JPH11228646A - Compounded rubber-reinforced thermoplastic resin, production and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compounded rubber-reinforced thermoplastic resin that has excellent weather resistance, chemical resistance and shock resistance and provide a thermoplastic resin composition containing the same. SOLUTION: In a rubber-reinforced thermoplastic resin prepared by grafting a monomer mixture including an aromatic vinyl monomer onto a rubber polymer, the rubber polymer is rubber-reinforced polymer having particle sizes of 0.05-1.2 μm and including a plurality of hard polymer particles of 0.01-0.5 μm sizes where the weight fraction of the hard polymer component is 0.01-15 pts.wt. in the rubber-reinforced polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite rubber-reinforced thermoplastic resin, a method for producing the same, and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a composite rubber-reinforced thermoplastic resin having excellent weather resistance and chemical resistance and also having extremely excellent impact resistance, a method for producing the same, and a composite rubber-reinforced thermoplastic resin composition containing the same.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resins represented by ABS resins have been used in a wide variety of applications because of their impact resistance, moldability and excellent appearance. Above all, it is used for a wide range of applications such as electrical equipment, housing of office equipment, and automobile parts. However, A
Since the BS resin uses a conjugated diene polymer having an unsaturated bond as a rubbery polymer as a base, it has a drawback of poor weather resistance and chemical resistance, and its use has been limited.

A rubber reinforced styrene resin (AAS resin, AES resin, respectively) using a highly saturated rubber as a base rubber, for example, a polyacrylate rubber, an ethylene / propylene / non-conjugated diene terpolymer rubber, etc. ) Can improve the above-mentioned weather resistance and chemical resistance. However, the rubber-reinforced styrene-based resin using these saturated rubbers as the base rubber has a disadvantage that sufficient impact resistance cannot be obtained. If the content of the rubbery polymer is increased, the impact resistance can be improved to some extent, but on the other hand, there is a drawback that the fluidity, rigidity, hardness, heat resistance, appearance, etc. of the obtained resin are deteriorated. Not preferred.

As an attempt to improve the impact resistance of a rubber-reinforced styrene-based resin using a highly saturated rubber as a base rubber, Japanese Patent Application Laid-Open No. 60-32811 discloses, for example,
Although a technique of enclosing a plurality of fine hard polymer particles inside the rubbery polymer particles of the AAS resin is disclosed, according to the experiments of the present inventors, the hard polymer particles and the rubbery polymer Probably because of the low interfacial adhesive strength (graft density) of the coalescence, the effect of improving the impact resistance was not sufficient.

Further, Japanese Patent Application Laid-Open No. 9-87340 discloses that an AAS resin containing a plurality of fine hard polymer particles in a rubbery polymer has a chloromethyl group for producing a fine hard polymer. By using a monomer mixture containing a vinyl monomer having, a technique for improving the interfacial adhesion strength between the hard polymer particles and the rubbery polymer has been disclosed, but a fine particle to be included inside the rubbery polymer is disclosed. The method of controlling the particle diameter and the content of the hard polymer particles is unclear, and according to the experiments of the present inventors, the impact resistance was not sufficiently improved. In addition, these publications describe the particle size of the fine hard polymer particles contained in the rubbery polymer, the content of the fine hard polymer particles, and the impact resistance exhibited by the obtained thermoplastic resin. No mention is made of the relationship.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have aimed at providing a composite rubber reinforced thermoplastic resin which is excellent in weather resistance and chemical resistance and also excellent in impact resistance. As a result of intensive studies, the present invention has been completed. The objects of the present invention are as follows. 1. To provide a composite rubber reinforced thermoplastic resin having excellent weather resistance and chemical resistance and also excellent impact resistance. 2. To provide a method for producing the above composite rubber reinforced thermoplastic resin. 3. Including the above composite rubber reinforced thermoplastic resin, weather resistance,
To provide a composite rubber-reinforced thermoplastic resin composition having excellent chemical resistance and also excellent impact resistance.

[0007]

In order to solve the above problems, the present invention provides a rubber obtained by graft copolymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of a rubbery polymer. In the reinforced thermoplastic resin, the rubbery polymer is a hard polymer having an average particle diameter of 0.05 to 1.5 μm and an average particle diameter (D _A ) of 0.01 to 0.05 μm inside. The composite rubber-based polymer particles include a plurality of particles, and the weight fraction (φ _{A / D} ) of the hard polymer component in the composite rubber-based polymer particles is 0.01 to 1
The present invention provides a composite rubber-reinforced thermoplastic resin characterized by being 5% by weight (first invention).

In the present invention, when producing a composite rubber-reinforced thermoplastic resin, a monomer mixture (I) containing an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group is prepared by an emulsion polymerization method. And polymerized by
In the presence of hard polymer particles (A) 0.01 to 40 parts by weight of the average particle diameter (D _A) is 0.01 to 0.05 [mu] m,
Latex of graft polymer particles (B) obtained by polymerizing 60 to 99.99 parts by weight (but 100 parts by weight in total) of monomer mixture (II) containing (meth) acrylic acid alkyl ester monomer Optionally, a monomer mixture containing a (meth) acrylic acid alkyl ester monomer (II
I) is obtained by polymerizing I) by an emulsion polymerization method, and is mixed with a latex of rubbery polymer particles (C) having an average particle diameter (D _C ) of 0.01 to 0.3 μm to increase the particle diameter. The average particle diameter (D _D ) containing a plurality of hard polymer particles (A) obtained by performing the operation is 0.05 to 1.5 μm.
Characterized in that, in the presence of the composite rubbery polymer particles (D), a monomer mixture (IV) containing an aromatic vinyl monomer is further graft-polymerized, the composite rubber-reinforced thermoplastic resin (E ) Is provided (second invention).

In the present invention, the monomer mixture (I)
Are 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, 0 to 50% by weight of a vinyl cyanide monomer, and The monomer mixture (II) comprises 70 to 100% by weight of a (meth) acrylic acid alkyl ester monomer and 0 to 70% by weight of a polyfunctional vinyl monomer. -3% by weight, and 0-30% by weight of another vinyl monomer copolymerizable therewith, and the monomer mixture (III) is composed of 70-100% by weight of an alkyl (meth) acrylate monomer. %, Polyfunctional vinyl monomer 0 to 3
% By weight, and 0 to 30% by weight of another vinyl monomer copolymerizable therewith, wherein the monomer mixture (IV) is 20 to 100% by weight of an aromatic vinyl monomer, and vinyl cyanide monomer 0 to 50% by weight of the polymer and 0 to 70% by weight of another vinyl monomer copolymerizable therewith, and 20 to 20 parts by weight based on 100 parts by weight of the composite rubbery polymer particles (D).
A method for producing a composite rubber-reinforced thermoplastic resin (E), characterized by graft copolymerizing 0 parts by weight of a monomer mixture (IV) (third invention).

In the present invention, the composite rubber-reinforced thermoplastic resin of the first invention, the composite rubber-reinforced thermoplastic resin (E) obtained by the method of the second invention, or the third
Composite rubber-reinforced thermoplastic resin (E) obtained by the method of the invention
A monomer comprising 20 to 100% by weight of an aromatic vinyl monomer, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 70% by weight of another vinyl monomer copolymerizable therewith; The present invention provides a composite rubber-reinforced thermoplastic resin composition characterized by comprising a thermoplastic resin (F) obtained by polymerizing a mixture (fourth invention).

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the composite rubber-reinforced thermoplastic resin is a rubber-reinforced thermoplastic resin obtained by graft copolymerizing a monomer mixture containing an aromatic vinyl monomer in the presence of the rubbery polymer (D). a resin, the rubbery polymer (D) is an average particle diameter of 0.05～1.5Myuemu, internal to an average particle diameter (D _a) is 0.01~0.05μm its hard It has a structure in which a plurality of polymer particles (A) are included.

The hard polymer particles (A) included in the rubber polymer (D) are obtained by polymerizing a monomer mixture (I) containing a vinyl monomer having a chloromethyl group by an emulsion polymerization method. Refers to polymer particles having a glass transition temperature of 20 ° C. or higher. The monomer mixture (I) used in the production of the hard polymer particles (A) essentially contains an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group. It may contain monomers and other vinyl monomers copolymerizable therewith.

The ratio of the aromatic vinyl monomer in the monomer mixture (I) is preferably selected in the range of 20 to 99.95% by weight. 20% by weight of aromatic vinyl monomer
If the amount is smaller, the coloring properties of the finally obtained resin and the appearance of the molded article obtained from this resin are unfavorably deteriorated. The preferred range of the ratio of the aromatic vinyl monomer is 4
0 to 99.95% by weight.

The aromatic vinyl monomer is typically styrene. In addition, α-alkylstyrenes such as α-methylstyrene, nuclear-substituted alkylstyrenes such as p-methylstyrene, bromostyrene, chlorostyrene Such as halogenated styrenes, alkoxystyrene, trifluoromethylstyrene, and vinylnaphthalene. These may be one kind or a mixture of two or more kinds.

The vinyl monomer having a chloromethyl group is
It is used for the purpose of efficiently graft-polymerizing the monomer mixture (II) used in the next step, and the proportion of the monomer mixture (I) in the range of 0.05 to 10% by weight. It is preferable to choose. If the proportion of the vinyl monomer having a chloromethyl group is less than 0.05% by weight, sufficient grafting cannot be achieved, resulting in a decrease in the adhesive force between the hard polymer particles and the rubbery polymer. The impact resistance of the obtained composite rubber-reinforced thermoplastic resin (hereinafter sometimes simply referred to as “resin finally obtained”) may be deteriorated. On the other hand, if the proportion is more than 10% by weight, the effect of improving the impact resistance is saturated, resulting in excessive use, which is economically disadvantageous. A preferred range of the ratio of the vinyl monomer having a chloromethyl group is
0.1 to 5% by weight.

The vinyl monomer having a chloromethyl group is
It has a vinyl group such as a vinyl ether group, an allyl ether group, a (meth) acryloyloxy group, a vinyl ester group, an allyl ester group, a styryl group, and a chloro group such as a chloromethylalkyl group, a chloroacetyl group, and a chlorobenzyl group. Any monomer having a methyl group may be used. These monomers may further have a functional group such as a hydroxyl group or an alkoxyl group. Specifically, chloromethyl styrene, chloroethyl vinyl ether, chloromethyl allyl ether, vinyl chloroacetate,
Allyl chloroacetate, 3-chloro-2-hydroxyl propyl methacrylate and the like are mentioned. The vinyl monomer having a chloromethyl group may be one type or a mixture of two or more types.

The ratio of the vinyl cyanide monomer in the monomer mixture (I) is preferably selected in the range of 0 to 50% by weight. If the proportion exceeds 50% by weight, the coloring properties and appearance of the finally obtained resin are unfavorably deteriorated.
A preferable ratio in the above range is 0 to 40% by weight. The ratio of the other copolymerizable vinyl monomer in the monomer mixture (I) is preferably selected in the range of 0 to 70% by weight. If the ratio exceeds 70% by weight, the colorability of the finally obtained resin and the appearance of the molded article obtained from this resin are unfavorably deteriorated as in the case where the amount of the vinyl cyanide monomer is large.

Specific examples of the vinyl cyanide monomer include:
Acrylonitrile, methacrylonitrile and the like can be mentioned. Specific examples of other polymerizable vinyl monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 1-butyl methacrylate and the like. Monomers. Among them, an alkyl methacrylate compound having 1 to 2 carbon atoms is preferable. These methacrylic acid ester compounds may be one kind or a mixture of two or more kinds.

For the purpose of increasing the hardness of the hard polymer particles (A), a small amount of a polyfunctional vinyl monomer may be copolymerized. Specific examples of these polyfunctional vinyl monomers include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, and (meth) acrylic acids such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate. Examples include polyhydric alcohol ester monomers, and allyl group-containing vinyl monomers such as diallyl fumarate, triallyl isocyanate, allyl methacrylate, and allyl acrylate.

The production of the hard polymer particles (A) can be carried out by a usual emulsion polymerization method. A part or all of the monomer mixture (I) and, if necessary, an emulsifier, a polymerization initiator, and a molecular weight regulator are charged into a reactor.
It is performed at the following temperature. Depending on the progress of the polymerization reaction, a method is employed in which the remaining monomer and the above-mentioned polymerization aids are additionally charged into the reactor.

The polymerization initiator used in the production of the hard polymer particles (A) includes, in addition to organic and inorganic peroxides known as radical polymerization initiators, so-called combinations of these with a reducing agent. A redox-based polymerization initiator is used.
As the emulsifier, conventionally used anionic, cationic, and nonionic emulsifiers can be used, and these can be combined as needed. As the chain transfer agent, conventionally known mercaptans, terpene compounds, and the like can be used.

According to experiments conducted by the present inventors, the average particle diameter (D _A ) of the hard polymer particles (A) included in the rubber polymer (D) is 0.01 to 0. .05 μm. When D _A is larger than 0.05 μm, the number of hard polymer particles (A) included in the rubber polymer particles (D) decreases, and the effect of improving the impact resistance of the finally obtained resin is sufficient. However, if it is less than 0.01 μm, production becomes difficult under ordinary emulsion polymerization conditions,
For example, a large amount of an emulsifier is required, which hinders the completion of graft polymerization in the next step, and both are not preferred. _A particularly preferred range of D _A is 0.01 to 0.04 μm.
m. The average particle diameter of the hard polymer particles (D _A) is, for example, the type and amount of the emulsifier, the type and amount of initiator, the reaction temperature, by appropriately changing the polymerization conditions such as reaction time, be readily adjusted Can be.

In the present invention, the average particle size is defined as a light scattering type dispersion obtained by using a dispersion obtained by diluting a polymer latex with an aqueous nonionic surfactant solution (a 0.1% aqueous solution of polyoxyethylene (10) octyl phenyl ether). Particle size measuring device (Coulter submicron particle analyzer-N
4S). When the average particle diameter (D _A ) of the hard polymer particles (A) is less than the lower limit of measurement (usually, about 0.05 μm) of the measuring device, the monomer mixture (II) described below is used. After performing the emulsion seed polymerization, the average particle diameter (D _B ) of the obtained graft polymer particles (B) is measured by this measuring device, and then the charged amount m of the hard polymer particles (A) used as the seed particles is measured. _a (parts by weight), and the following equation from the charged amount m _II of the monomer mixture (II) (parts by weight), _{i.e., D a = D B × {} m a / (m a + m
_II ) D _A (μm) can be obtained by calculating according to｝ ^1/3 .

The graft polymer particles (B) in the present invention
Means a monomer mixture (I) containing an alkyl (meth) acrylate monomer in the presence of the hard polymer particles (A).
Obtained by subjecting I) to emulsion seed polymerization, and
A hard polymer particle (A) having a core-shell structure in which a rubbery polymer composed of poly (meth) acrylic acid alkyl ester is grafted on the surface of the particle. The graft copolymer (B) is usually obtained in the form of an aqueous latex.

The monomer mixture (II) used for the production of the graft polymer particles (B) contains a (meth) acrylic acid alkyl ester monomer as a main component, and additionally contains a polyfunctional vinyl monomer and And other vinyl monomers copolymerizable therewith. The ratio of the (meth) acrylic acid alkyl ester monomer in the monomer mixture (II) is
It can be selected in the range of 70 to 100% by weight. If the ratio is less than 70% by weight, the dispersibility of the hard polymer particles (A) in the composite rubber particles is deteriorated, and the impact resistance of the finally obtained resin is unfavorably reduced. Particularly preferred in the above ratio is in the range of 80 to 100% by weight.

The alkyl (meth) acrylate monomers constituting the monomer mixture (II) include ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, and ethyl methacrylate. Propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These ester compounds may be a single compound or a mixture of two or more compounds. Usually, they are combined or selected so as to be easily compatible with the rubbery polymer constituting the rubbery polymer particles (C).

To the monomer mixture (II), a polyfunctional vinyl monomer can be added in the range of 0 to 3% by weight for the purpose of imparting elasticity by crosslinking the rubbery polymer. 3% by weight
If it exceeds, the dispersibility of the hard polymer particles (A) deteriorates, which is not preferred. A particularly preferred ratio of the polyfunctional vinyl monomer is from 0 to 1% by weight. Examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, and polyhydric alcohol esters of (meth) acrylic acid such as ethylenedaricol dimethacrylate and trimethylolpropane triacrylate. Examples include monomers, vinyl monomers having an allyl group such as diallyl fumarate, triallyl isocyanate, allyl methacrylate, and allyl acrylate. These polyfunctional vinyl monomers may be one kind or a mixture of two or more kinds.

The other copolymerizable vinyl monomer constituting the monomer mixture (II) can be added in the range of 0 to 30% by weight. When the ratio exceeds 30% by weight, the dispersibility of the hard polymer particles (A) similarly deteriorates, which is not preferable. A particularly preferred ratio of the other copolymerizable vinyl monomer is 0 to 20% by weight. Other copolymerizable vinyl monomers include (meth) acrylate compounds such as methyl acrylate and methyl methacrylate, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile,
Examples include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, and vinylnaphthalene. These may be one kind or a mixture of two or more kinds.

The graft polymer particles (B) are obtained by (i) using the hard polymer particles (A) obtained from the monomer mixture (I) as seed particles and adding the monomer mixture (II). (Ii) adding the monomer mixture (II) and, if necessary, the polymerization aids to the same reaction vessel after the production of the hard polymer particles (A); It can be produced by a method such as graft polymerization. In the case of the seed (seed) polymerization method (i), the hard polymer particles (A) latex and the monomer mixture (II)
A part or all of the above, if necessary, a polymerization aid such as an emulsifier, a polymerization initiator and a molecular weight regulator is charged into a reactor, and the polymerization reaction is usually carried out at a temperature of 100 ° C. or lower, depending on the progress of the polymerization reaction. Then, the remaining monomer and the above-mentioned polymerization aids are additionally added. In the case of the method (ii), the polymerization aids that can be used may be the same as those exemplified in the description relating to the production of the hard polymer particles (A).

In the production of the graft polymer particles (B), the monomer mixture (II) 60-99.99 parts by weight per 0.01-40 parts by weight of the hard polymer particles (A) used as seed particles. It must be in the range of 99 parts by weight (provided that the total amount of both is 100 parts by weight). When the amount of the monomer mixture (II) exceeds 99.99 parts by weight,
The content of the hard polymer (A) component in the composite rubber polymer particles (D) decreases, and the effect of improving the impact resistance of the finally obtained resin cannot be seen. ,
Since the hardness of the graft copolymer particles (B) is increased and the particles cannot be deformed or fused, the operation of enlarging the particle size in the next step cannot be performed, which is not preferable.

The weight fraction φ _{A / B} (% by weight) of the hard polymer (A) component in the graft polymer particles (B) is determined based on the amount of the hard polymer particles (A) used as seed particles. From the amount m _A (parts by weight) and the charged amount m _II (parts by weight) of the monomer mixture (II), the following formula: φ _{A / B} =
{ _{M A} / (m _A + m _II )} × 100. The weight fraction φ _{A / B} of the hard polymer (B) component in the graft polymer (B) is in the range of 1 to 40% by weight.

The average particle size of the graft polymer particles _(B) (D B) is preferably selected in the range of 0.01 to 0.3 [mu] m. And 0.3μm greater is D _B, at the time of particle径肥maximization operation for the next step, it may be difficult to adjust to the desired particle size, also, 0.01 [mu] m smaller particles usual emulsion The polymerization is difficult to produce, and may hinder the next step, for example, a large amount of an emulsifier is required. A particularly preferred range for DB is from 0.01 to 0.2 .mu.m.

The rubbery polymer particles (C) in the present invention are polymers obtained by polymerizing a monomer mixture (III) containing an alkyl (meth) acrylate monomer by an emulsion polymerization method. Refers to particles. The rubbery polymer particles (C) are usually obtained in the form of an aqueous latex.
The monomer mixture (III) used in the production of the rubbery polymer particles (C) contains a (meth) acrylic acid alkyl ester monomer as a main component, and further, a polyfunctional vinyl monomer, Other vinyl monomers copolymerizable therewith may be mixed.

The ratio of the alkyl (meth) acrylate monomer in the monomer mixture (III) is from 70 to 100.
It can be selected in the range of weight%. If the ratio is less than 70% by weight, the impact resistance of the finally obtained resin is undesirably reduced. Among them, a preferable ratio is 8
0 to 100% by weight. The polyfunctional vinyl monomer is mixed with the monomer mixture (III) for the purpose of imparting elasticity by crosslinking the rubbery polymer, and is usually selected in the range of 0 to 3% by weight. If the content exceeds 3% by weight, the dispersibility of the hard polymer particles (A) deteriorates, which is not preferable. A particularly preferable range is 0 to 1% by weight. The other copolymerizable vinyl monomer in the monomer mixture (III) is selected in the range of 0 to 30% by weight. If the content exceeds 30% by weight, the dispersibility of the hard polymer particles (A) similarly deteriorates, which is not preferable. A particularly preferable range is 0 to 20% by weight.

(Meth) used in the monomer mixture (III)
The alkyl acrylate monomer, the polyfunctional vinyl monomer, and the other copolymerizable vinyl monomer are the same as in the monomer mixture (II). Normally,
It is selected and combined so as to be easily compatible with the rubbery polymer constituting the surface of the graft copolymer particles (B).

The rubbery polymer particles (C) can be produced by a usual emulsion polymerization method. In manufacturing,
A part or all of the monomer mixture (III) and, if necessary, an emulsifier, a polymerization initiator, a molecular weight regulator and the like are charged into the reactor, and the polymerization reaction is usually performed at a temperature of 100 ° C. or lower. Depending on the progress of the polymerization reaction, the remainder of the monomers and the above-mentioned polymerization aids are additionally charged in the reactor. Examples of the polymerization aids include the same types as those exemplified in the description of the production of the hard polymer particles (A).

The average particle diameter (D) of the rubbery polymer particles (C)
_C ) must be between 0.01 and 0.3 μm. D _C
Is larger than 0.3 μm, it is difficult to adjust the particle diameter to a desired one in the subsequent step of enlarging the particle diameter.
When it is less than 01 μm, production becomes difficult under the usual conditions of emulsion polymerization, and it becomes a hindrance in the next step, for example, a large amount of emulsifier is required. A particularly preferred range for D _C is 0.01-0.2 μm.

In the present invention, the composite rubbery polymer particles (D) are the latexes of the graft polymer particles (B) or, if necessary, a mixed latex with the latex of the rubbery polymer particles (C) (hereinafter simply referred to as mixed). (Sometimes referred to as latex) refers to rubbery polymer particles obtained by enlarging the particle size and containing therein a plurality of hard polymer particles (A). The composite rubbery polymer particles (D) are usually obtained in the form of an aqueous latex.

In the present invention, the operation of enlarging the particle diameter means an operation of aggregating a polymer latex having a relatively small particle diameter having an average particle diameter of 0.3 μm or less to enlarge the average particle diameter. As the particle size enlargement operation, (i) a method of adding a flocculant such as an acid or a salt to the polymer latex, (ii) a method of shearing the polymer latex, (iii) thawing the polymer latex after freezing And other known methods. Among these, the method (i) is preferable,
For example, acid substances such as phosphoric acid and acetic acid, and inorganic salts such as calcium chloride and magnesium sulfate are added to the polymer latex to destabilize the emulsion system of the polymer latex,
The particles can be partially agglomerated. When producing a polymer latex, it is preferable to use an alkali metal salt of a long-chain fatty acid as an emulsifier, since the operation of enlarging the particle size can be performed efficiently.

In the production of the composite rubbery polymer particles (D), the mixing ratio of the graft polymer particles (B) and the rubbery polymer particles (C) is not particularly limited. ) The component is essential. The weight fraction of the graft polymer particles (B) in the mixed latex is 50 to 10
When the content is 0% by weight, the composite rubbery polymer particles (D)
It is particularly preferable because a sufficient number of the hard polymer particles (A) can be included therein, and the impact resistance of the finally obtained composite rubber-reinforced thermoplastic resin can be remarkably improved.

The average particle size (D _D ) of the composite rubbery polymer particles (D) must be 0.05 to 1.5 μm. When D _D is less than 0.05 .mu.m, the impact resistance of the finally obtained resin is not sufficiently improved, D _D is 1.5μm
If the ratio exceeds the above, the coloring property of the finally obtained thermoplastic resin and the appearance of the molded article obtained from this thermoplastic resin are deteriorated. A particularly preferred range of _DD is 0.1 to 1 μm.

The weight fraction φ _{A / D} (% by weight) of the hard polymer (A) component contained in the composite rubbery polymer particles (D) is as follows:
Weight fraction φ _{A / B} (weight%) of the hard polymer (A) component in the graft copolymer (B), weight fraction φ _{B / D} of the graft copolymer (B) component in the mixed latex ( Weight%), the following equation: φ _{A / D} = ｛(φ _{A / B} × φ
_{B / D} ) / 100 °.

In the present invention, according to the experiments of the present inventors, φ _{A / D} of the composite rubber-like polymer particles (D) is 0.1.
It is necessary to be within the range of 01 to 15% by weight. If φ _{A / D} is less than 0.01, the effect of improving the impact resistance of the finally obtained thermoplastic resin becomes insufficient, and if it exceeds 15% by weight, the composite rubbery polymer The elasticity of the particles (D) decreases, and the impact resistance of the finally obtained thermoplastic resin deteriorates.

The composite rubber-reinforced thermoplastic resin (E) according to the present invention refers to a monomer mixture (IV) containing an aromatic vinyl monomer using the composite rubber polymer particles (D) as seed particles. ) Is graft-polymerized by an emulsion seed polymerization method. The monomer mixture (IV) is
It is composed of 20 to 100% by weight of an aromatic vinyl monomer, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 70% by weight of another vinyl monomer copolymerizable therewith. Specific examples of these monomers may be the same as those mentioned for the monomer mixture (I).

The composite rubber-reinforced thermoplastic resin (E) can be produced by a usual emulsion seed polymerization method. A latex of the composite rubber polymer particles (D) and a monomer mixture (IV) are added to a reaction vessel. A part or all of, if necessary, charged together with polymerization aids such as an emulsifier, a polymerization initiator, a molecular weight regulator, or, as the polymerization reaction proceeds, additionally charge the polymerization reaction. Can be accomplished. The polymerization aids may be the same as those used when producing the graft polymer (B) and the rubbery polymer (C). After completion of the emulsion seed polymerization, the solid content in the latex is coagulated and precipitated by a technique such as salting out, and the obtained precipitate is recovered, washed with water, and dried to obtain a composite rubber-reinforced thermoplastic resin (E). . The production of the composite rubber-reinforced thermoplastic resin (E) is preferably performed consistently by an emulsion polymerization method in order to accurately control the morphology of the rubber particles.

The composite rubber-reinforced thermoplastic resin (E) according to the present invention can be used as it is as a molding material depending on the use. Further, the composite rubber-reinforced thermoplastic resin (E) is mixed with 20 to 100% by weight of an aromatic vinyl monomer, 0 to 50% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. Thermoplastic resin (F) obtained by polymerization of a monomer mixture comprising 0 to 50% by weight of a monomer, has excellent weather resistance and chemical resistance, and at the same time, has extremely excellent impact resistance. A resin composition is obtained.

The monomer mixture used for the production of the thermoplastic resin (F) may be the same as that described in the description of the monomer mixture (IV). However, it is not necessary that the kind, the use ratio, the amount, and the like be exactly the same as those of the monomer mixture (IV). The method for producing the thermoplastic resin (F) is not particularly limited, and the thermoplastic resin (F) can be produced by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof. Examples of the thermoplastic resin (F) include polystyrene (GPPS), AS resin (acrylonitrile-styrene copolymer), and SMA resin (styrene-styrene).
Maleic anhydride copolymer), AAS resin (acrylonitrile-acrylic acid ester-styrene copolymer), and the like, but are not limited thereto.

The composite rubber-reinforced thermoplastic resin (E) or the composite rubber-reinforced thermoplastic resin composition is used to reduce the content of the composite rubbery polymer particles (D) in the resin or resin composition finally obtained. It is preferably adjusted to be 4 to 40% by weight. When the content of the composite rubbery polymer particles (D) in the resin or the resin composition is less than 4% by weight, impact resistance and chemical resistance are not sufficiently exhibited, and the content exceeds 40% by weight. In such a case, the impact resistance is saturated, but the fluidity, rigidity, hardness, heat resistance, appearance and the like are deteriorated.

The composite rubber-reinforced thermoplastic resin (E) or the composite rubber-reinforced thermoplastic resin composition is further blended with another styrene resin to provide excellent coloring properties, molded appearance, and chemical resistance. It can be a molding material. Examples of styrene resins that can be blended include GPPS, impact-resistant polystyrene (HIPS), AS resin, SMA resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), and AES resin (acrylonitrile-EP).
DM-styrene copolymer), AAS resin, heat-resistant ABS
Resin (acrylonitrile butadiene-styrene-α-
Methyl styrene copolymer), super heat resistant ABS resin (acrylonitrile-butadiene-styrene-phenylmaleimide copolymer), MABS resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer), and the like. These may be one kind or a mixture of two or more kinds.

The mixing ratio of the composite rubber-reinforced thermoplastic resin (E) or the composite rubber-reinforced thermoplastic resin composition and the styrene-based resin blended with the composite rubber-reinforced thermoplastic resin (E) or the composite rubber It is preferable that the ratio of the composite rubbery polymer (D) contained in the reinforced thermoplastic resin composition to the final composition is in the range of 2 to 30% by weight. If it is less than 2% by weight, characteristics such as chemical resistance cannot be obtained. If it exceeds 30% by weight, the impact resistance is saturated, but the fluidity, rigidity, hardness, heat resistance,
Any of them is not preferable because the appearance and the like are deteriorated.

The rubber-reinforced thermoplastic resin (E) or the rubber-reinforced thermoplastic resin composition includes a kind and amount of a lubricant, a releasing agent, a coloring agent, an ultraviolet absorber, which do not inhibit the properties of the resin or the resin composition. Light fastness stabilizer, heat stabilizer, filler,
Various resin additives such as a flame retardant can be added in an appropriate combination.

The rubber-reinforced thermoplastic resin (E) and the rubber-reinforced thermoplastic resin composition according to the present invention are extremely excellent in impact resistance as well as weather resistance and chemical resistance. It can be used as a raw resin material for manufacturing electrical parts, automobile parts, housings of office equipment, and various industrial parts to be used. In order to manufacture (mold) the final product, injection molding, extrusion molding, compression molding,
Conventionally known various molding methods such as a hollow molding method and a differential pressure molding method can be used.

[0053]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the invention. In addition,
In the following examples, “parts” and “%｝” are based on weight unless otherwise specified.

In the following examples and comparative examples, the measurement and evaluation tests of various physical properties are based on the methods described below. (a) Average particle diameter of latex particles: Measured using a light-scattering particle diameter measuring device as described in detail in the above section. (b) Izod impact strength: (unit: kg-cm / cm) Measured on a 3.2 mm thick V-notched test piece according to JIS K7110. (c) Flexural modulus: (unit: kg / cm ² ) Measured by a method according to JIS K7203.

(D) Weather resistance: Using a xenon arc weatherometer (manufactured by Suga Test Instruments Co., Ltd.), a black panel temperature of 6
Light irradiation was performed for 300 hours under the conditions of 3 ° C., light intensity of 0.35 W, and no rain, and the color difference (ΔE *) before and after irradiation was measured to determine the weather resistance. The judgment results are shown in the following three stages.
○ means that the ΔE * value is less than 3 and the weather resistance is extremely good, and △ means that the ΔE * value is in the range of 3 to 6 and the weather resistance is good. , × means that the ΔE * value exceeds 6, and the weather resistance is poor.

(E) Chemical resistance: A test piece (thickness 2 mm, width 35 mm, length 230 mm) manufactured by a compression molding method was fixed to a bending form (a jig for continuously changing a curvature).
23 ° C. fluorohydrocarbon (HCFC-141
b) When left in an atmosphere for 17 hours, a critical strain value at which a crack was generated was measured to determine chemical resistance (bending foam method). The judgment results are shown in the following four stages. ◎
Means that the critical strain value exceeds 0.8% and the chemical resistance is extremely good, and ○ means that the critical strain value is 0.8 to 0.6.
% Means that the chemical resistance is good, △ means that the critical strain value is 0.6 to 0.4%, and the chemical resistance is slightly good, and × means that the critical strain value is good. Less than 0.4% means that the chemical resistance is poor.

[1] Production of Composite Rubber Reinforced Thermoplastic Resin (E) <Example of Production of Graft Polymer Latex (B)> [Production Example B-1] Stirrer, Heating / Cooling Device, Condenser, Raw Material 1300 g of deionized water was placed in a 3 liter glass flask equipped with an agent charging device.
20 g of higher fatty acid soap (a sodium salt having 18 carbon atoms as a main component) and 10 g of sodium hydrogen carbonate were charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Further, an aqueous solution obtained by dissolving 1.35 g of potassium persulfate (KPS) in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes. Then, 35 g of styrene (ST) and 15 g of acrylonitrile (AN) 15
g of chloromethylstyrene (CMS) and 0.5 g of allyl methacrylate (AMA). An exotherm occurred within a few minutes after the addition of the monomer mixture (I), indicating the start of the reaction. After maintaining the internal temperature at 75 ° C. for 22 minutes, 950 g of butyl acrylate (BA) and AMA
Continuous addition of 4.8 g of the monomer mixture (II) was started, and the entire amount was added over 180 minutes.

100 minutes after the start of continuous addition of the monomer mixture (II)
After a lapse of minutes, an aqueous solution obtained by dissolving 10 g of fatty acid soap (same as above) in 100 g of deionized water was further added to 13
At 0 minutes, 0.15 g of KPS was added to 15 parts of deionized water.
The aqueous solution dissolved in g was additionally charged. After the completion of the continuous addition of the monomer mixture (II), the polymerization reaction was continued at the same temperature for another 60 minutes, and then the internal temperature was cooled to obtain a latex containing the graft copolymer particles (B). The solid content of the latex is 39.2% (about 97.3% conversion), an average particle diameter D _B is 0.08 .mu.m, coagulum formed during the polymerization reaction was about 3g. Was determined by calculating the average particle size D _A of the hard resin particles (A), was 0.03 .mu.m. The latex obtained here is hereafter called B-1.

[Production Example B-2] A 300-liter glass flask equipped with a stirrer, a heating / cooling device, a condenser, and a raw material / auxiliary charging device was charged with 1300 g of deionized water and a higher fatty acid soap (above). 20g,
10 g of sodium hydrogen carbonate was charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Further, after an aqueous solution in which 1.35 g of KPS was dissolved in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes, ST 70 g, AN 30 g, CMS 1 g,
And 40 g of the monomer mixture (I) consisting of 1 g of AMA was added. An exotherm occurred within a few minutes after the addition of the monomer mixture (I), indicating the start of the reaction. After maintaining the internal temperature at 75 ° C. for 20 minutes, continuous addition of the remaining monomer mixture (I) was started, and the entire amount was added over 12 minutes.

Five minutes after the end of the continuous addition of the monomer mixture (I), the continuous addition of the monomer mixture (II) comprising 900 g of BA and 4.5 g of AMA was started, and the entire amount was added over 170 minutes. . 90 minutes after the start of the continuous addition of the monomer mixture (II), the fatty acid soap (same as above) 10
g in 100 g of deionized water.
At the time when 20 minutes had elapsed, an aqueous solution in which 0.15 g of KPS was dissolved in 15 g of deionized water was additionally charged.
After the continuous addition of the monomer mixture (II), an additional 60 minutes,
After the polymerization reaction was continued at the same temperature, the internal temperature was cooled to obtain a latex containing the graft copolymer particles (B). The solids concentration of the latex is 38.9% (conversion rate about 96.5).
%), The average particle diameter D _B is 0.08 .mu.m, coagulum formed during the polymerization reaction was about 2g. Also it was determined by calculating the average particle size D _A of the hard resin particles (A),
It was 0.04 μm. Latex obtained here,
Hereinafter, it is referred to as B-2.

[Production Example B-3] A 300-liter glass flask equipped with a stirrer, a heating / cooling device, a condenser, and a raw material / auxiliary charging device was charged with 1300 g of deionized water and a higher fatty acid soap (above). 20g,
10 g of sodium hydrogen carbonate was charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Further, an aqueous solution in which 1.35 g of KPS was dissolved in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes, then ST140 g, AN60 g, CMS2
g and 40 g of the monomer mixture (I) composed of 2 g of AMA. A few minutes after the addition of the monomer mixture (I), heat was generated and the reaction was started. After maintaining the internal temperature at 75 ° C. for 20 minutes, continuous addition of the remaining monomer mixture (I) was started, and the entire amount was added over 32 minutes.

After 5 minutes from the end of the continuous addition of the monomer mixture (I), 800 g of BA and 4 g of AMA
The continuous addition of the monomer mixture (II) consisting of
The entire amount was added over 0 minutes. 70 minutes after the start of the dropping of the monomer mixture (II), the fatty acid soap (same as above)
An aqueous solution obtained by dissolving 10 g in 100 g of deionized water was further added with 0.15 g of KPS in 15 minutes of deionized water at 100 minutes.
The aqueous solution dissolved in g was additionally charged. After the completion of the continuous addition of the monomer mixture (II), the polymerization reaction was continued at the same temperature for another hour, and then cooled to obtain a latex containing the graft copolymer particles (B). The solid content of the latex 39.0% (about 97.2% conversion), an average particle diameter D _B is 0.07 .mu.m, coagulum formed during the polymerization reaction was about 2g. Also was 0.04μm, which was determined by calculating the average particle size D _A of the hard resin particles (A). The latex obtained here is hereafter called B-3.

[Production Example B-4] A 300-liter glass flask equipped with a stirring device, a heating / cooling device, a condenser, and a raw material / auxiliary charging device was charged with 1300 g of deionized water and a higher fatty acid soap (above). 20g,
10 g of sodium hydrogen carbonate was charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Further, an aqueous solution in which 1.35 g of KPS was dissolved in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes, and then ST210 g, AN90 g, and CMS3
g and 40 g of the monomer mixture (I) consisting of 3 g of AMA. A few minutes after the addition of the monomer mixture (I), an exotherm occurred, indicating the start of the reaction. After maintaining the internal temperature at 70 ° C. for 20 minutes, continuous addition of the remaining monomer mixture (I) was started, and the entire amount was added over 50 minutes.

After 5 minutes from the end of the continuous addition of the monomer mixture (I), 700 g of BA and AMA3.
Start continuous addition of monomer mixture (II) consisting of 5 g
The entire amount was added over 130 minutes. At 50 minutes after the start of continuous addition of the monomer mixture (II), an aqueous solution obtained by dissolving 10 g of fatty acid soap (same as above) in 100 g of deionized water was further added at a time of 80 minutes.
Was dissolved in 15 g of deionized water. After the continuous addition of the monomer mixture (II) was completed, the polymerization reaction was continued at the same temperature for an additional hour, and then the temperature inside the flask was cooled to obtain a latex containing the graft copolymer particles (B). . Latex solids concentration 39.4
% (Conversion 97.8%), an average particle diameter D _B is 0.08μ
m and about 9 g of coagulate formed during the polymerization. Also was determined by calculating the average particle size D _A of the hard resin particles (A), was 0.06 .mu.m. The latex obtained here is hereafter called B-4.

[Production Example B-5] 1300 g of deionized water, a higher fatty acid soap (above) were placed in a 3-liter glass flask equipped with a stirrer, a heating / cooling device, a condenser, and a device for charging raw materials and auxiliaries. 20g,
10 g of sodium hydrogen carbonate was charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Further, an aqueous solution in which 1.35 g of KPS was dissolved in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes, and then ST350 g and acrylonitrile AN1
40 g of a monomer mixture (I) consisting of 50 g, 5 g of CMS, and 5 g of AMA was added. A few minutes after the addition of the monomer mixture (I), an exotherm occurred, indicating the start of the reaction. After maintaining the internal temperature at 75 ° C. for 20 minutes, continuous addition of the remaining monomer mixture (I) was started,
The whole amount was continuously added over 90 minutes.

Five minutes after the end of the continuous addition of the monomer mixture (I), 500 g of BA and AMA2.
5 g of the monomer mixture (II) was continuously added, and 9
The entire amount was added over 0 minutes. 10 minutes after the start of continuous addition of the monomer mixture (II), an aqueous solution obtained by dissolving 10 g of fatty acid soap (same as above) in 100 g of deionized water was used.
Further, after 40 minutes, an aqueous solution in which 0.15 g of KPS was dissolved in 15 g of deionized water was additionally charged. After the polymerization was continued at the same temperature for another hour after the continuous addition of the monomer mixture (II) was completed, the internal temperature of the flask was cooled to obtain a latex containing the graft copolymer particles (B). . Solid concentration 39.2% latex (conversion 97.0%), an average particle diameter D _B is 0.08 .mu.m, coagulum produced during polymerization was about 3g. Also was determined by calculating the average particle size D _A of the hard resin particles (A), was 0.07 .mu.m. The latex obtained here is hereafter called B-5.

<Production Example of Rubber Polymer Latex (C)> A 300-liter glass flask equipped with a stirrer, a heating / cooling device, a condenser, and a raw material / auxiliary charging device was charged with 1300 g of deionized water. , 20 g of a higher fatty acid soap (same as above) and 10 g of sodium hydrogen carbonate, and the internal temperature was raised to 75 ° C. under a nitrogen stream. Furthermore, K
An aqueous solution prepared by dissolving 1.35 g of PS in 135 g of deionized water was charged into a flask and allowed to stand for 5 minutes.
And 40 g of the monomer mixture (III) consisting of 5 g of AMA
Was added. A few minutes after the addition of the monomer mixture (III), an exotherm occurred, indicating the start of the reaction. After maintaining the internal temperature at 75 ° C. for 20 minutes, continuous addition of the remaining monomer mixture III) was started, and the entire amount was added over 200 minutes.

After 90 minutes from the start of the continuous addition of the monomer mixture (III), the fatty acid soap (same as above)
An aqueous solution obtained by dissolving 10 g in 100 g of deionized water and an aqueous solution obtained by dissolving 0.15 g of KPS in 15 g of deionized water were further charged after 120 minutes. After the polymerization was continued at the same temperature for another hour after the continuous addition of the monomer mixture (III) was completed, the temperature in the flask was cooled to obtain a latex containing the rubbery polymer particles (C). Was. The latex had a solid content of 39.5% (conversion 98.8%), an average particle diameter D _C of 0.08 μm, and 3 g of a coagulated product formed during the polymerization. The obtained latex is hereinafter referred to as C-1. Table 1 collectively shows production examples of the graft polymer (B) and the rubbery polymer (C).

[0069]

[Table 1]

<Production Example of Composite Rubbery Polymer (D)> [Production Example D-1] A 2-liter glass flask equipped with a stirrer, a heating / cooling device, and a raw material / auxiliary charging device was prepared. , Graft polymer latex (B-1) 1
061 g (solid content: 416 g) was weighed and charged, and the internal temperature was raised to 40 ° C. under a nitrogen stream. Then, 4 g of acetic anhydride
And 89 g of deionized water were weighed in a beaker, mixed and dispersed in a short time with a homomixer, and then added to a flask charged with the latex with stirring. When the mixture is homogeneously mixed, the stirring is stopped, and after allowing to stand for 10 minutes, a 10% aqueous solution of sodium dodecylbenzene sulfonate (DBS)
0 g, 29 g of 10% aqueous solution of potassium hydroxide (KOH)
Was added, and stirring was resumed. The average particle diameter D _D of the resulting latex, 0.31 .mu.m, resulting coagulum was 2g. This latex is hereafter referred to as D-1.

[Production Example D-2] 578 g of the graft polymer latex (B-2) (solid) was placed in a 2-liter glass flask equipped with a stirrer, a heating / cooling device, and a raw material / auxiliary charging device. 225 g) and 488 g of a rubbery polymer latex (C-1) (solid content 19
3 g) were weighed and charged, and the internal temperature was raised to 40 ° C. under a nitrogen stream. Next, 4 g of acetic anhydride and 89 g of deionized water were weighed into a beaker, mixed and dispersed in a short time with a homomixer, and then added to a flask charged with the latex with stirring. When the mixture is uniformly mixed, the stirring is stopped, and the mixture is left for 10 minutes.
g and 26 g of a 10% aqueous KOH solution were added, and stirring was resumed. The average particle diameter D _D of the resulting latex,
0.29 μm, and the formed coagulated product was 3 g. This latex is hereafter referred to as D-2.

[Production Example D-3] The procedure of Production Example D-1 was repeated except that the graft polymer latex was changed to 1069 g (solid content: 416 g) of the graft polymer (B-2). In the same procedure as described above, a particle size enlarging operation was performed to obtain a composite rubber latex D-3. Average particle diameter D _D
Was 0.29 μm, and the formed coagulate was 2 g.

[Production Example D-4] In the example described in Production Example D-1, the graft polymer latex was changed to 1053 g (solid content: 416 g) of the rubbery polymer (C-1), and acetic anhydride was used. Except that the amount was changed to 4.3 g, the procedure of enlarging the particle diameter was performed in the same procedure as in the same example to obtain a composite rubber latex D-4. The average particle diameter D _D is, 0.31Myu
m, the amount of the formed solid was 1 g.

[Production Example D-5] In the same manner as in Production Example D-1, except that the graft polymer latex was changed to 1066 g (solid content: 416 g) of the graft polymer latex, In the same procedure as described above, a particle size enlarging operation was performed to obtain a composite rubber latex D-5. Average particle diameter D _D
Was 0.30 μm, and the formed coagulated product was 2 g.

[Production Example D-6] In the example of Production Example D-2, 170 g (solid content: 67 g) of the graft polymer latex (B-4) and the rubbery polymer latex were used. Except that (C-1) was replaced by 883 g (solid content: 349 g), a procedure for enlarging the particle diameter was performed in the same procedure as in the same example, and the composite rubber latex D-
6 was obtained. The average particle diameter D _D is 0.30 .mu.m, resulting coagulum was 2g.

[Production Example D-7] In the example described in Production Example D-2, the graft polymer latex was obtained by adding 217 g (solid content: 85 g) of the graft polymer latex (B-5) and rubbery polymer RADEX. (C-1) Except for replacing with 838 g (solid content: 331 g), the particle size enlarging operation was performed in the same procedure as in the same example, but a precipitate of coagulated product was generated, and the composite rubber polymer particles were removed. I couldn't get it.
The average particle diameter D _D of this time the supernatant latex 0.2μ
m, and the produced coagulated product was 52 g. The same operation of increasing the particle size was repeated while changing the amount of acetic anhydride. However, the particles aggregated, and the particle size could not be further increased. Table 2 shows examples of the production of the composite rubbery polymer (D) (D-1 to D-7).

[0077]

[Table 2]

<Production Example of Composite Rubber-Reinforced Thermoplastic Resin (E)> [Production Example E-1] A 3-liter glass made up of a stirrer, a heating / cooling device, a condenser, and a raw material / auxiliary charging device. In the flask, add the composite rubber latex (D-
1) 1200 g (solid content: 358 g) was charged.
518 g of a 10% aqueous sodium hydrogen carbonate solution was charged, and the internal temperature was raised to 75 ° C. under a nitrogen stream. After an aqueous solution in which 5 g of KPS was dissolved in 160 g of deionized water was charged into a flask and allowed to stand for 5 minutes, continuous addition of a monomer mixture (IV) consisting of 375 g of ST and 161 g of AN was started, and was continued over 180 minutes. During this period, 80 g of a 10% fatty acid soap aqueous solution was deionized 90 minutes after the start of the continuous addition, and 80 g of a 10% fatty acid soap (same as above) aqueous solution and KPS 0.5 g were deionized at a time of 150 minutes. An aqueous solution dissolved in 18 g of water was additionally charged.
After the completion of the continuous addition of the monomer, the graft polymerization reaction was continued at the same temperature for 1 hour, and then the temperature inside the flask was cooled to terminate the polymerization reaction, thereby obtaining a graft copolymer E-1.

[Production Example E-2 to Production Example E-6] Production Example E
-1 in the composite rubber latex D-1
In place of the above, D-2 to D-6 were used to carry out a graft polymerization reaction in exactly the same procedure as in the same example to obtain composite rubber reinforced thermoplastic resins E-2 to E-6.

[2] Preparation and evaluation of resin composition Composite rubber-reinforced thermoplastic resin (E) (E-1 to E-
6), a styrene-acrylonitrile copolymer commercially available as a thermoplastic resin (F) (manufactured by Technopolymer Co., Ltd .;
Product name: Sunrex SAN-C) and ethylene bisstearylamide (manufactured by Kao Corporation, trade name: Kaowax EB-P) as a lubricant (G), respectively, the mixing ratio (parts by weight) described in Table-3 Was weighed. After mixing these with a tumbler, they were melt-kneaded using a twin-screw extruder with a vent to prepare pellets of the resin composition while removing volatile components. The resin composition was blended so that the content of the composite rubbery polymer particles (B) was 20% by weight. For the obtained pellets, test pieces for measuring physical properties and light resistance were prepared by injection molding, and test pieces for evaluating chemical resistance were prepared by press molding. An evaluation test was performed on the obtained test piece by the method described above. Table 3 shows the results.

[0081]

[Table 3]

From Tables 1 to 3, the following is clear. (1) The composite rubber-reinforced thermoplastic resin according to the present invention, by satisfying the requirements described in the claims, not only exhibits excellent weather resistance and chemical resistance unique to AAS resin, but also exhibits ordinary AAS resin. It can be seen that they also exhibit extremely excellent impact resistance that cannot be obtained (see Examples 1 to 3). (2) On the other hand, those in which the hard polymer particles are not included in the rubbery polymer particles are inferior in impact resistance to the weather resistance and the chemical resistance as compared with those of the examples (Comparative Example 1). (3) When the weight fraction (φ _{A / D} ) of the hard polymer component in the composite rubber polymer particles exceeds 15%, the impact resistance is poor (Comparative Example 2). (4) The average particle diameter of the hard polymer particles (A) is 0.05 μm
If it exceeds 1, the impact resistance is inferior (Comparative Example 3). (5) If the amount of the monomer mixture (I) exceeds 40 parts by weight in the production of the graft copolymer (B), a large amount of aggregates precipitate during the operation of enlarging the particle size. It can be seen that the composite rubbery polymer (D) was not obtained (Production Example D-7).

[0083]

The present invention has been described in detail above, and has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. The composite rubber-reinforced thermoplastic resin according to the present invention (first invention) includes a hard polymer component as a fine specific particle diameter in a base rubbery polymer and a weight occupying the rubbery polymer component. Since the fraction is in a specific range, it not only exhibits weather resistance and chemical resistance, but also exhibits extremely excellent impact resistance. 2. ADVANTAGE OF THE INVENTION According to the manufacturing method (2nd invention, 3rd invention) of the composite rubber reinforced thermoplastic resin which concerns on this invention, a hard polymer component with a fine particle diameter can be included in a specific amount in the rubbery polymer of a base material. This makes it possible to easily produce a rubber-reinforced thermoplastic resin having not only the desired weather resistance and chemical resistance but also excellent impact resistance. 3. The composite rubber-reinforced thermoplastic resin composition according to the present invention (the fourth invention) is not only excellent in weather resistance, chemical resistance, impact resistance and the like, but also excellent in fluidity, coloring property, rigidity, appearance and the like. Molding material.

Claims (4)

[Claims] 1. An aromatic vinyl monomer in the presence of a rubbery polymer.
Obtained by graft copolymerization of a monomer mixture containing
Rubber-reinforced thermoplastic resin
Is the average particle diameter (D_A) Is 0.05 to 1.5 μm
Having an average particle size of 0.01 to 0.05 μm
Composite rubbery polymer containing a plurality of hard polymer particles
Particles, and occupy in the composite rubbery polymer particles.
Weight fraction of the hard polymer component (φ _{A / D}) Is 0.01 to 1
5% by weight of composite rubber reinforced thermoplastic
Resin. 2. In producing a composite rubber-reinforced thermoplastic resin, a monomer mixture (I) containing an aromatic vinyl monomer and a vinyl monomer having a chloromethyl group is polymerized by an emulsion polymerization method. Obtained and average particle diameter (D _A )
Having a particle size of 0.01 to 0.05 μm (A)
In the presence of 0.01 to 40 parts by weight, a monomer mixture (II) 60 containing an alkyl (meth) acrylate monomer
The latex of the graft polymer particles (B) obtained by polymerizing ９９99.99 parts by weight (however, a total of 100 parts by weight) may be converted into a monomer containing a (meth) acrylic acid alkyl ester monomer, if necessary. The mixture (III) is obtained by polymerization by an emulsion polymerization method, and is mixed with a latex of rubbery polymer particles (C) having an average particle size (D _c ) of 0.01 to 0.3 μm to obtain a particle size. In the presence of composite rubbery polymer particles (D) containing a plurality of hard polymer particles (A) and having an average particle diameter (D _D ) of 0.05 to 1.5 μm, obtained by performing the enlargement operation. A method for producing a composite rubber-reinforced thermoplastic resin (E), further comprising graft-polymerizing a monomer mixture (IV) containing an aromatic vinyl monomer. 3. A monomer mixture (I) comprising 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 vinyl cyanide monomer The monomer mixture (II) is composed of 0 to 50% by weight of a body and 0 to 70% by weight of another vinyl monomer copolymerizable therewith. 100% by weight, 0 to 3% by weight of a polyfunctional vinyl monomer, and 0% of another vinyl monomer copolymerizable therewith.
And a monomer mixture (III) comprising 70 to 100% by weight of an alkyl (meth) acrylate monomer, 0 to 3% by weight of a polyfunctional vinyl monomer, and It is composed of 0 to 30% by weight of another polymerizable vinyl monomer, and the monomer mixture (IV) is an aromatic vinyl monomer 20.
To 100% by weight, 0 to 50% by weight of a vinyl cyanide monomer, and 0% of another vinyl monomer copolymerizable therewith.
20 to 200 parts by weight of the monomer mixture (IV) per 100 parts by weight of the composite rubbery polymer particles (D) by graft graft copolymerization. 2. The composite rubber-reinforced thermoplastic resin (E) according to 2.
Manufacturing method. 4. The composite rubber-reinforced thermoplastic resin according to claim 1, or the composite rubber-reinforced thermoplastic resin (E) obtained by the method according to claim 2, or the method according to claim 3. In the obtained composite rubber-reinforced thermoplastic resin (E), 20 to 100% by weight of an aromatic vinyl monomer, 0 to 50% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. A composite rubber-reinforced thermoplastic resin composition comprising a thermoplastic resin (F) obtained by polymerizing a monomer mixture comprising 0 to 70% by weight of a monomer.