JPH1112335A - Production of styrene-based copolymer having multilayer structure, styrene-based copolymer having multilayer structure, vinyl chloride-based resin composition and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer without lowering transparency, suitable as a material for improving impact resistance, etc., of vinyl chloride-based resins and prescribed thermoplastic resins. SOLUTION: (A) A monomer mixture comprising (i) 50-99.999 wt.% styrene, 0-45 wt.% either one of (ii) a 1-8C (meth)acrylate and (iii) a vinyl cyanide compound and (iv) 0.001-5 wt.% polyfunctional monomer is compounded and subjected to emulsion polymerization to afford (B) a copolymer having >=0 deg.C glass transition temperature (hereinafter referred to as Tg) and a monomer mixture comprising (C) 95-99.999 wt.% component (ii) and 0.001-5 wt.% component (iv) is compounded and subjected to emulsion polymerization in the presence of the component B to afford (D) a copolymer having >=0 deg.C Tg and (E) a monomer mixture comprising 20-99.999 wt.% component (i), 0-30 wt.% either one of the component (ii) and the component (iii) is compounded and subjected to emulsion polymerization in the presence of the component D to afford (F) a copolymer having >=0 deg.C Tg and 1.51-1.60 refractive index and (G) a monomer mixture comprising 60-85 wt.% component (i), 15-40 wt.% component (iii), 0-15 wt.% component (ii) and 0.001-10 wt.% component (iv) is compounded and subjected to emulsion polymerization in the presence of the component F to afford (H) a copolymer and a monomer mixture comprising 60-90 wt.% component (i), 10-35 wt.% component (iii) and 0-30 wt.% component (ii) is compounded and subjected to emulsion polymerization in the presence of the component H.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a multi-layer styrene copolymer, a multi-layer styrene copolymer,
The present invention relates to a vinyl chloride resin composition and a thermoplastic resin composition. More specifically, for example, a method for producing a styrene-based copolymer having a multilayer structure suitably used as a material for improving the impact resistance, weather resistance, gloss, and two-color weldability of a vinyl chloride resin and a predetermined thermoplastic resin, and a multilayer structure The present invention relates to a styrene copolymer, a vinyl chloride resin composition, and a thermoplastic resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins have many advantages such as flame retardancy and chemical resistance, but have the disadvantage that they are inferior in impact resistance, weather resistance, thermal deformation and workability. To improve the impact resistance, an MBS resin obtained by copolymerizing butadiene rubber, which is called an impact modifier, with methyl methacrylate (MMA) and styrene is known.

[0003] A vinyl chloride resin composition mixed with MBS resin has a remarkable improvement in impact strength. However, since butadiene rubber having many chemically unstable double bonds in its main chain is used, It is known that it is easily deteriorated by infrared rays, oxygen and the like, and has poor weather resistance.

[0004] In order to improve this drawback, there has been proposed a MAS resin using an acrylate polymer rubber and copolymerizing it with MMA and styrene. The vinyl chloride resin composition mixed with the MAS resin is certainly weather resistant,
Improves impact resistance. However, there is a disadvantage that the transparency of the vinyl chloride resin composition mixed with the MAS resin is reduced. This is because the refractive index of the acrylate polymer rubber, which is the rubber component, is very small compared to the refractive index of the vinyl chloride resin, so that visible light is irregularly reflected within the resin,
Due to the very low transmittance.

As a method for remedying this drawback, there is known a method for improving the transparency of the resin by bringing the refractive indices of the rubber component and the matrix resin as close as possible.
In many cases, a resin-rubber thermoplastic resin is used as a multilayer structure. For example, a three-layer structure is disclosed in JP-A-58-167605 and JP-A-60-63248.
JP-A-3-52910, U.S. Pat.
No. 473,679, etc., for a four-layer structure, JP-A-59-202213, JP-B-62-41241, JP-B-52-30996, etc. Japanese Patent Publication No. 55-2, for example, discloses a blend of a three-layer structure and a four-layer structure.
No. 7576 has been proposed. These methods are very effective when the matrix resin is an acrylic resin, but cannot provide a sufficient effect when the matrix resin is a vinyl chloride resin.

On the other hand, for a given thermoplastic resin, a method of alloying different kinds of thermoplastic resins to improve the characteristics is known. Representative examples thereof include an alloy of ABS resin and polycarbonate, and a method of ABS resin and polybutylene terephthalate. Alloys and the like. However, ABS
The resin, butadiene-based polymer used to impart impact resistance, because it has many chemically unstable double bonds in the main chain, easily deteriorated by ultraviolet rays,
Alloys with ABS resin also have insufficient weather resistance due to poor weather resistance. As a method for remedying this drawback, a method has been proposed in which a saturated rubber polymer having almost no double bond in the main chain is used instead of the butadiene-based polymer in the ABS resin. An alloy using an AAS resin using an acrylic rubber is known.

Although this saturated rubber is stable to ultraviolet rays and has excellent weather resistance, it has few reactive active sites, and therefore has a low crosslink density and it is difficult to form a graft structure. . For this reason, the rubber is deformed during molding, so-called weld dichroism is easily generated on the surface of the molded product, and irregular reflection of light on the surface of the molded product is apt to occur, so that the gloss is easily reduced. As a result, there was a defect that the appearance of the molded product was inferior to that of the alloy using the ABS resin.

To remedy this drawback, a method has been proposed in which a crosslinking agent for the acrylic rubber is selected and copolymerization is carried out, or peroxide peroxide is bridged. These methods can certainly increase the crosslink density of the acrylic rubber and improve the appearance of the molded article. However, since the glass transition temperature of the acrylic rubber also increases with an increase in the crosslink density, there is a disadvantage that the impact resistance decreases.

In order to achieve both the excellent impact resistance of a butadiene polymer rubber and the excellent weather resistance of an acrylic rubber, a butadiene polymer rubber latex is used as a core.
It has been proposed to use a two-layer graft polymer rubber obtained by emulsion graft copolymerization of an acrylic ester and a polyfunctional monomer as a crosslinking agent. In this case, it is known that the selection of the polyfunctional monomer and the method of copolymerization with the acrylate are very important technical elements. In particular, in this regard, there are disclosed, for example, those in which the polymerization of an acrylate ester is stopped in the middle of the polymerization without completing the polymerization (Japanese Patent Laid-Open No. 58-1).
No. 87411), when performing polymerization of an aromatic monomer in the presence of a graft polymer rubber obtained by graft copolymerizing an acrylate ester with a butadiene polymer rubber, a polyallyl monomer is used as a polyfunctional monomer. (Japanese Unexamined Patent Publication (Kokai) No. Sho 61-155412), and a combination of two different polyfunctional monomers as a graft-crosslinking agent and a crosslinking agent during the polymerization of an acrylate ester (Japanese Unexamined Patent Publication No. Sho. Gazette). By these methods,
Although remarkable improvements in impact resistance and weather resistance are observed, it is said that improvements in weld dichroism and low gloss of molded products, which are one of the drawbacks of using acrylic polymers, have been made. hard.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made to improve the impact resistance, weather resistance, gloss, and two-color weldability of a vinyl chloride resin and a predetermined thermoplastic resin. Provided are a method for producing a multilayered styrene-based copolymer, which is preferably used as a material and has little decrease in transparency, a multilayered styrene-based copolymer, a vinyl chloride-based resin composition, and a thermoplastic resin composition. The purpose is to:

[0011]

Means for Solving the Problems The present invention provides the following [1] to
The present invention relates to the invention having the subject matter of [9]. [1]: A method for producing a multilayer styrenic copolymer including the following steps (1) to (5). (1) 50 to 99.999% by weight of styrene, 0 to 45% by weight of at least one compound selected from the group consisting of a (meth) acrylate having 1 to 8 carbon atoms and a vinyl cyanide compound; Emulsion polymerization by blending a monomer mixture (a) having a composition of 0.001 to 5% by weight of a hydrophilic monomer so that the glass transition temperature of the obtained copolymer (A) is 0 ° C. or higher. Let it. (2): In the presence of the copolymer (A) obtained in the step (1), a (meth) acrylate ester having 1 to 8 carbon atoms 95 to
99.999% by weight, and a polyfunctional monomer 0.001 to 5
% By weight of a monomer mixture (b) having a composition of not more than 0% by weight so that the copolymer (B) newly obtained in this step (2) has a glass transition temperature of 0 ° C. or higher. . (3): in the presence of the copolymer (B) obtained in step (2), styrene 20 to 99.999% by weight and carbon number 1 to
At least one compound 0 selected from the group consisting of (meth) acrylates and vinyl cyanide compounds
A monomer mixture (c) having a composition of about 30% by weight and 0.001 to 50% by weight of a polyfunctional monomer is mixed with the copolymer (C) newly obtained in this step (3). Emulsion polymerization is carried out by blending such that the glass transition temperature is 0 ° C. or higher and the refractive index is in the range of 1.51 to 1.60. (4): In the presence of the copolymer (C) obtained in the step (3), 60 to 85% by weight of styrene, 15 to 40% by weight of a vinyl cyanide compound, and 1 to 8 carbon atoms (meth) 0) Acrylate 0-15% by weight and polyfunctional monomer 0.0
Monomer mixture (d) having a composition of from 0.01 to 10% by weight
Is mixed and emulsion-polymerized to obtain a new copolymer (D). (5): In the presence of the copolymer (D) obtained in the step (4), 60 to 90% by weight of styrene, 10 to 35% by weight of a vinyl cyanide compound, and ) A monomer mixture (e) having a composition of 0 to 30% by weight of an acrylate ester is blended and emulsion-polymerized to obtain a new copolymer (E).

[2]: The amount of each of the monomer mixtures (a) to (e) in the steps (1) to (5) is based on the total amount of the monomer mixtures (a) to (e). 5 to 55% by weight of the monomer mixture (a), 10 to 60% of the monomer mixture (b)
% Of monomer mixture (c) 1 to 20% by weight, monomer mixture (d) 5 to 35% by weight, and monomer mixture (e) 1
The method for producing a multilayer styrenic copolymer according to [1], wherein the amount is 0 to 79% by weight.

[3]: The multilayer styrene copolymer according to [1] or [2], wherein the particle size of the copolymer (E) at the end of the step (5) is in the range of 50 to 500 nm. Manufacturing method.

[4]: The polyfunctional monomer to be blended in the steps (1) to (4) is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, alkylene acrylate and divinylbenzene. It is preferable to use the method for producing a multilayer styrene-based copolymer according to any one of [1] to [3], which is a compound of [1] to [3].

[5] The method for producing a multi-layer styrene copolymer according to any one of [1] to [4], wherein the polyfunctional monomer blended in step (4) is allyl methacrylate.

[6] A multi-layer styrene copolymer obtained by the method for producing a multi-layer styrene copolymer according to any one of [1] to [5].

[7]: 5 to 60% by weight of the multilayer styrenic copolymer according to [6] and 95 to 95% of a vinyl chloride resin.
A vinyl chloride resin composition comprising 40% by weight.

[8] A thermoplastic resin composition comprising 10 to 90% by weight of the multilayer styrenic copolymer according to [6] and 90 to 10% by weight of a thermoplastic resin having an ester bond in a main chain. [9]: a thermoplastic resin having an ester bond in the main chain,
The thermoplastic resin composition according to [8], which is a polycarbonate and / or polybutylene terephthalate.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. I. Method for Producing Multilayer Styrenic Copolymer The method for producing a multilayer styrene copolymer (resin) of the present invention includes the following steps (1) to (5). 1. Stage (1) In stage (1), styrene 50-99.999% by weight
0 to 45% by weight of at least one compound selected from the group consisting of a (meth) acrylic acid ester having 1 to 8 carbon atoms and a vinyl cyanide compound, and at least one polyfunctional monomer 0.001 to 5 The monomer mixture (a) having a composition of 1% by weight is emulsion-polymerized under predetermined conditions to obtain a copolymer (A).

(1) Monomer Mixture (a) Styrene Styrene used in the present invention contains styrene or styrene as a main component, and styrene derivatives such as α-methylstyrene, chlorostyrene and vinyltoluene; methyl acrylate, Examples thereof include monomers mixed with acrylates such as ethyl acrylate and butyl acrylate; and methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

In the monomer mixture (a), the composition ratio of styrene is 50 to 50% based on the total amount of the monomer mixture (A).
99.999% by weight, preferably 95 to 99.9.
99% by weight. If the styrene content is too large or too small, the transparency of the molded article of the multilayer styrene-based copolymer obtained decreases, and the gloss and weld dichroism of the thermoplastic resin molded article decrease.

(Meth) acrylic acid ester having 1 to 8 carbon atoms Examples of the (meth) acrylic acid ester having 1 to 8 carbon atoms used in the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate and t-butyl acrylate. -Butyl (meth) acrylate, pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, 2-methylpenteracrylate, 3-methylpenteracrylate, 4-methylpenteracrylate, cyclohexyl acrylate, phenyl acrylate, 2,3-dimethyl Butyl acrylate, 2,2-
Dimethylbutyl acrylate, 3,3-dimethylbutyl acrylate, n-heptyl acrylate, 2-methylhexyl acrylate, 3-methylhexyl acrylate, 4-methylhexyl acrylate, 5-methylhexyl acrylate, 2,2-dimethylpentyl acrylate, 2 , 3-dimethylpentyl acrylate, 4,4
-Dimethylpentyl acrylate, 3,4-dimethylpentyl acrylate, n-octyl acrylate, 2-
Examples include methyl heptyl acrylate, 3-methyl heptyl acrylate, 4-methyl heptyl acrylate, 5-methyl heptyl acrylate, 3-ethyl hexyl acrylate, 4-ethyl hexyl acrylate, 5-ethyl hexyl acrylate, and methacrylic esters corresponding to these acrylic esters. Can be
All these isomers can be used. Among these, preferred are n-butyl methacrylate,
2-ethylhexyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate. More preferred are n-butyl acrylate and 2-ethylhexyl acrylate. Most preferred is n
-Butyl acrylate. These monomers may be used alone or in combination of two or more.

In the monomer mixture (a), the number of carbon atoms is 1 to 1.
The composition ratio of the (meth) acrylic acid ester or the vinyl cyanide compound in No. 8 is 0 to 45% by weight, preferably 0 to 15% by weight, based on the total amount of the monomer mixture (a). If the content is too large, the impact resistance of the molded article of the multilayered styrene copolymer decreases.

Vinyl cyanide compound As the vinyl cyanide compound used in the present invention, acrylonitrile or methacrylonitrile can be used. Most preferred is acrylonitrile.

Polyfunctional Monomer The polyfunctional monomer used in the present invention includes allyl methacrylate, allyl acrylate other than styrene, (meth) acrylic acid ester having 1 to 8 units and vinyl cyanide compound. Water-insoluble polyalkylene glycol methacrylate or polyalkylene glycol acrylate such as divinylbenzene or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and further, trimethylolpropane trimethacrylate, 1,6-hexane Diol dimethacrylate, dicyclopentadienyl methacrylate, trimethylolpropane triacrylate, 1,6
-Hexanediol diacrylate, dicyclopentadienyl acrylate, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate and the like. Among these, preferred are water-insoluble polyalkylene glycol diacrylate, alkyldidiol diacrylate and divinylbenzene. Even more preferred are polyalkylene glycol diacrylate, 1,4-butanediol diacrylate and 1,1
6-hexanediol diacrylate. Most preferred are 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate. These polyfunctional monomers may be used alone or in combination of two or more.

In the monomer mixture (a), the composition ratio of the polyfunctional monomer is 0.001 to 5% by weight, preferably 0.05 to 2% by weight based on the total amount of the monomer mixture (a). weight%
It is. If the amount of the polyfunctional monomer is too large, the resulting molded article of the multi-layered styrene-based copolymer will have reduced transparency, and if it is too small, the impact resistance will be reduced.

(2) Emulsion polymerization Compounding of each monomer In the step (1), each monomer of the monomer mixture (a) is
The obtained copolymer (A) is blended so that the glass transition temperature thereof is 0 ° C. or higher, preferably 25 ° C. or higher, and more preferably 60 ° C. or higher. Specifically, a predetermined amount of the monomer is weighed in a glass container such as a beaker, stirred until the mixture becomes uniform, and the mixture is subjected to a polymerization reaction. The glass transition temperature of the obtained copolymer (A) is determined by the method described later. If the glass transition temperature is less than 0 ° C., the transparency and impact resistance of the molded article of the multilayer styrene copolymer tend to decrease.

Polymerization rate In step (1), the polymerization rate is preferably 80% by weight or more. It is more preferably at least 90% by weight, most preferably at least 95% by weight. Polymerization rate is 8
If the amount is less than 0% by weight, the resulting multilayer molded styrene copolymer molded article tends to have reduced impact resistance and transparency.

2. Step (2) In step (2), the copolymer (A) obtained in step (1)
In the presence of 95 to 99.999% by weight of a (meth) acrylic acid ester having 1 to 8 carbon atoms and 0.1% of a polyfunctional monomer.
Emulsion polymerization of the monomer mixture (b) consisting of 001 to 5% by weight is performed under the condition that a predetermined copolymer (B) is obtained.

(1) Monomer mixture (b) (Meth) acrylic acid ester having 1 to 8 carbon atoms In step (2), the (meth) acrylic acid ester having 1 to 8 carbon atoms includes the step (1) Can be used in the same manner. Among them, preferred are n-butyl methacrylate, 2-ethylhexyl methacrylate,
n-butyl acrylate and 2-ethylhexyl acrylate. Even more preferred are n-butyl acrylate and 2-ethylhexyl acrylate. Most preferred is n-butyl acrylate. These monomers may be used alone or in combination of two or more.

In the monomer mixture (b), the number of carbon atoms is 1 to 1.
The composition ratio of the (meth) acrylic acid ester of No. 8 is in the range of 99.999 to 95% by weight, preferably 99.98 to 98.5% by weight, based on the total amount of the monomer mixture (b). (Meth) acrylic acid ester having 1 to 8 carbon atoms is 9
If it exceeds 9.999% by weight, the resulting molded article of the multilayered styrene-based copolymer will have reduced transparency, and if it is less than 95% by weight, the impact resistance will be reduced.

In the step (2), as the polyfunctional monomer, those usable in the step (1) can be similarly used, but preferred are water-insoluble polyalkylene glycol diacrylate and alkyl didiol. Diacrylate and divinylbenzene. More preferred are polyalkylene glycol diacrylates, 1,4
-Butanediol diacrylate and 1,6-hexanediol diacrylate. Among them, most preferred are 1,4-butanediol diacrylate and 1,6-
Hexanediol diacrylate. These polyfunctional monomers may be used alone or in combination of two or more.

The monomer mixture (b) of the polyfunctional monomer
Is 0.001 to 5% by mass, preferably 0.02 to 1.5% by mass based on the total amount of the monomer mixture (b).
% By weight. If the amount of the polyfunctional monomer is less than 0.001% by weight, the transparency of the molded article of the multilayer styrene copolymer is reduced, and if it exceeds 5% by weight, the impact resistance is reduced.

(2) Emulsion polymerization Incorporation of each monomer In step (2), each monomer of the monomer mixture (b) has a glass transition temperature of 0 ° C. of the obtained copolymer (B).
It is blended so as to be below, preferably below -20 ° C, particularly preferably below -30 ° C. Specifically, a predetermined amount of the monomer is weighed in a glass container such as a beaker, stirred until the mixture becomes uniform, and the mixture is subjected to a polymerization reaction. When the glass transition temperature of the copolymer (B) obtained in the step (2) exceeds 0 ° C., the impact resistance of the molded article of the multilayer styrene-based copolymer decreases.

The degree of polymerization in step (2) is preferably at least 80% by weight, more preferably at least 90% by weight,
Most preferably, it is at least 95% by weight. If the degree of polymerization is less than 80% by weight, the impact resistance and transparency of the molded article of the multilayered styrene-based copolymer tend to decrease. here,
The determination of the conversion includes the unreacted monomer in step (1).

3. Step (3) In step (3), the copolymer (B) obtained in step (2)
In the presence of 20 to 99.999% by weight of styrene, 0 to 30% by weight of at least one compound selected from the group consisting of (meth) acrylates having 1 to 8 carbon atoms and vinyl cyanide compounds. Functional monomer 0.001
Emulsion polymerization of the monomer mixture (c) consisting of 〜50% by weight is carried out under the condition that a predetermined copolymer (C) is obtained.

(1) Monomer mixture (c) Styrene In step (3), styrene which can be used in step (1) can be used in the same manner.

C1-8 (meth) acrylate, vinyl cyanide compound and polyfunctional monomer C1-8 (meth) acrylate used in step (3), vinyl cyanide As the compound and the polyfunctional monomer, those similar to those used in step (1) or step (2) can be used.

The composition ratio of each monomer in the monomer mixture (c) is 20 to 99.999% by mass (preferably 45 to 99.9%) based on the total amount of the monomer mixture (c).
99% by weight, more preferably 40 to 98.5% by weight), and 0 to 30% by weight of at least one compound selected from the group consisting of (meth) acrylates having 1 to 8 carbon atoms and vinyl cyanide compounds. (Preferably 0
20% by weight, more preferably 0 to 15% by weight, and 0.001 to 50% by weight of the polyfunctional monomer (preferably 0.0
01 to 35% by weight, more preferably 1.5 to 25% by weight). If the styrene content is less than 20% by weight, the transparency of the molded article of the multilayer styrene copolymer tends to decrease, and if it exceeds 99.999% by weight, the transparency and impact resistance of the molded article decrease. In addition, at least one compound selected from the group consisting of a (meth) acrylic acid ester having 1 to 8 carbon atoms and a vinyl cyanide compound contains 30 or more compounds.
If the content is more than 10% by weight, the transparency and impact resistance of the molded article decrease. When the amount of the polyfunctional monomer exceeds 50% by weight, the impact resistance of the molded article tends to decrease,
If it is less than 1, the transparency of the molded article is reduced.

In step (3), the polyfunctional monomers may be used alone or in combination of two or more.

(2) Emulsion polymerization Incorporation of each monomer In step (3), each monomer of the monomer mixture (c) has a glass transition temperature of 0 ° C. of the obtained copolymer (C).
It is used so that the refractive index is in the range of 1.51 to 1.60. Preferably, the glass transition temperature is in the range of 40 to 100 ° C, and the refractive index is 1.55 or more.
The refractive index is in the range of 0 ° C. and 1.56 or more. If the glass transition temperature is less than 0 ° C. or the refractive index is less than 1.51, the transparency of the molded article of the multilayered styrene copolymer decreases. Specifically, a predetermined amount of a monomer is weighed in a glass container such as a beaker, stirred until the mixture becomes uniform, and the mixture is subjected to a polymerization reaction.

Polymerization rate In step (3), the polymerization rate is preferably at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight. Polymerization rate is 7
If the amount is less than 0% by weight, the impact resistance and transparency of the molded article of the multilayered styrene-based copolymer tend to decrease. Here, the determination of the conversion includes the unreacted monomer at the end of step (2).

4. Step (4) In step (4), in the presence of the copolymer (C) obtained in step (3), 60 to 85% by weight of styrene, 15 to 40% by weight of a vinyl cyanide compound, and carbon Emulsion polymerization of a monomer mixture (d) consisting of 0 to 15% by weight of the (meth) acrylic acid ester of Formulas 1 to 8 and 0.001 to 10% by weight of a polyfunctional monomer is carried out to form a new copolymer. Coalescing (D) is obtained.

(1) Monomer mixture (d) The vinyl cyanide compound, the (meth) acrylate having 1 to 8 carbon atoms and the polyfunctional monomer used in the step (4) are prepared in the step (3) ) Can be used. Among the polyfunctional monomers, preferred are water-insoluble polyalkylene glycol diacrylate, alkyl diol diacrylate or allyl methacrylate, more preferred are alkyl diol diacrylate or allyl methacrylate, and further preferred are Allyl methacrylate, 1,
6-hexanediol diacrylate or 1,4-butanediol diacrylate. These polyfunctional monomers may be used alone or in combination of two or more. Among the (meth) acrylates having 1 to 8 carbon atoms, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-butyl acrylate, and 2-ethylhexyl acrylate are preferred. More preferred are n-butyl acrylate and 2-ethylhexyl acrylate. Most preferred is n-butyl acrylate. These monomers may be used alone or in combination of two or more.

The composition ratio of each monomer in the monomer mixture (d) is 60 to 85% by weight (preferably 73 to 80% by weight) with respect to the total amount of the monomer mixture (d).
15 to 40% by weight of the vinyl cyanide compound (preferably 2
2 to 35% by weight), 0 to 15% by weight (preferably 0 to 5% by weight) of a (meth) acrylate having 1 to 8 carbon atoms, and 0.001 to 10% by weight (preferably, a polyfunctional monomer) 0.1 to 5% by weight). If the styrene content exceeds 85% by weight, the impact resistance and chemical resistance of the molded article of the multilayered styrene copolymer decrease, and if it is less than 60% by weight, the transparency decreases. When the amount of the vinyl cyanide compound exceeds 40% by weight, the transparency is lowered. When the amount is less than 15% by weight, the impact resistance is lowered and the stability of the polymerized latex is lowered.
When the (meth) acrylate exceeds 15% by weight,
The impact resistance and chemical resistance of the molded article of the multilayer styrene copolymer are reduced. When the amount of the polyfunctional monomer exceeds 10% by weight, the impact resistance of the molded article of the multilayer styrene copolymer decreases, and when the amount is less than 0.001% by weight, the transparency decreases.

(2) Emulsion polymerization Incorporation of each monomer In step (4), each monomer of the monomer mixture (d) preferably has a glass transition temperature of the copolymer (D) obtained. It is used so as to be at least 60 ° C., more preferably at least 75 ° C., further preferably at least 95 ° C. If the glass transition temperature is less than 60 ° C., the impact resistance tends to decrease.

Polymerization rate In the step (4), the polymerization rate is preferably at least 70% by weight, more preferably at least 85% by weight, even more preferably at least 90% by weight. If the degree of polymerization is less than 70% by weight, the impact resistance and transparency of the molded article of the multilayer styrene copolymer tend to decrease. here,
The determination of the conversion includes the unreacted monomer at the end of step (3).

5. Step (5) In step (5), in the presence of the copolymer (D) obtained in step (4), 60 to 90% by weight of styrene, 10 to 35% by weight of a vinyl cyanide compound, and carbon Emulsion polymerization of the monomer mixture (e) consisting of 0 to 30% by weight of the (meth) acrylic acid ester of Formulas 1 to 8 gives a copolymer (E).

(1) Monomer mixture (E) Styrene, a vinyl cyanide compound and a (meth) acrylate having 1 to 8 carbon atoms are the same as those usable in step (4). Can be used. Preferred as (meth) acrylic acid esters having 1 to 8 carbon atoms are n-butyl methacrylate, 2-ethylhexyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate. More preferred are n-butyl acrylate and 2-ethylhexyl acrylate. Most preferred is n-butyl acrylate. These monomers may be used alone or in combination of two or more.

The composition ratio of each monomer in the monomer mixture (e) is 60 to 90% by weight (preferably 65 to 80% by weight) with respect to the total amount of the monomer mixture (e).
10 to 40% by weight (preferably 2%) of the vinyl cyanide compound
0 to 35% by weight), C1 to C8 (meth) acrylate 0 to 30% by weight (preferably 0 to 15% by weight)
It is. If the amount of styrene is less than 60% by weight, the transparency of the molded article of the multi-layered styrene-based copolymer decreases, and if it exceeds 90% by weight, the impact resistance decreases. If the amount of the vinyl cyanide compound is less than 10% by weight, the chemical resistance of the molded article of the multilayer styrene-based copolymer decreases, and if it exceeds 40% by weight, the transparency of the molded article decreases. If the amount of the (meth) acrylic ester exceeds 30% by weight, the impact resistance and the chemical resistance of the molded product are reduced.

(2) Emulsion Polymerization Polymerization Rate In step (5), the polymerization rate is preferably 85% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more. If the polymerization rate is less than 85% by weight, the impact resistance and transparency of the molded article of the multilayer styrene copolymer tend to decrease. here,
The determination of the conversion includes the unreacted monomer at the end of step (4).

6. Amounts of monomer mixtures (a) to (e) (1) Monomer mixture (a) Monomer mixtures (a) to (e) compounded in each of the steps (1) to (5) ) Is determined based on the amount of the monomer mixture (a)
To the total amount of (e).
That is, in step (1), the monomer mixture (a)
Preferably 5 to 55% by weight, more preferably 10 to 45% by weight.
If the amount of the monomer mixture (a) is less than 5% by weight, the transparency of the molded article of the multilayer styrene-based copolymer tends to be impaired. If it is% by weight, the impact resistance of the molded article tends to decrease.

(2) Monomer mixture (b) The monomer mixture (b) in step (2) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight,
More preferably, it is 20 to 40% by weight. When the amount of the monomer mixture (b) is less than 10% by weight, the impact resistance of a molded article of the multilayer styrene copolymer tends to decrease, and
If it exceeds 0% by weight, the transparency of the molded article tends to decrease.

(3) Monomer mixture (c) The monomer mixture (c) in step (3) is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, and still more preferably 4 to 10% by weight. % By weight. If the amount of the monomer mixture (c) is less than 1% by weight, the transparency of the molded article of the multilayered styrene copolymer tends to decrease, and if it exceeds 20% by weight, the impact resistance and heat resistance of the molded article Tends to decrease.

(4) Monomer mixture (d) The monomer mixture (d) in step (4) is preferably 5-35% by weight, more preferably 7-20% by weight, most preferably 10-15% by weight. % By weight. When the amount of the monomer mixture (d) is less than 5% by weight, the impact resistance and chemical resistance of the molded article of the multilayer styrene copolymer tend to decrease. The impact properties tend to decrease.

(5) Monomer mixture (e) The monomer mixture (e) in step (5) is preferably 10 to 79% by weight, more preferably 30 to 65% by weight, and most preferably 35 to 55% by weight. % By weight. When the monomer mixture (e) is less than 10% by weight, salting out after polymerization,
Not only does the workability regarding drying of the multi-layered styrene-based copolymer tend to decrease, but also the transparency, chemical resistance and heat resistance of the molded article of the multi-layered styrene-based copolymer tend to decrease. If the amount is more than 10% by weight, the impact resistance of the molded article tends to decrease.

7. Polymerization Conditions in Emulsion Polymerization (1) Polymerization Temperature In the method for producing a multilayered styrenic copolymer of the present invention, an emulsion polymerization method is used, but an appropriate polymerization temperature at that time is not different at each stage. , 40 at each stage
１００100 ° C. A preferred polymerization temperature is selected in the range of 50 to 80C.

(2) Seed Polymerization Method In the method for producing a multilayered styrenic copolymer of the present invention, in the step (2) and subsequent steps, the next step is carried out in the presence of the copolymer formed up to the preceding step. The polymerization reaction is performed by sequentially adding the monomer mixture. Therefore, after the step (2), it can be said that the seed polymerization method is applied. At this time, when performing the polymerization after the step (2), it is important to select polymerization conditions that do not cause generation of new particles. For this, it is important that the amount of surfactant used is below the critical micelle concentration.

(3) Surfactant The surfactant used in the emulsion polymerization is not particularly limited, and a commonly used surfactant can be used. For example, long-chain alkyl carboxylate, dialkyl sulfosuccinate, alkylbenzene sulfonate and the like can be mentioned. The amount of these surfactants is preferably such that the particle size at the time when the emulsion polymerization of step (5) is completed is preferably 50 to 50.
It is determined to be 500 nm, more preferably 50-350 nm, most preferably 100-250 nm.

(4) Polymerization Initiator The polymerization initiator used in the emulsion polymerization is not particularly limited, and a usual initiator can be used. For example, lead persulfate, perborate, or the like alone, or a redox-initiating system using them together with sulfite, lead thiosulfate, or the like, or an organic peroxide and a ferrous salt, an organic oxide and sodium formaldehyde Redox initiation systems using sulfoxylates can also be used.

II. Multilayer Styrenic Copolymer (1) Particle Size The multilayer styrene copolymer of the present invention has a particle size of 50 to 500 nm immediately after the completion of the polymerization in step (5) (copolymer (E)). Preferably, there is. If it is less than 50 nm, the impact resistance of the molded article tends to decrease, and if it exceeds 500 nm, the transparency of the molded article tends to decrease. More preferably, it is 50 to 350 nm, most preferably, 1 to 350 nm.
00 to 250 nm.

(2) Structure of Copolymer The detailed structure of the multilayer styrene copolymer can be examined by observation with an electron microscope.

(3) Determination of Glass Transition Temperature of Copolymer The glass transition temperature (Tg) of the copolymers (A) to (E) obtained in each step is determined by the following equation (1).

[0064]

(Equation 1)

[0065] (1) where, m _i is the mole fraction of i component in the copolymer, Tg _i represents the glass transition temperature of component i, i
Is a serial number conveniently assigned to the monomers constituting the copolymer, and varies from 1 to a maximum number k (total number of types of monomers). The glass transition temperature of the i component other than the polyfunctional monomer represents the glass transition temperature of a polymer obtained by bulk polymerization of each component alone. The measurement of the glass transition temperature at this time is defined as the temperature at which tan δ reaches a peak in the dynamic viscoelasticity measurement performed at a frequency of 5 Hz and a heating rate of 1 ° C./min. The glass transition temperature of the polyfunctional monomer was found to be inconsistent with the coefficient of linear expansion in a thermal expansion measurement performed at a rate of 1 ° C./min for a polymer obtained by bulk polymerization of the polyfunctional monomer alone. Defined as a continuously changing temperature. Stage (2)
In calculating the glass transition temperature of the copolymer (B) obtained in the above, the unreacted monomer at the end of the step (1) and the monomer mixture (b) newly added in the step (2) are combined. The calculation is made assuming that the copolymer (B) is obtained in step (2) from the monomers obtained. Calculation of the glass transition temperature after step (3) was performed in the same manner. Gas chromatographic measurement can be used for determining and quantifying the unreacted monomer in each step,
In the examples described later, the measurement was performed by this method.

(4) Determination of the refractive index of the copolymer The refractive index of the copolymer obtained in each step is determined by the following equation (2).

[0067]

(Equation 2)

[0068] (2) where, m _i is the mole fraction of i component in the copolymer, n _i is the refractive index of the monomer of component i, i is a monomer constituting the copolymer , And varies from 1 to the maximum number k (total number of types of monomers). The refractive index of the monomer of the i component is measured at 25 ± 0.05 ° C. In calculating the refractive index of the copolymer (B) obtained in the step (2), the unreacted monomer at the end of the step (1) and the monomer mixture (b) newly blended in the step (2) The copolymer (B) is converted into the step (2) from the monomer combined with
Calculate as obtained by Calculation of the glass transition temperature after step (3) was performed in the same manner. The composition of the unreacted monomer in each step can be measured by gas chromatography, and in the examples described later, it was measured by this method.

III. Vinyl Chloride Resin Composition The vinyl chloride resin composition of the present invention comprises 5 to 60% by weight of the multilayer structure styrene copolymer,
5 to 40% by weight, and can be obtained by melt-kneading both. This composition can be used as a thermoplastic molding material. At this time, the compounding amount of the multi-layered styrene-based copolymer is preferably 5 to 60% by weight of the whole composition. If the amount is less than 5% by weight, the impact resistance of the molded article of the resin composition is reduced, and if it is more than 60% by weight, the fluidity of the resin composition is reduced. The multilayer structure styrene-based copolymer can be melt-kneaded by appropriately adding a usual additive such as a colorant or a stabilizer and, if necessary, mixing with another copolymer. The method for producing the vinyl chloride resin used here is not particularly limited and can be produced by a known method, for example, bulk polymerization, suspension polymerization,
Polymerization methods such as solution polymerization and emulsion polymerization are used. IV. Thermoplastic resin composition The thermoplastic resin composition of the present invention comprises 10 to 90% by weight of the multilayer styrene copolymer and 90 to 10% by weight of a thermoplastic resin having an ester bond in the main chain. Can be obtained by melt-kneading. Examples of the thermoplastic resin having an ester bond in the main chain used in the present invention include an aromatic saturated polyester, an aromatic polycarbonate, and a mixture thereof. Examples of the aromatic polycarbonate resin include an aromatic dihydroxy compound or an aromatic polycarbonate polymer obtained by reacting a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester. Specifically, for example, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane [= tetramethylbisphenol A], 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane [= tetrabromobisphenol A], 2,2-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) Sulfone, 2,2-bis (4-hydroxyphenyl ) Sulfide, 2,2-bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) Cyclohexane and the like are exemplified. The most preferred aromatic dihydroxy compound is 2,2-bis (4-
An aromatic polycarbonate using (hydroxyphenyl) propane [bisphenol A] can be mentioned.
As the aromatic saturated polyester, a condensate of an aromatic dicarboxylic acid (or a derivative thereof) and an aliphatic diol or an alicyclic diol, particularly, terephthalic acid (or a derivative thereof) and a C 2-10 (cyclo) Polyalkylene terephthalate obtained from alkylene diol can be mentioned. Among them, polyethylene terephthalate and polybutylene terephthalate are preferred, and polybutylene terephthalate is more preferred. The aromatic saturated polyester and the aromatic polycarbonate can be used alone or in combination at an arbitrary ratio.

The composition ratio of the multilayered styrene copolymer to the thermoplastic resin having an ester bond in the main chain is 90 to 1
0/10 to 90 (% by weight), preferably 20 to 80/8
0-20, more preferably 30-70 / 70-30. When the amount of the multilayer styrene copolymer is less than 10% by weight, the weather resistance of a molded article of the resin composition is lowered, and
If the ratio exceeds the above range, the heat resistance of the molded article of the resin composition will decrease.

The kneading of the multi-layered styrene copolymer and the thermoplastic resin having an ester bond in the main chain can be carried out by using a known mixing apparatus, for example, a roll, kneader, single-screw or multi-screw extruder. . Among them, a twin-screw extruder is preferable. In addition, at the time of kneading, known plasticizers, lubricants, stabilizers, coloring agents, flame retardants, reinforcing agents, and the like can be added.

[0072]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

The measurement in the examples or comparative examples was performed using the following equipment or method. 1. Polymerization rate: After drying the sampled polymerization reaction liquid using an infrared moisture system, the weight of the non-volatile components was measured, and determined from this value and the incorporation ratio using the following formula (3).

[0074]

## EQU3 ## Polymerization ratio of n-layer = ((α × β ÷ γ-δ) / ε) × 100% (3)

The meanings of the symbols in the formula (3) are shown below. n: an integer of 1 to 5 α: total weight of the reaction mixture present in the polymerization system at the end of the polymerization of step (n) β: non-volatile content weight of the reaction mixture collected at the end of the polymerization of step (n) γ: step (n) Δ: Total weight of non-volatile components present in the polymerization system at the end of the polymerization in step (n-1) ε: Monomer and polyfunctional monomer newly added in the step (n) Weight of the monomer and the unreacted monomer mixture present in the polymerization system at the end of the polymerization in step (n-1). In the above, when n-1 is 0, the value of δ is 0, and ε is This is the amount of the monomer mixture (A) added in (1).

2. Particle size: The particle size of the multilayered structure latex was measured using a laser scattering method. The equipment used was BIC
It was a BI-90 made by the company.

3. Izod impact strength: ASTM-D2
Performed according to 56. The test piece was 1/8 inch thick and notched. The measurement temperature was 23 ° C. ± 2 ° C.
The Izod impact tester used was manufactured by Toyo Seiki.

4. Danestadt impact strength: DIN-
Performed according to 53453. The thickness of the test piece was 1/8 inch and no notch was used. The measurement temperature was 23 ° C. ± 2 ° C. The Izod impact tester used was manufactured by Toyo Seiki.

5. Weather resistance Sunshine weather meter (WEL- manufactured by Suga Test Instruments Co., Ltd.)
(SUN-HCH type) and measured according to JIS A1415. The hue change after 1000 h irradiation was measured.
The hue change was measured by using a spectral colorimeter (Macbeth) to measure ΔE.

6. Visible light transmittance: wavelength range 400 to 80
The transmittance at 0 nm was examined, and the value obtained by dividing the area surrounded by the transmittance curve and the baseline of the test piece by the area measured in the same manner as in the case of the matrix resin containing no multilayer structure was calculated as the transmittance of the test piece. And The thickness of the test piece is 2 mm,
Using a spectrophotometer (model 228A, manufactured by Hitachi, Ltd.),
It was measured at a temperature of 3 ° C. ± 2 ° C.

7. Heat deformation temperature: ASTM D-648-
Performed according to 56. The test piece used was a 1/2 inch, load was 18.4 kgf, the temperature was raised at a rate of 2.0 ± 2 ° C / min, and the temperature at which the deformation of the test piece reached 0.26 mm was determined by thermal deformation. Temperature.

8. Tensile strength: A tensile tester (UTM manufactured by Orientec Co., Ltd.) according to JIS K6319.
-III-500).

9. Chromogenicity: The blackness of the molded article was measured using a spectral colorimeter (manufactured by Sakata Inx Co., Ltd.) and used as a measure of the chromogenicity.

10. Gloss: The plane gloss at an incident angle of 60 degrees was measured according to JIS Z8741. The photometer used was a VG-IB type manufactured by Nippon Denshoku Industries Co., Ltd.

The abbreviations of the compounds used are shown below. St: styrene, BuA: butyl acrylate AN: acrylonitrile, MMA: methyl methacrylate, HDA: 1,6-hexanediol diacrylate, DVB: divinylbenzene, AMA: allyl methacrylate, PPDA: polypropylene glycol diacrylate, TDM: t -Dodecyl mercaptan, KPS: potassium persulfate, DAS: sodium di-2-ethylhexyl sulfosuccinate

Example 1 <Production of Multilayer Styrenic Copolymer> (Step (1)) In a 4 L flask equipped with a reflux condenser, 1614 g of distilled water and 35 g of DAS were collected and stirred at a rotation speed of 320 rpm. Then, the temperature was raised to 40 ° C. When the temperature reached 40 ° C., nitrogen gas was blown into the water while maintaining the temperature, and oxygen dissolved in the water was replaced over about 1 hour. Thereafter, the temperature was raised to 70 ° C. under a nitrogen gas stream, and 25.3 g of a 1.19 wt% KPS aqueous solution was added. Then, a mixture of St371.03 g and 0.565 g of HDA was added at a rate of 9.3 g / min. It was dropped. After dripping the whole amount, it was kept at the same temperature for 2 hours. At this time, the polymerization rate (the polymerization rate in step (1)) was 96.5%.

(Step (2)) Then, the concentration was 1.1% by weight.
After adding 25.3 g of a KPS aqueous solution of BuA37,
A mixture consisting of 1.03 g, 0.458 g of HDA,
It was dropped at a rate of 9.3 g / min. After dropping the whole amount, the same temperature was maintained for 2.5 hours. The polymerization rate of the monomer mixture newly added in step (2) and the unreacted monomer in step (1) (this is referred to as “polymerization rate in step (2)”) is 96.2. %. The polymerization rate of the total amount of the monomers used in step (1) and step (2) was 98.0%.

(Step (3)) Then, the concentration was 2.9% by weight.
After adding 25.8 g of a KPS aqueous solution and 1.0 g of DAS, St68.7 g, BuA 13.8 g, HDA1.
A mixture consisting of 736 g was dropped at a rate of 9.3 g / min. After dropping the whole amount, the same temperature was maintained for 4 hours. The polymerization rate of the unreacted monomer at the end of step (2) and the monomer mixture newly added in step (3) (this is referred to as the “polymerization rate in step (3)”) is 9
3.0%, and the polymerization rate of the total amount of monomers in the steps (1) to (4) was 99.1%.

(Step (4)) Then, the concentration was 1.4% by weight.
After adding 25.4 g of a KPS aqueous solution of St112.
A mixture composed of 1 g, 35.4 g of AN, and 4.399 g of AMA was dropped at a rate of 9.3 g / min. After dropping the whole amount, the same temperature was maintained for 1.5 hours. The polymerization rate of the unreacted monomer at the end of step (3) and the monomer mixture newly added in step (4) (this is referred to as “polymerization rate in step (4))” is 93. 0%, and the polymerization rate of the total amount of monomers in steps (1) to (4) was 99.
1%.

(Step (5)) Then, the concentration was 1.3% by weight.
Was added, and a predetermined amount of a previously prepared mixture was added dropwise at a rate of 9.3 g / min. The mixtures prepared in advance are as follows. MMA 51.1 in 250 g of distilled water
g, St 194.2 g, AN 95.4 g and TDM2.
A mixture consisting of 308 g was added and DAS1.
908 g was added, stirred and emulsified. This mixture was added dropwise at a rate of 13 g / min, and the whole amount was added dropwise, and the same temperature was maintained for 1.5 hours. At the end of step (4), the polymerization rate of the unreacted monomer and the monomer mixture of step (5) combined (this is referred to as “polymerization rate in step (4)”) is 95.5%. The polymerization rate of the total amount of the monomers in the steps (1) to (5) was 99.6%.

(Post-treatment) Next, the whole amount of the latex thus obtained was dropped into 3000 g of an aqueous solution of aluminum sulfate having a concentration of 1.3% by weight at 80 ° C for about 30 minutes while being vigorously stirred. Was deposited. Thereafter, the resultant was dehydrated and dried to obtain a target multilayer-structured styrene copolymer powder.

<Mixing with vinyl chloride resin> Degree of polymerization: 105
To a suitable amount of the obtained vinyl chloride resin and the obtained multilayer styrene copolymer, 3.0 parts by weight of dibutyltin maleate was added, and the mixture was mixed with a Henschel mixer for about 5 minutes, and then mixed with 30 m.
Extruded pellets were produced at a cylinder temperature of 180 ° C. using a twin screw extruder with mΦ. The pellet was injection molded at 180 ° C. to obtain a test piece for performance evaluation.

[Example 2] The monomer mixture of step (1) was prepared as a mixture consisting of 695.44 g and HDA of 1.115 g, and the monomer mixture newly added in step (3) was BuA
4.5 g, St 22.5 g, HDA 0.566 g, and the monomer mixture newly added in step (4) was St 79.7 g, AN 31.0 g, AMA
3.407 g, and the monomer mixture newly added in step (5) was prepared by adding 19.8 g of MMA and 75.0 St.
g, 36.8 g of AN, and 0.894 g of TDM. In addition,
95.2% conversion in step (1), 96.4% conversion in step (2), 89.2% conversion in step (3), 90.7% conversion in step (4) %, Conversion in step (5) 9
It was 5.8%.

Example 3 The monomer mixture of step (1) was composed of 297.8 g of St and 0.454 g of HDA, and the monomer mixture newly added in step (2) was BuA
623.0 g and 1.100 g of HDA,
The monomer mixture newly added in step (5) is MMA2
4.2 g, St 91.9 g, AN 45.2 g, TDM
The procedure was exactly the same as in Example 1 except that the weight was 1.093 g. Incidentally, the polymerization rate in the step (1) was 97.
2%, 95.4% conversion in step (2), 91.2% conversion in step (3), 94.6% conversion in step (4)
%, And the polymerization rate in the step (5) was 93.2%.

[Example 4] 67.3 g of BuA, 140.6 g of St, and
HDA 4.243 g, and 33.3 g of MMA, St1
The procedure was performed in exactly the same manner as in Example 1 except that 26.6 g of AN, 62.2 g of AN, and 1.503 g of TDM were used. The polymerization rate in the step (1) was 92.9%, the polymerization rate in the step (2) was 94.0%, and the polymerization rate in the step (3) was 8
5.6%, the conversion in the step (4) was 94.4%, and the conversion in the step (5) was 93.6%.

Example 5 A monomer mixture newly added in step (2) was prepared by mixing 59.9 g of St, 11.7 g of BuA, and H
The procedure was exactly the same as in Example 1 except that the composition consisted of 12.635 g of DA. The polymerization rate in the step (1) was 87.1%, the polymerization rate in the step (2) was 95.8%, the polymerization rate in the step (3) was 91.2%, and the polymerization rate in the step (4) was 9
3.5%, and the conversion in the step (5) was 96.2%.

Example 6 The same procedure as in Example 1 was carried out except that DVB was used as the polyfunctional monomer in the steps (1), (2) and (3). The polymerization rate in the step (1) was 92.2%, the polymerization rate in the step (2) was 95.4%, the polymerization rate in the step (3) was 91.4%, and the polymerization rate in the step (4) was 90. 9.9%, and the conversion in the step (5) was 94.6%.

Comparative Example 1 The monomer mixture of step (1) was composed of 41.5 g of BuA and 0.063 g of HDA, and the monomer mixture newly added in step (2) was BuA
The procedure was performed in exactly the same manner as in Example 1 except that 700.6 g and 0.865 g of HDA were used. 92.7% conversion in step (1), 96.1% conversion in step (2)
%, The polymerization rate in the step (3) was 90.2%, the polymerization rate in the step (4) was 95.1%, and the polymerization rate in the step (5) was 93.2%.

Comparative Example 2 The monomer mixture of step (1) was composed of 672.8 g of St and 1.024 g of HDA, and the monomer mixture newly added in step (2) was St6.
The procedure was performed in exactly the same manner as in Example 1 except that 9.2 g and 0.085 g of HDA were used. 97.3% conversion in step (1), 94.9% conversion in step (2), 85.1% conversion in step (3), 88.6 conversion in step (4) %, And the conversion in the step (5) was 92.7%.

Comparative Example 3 82.5 g of BuA and 1.736 g of HDA were added to the monomer mixture newly added in step (3).
The procedure was performed in exactly the same manner as in Example 1 except that it was composed of 94.0% conversion in step (1), 95.2% conversion in step (2), 88.2% conversion in step (3)
%, The polymerization rate in the step (4) was 89.4%, and the polymerization rate in the step (5) was 93.5%.

[Comparative Example 4] St. 109.5 g, BuA 38.0 g, and a monomer mixture newly blended in step (4) were prepared.
The procedure was exactly the same as in Example 1 except that AMA consisted of 4.40 g. 92.3 polymerization rate in step (1)
%, 96.5% conversion in step (2), 89.1% conversion in step (3), 93.9% conversion in step (4),
The conversion in the step (5) was 94.8%.

[Comparative Example 5] St. 170.36 g of the monomer mixture newly added in step (5) and BuA.
The procedure was exactly the same as in Example 1 except that the weight was 6 g. 92.4% conversion in step (1), 94.5% conversion in step (2), 9 conversion in step (3)
3.5%, the polymerization rate in the step (4) was 92.6%, and the polymerization rate in the step (5) was 93.8%.

Comparative Example 6 The procedure of Example 1 was repeated except that the polymerization in the step (5) was not carried out. 92.4% conversion in step (1), 9 conversion in step (2)
The conversion was 4.5%, the conversion in the step (3) was 93.5%, and the conversion in the step (4) was 92.6%.

The composition of the monomer mixture newly blended in each stage in Examples 1 to 6 and Comparative Examples 1 to 6 and the ratio (% by weight) of the monomer mixture newly blended in each stage. Tables 1 to 12 show the polymerization rate at each stage and the glass transition point and refractive index of the copolymer purified at each stage.

[Comparative Example 7] Using an MBS-based vinyl chloride-based resin modifier (Kane Ace B manufactured by Kaneka Chemical Industry Co., Ltd.), the mixing and the test of Example 1 were carried out in the same manner.

[Comparative Example 8] Using a MAS-based vinyl chloride-based resin improving material (Kaneace FT manufactured by Kaneka Corporation),
The mixing and testing of Example 1 were performed in the same manner.

Table 13 shows the test results in Examples 1 to 6 and Comparative Examples 7 and 8.

Table 14 shows the test results of the weather resistance (impact strength) of the compositions in Example 1 and Comparative Examples 7 and 8.

[Examples 7 to 12] The multilayer styrenic copolymer obtained in Example 1, polybutylene terephthalate (1401-X06, manufactured by Toray Industries, Inc.) and polycarbonate (Taflon FN2200, manufactured by Idemitsu Petrochemical Co., Ltd.) Table 1
Mix at the mixing ratio (parts by weight) shown in Fig. 5, and
Using a CM30 type twin screw extruder, cylinder temperature 260
The mixture was melted and kneaded at a temperature of 0 ° C. and pelletized. Test pieces were formed from the pellets at a cylinder temperature of 260 ° C. using a Ti50G injection molding machine manufactured by Toyo Machine Metal Co., Ltd., and the characteristics were evaluated.
Table 15 shows the characteristics of Examples 7 to 12.

[0110]

[Table 1]

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

[Table 4]

[0114]

[Table 5]

[0115]

[Table 6]

[0116]

[Table 7]

[0117]

[Table 8]

[0118]

[Table 9]

[0119]

[Table 10]

[0120]

[Table 11]

[0121]

[Table 12]

[0122]

[Table 13]

[Table 13-2]

[0123]

[Table 14]

[0124]

[Table 15]

[0125]

As described above, according to the present invention, it is used as a material for improving the impact resistance, weather resistance, gloss and weld dichroism of a vinyl chloride resin and a predetermined thermoplastic resin, and has a high transparency. The present invention can provide a method for producing a multilayered styrene-based copolymer without lowering the styrene copolymer resistance, a multilayered styrene-based copolymer, a vinyl chloride-based resin composition, and a thermoplastic resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67/00 C08L 67/00 69/00 69/00 (72) Inventor Tatsuo Ishikawa 14 Goi south coast, Ichihara city, Chiba prefecture Hitachi Chemical Industrial Co., Ltd.

Claims (9)

[Claims] 1. A method for producing a multilayer styrenic copolymer comprising the following steps (1) to (5). (1) 50 to 99.999% by weight of styrene, 0 to 45% by weight of at least one compound selected from the group consisting of a (meth) acrylate having 1 to 8 carbon atoms and a vinyl cyanide compound; Emulsion polymerization by blending a monomer mixture (a) having a composition of 0.001 to 5% by weight of a hydrophilic monomer so that the glass transition temperature of the obtained copolymer (A) is 0 ° C. or higher. Let it. (2): In the presence of the copolymer (A) obtained in the step (1), a (meth) acrylate ester having 1 to 8 carbon atoms 95 to
99.999% by weight, and a polyfunctional monomer 0.001 to 5
% By weight of a monomer mixture (b) having a composition of 2% by weight so that the glass transition temperature of the copolymer (B) newly obtained in this step (2) is 0 ° C. or higher and emulsion-polymerized. . (3): in the presence of the copolymer (B) obtained in step (2), styrene 20 to 99.999% by weight and carbon number 1 to
At least one compound 0 selected from the group consisting of (meth) acrylates and vinyl cyanide compounds
A monomer mixture (c) having a composition of about 30% by weight and 0.001 to 50% by weight of a polyfunctional monomer is mixed with the copolymer (C) newly obtained in this step (3). Emulsion polymerization is carried out by blending such that the glass transition temperature is 0 ° C. or higher and the refractive index is in the range of 1.51 to 1.60. (4): In the presence of the copolymer (C) obtained in the step (3), 60 to 85% by weight of styrene, 15 to 40% by weight of a vinyl cyanide compound, and (C) having 1 to 8 carbon atoms 0) Acrylate 0-15% by weight and polyfunctional monomer 0.0
Monomer mixture (d) having a composition of from 0.01 to 10% by weight
Is mixed and emulsion-polymerized to obtain a new copolymer (D). (5): In the presence of the copolymer (D) obtained in the step (4), 60 to 90% by weight of styrene, 10 to 35% by weight of a vinyl cyanide compound, and (C) having 1 to 8 carbon atoms ) A monomer mixture (e) having a composition of 0 to 30% by weight of an acrylate ester is blended and emulsion-polymerized to obtain a new copolymer (E). 2. The amount of each of the monomer mixtures (a) to (e) in the steps (1) to (5) is a single amount relative to the total amount of the monomer mixtures (a) to (e). Body mixture (a) 5
55% by weight, monomer mixture (b) 10 to 60% by weight, monomer mixture (c) 1 to 20% by weight, monomer mixture (d)
The method for producing a multi-layer styrene-based copolymer according to claim 1, wherein the amount is 5 to 35% by weight and the monomer mixture (e) is 10 to 79% by weight. 3. The method according to claim 1, wherein the particle size of the copolymer (E) at the end of the step (5) is in the range of 50 to 500 nm. . 4. The polyfunctional monomer compounded in the steps (1) to (4) is at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol, acrylate of alkylene diol and divinylbenzene. 4. The method according to claim 1, wherein
The method for producing a multilayer styrenic copolymer according to the above item. 5. The method according to claim 1, wherein the polyfunctional monomer blended in step (4) is allyl methacrylate. 6. A multilayer styrene copolymer obtained by the method for producing a multilayer styrene copolymer according to any one of claims 1 to 5. 7. A vinyl chloride resin composition comprising 5 to 60% by weight of the multilayered styrene copolymer according to claim 6 and 95 to 40% by weight of a vinyl chloride resin. 8. A thermoplastic resin composition comprising 10 to 90% by weight of the multilayer styrene copolymer according to claim 6 and 90 to 10% by weight of a thermoplastic resin having an ester bond in the main chain. 9. The thermoplastic resin composition according to claim 8, wherein the thermoplastic resin having an ester bond in the main chain is polycarbonate and / or polybutylene terephthalate.