JP2980735B2 - Multilayer polymer, thermoplastic resin composition containing the same, and molded article thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer polymer, a thermoplastic resin composition containing the same, and a molded article thereof. More specifically, the present invention provides a multilayer polymer useful as an impact modifier for a thermoplastic resin containing a polycarbonate resin and a polyester resin, a thermoplastic resin composition containing the same, and having improved impact resistance. And, with respect to a molded product obtained by molding such a resin composition, further, in the production of a molded product colored with a coloring agent, coloring properties such as color unevenness and a peeling phenomenon near a gate of the molded product are improved. And a molded article thereof.

[0002]

2. Description of the Related Art Polycarbonate resins are tough, have excellent impact resistance and electrical properties, and have excellent dimensional stability, but have high melt viscosity, poor moldability, and thickness dependency on impact resistance. In addition, it has drawbacks in that it has a problem in chemical resistance such as generation of cracks when it comes into contact with aromatic solvents or gasoline, and its application range is limited.

[0003] In order to solve such disadvantages, various improvements have been proposed. For example,
JP-B-36-14035 proposes to improve the chemical resistance by blending a polyethylene terephthalate resin with an aromatic polycarbonate resin. Also,
JP-A-48-54150 proposes to improve the surface hardness and chemical resistance by blending a polybutylene terephthalate resin with an aromatic polycarbonate resin. However, such a resin composition has insufficient impact resistance.

Further, Japanese Patent Publication No. 62-37671 proposes a method of improving impact resistance by blending an aromatic polycarbonate resin with a polyester resin and an acrylic elastomer. According to this method, although the impact resistance is certainly improved, in a colored molded product, so-called unevenness of color or unevenness of the color appearance called pearl occurs. This phenomenon is remarkable in a portion where high shear is loaded, such as in the vicinity. Therefore, the use of such a colored molded article must be limited without treatment such as surface coating. Further, as described above, in the portion where high shear is applied to the resin composition during molding, the peeling phenomenon, that is,
Delamination often occurs, and sometimes gives a molded article that cannot be put to practical use.

[0005] In order to solve the problem of color unevenness in the production of such a colored molded article, Japanese Patent Publication No. Hei.
Japanese Patent Application Publication No. JP-A-2005-64139 discloses a first-stage polymer obtained by polymerizing a styrene-based monomer and a second-stage polymer obtained by polymerizing an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms. And a polymer having a multilayer structure consisting of a third-stage polymer obtained by polymerizing an alkyl methacrylate monomer having 1 to 8 carbon atoms in an alkyl group is blended with a mixture of a colored polycarbonate resin and a polyester resin. It has been proposed. However, even with this method, the color unevenness still
Not fully resolved.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems, and is suitable for blending as an impact-resistant agent in a thermoplastic resin containing a polycarbonate resin and a polyester resin. Certain multilayer polymers, including such multilayer polymers, impact resistance,
Thermoplastic resin composition containing polycarbonate resin and polyester resin that not only excels in mechanical properties such as chemical resistance, surface hardness, and dimensional stability, but also gives a molded product without color unevenness even when a coloring agent is contained. An object of the present invention is to provide a resin molded product obtained by molding such a resin composition.

[0007]

The multilayer polymer according to the present invention is obtained by three-stage emulsion polymerization, and has a core layer formed of an aromatic vinyl monomer and an alkyl group having 2 to 8 carbon atoms. And an intermediate layer made of a rubbery polymer formed from an alkyl acrylate monomer, and a hard polymer formed of an aromatic vinyl monomer and having a glass transition temperature of 50 ° C or more. 0.5 to 20 with respect to the total amount of the monomer.
It has an outermost layer cross-linked with the cross-linkable monomer of weight% .

Further, the thermoplastic resin composition according to the present invention contains a thermoplastic resin containing a polycarbonate resin and a polyester resin, together with such a multilayer polymer. The resin molded product according to the present invention is obtained by molding the above-mentioned thermoplastic resin composition. First, the thermoplastic resin composition according to the present invention will be described. In the present invention, as the polycarbonate resin, one generally known as engineering plastic is used. Of these, an aromatic dihydroxy compound or a thermoplastic polycarbonate resin which may be branched, obtained by reacting an aromatic dihydroxy compound or a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester is preferably used.

As the aromatic dihydroxy compound, for example, 2'2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4- (Hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl and the like.

In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptene-
Polyhydroxy compounds such as 3,1,3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-
Hydroxyaryl) oxindole (also called isatin bisphenol), 5-chlorisatin,
5,7-Dichloroisatin, 5-bromoisatin and the like may be substituted with a part of the dihydroxy compound, for example, about 0.1 to 2 mol%.

Further, in order to adjust the molecular weight of the obtained polycarbonate resin, a monovalent aromatic hydroxy compound can be used. Examples of such a monovalent aromatic hydroxy compound include, for example, m- or p-methylphenol, m- or p-propylphenol, p-promphenol, p-tert-butylphenol, p-long-chain alkyl-substituted phenol, and the like. Is preferably used.

Representative examples of the polycarbonate resin used in the present invention include a bis (4-hydroxyphenyl) alkane-based dihydroxy compound, particularly, a polycarbonate resin containing bisphenol A as a main raw material. However, a polycarbonate copolymer obtained by using two or more aromatic dihydroxy compounds in combination or a branched polycarbonate resin obtained by using a small amount of a trivalent phenol compound in combination can also be used. Further, in the present invention, a mixture of these polycarbonate resins can also be used.

As the polyester resin used in the present invention, those generally known as engineering plastics are used. Among them, polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or a dialkyl ester thereof with an aliphatic diglycol or a copolymer mainly containing the same is preferably used. As such a polyester resin, for example,
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and the like are preferably used.

As the above aliphatic glycol, for example,
Ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol and the like are used. These aliphatic glycols are used in combination with other diols and polyhydric alcohols such as cyclohexanediol, cyclohexanedimimethanol, xylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, and pentaerythritol. can do. The use amount of these diols or polyhydric alcohols is preferably within a range of 40 parts by weight or less based on 100 parts by weight of the aliphatic glycol.

In the production of the polyester resin, together with terephthalic acid or its dialkyl ester,
Dibasic acids, tribasic acids and the like such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, trimellitic acid and their dialkyl esters, and a combination of these dialkyl esters Can be. The amount used is 40 parts by weight based on 100 parts by weight of terephthalic acid or its dialkyl ester.
It is preferably in the range of not more than parts by weight. The multi-layer polymer according to the present invention can be obtained by a continuous multi-stage seed emulsion polymerization method in which the polymer of the previous stage is sequentially coated with the polymer of the subsequent stage. The multilayer structure polymer according to the present invention is generally preferably a multilayer structure polymer obtained by three-stage emulsion polymerization.

The first-stage polymerization is for forming a core layer of a multilayer polymer, and is carried out using an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene,
Monochlorostyrene, 3,4-dichlorostyrene, bromostyrene and the like can be mentioned. Of these, styrene is particularly preferably used.

In the first stage polymerization, a non-aromatic monomer can be used together with the aromatic vinyl monomer. The amount used is preferably in the range of 50% by weight or less, more preferably in the range of 20% by weight or less, based on the total amount of the monomers used for the first-stage polymerization. Examples of such non-aromatic monomers include alkyl acrylates such as ethyl acrylate and butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, acrylonitrile, vinyl cyanide such as methacrylonitrile, and vinylidene cyanide. Can be mentioned.

In the present invention, the core layer of the multilayer polymer may be crosslinked with a crosslinking monomer. The amount of the crosslinkable monomer to be used is generally 30% by weight or less, preferably 0.5 to 20% by weight, based on the total amount of the monomers used in the first stage polymerization. And more preferably in the range of 5 to 15% by weight. As such a crosslinkable monomer, a monomer having two or more polymerizable ethylenically unsaturated bonds in the molecule is preferably used. Specific examples include, for example, aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol (meth) acrylate, oligoethylene glycol di (meth) acrylate, Examples include alkane polyol poly (meth) acrylates such as trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate. Among them, divinylbenzene is particularly preferably used.

In the first-stage polymerization, a grafted monomer can also be used. The amount used is usually in the range of 5% by weight or less, and preferably in the range of 0.1 to 2% by weight, based on the total amount of the monomers used in the first stage polymerization. As such a grafting monomer, a monomer having two or more ethylenically unsaturated bonds having different reactivities in a molecule is used. Specific examples thereof include allyl (meth) acrylate, diallyl maleate, diallyl fumarate, and allyl unsaturated carboxylic acid esters such as diallyl itaconate. Of these, allyl methacrylate is particularly preferably used.

In the second stage polymerization, an alkyl acrylate having 2 to 8 carbon atoms in an alkyl group or a mixture thereof is polymerized to form an intermediate layer of a rubbery polymer having a multilayer structure. It is. It is desirable that such a rubbery polymer usually has a glass transition temperature of −30 ° C. or less. Examples of the acrylate in which the alkyl group has 2 to 8 carbon atoms include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. Of these, butyl acrylate and 2-ethylhexyl acrylate are particularly preferably used.

In the second stage polymerization, other vinyl monomers copolymerizable therewith can be used together with the above-mentioned alkyl acrylate. The amount of such a vinyl monomer is usually in the range of 50% by weight or less, preferably in the range of 30% by weight or less, based on the total amount of the monomers used in the second stage polymerization. is there. Specific examples of such vinyl monomers copolymerizable with the alkyl acrylate include, for example, aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene, aromatic vinylidene compounds, acrylonitrile and methacrylonitrile. Of vinyl cyanide, vinylidene cyanide, alkyl methacrylate such as methyl methacrylate and butyl methacrylate.

The intermediate layer of the rubbery polymer may also be cross-linked by the above-mentioned cross-linkable monomer. As the crosslinkable monomer, divinylbenzene, butylene glycol diacrylate, hexanediol diacrylate and the like are particularly preferably used, and among them, divinylbenzene is preferably used. The amount of the crosslinkable monomer used is usually in the range of 0.01 to 5% by weight, preferably 0.1 to 5% by weight, based on the total amount of the monomers used for the second stage polymerization.
It is in the range of 1-2% by weight.

In the second stage polymerization, the above-mentioned grafted monomer can also be used. In particular, allyl methacrylate is preferably used. The amount of the grafting monomer used is usually 5% by weight or less, preferably 0.1 to 2% by weight, based on the total amount of the monomers used for the second stage polymerization. It is. In the present invention,
The polymerization for forming the outermost layer of the third step is performed using an aromatic vinyl monomer so that a hard polymer having a glass transition temperature of 50 ° C. or more covers the rubber-like polymer. . Examples of the aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene, monochlorostyrene, 3,4-dichlorostyrene, and bromostyrene. Styrene is particularly preferably used.

In the third stage polymerization, a non-aromatic monomer which can be copolymerized with the aromatic vinyl monomer can be used. The amount used is preferably in the range of 50% by weight or less, more preferably in the range of 30% by weight or less, based on the total amount of the monomers used in the third stage polymerization. Such non-aromatic monomers include, for example, alkyl acrylates such as ethyl acrylate and butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, cyanide such as acrylonitrile and methacrylonitrile. Examples thereof include vinyl and vinylidene cyanide.

According to the present invention, the outermost layer obtained Te cowpea polymerization of third stage, that is cross-linked by, as described above crosslinking monomer. The amount of the crosslinkable monomer to be used is generally in the range of 0.5 to 20% by weight, and preferably in the range of 5 to 15% by weight , based on the total amount of the monomers used in the third stage polymerization. It is. As the crosslinkable monomer, divinylbenzene and butylene glycol dimethacrylate are preferably used, and divinylbenzene is particularly preferably used.

According to the present invention, such a hard outermost layer is particularly preferably composed mainly of a styrene-acrylonitrile copolymer. Further, in the present invention, a hard intermediate layer can be introduced between the intermediate layer made of the rubbery polymer and the hard outermost layer. This hard intermediate layer is made of a hard polymer having a glass transition temperature of 50 ° C. or higher, and is preferably formed of an alkyl methacrylate having 1 to 5 carbon atoms, such as methyl methacrylate or butyl methacrylate.

This hard intermediate layer may also be cross-linked by the above-mentioned cross-linkable monomer. As the crosslinkable monomer, for example, divinylbenzene, butylene glycol dimethacrylate, or the like is preferably used, and divinylbenzene is particularly preferably used. The amount of the crosslinkable monomer to be used is usually 30% by weight or less, preferably 0.5 to 20% by weight, based on the total amount of the monomers used for forming the hard intermediate layer. And particularly preferably 5
-15% by weight.

In the formation of the hard intermediate layer, the above-mentioned grafting monomer can be used in combination. The amount used is usually in the range of 5% by weight or less, preferably in the range of 0.1 to 2% by weight, based on the total amount of the monomers used for forming the hard intermediate layer. Conventionally known multilayer structure polymers, when blended in a thermoplastic resin composition, to prevent the impact resistance of the resin from lowering, each layer, even if it is crosslinked, has a very small amount. Is merely cross-linked by the cross-linkable monomer of On the contrary,
According to the present invention, as described above, the core layer, the hard intermediate layer and / or the outermost layer each have 5 to 15% by weight of a crosslinked monomer based on the total amount of the monomers used to form the layer. It is preferably crosslinked with a hydrophilic monomer.

In the multilayer polymer according to the present invention,
As described above, the core layer, the hard intermediate layer and / or the outermost layer are cross-linked with a large amount of a cross-linkable monomer. According to the present invention, such a multilayer structure polymer is mixed with a polycarbonate resin and a polyester resin. By blending the above, a resin composition having excellent impact resistance and improved color unevenness can be obtained.

However, the total amount of the crosslinkable monomer used for the core layer, the hard intermediate layer and the outermost layer is based on the total amount of the monomers used for forming the core layer, the hard intermediate layer and the outermost layer. It is preferably in the range of 1 to 30% by weight, particularly preferably in the range of 3 to 20% by weight. The multilayer polymer according to the present invention is prepared by preparing a latex by a known seed emulsion polymerization method, separating the polymer by freeze-thawing or salting-out, centrifugally dewatering and drying. , Granules, flakes, or powder. According to the spray drying by the spray drier, the polymer can be directly taken out from the latex. The thus obtained multilayer structure polymer can be used as it is, but if necessary, can be made into a pellet by an extruder and a pelletizer.

According to the present invention, the multilayer structure polymer preferably has a toluene-soluble content of 10% by weight or less, particularly preferably 6% by weight or less. By blending such a multilayer polymer with a mixture of a polycarbonate resin and a polyester resin, the resulting colored resin composition gives a molded article with improved color unevenness. Here, the toluene-soluble component is defined as the percentage of the multilayer structure polymer dissolved in toluene when the multilayer structure polymer is dispersed in 100 times by weight of toluene and left at room temperature for 48 hours.

Further, according to the present invention, the multi-layered polymer is used in an amount of 100 to 700 nm, preferably 200 to 50 nm, so that the obtained resin composition has satisfactory impact resistance.
Preferably, it has a particle size of 0 nm. In the present invention, the multilayer structure polymer comprises 10 to 40% by weight of a core layer, 30 to 80% by weight of a rubbery intermediate layer, and 10 to 40% by weight of an outermost layer.
And preferably 15 to 30% by weight of a core layer, 40 to 70% by weight of a rubbery intermediate layer and 15 to 25% by weight of an outermost layer.
Consists of

As described above, the multilayer polymer may have a hard intermediate layer. This hard intermediate layer has a total amount of the hard intermediate layer and the outermost layer of 10 to 4 of the entire multilayer structure polymer.
0% by weight, preferably 15 to 25% by weight. Further, the hard intermediate layer is contained in a range of 100 parts by weight or less based on 100 parts by weight of the outermost layer. The total amount of the core layer, the rubbery intermediate layer, the hard intermediate layer and the outermost layer is 100% by weight.

The thermoplastic resin composition according to the present invention comprises 5-95% by weight of a polycarbonate resin and 9% by weight of a polyester resin 9
With respect to 100 parts by weight of the thermoplastic resin mixture containing 5 to 5 parts by weight, 0.5 to 50 parts by weight, preferably 1 to 25 parts by weight of the above-mentioned multilayer polymer is contained. The ratio between the polycarbonate resin and the polyester resin can be appropriately selected within the above range. For example, when the property of the polycarbonate resin is emphasized, the polyester resin 5 to 5 to the polycarbonate resin 95 to 50% by weight is used.
The range of 0% by weight is preferable, and when importance is placed on the properties of the polyester resin, 5 to 50% by weight of the polycarbonate resin is used.
The polyester is preferably in the range of 95 to 50% by weight.

50 to 95% by weight of a polycarbonate resin,
Preferably 60 to 95% by weight and 50% polyester resin
The thermoplastic resin composition according to the invention, comprising a thermoplastic resin mixture of from 5 to 5% by weight, preferably of from 40 to 5% by weight, comprises a continuous matrix of polycarbonate resin in which the polyester resin is dispersed, and The coalescence is substantially dispersed in this polyester resin phase. This is best shown in resin compositions using polybutylene terephthalate resin as the polyester resin.

The thermoplastic resin composition according to the present invention can be obtained by blending a polycarbonate resin, a polyester resin and a multi-layer polymer in the above-mentioned ratio. The method and means for this blending are not particularly limited, but a melt blend is preferably employed. This melt blending is usually performed at a temperature of 200 to 300 ° C. using a heated roll, a Banbury mixer, or a single-screw or twin-screw extruder.

Further, the thermoplastic resin composition according to the present invention may contain various additives in appropriate amounts. Examples of such additives include stabilizers, pigments, flame retardants, lubricants, inorganic fillers, antistatic agents, release agents, ultraviolet absorbers, and the like. In particular, various pigments such as titanium-based, azo-based, phthalocyanine-based dyes and pigments, and carbon black can be used. The pigment of this resin is usually added to 100 parts by weight of the resin composition.
It is used in the range of 0.01 to 20 parts by weight.

[0038] Such a resin composition according to the present invention comprises 2
At a temperature of 00 to 300 ° C., it can be molded into a molded article of a desired shape by a usual molding method such as injection molding, extrusion molding, compression molding and the like. Such a molded product can be used, for example, for automobile parts such as bumpers, huenders, and door handles, so-called office automation equipment and household electric appliances.

[0039]

The thermoplastic resin composition according to the present invention not only retains the excellent mechanical properties and dimensional stability inherent to the polycarbonate resin, but also has good moldability due to the polyester resin. Also excellent in chemical resistance. Further, the thermoplastic resin composition according to the present invention contains the above-mentioned multilayer structure polymer, and the impact resistance at low temperatures is remarkably improved without losing the above-mentioned various excellent properties.

In the case of a colored molded article to which a pigment is added, the color unevenness and the whitening phenomenon are improved, and the peeling phenomenon near the gate during molding is also improved.

[0041]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the examples, all parts mean parts by weight, and
Abbreviations used in Examples and Comparative Examples mean the following. 2-Ethylhexyl acrylate 2EH
A n-butyl acrylate BA methyl methacrylate MMA styrene St acrylonitrile AN allyl methacrylate AlM
A 1,4-butylene glycol diacrylate BGA divinylbenzene DVB deionized water DIW dioctyl sulfosuccinate sodium salt SSS sodium persulfate SPS sodium bicarbonate SHC polycarbonate PC polybutylene terephthalate PBT polyethylene terephthalate PET weight average particle size of multilayer polymer Was measured with a laser particle size analysis system LPA-3000 manufactured by Otsuka Electronics Co., Ltd. Production of multilayer polymer Example 1 ( Production of multilayer polymer A) DIW was placed in a 5-liter capacity polymerization vessel equipped with a reflux condenser.
448 g, 12 g of a 1% aqueous solution of SSS and 32 g of a 1% aqueous solution of SHC were charged and heated to 70 ° C. while refluxing under a nitrogen stream. Next, 30 g of MMA was added and dispersed for 10 minutes, and then 80 g of a 2% aqueous solution of SPS was added to start seed polymerization.

Subsequently, the temperature was raised to 75 ° C., and 918 g of the following first-stage monomer emulsion was continuously supplied over 60 minutes.
Then, it was aged at 80 ° C. for 1 hour. First-stage monomer emulsion St 332 g DVB 36 g AlMA 2 g SSS 1% aqueous solution 308 g SHC 1% aqueous solution 48 g DIW 192 g Subsequently, 80 g of SPS 2% aqueous solution was added, and then
The following second-stage monomer emulsion (2,320 g) was added over 180 minutes, and the second-stage polymerization was carried out at 80 ° C.
Aged at 0 ° C. for 1 hour. Second-stage monomer emulsion 2EHA 1176 g DVB 18 g AlMA 6 g SSS 1% aqueous solution 960 g SHC 1% aqueous solution 80 g DIW 80 g Subsequently, 50 g of SPS 2% aqueous solution is added, and then the following third-stage monomer emulsion 680 g was added over 60 minutes, the third stage polymerization was carried out at 80 ° C., and 1 hour at 80 ° C.
Aged for hours. Third-stage monomer emulsion St 240 g AN 100 g DVB 60 g SSS 1% aqueous solution 100 g SHC 1% aqueous solution 40 g DIW 40 g After completion of the reaction, the reaction mixture was cooled to room temperature and filtered through a 300 mesh stainless steel wire mesh to obtain a solid content of 44. A 5%, latex of a multilayer polymer having a weight average particle size of 276 nm was obtained. The latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a multi-layer polymer A. Examples 2 to 4 (Production of Multi-Layered Polymers B to D) Emulsion polymerization was performed in the same manner as in Example 1 with the compositions shown in Tables 1 and 2, and the obtained latex was freeze-thawed, washed with water, dehydrated, and dried. Thus, multilayer structure polymers B, C and D were obtained. Comparative Example 1 (Production of Multilayer Polymer E) DIW was placed in a 2-liter capacity polymerization vessel equipped with a reflux condenser.
600 g, 20 g of a 2% aqueous solution of SSS and 40 g of a 1% aqueous solution of SHC were charged and heated to 70 ° C. while refluxing under a nitrogen stream. Next, 40 g of the first-stage monomer described below was added, and the mixture was dispersed for 10 minutes.
0 g was added to initiate seed polymerization. First-stage monomer 2EHA 792 g AlMA 4 g BGA 4 g Subsequently, the following first-stage monomer emulsion 1080 g was added to 180
The mixture was continuously supplied over a period of 1 minute, and after the first stage polymerization was performed, the temperature was raised to 90 ° C., and the mixture was aged for 1 hour. First-stage monomer emulsion 760 g of the first-stage monomer 760 g of 2% aqueous solution of SSS 40 g of 1% aqueous solution of SHC Then, it was cooled to 70 ° C., and 20 g of 2% aqueous solution of SPS was added. After adding 360 g of the eye monomer emulsion over 45 minutes and performing the second stage polymerization,
The temperature was raised to 90 ° C., and the mixture was aged for 1 hour. Second-stage monomer emulsion MMA 200 g SSS 1% aqueous solution 60 g SHC 1% aqueous solution 20 g DIW 80 g After completion of the reaction, the mixture was cooled to room temperature, filtered through a 300 mesh stainless steel wire mesh, and solid content of 44.7%, weight. A latex of a multilayer polymer having an average particle diameter of 293 nm was obtained. This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a multilayer polymer E. Comparative Examples 2 and 3 (Production of Multilayer Polymers F and G) Emulsion polymerization was carried out in the same manner as in Example 1 with the compositions shown in Tables 1 and 2, and the obtained latex was freeze-thawed, washed with water, dehydrated and dried. Thus, multilayer polymers F and G were obtained.

[0043]

[Table 1]

[0044]

[Table 2] Production of Thermoplastic Resin Composition Example 5 ( Production of Thermoplastic Resin Composition (1)) Polycarbonate resin using bisphenol A as a raw material (Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd .; hereinafter referred to as E-2000) 66.5 parts, poly (1,4-butylene terephthalate) (N-1100 manufactured by Mitsubishi Rayon Co., Ltd .; hereinafter, abbreviated as N-1100), 28.5 parts, and 5 parts of a multilayer polymer A 0.25 parts of carbon black was added to the mixture, and the mixture was melt-blended with a 40 mm single screw extruder at a cylinder temperature of 240 to 260 ° C. to obtain a pellet of a thermoplastic resin composition (1). Examples 6 to 8 (Production of Thermoplastic Resin Compositions (2) to (4)) Examples 1 and 2 were repeated except that multilayer polymers B, C and D were used instead of multilayer polymer A. Similarly, thermoplastic resin compositions (2) to (4) were obtained. Comparative Examples 4 to 6 (Production of Thermoplastic Resin Compositions (5) to (7)) Examples 1 and 2 were repeated except that multilayer polymers E, F and G were used instead of multilayer polymer A. Similarly, thermoplastic resin compositions (5) to (7) were obtained. Comparative Example 7 (Production of thermoplastic resin composition (8)) 70 parts of polycarbonate resin (E-2000) and poly (1,4-butylene terephthalate) (N-1100)
Add 0.25 part of carbon black to 30 parts, and add 40 mm
The resulting mixture was melt-blended with a single screw extruder at a cylinder temperature of 240 to 260 ° C to obtain a pellet of a thermoplastic resin composition (8). Example 9 (Production of thermoplastic resin composition (9)) 75.04 parts of a polycarbonate resin (E-2000),
Polyethylene terephthalate) (RT made by Nippon Unipet)
-580, hereinafter abbreviated as RT-580. ) 19.9
Carbon black was added to 6 parts and 5 parts of the multilayer structure polymer A.
Add 25 parts and use a 40 mm single screw extruder to set the cylinder temperature to 2
The mixture was melt-blended at 40 to 260 ° C to obtain a pellet of the thermoplastic resin composition (9). Example 10 (Production of thermoplastic resin composition (10)) A thermoplastic resin composition (10) was prepared in the same manner as in Example 9 except that multilayer polymer C was used instead of multilayer polymer A. ) Got. Comparative Example 8 (Production of Thermoplastic Resin Composition (11)) A thermoplastic resin composition (11) was prepared in the same manner as in Example 10 except that multilayer polymer E was used instead of multilayer polymer C. ) Got. Comparative Example 9 (Production of thermoplastic resin composition (12)) Carbon black (0.25 part) was added to polycarbonate resin (E-2000) 79 parts and polyethylene terephthalate (RT-580) 21 parts, and a 40 mm single screw extruder was used. The mixture was melt-blended at a cylinder temperature of 240 to 260 ° C. to obtain a pellet of a thermoplastic resin composition (12). Test Example 1 (Impact resistance test) Each of the thermoplastic resin compositions (1) to (12) was 110
After drying at ℃ for 6 hours or more, 240-
A physical property test piece was formed at 260 ° C., and a notch was inserted by cutting to produce a 3.2 mm thick Izod impact test piece specified in JIS K7113.

Using these test pieces, the impact value at each of 23 ° C., 0 ° C. and -30 ° C. was measured in accordance with JIS.
It was measured by a method according to K7113. The results are shown in Tables 3 and 4. Further, the peeling phenomenon near the gate of the molded product was visually determined. Test Example 2 Each of the thermoplastic resin compositions (1) to (12) was 110
After drying at ℃ for 6 hours or more, 240-
The test piece was molded at 260 ° C. and had three different thicknesses of 2 mm, 3 mm and 4 mm in a single test piece.

For each test piece, the L value of the 4 mm thick portion was measured, and the color difference (ΔE value) between the 2 mm thick portion and the 4 mm thick portion of the single test piece was measured by SM (manufactured by Suga Test Instruments Co., Ltd.). It was measured using a color computer. The results are shown in Tables 3 and 4. The L value indicates the depth of the color,
The lower the value, the closer the color is to perfect black. ΔE
Values are two colors (2mm thick part color and 4mm thick part color)
Represents the degree of color unevenness during the period, the larger the ΔE value,
The color unevenness between the two is large. Therefore, in order for the resin composition to have excellent coloring properties, the smaller the L value and the ΔE value, the better. The results are shown in Tables 3 and 4.

[0047]

[Table 3]

[0048]

[Table 4] Test Example 5 A thin section was prepared using a microtome from a molded product obtained using the resin compositions of Example 5 and Comparative Example 6, and dyed.
The dispersibility of the multilayer polymer in the resin composition was examined by observation with a transmission electron microscope.

FIG. 1 shows an electron micrograph (50000 times) of the resin composition of Example 5. The resin composition has a polycarbonate resin as a continuous gray matrix, and the polybutylene terephthalate resin is dispersed as amorphous particles in the matrix. The multilayer polymer is substantially dispersed in the polybutylene terephthalate resin phase as black spherical particles having a white periphery.

FIG. 2 shows an electron micrograph (50000 times) of the resin composition of Comparative Example 6. This resin composition also has a polycarbonate resin as a gray continuous matrix, in which the polybutylene terephthalate resin is dispersed as amorphous particles or elongated elongated phases. The multilayer polymer is substantially dispersed in the polycarbonate resin phase as substantially spherical particles.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph (magnification: 50000) showing the particle structure of a multilayer polymer in a thermoplastic resin composition according to the present invention.

FIG. 2 is a transmission electron micrograph (magnification: 50,000) showing the particle structure of a multilayer polymer in a thermoplastic resin composition as a comparative example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FIC08F 212: 06) (72) Inventor Goro Shimaoka 5-6-2 Higashi-Yawata, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Plastics Chemical Co., Ltd. Plastics Center (72) Inventor Makoto Mizutani 5-6-1-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Gas Chemical Co., Ltd. Plastics Center (72) Inventor Kazuhiko Ishii 5-5-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Gas Chemical Co., Ltd. In the plastics center (56) References JP-A-61-26646 (JP, A) JP-A-61-181854 (JP, A) JP-A-60-28447 (JP, A) JP-A-60-32849 (JP, A) , A) JP-A-63-152612 (JP, A) JP-A-46-942 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 251/00-292/00 C08L 51/00-51/10 C08L 67/00-69/00

Claims (4)

(57) [Claims] 1. A core layer obtained by three-stage emulsion polymerization and formed of an aromatic vinyl monomer, and a rubber layer formed of an alkyl acrylate monomer having an alkyl group having 2 to 8 carbon atoms. An intermediate layer made of a polymer, and a hard glass having a glass transition temperature of 50 ° C. or more formed of an aromatic vinyl monomer.
Ri Do a polymer of quality, 0.5 with respect to the total amount of the monomer
A multilayer polymer having an outermost layer crosslinked with 20% by weight of a crosslinking monomer . 2. The multilayer polymer according to claim 1, wherein the outermost layer is a styrene-acrylonitrile copolymer. 3. (a) a thermoplastic resin containing a polycarbonate resin and a polyester resin, and (b) a core layer obtained by three-stage emulsion polymerization and formed of an aromatic vinyl monomer, Number 2
An intermediate layer consisting of an alkyl acrylate monomer rubber formed from material polymers 8, and a glass transition temperature formed by the aromatic vinyl monomer is Ri Do a polymer of 50 ° C. or more rigid, the 0.5 to 20 weight based on the total amount of monomers
% Of a thermoplastic resin composition having a multilayer structure polymer having an outermost layer cross-linked with a% cross-linkable monomer . 4. A (a) thermoplastic resin containing a polycarbonate resin and a polyester resin; and (b) a core layer formed of an aromatic vinyl monomer obtained by three-stage emulsion polymerization, and a carbon of an alkyl group. Number 2
An intermediate layer consisting of an alkyl acrylate monomer rubber formed from material polymers 8, and a glass transition temperature formed by the aromatic vinyl monomer is Ri Do a polymer of 50 ° C. or more rigid, the 0.5 to 20 weight based on the total amount of monomers
% . A resin molded article obtained by molding a thermoplastic resin composition containing a multilayer structure polymer having an outermost layer crosslinked with a% crosslinkable monomer .