JP2020139054A - Transparent thermoplastic resin composition and its molded article - Google Patents

Abstract

To provide a transparent thermoplastic resin composition having both high transparency and excellent impact resistance, and its molded article.SOLUTION: A transparent thermoplastic resin composition contains a graft copolymer (A) obtained by graft copolymerization of a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth)acrylate-based monomer (a2) in the presence of a rubbery polymer (r), a vinyl-based copolymer (B) obtained by copolymerization of a monomer mixture (b) containing at least an aromatic vinyl-based monomer (b1), a (meth)acrylate-based monomer (b2) and a vinyl cyanide-based monomer (b3), the following ester wax (C) and the following ester wax (D). Ester wax (C): castor hardened oil. Ester wax (D): fatty acid ester composed of at least one alcohol selected from the group consisting of a straight chain saturated monocarboxylic acid having 12 to 30 carbon atoms, straight chain saturated monohydric alcohol having 14 to 30 carbon atoms and dihydric to hexahydric alcohol having 2 to 30 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a transparent thermoplastic resin composition and a molded product thereof.

Rubberic polymers such as diene rubber, aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate. A transparent ABS (Acrylonitrile Butadiene Styrene) resin containing a graft copolymer obtained by copolymerizing a compound has a balance of mechanical strength such as transparency, impact resistance, and rigidity, and moldability and cost performance due to fluidity. Because of its excellent properties, it is widely used in home appliances, communication-related equipment, general miscellaneous goods, and medical equipment.

For example, Patent Document 1 states that in the presence of 10 to 80 parts by mass of a rubber-like polymer (Ia), 10 to 95% by mass of a styrene-based monomer, a vinyl cyanide-based monomer, and a (meth) acrylic acid ester alone. Copolymerize 90 to 20 parts by mass of a monomer mixture (Ib) consisting of 90 to 5% by mass of at least one type of monomer selected from the metric and 0 to 20% by mass of other copolymerizable monomers. At least selected from 10 to 90% by mass of the graft copolymer (I), 10 to 95% by mass of a styrene-based monomer, a vinyl cyanide-based monomer and a (meth) acrylic acid ester monomer. 100% by mass of a resin component (III) consisting of 90 to 10% by mass of a styrene-based copolymer (II) consisting of 90 to 0% by mass of one type of monomer and 0 to 60% by mass of another copolymerizable monomer. 0.1 to 3.5 parts by mass of (A1) higher fatty acid and / or higher fatty acid salt, 0.01 to 5 parts by mass of (A2) (di) pentaerythritol-based ester and / or sorbitan-based ester, with respect to parts. A3) A rubber-modified styrene-based resin composition characterized by containing a processing aid containing 0.01 to 5 parts by mass of a fatty acid monoglyceride and / or a fatty acid diglyceride as an essential component has been proposed. The rubber-modified styrene resin composition described in Patent Document 1 is said to be excellent in processability in calendar molding, and the obtained sheet-like material is excellent in printing characteristics and adhesion to an acrylic laminated film.

Further, Patent Document 2 describes (I) a styrene-based monomer, a (meth) acrylic acid ester-based monomer, and a vinyl-based single amount copolymerizable with these monomers, which is used as needed. A continuous phase of 60 to 80% by mass of a styrene- (meth) acrylic acid ester-based copolymer, which is a body copolymer, and (II) a rubber-like elastic body, a styrene-based monomer, and (meth) acrylic acid. Styrene- (meth) acrylic acid ester-based copolymer, which is a copolymer of an ester-based monomer and a vinyl-based monomer copolymerizable with these monomers, which is used as needed, is grafted. A rubber-modified styrene resin composition containing 40 to 20% by mass of the dispersed phase of the graft copolymer, wherein the dispersed phase has a volume average particle size of 0.3 to 0.6 μm and is a continuous phase. The resin composition defines a specific range of values used in a specific formula between the weight average molecular weight (Mw), the (meth) acrylic acid ester-based monomer unit, and the styrene-based monomer unit. A thermoplastic resin composition characterized by containing 0.005 to 0.05 parts by mass of an organic polysiloxane with respect to 100 parts by mass has been proposed. The thermoplastic resin composition described in Patent Document 2 is said to be able to obtain a molded product having excellent transparency and exhibiting excellent impact resistance and molding processability even with an extremely thin wall.

JP-A-2002-284957 International Publication No. 2003/102076

However, the conventional thermoplastic resin composition cannot provide both transparency and impact resistance at a high level, and further improvement has been required.

An object of the present invention is to solve the above-mentioned problems in the prior art, and it is excellent in both transparency and impact resistance, that is, while maintaining particularly high transparency and good color tone. An object of the present invention is to provide a transparent thermoplastic resin composition having both impact resistance and fluidity, and a molded product thereof.

As a result of diligent studies to achieve the above object, the present inventors have contained a vinyl-based copolymer obtained by copolymerizing a vinyl-based monomer mixture and a rubbery polymer-containing graft copolymer. Furthermore, they have found that a resin composition containing two specific types of ester wax has excellent impact resistance and fluidity while maintaining a particularly high degree of transparency and good color tone, and have reached the present invention. ..

That is, the present invention is characterized by the following (1) to (8).
(1) In the presence of the rubbery polymer (r), a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth) acrylic acid ester-based monomer (a2) is grafted together. A graft copolymer (A) obtained by polymerization, at least an aromatic vinyl-based monomer (b1), a (meth) acrylic acid ester-based monomer (b2), and a vinyl cyanide-based monomer (b3) A transparent thermoplastic resin composition containing a vinyl-based copolymer (B) obtained by copolymerizing a monomer mixture (b) containing the mixture, the following ester wax (C) and the following ester wax (D).
Ester wax (C): Hardened oil of castor Ester wax (D): Linear saturated monocarboxylic acid having 12 to 30 carbon atoms, linear saturated monohydric alcohol having 14 to 30 carbon atoms, and 2 to 30 carbon atoms. Fatty acid ester consisting of at least one alcohol selected from the group consisting of hexavalent polyhydric alcohols (2) The mass ratio of the ester wax (C) to the ester wax (D) is 95: 5 to 80:20. The transparent thermoplastic resin composition according to the above (1).
(3) The transparent thermoplastic resin composition according to (1) or (2) above, wherein the ester wax (D) is at least one of pentaerythritol tetrabehenate and pentaerythritol tetrastearate.
(4) In the presence of the rubbery polymer (r), a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth) acrylic acid ester-based monomer (a2) is grafted together. A graft copolymer (A) obtained by polymerization, at least an aromatic vinyl-based monomer (b1), a (meth) acrylic acid ester-based monomer (b2), and a vinyl cyanide-based monomer (b3) A method for producing a transparent thermoplastic resin composition, which comprises a vinyl-based copolymer (B) obtained by copolymerizing a monomer mixture (b) containing the mixture, the following ester wax (C) and the following ester wax (D).
Ester wax (C): Hardened oil of castor Ester wax (D): Linear saturated monocarboxylic acid having 12 to 30 carbon atoms, linear saturated monohydric alcohol having 14 to 30 carbon atoms, and 2 to 30 carbon atoms. Fatty acid ester composed of at least one alcohol selected from the group consisting of hexavalent polyhydric alcohols (5) The mass ratio of the ester wax (C) to the ester wax (D) is 95: 5 to 80:20. A method for producing a transparent thermoplastic resin composition according to (4) above.
(6) Production of the transparent thermoplastic resin composition according to (4) or (5) above, wherein the ester wax (D) is at least one of pentaerythritol tetrabehenate and pentaerythritol tetrastearate. Method.
(7) A molded product obtained by molding the transparent thermoplastic resin composition according to any one of (1) to (3) above.
(8) A method for producing a molded product obtained by molding a transparent thermoplastic resin composition obtained by the production method according to any one of (4) to (6) above.

According to the present invention, it is possible to obtain a transparent thermoplastic resin composition having excellent impact resistance and also excellent fluidity while maintaining particularly high transparency and good color tone.

It is the schematic of one embodiment of the manufacturing apparatus for manufacturing the transparent thermoplastic resin composition of this invention.

Hereinafter, the present invention will be described in detail, but these are examples of desirable embodiments, and the present invention is not specified in these contents.
In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid.

The transparent thermoplastic resin composition of the present invention contains a graft copolymer (A), a vinyl-based copolymer (B), which will be described later, and two specific types of ester waxes. By containing the graft copolymer (A), the moldability of the transparent thermoplastic resin composition can be improved, and the impact resistance, transparency, and color tone of the molded product can be improved. Further, by containing the vinyl copolymer (B), the fluidity of the transparent thermoplastic resin composition can be improved, and the transparency and color tone of the molded product can be improved. By containing two specific types of ester wax, the impact resistance of the molded product is further improved without deteriorating the transparency and color tone of the molded product, and the fluidity of the transparent thermoplastic resin composition is improved. It can be improved and good moldability can be obtained.

(Graft copolymer (A))
The graft copolymer (A) constituting the transparent thermoplastic resin composition of the present invention is at least an aromatic vinyl-based monomer (a1) and a (meth) acrylic acid ester in the presence of the rubbery polymer (r). It is obtained by graft-copolymerizing a monomer mixture (a) containing a system monomer (a2). The monomer mixture (a) may further contain the above (a1) and another monomer (a3) copolymerizable with the above (a2).

Examples of the rubbery polymer (r) include polybutadiene, poly (butadiene-styrene) (SBR), poly (butadiene-acrylonitrile) (NBR), poly (butadiene-butyl acrylate), and poly (butadiene-methyl methacrylate). ), Poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), natural rubber and the like. These may be used alone or in combination of two or more. Of these, polybutadiene, SBR, NBR, and natural rubber are preferable, and polybutadiene is more preferable, from the viewpoint of further improving the impact resistance, transparency, and color tone of the resin composition.

The mass average particle size of the rubbery polymer (r) is preferably 0.15 to 0.4 μm, more preferably 0.25 to 0.35 μm, and even more preferably 0.25 to 0.35 μm. If the mass average particle size of the rubbery polymer (r) is less than 0.15 μm, the impact resistance of the molded product may decrease. On the other hand, when the mass average particle size of the rubbery polymer (r) exceeds 0.4 μm, the transparency and color tone of the molded product may deteriorate.

The mass average particle size of the rubbery polymer (r) is determined by diluting and dispersing the latex of the rubbery polymer (r) with an aqueous medium, and using a laser scattering diffraction method particle size distribution measuring device (for example, "LS 13 320" (Beckman). -The particle size distribution can be measured by (Coulter Co., Ltd.)) and calculated from the particle size distribution.

The content of the rubber polymer (r) is 20 to 80% by mass with respect to the total amount of the rubber polymer (r) constituting the graft copolymer (A) and the monomer mixture (a) described later. Is preferable. When the content of the rubbery polymer (r) is 20% by mass or more, the impact resistance, color tone, and transparency of the molded product can be further improved. The content of the rubbery polymer (r) is more preferably 35% by mass or more. On the other hand, when the content of the rubbery polymer (r) is 80% by mass or less, the fluidity of the transparent thermoplastic resin composition and the impact resistance of the molded product can be further improved. The content of the rubbery polymer (r) is more preferably 60% by mass or less.

Examples of the aromatic vinyl-based monomer (a1) in the monomer mixture (a) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, vinyltoluene, and t. -Styrene-based monomers such as butylstyrene can be mentioned. These may be used alone or may contain two or more. Among these, styrene is preferable from the viewpoint of further improving the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded product.

The content of the aromatic vinyl-based monomer (a1) in the monomer mixture (a) is a single mass from the viewpoint of further improving the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded product. Of the total 100% by mass of the body mixture (a), 5% by mass or more is preferable, 10% by mass or more is more preferable, and 20% by mass or more is further preferable. On the other hand, the content of the aromatic vinyl-based monomer (a1) in the monomer mixture (a) is preferably 40% by mass or less, preferably 35% by mass, from the viewpoint of improving the impact resistance and transparency of the molded product. % Or less is more preferable, and 30% by mass or less is further preferable.

As the (meth) acrylic acid ester-based monomer (a2) in the monomer mixture (a), for example, an ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid is preferable. The ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group. Examples of the ester of alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic Examples thereof include acid 2,3,4,5,6-pentahydroxyhexyl and (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl. These may be used alone or may contain two or more. Among these, methyl (meth) acrylate is preferable from the viewpoint of improving the transparency of the molded product.

The content of the (meth) acrylic acid ester-based monomer (a2) in the monomer mixture (a) is 100% by mass in total of the monomer mixture (a) from the viewpoint of improving the transparency of the molded product. Of these, 30% by mass or more is preferable, 50% by mass or more is more preferable, and 70% by mass or more is further preferable. On the other hand, the content of the (meth) acrylic acid ester-based monomer (a2) in the monomer mixture (a) is 100 in total of the monomer mixture (a) from the viewpoint of improving the transparency of the molded product. Of the mass%, 85% by mass or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is further preferable.

Further, the other monomer (a3) copolymerizable with these is a vinyl-based single amount other than the above-mentioned aromatic vinyl-based monomer (a1) and (meth) acrylic acid ester-based monomer (a2). There is no particular limitation as long as it is a body and does not impair the effects of the present invention.

Specific examples of the other monomer (a3) include vinyl cyanide-based monomers, unsaturated fatty acids, acrylamide-based monomers, and maleimide-based monomers. These may be used alone or may contain two or more.
Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, and etacrylonitrile. These may be used alone or may contain two or more. Among these, acrylonitrile is preferable from the viewpoint of further improving the impact resistance of the molded product.
Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid.
Examples of the acrylamide-based monomer include acrylamide, methacrylamide, N-methylacrylamide and the like.
Examples of the maleimide-based monomer include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, and N-cyclohexylmaleimide. Examples thereof include N-phenylmaleimide.

The content of the other monomer (a3) in the monomer mixture (a) is preferably 2% by mass or more from the viewpoint of improving the impact resistance of the molded product. On the other hand, from the viewpoint of improving the color tone of the molded product, 50% by mass or less is preferable, 20% by mass or less is preferable, and 5% by mass or less is further preferable.

The graft ratio of the graft copolymer (A) is not particularly limited, but is preferably 10 to 100% from the viewpoint of improving the impact resistance of the molded product.
Here, the graft ratio of the graft copolymer (A) can be determined by the following method. First, 80 ml of acetone was added to about 1 g (m: sample mass) of the graft copolymer (A), and the mixture was refluxed in a hot water bath at 70 ° C. for 3 hours, and this solution was mixed with 8000 r. p. After centrifugation at m (10000 G) for 40 minutes, the insoluble matter is filtered to obtain an acetone insoluble matter. The obtained insoluble acetone is dried under reduced pressure at 80 ° C. for 5 hours, its mass (n) is measured, and the graft ratio is calculated from the following formula. Here, X is the rubbery polymer content (%) of the graft copolymer (A).
Graft rate (%) = {[(n)-((m) x X / 100)] / [(m) x X / 100]} x 100

In the present invention, the method for producing the graft copolymer (A) is such that the mass average particle size of the rubbery polymer (r) can be easily adjusted within a desired range, and the polymerization stability is achieved by removing heat during polymerization. The emulsion polymerization method is more preferable because it can be easily adjusted.

When the graft copolymer (A) is produced by an emulsion polymerization method, the method for charging the rubbery polymer (r) and the monomer mixture (a) is not particularly limited. For example, all of these may be initially charged in a batch, or a part of the monomer mixture (a) may be continuously charged in order to adjust the distribution of the copolymer composition, or the monomer mixture ( Part or all of a) may be divided and charged. Here, the continuous charging of a part of the monomer mixture (a) means that a part of the monomer mixture (a) is initially charged and the rest is continuously charged over time. Further, charging a part or all of the monomer mixture (a) in a divided manner means that a part or all of the monomer mixture (a) is charged at a time after the initial preparation.

When the graft copolymer (A) is produced by an emulsion polymerization method, various surfactants may be added as emulsifiers. As various surfactants, anionic surfactants such as carboxylate type, sulfate ester salt type and sulfonate type are particularly preferably used. These may be used alone or in combination of two or more. Examples of the salt referred to here include alkali metal salts such as sodium salt, lithium salt and potassium salt, and ammonium salt.

Examples of the carboxylate type emulsifier include caprylate, caprinate, laurylate, mystilate, palmitate, stearate, oleate, linoleate, linolenate, and rosinate. , Behenate, dialkylsulfosuccinate and the like.

Examples of the sulfate ester salt type emulsifier include castor oil sulfate, lauryl alcohol sulfate, polyoxyethylene lauryl sulfate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl phenyl ether sulfate. ..

Examples of the sulfonate type emulsifier include dodecylbenzene sulfonate, alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonate, naphthalene sulfonate condensate and the like.

When the graft copolymer (A) is produced by an emulsion polymerization method, an initiator may be added if necessary. Examples of the initiator include peroxides, azo compounds, and water-soluble potassium persulfate. These may be used alone or in combination of two or more.

Examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t. -Butylisopropylcarbonate, di-t-butyl peroxide, t-butylperoxyoctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis Examples thereof include (t-butylperoxy) cyclohexane and t-butylperoxy-2-ethylhexanoate. Of these, cumene hydroperoxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclohexane are particularly preferably used. Be done.

Examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethyl) valeronitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and 2-cyano-2-propylazo. Formamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethyl) valeronitrile, dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2 Examples thereof include −cyanobutane and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane. Of these, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used.

The amount of the initiator added to produce the graft copolymer (A) is not particularly limited, but from the viewpoint of the productivity of the graft copolymer (A), it is simple with the rubbery polymer (r). 0.1 to 0.5 parts by mass is preferable with respect to 100 parts by mass of the total of the polymer mixture (a).

When the graft copolymer (A) is produced by an emulsion polymerization method, a chain transfer agent may be used. By using a chain transfer agent, the graft ratio of the graft copolymer (A) can be easily adjusted to a desired range. Examples of the chain transfer agent include mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and terpenes such as terpinolen. These may be used alone or in combination of two or more. Of these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.

The amount of the chain transfer agent added to produce the graft copolymer (A) is not particularly limited, but from the viewpoint that the graft ratio of the graft copolymer (A) can be easily adjusted, it is a rubbery polymer. 0.2 to 0.7 parts by mass is preferable with respect to 100 parts by mass of the total of (r) and the monomer mixture (a). The lower limit is more preferably 0.4 parts by mass or more, and the upper limit is more preferably 0.6 parts by mass or less.

When the graft copolymer (A) is produced by emulsion polymerization, the polymerization temperature is not particularly limited, but 40 to 70 ° C. is preferable from the viewpoint of emulsion stability.

When the graft copolymer (A) is produced by an emulsion polymerization method, it is common to add a coagulant to the graft copolymer latex to recover the graft copolymer (A). As the coagulant, an acid or a water-soluble salt is preferably used.

Examples of the acid include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and the like. Examples of the water-soluble salt include calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, aluminum ammonium sulfate, potassium aluminum sulfate, sodium aluminum sulfate and the like. These may be used alone or in combination of two or more. From the viewpoint of improving the color tone of the molded product, it is preferable that no emulsifier remains in the thermoplastic resin composition, and it is preferable to use an alkaline fatty acid salt as the emulsifier and acid-coagulate. In this case, it is then preferable to neutralize with an alkali such as sodium hydroxide to remove the emulsifier.

(Vinyl copolymer (B))
The vinyl-based copolymer (B) constituting the transparent thermoplastic resin composition of the present invention contains at least an aromatic vinyl-based monomer (b1), a (meth) acrylic acid ester-based monomer (b2), and cyanide. It is obtained by copolymerizing a monomer mixture (b) containing a vinyl-based monomer (b3). The monomer mixture (b) may further contain another monomer (b4) copolymerizable with the above (b1) to (b3).

Examples of the aromatic vinyl-based monomer (b1) include those exemplified as the aromatic vinyl-based monomer (a1), and styrene is preferable.

The content of the aromatic vinyl-based monomer (b1) in the monomer mixture (b) is a single mass from the viewpoint of further improving the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded product. Of the total 100% by mass of the body mixture (b), 5% by mass or more is preferable, 10% by mass or more is more preferable, and 20% by mass or more is further preferable. On the other hand, the content of the aromatic vinyl-based monomer (b1) in the monomer mixture (b) is preferably 40% by mass or less, preferably 30% by mass, from the viewpoint of improving the impact resistance and transparency of the molded product. % Or less is more preferable, and 25% by mass or less is further preferable.

Examples of the (meth) acrylate-based monomer (b2) include those exemplified as the (meth) acrylate-based monomer (a2), and methyl (meth) acrylate is preferable.

The content of the (meth) acrylic acid ester-based monomer (b2) in the monomer mixture (b) is 100% by mass in total of the monomer mixture (b) from the viewpoint of improving the transparency of the molded product. Of these, 30% by mass or more is preferable, 50% by mass or more is more preferable, and 60% by mass or more is further preferable. On the other hand, the content of the (meth) acrylic acid ester-based monomer (b2) in the monomer mixture (b) is preferably 85% by mass or less, preferably 80% by mass, from the viewpoint of further improving the transparency of the molded product. % Or less is more preferable, and 75% by mass or less is further preferable.

Examples of the vinyl cyanide-based monomer (b3) include acrylonitrile, methacrylonitrile, and etacrylonitrile. These may be used alone or may contain two or more. Among these, acrylonitrile is preferable from the viewpoint of further improving the impact resistance of the molded product.

The content of the vinyl cyanide-based monomer (b3) in the monomer mixture (b) is 100% by mass in total of the monomer mixture (b) from the viewpoint of further improving the impact resistance of the molded product. 2, 2% by mass or more is preferable, and 3% by mass or more is more preferable. On the other hand, the content of the vinyl cyanide-based monomer (b3) in the monomer mixture (b) is preferably 50% by mass or less, more preferably 20% by mass or less, from the viewpoint of improving the color tone of the molded product. It is more preferably 10% by mass or less, and most preferably 5% by mass or less.

The other monomers (b4) copolymerizable with these are the above-mentioned aromatic vinyl-based monomer (b1), (meth) acrylic acid ester-based monomer (b2), and vinyl cyanide-based single. There is no particular limitation as long as it is a vinyl-based monomer other than the dimer (b3) and does not impair the effect of the present invention.

Specific examples of the other monomer (b4) include unsaturated fatty acids, acrylamide-based monomers, and maleimide-based monomers. These may be used alone or may contain two or more.
Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid.
Examples of the acrylamide-based monomer include acrylamide, methacrylamide, N-methylacrylamide and the like.
Examples of the maleimide-based monomer include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, and N-cyclohexylmaleimide. Examples thereof include N-phenylmaleimide.

The content of the other monomer (b4) in the monomer mixture (b) is 20% by mass from the viewpoint of the fluidity of the transparent thermoplastic resin composition, the impact resistance of the molded product, the transparency and the color tone. The following is preferable, and 10% by mass or less is more preferable.

In the present invention, the method for producing the vinyl copolymer (B) is not particularly limited, but from the viewpoint of the fluidity of the obtained transparent thermoplastic resin composition, the transparency of the molded product, and the color tone, the continuous massive polymerization method or The continuous solution polymerization method is preferably used. In particular, by using the continuous massive polymerization method or the continuous solution polymerization method, the molecular weight distribution of the vinyl-based copolymer (B) can be narrowed, so that the fluidity is improved.

As a method for producing the vinyl-based copolymer (B) by the continuous massive polymerization method or the continuous solution polymerization method, any conventionally known method can be adopted. For example, the monomer mixture (b) is placed in a polymerization tank. Examples thereof include a method of demonomerizing (desolvating / devolving) after polymerization.

Examples of the polymerization tank include a mixing type polymerization tank having stirring blades such as paddle blades, turbine blades, propeller blades, bull margin blades, multi-stage blades, anchor blades, max blend blades, and double helical blades, and various tower types. Reactor etc. can be used. In addition, a multi-tube reactor, a kneader reactor, a twin-screw reactor and the like can also be used as the polymerization reactor (for example, Assessment 10 of the polymer manufacturing process "Assessment of impact-resistant polystyrene", Polymer Society, 1989 See issued January 26, 2014, etc.).

Two or more of these polymerization tanks or polymerization reactors may be used, or two or more types of polymerization tanks or polymerization reactors may be combined as required. From the viewpoint of narrowing the molecular weight distribution of the vinyl-based copolymer (B), the number of polymerization tanks or polymerization reactors is preferably two or less, and a one-tank complete mixing type polymerization tank is more preferable.

The reaction mixture obtained by polymerization in these polymerization tanks or polymerization reactors is usually then subjected to a demonomerization step to remove monomers, solvents and other volatile components. Examples of the demonomerization method include a method of removing volatile components from a vent hole under normal pressure or reduced pressure under heating with a uniaxial or biaxial extruder having a vent, and a plate fin type heater such as a centrifugal type drum. A method of removing volatile components with a built-in evaporator, a method of removing volatile components with a thin-film evaporator such as a centrifugal type, preheating using a multi-tube heat exchanger, foaming and flushing to a vacuum chamber to volatile components There is a method of removing the water. Among these, a method of removing volatile components with a uniaxial or biaxial extruder having a vent is particularly preferably used.

When producing the vinyl-based copolymer (B), an initiator or a chain transfer agent may be used if necessary. Examples of the initiator and the chain transfer agent include the initiator and the chain transfer agent exemplified in the method for producing the graft copolymer (A). Initiators are also used in redox systems.

The amount of the initiator used to produce the vinyl-based copolymer (B) is not particularly limited, but from the viewpoint of increasing the polymerization rate of the vinyl-based copolymer (B), the monomer mixture (b) 0.01 to 0.03 parts by mass is preferable with respect to 100 parts by mass in total.

The amount of the chain transfer agent added to produce the vinyl-based copolymer (B) is not particularly limited, but from the viewpoint of improving the fluidity of the vinyl-based copolymer (B), the monomer mixture 0.10 to 0.15 parts by mass is preferable with respect to 100 parts by mass in total of (b).

When the vinyl-based copolymer (B) is produced by the continuous massive polymerization method or the continuous solution polymerization method, the polymerization temperature is not particularly limited, but from the viewpoint of the productivity of the vinyl-based copolymer (B), it is 120 to 140. ℃ is preferable.

When the vinyl copolymer (B) is produced by the continuous solution polymerization method, the amount of the solvent is preferably 30% by mass or less, more preferably 20% by mass or less in the polymerization solution from the viewpoint of productivity. As the solvent, ethylbenzene or methylethylketone is preferable from the viewpoint of polymerization stability, and ethylbenzene is particularly preferably used.

In the transparent thermoplastic resin composition of the present invention, the graft copolymer (A) is 10 to 60 parts by mass with respect to a total of 100 parts by mass of the graft copolymer (A) and the vinyl-based copolymer (B). The vinyl-based copolymer (B) is preferably 40 to 90 parts by mass. If the content of the graft copolymer (A) is less than 10 parts by mass and the content of the vinyl-based copolymer (B) exceeds 90 parts by mass, the impact resistance of the molded product may decrease. 20 parts by mass or more of the graft copolymer (A) and 80 parts by mass or less of the vinyl-based copolymer (B) with respect to a total of 100 parts by mass of the graft copolymer (A) and the vinyl-based copolymer (B). It is more preferable to contain in. On the other hand, when the content of the graft copolymer (A) exceeds 60 parts by mass and the content of the vinyl-based copolymer (B) is less than 40 parts by mass, the melt viscosity of the transparent thermoplastic resin composition increases. As a result, the fluidity may decrease, and the transparency and color tone of the molded product may also decrease. 50 parts by mass or less of the graft copolymer (A) and 50 parts by mass or more of the vinyl-based copolymer (B) with respect to a total of 100 parts by mass of the graft copolymer (A) and the vinyl-based copolymer (B). It is more preferable to contain in.

The transparent thermoplastic resin composition of the present invention further contains an ester wax (C) and an ester wax (D) in addition to the graft copolymer (A) and the vinyl-based copolymer (B). The ester wax (C) is a hardened oil, and the ester wax (D) is a linear saturated monocarboxylic acid having 12 to 30 carbon atoms, a linear saturated monohydric alcohol having 14 to 30 carbon atoms, and 2 to 2 carbon atoms. A fatty acid ester consisting of at least one alcohol selected from the group consisting of 30 2- to 6-valent polyhydric alcohols.

The ester wax (C) is a castor oil, and the castor oil is obtained by hydrogenating castor oil. Castor oil is an ester composed of a mixed fatty acid containing 12-hydroxystearic acid as a main component and glycerin.

The iodine value of the ester wax (C) is not particularly limited, but is preferably 5 or less, and more preferably 3 or less, from the viewpoint of improving the transparency and color tone of the molded product. When the iodine value is 5 or less, discoloration due to thermal deterioration during processing can be suppressed.

The ester wax (D) of the present invention is an ester compound obtained from a carboxylic acid (d1 component) and an alcohol (d2 component). This carboxylic acid (d1 component) is a linear saturated monocarboxylic acid having 12 to 30 carbon atoms, and the alcohol (d2 component) is a linear saturated monohydric alcohol (d2-1 component) having 14 to 30 carbon atoms. It is at least one alcohol selected from the group consisting of 2 to 6-valent polyhydric alcohols (d2-2 component) having 2 to 30 carbon atoms.

The linear saturated monocarboxylic acid has 12 to 30 carbon atoms, preferably 18 to 22 carbon atoms. When the number of carbon atoms is less than 12, the melting point is low, which is not preferable because it contaminates the surface of the molded product during molding of the transparent thermoplastic resin composition and lowers the impact resistance and heat resistance of the molded product. On the other hand, a linear saturated monocarboxylic acid having 31 or more carbon atoms is not preferable because it is difficult to obtain as an industrial product and there is a risk of reducing the transparency of the molded product.

Examples of the linear saturated monocarboxylic acid having 12 to 30 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, hexacosanoic acid, octacosanoic acid, triacontane acid and the like.

Examples of the linear saturated monohydric alcohol (d2-1 component) include myristyl alcohol, cetyl alcohol, stearyl alcohol, araquil alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, triacontanol and the like. Can be mentioned.

Among the above 2 to 6-valent polyvalent alcohols (d2-2 component), the divalent alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecandiol, 1,18-octadecanediol, 1,20- Eikosandiol, 1,30-triacanthandiol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1, Examples thereof include 4-phenylene glycol, bisphenol A, and hydrogenated bisphenol A. Examples of trihydric alcohols include 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,4-butanetriol, glycerin, 2-methylpropanetriol, trimethylolethane, Examples thereof include trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like. Examples of the tetravalent alcohol include 1,2,3,6-hexaneterol and pentaerythritol, examples of the pentavalent alcohol include glucose and the like, and examples of the hexavalent alcohol include dipentaerythritol.

The ester wax (D) of the present invention obtained from the carboxylic acid and alcohol shown above is a linear saturated monohydric alcohol having 14 to 24 carbon atoms from the viewpoint of impact resistance and heat resistance of a molded product containing the same. Alternatively, it is preferably a fatty acid ester composed of a dihydric or higher polyhydric alcohol having 2 to 12 carbon atoms and a linear saturated monocarboxylic acid having 12 to 30 carbon atoms, and a linear saturated monohydric alcohol having 14 to 24 carbon atoms. Alternatively, a fatty acid ester composed of a dihydric or higher polyhydric alcohol having 2 to 12 carbon atoms and a linear saturated monocarboxylic acid having 12 to 24 carbon atoms is more preferable, and pentaerythritol or hexavalent is a tetrahydric alcohol. It is more preferably a fatty acid ester composed of the alcohol dipentaerythritol and a linear saturated monocarboxylic acid having 12 to 22 carbon atoms, and particularly preferably pentaerythritol tetrastearate and pentaerythritol tetrabehenate.

The acid value of the ester wax (D) of the present invention is preferably 15 mgKOH / g or less. The acid value is more preferably 10 mgKOH / g or less, still more preferably 8 mgKOH / g or less, and particularly preferably 1.0 mgKOH / g or less. When the acid value is 15 mgKOH / g or less, the heat resistance of the ester wax (D) is high, and gasification of unreacted residual fatty acid, which is a low molecular weight component, can be suppressed.

The hydroxyl value of the ester wax (D) of the present invention is not particularly limited, but is preferably 25 mgKOH / g or less, more preferably 10 mgKOH / g or less, and even more preferably 5 mgKOH / g or less. When the hydroxyl value is 25 mgKOH / g or less, the heat resistance of the ester wax (D) is high, and decomposition during the production and processing of the resin composition can be suppressed.

In the synthesis of the ester wax (D) of the present invention, an esterification reaction (condensation reaction) is carried out using an excessive amount of the carboxylic acid (d1 component). The reaction is usually carried out at a temperature of 120-240 ° C. in the presence or absence of a catalyst. By such an esterification reaction, a crude esterified product is obtained.

Then, the excess carboxylic acid (d1 component) in the crude esterification product is removed by deoxidation using an alkaline aqueous solution. Examples of the alkaline aqueous solution used at the time of deoxidation include aqueous solutions of alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate, and ammonium salts such as ammonium carbonate. Usually, an alkaline aqueous solution having a concentration of 5 to 20% by mass is used. The amount of alkali is preferably 1 to 2 times the acid value of the crude esterified product obtained by reacting a carboxylic acid with an alcohol.

The ester wax (D) thus obtained has an acid value and a hydroxyl value within a predetermined range.

In the ester wax of the present invention, a specific organic solvent is added when the crude esterified product obtained by the esterification reaction of the carboxylic acid (d1 component) and the alcohol (d2 component) is deoxidized with an alkaline aqueous solution. It is possible to obtain it more easily. This organic solvent is a hydrocarbon solvent. By using these specific organic solvents, a better layer separation state can be obtained at the time of washing with water.

Examples of the hydrocarbon solvent include toluene, xylene, cyclohexane, normal heptane and the like. When a hydrocarbon solvent is used, the amount of the solvent added is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the crude esterified product. If the amount of the hydrocarbon solvent added is less than 5 parts by mass, layer separation may be poor or an emulsified state may occur. Further, even if it exceeds 100 parts by mass, there is no improvement commensurate with the amount of addition, and on the contrary, the process of removing the solvent takes a long time, and the productivity may decrease.

In addition to the above hydrocarbon solvent, alcohol having 1 to 3 carbon atoms (alcohol for separation) is added at a ratio of 3 to 30 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the crude esterified product. The layer separation state becomes even better. Examples of such separation alcohols include methanol, ethanol, normal propanol, isopropanol and the like.

For deoxidation, the above crude esterification product, a hydrocarbon solvent, an alkaline aqueous solution, and an alcohol for separation (used in combination with the hydrocarbon solvent) are mixed as necessary, and the acid present in the crude esterification product is alkaline. It is done by neutralizing with. Usually, deoxidation is performed by mixing these sufficiently. Deoxidation is carried out by holding the crude esterified product at a temperature higher than the melting temperature. It is usually 50 to 100 ° C, preferably 70 to 90 ° C. If the temperature is lower than 50 ° C, layer separation failure or emulsification may occur, and if it exceeds 100 ° C, the ester may be hydrolyzed.

Since the oil layer (ester layer) containing an ester and the alkaline aqueous layer are separated by the deoxidation, the alkaline aqueous layer is removed. Next, the ester layer is washed with warm water or hot water (50 to 100 ° C.). The water washing is repeated until the water washing wastewater becomes almost neutral (for example, the pH is 7 or less). The above-mentioned hydrocarbon solvent and a solvent such as a separating alcohol used as needed can be removed from the ester layer by repeatedly washing with water after deoxidation. Further, the solvent remaining in the ester after washing with water can be completely removed under reduced pressure conditions. In this way, the desired ester wax can be obtained.

When the above method is adopted, high quality ester wax (D) can be produced in high yield without causing layer separation failure or emulsification during deoxidation. The ester wax (D) thus obtained has a low content of a low volatile substance, a raw material alcohol, a raw material carboxylic acid, an ester component having a hydroxyl group, and the like, and exhibits high heat resistance characteristics. Therefore, it can be effectively used for a transparent thermoplastic resin.

Since the ester wax (C) has a hydroxyl group which is a polar group in the structure, the transparent thermoplastic resin composition has good dispersibility in the matrix phase, and the transparent thermoplastic resin composition does not deteriorate the transparency and color tone of the molded product. The fluidity of goods can be improved. Further, it disperses in the entire transparent thermoplastic resin composition, lowers the elastic modulus of the entire resin composition, and exhibits a certain effect in improving the impact resistance.

On the other hand, since the ester wax (D) has a low hydroxyl value and exhibits lipophilicity, it is unevenly distributed around the rubber polymer (r) in the transparent thermoplastic resin composition, and is around the rubber polymer (r). The elastic modulus of the rubber phase and the matrix phase can be alleviated, and the stress concentration at the interface can be alleviated. Further, since the rubber polymer (r) is unevenly distributed around the rubber polymer (r), the slipperiness of the rubber polymer (r) to impact can be improved and the impact absorption ability of the rubber polymer (r) can be enhanced. As a result, the impact resistance of the molded product can be further improved as compared with the case where the ester wax (C) is used alone while maintaining the transparency and color tone of the molded product.

In the transparent thermoplastic resin composition of the present invention, the ester wax (C) and the ester wax (D) are 0 in total with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl-based copolymer (B). It is preferably contained in an amount of .6 parts by mass or more, more preferably 1.0 part by mass or more, and further preferably 1.4 parts by mass or more. When the total amount of the ester wax (C) and the ester wax (D) is 0.6 parts by mass or more, the impact resistance of the molded product can be improved and the fluidity during molding can be improved. On the other hand, the total amount of the ester wax (C) and the ester wax (D) is 3.0 parts by mass or less with respect to the total of 100 parts by mass of the graft copolymer (A) and the vinyl-based copolymer (B). It is preferably 2.5 parts by mass or less, more preferably 2.0 parts by mass or less. When the total of ester wax (C) and ester wax (D) is 3.0 parts by mass or less, the impact resistance of the molded product is improved without impairing the transparency and color tone of the molded product, and the fluidity during molding is further improved. Can be improved.

The transparent thermoplastic resin composition of the present invention preferably contains the ester wax (C) and the ester wax (D) in a mass ratio of 98: 2 to 75:25, more preferably 95: 5 to 80:20. It is preferable, and 93: 7 to 81:19 is more preferable. When the ester wax (C) exceeds 98% by mass and the ester wax (D) is less than 2% by mass, the impact resistance of the molded product may not be sufficiently obtained. In particular, when the ester wax (C) is 95% by mass or less and the ester wax (D) is 5% by mass or more, the impact resistance of the molded product can be further improved. On the other hand, when the ester wax (C) is less than 75% by mass and the ester wax (D) is more than 25% by mass, the transparency and color tone of the molded product may deteriorate. When the ester wax (C) is 80% by mass or more and the ester wax (D) is 20% by mass or less, the transparency and color tone of the molded product can be further improved.

The ester wax (C) and the ester wax (D) may be added separately or as a pre-prepared mixture. Further, the ester wax (C) and the ester wax (D) may be heated and melted at a temperature equal to or higher than the transparent melting point to be uniformly mixed, and then cooled and individualized, and pulverized or constructed may be added.

The transparent thermoplastic resin composition of the present invention further contains, if necessary, glass fiber, glass powder, glass beads, glass flakes, alumina, alumina fiber, carbon fiber, graphite fiber, as long as the object of the present invention is not impaired. , Stainless fiber, whisker, potassium titanate fiber, wallastenite, asbestos, hard clay, fired clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide and minerals; hindered phenolic, including Antioxidants such as sulfur compounds or phosphorus-containing organic compounds; heat stabilizers such as phenols and acrylates; UV absorbers such as benzotriazoles, benzophenones or salicylates; hindered amine light stabilizers; higher fatty acids, Lubricants and plasticizers such as acid esters, acid amides or higher alcohols; mold release agents such as montanoic acid and its salts, their esters, their half esters, stearyl alcohols, stearamides and ethylene wax; various flame retardants; flame retardants Anticoloration agents such as phosphate and hypophosphate; neutralizers such as phosphoric acid, monosodium phosphate, maleic anhydride, succinic anhydride; nucleating agents; amine-based, sulfonic acid-based, polyether Antistatic agents such as systems; colorants such as carbon black, pigments, and dyes can be blended.

(Manufacturing method of transparent thermoplastic resin composition)
Next, a method for producing the transparent thermoplastic resin composition of the present invention will be described. The transparent thermoplastic resin composition of the present invention contains, for example, the above-mentioned graft copolymer (A), vinyl copolymer (B), ester wax (C), ester wax (D), and other components as required. Can be obtained by blending and melt-kneading. A method in which the vinyl-based copolymer (B) is continuously bulk-polymerized, and then the graft copolymer (A), the ester wax (C), the ester wax (D), and other components are melt-kneaded if necessary. More preferred. By continuously producing the final transparent thermoplastic resin composition from the production of the vinyl copolymer (B), the thermal history is reduced and the color tone of the transparent thermoplastic resin composition is improved. ..

FIG. 1 shows a schematic view of an embodiment of an apparatus for producing a transparent thermoplastic resin composition preferably used in the present invention. The apparatus for producing the transparent thermoplastic resin composition shown in FIG. 1 heats the reaction tank (1) for producing the vinyl-based copolymer (B) and the obtained vinyl-based copolymer (B) to a predetermined temperature. A preheater (2) and a twin-screw extruder type depolymerizer (3) are provided, and each is connected. Further, a twin-screw extruder for supplying the graft copolymer (A), the ester wax (C) and the ester wax (D) so as to side-feed to the twin-screw extruder type demonomer (3). The mold feeder (5) is connected. The reaction tank (1) has a stirrer (helical ribbon blade) (7), and the twin-screw extruder type demonomer (3) has a vent port (3) for removing volatile components such as unreacted monomers. 8).

The reaction product (vinyl-based copolymer (B)) continuously supplied from the reaction tank (1) is heated to a predetermined temperature by the preheater (2), and then the twin-screw extruder type demonomerizer. It is supplied to (3). In the twin-screw extruder type demonomer machine (3), generally, volatile components such as unreacted monomers are released from the vent port (8) at a temperature of about 150 to 280 ° C. under normal pressure or reduced pressure. It is removed from the system. The removal of the volatile component is generally carried out until the volatile component is a predetermined amount, for example, 10% by mass or less, more preferably 5% by mass or less. Further, it is preferable that the removed volatile components are supplied to the reaction tank (1) again.

From the twin-screw extruder type feeder (5) through the opening provided near the downstream side in the middle of the twin-screw extruder type demonomer (3), the graft copolymer (A) and the ester wax (C) ), Ester wax (D) is supplied. The twin-screw extruder type feeder (5) preferably has a heating device, and by supplying the graft copolymer (A) to the twin-screw extruder type demonomer (3) in a semi-molten or molten state. The mixed state can be improved. The heating temperature of the graft copolymer (A) is generally 100 to 220 ° C. Examples of the twin-screw extruder type feeder (5) include a twin-screw extruder type feeder composed of a screw, a cylinder and a screw drive unit, and the cylinder has a heating / cooling function.

At the position where the twin-screw extruder type demonomer (3) is connected to the twin-screw extruder type feeder (5), in order to suppress thermal deterioration of the rubber component due to the subsequent operation of removing the unreacted monomer. In addition, the content of the unreacted monomer is preferably reduced to 10% by mass or less, more preferably 5% by mass or less.

In the melt-kneading area (4), which is a downstream area after the position where the twin-screw extruder type demonomer (3) is connected to the twin-screw extruder type feeder (5), the vinyl copolymer (B), The graft copolymer (A), ester wax (C) and ester wax (D) are melt-kneaded, and the transparent thermoplastic resin composition is discharged from the discharge port (6) to the outside of the system. It is preferable to provide a water injection port (9) in the melt-kneading area (4) and add a predetermined amount of water, and the injected water and volatile components such as unreacted monomers are further downstreamly provided as a final vent. It is removed from the system from the mouth (10).

The transparent thermoplastic resin composition of the present invention can be molded by any molding method. Examples of the molding method include injection molding, extrusion molding, inflation molding, blow molding, vacuum molding, compression molding, gas assist molding and the like, and injection molding is preferably used. The cylinder temperature at the time of injection molding is preferably 210 to 320 ° C., and the mold temperature is preferably 30 to 80 ° C.

The transparent thermoplastic resin composition of the present invention can be widely used as a molded product having an arbitrary shape. Examples of the molded product include a film, a sheet, a fiber, a cloth, a non-woven fabric, an injection molded product, an extrusion molded product, a vacuum pressure pneumatic molded product, a blow molded product, and a composite with other materials.

Since the transparent thermoplastic resin composition of the present invention can have excellent impact resistance and fluidity while maintaining particularly high transparency and good color tone, it can be used for home appliances, communication-related equipment, general miscellaneous goods, and the like. It is useful as an application for medical equipment.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in the examples will be described.

<Evaluation method of transparent thermoplastic resin composition>
(1) Transparency (HAZE, haze)
The transparent thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 3 hours, and then the cylinder temperature was set to 230 ° C., SE180EV- manufactured by Sumitomo Heavy Industries, Ltd. It was filled in the A molding machine, and a square plate molded product having a thickness of 4 mm was immediately molded. Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., HAZE (%) was measured for each of the five obtained square plate molded products by a method in accordance with ISO 14782, and the average value thereof was calculated.

(2) Transparency (total light transmittance)
The transparent thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 3 hours, and then the cylinder temperature was set to 230 ° C., SE180EV- manufactured by Sumitomo Heavy Industries, Ltd. It was filled in the A molding machine, and a square plate molded product having a thickness of 4 mm was immediately molded. Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) was measured for each of the five obtained square plate molded products by a method conforming to ISO 13468, and the average value was calculated. ..

(3) Impact resistance (Charpy impact strength)
The transparent thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 3 hours, and then the cylinder temperature was set to 230 ° C. SE- manufactured by Sumitomo Heavy Industries, Ltd. It was filled in a 50 DU molding machine, and a dumbbell test piece having a thickness of 4 mm was immediately molded. For each of the five dumbbell test pieces obtained, the Charpy impact strength was measured by a method conforming to ISO179, and the average value thereof was calculated.

(4) Moldability (melt flow rate (MFR))
The transparent thermoplastic resin composition pellets obtained in each Example and Comparative Example were dried in a hot air dryer at 80 ° C. for 3 hours, and then MFR was carried out by a method compliant with ISO113 under the conditions of a measurement temperature of 220 ° C. and a load of 98N. Was measured.

<Ester wax (D) evaluation method>
(1) Acid value JOCS (Japan Overseas Christian Medical Cooperative Association) 2.3.1 was compliant.

(2) Hydroxy group value JOCS (Japan Overseas Christian Medical Cooperative Association) 2.3.6.2 was compliant.

<Manufacturing of transparent thermoplastic resin composition>
(Production Example 1) Graft copolymer (A-1)
In a polymerization tank equipped with a stirring blade, 50 parts by mass (solid content equivalent) of polybutadiene latex (mass average particle diameter of rubber 0.30 μm, refractive index 1.516), 130 parts by mass of pure water, lauric acid as a rubber polymer 0.4 parts by mass of sodium, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate and 0.01 parts by mass of ferrous sulfate were charged, and after nitrogen substitution, the temperature was adjusted to 60 ° C. and stirred. A monomer mixture of 3 parts by mass of styrene, 12 parts by mass of methyl methacrylate and 0.07 parts by mass of t-dodecyl mercaptan was initially added over 45 minutes.
Then, 0.3 parts by mass of cumene hydroperoxide, 1.6 parts by mass of sodium laurate as an emulsifier, and 25 parts by mass of pure water were continuously added as an initiator mixture over 5 hours. At the same time, in parallel, a monomer mixture of 2 parts by mass of styrene, 8 parts by mass of methyl methacrylate and 0.08 part by mass of t-dodecyl mercaptan was continuously added over 50 minutes, and then 7.5 parts by mass of styrene and methacryl were added. A monomer mixture of 17.5 parts by mass of methyl acid acid and 0.17 parts by mass of t-dodecyl mercaptan was continuously added over 130 minutes. After the addition of the monomer mixture, the polymerization was completed by holding for 1 hour. The obtained graft copolymer latex was coagulated with 1.5% by mass sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain a powdery graft copolymer (A-1) (A-1). Polymer ratio: styrene 25% by mass, methyl methacrylate 75% by mass) was obtained.
The refractive index of the acetone-insoluble component of the obtained graft copolymer (A-1) was 1.516, and the difference in refractive index from the rubbery polymer was 0.000. The graft rate was 50%.

(Production Example 2) Graft copolymer (A-2)
In a polymerization tank equipped with a stirring blade, 50 parts by mass (solid content equivalent) of polybutadiene latex (mass average particle diameter of rubber 0.30 μm, refractive index 1.516), 130 parts by mass of pure water, lauric acid as a rubber polymer 0.4 parts by mass of sodium, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate and 0.01 parts by mass of ferrous sulfate were charged, and after nitrogen substitution, the temperature was adjusted to 60 ° C. and stirred. A monomer mixture of 3.6 parts by mass of styrene, 0.6 parts by mass of acrylonitrile, 10.8 parts by mass of methyl methacrylate and 0.15 parts by mass of t-dodecyl mercaptan was initially added over 45 minutes.
Then, 0.3 parts by mass of cumene hydroperoxide, 1.6 parts by mass of sodium laurate as an emulsifier, and 25 parts by mass of pure water were continuously added as an initiator mixture over 5 hours. At the same time, in parallel, a monomer mixture of 8.4 parts by mass of styrene, 1.4 parts by mass of acrylonitrile, 25.2 parts by mass of methyl methacrylate and 0.36 parts by mass of t-dodecyl mercaptan was continuously added over 5 hours. did. After the addition of the monomer mixture, the polymerization was completed by holding for 1 hour. The obtained graft copolymer latex was coagulated with 1.5% by mass sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain a powdery graft copolymer (A-2) (A-2). Polymer ratio: 24% by mass of styrene, 4% by mass of acrylonitrile, 72% by mass of methyl methacrylate) was obtained.
The refractive index of the acetone-insoluble component of the obtained graft copolymer (A-2) was 1.517, and the difference in refractive index from that of the rubbery polymer was 0.001. The graft rate was 47%.

<Manufacturing of ester wax (D)>
(Production Example 3) Ester wax (D-1)
To a reaction vessel equipped with a thermometer, a nitrogen introduction tube, a stirrer, a Dean-Stark trap and a Dimroth condenser, 100 g (0.73 mol) of pentaerythritol and 1050 g (3.08 mol) of bechenic acid were added, and the mixture was charged at 220 ° C. under a nitrogen stream. The reaction was carried out at atmospheric pressure for 20 hours while distilling off the water generated by the reaction to obtain a crude ester product. To this crude ester product, 262 g of toluene (25 parts by mass with respect to the crude ester product) and 105 g of isopropanol (10 parts by mass with respect to the crude ester product) were added, and the acid value of the crude ester product was 1.5. 79 g (acid value of crude ester product = 5 mgKOH / g, 7.5 parts by mass with respect to crude ester product) was added in an amount corresponding to a double equivalent amount, and the mixture was stirred at 70 ° C. for 30 minutes. did. After allowing to stand for 30 minutes, the aqueous layer was removed to complete the deoxidation step. Next, 209 g of ion-exchanged water (20 parts by mass with respect to the crude ester product) was added to the obtained oil layer portion, and the mixture was stirred at 70 ° C. for 30 minutes and then allowed to stand for 30 minutes to remove the aqueous layer portion. Washing with water was repeated 4 times until the pH of the removed aqueous layer became neutral. The oil layer after washing with water was depressurized under the conditions of 180 ° C. and 1 kPa to distill off the solvent, and filtration was performed to obtain the target product ester wax (D-1) (pentaerythritol tetrabehenate).
The acid value of the ester wax (D-1) was 0.1 mgKOH / g, and the hydroxyl value was 3.5 mgKOH / g.

(Production Example 2) Ester wax (D-2)
To a reaction vessel equipped with a thermometer, a nitrogen introduction tube, a stirrer, a Dean-Stark trap and a Dimroth condenser, 100 g (0.73 mol) of pentaerythritol and 629 g (3.08 mol) of stearic acid were added, and the temperature was 220 ° C. under a nitrogen stream. The reaction was carried out at normal pressure for 20 hours while distilling off the water generated by the reaction to obtain a crude ester product. To this crude ester product, 262 g of toluene (25 parts by mass with respect to the crude ester product) and 87 g of isopropanol (10 parts by mass with respect to the crude ester product) were added, and the acid value of the crude ester product was 1.5. Add 66 g (acid value of crude ester product = 5 mgKOH / g, 7.5 parts by mass with respect to crude ester product) of a 10% potassium hydroxide aqueous solution equivalent to a double equivalent, and stir at 70 ° C. for 30 minutes. did. After allowing to stand for 30 minutes, the aqueous layer portion was removed to complete the deoxidation step. Next, 175 g of ion-exchanged water (20 parts by mass with respect to the crude ester product) was added to the obtained oil layer portion, and the mixture was stirred at 70 ° C. for 30 minutes and then allowed to stand for 30 minutes to remove the aqueous layer portion. Washing with water was repeated 4 times until the pH of the removed aqueous layer became neutral. The oil layer portion after washing with water was depressurized under the conditions of 180 ° C. and 1 kPa to distill off the solvent, and filtration was performed to obtain the target product ester wax (D-2) (pentaerythritol tetrastearate).
The acid value of the ester wax (D-2) was 0.2 mgKOH / g, and the hydroxyl value was 3.3 mgKOH / g.

[Example 1]
A complete mixing type polymerization vessel 2m ³ with evaporation carbonization for condenser and helical ribbon blade of the monomer vapor, and a single screw extruder type preheater, and a twin-screw extruder type de-monomer machine, downstream of the de-monomer machine ( Using a continuous bulk polymerization device consisting of a twin-screw extruder type feeder connected so as to side-feed from the tip on the exit) side to the barrel portion 1/3 of the length in front, a vinyl-based copolymer (extrusion) is obtained by the following method. B) and the thermoplastic resin composition were produced.

First, 23.5 parts by mass of styrene, 4.5 parts by mass of acrylonitrile, 72 parts by mass of methyl methacrylate, 0.26 parts by mass of n-octyl mercaptan and 0.015 parts by mass of 1,1-bis (t-butylperoxy) cyclohexane. The monomer mixture (b) composed of parts was continuously supplied to a complete mixing type polymerization tank at 150 kg / hour, and continuous bulk polymerization was carried out while maintaining the polymerization temperature at 130 ° C. and the tank internal pressure at 0.08 MPa. The polymerization rate of the polymerization reaction mixture at the outlet of the complete mixing type polymerization tank was controlled to 70 ± 5%.
Next, the polymerization reaction mixture is preheated by a single-screw extruder type preheater, then supplied to a twin-screw extruder type demonomer, and the unreacted monomer is depressurized from the vent port of the twin-screw extruder type demonomer. Evaporated and recovered. The recovered unreacted monomer was continuously refluxed into a fully mixed polymerization tank. Styrene / acrylonitrile / methyl methacrylate copolymer with an apparent polymerization rate of 99% or more at a position 1/3 before the total length from the downstream tip of the twin-screw extruder type depolymerizer 150 kg / hour (77) By mass part), a twin-screw extruder type feeder was used to obtain 0.225 kg / hour of t-butylhydroxytoluene as a phenol-based stabilizer, 0.225 kg / hour of tri (nonylphenyl) phosphite as a phosphorus-based stabilizer, and Himashi. Hardened oil (ester wax (C)) 1.36 kg / hour (0.68 parts by mass), ester wax (D-1) 0.04 kg / hour (0.02 parts by mass) produced in Production Example 3, and production. 50 kg / hour (25 parts by mass) of the semi-molten state of the graft copolymer (A-1) produced in Example 1 was supplied, and the styrene / acrylonitrile / methyl methacrylate copolymer was added in a twin-screw extruder type demonomerizer. Combined and melt-kneaded. During the melt-kneading step, 2 kg / hour of water was supplied at a position 1/6 before the total length from the downstream tip of the twin-screw extruder type demonomer. This water and other volatile components were removed by evaporation under reduced pressure from a vent port installed further downstream of the twin-screw extruder type demonomer. Then, the melt-kneaded product was discharged in a strand shape and cut with a cutter to obtain pellets of a transparent thermoplastic resin composition.

[Example 2]
Except that the supply amount of ester wax (C) was 1.3 kg / hour (0.65 parts by mass) and the supply amount of ester wax (D-1) was 0.1 kg / hour (0.05 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 3]
Except that the supply amount of ester wax (C) was 1.14 kg / hour (0.57 parts by mass) and the supply amount of ester wax (D-1) was 0.26 kg / hour (0.13 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 4]
Except that the supply amount of ester wax (C) was 1.06 kg / hour (0.53 parts by mass) and the supply amount of ester wax (D-1) was 0.34 kg / hour (0.17 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 5]
Except that the supply amount of ester wax (C) was 2.8 kg / hour (1.4 parts by mass) and the supply amount of ester wax (D-1) was 0.2 kg / hour (0.1 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 6]
Except that the supply amount of ester wax (C) was 5.44 kg / hour (2.72 parts by mass) and the supply amount of ester wax (D-1) was 0.16 kg / hour (0.08 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 7]
Except that the supply amount of ester wax (C) was 5.2 kg / hour (2.6 parts by mass) and the supply amount of ester wax (D-1) was 0.4 kg / hour (0.2 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 8]
Except that the supply amount of ester wax (C) was 4.6 kg / hour (2.3 parts by mass) and the supply amount of ester wax (D-1) was 1.0 kg / hour (0.5 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 9]
Except that the supply amount of ester wax (C) was 4.26 kg / hour (2.13 parts by mass) and the supply amount of ester wax (D-1) was 1.34 kg / hour (0.67 parts by mass). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1.

[Example 10]
The graft copolymer (A-1) is used as the graft copolymer (A-2), the supply amount of the ester wax (C) is 2.8 kg / hour (1.4 parts by mass), and the ester wax (D-1). A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1 except that the supply amount of the resin was 0.2 kg / hour (0.1 part by mass).

[Example 11]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 1 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 12]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 2 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 13]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 3 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 14]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 4 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 15]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 5 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 16]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 6 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 17]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 7 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 18]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 8 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 19]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 9 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Example 20]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Example 10 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Comparative Example 1]
The transparent thermoplastic resin was supplied by the same method as in Example 1 except that the ester wax (C) was supplied at 1.4 kg / hour (0.7 parts by mass) and the ester wax (D) was not added. Composition pellets were obtained.

[Comparative Example 2]
The transparent thermoplastic resin was supplied by the same method as in Example 1 except that the ester wax (C) was supplied at 5.6 kg / hour (2.8 parts by mass) and the ester wax (D) was not added. Composition pellets were obtained.

[Comparative Example 3]
The amount of ester wax (D-1) supplied was 1.4 kg / hour (0.7 parts by mass), and the transparent heat was obtained by the same method as in Example 1 except that the ester wax (C) was not added. Plastic resin composition pellets were obtained.

[Comparative Example 4]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Comparative Example 3 except that the ester wax (D-1) was changed to the ester wax (D-2).

[Comparative Example 5]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Comparative Example 1 except that the graft copolymer (A-1) was used as the graft copolymer (A-2).

[Comparative Example 6]
A transparent thermoplastic resin composition pellet was obtained by the same method as in Comparative Example 3 except that the graft copolymer (A-1) was used as the graft copolymer (A-2).

[Comparative Example 7]
The amount of ester wax (D-1) supplied was 0.1 kg / hour (0.05 parts by mass), and the transparent thermoplastic method was the same as in Example 1 except that the ester wax (C) was not added. Resin composition pellets were obtained.

[Comparative Example 8]
The amount of ester wax (D-2) supplied was 0.1 kg / hour (0.05 parts by mass), and the transparent thermoplastic method was the same as in Example 1 except that the ester wax (C) was not added. Resin composition pellets were obtained.

The compositions of the transparent thermoplastic resin composition and the ester wax, and the evaluation results are shown in Tables 1 to 3.

As shown in the evaluation results of Examples 1 to 20, the transparent thermoplastic resin composition of the present embodiment has excellent impact resistance and fluidity while maintaining particularly high transparency and good color tone. I understood.
On the other hand, Comparative Example 1, Comparative Example 2 and Comparative Example 5 were inferior in impact resistance because the ester wax (D) was not added. Comparative Example 3, Comparative Example 4 and Comparative Example 6 were inferior in fluidity and transparency. In Comparative Example 7 and Comparative Example 8, the impact resistance and fluidity were inferior because the ester wax (C) was not added.

The transparent thermoplastic resin composition and molded product of the present embodiment can be widely used in applications such as home appliances, communication-related equipment, general miscellaneous goods, and medical-related equipment.

1 ... Reaction tank, 2 ... Preheater, 3 ... Twin-screw extruder type demonomer machine, 4 ... Melt-kneading area, 5 ... Twin-screw extruder type feeder, 6 ... Discharge port, 7 ... Stirrer (helical ribbon blade) , 8 ... Vent port, 9 ... Water inlet, 10 ... Final vent port

Claims (8)

In the presence of the rubbery polymer (r), a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth) acrylic acid ester-based monomer (a2) is graft-copolymerized. A single amount containing the obtained graft copolymer (A), at least an aromatic vinyl-based monomer (b1), a (meth) acrylic acid ester-based monomer (b2), and a vinyl cyanide-based monomer (b3). A transparent thermoplastic resin composition containing a vinyl-based copolymer (B) obtained by copolymerizing the body mixture (b), the following ester wax (C) and the following ester wax (D).
Ester wax (C): Hardened oil of Himashi Ester wax (D): Linear saturated monocarboxylic acid having 12 to 30 carbon atoms, linear saturated monohydric alcohol having 14 to 30 carbon atoms, and 2 to 30 carbon atoms. Fatty acid ester consisting of at least one alcohol selected from the group consisting of hexavalent polyhydric alcohols The transparent thermoplastic resin composition according to claim 1, wherein the mass ratio of the ester wax (C) to the ester wax (D) is 95: 5 to 80:20. The transparent thermoplastic resin composition according to claim 1 or 2, wherein the ester wax (D) is at least one of pentaerythritol tetrabehenate and pentaerythritol tetrastearate. In the presence of the rubbery polymer (r), a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth) acrylic acid ester-based monomer (a2) is graft-copolymerized. A single amount containing the obtained graft copolymer (A), at least an aromatic vinyl-based monomer (b1), a (meth) acrylic acid ester-based monomer (b2), and a vinyl cyanide-based monomer (b3). A method for producing a transparent thermoplastic resin composition, which comprises a vinyl-based copolymer (B) obtained by copolymerizing the body mixture (b), the following ester wax (C) and the following ester wax (D).
Ester wax (C): Hardened oil of Himashi Ester wax (D): Linear saturated monocarboxylic acid having 12 to 30 carbon atoms, linear saturated monohydric alcohol having 14 to 30 carbon atoms, and 2 to 30 carbon atoms. Fatty acid ester consisting of at least one alcohol selected from the group consisting of hexavalent polyhydric alcohols The method for producing a transparent thermoplastic resin composition according to claim 4, wherein the mass ratio of the ester wax (C) to the ester wax (D) is 95: 5 to 80:20. The method for producing a transparent thermoplastic resin composition according to claim 4 or 5, wherein the ester wax (D) is at least one of pentaerythritol tetrabehenate and pentaerythritol tetrastearate. A molded product obtained by molding the transparent thermoplastic resin composition according to any one of claims 1 to 3. A method for producing a molded product obtained by molding a transparent thermoplastic resin composition obtained by the production method according to any one of claims 4 to 6.

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