JPH07207103A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in chemical resistance and shock resistance by compounding a graft copolymer containing an acrylic-acid alkyl ester rubber, a graft copolymer containing a conjugated diene rubber and a specific copolymer in such a manner that the rubbery polymers are contained at a specific ratio in the composition. CONSTITUTION:This composition is obtained by compounding (A) a graft copolymer, etc., obtained by the graft copolymerization of 20-80 pts.wt. of an unsaturated cyano compound, etc., in the presence of 20-80 pts.wt. of an enlarged rubbery copolymer latex obtained by adding an acid-group containing copolymer latex, etc., to an acrylic- acid alkyl-ester rubbery copolymer latex obtained by the emulsion polymerization of 15-99.9wt.% of an acrylic acid alkyl ester with 0.1-85wt.% of a conjugated diene, etc., and a copolymerizable monomer and (B) a graft copolymer, etc., obtained by the graft copolymerization of an unsaturated cyano compound, etc., in the presence of an enlarged rubbery copolymer latex obtained by adding an acid group-containing copolymer latex, etc., to a rubbery conjugated diene copolymer latex obtained by the emulsion polymerization of 70-100wt.% of a conjugated diene with 0-30wt.% of another monomer. In the obtained composition, the total content of the rubbery polymers is 15-30wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent chemical resistance and impact resistance.

[0002]

BACKGROUND OF THE INVENTION A graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a crosslinked acrylic ester rubber, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. ASA resin consisting of polymer has good chemical resistance to relatively polar solvents such as alcohols, organic halides and fatty acids (property to prevent cracking under environmental stress).
Is known to have. However, the conventional ASA resin is not sufficient for chemicals that have a great influence on resins such as CFC 141D, dioctyl phthalate, and brake oil, and the ASA resin also has a defect that impact strength development is low. In order to obtain high impact strength expression, a means of increasing the rubber content is usually adopted,
In this method, the surface hardness and the rigidity are lowered, so that the usage of the resin is significantly limited, which is not preferable.

[0003]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to obtain a resin composition having an excellent physical property balance between chemical resistance and impact strength development, a graft copolymer having an acrylate ester rubber component was obtained. By blending a polymer with a graft copolymer using a conjugated diene rubber and a high-acrylonitrile copolymer, a resin can be obtained that is excellent in the physical property balance between chemical resistance and impact strength development. It has been found that a composition is obtained and the invention has been reached.

The gist of the present invention is to provide (I) 15 to 99.9% by weight of an alkyl acrylate and 0.1 to 85% by weight of a monomer copolymerizable with a conjugated diene and / or an alkyl acrylate. The acrylic acid alkyl ester rubbery copolymer (a) latex obtained by emulsion polymerization is added to the acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex (i) is oxygenated. In the presence of 20 to 80 parts by weight (as solid content) of the enlarged rubbery copolymer (a ') latex obtained by adding the metal salt (ii) of A graft copolymer (A) obtained by graft-polymerizing 20 to 80 parts by weight of one or more monomers selected from compounds and unsaturated ester compounds, and a conjugated diene rubbery polymer (b-1) latex or Monoorganic mixture of alkyl acrylate ester and a monomer copolymerizable therewith in the presence of 5 to 80% by weight (as solid content) of the polyorganosiloxane rubber-like polymer (b-2) latex 20
Unsaturated rubber compound, aromatic vinyl compound, unsaturated ester compound in the presence of 20 to 80 parts by weight (as solid content) of the composite rubbery polymer (b ′) latex obtained by seed polymerization of ˜95% by weight. One or more kinds of monomers selected from 20 to 80 parts by weight of graft copolymer (B) and one or more kinds of graft copolymers selected from (II) conjugated diene 70 to 100 parts by weight % And 0 to 30% by weight of a copolymerizable monomer therewith, the conjugated diene rubbery copolymer (c) latex obtained by emulsion polymerization is added to the acid group-containing copolymer latex (i) or required. In the presence of the enlarged rubber-like copolymer (c ') latex obtained by adding the metal salt of oxygen acid (ii) to the acid group-containing copolymer latex in accordance with , Aromatic vinyl compounds A graft copolymer obtained by graft-polymerizing at least one monomer selected from unsaturated ester compounds, and (III) 35-65% by weight of unsaturated cyan compound and 35-65% by weight of aromatic vinyl compound A thermoplastic resin composition comprising a copolymer obtained by copolymerizing a monomer consisting of: a bloated rubber-like copolymer (a ') in 100% by weight of the thermoplastic resin composition; The total ratio of the composite rubber-like polymer (b ') and the enlarged rubber-like copolymer (c') is 15 to 30% by weight, and the ratio of the alkyl acrylate unit forming the rubber-like polymer is It is 5 to 25% by weight with respect to 100% by weight of the thermoplastic resin composition.

The present invention will be described in more detail below. The acrylic acid alkyl ester-based rubbery copolymer (a) used for the graft copolymer (A) is copolymerized with 15 to 99.9% by weight of an alkyl acrylate and a conjugated diene and / or an alkyl acrylate. Possible monomers 0.
It is obtained by emulsion copolymerization with 1 to 85% by weight. The acrylic acid alkyl ester used herein refers to an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, a phenyl group, an acrylic acid aromatic ester having a benzene ring such as a benzyl group. n-butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate and the like are mentioned, and 1
One kind or two or more kinds can be used. If the amount used is 30% by weight or less, glycidyl acrylate,
It is also possible to use an acrylic acid ester compound having a functional group such as 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate or dimethylaminoethyl acrylate in combination with the above.

Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene and the like. Further, as the monomer copolymerizable with the acrylic acid alkyl ester, allyl acrylate, allyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trichloride are used. Polyfunctional monomers such as acrylate and pentaerythritol tetraacrylate, unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, methacrylic acid alkyl esters such as methyl methacrylate, unsaturated carboxylic acid compounds such as methacrylic acid And the like, and one or more of them can be used. When the amount of conjugated diene used is small, one or more polyfunctional monomers are usually used.

The proportion of alkyl acrylate in the rubber acrylic copolymer (a) is 15 to 99.9% by weight, which is 35 to 35 in terms of performance balance between impact strength development and chemical resistance. It is more preferably 85% by weight. If the blending amount is less than 15% by weight, the chemical resistance of the resin composition becomes poor, which is not preferable.
If the amount exceeds 9.9% by weight, the crosslinked structure of the rubber-like polymer is insufficient, and the impact strength development and appearance of the resin composition are impaired, which is not preferable. From the viewpoint of impact strength development, the gel content of the rubbery copolymer (a) needs to be 70% by weight or more.

The average particle diameter of the rubbery copolymer (a) is
The range of 0.03 to 0.2 μm is preferable. The rubbery copolymer (a) is an acid group-containing copolymer latex (i).
Alternatively, if necessary, by adding a metal salt of oxyacid (ii) to the acid group-containing copolymer latex (i),
0.15-0.5 μm, preferably 0.2-0.4 μm
Is enlarged to the size of. By using the enlargement operation, a rubber having a large particle size can be stably obtained in a short time.

The acid group-containing copolymer latex (i) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid. 3 to 40% by weight of one or more unsaturated acids, the number of carbon atoms of the alkyl group is 1 to 12
It can be obtained by emulsion polymerization of 97 to 35% by weight of at least one kind of the acrylic acid alkyl ester and 0 to 40% by weight of another monomer copolymerizable therewith. Of these, a copolymer of methacrylic acid and butyl acrylate is a good example.

Metal salt of oxygen acid used in the present invention (ii)
Is an alkali metal salt or alkaline earth metal salt of oxyacid mainly containing an element selected from the group of elements belonging to the second and third periods of Groups IIIA to VIA in the periodic table of elements. ,
One or more oxyacid salts selected from salts of zinc, nickel and aluminum, specifically, salts of sulfuric acid, nitric acid, phosphoric acid with potassium, sodium, magnesium, calcium, zinc and aluminum, Preferred examples include potassium sulfate, sodium sulfate, and sodium phosphate. The metal salt of oxyacid (ii) is added in the form of an aqueous solution.

The amount of the above-mentioned thickening agent added is 100 parts by weight of the acrylic acid alkyl ester rubber copolymer (a) (as a solid content), and the acid group-containing copolymer latex (i) of 0. 5 to 8 parts by weight (as solid content), and 0.5 to 5 parts by weight (as solid content) of the acid group-containing copolymer latex (i) when the metal salt of oxygen acid (ii) is used in combination.
And 0.05 to 2 parts by weight (as solid content) of an aqueous solution of a metal salt of oxyacid (ii).

The enlarged rubber-like copolymer (a ') latex thus obtained is subsequently subjected to graft polymerization. Graft polymerization is carried out by using the enlarged rubber-like copolymer (a ')
It is carried out by graft-polymerizing 20 to 80 parts by weight of at least one monomer selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 20 to 80 parts by weight of latex. If the amount of the monomer used in the graft polymerization is less than 20 parts by weight, coarse particles may be generated in the coagulation step after the graft polymerization or the appearance of the resin composition may be deteriorated, which is not preferable. Further, when it is used in an amount of more than 80 parts by weight, a large amount of emulsifier is required in order to stably carry out the graft polymerization, and this causes coloring of the resin composition during thermal processing, which is not preferable.

Examples of the unsaturated cyan compound used in the graft polymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile and fumaronitrile. As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
p-ethylstyrene, p-tert-butylstyrene,
Halogenated styrene and the like are exemplified. Further, examples of the unsaturated ester compound include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic acid such as methyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and 2-hydroxyethyl methacrylate. Ester compounds are exemplified, and one or more of these are used in combination.

As the graft polymerization method, a known emulsion polymerization method can be adopted. It is possible to carry out a method in which the monomers are collectively charged and then polymerized, a method in which a part is charged first and the rest is dropped, and a method in which the entire amount is dropped and optionally polymerized, in one step or in two or more steps. It is also possible to change the kind and composition ratio of the monomer in each stage. The obtained graft copolymer latex is coagulated by a known method and is obtained as a graft copolymer (A) through steps such as dehydration, washing and drying.

The composite rubbery polymer (b ') latex used for the graft copolymer (B) is a conjugated diene rubbery polymer (b-1) latex or a polyorganosiloxane rubbery polymer (b). -2) seed polymerizing 20 to 95% by weight of a monomer mixture consisting of an alkyl acrylate ester and a monomer copolymerizable therewith in the presence of 5 to 80% by weight (as solid content) of a latex. Is obtained by

The conjugated diene rubbery polymer (b-1) used here is a copolymer comprising 50% by weight or more of conjugated diene and 50% by weight or less of a monomer copolymerizable therewith. is there. Examples of the conjugated diene include 1,3-butadiene, isoprene and chloroprene, and examples of the copolymerizable monomer include unsaturated cyan compounds such as acrylonitrile and aromatic vinyl compounds such as styrene. Preferable examples of the conjugated diene rubbery polymer include polybutadiene, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber and the like. They are,
Obtained by emulsion polymerization.

The conjugated diene rubbery polymer (b-1) latex is preferably large particles having an average particle diameter of 0.2 to 0.8 μm. The rubber of such a large particle is 0.03
By stably adding a thickening agent similar to the acid group-containing copolymer latex (i) used in the graft copolymer (A) to the base rubber latex having a particle diameter of 0.15 μm, the stability and efficiency can be improved. can get. In order to obtain a large particle of enlarged rubber as shown here, the pH of the base rubber latex should be
Is 9 or more and it is necessary to use an acid group-containing copolymer latex having a high unsaturated acid content. In the bloat operation, it is rare that all the base rubbers become bloated rubbers, and usually a certain amount of unbloated base rubber remains. Therefore, the enlarged rubber has a two-dispersion particle size distribution. The preferred average particle size range of the conjugated diene rubber is 0.2 to 0.8 μm.
However, when focusing only on the large particle size side in the expanded rubber excluding the unexpanded base rubber, the average particle size is
0.4 to 1.0 μm is a preferable range.

On the other hand, the polyorganosiloxane rubber-like polymer (b-2) is a rubber-like polymer comprising an organosiloxane, a cross-linking agent and, if necessary, a graft crossing agent. Examples of the organosiloxane include various cyclic compounds having a 3-membered ring or more, and a 3- to 6-membered ring is preferably used. For example hexamethylcyclotrisiloxane,
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane,
Tetramethyltetraphenylcyclotetrasiloxane,
Octaphenylcyclotetrasiloxane and the like,
These may be used alone or in combination of two or more.

As the crosslinking agent, a trifunctional or tetrafunctional silane type crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,
Tetrabutoxysilane or the like is used. Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The amount of the crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber-like polymer (b-2).

Examples of the graft crossing agent include the following formula: CH ₂ = C (R ² ) -COO- (CH ₂ ) _p -SiR ¹ _{n
O (3-n) / 2} - (I) CH 2 = CH-SiR 1 n O (3-n) / 2 - (II) HS- (CH 2) p -SiR 1 n O (3-n) / _2- (III)

(Wherein R ¹ is a methyl group, an ethyl group, a propyl group or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1 or 2 and p is a number from 1 to 6). The compound etc. which can form the unit represented by these are used. The (meth) acryloyloxysiloxane capable of forming the unit of the formula (I) has a high grafting efficiency and thus can form an effective graft chain, which is advantageous in terms of impact resistance expression. Methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of formula (I). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane,
γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like. . The amount of the graft crossing agent used is 0 to 10% by weight in the polyorganosiloxane rubber-like polymer (b-2).

The polyorganosiloxane rubber-like polymer (b-2) latex has an average particle size of 0.08 to 0.6.
It is preferably in the range of μm. Average particle size 0.0
When the average particle size is less than 8 μm, the impact resistance of the molded product from the resin composition deteriorates, and when the average particle size exceeds 0.6 μm, the impact resistance of the molded product from the resin composition deteriorates. The appearance of the molded surface is unfavorably deteriorated.

The production of the polyorganosiloxane rubber-like polymer (b-2) latex is described in, for example, US Pat.
The methods described in Japanese Patent No. 91920, No. 3294725 and the like can be used, but an organobenzene, a cross-linking agent and, if necessary, a mixed solution of a graft crossing agent, an alkylbenzene sulfonic acid, an alkyl sulfonic acid. It is preferably produced by shear mixing with water using a homogenizer in the presence of a sulfonic acid emulsifier such as Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization.

The polyorganosiloxane rubber-like polymer (b-2) latex is neutralized by the addition of an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or sodium carbonate, and then the following alkyl acrylate is mainly added. It is used for seed polymerization of the monomer as a component.

The composite rubbery polymer (b ') latex is
In the presence of the conjugated diene rubber-like polymer (b-1) latex or the polyorganosiloxane rubber-like polymer (b-2) latex in an amount of 5 to 80% by weight (as a solid content), an alkyl acrylate and It is obtained by seed polymerization of 20 to 95% by weight of a monomer mixture containing a copolymerizable monomer.

Examples of the alkyl acrylate include the same as those used in the graft copolymer (A). Examples of the monomer copolymerizable with the acrylic acid alkyl ester include monofunctional monomers such as acrylonitrile, styrene, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, and crosslinking agents and grafts shown below. Examples include polyfunctional monomers such as crossing agents. Of these, it is preferable to use a cross-linking agent and a graft crossing agent in combination in terms of impact strength development.

Examples of the cross-linking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate, and examples of the graft crossing agent include allyl methacrylate. , Triallyl cyanurate, triallyl isocyanurate and the like. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more.

The total amount of the above-mentioned crosslinking agent and graft crossing agent used is 0.1 to 10% by weight in the monomer mixture containing alkyl acrylate as a main component, and the monofunctional monomer is 0 to 0% by weight. It is preferably 30% by weight. In addition, the composite rubber-like polymer (b ') needs to have a gel content of 70% by weight or more from the viewpoint of impact strength development.

Conjugated diene rubber-like polymer (b-1) latex or polyorganosiloxane rubber-like polymer (b)
-2) The method of seed polymerization of a monomer mixture containing an acrylic acid alkyl ester as a main component in the presence of latex is
A method of dropping a monomer mixture while polymerizing at any time, a method of preliminarily impregnating a base rubber-like polymer with a monomer mixture and then polymerizing by adding an initiator or the like, a polymerization after impregnating a monomer mixture A method of continuously performing the operation for several times while changing the composition of the monomer mixture in each stage can be mentioned. Of these, the method of preliminarily impregnating the base rubber-like polymer with the monomer mixture and then polymerizing is preferred. Also,
During seed polymerization, an emulsifier may be newly added for the purpose of improving polymerization stability, but the amount thereof is preferably as small as possible.

The obtained composite rubbery polymer (b ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by using a composite rubber-like polymer (b ') latex 20-8.
It is carried out by graft-polymerizing 20 to 80 parts by weight of one or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 0 parts by weight (as solid content). .

The kind and amount of the monomer used in the graft polymerization and the method of the graft polymerization are the same as those in the graft copolymer (A). The latex obtained is coagulated,
The graft copolymer (B) is obtained through steps such as dehydration, washing and drying.

The latex of the conjugated diene rubbery copolymer (c) used in the graft copolymer (II) is 70 to 100% by weight of the conjugated diene and 0 to 3 monomers copolymerizable therewith.
It is obtained by emulsion polymerization with 0% by weight. The conjugated diene used here is 1,3-butadiene, isoprene,
Chloroprene is mentioned as a good example, and it is preferably used in an amount of 70% by weight or more in terms of impact strength development. Also,
Examples of the monomer copolymerizable with the conjugated diene include unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, methacrylic acid alkyl esters such as methyl methacrylate, unsaturated carboxylic acid compounds such as methacrylic acid, and the like. Examples thereof include monomers, and one kind or two or more kinds can be used.

The average particle size of the latex of the conjugated diene rubbery copolymer (c) is preferably 0.03 to 0.2 μm. The latex of the conjugated diene-based rubbery copolymer (c) is the acid group-containing copolymer latex (i) of the type and amount described in the description of the graft copolymer (A) or, if necessary, a metal salt of oxygen acid. Addition of (ii) up to 0.15-0.5 μm, preferably 0.2-0.
Enlarged to 4 μm. By this bloat operation,
It is possible to stably obtain an enlarged rubber-like copolymer (c ′) latex having a large particle size suitable for impact strength development in a short time.

The enlarged rubber-like copolymer (c ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by expanding rubber-like copolymer (c ') latex 20 to 8
It is carried out by graft-polymerizing 20 to 80 parts by weight of one or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 0 parts by weight (as solid content). .

Preferred examples of the monomer used in the graft polymerization include those described in the description of the graft copolymer (A). As for the graft polymerization method, a known emulsion polymerization method can be adopted as in the case of the graft copolymer (A). The obtained graft copolymer latex is coagulated by a known method, and is subjected to steps such as dehydration, washing and drying to obtain a graft copolymer (II).

The copolymer used in the present invention is 35 to 6
It is obtained by polymerizing a monomer mixture consisting of 5% by weight of an unsaturated cyanide compound and 35 to 65% by weight of an aromatic vinyl compound.

Here, examples of the unsaturated cyan compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile and the like, of which acrylonitrile is a preferable example.
Aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4.
-Dimethyl styrene, halogenated styrene, etc. are exemplified, and among these, styrene and α-methyl styrene are preferable.

The unsaturated cyan compound used in the copolymer (III) is required to be 35 to 65% by weight in the monomer mixture, and more preferably 40 to 60% by weight. The amount of unsaturated cyanide compound is 3 in the monomer mixture.
If it is less than 5% by weight, the chemical resistance of the resulting molded article will be insufficient, and if it exceeds 65% by weight, the fluidity at the time of molding will be inferior and yellowing will tend to occur during polymerization.

The thermoplastic resin composition of the present invention comprises at least one graft copolymer (I) or graft copolymer (I) selected from the group of graft copolymer (A) and graft copolymer (B). II) and the copolymer (III).

The blending ratio of the graft copolymer (I), the graft copolymer (II) and the copolymer (III) is such that the proportion of the rubber-like polymer in the thermoplastic resin composition is within the preferred range. Is decided. That is, the total proportion of the enlarged rubber-like copolymer (a '), the composite rubber-like polymer (b') and the enlarged rubber-like copolymer (c ') in 100% by weight of the thermoplastic resin composition. Is 15 to 30% by weight, and the proportion of the alkyl acrylate unit forming the rubbery polymer is 5 to 25% by weight based on 100% by weight of the thermoplastic resin composition.

When the total amount of the rubber-like polymer is less than 15% by weight, impact strength is poorly expressed, which is not preferable, and when it exceeds 30% by weight, surface hardness and rigidity are lowered, so that the use thereof is limited. Therefore, it is not preferable.
Further, if the acrylic acid alkyl ester unit forming the rubber-like polymer is less than 5% by weight, the chemical resistance is poor, which is not preferable, and if it exceeds 25% by weight, it is difficult to obtain excellent impact strength expression. Is not preferable.

To incorporate the graft copolymer (I), the graft copolymer (II) and the copolymer (III), usually,
It is mixed with a V-type blender, a Henschel mixer, etc., but various stabilizers, lubricants, plasticizers, release agents, dyes, pigments, inorganic fillers, metal fine particles, antistatic agents, etc. are added as necessary at this time. can do. These mixtures are melt-kneaded using a mixing roll, a screw type extruder or the like, and then pelletized by a pelletizer.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "part" in the following Examples and Comparative Examples represents parts by weight. Further, the average particle size of the rubber-like polymer latex was measured from an image photographed with a transmission electron microscope after being immobilized with osmium tetroxide or the like.

Alkyl acrylate rubber type rubber
Synthesis of polymer (a-1) n-butyl acrylate 40 parts 1,3-butadiene 60 parts diisopropylbenzene hydroperoxide 0.2 parts tert-dodecyl mercaptan 0.4 parts potassium oleate 1 part sodium N-lauroyl sarcosinate 1 Parts Rongalit 0.5 parts Distilled water 195 parts With respect to the substances other than 1,3-butadiene in the above composition, oxygen contained therein was replaced with nitrogen so that the reaction was practically not hindered. After that, add all substances to 5
A 0 liter autoclave was charged and the temperature was raised to 55 ° C with vigorous stirring. Add the following mixture to this,
Polymerization was carried out at 55 ° C. for 8 hours. As a result, an acrylic acid alkyl ester rubbery copolymer (a-1) latex having a monomer conversion rate of 99% and a particle size of 0.07 μm was obtained. Ethylenediaminetetraacetic acid disodium salt dihydrate 0.012 part Ferrous sulfate heptahydrate heptahydrate 0.004 part Distilled water 5 parts Acrylic acid alkyl ester-based rubbery copolymer (a-
Synthesis of 2) n-butyl acrylate 79.4 parts 1,3-butadiene 20 parts allyl methacrylate 0.6 parts diisopropylbenzene hydroperoxide 0.15 parts potassium oleate 1 part sodium N-lauroyl sarcosinate 1 part Rongalit 0.1. 5 parts distilled water 195 parts and ethylenediaminetetraacetic acid disodium dihydrate 0.009 parts ferrous sulfate heptahydrate 0.007 parts distilled water 5 parts The above composition is used as an acrylic acid alkyl ester rubber Polymerization was performed by the same operation as the synthesis of the combined product (a-1). As a result, the monomer conversion rate was 97% and the particle size was 0.07.
As a result, an acrylic acid alkyl ester-based rubbery copolymer (a-2) latex having a thickness of μm was obtained.

Acrylic acid alkyl ester-based rubber-like copolymer
Synthesis of polymer (a-3) n-butyl acrylate 99 parts Allyl methacrylate 0.8 parts Divinylbenzene 0.2 parts Diisopropylbenzene hydroperoxide 0.02 parts Potassium oleate 1.2 parts N-lauroyl sarcosinate sodium 0. 8 parts Rongalit 0.4 parts Distilled water 198 parts The above composition was charged into a 50 liter polymerization vessel, oxygen in the vessel was completely removed with nitrogen, and the temperature was raised to 50 ° C. The following mixture was added thereto, and polymerization was carried out at 50 ° C. for 5 hours. As a result, an alkyl acrylate-based rubbery copolymer (a-3) latex having a monomer conversion rate of 98% and a particle diameter of 0.14 μm was obtained. Ethylenediaminetetraacetic acid disodium salt dihydrate 0.000015 part Ferrous sulfate heptahydrate 0.000005 part Distilled water 2 parts Synthesis of conjugated diene rubbery copolymer (c-1) 1,3-butadiene 100 Part Diisopropylbenzene hydroperoxide 0.2 part tert-dodecyl mercaptan 0.5 part potassium oleate 1 part disproportionated potassium rosinate 1 part dextrose 0.3 part anhydrous sodium sulfate 0.18 part sodium hydroxide 0.02 part Distilled water 195 parts and sodium pyrophosphate ・ 10 hydrate 0.5 part Ferrous sulfate ・ heptahydrate 0.005 part Distilled water 5 parts The above composition was treated with an alkyl acrylate rubber polymer (a- Polymerization was carried out for 9 hours by the same operation as in the synthesis of 1). As a result, a conjugated diene rubbery copolymer (c- having a monomer conversion of 97% and a particle diameter of 0.08 μm)
1) A latex was obtained.

Of the acid group-containing copolymer (i-1) latex
Synthetic potassium oleate 2.5 parts Dioctyl potassium sulfosuccinate 2.5 parts Ethylenediaminetetraacetic acid disodium salt dihydrate 0.012 parts Ferrous sulfate heptahydrate 0.004 parts Rongalit 0.5 parts Distilled water 200 parts The above composition was placed in a 5 liter glass separable flask, oxygen in the system was replaced with nitrogen while stirring, and the temperature was raised to 70 ° C. The following monomer mixture, which had been subjected to nitrogen substitution, was added dropwise to the mixture over 4 hours for polymerization. n-Butyl acrylate 85 parts Methacrylic acid 15 parts Cumene hydroperoxide 0.5 parts After that, by holding at 70 ° C. for 1 hour, an acid group-containing copolymer (i-1) latex having a monomer conversion of 97% was obtained. Was obtained.

Synthesis of acid group-containing copolymer (i-2) Synthesis of acid group-containing copolymer (i-1) latex except that the composition of the monomer mixture to be dropped is changed as follows. Polymerization was performed by the same operation. As a result, an acid group-containing copolymer (i-2) latex having a monomer conversion rate of 96% was obtained. n-Butyl acrylate 80 parts Methacrylic acid 20 parts Cumene hydroperoxide 0.5 part Graft copolymer (A-1) synthetic rubber-like copolymer (a-1) latex 50 parts (as solid content) 20 liters Charge in a separable flask,
After adding 0.4 parts of a 10% aqueous solution of sodium sulfate in solid content with stirring, the acid group-containing copolymer (i-1) is further added.
The latex was added in an amount of 1.3 parts by solid content, and the mixture was kept as it was for 30 minutes while stirring, and then 95 parts of distilled water was added.
As a result, an enlarged rubber-like copolymer (a'-1) latex having an average particle diameter of 0.27 µm was obtained. Sodium N-lauroyl sarcosinate 1.25 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.003 parts Ferrous sulfate heptahydrate 0.001 part Rongalit 0.5 parts Enlarged rubbery copolymer (a ' -1) The above composition was added to the latex, and the temperature was raised to 75 ° C with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After the dropping of the monomer mixture, the graft copolymer latex was obtained by further holding for 1 hour. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed, and dried to obtain a graft copolymer (A-1).

Synthesis of Graft Copolymer (A-2) The rubber-like copolymer (a-2) is used as the rubber-like polymer, and the acid group-containing copolymer is used as the sizing agent used in the swelling operation. (I-1) The graft copolymer (A) except that the acid group-containing copolymer (i-2) is used instead of the latex.
-1) is carried out in the same manner as in the synthesis of the graft copolymer (A-
2) was obtained. At this time, the enlarged rubber-like copolymer (a'-
The average particle diameter of 2) was 0.30 μm.

Synthesis of Graft Copolymer (A-3) Up to the point of obtaining an enlarged rubbery copolymer, the same procedure as in the synthesis of graft copolymer (A-1) was carried out. Enlarged rubbery copolymer (a'-1) latex (as solid content) 60 parts Sodium N-lauroyl sarcosinate 0.75 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.0015 parts Ferrous sulfate-7 Water salt 0.0005 parts Rongalit 0.4 parts The above composition was charged into a 20 liter separable flask, heated to 75 ° C. with stirring, and then the following monomer mixture was added dropwise over 90 minutes. Graft polymerization was performed. Methyl methacrylate 36 parts Ethyl acrylate 4 parts Cumene hydroperoxide 0.15 parts n-octyl mercaptan 0.05 parts After the dropping of the monomer mixture, the graft copolymer latex was obtained by further holding for 1 hour. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate it, and then dehydrated, washed and dried to obtain a graft copolymer (A-3).

Synthesis of Graft Copolymer (A-4) The rubber-like copolymer (a-3) is used as the rubber-like polymer, and the acid group-containing copolymer is used as the swelling agent used in the swelling operation. (I-1) Graft copolymer (A) except that acid group-containing copolymer (i-2) was used instead of latex.
-1) is carried out in the same manner as in the synthesis of the graft copolymer (A-
4) was obtained. At this time, the enlarged rubber-like copolymer (a'-
The average particle diameter of 4) was 0.31 μm.

Synthesis of composite rubber-like polymer (b'-1) A rubber-like copolymer (c) was placed in a 20 liter separable flask.
-1) Charge 20 parts of latex in solid content. To this, 0.5 part of the acid group-containing copolymer (i-2) latex was added as a solid content while stirring, and the mixture was kept for 30 minutes as it was, and then 160 parts of distilled water was added to carry out the enlargement operation. .
As a result, an enlarged rubber-like copolymer having an average particle diameter of 0.37 μm was obtained. n-Butyl acrylate 79.25 parts Allyl methacrylate 0.5 parts Ethylene glycol dimethacrylate 0.25 parts tert-Butyl hydroperoxide 0.2 parts To this, after adding the above monomer mixture and stirring sufficiently,
0.5 part of sodium N-lauroyl sarcosinate is dissolved, and the system is replaced with nitrogen to remove oxygen. Internal temperature 45
At the time when the temperature was raised to ° C, the following composition was added. Rongalit 0.5 parts Ferrous sulfate heptahydrate 0.0003 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.0009 parts Distilled water 10 parts As a result, polymerization started and the internal temperature rose to about 70 ° C.
Then, the composite rubber-like polymer (b′-1) latex was obtained by holding the mixture at 75 ° C. for 90 minutes while stirring.

Synthesis of graft copolymer (B-1) Composite rubber-like polymer (b'-1) latex (as solid content) 50 parts Sodium N-lauroyl sarcosinate 1.2 parts Rongalit 0.4 parts Sulfuric acid No. Monoiron / heptahydrate 0.001 part Ethylenediaminetetraacetic acid disodium / dihydrate 0.003 part Distilled water 100 parts The above composition was charged in a 20 liter separable flask and heated to 75 ° C with stirring. . Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After completion of dropping the monomer mixture, the mixture is kept for 1 hour while stirring to give a graft copolymer latex. Was obtained. The graft copolymer latex was obtained as a powdery graft copolymer (B-1) by adding it to a dilute sulfuric acid aqueous solution to coagulate it, followed by dehydration, washing and drying.

Synthesis of composite rubbery polymer (b'-2) Dodecylbenzene sulfonic acid 1 part Sodium docecilbenzene sulfonate 1 part Distilled water 200 parts To the above composition, a siloxane mixture having the following composition is added, and a homomixer is used. After premixing at 10,000 rpm with a homogenizer, the mixture was emulsified and dispersed at a pressure of 300 kg / cm ^{2 with} a homogenizer to obtain an organosiloxane latex. Tetraethoxysilane 1.2 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.3 parts Octamethylcyclotetrasiloxane 58.5 parts This mixed solution is transferred to a 20 liter separable flask and heated at 80 ° C. for 5 hours while stirring. After that, the mixture was allowed to stand at 20 ° C. for 48 hours, and then the pH of this latex was neutralized to 7.5 with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber-like polymer (b-2) latex. The average particle diameter was 0.16 μm. To this, 70 parts of distilled water was added, and the following monomer mixture was added to the mixture while stirring and mixed sufficiently. n-Butyl acrylate 38.4 parts Allyl methacrylate 1.2 parts Ethylene glycol dimethacrylate 0.4 parts tert-Butyl hydroperoxide 0.3 parts After replacing the system with nitrogen to remove oxygen, the internal temperature was 50 ° C. The temperature was raised to and the polymerization was started by adding the following mixture. Rongalit 0.3 part Ferrous sulfate heptahydrate 0.002 part Ethylenediaminetetraacetic acid disodium dihydrate 0.006 part Distilled water 10 parts As a result, the internal temperature was raised to about 65 ° C. Then 70
The composite rubbery polymer (b'-2) latex was obtained by keeping it at 2 ° C for 2 hours.

Synthesis of graft copolymer (B-2) Composite rubber-like polymer (b'-2) latex (as solid content) 60 parts Sodium dodecylbenzenesulfonate 0.3 parts Distilled water 80 parts , 20 liter separable flask, and heated to 70 ° C. with stirring. The following monomer mixture was added dropwise to this over 60 minutes for graft polymerization. Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 part tert-Dodecyl mercaptan 0.1 part After the dropwise addition, the graft copolymer latex was obtained by holding for 2 hours with stirring. This graft copolymer latex was put into a calcium chloride aqueous solution to coagulate, dehydrated, washed, and dried to obtain a powdered graft copolymer (B-2).

Synthesis of Graft Copolymer (C-1) Conjugated Diene Rubber Copolymer (c-1) Latex 60
Parts (as solid content) were placed in a 20 liter separable flask, and the acid group-containing copolymer (i-1) was stirred with stirring.
The latex was added in an amount of 1.2 parts by solid content, and the mixture was kept for 30 minutes while stirring, and then 80 parts of distilled water was added. As a result, an enlarged rubber-like copolymer (c'-1) latex having an average particle diameter of 0.28 μm was obtained. Disproportionated potassium rosinate 0.4 parts Sodium pyrophosphate ・ 10 hydrate 0.02 parts Ferrous sulfate ・ 7 hydrate 0.005 parts Dextrose 0.4 parts Sodium hydroxide 0.02 parts The above composition was added to the polymer (c′-1) latex, and the temperature was raised to 60 ° C. with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 parts tert-Dodecyl mercaptan 0.4 parts After completion of dropping the monomer mixture, the mixture was kept for 1 hour to obtain a graft copolymer latex. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed and dried to obtain a graft copolymer (C-1).

Synthesis of Copolymer (III-1) Acrylonitrile 45 parts Styrene 10 parts Terpene oil 0.50 parts Di-tert-butyl paracresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and dissolved in a small amount of styrene 1-t-butylazo-1. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 45 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-1).

Synthesis of copolymer (III-2) Acrylonitrile 50 parts Styrene 8 parts Terpene oil 0.55 parts Di-tert-butyl paracresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and dissolved in a small amount of styrene 1-t-butylazo-1. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 42 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-2).

Synthesis of Copolymer (III-3) Acrylonitrile 60 parts Styrene 5 parts Terpene oil 0.58 parts Di-tert-butyl paracresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and dissolved in a small amount of styrene 1-t-butylazo-1. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 35 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-3).

Synthesis of copolymer (III-4) acrylonitrile 29 parts styrene 55 parts terpene oil 0.58 parts di-tert-butyl paracresol 0.04 parts deionized water 100 parts acrylic acid-octyl acrylate copolymer 0. 02 parts Sodium chloride 0.14 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and 1-t-butylazo-1 dissolved in a small amount of styrene. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 16 parts by weight of styrene was continuously added to the reaction system over 1 hour. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-4).

Production of thermoplastic resin composition Predetermined amount of graft copolymer (I), graft copolymer (I
I) and the copolymer (III) were added to the Henschel mixer together with the following substances and blended. ADEKA STAB Mark AO-20 (manufactured by Asahi Denka) 0.3 parts ADEKA STAB Mark AO-412S (manufactured by Asahi Denka) 0.3 parts Ethylene bis-stearamide 1 part Magnesium stearate 0.3 parts Silicon Oil SH200 (Toray Dow Corning Silicone) Manufacture) 0.03 parts The above mixture was melt-kneaded at 220 ° C to 260 ° C using a screw extruder, and then pelletized by a pelletizer. The pellets were molded into various test pieces using an injection molding machine or a press molding machine.

The resin composition thus obtained was evaluated by the following methods. (1) Izod impact strength (IZ): ASTM D-2
It was measured by 56 (unit: kg · cm / cm). (2) Rockwell hardness (R): ASTM D-785
(R scale). (3) Vicat softening temperature (VST): ISO R-30
6 (unit: ° C). (4) Chemical resistance: A test piece of 35 × 120 mm was cut out from a 2 mm thick press-molded plate of the resin composition, and the major axis was 120 m.
It is attached to a 1/4 elliptical jig with a diameter of m and a short diameter of 40 mm. After the chemical was applied to the surface of the test piece, it was covered with a polyethylene film and exposed to the chemical at 25 ° C. for 4 hours. For low boiling point chemicals, the jig was placed in a desiccator with an opening / closing cock and exposed to the chemicals at 25 ° C. for 24 hours while being filled with the chemical vapor. After the exposure, the surface condition of the test piece was observed, and the maximum stress-strain value at which cracks did not occur was used as an index of chemical resistance. The following chemicals were used.・ 1,1-Dichloro-1-fluoroethane (CFC 14
1b) -Brake oil (Toyota 2400G) -Wax remover (Yushiro Chemical ST-7) -Salad oil (Nisshin Oil) -Dioctyl phthalate (DOP)

[0062]

[Table 1]

INDUSTRIAL APPLICABILITY According to the present invention, a graft copolymer graft-polymerized on an acrylic acid alkyl ester rubber, a graft copolymer graft-polymerized on a conjugated diene rubber, and a specific copolymer are mixed in an optimum ratio. It is a thermoplastic resin composition and has extremely excellent chemical resistance and impact resistance. Therefore, the thermoplastic resin composition of the present invention,
It is extremely useful as a component for home electric appliances and vehicles that come into contact with urethane foaming agents, various oils and cleaning agents.

Front Page Continuation (72) Inventor Seizo Fujii 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Office

Claims (1)

[Claims] 1. (I) Acrylic acid alkyl ester 15
.About.99.9% by weight and an acrylic acid alkyl ester-based rubbery copolymer (obtained by emulsion-polymerizing 0.1 to 85% by weight of a monomer copolymerizable with a conjugated diene and / or alkyl acrylate) ( a) Enlargement obtained by adding the acid group-containing copolymer latex (i) to the latex or, if necessary, the acid group-containing copolymer latex (i) in combination with the metal salt of oxyacid (ii) Rubbery copolymer (a ')
One or more monomers 20 to 8 selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 20 to 80 parts by weight of latex (as solid content).
Graft copolymer (A) obtained by graft polymerization of 0 part by weight, and conjugated diene rubber-like polymer (b-1) latex or polyorganosiloxane rubber-like polymer (b-)
2) Obtained by seed polymerization of 20 to 95% by weight of a monomer mixture consisting of an alkyl acrylate and a monomer copolymerizable therewith in the presence of 5 to 80% by weight (as solid content) of a latex. One or more monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 20 to 80 parts by weight (as solid content) of the composite rubbery polymer (b ') latex obtained. One or more graft copolymers selected from the graft copolymer (B) obtained by graft polymerizing 20 to 80 parts by weight, (II) 70 to 100% by weight of a conjugated diene and a monomer which is copolymerizable therewith. To the conjugated diene rubbery copolymer (c) latex obtained by emulsion polymerization of 0 to 30% by weight of the polymer, and the acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex In the presence of the enlarged rubbery copolymer (c ') latex obtained by adding the metal salt of oxyacid (ii) together, it is selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds. A graft copolymer obtained by graft-polymerizing one or more kinds of monomers
I) 35-65% by weight of unsaturated cyanide compound and 35-6
In a thermoplastic resin composition comprising a copolymer obtained by copolymerizing a monomer comprising 5% by weight of an aromatic vinyl compound, a bloated rubber-like material occupying in 100% by weight of the thermoplastic resin composition. The total proportion of the copolymer (a '), the composite rubber-like polymer (b') and the enlarged rubber-like copolymer (c ') is 15 to 30% by weight, and the rubber-like polymer is formed. A thermoplastic resin composition, wherein the proportion of acrylic acid alkyl ester units is 5 to 25% by weight based on 100% by weight of the thermoplastic resin composition.