St) 693 was added.
g, 267 g of acrylonitrile (AN), and 40 g of a monomer mixture consisting of 10 g of chloromethylstyrene (CMS) were charged. After a few minutes, heat was generated and it was confirmed that the polymerization had started.

After holding for 20 minutes as it was, continuous charging of the remaining monomer mixture (960 g) was started. The total amount of the monomer mixture was charged over 3 hours (about 59 ml / 10).
Minutes). On the way, 1 hour and 40 minutes after starting the continuous charging, 100 ml of an aqueous solution in which 10 g of fatty acid soap was dissolved was charged, and further 2 hours and 10 minutes, KPS was 0.015 g.
5 ml of an aqueous solution in which was dissolved was additionally charged. After the continuous charging of the monomer mixture was completed, the polymerization reaction was continued for another 1 hour and then cooled to obtain a copolymer latex (Production Example 1
The copolymer latex obtained in -1 is abbreviated as "1-1",
The same shall apply hereinafter. ) Got. The obtained latex had a solid content concentration of 38.9% (conversion rate of about 97.8%), and the average particle size of the particles was 0.07 μm. In addition, the amount of solidified product generated during the polymerization was about 1.5 g.

[Production Example 1-2 to Production Example 1-6] Production Example 1
In the example described in -1, the monomer mixture is St700.
g, AN was changed to 300 g, and the polymerization reaction was performed by the same procedure as in the same example. The solid content concentration of the obtained copolymer latex (1-2) was 38.3%, and the average particle size of the particles was 0.08 μm (Production Example 1-2). In addition, also in Production Examples 1-3 to 1-6, 0.2 g (Production Example 1-3) and 1 g (Production Example 1-) of CMS were added to 1000 g of the monomer mixture (St / AN ratio constant), respectively. 4), 5
Polymerization reaction was performed by the same procedure as in the same example except that the amounts were changed to 0 g (Production Example 1-5) and 150 g (Production Example 1-6) to obtain a copolymer latex. The average particle size of the obtained latex is shown in Table 1.

[Production Example 1-7 to Production Example 1-8] Production Example 1
In the example described in -1, instead of 10 g of CMS, 10 g of chlorovinyl acetate (CVA) (Production Example 1-7) or 10 g of 2-chloroethyl vinyl ether (CEVE).
Polymerization reaction was carried out by the same procedure as in the same example except that was used. The average particle size of the obtained latex is shown in Table 1.

[Production Example 1-9] In the example described in Production Example 1-1, the monomer mixture was St560 g, AN240.
g, methyl methacrylate (MMA) 190 g, and CMS 10 g, except that the polymerization reaction was carried out by the same procedure as in the example. Table 1 shows the average particle sizes of the obtained latex (1-9).

[Production Example 1-10] In the example described in Production Example 1-1, the monomer mixture was St594 g, AN396.
g and CMS10g, except that
The polymerization reaction was performed by the same procedure as in the same example. Table 1 shows the average particle size of the obtained latex (1-10).
It is shown in FIG. Table 1 collectively shows the composition of the monomer mixture of the copolymer latexes 1-1 to 1-10 produced in the first step and the average particle size of the latex.

[0054]

[Table 4]

Second Step [Production Example 2-1] A glass flask having a capacity of 3 liters equipped with a stirrer, a heating / cooling device, a condenser, a thermometer, and a raw material / auxiliary charging device was obtained in the first step. 1325 g of copolymer latex (1-1) (solid content excluding emulsifier: 500 g) was charged, diluted with 500 ml of deionized water, and then the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream, and KPS0 20 ml of an aqueous solution containing 0.5 g was added. Then, after standing for 5 minutes, 500 g of acrylic acid butyl ester (BA) was continuously charged. The total amount of BA was charged over 3 hours (about 31 ml / 10 minutes). On the way, 100 ml of an aqueous solution in which 10 g of fatty acid soap was dissolved was charged one hour after the continuous charging was started, and further 2
At the hour, 50 ml of an aqueous solution prepared by dissolving 5 g of fatty acid soap,
50 ml of an aqueous solution containing 5 g of sodium hydrogen carbonate and 10 ml of an aqueous solution in which 0.25 g of KPS was dissolved were additionally charged. After the continuous charging of BA was completed, the polymerization reaction was continued for another hour and then cooled to obtain a copolymer latex. The method of Production Example 2-1 is abbreviated as "2-1",
The same shall apply hereinafter. The details of the formulation are shown in Table-2, and Examples and Comparative Examples in combination with the first step and the third step are shown in Table-5 to Table-8. Solid content concentration of the obtained latex 39.
6%, and the average particle size of the particles was 0.09 μm. In addition, the amount of solidified product formed during the polymerization was about 2 g.

[Production Example 2-2 to Production Example 2-5] Production Example 2
In the example described in -1, the polymerization reaction was carried out by the same procedure as in the same example except that BA was replaced with a mixture in which BA and CMS were mixed in the ratio shown in Table-2. These manufacturing methods are referred to as 2-2 to 2-5.

[Production Example 2-6] In the example described in Production Example 2-1, BA was 494.9 g, ethylene glycol dimethacrylate (EGDM) 0.1 g and CM.
The polymerization reaction was performed by the same procedure as in the same example except that the mixture was changed to S5g. This manufacturing method is referred to as 2-6.

[Production Example 2-7] A polymerization reaction was carried out by the same procedure as in the same example except that BA in the example described in Production Example 2-1 was changed to a mixture of BA485g, EGDM 10g and CMS 5g. . This manufacturing method is referred to as 2-7.

MANUFACTURING EXAMPLE 2-8 In the example described in Manufacturing Example 2-1, BA is BA 445 g, AN 50 g and C.
The polymerization reaction was carried out by the same procedure as in the same example except that the mixture was changed to 5 g of MS. This manufacturing method is referred to as 2-8.

[Production Example 2-9] In the example described in Production Example 2-1, BA was added to BA of 445 g, St of 50 g and C.
The polymerization reaction was carried out by the same procedure as in the same example except that the mixture was changed to 5 g of MS. This manufacturing method is referred to as 2-9.

[Production Example 2-10] A polymerization reaction was carried out by the same procedure as in the same Example except that BA was replaced with a mixture of BA495g and CAV5g in the example described in Production Example 2-1. This manufacturing method is referred to as 2-10.

[Production Example 2-11] In the example described in Production Example 2-1, BA was added in an amount of 495 g of BA and 5 g of CEVE.
Polymerization reaction was carried out by the same procedure as in the same example except that the mixture was replaced by the mixture. This manufacturing method is referred to as 2-11.

[Production Example 2-12] The copolymer obtained in the first step was placed in a glass flask having a capacity of 3 liters, which was equipped with a stirrer, a heating / cooling device, a condenser, a thermometer, and a raw material / auxiliary charging device. 2203 g of latex (1-1)
(The solid content excluding the emulsifier is 833 g), diluted with 100 ml of deionized water, and then stirred under a nitrogen stream while stirring.
The internal temperature was raised to 75 ° C., and 10 ml of an aqueous solution containing 0.25 g of KPS was added. Then, after leaving for 5 minutes, BA
Continuous charging of a monomer mixture consisting of 165.3 g and CMS 1.67 g was started. The total amount of the monomer mixture was charged over 1 hour (about 31 ml / 10 minutes). After the continuous charging of the monomer mixture was completed, the polymerization reaction was continued for another hour, and then the internal temperature was cooled to complete the reaction. The obtained copolymer latex had a solid content concentration of 39.9% and an average particle diameter of 0.07 μm. This manufacturing method is referred to as 2-12.

[Production Example 2-13] To a glass flask of the same type as used in Production Example 2-12, 1060 g (400 g of solid content excluding emulsifier) of copolymer latex (1-1) was charged and demolded. After diluting with 600 ml of ionized water, the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream, and 25 ml of an aqueous solution containing 0.7 g of KPS was added.
Then, after leaving for 5 minutes, BA594g and CMS6g
Continuous charging of the monomer mixture consisting of was started. The total amount of the monomer mixture was charged over 3 hours and 40 minutes. On the way, 100 ml of an aqueous solution in which 10 g of fatty acid soap was dissolved was charged one hour after the continuous charging was started, and further 2
80 ml of an aqueous solution containing 8 g of fatty acid soap
Then, 10 ml of an aqueous solution containing 0.2 g of KPS was charged.
This manufacturing method is referred to as 2-13.

[Production Example 2-14] In a glass flask of the same type as used in Production Example 2-12, 662.5 g of copolymer latex (solid content excluding emulsifier was 250).
g) After charging and diluting with 800 ml of deionized water, the internal temperature was raised to 75 ° C. with stirring under a nitrogen stream, and KPS was applied.
30 ml of an aqueous solution containing 0.8 g was added. Then 5
After standing for a minute, continuous charging of a monomer mixture consisting of 742.5 g of BA and 7.5 g of CMS was started. The total amount of the monomer mixture was charged over 4 hours and 30 minutes. On the way
One hour after starting continuous preparation, fatty acid soap 1
125 ml of an aqueous solution in which 2.5 g was dissolved was charged, and 100 g of an aqueous solution in which 10 g of fatty acid soap was dissolved was further prepared in 3 hours.
ml and 15 ml of an aqueous solution containing 0.3 g of KPS were charged. This manufacturing method is referred to as 2-14.

[Production Example 2-15] In the example described in Production Example 1-1, the composition of the monomer mixture (I) was BA990 g,
The polymerization reaction was performed by the same procedure as in the same example except that the mixture with 10 g of CMS was used. This manufacturing method is 2-1
Five.

[Production Example 2-16] In the example described in Production Example 1-1, the composition of the monomer mixture (I) was BA989.8.
g, CMS 10 g, and EGDM 0.2 g, except that the mixture was replaced by the same procedure as in the above example. This manufacturing method is referred to as 2-16.

[0068]

[Table 5]

Third Step [Production Example 3-1] In a glass flask having a capacity of 3 liters equipped with a stirrer, a heating / cooling apparatus, a condenser, a thermometer, and a raw material / auxiliary agent charging apparatus, Production Example 2 of the second step 1735 g of the copolymer latex obtained in -1 (667 g as solid content excluding emulsifier) and 350 g of deionized water containing 3.3 g of sodium bicarbonate were charged, and the internal temperature was raised to 75 ° C while stirring under a nitrogen stream. Warmed. After adding 20 ml of an aqueous solution containing 0.4 g of KPS and 5 minutes have passed, St233.
Continuous charging of a monomer mixture consisting of 3 g and AN100 g was started and completed over 2 hours (about 32
ml / 10 minutes). During this time, KPS0.
5 ml of an aqueous solution containing 1 g and 70 ml of an aqueous solution containing 6.7 g of fatty acid soap were added, and after the completion of charging the monomer mixture, the reaction was further continued at the same temperature for 1 hour. This manufacturing method is referred to as 3-1. This Production Example 3-1 was carried out according to the method "3-
1 ”is abbreviated, and the same applies hereinafter. The details of the formulation are shown in Table-3, and Examples and Comparative Examples in which the first step and the second step are combined are shown in Table-5 to Table-8. The solid content concentration of the obtained copolymer latex was 40.6%. This copolymer latex was coagulated, washed with water, dried and provided for evaluation.

[Production Example 3-2] A glass flask having a volume of 3 l was charged with the copolymer latex obtained in Production Example 2-3 in the second step (equivalent to 400 g of the acrylic copolymer in the second step). The same procedure as in Production Example 3-1 was performed until the temperature was raised. After 5 minutes had elapsed after adding 10 ml of an aqueous solution containing 0.2 g of KPS, continuous charging of a monomer mixture of St140 g and AN60 g was started, and the charging was completed over 1 hour and 20 minutes. During this period, 40 ml of an aqueous solution containing 4 g of fatty acid soap was added to the KPS0.
5 ml of an aqueous solution containing 1 g was added to each, and after the completion of charging the monomer mixture, the reaction was continued at the same temperature for 1 hour.
This manufacturing method is referred to as 3-2.

[Production Example 3-3] A glass flask having a volume of 3 l was charged with the copolymer latex obtained in Production Example 2-3 of the second step (equivalent to 250 g of the second step acrylic copolymer), The same procedure as in Production Example 3-1 was performed until the temperature was raised. After 5 minutes had elapsed after adding 20 ml of an aqueous solution containing 0.5 g of KPS, continuous charging of a monomer mixture of St350 g and AN150 g was started, and the charging was completed over 3 hours. During this time, KPS 0.2 at the second hour
10 ml of an aqueous solution containing 5 g and 100 ml of an aqueous solution containing 10 g of fatty acid soap were added, and after the completion of charging the monomer mixture, the reaction was further continued at the same temperature for 1 hour. This manufacturing method is referred to as 3-3.

[Production Example 3-4] A glass flask having a volume of 3 liters was charged with the copolymer latex obtained in the production example of the second step (equivalent to 143 g of the acrylic copolymer of the second step) and the internal temperature was raised. Until heating, the same procedure as in Production Example 3-1 was performed. After adding 30 ml of an aqueous solution containing 0.8 g of KPS and 5 minutes have passed, St500 g, AN214.3 g
The continuous charging of the monomer mixture consisting of
The preparation was completed in 0 minutes. During this time, 100 ml of an aqueous solution containing 10 g of fatty acid soap at 2 hours, KP at 3 hours
15 ml of an aqueous solution containing 0.3 g of S and 40 ml of an aqueous solution containing 4 g of fatty acid soap at 3 hours and 30 minutes, respectively,
After the completion of charging the monomer mixture, the reaction was further continued at the same temperature for 1 hour. This manufacturing method is referred to as 3-4.

[Production Example 3-5] In Production Example 3-1,
The composition of the monomer mixture is St 186.6 g, AN80.0
g, MMA was 66.7 g, and the polymerization was carried out by the same procedure as described in the same example. This manufacturing method is referred to as 3-5.

[Production Example 3-6] In Production Example 3-1,
The composition of the monomer mixture is St 200 g, AN 133.3 g
Polymerization was carried out by the same procedure as described in the same example except that the above was changed to. This manufacturing method is referred to as 3-6. Table 3 shows the composition of the monomer mixture in the third step.

[0075]

[Table 6]

Manufacture of Styrene Resin (B) B-1 (1) Manufacture of Rubbery Polymer Made of SUS with a capacity of 5 l equipped with a stirrer, heating and cooling device, condenser, thermometer, and raw material / auxiliary agent charging device In an autoclave, 150 parts of deionized water, higher fatty acid soap (sodium salt of fatty acid containing 18 carbon as the main component)
4.0 parts and 0.075 parts of sodium hydroxide were charged, the atmosphere was replaced with nitrogen, and then the internal temperature was raised to 68 ° C. while stirring. The autoclave was charged with 20% of a separately prepared monomer mixture consisting of 90 parts of 1,3-butadiene (BD), 10 parts of St and 0.3 part of t-dodecyl mercaptan (TDM), and 0.135 parts of KPS. 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. Obtained conjugated diene rubbery material (SBR)
The latex had a solid content concentration of 39.5% by weight, an average particle size of 0.08 μm, and a gel content of 95.0%.

(2) Preparation of Graft Copolymer The particle size of the above conjugated diene rubbery latex was enlarged by 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 of the above conjugated diene rubbery latex as a solid content (0.25 μm 8
0 part, a mixture of 20 parts of 0.65 μm) and 347 parts of deionized water (including water in the latex) were charged, and the internal temperature was raised to 70 ° C. while stirring under a nitrogen stream. When the internal temperature reached 60 ° C during the temperature rise, an aqueous solution prepared by dissolving 1.0 part of sodium pyrophosphate, 0.8 part of dextrose and 0.01 part of ferrous sulfate in 20 parts of deionized water was added to the reaction vessel. I put it in.

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 1 part was dissolved was continuously charged over 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, high-grade 2 parts of fatty acid soap (sodium salt of fatty acid having 18 carbon atoms as a main component) and 1 part of sodium hydrogencarbonate were charged, and the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream. KPS0.1 in the same autoclave
After adding 35 parts and 5 minutes, 4 parts of a monomer mixture containing 95 parts of BA, 5 parts of AN and 0.5 part of allyl methacrylate (AMA) were charged.

After a few minutes, heat was generated and the initiation of polymerization was confirmed. 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, 2 hours after adding the first monomer mixture, fatty acid soap 1
Then, 2 hours and 30 minutes later, 0.015 part of KPS was additionally charged. 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) Production of Graft Copolymer The above acrylic rubber-like (hereinafter referred to as AR) latex was made to have an average particle size of 0.15 μm by enlarging the particle size with acetic anhydride. 100 parts of the above AR latex as a solid content, 1 part of sodium hydrogen carbonate, and 274 parts of deionized water were placed in a reaction vessel having a capacity of 5 l equipped with a stirrer, a heating / cooling device, a thermometer, and a raw material / auxiliary charging device. Charge (including water in latex),
The internal temperature was raised to 80 ° C. while stirring under a nitrogen stream.

When the internal temperature reaches 70 ° C. during the heating,
0.5 part of AMA was added. When the internal temperature reached 80 ° C, deionization was performed with a monomer mixture containing 70 parts of St, 30 parts of AN, and 0.2 part of TDM, and 0.5 part of KPS, 1.8 parts of disproportionated potassium rosinate soap. An aqueous solution dissolved in 45 parts of water was 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, 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
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
After charging 4 parts, di-ter-butyl peroxide 0.
357 parts, ter-butyl peracetate 0.093 parts, and tapinolene 0.357 parts were charged, the temperature was raised to 97 ° C., and 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 part of di-ter-butyl peroxide and 0.357 part of tapinolene were dissolved in 36 parts of St was charged into an autoclave.
The average particle size of EPDM at the end of bulk polymerization is 1.6 μm.
Met.

An autoclave having 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 4 collectively shows production examples of the styrene resin (B).

[0085]

[Table 7]

Examples 1 to 22 The thermoplastic resin (A), the styrene resin (B) and the diluting AS resin (SAN-L manufactured by Mitsubishi Chemical Corporation) are shown in Table-5.
0.4 parts of magnesium stearate, 0.2 parts of hindered phenolic stabilizer, and 4.0 parts of titanium oxide were weighed and mixed into the resin raw materials in the ratios shown in Table-7, and uniformly blended with a blender. The mixture was mixed, kneaded with a Banbury mixer, and pelletized. For the resulting pellets,
Injection molding method for physical property measurement, appearance, gloss, chemical resistance,
Various evaluation tests such as low-temperature whitening occurrence strain value and delamination property were performed. The results of the evaluation test are shown in Table-5 to Table-7.

Comparative Examples 1 to 12 The thermoplastic resin (A), the styrene resin (B) and the diluting AS resin (SAN-L) were applied to the resin raw materials in the proportions shown in Tables 7 to 8. Additives of the same type as in the examples were weighed and blended in the same amounts, and pelletized by the same procedure as in the examples. Various evaluation tests were performed on the obtained pellets in the same procedure as in the examples. The results of the evaluation test are shown in Table-7 to Table-8.

[0088]

[Table 8]

[0089]

[Table 9]

[0090]

[Table 10]

[0091]

[Table 11]

From Table-5 to Table-8, the following is clarified. (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, is excellent in stress cracking resistance at low temperatures, and is layered. Not only peeling hardly occurs, but also chemical resistance is excellent, and physical properties such as tensile strength and impact resistance are not deteriorated (see Examples 1 to 22). (2) On the other hand, when the monomer having a chloromethyl group is not included in the first step (Comparative Example 1 to Comparative Example 2) or when the amount of the monomer is extremely small (Comparative Example 5), a molded article is obtained. The appearance (including flow marks, gloss, etc.), stress cracking resistance at low temperatures, chemical resistance, delamination, etc. are not well balanced. (3) When a large amount of a monomer having a chloromethyl group is included (Comparative Example 6), when the copolymer produced in the third step is excessive (Comparative Example 8), and when the second step has a large amount of crosslinking ( Comparative Example 1
0) in the case of omitting the first step (Comparative Example 3 and Comparative Example 4) or in the case where the copolymer produced in the second step was excessive in terms of chemical resistance and stress cracking resistance at low temperatures ( In Comparative Example 9), the appearance and delamination of the molded product are not excellent, and the balance is not good.

[0093]

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, 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 (6)

[Claims] 1. An aromatic vinyl monomer and 0.05 to 10
In the presence of the first step of polymerizing a monomer mixture (I) containing a vinyl monomer having a chloromethyl group in weight% (I), the copolymer obtained in the first step, the number of carbon atoms of the alkyl group is 2-1
Two (meth) acrylic acid alkyl ester monomers,
In the presence of the copolymer obtained in the second step of graft-polymerizing a monomer mixture (II) containing 0 to 10% by weight of a vinyl monomer having a chloromethyl group, and the copolymer of the second step. A thermoplastic resin obtained by the third step of graft-polymerizing a monomer mixture (III) containing a vinyl monomer. 2. The monomer mixture (I) comprises 20 to 99.95% by weight of an aromatic vinyl monomer, 0.05 to 10% by weight of a vinyl monomer having a chloromethyl group, and the number of carbon atoms of an alkyl group. Is 0 to 70% by weight of 1 to 4 (meth) acrylic acid alkyl ester monomers, and 0 to 50% by weight of other vinyl monomers copolymerizable therewith, and a monomer mixture (II)
Is 70 to 100% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 to 12 carbon atoms, 0 to 10% by weight of a vinyl monomer having a chloromethyl group, and other copolymerizable with them. Vinyl monomer of 0 to 30% by weight, and polyfunctional vinyl monomer of 0 to 1% by weight, and the monomer mixture (III) comprises 20 to 100% by weight of an aromatic vinyl monomer and an alkyl group. 0 to 70% by weight of a (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms in the group, and 0 to 50% by weight of another vinyl monomer copolymerizable therewith,
The thermoplastic resin according to claim 1, wherein the thermoplastic resin comprises: 3. In producing a thermoplastic resin, a monomer mixture (I) containing an aromatic vinyl monomer and 0.05 to 10% by weight of a vinyl monomer having a chloromethyl group is polymerized. In the presence of the first step, the copolymer obtained in the first step, a (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 to 12 carbon atoms and 0 to 10% by weight of chloro ester. A second step of graft-polymerizing a monomer mixture (II) containing a vinyl monomer having a methyl group, and a monomer containing an aromatic vinyl monomer in the presence of the copolymer obtained in the second step. A method for producing a thermoplastic resin, comprising a third step of graft-polymerizing the monomer mixture (III). 4. The monomer mixture (I) comprises 20 to 99.95% by weight of an aromatic vinyl monomer, 0.05 to 10% by weight of a vinyl monomer having a chloromethyl group, and the number of carbon atoms of an alkyl group. Is 0 to 70% by weight of 1 to 4 (meth) acrylic acid alkyl ester monomers, and 0 to 50% by weight of other vinyl monomers copolymerizable therewith, and a monomer mixture (II)
Is an alkyl group having 2 to 12 carbon atoms (meth) acrylic acid alkyl ester monomer 70 to 100% by weight, a chloromethyl group-containing vinyl monomer 0 to 10, and other vinyl copolymerizable with these. The monomer mixture (III) comprises 20 to 100% by weight of an aromatic vinyl monomer, and 0 to 30% by weight of a monomer, and 0 to 1% by weight of a polyfunctional vinyl monomer.
An alkyl group having 0 to 70% by weight of a (meth) acrylic acid alkyl ester monomer having 1 to 4 carbon atoms, and 0 to 50% by weight of another vinyl monomer copolymerizable therewith. The method for producing a thermoplastic resin according to claim 3, which is characterized in that. 5. The method for producing a thermoplastic resin according to claim 3, wherein the reaction in the first step to the third step is carried out by an aqueous emulsion polymerization method. 6. The thermoplastic resin (A) according to claim 1.
And a styrene resin (B) different from the thermoplastic resin (A), a thermoplastic resin composition (C).