TW201837099A - Chlorine-containing resin composition and molded article using same - Google Patents

Abstract

The present invention provides a chlorine-containing resin composition which enables the production of a molded article that can achieve both of high transparency and high heat resistance and has excellent acidity resistance. The present invention also provides a molded article produced using the chlorine-containing resin composition. The present invention is a chlorine-containing resin composition which contains a liquid stabilizer in an amount of 1 to 10 parts by weight and maltitol in an amount of 0.01 to 1 part by weight both relative to 100 parts by weight of a chlorine-containing resin, wherein the liquid stabilizer contains a perbasic barium salt and an organic acid zinc.

Description

 Chlorine-containing resin composition and molded body using the same  

The present invention relates to a chlorine-containing resin composition and a molded body using the same.

The chlorine-containing resin represented by polyvinyl chloride is not only soft and easy to process, but also has physical properties such as mechanical strength, and is therefore widely used for various applications such as piping materials. On the other hand, the chlorine-containing resin has a problem in terms of thermal stability, which is unstable to heat during processing or use, and is easily decomposed by heating, so that from the viewpoint of thermal stability or improvement of workability, it is usually A chlorine-containing resin is used in combination with a stabilizer.

As a stabilizer, a heavy metal stabilizer such as tin, lead, or cadmium has been generally used. However, since the awareness of environmental problems has increased in recent years, the use of such heavy metals has been gradually avoided. Therefore, for example, in addition to a stabilizer called bismuth zinc (Ba/Zn) or calcium-zinc (Ca/Zn), the industry has also developed a combination of sugar alcohols and hydrotalcite (see Patent Document 1), organic acids. A stabilizer such as a zinc salt, a zinc-modified hydrotalcite-based compound, and a sugar alcohol (see Patent Document 2).

Prior technical literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-175868

Patent Document 2: International Publication No. 2011/024399

Various stabilizers were developed as described above. However, even if a bismuth zinc-based or calcium-zinc-based stabilizer is used for a chlorine-containing resin, heat resistance is insufficient, so that it cannot be processed under severe molding conditions. Further, an overbased sulfonium salt is known as a heat resistance stabilizer, but has problems in terms of transparency and color tone. Thus, when a conventional stabilizer is used for a chlorine-containing resin, even if the heat resistance of the resin composition can be improved, transparency and color tone are easily impaired, and if transparency or color tone is improved, heat resistance is large. Since the amplitude is lowered, the molded article cannot simultaneously achieve high transparency and high heat resistance. Further, the stabilizers described in Patent Documents 1 and 2 are kneaded into polyvinyl chloride in a powder state, but are not only insufficient in heat resistance, but also have problems in terms of transparency and color tone. Further, in a hard transparent resin composition such as an industrial sheet, particularly high transparency and heat resistance are required, but the transparency and heat resistance of the stabilizers are insufficient. Further, in industrial use, particularly in corrugated sheets and the like, it is necessary to have both acid resistance, but the acid resistance of the stabilizers is also insufficient.

In view of the above circumstances, it is an object of the present invention to provide a chlorine-containing resin composition which can provide a molded article which can simultaneously achieve high transparency and high heat resistance and is excellent in acid resistance. Further, it is an object of the invention to provide a molded body obtained by using such a chlorine-containing resin composition.

When the inventors of the present invention conducted an effort to study a chlorine-containing resin composition, it was found that if a chlorine-containing resin is contained and a specific amount of a liquid stabilizer containing an overbased barium salt and an organic acid zinc is contained, In the resin composition of maltitol, a molded article which specifically achieves both high transparency and high heat resistance can be obtained. The reason is considered to be that the liquid stabilizer containing the overbased cerium salt and the organic acid zinc has higher dispersibility and higher heat resistance than the powdery stabilizer, and the maltitol is easily fused to the chlorine-containing resin. When the resin composition does not contain a plasticizer or is contained in a small amount, it can provide a molded article excellent in both transparency and heat resistance. Therefore, it is particularly useful for hard resin applications, and is suitable for chlorine-containing resins. Great contributions have been made in the field of shaped bodies. Further, the molded body obtained by using such a resin composition is also excellent in acid resistance, and can sufficiently suppress plate out during molding thereof (i.e., the resin composition adheres to a mold or a sizing mold (sizing) The phenomenon or the like). Therefore, it is possible to omit or simplify the cleaning operation of the mold or the repair mold or the like which is performed along with the generation of the mold scale, and it is also advantageous in terms of the productivity of the molded body. The inventors of the present invention have thought that the above problems can be satisfactorily solved in this way, and the present invention has been completed.

That is, the present invention is a chlorine-containing resin composition containing 1 to 10 parts by weight of a liquid stabilizer containing an overbased cerium salt and an organic acid zinc, and 0.01 to 1 by weight of maltitol, based on 100 parts by weight of the chlorine-containing resin. Share.

The content of the plasticizer in the chlorine-containing resin composition is preferably from 0 to 5% by mass based on 100% by mass of the chlorine-containing resin composition.

Further, the present invention is also a molded body obtained by using the above chlorine-containing resin composition.

The molded body is preferably a transparent molded body.

Further, the molded body is preferably in the form of a plate, a film or a sheet.

The chlorine-containing resin composition of the present invention can provide a molded article which can simultaneously achieve high transparency and high heat resistance and is excellent in acid resistance. The molded article is excellent in various physical properties derived from a chlorine-containing resin, and has a small initial coloration, so that it can express a vivid color tone. Further, since the resin composition can be made to contain no heavy metal components such as tin, lead, or cadmium, it is extremely useful to sufficiently satisfy the demand for safety in recent years. Further, when the resin composition is used, mold generation or foaming can be sufficiently suppressed at the time of molding, which is advantageous in terms of productivity of the molded body.

In the following, the preferred embodiments of the present invention are specifically described, but the present invention is not limited to the following description, and may be appropriately modified without departing from the spirit and scope of the invention.

In the present specification, "liquid" means liquid at any temperature from 0 to 35 °C.

The "liquid stabilizer" is a viscosity at 25 ° C of 10,000 cps or less, and is liquid at any temperature of 0 to 35 ° C, and the component is dissolved in a solvent.

1. Chlorine-containing resin composition

The chlorine-containing resin composition (also referred to simply as "resin composition") of the present invention contains a chlorine-containing resin, a liquid stabilizer containing an overbased cerium salt and an organic acid zinc, and maltitol. Further, other components may be contained as needed, and each of the components may be one type or two or more types.

1) Chlorine-containing resin

The chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing a chlorine atom, and is preferably a vinyl chloride resin. Thereby, a molded body excellent in flexibility or flame retardancy can be obtained.

Examples of the vinyl chloride-based resin include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer, and vinyl chloride-ethylene-acetic acid. Vinyl ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-amine copolymer , vinyl chloride-acrylate copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isopentane Ene copolymer, vinyl chloride-chloropropene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride - a copolymer such as an acrylonitrile copolymer or a vinyl chloride-methyleneimine copolymer.

Further, a blend of a chlorine-containing resin and a chlorine-free resin may be used, and a polymerization method for obtaining a vinyl chloride resin is not particularly limited.

Further, regarding the vinyl chloride resin, the vinyl chloride raw resin is more suitable than the paste vinyl chloride resin. This makes it more suitable for transparent use.

2) Liquid stabilizer

In the present invention, a liquid stabilizer containing an overbased cerium salt and an organic acid zinc is used.

Such a liquid stabilizer has higher dispersibility than a powder stabilizer, and the liquid stabilizer itself has higher transparency, so that a molded body which maintains high transparency can be provided. Moreover, it is also possible to improve the acid resistance of the molded body and to exhibit the mold scale inhibiting ability and the foam suppressing ability. Further, one type or two or more types of the overbased cerium salt and the organic acid zinc may be used.

-organic acid zinc -

As the organic acid zinc, a salt composed of zinc and a carboxylic acid is preferred. The carboxylic acid is not particularly limited, and may be an aliphatic carboxylic acid or an aromatic carboxylic acid. The carbon number of the aliphatic skeleton constituting the aliphatic carboxylic acid is not particularly limited, and is, for example, preferably from 1 to 20, more preferably from 5 to 10. The number of the carboxyl groups of the carboxylic acid is not particularly limited, and may be any of a monocarboxylic acid, a dicarboxylic acid, and a tricarboxylic acid. Among them, from the viewpoint of heat resistance, a monocarboxylic acid is preferred, and an aliphatic carboxylic acid or an aromatic carboxylic acid having a carbon number of 5 to 10 is more preferred. The organic acid zinc is preferably zinc octoate or zinc toluate, and is preferably zinc toluate, from the viewpoint of further exerting the effects of the present invention.

Further, as the zinc toluate, any of o-, p-, and inter-preferable can be preferably used, and from the viewpoint of further improving transparency, zinc m-toluate (also referred to as zinc m-toluate) is preferred. .

The total amount of the organic acid zinc in the liquid stabilizer is preferably from 1 to 30% by mass, more preferably from 2 to 20% by mass, even more preferably from 5 to 15% by mass, based on 100% by mass of the total of the liquid stabilizer.

- Overbased strontium salt -

The overbased cerium salt is not particularly limited, and examples thereof include an overbased ceric acid cerium salt and an overbased neodecanoic acid cerium salt. Specifically, for example, Plastisab 2106, Plastistab 2116, Plastisab 2508, Plastisab 2513, and the like, manufactured by AM Stabilizers, Inc. are preferable.

The total amount of the overbased cerium salt in the liquid stabilizer is preferably from 5 to 80% by mass, more preferably from 30 to 70% by mass, even more preferably from 45 to 65% by mass based on 100% by mass of the total amount of the liquid stabilizer. %.

The total content of the organic acid zinc and the overbased cerium salt in the liquid stabilizer is preferably 100% by mass or more, more preferably 40% by mass or more, more preferably 40% by mass or more, based on the total amount of the liquid stabilizer. It is 50% by mass or more.

-phosphorus compound -

The liquid stabilizer preferably further contains a phosphorus compound. Among them, a phosphite compound is preferable, whereby the molded article can further improve various physical properties such as transparency, color tone, and weather resistance.

The phosphite compound is not particularly limited, and examples thereof include triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and tris(nonylphenyl) phosphite. Tris(didecylphenyl) phosphate, tris(mono- and di-m-decylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di Tributylphenyl)octyl phosphite, decyl phosphite, isooctyl phosphite, tridecyl phosphite, diisodecyl phenyl phosphite, sub Tributyl phosphate, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trithiophosphorous acid Trilauryl ester, bis(neopentyl glycol)-1,4-cyclohexanedimethyl diphosphite, bis(2,4-di-t-butylphenyl)neopentanol diphosphite, Bis(2,6-di-t-butyl-4-methylphenyl)neopentitol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4'-sub diisopropyl phenol - new pentaerythritol diphosphite, tetra (C _{12 ~ 15} mixed alkyl) -4,4'-isopropylidene diphenyl Phosphate, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl)-bis[4,4'-n-butylidene bis(2-tert-butyl-5 -methylphenol)]-1,6-hexanediol-diphosphite, tetrakis(tridecyl)-4,4'-butylenebis(2-tert-butyl-5-methylphenol) Diphosphite, hexatridecyl-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane-triphosphite, 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.

In addition to the above, there may be mentioned: tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, and tris[2-t-butyl-4-phosphate. (3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]ester, tridecyl phosphite, octyl phosphite diphenyl ester, dinonyl phosphite mono Phenyl ester, monodecyl diphenyl phosphite, bis(nonylphenyl) bisphosphonate, di(tridecyl) pentaerythritol diphosphite, di-hard Lithofyl pentaerythritol diphosphite, bis(nonylphenyl)neopentitol diphosphite, bis(2,4-di-t-butylphenyl)neopentanol diphosphite, Bis(2,6-di-t-butyl-4-methylphenyl)neopentitol diphosphite, tetrakis(tridecyl)isopropylidene diphenol diphosphite, tetra (13 Alkyl) isopropylidene diphenol diphosphite, tetra (C _12-15 mixed alkyl)-4,4'-n-butylene bis(2-tert-butyl-5-methylphenyl) Diphosphite, hexatridecyl-1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, tetra (2,4 -di-tert-butylphenyl)-linked phenylphosphinate, 2,2'-methylene Bis (4,6-di-t-butylphenyl) octyl phosphite and the like.

In the case where the liquid stabilizer contains a phosphorus compound (preferably a phosphite compound), the content thereof is not particularly limited, and is, for example, 100% by mass based on the total amount of the liquid stabilizer, preferably 0 to 30% by mass. . Thereby, the effect by the phosphorus compound can be further exhibited. More preferably, it is 5 to 25% by mass, and further preferably 15 to 25% by mass.

In addition, the liquid stabilizer may further contain other components as needed. Examples of the other component include a solvent, benzotrimethane, and the like.

Here, the ratio of the organic acid zinc, the overbased cerium salt, and the phosphorus compound is preferably 50% by mass or more based on 100% by mass of the total amount of the liquid stabilizer. More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more.

In the resin composition of the present invention, the content of the liquid stabilizer is from 1 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin. As a result, the effect of the liquid stabilizer is exhibited, and the resin composition is a molded article excellent in heat resistance and thermal stability. It is preferably 2 to 9 parts by weight, more preferably 2.5 to 8 parts by weight. Further, the total content of the overbased cerium salt and the organic acid zinc contained in the liquid stabilizer is preferably from 1 to 8 parts by weight based on 100 parts by weight of the chlorine-containing resin. More preferably, it is 1.1 to 4 parts by weight, and further preferably 1.5 to 3 parts by weight.

3) Maltitol

Commercially available products can be used for maltitol. Since maltitol has high compatibility with a chlorine-containing resin and has a melting point lower than a usual kneading temperature with a chlorine-containing resin, it is considered that the transparency of the chlorine-containing resin is not impaired even if it is added.

In the resin composition of the present invention, the content of maltitol is 0.01 to 1 part by weight based on 100 parts by weight of the chlorine-containing resin. Thereby, the effect produced by maltitol is exhibited, and it becomes a resin composition which provides the molded object excellent in heat resistance and thermal stability. It is preferably 0.05 to 0.8 parts by weight, more preferably 0.1 to 0.5 parts by weight.

4) Plasticizer

The resin composition of the present invention may further contain a plasticizer as needed. The plasticizer is not particularly limited, and is preferably at least selected from the group consisting of phthalic acid esters, alkyl adipates, non-phthalic acid plasticizers, and epoxidized vegetable oils. One.

When the resin composition of the present invention is used as a hard resin composition as described above, transparency and heat resistance can be exhibited, and surface deterioration of the molded body due to passage of time can be sufficiently suppressed. When it is used as a hard resin composition, it is preferably not contained in a plasticizer or even if it is contained in a small amount, so that the content of the plasticizer in 100% by mass of the resin composition of the present invention is preferably 0 to 5 by mass. %. More preferably, it is 0 to 3 mass%, and further preferably 0 to 1 mass%.

Further, it is known that, in general, the resin composition having a smaller content of the plasticizer has lower transparency and initial coloring property. However, in the present invention, contrary to such technical knowledge, even when the content of the plasticizer is a small amount or a plasticizer as described above, it is possible to exhibit high transparency and initial coloring property.

5) Other ingredients

Further, the resin composition of the present invention may contain other components as needed. For example, various additives such as a metal soap-based heat stabilizer, a processing aid, a reinforcing agent, a lubricant, an antioxidant, a coloring agent, a heat-resistant auxiliary agent, a crosslinking assistant, and a stabilizer can be mentioned. Among them, if hydrotalcite or benzotrimethane is further contained, heat resistance is further improved, which is preferable.

Each of the additives is not particularly limited. For example, as the metal soap-based heat stabilizer, a fatty acid metal salt such as calcium stearate, barium stearate or zinc stearate may be mentioned.

Examples of the processing aid include an acrylic processing aid such as a (meth)acrylate polymer. Examples of the acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. Examples of the methacrylate include methyl group. Methyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like. The acrylic processing aid may be a homopolymer of the above acrylic acid and/or its ester or methacrylic acid and/or its ester, or a copolymer of two or more kinds. The weight average molecular weight of the polymer is preferably from 200,000 to 7,000,000.

Examples of the commercial product of the acrylic processing aid include Metablen P type manufactured by Mitsubishi Rayon Co., Ltd., Kane Ace PA series manufactured by Kaneka Co., Ltd., and Paraloid K series manufactured by Rohm and Haas Co., Ltd., and the like.

Examples of the reinforcing agent include butadiene-based reinforcing agents such as MBS (methyl methacrylate-butadiene styrene copolymer), and chlorinated polyethylene.

Examples of the lubricant include liquid paraffin, industrial white mineral oil, synthetic paraffin wax, petroleum wax, and paraffin wax; odorless light hydrocarbon, polyoxynoxyorganopolyoxyalkylene, fatty acid, aliphatic alcohol higher fatty acid, and animal. Or fatty acids obtained from vegetable fats and oils and hydrogenated from the fatty acids of 8 to 22; linear fatty acids such as hydroxystearic acid; or animal or vegetable fats or fatty acid esters or natural waxes The number of carbons obtained by decomposition distillation is 4 or more; tridecyl alcohol, polyethylene glycol polyethylene glycol (molecular weight: 200 to 9,500); polypropylene glycol (having a molecular weight of 1,000 or more); polyoxypropylene-polyoxyethylene Segment polymer (molecular weight 1900~9000); and oil-based palmitoylamine, stearyl mesaconamine, 2-stearylamine ethyl stearate, ethylidene fatty amine, N, N' - oil-based stearyl ethylene diamine, N, N'-bis(2-hydroxyethyl)alkyl (C12-C18) decylamine, N, N'-bis(hydroxyethyl) laurylamine, and Oleic acid fatty acid diethanolamine, di(hydroxyethyl)diethylenetriamine monoacetate monostearate obtained by reaction of N-alkyl (C16~C18) trimethylene diamine Ester, n-butyl hydrogenated rosin methyl stearate, dibutyl sebacate <including n-butyl ester, isobutyl ester>, dioctyl sebacate <including 2-ethylhexyl ester, n-octyl ester>, Glycerol fatty acid ester, glyceryl glyceryl lactate, pentaerythritol stearate <including mono-, di-, tri-, tetra->, sorbitan fatty acid ester, polyethylene glycol monostearate, poly Diol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol coconut fatty acid ester, polyethylene glycol tall oil fatty acid ester, ethylene glycol brown coal Acid ester, 1,3-butylene glycol montanate, diethylene glycol stearate, propylene glycol fatty acid ester, triglyceride, linseed oil, palm oil, glycerol 12-hydroxystearic acid, Hydrogenated fish oil, tallow, spermaceti wax, montan wax, carnauba wax, beeswax, wood wax, hydrogenated whale oil lauryl ester, stearyl stearate, etc. aliphatic saturated acid ester of monohydric aliphatic alcohol Alkali metal, alkaline earth metal salt, low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene of higher fatty acids such as lanolin, zinc stearate and calcium stearate , fluorine resin, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl fluoride, and propylene glycol alginate, dialkyl ketone, acrylic copolymer (for example, manufactured by Monsanto Co., Ltd.) Modaflow, etc.).

Examples of the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and (3,5-di-t-butyl group). -4-hydroxyphenyl)propionate stearyl ester, phosphonic acid (3,5-di-t-butyl-4-hydroxybenzyl) ester distearyl ester, thiodiethylene glycol bis [(3,5 -di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propanamide], 4,4'-thiobis(6-t-butyl-m-cresol) , 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylenebis(4-ethyl-6-tert-butylphenol), double 3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid]ethylene glycol ester, 4,4'-butylene bis(6-t-butyl-m-cresol), 2,2 '-Ethylene bis(4,6-di-t-butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tert-butylphenol), 1,1,3 -Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3) -T-butyl-5-methylbenzyl)phenyl]ester, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl Isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris (3,5-di Third butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tri[(3,5-di-t-butyl-4-hydroxyphenyl)propanoid Oxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4 -methyl-6-(2-propenyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3- Third butyl-4-hydroxy-5-methylphenyl)propenyloxy}]ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene Alcohol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl ester and distearyl ester, and pentaerythritol tetra (β-twelfth). A β-alkylthiopropionate of a polyhydric alcohol such as an alkylthiopropionate.

Examples of the coloring agent include TiO ₂ , zirconia, BaSO ₄ , zinc oxide (zinc white), zinc lanthanum (a mixture of zinc sulfide and barium sulfate), carbon black, a mixture of carbon black and titanium oxide, iron oxide, and the like. Sb ₂ O ₃ , Cr ₂ O ₃ , cobalt blue, cobalt green and other inorganic pigments such as spinel, ultramarine blue, or azo pigment, phthalocyanine pigment, quinacridone pigment, anthraquinone pigment, pyrrolopyrroledione pigment , organic pigments such as enamel pigments. Further, a composite pigment obtained by compounding the above pigments may also be mentioned.

Examples of the heat-resistant auxiliary agent include hydrotalcite, zeolite, partial ester of dipentaerythritol and adipic acid, polyhydric alcohols, and tris(2-hydroxyethyl) isocyanurate. Among them, when the resin composition of the present invention further contains hydrotalcite, heat resistance is further improved, which is preferable. The content of the hydrotalcite is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the chlorine-containing resin. More preferably, it is 0.05 to 3 parts by weight.

The method for obtaining the above resin composition is not particularly limited, and a chlorine-containing resin, a liquid stabilizer, maltitol, and optionally any optional component may be mixed. The mixing method is not particularly limited. For example, it is preferably mixed by a Henschel mixer or a super mixer, and the obtained mixture is uniformly kneaded using a roll, a Banbury mixer, an extruder, or the like.

The resin composition can provide a molded article which is capable of achieving both high transparency and high heat resistance and excellent in various physical properties derived from a chlorine-containing resin without deteriorating the appearance. Therefore, it is particularly useful for the use of shaped bodies.

2. Shaped body

The molding system of the present invention is obtained by using the above-described chlorine-containing resin composition of the present invention. That is, it is a molded body of the above-mentioned chlorine-containing resin composition. Therefore, heat resistance and transparency are particularly excellent, and acid resistance can also be exhibited. Further, when the resin composition of the present invention is used, mold scale or foaming at the time of molding can be sufficiently suppressed, so that the obtained molded body is also excellent in appearance and excellent in productivity.

The formed body of the present invention is particularly preferably a transparent formed body.

The shape of the molded body is not particularly limited, and examples thereof include a planar shape such as a plate shape, a sheet shape, a film shape, and a film shape, and other shapes such as a rope shape, a rod shape, a pellet shape, and a tubular shape. Among them, from the viewpoint of usability and the like, it is preferably a plate shape, a film shape or a sheet shape. Further, as the molded body, specifically, various films, electric wires, tubes, resin window frames, and the like are preferable.

The molding (also referred to as molding) method is not limited, and examples thereof include extrusion molding, injection molding, roll forming, dip molding, and blow molding. Further, the molded body is preferably a molded body (extrusion molded body) obtained by extrusion molding. Extrusion molding (extrusion molding) is preferably carried out using an extrusion molding machine, and according to this method, a molded article excellent in various physical properties can be provided with good workability, easily and easily, and with good productivity.

The molded body (particularly a plate-shaped, film-shaped or sheet-shaped molded body) preferably has a total light transmittance of 85% or more when the thickness is 2 mm. More preferably, it is more than 90%. Further, the haze at a thickness of 2 mm is preferably 40% or less. More preferably, it is 30% or less, and further preferably 20% or less.

In the present specification, the total light transmittance is the ratio of all the light passing through the formed body, and the haze is the ratio of the diffuse transmitted light in the total light transmitted light. Specifically, the haze value can be measured by the method described in the following examples, and the total light transmittance can be obtained by subtracting the haze value from 100%.

Example

Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples. Unless otherwise stated, "parts" means "parts by weight (or parts by weight)".

Example 1

Each of the additives described in Table 1 was blended in 100 parts of a vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-700) at the ratios shown in Table 1, and mixed to obtain a vinyl chloride resin composition. The obtained vinyl chloride resin composition was kneaded by an 8-inch roll press (manufactured by KANSAI ROLL Co., Ltd.) having a roll surface temperature of 170 ° C for 5 minutes to prepare a rolled sheet having a thickness of 0.6 mm. The following evaluation test was carried out using this sheet. The results are shown in Table 1.

1) Oven heat resistance

The sheet prepared in Example 1 was placed in a Gil oven manufactured by ESPEC Inc., which was kept at a temperature of 190 ° C, and held for 40 minutes. The chromatic aberration was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., and a photometric type spectrophotometer SQ-2000) to obtain ΔE. Based on this ΔE, the coloring property was evaluated based on the following criteria. Further, the smaller the ΔE, the better the color tone and the lower the possibility of occurrence of a problem.

◎: ΔE is 15 or less.

○: ΔE is more than 15 and 40 or less.

△: ΔE exceeds 40 and is 60 or less.

×: ΔE exceeds 60.

2) Pressurization and heat resistance

Using a press machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., MINI TEST PRESS-10) having a pressurization surface temperature of 190 ° C, four sheets of the sheet prepared in Example 1 were stacked and kept at 100 kg/cm ² for 30 minutes to have a thickness. Become 2mm. The YI value was measured for the held sheet using the above color difference meter. Based on this YI, the coloring property was evaluated based on the following criteria. Further, the smaller the YI value, the better the hue, and the lower the possibility of occurrence of a malfunction.

◎: YI is 25 or less.

○: YI exceeds 25 and is 40 or less.

△: YI exceeds 40 and is 45 or less.

×: YI exceeds 45.

3) Transparency

The sheet prepared in Example 1 was cut into a length of 50 mm × a width of 50 mm, and four sheets were stacked thereon, and pressed at 190 ° C for 10 minutes by an electrothermal press (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to have a thickness of 2 mm. Audition. The haze value of the test piece was measured using a measuring machine (haze meter NDH4000) manufactured by Nippon Denshoku Industries Co., Ltd.

4) Acid resistance

The sheet prepared in Example 1 was cut into a length of 50 mm × a width of 50 mm, and four sheets were stacked thereon, and pressed at 190 ° C for 10 minutes by an electrothermal press (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to have a thickness of 2 mm. Audition. The sheet prepared in Example 1 was immersed in hydrochloric acid, and the weight change after one week was measured.

○: 0.05% by weight or less

△: 0.1% by weight or less

×: more than 0.1% by weight

5) mold scale

The presence or absence of mold scale on the surface of the roll after the kneading was visually observed by an 8-inch roll press used in Example 1, and evaluated based on the following criteria.

○: The attached matter could not be confirmed.

△: A slight attachment was confirmed.

×: A large deposit was confirmed.

6) Foaming

The sheet prepared in Example 1 was cut into a length of 50 mm × a width of 50 mm, and four sheets were stacked thereon, and pressed at 190 ° C for 10 minutes by an electrothermal press (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to have a thickness of 2 mm. Audition. The foaming property of the surface of the test piece obtained was evaluated by visual observation based on the following criteria.

○: There is no foaming on the surface or inside of the test piece. Good appearance without bad appearance.

△: There are 1 to 5 foams on the surface or inside of the test piece.

×: There are more than 5 foaming on the surface or inside of the test piece. Become a bad grade.

Examples 2 to 7, Comparative Examples 1 to 7

A vinyl chloride resin composition and a rolled sheet were produced in the same manner as in Example 1 except that the various additives described in Tables 1 and 2 were used at the ratios shown in the Table. Using this sheet, an evaluation test was carried out in the same manner as in Example 1. The results are shown in Tables 1 and 2.

The symbols, abbreviations, and the like in Tables 1 and 2 are as follows.

Vinyl chloride resin: TK-700 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Enhancer: Kane Ace B-513 (manufactured by Kaneka)

Processing aids: Kane Ace PA-20 (manufactured by Kaneka), and Metablen P-700 (manufactured by Mitsubishi Rayon Co., Ltd.)

Lubricants: Rikemal S-100 (manufactured by Riken Vitamin), Rikemal SL-02 (manufactured by Riken Vitamin), and Loxiol G-78 (manufactured by Cognis Japan)

Overbased strontium salt: PS-2513 (Plastistab 2513) (manufactured by AM Stabilizers)

Phosphorus compound: diphenyl phosphite isooctyl ester (ODPP, manufactured by Chengbei Chemical Co., Ltd.) and diphenyl phosphite tridecyl ester (PX-257, manufactured by Co-Pharma)

Solvent: BDG (manufactured by Dow Chemical Co., Ltd.) and Fog Solvent (manufactured by JX Energy Co., Ltd.)

Maltitol: Amalty MR-100, manufactured by Mitsubishi shoji Foodtech

Hydrotalcite: STABIACE HT-7 (manufactured by Dai Chemical Industry Co., Ltd.)

DBM: benzotrimethane (manufactured by Rhodia)

Ba/Zn stabilizer (powder): a mixture of barium laurate (B-12, manufactured by Nippon Chemical Industry Co., Ltd.) and zinc laurate (LZ-P, manufactured by Nippon Chemical Industry Co., Ltd.)

Ca/Zn stabilizer (powder): a mixture of zinc laurate (manufactured by Suga Chemical Industry Co., Ltd.) and Zn modified hydrotalcite (manufactured by Sigma Chemical Industry Co., Ltd.)

Sorbitol: Made by B Food Science

Mannitol: manufactured by B Food Science

Lactitol: manufactured by B Food Science

According to Tables 1 and 2 above, the following items were confirmed.

In the examples 1 to 7, an example of the resin composition of the present invention containing "liquid stabilizer containing an overbased cerium salt and an organic acid zinc" and "maltitol" in a specific amount is used for each of the chlorine-containing resins. On the other hand, Comparative Example 1 was different from Examples 1 to 7 in that it did not contain maltitol, and Comparative Example 2 was different from Examples 1 to 7 in that sorbitol was used instead of Maltitol, and Comparative Examples 3 to 5 were used. Conventional powder stabilizers (Ba/Zn stabilizers or Ca/Zn stabilizers) are not the same as Examples 1 to 7 in terms of liquid stabilizers, and Comparative Examples 6 to 7 use lactitol and mannose, respectively. The aspect in which the alcohol is substituted for maltitol is different from Examples 1 to 7. When the results of the evaluation of the heat resistance and the transparency were compared, it was found that the physical properties of any one or more of heat resistance and transparency were significantly higher in Examples 1 to 7 than in Comparative Examples 1 to 7. Further, in the resin compositions obtained in Examples 1 to 7, the molded article had better acid resistance than Comparative Examples 1 to 7, and also had mold scale inhibiting ability or foam suppressing ability.

Therefore, it is understood that the resin composition containing a "liquid stabilizer containing an overbased cerium salt and an organic acid zinc" and a "maltitol" in a specific amount with respect to the chlorine-containing resin can sufficiently suppress foaming or molding. In addition to transparency and heat resistance, a molded article excellent in acid resistance is produced.

Claims (5)

 A chlorine-containing resin composition containing 1 to 10 parts by weight of a liquid stabilizer containing an overbased barium salt and an organic acid zinc, and 0.01 to 1 with maltitol, based on 100 parts by weight of the chlorine-containing resin. Parts by weight.    The chlorine-containing resin composition according to claim 1, wherein the content of the plasticizer in the chlorine-containing resin composition is 0 to 5% by mass based on 100% by mass of the chlorine-containing resin composition.    A molded body obtained by using the chlorine-containing resin composition described in claim 1 or 2.    The formed body according to claim 3, which is a transparent formed body.    The formed body according to claim 3 or 4, which is in the form of a plate, a film or a sheet.