JPH0693057A - Multilayer-structured polymer, thermoplastic resin composition containing the same and molded product from the composition - Google Patents

Abstract

PURPOSE:To provide a polymer capable of giving molded products of excellent impact resistance, colorability etc., made up of core layer consisting of an aromatic vinyl polymer, interlayer consisting of a butadiene-based rubbery polymer and outermost layer consisting of an aromatic vinyl rigid glassy polymer. CONSTITUTION:The polymer can be obtained by pref. multistage seed emulsion polymerization so as to be made up of (A) 12-42wt.% of core layer consisting of an aromatic vinyl polymer (pref. polystyrene), (B) 48-78wt.% of interlayer consisting of a butadiene-based rubbery polymer (pref. polybutadiene or a copolymer of butadiene and an alkyl acrylate) and (C) 10-40wt.% of outermost layer consisting of an aromatic vinyl rigid glassy polymer (pref. (co)polymer of styrene and/or alkyl acrylate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer structure polymer, a thermoplastic resin composition containing the same, and a molded article thereof. More specifically, the present invention provides a multilayer structure polymer useful as an impact resistance agent for a thermoplastic resin containing a polycarbonate resin and / or a polyester resin, and an impact resistance property comprising the same, especially at low temperatures. The present invention relates to an improved thermoplastic resin composition, and a molded article obtained by molding such a resin composition. Furthermore, in the production of a molded article colored with a colorant, coloring properties such as color unevenness and the vicinity of a gate are used. The present invention relates to a thermoplastic resin composition which gives a molded article having an improved peeling phenomenon and its molded article.

[0002]

2. Description of the Related Art Polycarbonate resins are tough, have excellent impact resistance and electrical characteristics, and have excellent dimensional stability, but have a high melt viscosity, poor moldability, and impact resistance that is thickness-dependent. However, it has a drawback in that it has a difficulty in chemical resistance such as cracking when it comes into contact with an aromatic solvent or gasoline. For example, at 23 ° C., at a thickness of 1/4 inch or more, brittle fracture occurs, and even in a test piece having a thickness of 1/8 inch, the impact resistance decreases as the temperature becomes lower. For this reason, the application range of the polycarbonate resin is limited.

Therefore, in order to eliminate such drawbacks, various proposals for improvement have hitherto been made. For example,
JP-A-56-45946 and JP-A-56-459
In Japanese Patent Publication No. 47, it is proposed to blend an aromatic polycarbonate resin with an acrylic impact modifier to improve low temperature impact resistance. According to this method, although impact resistance is certainly improved, in a colored molded product, so-called color unevenness or non-uniform color appearance called pearl occurs. This phenomenon is remarkable in a portion where high shear is loaded, such as in the vicinity. Therefore, there is no choice but to limit the applications of such colored molded articles without treatment such as surface coating. In addition, as described above, a peeling phenomenon, that is, delamination often appears in a portion where the resin composition is loaded with high shear during molding, which may give a molded product that cannot be put to practical use. JP-A-56-2823
Japanese Patent Publication No. 4 discloses a thermoplastic resin composition containing an aromatic polycarbonate resin and a multi-stage graft copolymer containing a diene rubber to give a molded article excellent in impact resistance. The appearance of uneven color and pearls in the product is still remarkable.

On the other hand, in Japanese Patent Publication No. 61-9982, a first-stage polymer obtained by polymerizing an aromatic vinyl monomer, an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms is disclosed. The glass transition temperature obtained by polymerizing the second stage polymer obtained by polymerization and the aromatic vinyl monomer is 5
By blending a polymer having a multi-layered structure consisting of a third stage polymer having a temperature of 0 ° C. or higher with a polycarbonate resin together with a homopolymer or a copolymer of an aromatic vinyl monomer, the transparency of the polycarbonate resin can be improved. Without losing
It is said that the impact resistance can be improved. Thus, according to this method, the purpose is basically different from that for improving color unevenness, even if the obtained resin composition does not lose transparency. Also, regarding impact resistance, there is no description regarding thickness dependence and low temperature impact resistance, and the improvement effect thereof is far from satisfactory.

Further, in order to eliminate the drawback that the polycarbonate resin is inferior in moldability and chemical resistance, various improvements have been proposed in the past. For example, Japanese Patent Publication Sho 36-1
Japanese Patent No. 4035 proposes that an aromatic polycarbonate resin is mixed with a polyethylene terephthalate resin to improve chemical resistance. In addition, JP-A-48-5
Japanese Patent No. 4160 proposes blending an aromatic polycarbonate resin with a polybutylene terephthalate resin to improve surface hardness and chemical resistance. However, such a resin composition does not have sufficient impact resistance.

Further, Japanese Patent Publication No. 55-9435 discloses that
A method for improving impact resistance by blending an aromatic polycarbonate with an aromatic polyester and a butadiene-based elastomer, and Japanese Patent Publication No. 62-37671 discloses that an aromatic polycarbonate resin contains a polyester resin and an acrylic elastomer. A method of blending to improve impact resistance has been proposed. According to this method, although the impact resistance is certainly improved, color unevenness or pearls occur in a colored molded product, and this phenomenon is remarkable particularly in a portion where high shear is applied during molding. . Further, a peeling phenomenon, that is, delamination often appears in a portion where the resin composition is loaded with a high shear during molding, and a molded product which cannot be put to practical use may be provided.

[0007] In order to solve the problem of color unevenness in the production of such colored molded articles, Japanese Patent Publication No. 1-34463.
In the publication, 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 with 1 to 8 carbon atoms are disclosed. And a polymer having a multi-layered structure consisting of a third stage polymer obtained by polymerizing an alkyl methacrylate monomer having an alkyl group having 1 to 8 carbon atoms in a mixture of a colored polycarbonate resin and a polyester resin. Is proposed. However, even with this method, color unevenness is still
Not fully resolved. Furthermore, the impact resistance at low temperature is not sufficient.

On the other hand, the polyester resin is excellent in chemical resistance, heat resistance, weather resistance and moldability, but is inferior in impact resistance. In order to improve impact resistance, various proposals for improvement have hitherto been made. For example, JP-A-52-74652
Japanese Patent Application Laid-Open No. 2-191614 discloses a method of blending a polyester resin with a core-shell type elastomer containing an epoxy group, and Japanese Patent Laid-Open No. 52-150466 discloses a core-shell type elastomer containing no epoxy group in a polyester resin. Has been proposed. However, color irregularity or pearls also occur in colored molded articles of these compositions, and the color appearance becomes a problem.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems, and is to be incorporated in a thermoplastic resin containing a polycarbonate resin and / or a polyester resin as an impact resistance agent. Suitable multi-layered polymer, not only excellent in mechanical properties such as low temperature impact resistance, surface hardness, rigidity, etc., including such multi-layered polymer, color unevenness even when containing a colorant It is an object of the present invention to provide a thermoplastic resin composition containing a polycarbonate resin and / or a polyester resin, which gives a molded article free from the above, and a resin molded article obtained by molding the resin composition.

[0010]

That is, the present invention is
(a) a core layer made of an aromatic vinyl polymer, (b) an intermediate layer made of a butadiene rubber polymer, and (c) an outermost layer made of an aromatic vinyl hard glassy polymer, ) Component is 12 to 42% by weight, component (b) is 48 to 78% by weight, (c)
A multilayer structure polymer having a component of 10 to 40% by weight, a thermoplastic resin composition containing a polycarbonate resin and / or a polyester resin together with the multilayer structure polymer, and a resin molded product obtained by molding the same.

The multi-layered 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 usually preferably a multilayer structure polymer obtained by three-step emulsion polymerization. The first stage polymerization forms the core layer of the multi-layered polymer. An aromatic vinyl monomer is used as the constituent component, and specific examples thereof include, for example,
Examples thereof include styrene, vinyltoluene, α-methylstyrene, monochlorostyrene, 3,4-dichlorostyrene and bromostyrene. Of these, styrene is particularly preferably used. In this first stage polymerization, a non-aromatic monomer can be used together with the aromatic vinyl monomer. The amount used is preferably 5 with respect to the total amount of the monomers used for the first-stage polymerization.
The range is 0% by weight or less, and more preferably 20% by weight or less. As such a non-aromatic monomer, for example,
Examples thereof include alkyl acrylates such as ethyl acrylate and butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, vinyl cyanide and vinylidene cyanide such as acrylonitrile and methacrylonitrile.

In the present invention, the core layer of the multilayer structure polymer may be crosslinked with a crosslinkable monomer. The amount of the crosslinkable monomer 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 the first-stage polymerization. Yes, more preferably 5 to 15% by weight. As such a crosslinkable monomer, a monomer having two or more polymerizable ethylenic 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 these, divinylbenzene is particularly preferably used.

Grafted monomers can also be used in the first-stage polymerization. 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 for the first-stage polymerization. As such a grafting monomer, a monomer having two or more ethylenically unsaturated bonds with different reactivity is used in the molecule. Specific examples thereof include unsaturated carboxylic acid allyl esters such as allyl (meth) acrylate, diallyl maleate, diallyl fumarate and diallyl itaconate. Of these, allyl methacrylate is particularly preferably used.

The second-stage polymerization is to form an intermediate layer of the multilayer structure polymer. Butadiene is used as its constituent component. In addition, in the second-stage polymerization, a vinyl-based monomer copolymerizable with butadiene can be used together with butadiene. The amount used is preferably 90% by weight or less based on the total amount of the monomers used for the second-stage polymerization. Since it is generally desired that the intermediate layer has a glass transition temperature of −30 ° C. or lower, the more preferable amount of the copolymerizable monomer used varies depending on the kind of the monomer. For example, in alkyl acrylates such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate, it can be used at 90% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less. is there. In addition, for example, alkyl methacrylate such as methyl methacrylate and butyl methacrylate, aromatic vinyl monomer such as styrene, vinyltoluene and α-methylstyrene, and vinyl cyanide monomer such as acrylonitrile and methacrylonitrile are preferably used. Is 50% by weight or less, more preferably 30% by weight or less.

The intermediate layer of the butadiene rubber-like polymer may also be crosslinked with the above-mentioned crosslinkable monomer. As the crosslinkable monomer, especially divinylbenzene,
Butylene glycol diacrylate, hexanediol diacrylate and the like are 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 2% by weight, based on the total amount of the monomers used in the second-stage polymerization. % Range. 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 grafted monomer 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 in the second-stage polymerization. Is.

Polymerization for forming the outermost layer of the third step uses an aromatic vinyl monomer as its constituent component,
A hard polymer having a glass transition temperature of 50 ° C. or higher is applied so as to cover the rubber-like polymer. Examples of the aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene, monochlorostyrene, 3,4
-Dichlorostyrene, bromostyrene and the like can be mentioned, but styrene is particularly preferably used. Also in this third stage polymerization, a non-aromatic monomer that can be copolymerized with the aromatic vinyl monomer can be used. The amount used is preferably 45% by weight or less, more preferably 30% by weight or less, based on the total amount of the monomers used for the third stage polymerization. Examples of such non-aromatic monomers include ethyl acrylate,
Examples thereof include alkyl acrylates such as butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, vinyl cyanide such as acrylonitrile and methacrylonitrile, and vinylidene cyanide.

Further, the outermost layer obtained by the third stage polymerization may also be crosslinked with the above-mentioned crosslinkable monomer. The amount of the crosslinkable monomer used is usually in the range of 30% by weight or less based on the total amount of the monomers used for the third stage polymerization. It is preferably in the range of 0.5 to 20% by weight, more preferably in the range of 5 to 15% by weight. As the crosslinkable monomer, divinylbenzene or butylene glycol dimethacrylate is preferably used, but divinylbenzene is particularly preferably used. According to the present invention, such a hard outermost layer is preferably composed mainly of a styrene-acrylonitrile-based copolymer.

Further, in the present invention, a hard intermediate layer may be introduced between the rubbery polymer intermediate layer and the hard outermost layer. The 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 crosslinked with the above-mentioned crosslinkable monomer. As the crosslinkable monomer, for example, divinylbenzene, butylene glycol dimethacrylate, etc. are preferably used, and particularly divinylbenzene is preferably used. The amount of the crosslinkable monomer used is usually in the range of 30% by weight or less, preferably in the range of 0.5 to 20% by weight, based on the total amount of the monomers used for forming the hard intermediate layer. And particularly preferably in the range of 5 to 15% by weight. Further, in the formation of the hard intermediate layer, the above-mentioned grafting monomer can be used together. 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 for forming the hard intermediate layer.

The conventionally known multilayer structure polymers are
When compounded in a thermoplastic resin composition, each layer is only cross-linked with a very small amount of cross-linking monomer, even if cross-linked, in order to prevent deterioration of impact resistance of the resin. Absent. On the other hand, according to the present invention, as described above, the core layer, the hard intermediate layer, and / or the outermost layer each has 5 to 5 parts of the total amount of the monomers used to form the layer. It is preferably crosslinked with 15% by weight of a crosslinkable monomer. In the multilayer structure polymer according to the present invention, the core layer, the hard intermediate layer and / or the outermost layer are thus crosslinked with a large amount of the crosslinkable monomer. By blending with a polycarbonate resin, a polyester resin or a mixture thereof, a resin composition having excellent impact resistance and improved color unevenness can be obtained. However,
The total amount of the crosslinkable monomers used for the core layer, the hard intermediate layer and the outermost layer is 1 to 30% by weight based on the total amount of the monomers used for forming the core layer, the hard intermediate layer and the outermost layer.
It is preferable to be in the range of, and it is particularly preferable to be in the range of 3 to 20 wt%.

The multi-layered polymer according to the present invention is produced by producing a latex by a known seed emulsion polymerization method, separating the polymer by freeze-thawing or salting out, centrifuge dehydration and drying, It can be taken out in the form of particles, flakes or powder. The polymer can also be directly extracted from the latex by spray drying with a spray dryer. The multilayer structure polymer thus obtained can be used as it is, but can be pelletized by an extruder and a pelletizer, if necessary.

According to the present invention, the multilayer structure polymer preferably has a toluene-soluble content of 10% by weight or less, particularly 6% by weight or less. The resin composition obtained by blending such a multilayer structure polymer with a polycarbonate resin, a polyester resin, or a mixture thereof gives a molded article with improved color unevenness in the case of a colored resin composition. 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 its weight of toluene and left at room temperature for 48 hours. Furthermore, the multi-layer structure polymer according to the present invention has a impact resistance of 100 to 700 nm, preferably 200, so that the resulting resin composition has satisfactory impact resistance.
It is preferred to have a weight average particle size of ˜500 nm.
In the present invention, the multilayer structure polymer is the core layers 12 to 4
2% by weight, 48 to 78% by weight of rubber-like intermediate layer and outermost layer 1
0 to 40% by weight, preferably core layers 15 to 3
0% by weight, 50 to 65% by weight of rubber-like intermediate layer and outermost layer 1
It consists of 5 to 25% by weight.

As mentioned above, the multilayer structure polymer may have a hard intermediate layer. In this hard intermediate layer, the total amount of the hard intermediate layer and the outermost layer is 10 to 4 of the whole multilayer structure polymer.
It is contained in a proportion of 0% by weight, preferably 15 to 25% by weight. Further, the hard intermediate layer is contained in the range of 100 parts by weight or less with respect to 100 parts by weight of the outermost layer. The total amount of the core layer, the rubber-like intermediate layer, the hard intermediate layer and the outermost layer is 100% by weight.

Next, 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. Among them, a thermoplastic polycarbonate resin which may be branched and which is obtained by reacting an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with phosgene or carbonic acid diester is preferably used.

Examples of the aromatic dihydroxy compound include 2'2-bis (4-hydroxyphenyl) propane (also called bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl)-. Examples thereof include p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl and the like. Further, 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-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ) Polyhydroxy compounds such as ethane, 3,
3-bis (4-hydroxyaryl) oxindole (also referred to as isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like are used as a part of the dihydroxy compound, for example,
It may be replaced with about 0.1 to 2 mol%.

Further, a monovalent aromatic hydroxy compound can be used for controlling the molecular weight of the obtained polycarbonate resin. Examples of such monovalent aromatic hydroxy compounds include m- or p-methylphenol, m- or p-propylphenol, p-bromophenol, p-tert-butylphenol, p-long-chain alkyl-substituted phenol and the like. It is preferably used. Typical 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, it is also possible to use a polycarbonate copolymer obtained by using two or more kinds of aromatic dihydroxy compounds in combination, and a branched polycarbonate resin obtained by using a small amount of trivalent phenol compounds in combination. Furthermore, in the present invention, a mixture of these polycarbonate resins can also be used.

As the polyester resin used in the present invention, those known as engineering plastics are usually used. Among them, polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its dialkyl ester and an aliphatic glycol, or a copolymer mainly containing this is preferably used. As such a polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or the like is preferably used. As the aliphatic glycol, for example, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol or the like is used. These aliphatic glycols are used in combination with other diols such as cyclohexanediol, cyclohexanedimethanol, xylylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol and polyhydric alcohols. can do. The amount of these diols or polyhydric alcohols used is preferably 40 parts by weight or less with respect to 100 parts by weight of the aliphatic glycol.

In the production of the polyester resin, terephthalic acid or its dialkyl ester,
Dibasic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, trimellitic acid and their dialkyl esters, tribasic acids, etc., and use of dialkyl esters thereof in combination You can The amount used is 40 with respect to 100 parts by weight of terephthalic acid or its dialkyl ester.
It is preferably within the range of parts by weight or less.

The thermoplastic resin composition according to the present invention comprises the above-mentioned multi-layer structure polymer of 0.1 to 100 parts by weight of a thermoplastic resin mixture containing 0 to 100% by weight of a polycarbonate resin and 100 to 0% by weight of a polyester resin. It contains 5 to 50 parts by weight, preferably 1 to 25 parts by weight. The ratio of the polycarbonate resin and the polyester resin can be appropriately selected within the above range. For example, when importance is attached to the properties of the polycarbonate resin, the polyester resin is 0 to 100% by weight of the polycarbonate resin.
Is preferably in the range of 50 to 50% by weight, and when the properties of the polyester resin are emphasized, the range of 100 to 50% by weight of the polyester is preferable with respect to 0 to 50% by weight of the polycarbonate resin. Polycarbonate resin 50-95% by weight,
Preferably 60 to 95% by weight and polyester resin 50
The thermoplastic resin composition according to the present invention comprising a thermoplastic resin mixture consisting of ˜5% by weight, preferably 40 to 5% by weight, has a polyester resin dispersed in a continuous matrix of polycarbonate resins and has a multilayer structure The coalescence is substantially dispersed in this polyester resin phase. This is best shown in a resin composition using a polybutylene terephthalate resin as the polyester resin.

The thermoplastic resin composition according to the present invention is obtained by blending a polycarbonate resin and / or a polyester resin and a multilayer structure polymer in the above-mentioned proportions. The method and means of this blending are not particularly limited, but melt blending is preferably adopted. This melt blending is usually carried out at a temperature of 200 to 300 ° C. using a heating roll, Banbury mixer, single-screw or twin-screw extruder. Further, the thermoplastic resin composition according to the present invention may contain various additives in appropriate amounts. As such additives, for example, stabilizers, pigments, flame retardants, lubricants, inorganic fillers, antistatic agents, release agents,
Examples thereof include ultraviolet absorbers. Particularly, it is important to add an antioxidant as a stabilizer, and a hindered phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant can be added alone or as a mixture. As the pigment, various pigments such as titanium-based, azo-based, phthalocyanine-based dyes and pigments and carbon black can be used. This resin pigment is a resin composition 100
It is usually used in the range of 0.01 to 20 parts by weight based on parts by weight.

Such a thermoplastic resin composition according to the present invention may be injection molded, extruded, or molded at a temperature of 200 to 300 ° C.
A molded product having a desired shape can be molded by an ordinary molding method such as compression molding. Such a molded product can be used, for example, in automobile parts such as bumpers, fenders, door handles, so-called office automation equipment and household electric appliances.

[0031]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. All "parts" in Examples and Comparative Examples represent parts by weight. Abbreviations used in Examples and Comparative Examples are as follows. Butadiene Bd Ethyl acrylate EA Butyl acrylate BA 2-Ethylhexyl acrylate 2EHA Methyl methacrylate MMA Styrene St Acrylonitrile AN Allyl methacrylate AlMA 1,4-butylene glycol diacrylate BGA Divinylbenzene DVB DIW dioctyl sulfosuccinate sodium salt SSS Perex SS-L [Kao Corporation] (Sodium alkyl diphenyl ether disulfonate) SSL ADEKA STAB AO-80 [Asahi Denka Kogyo KK] (Hindered phenolic antioxidant) AO-80 ADEKA STAB AO-412S [Asahi Denka Kogyo KK] (Thioether antioxidant) AO-412S ADEKA STAB 260 [Asahi Denka Kogyo KK] (phosphite antioxidant) 260 sodium persulfate SPS sodium hydrogencarbonate SHC polycarbonate PC PC polybutylene terephthalate PBT In addition, the weight average particle diameter of the multilayer structure polymer was measured by Otsuka Electronics Co., Ltd. laser particle size analysis system LPA-3000.

Production of Multi-Layered Polymer Example 1 (Production of Multi-Layered Polymer A) DIW (930 g) in a 2-liter polymerization vessel equipped with a reflux condenser.
15 g of SSL 2% aqueous solution and 60 g of SHC 1% aqueous solution were charged, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. M
After adding 15 g of MA and dispersing for 10 minutes, S
75 g of a 2% PS aqueous solution was added to initiate seed polymerization. First-stage monomer emulsion St 388.5 g DVB 45.0 g AlMA 1.5 g SSL 2% aqueous solution 360.0 g SHC 1% aqueous solution 30.0 g Then, after heating to 75 ° C., the first-stage monomer emulsion 825
g was continuously fed over 90 minutes and aged at 90 ° C. for 1 hour. After cooling to 70 ° C., the reaction solution was transferred to a 5 liter autoclave and the second stage polymerization was started. SP
60 g of an S2% aqueous solution was added, 1425 g of a second-stage monomer emulsion having the following composition was fed over 180 minutes, and aging was carried out at 70 ° C. for 16 hours.

Second stage monomer emulsion Bd 322.7 g 2EHA 484.3 g DVB 15.0 g AlMA 3.0 g SSL 2% aqueous solution 450.0 g SHC1% aqueous solution 60.0 g DIW 90.0 g Third stage at 75 ° C. Was polymerized. SPS 2%
30 g of an aqueous solution was added, 375 g of a third-stage monomer emulsion having the following composition was fed over 60 minutes, and the mixture was aged at 90 ° C. for 1 hour.

Third Stage Monomer Emulsion St 157.5g AN 52.5g DVB 15.0g SSL 2% aqueous solution 75.0g SHC 1% aqueous solution 30.0g DIW 45.0g After cooling to room temperature, the following antioxidants are added. It was fed in the form of the emulsion shown in (1) over 30 minutes and then stirred for 30 minutes. Finally, it was filtered through a stainless steel mesh of 300 mesh to obtain a core-shell polymer latex having a solid content of 39.9% and a weight average particle diameter of 270 nm. This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a multi-layered polymer A.

Antioxidant Emulsion AO-80 4.5 g AO-412S 7.5 g 260 3.8 g SSL 2% aqueous solution 45.0 g Toluene 45.0 g

Examples 2 to 4 (Production of Multilayer Structured Polymers B to D) Emulsion polymerization was carried out in the same manner as in Example 1 with the composition shown in [Table 1], and the obtained latex was freeze-thawed, washed with water and dehydrated. It was then dried to obtain multi-layer structure polymers BD. Comparative Example 1 (Production of Multilayered Polymer E) 600 g of DIW in a 2 liter polymerization vessel equipped with a reflux condenser.
20 g of SSS 1% aqueous solution and 40 g of SHC 1% aqueous solution were charged, and the temperature was raised to 70 ° C. with stirring under a nitrogen stream. E
A 40 g was added and dispersed for 10 minutes, then SP
Seed polymerization was initiated by adding 80 g of an S2% aqueous solution. First-stage monomer emulsion 2EHA 752.0 g BGA 1.6 g AlMA 6.4 g SSS 2% aqueous solution 280.0 g SHC 1% aqueous solution 40.0 g Then, the first-stage monomer emulsion 1,080 g is continuously fed over 180 minutes. After that, the temperature was raised to 90 ° C. and aging was performed for 1 hour. After cooling to 70 ° C., the second-stage polymerization was started. 20 g of 2% SPS aqueous solution was added, and 360 g of the second stage monomer emulsion having the following composition was fed over 45 minutes, and then 9
The temperature was raised to 0 ° C., and aging was performed at that temperature for 60 minutes.

Second-stage monomer emulsion MMA 180 g EA 20 g SSS 1% aqueous solution 60 g SHC 1% aqueous solution 20 g DIW 80 g After cooling to room temperature, it is filtered through a 300-mesh stainless wire mesh to obtain a solid content of 44.7% and weight average particles. Diameter 293
nm core-shell polymer latex was obtained. This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a multilayer structure polymer E.

Comparative Example 2 (Production of Multilayer Polymer F) DIW1158 was placed in a 2 liter polymerization vessel equipped with a reflux condenser.
g, SSL 2% aqueous solution 16 g, SHC 1% aqueous solution 80 g
Was charged, and the temperature was raised to 70 ° C. with stirring under a nitrogen stream. After adding 80 g of EA and dispersing for 10 minutes,
Seed polymerization was initiated by adding 160 g of 2% SPS aqueous solution. First-stage monomer emulsion Bd 640 g 2EHA 876 g BGA 2 g AlMA 2 g SSL 2% aqueous solution 160 g SHC 1% aqueous solution 60 g DIW 600 g After reaction for 30 minutes, the reaction solution was transferred to a 5-liter autoclave and 2340 g of the first-stage monomer emulsion was used for 8 hours. It was continuously fed over. After further aging for 16 hours at 70 ° C., the second stage polymerization was started. SPS 2% aqueous solution 40
g was added, and 600 g of the second-stage monomer emulsion having the following composition was fed over 60 minutes, and then aged for 60 minutes at 70 ° C.

Second Stage Monomer Emulsion MMA 360g EA 40g SSL 2% Aqueous Solution 40g SHC 1% Aqueous Solution 40g DIW 120g After cooling to room temperature, an antioxidant is fed in the form of an emulsion shown below over 30 minutes, Then, stirring was performed for 30 minutes. Finally, it was filtered through a 300-mesh stainless wire mesh to obtain a core-shell polymer latex having a solid content of 43.8% and a weight average particle diameter of 294 nm. This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a multi-layered polymer F. Antioxidant emulsion AO-80 6.0 g AO-412S 10.0 g 260 5.1 g SSL 2% aqueous solution 60.0 g Toluene 60.0 g

[0040]

[Table 1]

Production of Thermoplastic Resin Composition Example 5 (Production of Thermoplastic Resin Composition (1)) Polycarbonate resin using bisphenol A as a raw material (Ubilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Inc., E-2000) 66.5 parts, poly (1,4-butylene terephthalate) (manufactured by Mitsubishi Rayon Co., Ltd., N-1100 or less, abbreviated as N-1100) 28.5 parts and a multilayer structure polymer A 5. 1.39 parts of carbon black was added to the parts and melt-blended with a 40 mm single screw extruder at a cylinder temperature of 240 to 260 ° C. to obtain pellets of the resin composition (1).

Examples 6 to 8 (thermoplastic resin composition (2))
Production of (4)) A resin composition (2) was produced in the same manner as in Example 1 except that the multi-layered polymers B to D were used in place of the multi-layered polymer A.
The pellet of (4) was obtained. Comparative Examples 3 and 4 (Production of Thermoplastic Resin Compositions (5) and (6)) In the same manner as in Example 1 except that the multilayer structure polymers A and F were used in place of the multilayer structure polymer A. Resin composition (5),
The pellet of (6) was obtained. Comparative Example 5 (Production of thermoplastic resin composition (7)) Polycarbonate resin (E-2000) 70 parts, poly (1,4-butylene terephthalate) (N-1100)
1.39 parts of carbon black was added to 30 parts and melt-blended with a 40 mm single-screw extruder at a cylinder temperature of 240 to 260 ° C. to obtain pellets of the resin composition (7).

Test Example 1 (Impact Resistance Test) After drying each of the resin compositions (1) to (7) at 110 ° C. for 6 hours or more, a physical property test piece is molded at 240 to 260 ° C. with an injection molding machine. And make a notch by cutting, JIS
An Izod impact test piece having a thickness of 3.2 mm specified in K7110 was prepared. 23 ° C, 0 ° C using these test pieces
And the Izod impact value at each temperature of −30 ° C. were measured by the method according to JIS K7110. Further, the peeling phenomenon near the gate of the molded product was visually determined. The results are shown in [Table 2]. Test Example 2 (Measurement of L value and ΔE value) Each of the resin compositions (1) to (7) was dried at 110 ° C. for 6 hours or more, and then molded at 240 to 260 ° C. with an injection molding machine to obtain a single piece. The test pieces with different thicknesses of 2 mm, 3 mm and 4 mm were prepared. 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 a single test piece was measured by Suga Test Machine Co., Ltd. SM color computer. It was measured using. The results are shown in [Table 2]. Here, the L value represents the depth of a color, and the smaller the value, the closer the color is to perfect black. In addition, ΔE value is 2 places (2m
The degree of color unevenness (color difference) between the m-thick portion and the 4 mm-thick portion
The larger this value, the larger the color unevenness between the two. Therefore, in order for the resin composition to have excellent coloring properties,
The smaller both the L value and the ΔE value are, the more preferable.

[0044]

[Table 2] As is clear from the results shown in [Table 1] and [Table 2], the molded article according to the present invention is superior to the molded article according to the comparative example in both impact resistance and colorability.

[0045]

EFFECT OF THE INVENTION The thermoplastic resin composition according to the present invention inherently retains excellent electrical and mechanical properties and dimensional stability of a polycarbonate resin, and / or molding processability and chemical resistance of a polyester resin. In addition to
It has excellent impact resistance at low temperatures, and the thickness dependency of impact resistance is also significantly improved. Further, in the case of a colored molded product obtained by molding a colored composition containing a pigment, color unevenness and whitening phenomenon are improved, and peeling phenomenon near the gate at the time of molding is also improved.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 69/00 LPR 9363-4J (72) Inventor Junji Oshima 3-10-8 Uenohigashi, Toyonaka, Osaka ( 72) Inventor Goro Shimaoka 5-6-2 Higashi Yawata, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastic Center (72) Makoto Mizutani 5, 6-2 Higashi Hachiman, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Inside the Plastic Center (72) Inventor Kazuhiko Ishii 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastic Center

Claims (4)

[Claims] 1. A core layer comprising (a) an aromatic vinyl polymer, (b) an intermediate layer comprising a butadiene rubber polymer, and
(c) It has an outermost layer made of an aromatic vinyl-based hard glassy polymer, the component (a) is 12 to 42% by weight, and the component (b) is 48 to
A multilayer structure polymer containing 78% by weight and 10 to 40% by weight of the component (c). 2. A thermoplastic resin containing (1) a polycarbonate resin and / or a polyester resin, (2) a core layer made of (a) an aromatic vinyl polymer, and (b) made of a butadiene rubber-like polymer. It has an intermediate layer and (c) an outermost layer composed of an aromatic vinyl-based hard glassy polymer, and the component (a) is 12 to 4
2% by weight, 48-78% by weight of component (b), 10% of component (c)
A thermoplastic resin composition comprising a multi-layered polymer in an amount of ˜40% by weight. 3. The thermoplastic resin composition according to claim 2, which contains a pigment. 4. A thermoplastic resin containing (1) a polycarbonate resin and / or a polyester resin, (2) (a) a core layer made of an aromatic vinyl polymer, and (b) made of a butadiene rubber-like polymer. It has an intermediate layer and (c) an outermost layer composed of an aromatic vinyl-based hard glassy polymer, and the component (a) is 12 to 4
2% by weight, 48-78% by weight of component (b), 10% of component (c)
A resin molded product obtained by molding a thermoplastic resin composition containing a multi-layer structure polymer in an amount of ˜40 wt%.