TWI586742B - Halogen atom containing resin composition, method for producing the same, and molded article comprising the same - Google Patents

Description

Resin composition containing a halogen atom, a method for producing the same, and a molded article comprising the same

The present invention relates to a halogen atom-containing resin composition, a method for producing the same, and a molded article formed therefrom, which are applied to the field of general use such as food use, medical use, and daily necessities. In particular, a halogen atom-containing resin composition of a molded article having good heat stability and a low coloration, a method for producing the same, and a molded article comprising the same.

A resin containing a halogen atom, such as a polyvinyl chloride, is formed by blending a stabilizer such as a Ca-Zn system or a Ba-Zn system, and the molded article can be widely used for food use in addition to general use. , medical use, etc.

However, these stabilizers have insufficient ability to suppress thermal degradation of a resin containing a halogen atom, and are colored on a molded article shortly after molding, which is disadvantageous in that thermal stability during molding is insufficient. Therefore, it has been proposed to add an antioxidant or a halogen atom-containing resin composition of a compound having a hydroxyl group as a means for improving these disadvantages.

A method of adding a calcium soap, a zinc soap, a polyhydric alcohol or a derivative thereof, and a neutral inorganic calcium salt to a chlorine-containing resin is disclosed in Patent Document 1 (JP-A-50-92947).

A method of adding a water-soluble polymer to a chlorine-containing polymer is disclosed in Patent Document 2 (JP-A-54-81359).

A method of adding a reaction condensate of dipentaerythritol and a dicarboxylic acid, a zinc compound, and hydrotalcite to a chlorine-containing resin is disclosed in Patent Document 3 (JP-A-57-147552).

In the thermoplastic resin such as polyvinyl chloride, an ethylene-acetic acid having an ethylene unit content of 20 to 50% and a vinyl acetate unit saponification degree of 96% or more is disclosed in the patent document 4 (JP-A-60-238345). A method of a vinyl ester copolymer saponified product, a hydrotalcite-based compound, or the like.

In the halogen-containing thermoplastic resin, a metal soap is added, and an ethylene content of 20 to 75 mol% and a vinyl acetate fraction of 50 mol% or more are disclosed in Patent Document 5 (JP-A No. Hei 1-178543). A method of copolymerizing a composition of an ethylene-vinyl acetate copolymer saponified product.

A method of adding a metal salt of an organic acid or an acetal of polyvinyl alcohol to a vinyl chloride resin is disclosed in Patent Document 6 (JP-A-6-287387).

In the vinyl chloride resin, a partially saponified polyethylene having a degree of saponification of 70 to 95 mol%, an average degree of polymerization of 300 to 2,000, and a mercapto group at the end of the molecular chain is disclosed in Patent Document 7 (JP-A-9-3286). The method of alcohol.

A method of adding a zinc compound, a hydrotalcite, a polyvinyl alcohol, and a polymethyl methacrylate to a vinyl chloride resin is disclosed in Patent Document No. 8 (JP-A-H09-31281).

Non-Patent Document 1 (Polyphnical Proceedings, Vol. 47, No. 3, p. 197 (1990)) discloses that zinc stearate-calcium stearate complex soap is added to polyvinyl chloride, and the degree of polymerization is 600. The above method for completely saponifying polyvinyl alcohol.

Non-Patent Document 2 (Polyphnical Proceedings, Vol. 47, No. 6, p. 509 (1990)) discloses that in polyvinyl chloride, zinc stearate-calcium stearate complex soap has a degree of polymerization of 500. A method of partially saponifying polyvinyl alcohol having a degree of saponification of 73.6 mol%.

Non-Patent Document 3 (Polyphnical Proceedings, Vol. 50, No. 2, p. 65 (1993)) discloses that zinc stearate-calcium stearate complex soap is added to polyvinyl chloride, and the ethylene content is A method of 29 mol% or more of an ethylene-vinyl alcohol copolymer.

Non-Patent Document 4 (Polymers & Polymer Composites, Vol. 11, p. 649 (2003)) discloses the addition of zinc stearate-calcium stearate complex soap to polyvinyl chloride, and a degree of polymerization of 500, saponification degree. A method of 98.5 mol% of polyvinyl alcohol or an ethylene-vinyl alcohol copolymer having an ethylene content of 29 mol% or more.

Non-Patent Document 5 (Japanese Society of Science, Vol. 43, No. 2, p. 43 (2007)) discloses the addition of polyvinyl alcohol having a degree of polymerization of 500 and a degree of saponification of 88 mol% in polyvinyl chloride. Or a method of polyvinyl alcohol or polymethyl methacrylate having a degree of polymerization of 1700 and a degree of saponification of 78 mol% or more.

However, the resin composition containing a halogen atom described in Patent Documents 1 to 8 and Non-Patent Documents 1 to 5 has the following problems.

In other words, when a low molecular weight polyol is added, the following problems are likely to occur: the low molecular polyol oozes out of the surface during molding, and the kneaded material adheres to the surface of the screw inside the extruder or the like during kneading. Further, in the obtained molded article, problems such as volatilization of the polyol, occurrence of adhesion, deterioration in transparency, reduction in adhesion and adhesion, and the like are likely to occur.

Further, when a high molecular weight polyol is added, especially when molded at a relatively low temperature, the dispersibility of the polymer polyol in the resin composition containing a halogen atom is insufficient, and the thermal stability is insufficient.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 50-92947

Patent Document 2 Japanese Patent Laid-Open No. 54-81359

Patent Document 3 Japanese Patent Laid-Open Publication No. SHO 57-147552

Patent Document 4 Japanese Patent Laid-Open No. 60-238345

Patent Document 5 Japanese Patent Laid-Open No. 1-178543

Patent Document 6 Japanese Patent Laid-Open No. Hei 6-287387

Patent Document 7 Japanese Patent Laid-Open No. 9-3286

Patent Document 8 Japanese Patent Publication No. 9-31281

Non-patent literature

Non-Patent Document 1 Proceedings of Polymers, Vol. 47, No. 3, p. 197 (1990)

Non-Patent Document 2 Polymer Proceedings, Vol. 47, No. 6, p. 509 (1990)

Non-Patent Document 3 Polymer Proceedings, Vol. 50, No. 2, p. 65 (1993)

Non-Patent Document 4 Polymers & Polymer Composites, Vol. 11, p. 649 (2003)

Non-Patent Document 5 Japanese Society of Learning, Vol.43, No.2, p.43 (2007)

An object of the present invention is to provide a resin composition containing a halogen atom of a molded article having a small coloration, which is excellent in heat stability during molding, a method for producing the same, and a molded article formed therefrom.

The inventors of the present invention have repeatedly conducted intensively reviewing and found that a resin composition containing a halogen atom in a specific amount of a specific polyvinyl alcohol, a specific polyhydric alcohol, and a zinc compound is added to a resin containing a halogen atom, even if it is special. When the molding process is carried out at a low temperature, the thermal stability is also sufficient, and the molded article obtained by molding the resin composition containing a halogen atom is less colored. Based on this knowledge, the review is further repeated to complete the present invention.

That is, the above problem can be solved by providing a resin composition containing a halogen atom having a degree of saponification of 60 to 99.9 mol% and viscosity with respect to 100 parts by mass of the resin containing a halogen atom. The average polymerization degree is 0.01 to 2.5 parts by mass of polyvinyl alcohol having a molecular weight of 100 to 1,000, 0.01 to 2.5 parts by mass of a polyol having a molecular weight of 2,000 or less, a hydroxyl group content of 10% by mass or more, and 0.01 to 5 parts by mass of a zinc compound.

The quality of the above polyvinyl alcohol and the above polyol is preferably satisfied (mass of polyvinyl alcohol) / (mass of polyol) = 30/70 to 90/10.

The polyvinyl alcohol preferably has a viscosity average degree of polymerization of from 100 to 450.

The resin composition containing a halogen atom is preferably contained by adding a polyvinyl alcohol, a polyhydric alcohol, and a zinc compound to a resin containing a halogen atom.

Further, the above problem can also be solved by providing a method for producing a resin composition containing a halogen atom having a saponification degree of 60 to 99.9 mol% and an average viscosity of 100 parts by mass of a resin containing a halogen atom. The polymerization degree is 0.01 to 2.5 parts by mass of polyvinyl alcohol having a degree of polymerization of from 100 to 1,000, a polyol having a molecular weight of 2,000 or less, a hydroxyl group content of 10% by mass or more, 0.01 to 2.5 parts by mass, and a zinc compound of 0.01 to 5 parts by mass.

Furthermore, the above problem can also be solved by a molded article formed of the above-mentioned resin composition containing a halogen atom.

When the halogen atom-containing resin composition of the present invention is used, it has sufficient thermal stability even when molded at a low temperature, and the adhesion of the adhesive to the inside of the extruder or the like is small during molding. Further, the molded article obtained by molding the resin composition containing a halogen atom is less colored.

[Formation of the Invention]

Hereinafter, the halogen atom-containing resin composition of the present invention, a method for producing the same, and a molded article formed therefrom will be described in detail.

[Resin containing halogen atom]

For the halogen atom-containing resin used in the present invention, for example, a chlorine-containing resin such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyolefin, vinyl chloride-vinyl acetate copolymer or the like can be used. In the bromine-containing resin or the like, a bromine-containing resin or the like may be used in accordance with the use of the molded article or the like, and one or two or more of these may be used. From the viewpoint of availability, physical properties, etc., it is preferable to contain The chlorine resin is more preferably polyvinyl chloride or polyvinylidene chloride, and particularly preferably polyvinyl chloride.

As the monomer for producing the raw material of the above polyvinyl chloride, a vinyl chloride monomer may be used alone, or a mixture of 50% by mass or more of a vinyl chloride monomer and another monomer copolymerizable therewith may be used. Further, examples of other monomers copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; and (meth)acrylates such as methyl acrylate and ethyl acrylate. An olefin such as ethylene or propylene; maleic anhydride, acrylonitrile, styrene, vinylidene chloride or the like.

Further, the method for producing the above polyvinyl chloride by using such a monomer is not particularly limited, and a method of suspending polymerization of the monomer in the presence of a polymerization initiator can be suitably employed. In the case of the dispersion stabilizer in this case, for example, a water-soluble cellulose ether such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose; polyvinyl alcohol, Water-soluble polymer such as gelatin; oil-soluble emulsifier such as sorbitan monolaurate, sorbitan trioleate, glyceryl tristearate, ethylene oxide propylene oxide block copolymer A water-soluble emulsifier such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate or sodium laurate. Among them, polyvinyl alcohol is preferably used.

As the polymerization initiator to be used, an oil-soluble or water-soluble polymerization initiator conventionally used for polymerization of a vinyl chloride monomer or the like can be used. Examples of the oil-soluble polymerization initiator include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate. Carbonate compound; tert-butyl peroxy neodecanoate, tert-butyl peroxytrimethyl acetate, third hexyl peroxytrimethyl acetate, α-isopropylphenyl peroxy neodymium a perester compound such as an acid ester; ethenylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, 3,5,5-three a peroxide such as methyl hexyl peroxide or lauryl peroxide; azobis-2,4-dimethylvaleronitrile or azobis(4-methoxy-2,4-di An azo compound such as methylvaleronitrile or the like. Examples of the water-soluble polymerization initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide, and cumene hydroperoxide. These oil-soluble or water-soluble polymerization initiators can be used singly or in combination of two or more types.

At the time of polymerization, other various additives may be added to the polymerization reaction system as needed. Examples of the additive include a polymerization regulator such as an aldehyde, a halogenated hydrocarbon, or a mercaptan, a polymerization inhibitor such as a phenol compound, a sulfur compound, or an N-oxide compound, a pH adjuster, a crosslinking agent, and a preservative. Anti-mold agent, anti-adhesion agent, antifoaming agent, anti-scaling agent, antistatic agent, etc.

In the polymerization, the polymerization temperature is not particularly limited, and may of course be a temperature of about 20 ° C or a high temperature of more than 90 ° C. Further, in order to increase the heat removal efficiency of the polymerization reaction system, it is also preferred to use a polymerization reactor equipped with a reflux condenser.

[polyvinyl alcohol]

The method of containing the polyvinyl alcohol (hereinafter also referred to as "PVA") contained in the halogen atom-containing resin composition of the present invention in the halogen atom-containing resin is not particularly limited, and is preferably formed by formation. After polymerization of a monomer for a resin of a halogen atom, it is added to a resin containing a halogen atom and contained. The PVA may be a powder, or dissolved in water or an organic solvent, and added to a resin containing a halogen atom. When the PVA is added before or during the polymerization of the monomer for forming a resin containing a halogen atom, the PVA acts as a dispersant for the monomer and the obtained halogen atom-containing resin, so that the halogen The quality of the resin such as the average particle diameter or the absorbability of the plasticizer adversely affects. In addition, the PVA is substantially removed by washing the resin after the resin containing a halogen atom, and the content of PVA in the resin composition containing a halogen atom is small, and the thermal stability is insufficient.

The saponification degree of the above PVA is 60 to 99.9 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%. When the degree of saponification is less than 60 mol% or exceeds 99.9 mol%, the long-term heat stability is lowered. Further, the degree of saponification of PVA is a value measured in accordance with JIS K6726.

The viscosity average polymerization degree (hereinafter also referred to as "polymerization degree") of the above PVA is 100 to 1,000, more preferably 150 to 800, and particularly preferably 200 to 700. The upper limit of the degree of polymerization of PVA is more preferably 450 from the viewpoint of further improving the thermal stability even when molding at a low temperature, and further suppressing the adhesion of the adherend to the inside of the extruder at the time of molding. When the degree of polymerization of PVA exceeds 1,000, the long-term thermal stability is lowered. Further, it is difficult to manufacture a PVA having a degree of polymerization of less than 100. Further, the degree of polymerization of PVA is a value measured in accordance with JIS K6726. In other words, the PVA can be further saponified to a degree of saponification of 99.5 mol% or more, and after purification, the ultimate viscosity [η] (unit: deciliter/g) measured in water at 30 ° C can be obtained by the following formula. .

Degree of polymerization = ([η] × 1000 / 8.29) ( ^{1 / 0.62} )

The PVA can be produced, for example, by polymerizing a vinyl ester monomer by a conventional method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a dispersion polymerization method, and saponifying the obtained polyvinyl ester. From the industrial viewpoint, preferred polymerization methods are solution polymerization, emulsion polymerization, and dispersion polymerization. In the polymerization operation, any one of a batch method, a semi-batch method, and a continuous method may be employed.

Examples of the vinyl ester monomer which can be used for the polymerization include vinyl acetate, vinyl formate, vinyl propionate, vinyl octanoate, vinyl acetate, and the like, from an industrial viewpoint. Among them, vinyl acetate is preferred.

In the polymerization of the vinyl ester monomer, the vinyl ester monomer may be copolymerized with another monomer as long as it does not impair the scope of the present invention. Examples of other monomers that can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. Acrylates, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.; methacrylic acid and its salts; methacrylic acid Methyl ester, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methacrylate 2- Methacrylates such as ethylhexyl ester, dodecyl methacrylate, octadecyl methacrylate; acrylamide; N-methyl acrylamide, N-ethyl acrylamide, N, N-II Methyl acrylamide, diacetone acrylamide, acrylamide propyl sulfonic acid and salts thereof, acrylamide propyl dimethylamine and salts thereof or quaternary salts thereof, N-methylol acrylamide and Acrylamide derivatives such as derivatives; methacrylamide; N-methyl methacrylamide , N-ethylmethacrylamide, methacrylamide, propanesulfonic acid and its salt, methacrylamidamine dimethylamine and its salt or its quaternary salt, N-methylolmethyl A methacrylamide derivative such as acrylamide or a derivative thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or different Vinyl ether such as butyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether or stearyl vinyl ether; nitrile such as acrylonitrile or methacrylonitrile; vinyl chloride, vinyl fluoride, etc. Halogen ethylene; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid, itaconic acid, fumaric acid, etc. a saturated dicarboxylic acid and a salt thereof or an ester thereof; a vinyl sulfonyl compound such as vinyltrimethoxydecane; isopropyl acrylate or the like.

In the polymerization of the vinyl ester monomer, the chain transfer agent may be coexisted for the purpose of adjusting the polymerization degree of the obtained PVA or the like. Examples of the chain transfer agent include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone; and 2-hydroxyethanethiol. Mercaptan; thiocarboxylic acid such as thioacetic acid; halogenated hydrocarbon such as trichloroethylene or perchloroethylene; and aldehyde and ketone are preferably used. The amount of the chain transfer agent to be added is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the intended PVA, and is usually 0.1 to 10% by mass based on the vinyl ester monomer to be used. When a thiocarboxylic acid or the like is used as the chain transfer agent, the functional group derived from the chain transfer agent is introduced into the terminal of the vinyl ester polymer, and PVA having an SH group at the terminal is obtained by saponification. However, when such a PVA is used, the heat stability improvement effect of the obtained polyvinyl chloride resin composition is not so large. Therefore, it is preferred not to use a thiocarboxylic acid as a chain transfer agent. Further, at the end of the PVA, it is preferred not to have an SH group.

In the present invention, a PVA having a large amount of 1,2-diol bond obtained by polymerizing a vinyl ester monomer under a temperature condition higher than usual can also be used. In this case, the 1,2-diol binding amount in the PVA is preferably 1.9 mol% or more, more preferably 2.0 mol% or more, and particularly preferably 2.1 mol% or more. Further, the upper limit of the amount of 1,2-diol bond is, for example, 3.0 mol%.

In the saponification reaction of the polyvinyl ester, an alcoholysis or hydrolysis reaction using a conventional alkaline catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be used. Examples of the solvent used for the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; and the like. These may be used alone or in combination of two or more. Among them, it is simple and preferable to carry out a saponification reaction using a mixed solution of methanol or methanol and methyl acetate as a solvent in the presence of sodium hydroxide of a basic catalyst.

The content of the PVA in the resin composition containing a halogen atom is 0.01 to 2.5 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the resin containing a halogen atom. When the content of the PVA is less than 0.01 parts by mass, the long-term thermal stability is insufficient. When the content is more than 2.5 parts by mass, the molded article formed from the obtained resin composition containing a halogen atom is likely to be colored.

The PVA used may be in the form of a composition containing an acid having a pKa of 3.5 to 5.5 at 25 ° C and/or a metal salt thereof. The type of such an acid is not particularly limited, and examples thereof include acetic acid (pKa 4.76), propionic acid (pKa 4.87), butyric acid (pKa 4.63), octanoic acid (pKa 4.89 ), and adipic acid (pKa 5 ). .03), benzoic acid (pKa4.00), formic acid (pKa3.55), gemic acid (pKa4.63), heptanoic acid (pKa4.66), lactic acid (pKa3.66), phenylacetic acid (pKa4.10) Isobutyric acid (pKa 4.63), cyclohexanecarboxylic acid (pKa 4.70), and the like. Among them, acetic acid, propionic acid and lactic acid are preferred. The type of the metal salt is not particularly limited, and a salt of an alkali metal such as sodium or potassium or a salt of an alkaline earth metal such as magnesium or calcium is usually used.

The content of the above acid and/or its metal salt is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, even more preferably 0.15 to 2 parts by mass, per 100 parts by mass of the PVA. When the content of the acid and/or the metal salt thereof is less than 0.05 parts by mass, the long-term heat stability is lowered, and if it exceeds 5 parts by mass, the obtained content is contained. A molded article formed of a resin composition of a halogen atom tends to be easily colored.

In addition, the method of containing a predetermined amount of the acid and/or a metal salt thereof in PVA is not particularly limited, and for example, the type or amount of the alkali catalyst used for the saponification reaction of the polyvinyl ester may be adjusted. Method; a method of adding or removing the acid and/or its metal salt after the production of PVA.

[Polyol]

The method of the polyhydric alcohol contained in the halogen atom-containing resin composition of the present invention contained in the halogen atom-containing resin is not particularly limited, but is preferably a monomer for forming a resin containing a halogen atom. After the polymerization, it is contained by being added to the obtained halogen atom-containing resin. The polyol may be a powder or a viscous liquid, or dissolved in water or an organic solvent, and added to a resin containing a halogen atom.

The polyol contained in the halogen atom-containing resin composition of the present invention has a molecular weight of 2,000 or less, preferably 1,500 or less, particularly preferably 1,000 or less. When the molecular weight exceeds 2,000, the long-term thermal stability is lowered. The lower limit of the molecular weight is not particularly limited, but is preferably 100 or more from the viewpoint of suppressing bleeding or volatilization from the resin composition containing a halogen atom.

The hydroxyl group content in the polyol-based molecule contained in the halogen atom-containing resin composition of the present invention is 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more. When the hydroxyl group content is less than 10% by mass, long-term heat stability is impaired. On the other hand, the hydroxyl group content is usually 60% by mass or less. Further, the hydroxyl group content (% by mass) of the polyol can be determined by the following formula.

(Hydroxyl content) = {(the total atomic weight of the hydrogen atom and the oxygen atom constituting the hydroxyl group contained in one molecule of the polyol) / (molecular weight of the polyol)} × 100

The polyhydric alcohol contained in the halogen atom-containing resin composition of the present invention includes polyglycerin having a repeating number of glycerin, diglycerin, and glycerin of 3 or more, an aliphatic carboxylic acid ester of glycerin, and diglycerin. An aliphatic carboxylic acid ester, an aliphatic carboxylic acid ester of polyglycerol having a repeating number of 3 or more, an alkyl ether of glycerin, an alkyl ether of diglycerin, or a polyglycerol having a repeating number of glycerin of 3 or more Alkyl ether, erythritol, xylitol, sorbitol, mannitol, pentaerythritol, an aliphatic carboxylic acid ester of pentaerythritol, dipentaerythritol, an aliphatic carboxylic acid ester of dipentaerythritol, ribose, deoxyribose, glucose , fructose, galactose, trehalose, etc. Among these polyols, polyglycol and dipentaerythritol having a repeat number of sorbitol, diglycerin, and glycerin of 3 or more are suitable from the viewpoint of maintaining excellent thermal stability in the long term, and the ease of handling is easy. From the viewpoint of view, sorbitol and dipentaerythritol are more suitable. Further, as the above-mentioned ester and ether of the polyol, the polyol before esterification or etherification has a part of a plurality of hydroxyl groups in the molecule which is esterified or etherified, even after esterification or etherification. A compound having a plurality of hydroxyl groups in a molecule.

The content of the polyol in the resin composition containing a halogen atom is 0.01 to 2.5 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the resin containing a halogen atom. When the content of the polyol is less than 0.01 parts by mass, the long-term thermal stability is insufficient. When the content is more than 2.5 parts by mass, the molded article formed from the obtained halogen atom-containing resin composition is likely to be colored or generated. The resin composition containing a halogen atom or a molded article formed therefrom volatilizes or bleeds out to the surface.

One of the characteristics of the above polyol and the PVA-based resin composition containing a halogen atom of the present invention. Thereby, the resin composition containing a halogen atom has sufficient thermal stability even when it is formed at a low temperature. Therefore, the applicable forming temperature range becomes wider. Further, when the above-mentioned polyol and the PVA are contained in the resin composition containing a halogen atom, the adhesion of the adhesive to the inside of the extruder or the like during molding is small, and the color of the obtained molded article is also small.

The mass ratio of the PVA to the aforementioned polyol is not particularly limited, but the thermal stability is further improved from the viewpoint of molding processing at a low temperature, and the adhesion of the adherend to the inside of the extruder is further suppressed during molding. In terms of quality, the quality of both is better (PVA quality) / (mass of polyol) = 30/70~90/10, better than 35/65~85/15, especially for 40/ 60~80/20, especially good for 45/55~80/20, best for 50/50~80/20.

[zinc compound]

The method of containing the zinc compound contained in the halogen atom-containing resin composition of the present invention in the halogen atom-containing resin is not particularly limited, and is preferably a monomer for forming a resin containing a halogen atom. After the polymerization, it is added to the obtained halogen atom-containing resin and contained. The zinc compound may be a powder, or dissolved or dispersed in water or an organic solvent, and added to a resin containing a halogen atom.

The zinc compound contained in the halogen atom-containing resin composition of the present invention may, for example, be a zinc salt of an organic acid or an inorganic zinc salt. Examples of the zinc salt of the organic acid include zinc salts of aliphatic carboxylic acids such as zinc stearate, zinc laurate, and zinc oleate, and zinc such as zinc benzoate and zinc butyl benzoate. a zinc salt of a carboxylic acid; a zinc salt of an amino acid; a zinc salt of a phosphoric acid monoester or a phosphoric acid diester; and the like. Further, examples of the inorganic zinc salt include zinc oxide and zinc carbonate. Among these, a zinc salt of an aliphatic carboxylic acid is preferred, and zinc stearate is more preferred.

The content of the zinc compound in the resin composition containing a halogen atom is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, per 100 parts by mass of the resin containing a halogen atom. When the content of the zinc compound is less than 0.01 parts by mass, a sufficient heat stabilization effect cannot be obtained, and if it exceeds 5 parts by mass, the molded article formed of the obtained halogen atom-containing resin composition is blackened.

When the PVA, the polyol, and the zinc compound are contained in the halogen atom-containing resin, the PVA, the polyol, and the zinc compound are preferably added to the halogen atom-containing resin. Thereby, the effect of the present invention is more easily achieved.

The halogen atom-containing resin composition of the present invention may contain only a halogen atom-containing resin, the PVA, the polyol, and the zinc compound. However, in addition to these components, a commonly used lubricant or stabilizer may be further contained. , plasticizer, phenolic antioxidant, phosphorus antioxidant, ultraviolet absorber, light stabilizer, antifogging agent, antistatic agent, flame retardant, modifier, strengthening agent, pigment, foaming agent, etc. Further, the resin composition containing a halogen atom of the present invention may contain other resins than the above.

In the halogen atom-containing resin composition of the present invention, the total proportion of the halogen atom-containing resin, the PVA, the polyol, and the zinc compound is preferably in the range of 50 to 100% by mass, more preferably It is in the range of 70 to 100% by mass, and particularly preferably in the range of 80 to 100% by mass.

Examples of the slip agent include hydrocarbons such as liquid paraffin, natural paraffin, microcrystalline wax, and polyethylene wax; fatty acids such as stearic acid and lauric acid; decyl stearate, decyl palmitate, and methylene double. Fatty acid decylamine such as stearylamine or ethylene bis-lipidamine; fatty acid ester of monohydric alcohol such as butyl stearate; hardened castor oil, ethylene glycol monostearate, glyceryl monostearate And a triglyceride di-2-ethylhexanoate or the like, wherein the fatty acid ester of the polyhydric alcohol has a hydroxyl group content of less than 10% by mass; an alcohol such as cetyl alcohol or stearyl alcohol; Among them, those having a hydroxyl group content in a fatty acid ester using a polyol are preferably less than 10% by mass. In this case, the compound is preferably a fatty acid monoester of a polyhydric alcohol, more preferably a fatty acid monoester of glycerin. Further, the fatty acid in the fatty acid ester of the polyhydric alcohol is preferably a carbon number of 8 to 22, more preferably stearic acid. Among the above compounds, glyceryl monostearate is particularly suitable. The content of the lubricant is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the resin containing a halogen atom.

As the above-mentioned stabilizer, a well-known person can be used, and specific examples thereof include an alkaline earth metal soap such as a calcium soap or a barium soap, an organometallic salt such as an aluminum soap or an organic phosphoric acid metal salt, a metal oxide, or a metal hydroxide. An inorganic metal salt such as an inorganic complex metal salt such as a metal carbonate or a zeolite, a bismuth chlorate, a bismuth perchlorate or a sodium chlorate, a β-diketone or an epoxy compound. Metal stabilizers, etc.

The plasticizer may, for example, be an acid such as phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid or sebacic acid, and n-propanol or isopropanol. , n-butanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, third pentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2 - linear or branched alkyl monohydric alcohols of -ethylhexanol, n-nonanol, isodecyl alcohol, n-nonanol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmitol, stearyl alcohol, etc. Or an ester formed by the mixture, or an ester plasticizer of an ester of butanediol and adipic acid; such as epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized linseed oil fatty acid butyl ester, Epoxy plasticizer of low molecular weight reaction product resin of octyl epoxy stearate, epoxy triglyceride, diisodecyl epoxide or epichlorohydrin and bisphenol A; A phosphate ester plasticizer such as decyl ester, tris(xylylene) phosphate, monobutyl bis(xylene) phosphate, or trioctyl phosphate.

The phenolic antioxidant may be any one as long as it is a usual user, and examples thereof include 2,6-di-t-butyl-p-cresol and 2,6-diphenyl-4-de. Octaoxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl)-propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) Phosphonate, thiodiglycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di Tributyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid decylamine], 4, 4'-thiobis(6-t-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylene Bis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid] glycolate, 2,2'- Ethylene bis(4,6-di-t-butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tert-butylphenol), 1,1,3-parameter (2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-t-butyl- 5-methylbenzyl)phenyl]terephthalate, 1,3,5-paran (3,5-di-t-butyl-4- Hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-gin[(3,5-di-t-butyl-4-hydroxyphenyl)propanoxyethyl]iso-tri Polycyanate, hydrazine [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-tert-butyl-4) -hydroxy-5-methylphenyl)propoxycarbonyl}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-third butyl) 4--4-hydroxy-5-methylphenyl)propionate]. The content of the phenolic antioxidant is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the resin containing a halogen atom.

The phosphorus-based antioxidant may be any of ordinary users, and examples thereof include decylphenyl phosphite and bis(2,4-di-t-butylphenyl) phosphite. , [2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, Octyl diphenyl phosphite, bis(indenyl)monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol II Phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, double (2,4,6-tri-t-butylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'- n-Butyl bis(2-tert-butyl-5-methylphenol) diphosphite, hexakis(tridecyl)-1,1,3-para (2-methyl-4-hydroxy-5- Tributylphenyl)butane triphosphite, bismuth (2,4-di-t-butylphenyl)-biphenyldiphosphinate, 9,10-dihydro-9-oxa-10- Phosphorus phenanthrene-10-oxidation And 2,2'-methylenebis(4-methyl-6-t-butylphenyl)-2-ethylhexylphosphite. The content of the phosphorus-based antioxidant is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, per 100 parts by mass of the resin containing a halogen atom.

Examples of the above ultraviolet absorber include 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, and 2-hydroxy-4-octyloxydiphenyl ketone. 2-hydroxydiphenyl ketone of 5,5'-methylenebis(2-hydroxy-4-methoxydiphenyl ketone); 2-(2-hydroxy-5-th-octylphenyl) Benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-t-butyl-5- Methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-diisopropylphenylphenyl)benzotriazole, 2,2'-methylenebis(4- 2-(octyl-6-benzotriazolyl)phenol, 2-(2-hydroxy-3-t-butyl-5-carboxyphenyl)benzotriazole, polyethylene glycol ester, etc. 2-( 2-hydroxyphenyl)benzotriazole; phenyl salicylate resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 a benzoate such as hydroxybenzoate or hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyxantanilide , 2-ethoxy-4'-dodedodecanolide, substituted oxalic acid; ethyl-α-cyano-β,β-diphenyl acrylate, methyl-2-cyano -3-methyl-3 a cyanoacrylate such as -(p-methoxyphenyl) acrylate. The content of the ultraviolet absorber is preferably 0.005 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the resin containing a halogen atom.

Examples of the above photostabilizer include 2,2,6,6-tetramethyl-4-piperidinyl stearate and 1,2,2,6,6-pentamethyl-4- Piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) Sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, hydrazine (2,2,6,6-tetramethyl-4-piperidine Butane tetracarboxylate, hydrazine (1,2,2,6,6-pentamethyl-4-piperidyl)butane tetracarboxylate, bis(1,2,2,6,6- Pentamethyl-4-piperidinyl)‧bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4 -Hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6 -bis(2,2,6,6-tetraethyl-4-piperidinylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl 4-piperidinylamino)hexane/2,4-dichloro-6- Lolinyl-s-three Polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperazinyl)hexane/2,4-dichloro-6-th-octylamino-s- three Polycondensate, 1,5,8,12-anthracene [2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)- S-three -6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-para [2,4-bis(N-butyl-N-(2,2,6,6) -tetramethyl-4-piperidinyl)amino)-s-three -6-ylamino]undecane, 1,6,11-para [2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidin) Amino)-s-three A hindered amine compound such as -6-ylamino]undecane or the like. The content of the light stilbene is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the resin containing a halogen atom.

The molding processing method of the halogen atom-containing resin composition of the present invention may be extrusion processing, calendering, blow molding, press processing, powder molding, or injection molding.

The molded article of the present invention is formed of the above-described resin composition containing a halogen atom. The shape of the molded article is not particularly limited, and examples thereof include pellets, films, sheets, tubes, straws, and various other three-dimensional molded articles.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. In the following examples and comparative examples, the parts and % each represent a part by mass and a mass%, unless otherwise specified.

[Analysis method of PVA]

The analysis of PVA was carried out in accordance with the method described in JIS K6726 unless otherwise specified.

[Example 1] (Manufacture of polyvinyl chloride)

The polyvinyl alcohol having a polymerization degree of 850 and a saponification degree of 72 mol% was dissolved in deionized water in an amount equivalent to 600 ppm with respect to vinyl chloride to prepare a dispersion stabilizer. The dispersion stabilizer thus obtained was placed in a glass-lined autoclave coated with a scale adhesion preventing agent NOXOL WSW (manufactured by CIRS) at a solid content of 0.3 g/m ² . Next, 0.04 part of a 70% toluene solution of diisopropylperoxydicarbonate was placed in a glass-lined autoclave, and the mixture was evacuated until the pressure in the autoclave became 0.0067 MPa, and then oxygen was removed, and 30 parts of chlorine was introduced. Ethylene, the contents of the autoclave were heated to 57 ° C, and polymerization was started with stirring. The pressure in the autoclave at the start of the polymerization was 0.83 MPa. After the initiation of the polymerization, the polymerization was stopped after the pressure in the autoclave became 0.44 MPa, and the unreacted vinyl chloride was removed. Then, the polymerization reaction product was taken out and dried at 65 ° C overnight to obtain polyvinyl chloride ( PVC).

(Manufacture of PVA)

900 g of vinyl acetate and 2,100 g of methanol were placed in a 6 L reaction vessel equipped with a stirrer, a nitrogen inlet, an additive inlet, and an initiator addition port, and the temperature was raised to 60 ° C, and then bubbling with nitrogen for 30 minutes was carried out in the system. Nitrogen replacement. The internal temperature of the above reaction vessel was adjusted to 60 ° C, and 2.3 g of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) was added to initiate polymerization. The polymerization temperature was maintained at 60 ° C during the polymerization, and when the polymerization rate reached 70% after 5 hours, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed under reduced pressure to obtain a methanol solution of polyvinyl acetate (PVAc). In a PVAc solution adjusted to a concentration of 30%, a NaOH methanol solution (10% concentration) was added in such a manner that the alkali molar ratio (the number of moles of NaOH/the number of moles of vinyl ester units in PVAc) was 0.006. Saponification is carried out. The obtained PVA was washed with methanol. By the above operation, a PVA having a degree of polymerization 320 and a degree of saponification of 80 mol% was obtained.

(Manufacture of polyvinyl chloride composition and molded article (sheet) formed therefrom)

100 parts of the above-obtained polyvinyl chloride, 0.75 parts of the above-obtained PVA, 0.25 parts of commercially available sorbitol, 1 part of commercially available zinc stearate, and 0.5 part of each were added to a porcelain beaker. Commercially available calcium stearate is mixed to obtain a polyvinyl chloride composition.

The obtained polyvinyl chloride composition was kneaded at 160 ° C for 5 minutes by a test roll to prepare a sheet having a thickness of 0.45 mm.

(thermal stability test)

The sheet was cut into 50 × 70 mm, and the obtained sheet was placed in a Geer oven, and the time (blackening time) until it completely turned black at a temperature of 180 ° C was measured, and it was used as an index of thermal stability. The evaluation results are shown in Table 1.

(Coloring test)

The sheet was cut into a plurality of sheets of 45×30 mm, and 12 to 14 sheets of the sheet were laminated, and pressed at 185 ° C for 5 minutes to prepare a test piece having a thickness of 5 mm, and the coloring property was compared by visual observation, and the following criteria were used. determination. The evaluation results are shown in Table 1.

A: There is almost no coloration.

B: I saw the coloring slightly.

C: yellow.

D: yellowish brown.

(Adhesion of adhesions is evaluated)

In order to evaluate the degree of adhesion of the adhesive to the inside of the extruder or the like during the kneading of the polyvinyl chloride composition, the surface of the test roll used in the kneading of the polyvinyl chloride composition was visually observed. The following criteria were used to determine the degree of adhesion of the adhesive to the surface of the test roll. The evaluation results are shown in Table 1.

A: There is no attachment at all.

B: I saw the attachment slightly.

C: I saw a lot of adhesion.

[Examples 2 to 8]

In the same manner as in Example 1, except that the content of the polyol used, the PVA, the polyol, and the zinc stearate were changed as shown in Table 1, a sheet was formed in the same manner as in Example 1. Then, in the same manner as in Example 1, the thermal stability test, the coloring property test, and the adhesion of the adherend were evaluated. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 14]

In the same manner as in Example 1, except that the content of the polyol used, the PVA, the polyol, and the zinc stearate were changed as shown in Table 1, a sheet was formed in the same manner as in Example 1. Then, in the same manner as in Example 1, the thermal stability test, the coloring property test, and the adhesion of the adherend were evaluated. The evaluation results are shown in Table 1.

In Examples 1 to 8, PVA having a degree of saponification of 80 mol% and a degree of polymerization of 320, and sorbitol, diglycerin, polyglycerol (polymer of 10 or 20 glycerol) as a polyol were shown. Or the evaluation result of the polyvinyl chloride composition of dipentaerythritol. The polyvinyl chloride composition has sufficient thermal stability and the adhesion of the adhesive to the surface of the test roll is small. Further, each of the sheets obtained by molding the polyvinyl chloride composition has less coloration.

On the other hand, in Comparative Examples 1 and 2, the evaluation results of the polyvinyl chloride composition containing no polyol were shown. When the polyol is not contained, the blackening time is short and the thermal stability is insufficient.

Comparative Example 3 shows the results of evaluation of a polyvinyl chloride composition containing 1 part of sorbitol as a polyol, which does not contain PVA. When PVA was not contained, the blackening time was short and the thermal stability was insufficient, the flakes were colored yellow, and a large amount of adhesion of the adhesive to the surface of the test roll was also observed.

Comparative Example 4 shows the results of evaluation of a polyvinyl chloride composition containing 3 parts of PVA and 1 part of sorbitol as a polyol. If 3 parts of PVA is contained, the blackening time is very long, but the flakes are colored yellow.

Comparative Example 5 shows the results of evaluation of a polyvinyl chloride composition containing 1 part of PVA and 3 parts of sorbitol as a polyol. If 3 parts of the polyol is contained, the blackening time is very long, but the flakes are colored yellowish brown, and a large amount of adhesive adheres to the surface of the test roll.

Comparative Example 6 shows the results of evaluation of a polyvinyl chloride composition containing 0.005 parts of PVA and 1 part of sorbitol as a polyol. When the PVA was 0.005 parts, the blackening time was short and the thermal stability was insufficient, the flakes were colored yellow, and a large amount of adhesion of the adhesive to the surface of the test roll was also observed.

Comparative Example 7 shows the results of evaluation of a polyvinyl chloride composition containing 1 part of PVA and 0.005 part of sorbitol as a polyol. When the sorbitol is 0.005 parts, the blackening time is short and the thermal stability is insufficient.

Comparative Examples 8 to 10 show polyvinyl chloride containing no polyphenol (Comparative Example 8), polyglycerol (10-mer of glycerin, Comparative Example 9) or dipentaerythritol (Comparative Example 10) without containing PVA. The evaluation result of the composition. When PVA is not contained, the blackening time is short and the thermal stability is insufficient.

Comparative Example 11 shows the results of evaluation of a polyvinyl chloride composition containing 1 part of PVA and 1 part of glycerol monostearate as a polyol. The glycerol monostearate-based hydroxyl group content was 9% by mass. As described above, when the hydroxyl group content of the polyol is low, the blackening time is short and the thermal stability is insufficient.

Comparative Example 12 shows the results of evaluation of a polyvinyl chloride composition containing 1 part of PVA and 1 part of polyglycerol (about 50 mer of glycerin) as a polyol. Polyglycerol (about 50 mers of glycerol) has a molecular weight of about 3,700. As described above, when the molecular weight of the polyol is large, the blackening time is short and the thermal stability is insufficient.

Comparative Example 13 shows the results of evaluation of a polyvinyl chloride composition containing 0.75 parts of PVA, 0.25 parts of sorbitol as a polyol, and 0.005 parts of zinc stearate. When the content of zinc stearate is 0.005 parts, the blackening time is short and the thermal stability is insufficient.

Comparative Example 14 shows the results of evaluation of a polyvinyl chloride composition containing 0.75 parts of PVA, 0.25 parts of sorbitol as a polyol, and 10 parts of zinc stearate. When the content of zinc stearate is 10 parts, the blackening time is short and the thermal stability is insufficient.

[Comparative Example 15]

In the same manner as in Example 1, the PVA shown in Table 1 was obtained in the same manner as in Example 1 except that the base molar ratio was changed from 0.006 to 0.003 in the saponification at the time of production of PVA. Using this PVA, a polyvinyl chloride composition was obtained in the same manner as in Example 1, and a sheet was formed in the same manner as in Example 1. Then, in the same manner as in Example 1, the thermal stability test, the coloring property test, and the adhesion of the adherend were evaluated. The evaluation results are shown in Table 1.

Comparative Example 15 shows the results of evaluation of a polyvinyl chloride composition containing PVA having a degree of saponification of 55 mol% and a degree of polymerization of 320 and sorbitol as a polyol. When the degree of saponification of PVA is 55 mol%, the blackening time is short and the thermal stability is insufficient.

As shown in the above examples, when the halogen atom-containing resin composition of the present invention is used, since it has sufficient thermal stability even when molded at a relatively low temperature, a suitable molding temperature range is wide. Further, it is also possible to suppress the adhesion of the adherend to the inside of the extruder or the like during molding, and it is possible to obtain a molded article having little coloration, which is very significant.

Claims (5)

A resin composition containing a halogen atom, which comprises: polyvinyl alcohol 0.01 to 2.5 having a degree of saponification of 60 to 99.9 mol% and an average degree of polymerization of a viscosity of 100 to 450 with respect to 100 parts by mass of the resin containing a halogen atom. a mass fraction of 0.01 to 2.5 parts by mass of a polyol having a molecular weight of 2,000 or less and a hydroxyl group content of 10% by mass or more, and 0.01 to 5 parts by mass of a zinc compound; the polyol is a repeating number of sorbitol, diglycerin, and glycerin units It is 3 or more of polyglycerin or dipentaerythritol. The resin composition containing a halogen atom according to Item 1 of the patent application, wherein the mass ratio of the polyvinyl alcohol to the polyol satisfies (the mass of the polyvinyl alcohol) / (the mass of the polyol) = 30/70 to 90/10 . A resin composition containing a halogen atom according to claim 1 or 2, which is contained by adding a polyvinyl alcohol, a polyhydric alcohol, and a zinc compound to a resin containing a halogen atom. A method for producing a resin composition containing a halogen atom, which comprises, for 100 parts by mass of a resin containing a halogen atom, a polyvinyl alcohol having a degree of saponification of 60 to 99.9 mol% and an average degree of polymerization of a viscosity of 100 to 450 of 0.01 to 2.5. a step of 0.01 to 2.5 parts by mass of a polyol having a molecular weight of 2,000 or less and a hydroxyl group content of 10% by mass or more, and 0.01 to 5 parts by mass of a zinc compound; the polyol is sorbitol, diglycerin, or glycerin unit The number of repeats is 3 or more of polyglycerol or dipentaerythritol. A molded article formed of a resin composition containing a halogen atom as in the first or second aspect of the patent application.