JP2016089101A - Vinyl chloride resin composition for tap water contact and hose and flexible pool using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition with less odor by blending phosphite compounds having a specific structure, and a hose and a flexible pool using the same.SOLUTION: There is provided a vinyl chloride resin composition containing 100 pts.mass of (A) a vinyl chloride resin and 0.01 to 10 pts.mass of (B) phosphite. The (B) phosphite is preferably manufactured from phosphorus trichloride as a raw material, and phenol is preferably 0.1 mass% or less based on the (B) phosphite as impurity in the (B) phosphite.SELECTED DRAWING: None

Description

  The present invention relates to a vinyl chloride resin composition for contact with tap water (hereinafter also simply referred to as “resin composition”), a hose and a flexible pool using the composition, and more particularly, a phosphite having a specific structure. TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition for contacting tap water with little odor, which is formulated with a compound, a hose and a flexible pool using the same.

  Molded articles using a vinyl chloride resin composition are used in a wide variety of fields because of their economical efficiency. Among them, hoses, flexible pools, home outdoor baths, emergency water storage tanks, agricultural sheets, and the like are one of the typical applications that come into contact with tap water. Since the vinyl chloride resin is a halogen-containing resin, the resin itself has a drawback that it tends to deteriorate during processing and molding. In order to compensate for this, it is necessary to add a large number of additives. However, in the case of hose and flexible pool use, these additives are eluted, and the water passing through the hose and the water of the flexible pool often used for children are said to smell. There was a problem.

  For such a problem, for example, Patent Document 1 discloses that a vinyl chloride molded product having no odor can be obtained by adding only hydrotalcite to a vinyl chloride resin. Further, in Patent Document 2, a hose having good heat distortion resistance and excellent hygiene and water resistance can be obtained by adding a plasticizer and a stabilizer to a gel-containing vinyl chloride resin. Is disclosed. Furthermore, in Patent Document 3, by adding a plasticizer, an alkaline earth metal salt or hydrotalcite to a vinyl chloride resin, the heat resistance and weather resistance of the hose are improved, and the odor during water passage It is disclosed that this problem can be remarkably improved.

JP 2004-323734 A Japanese Patent Laid-Open No. 10-084844 JP-A-10-330567

  However, the formulation disclosed in Patent Document 1 is only the addition of hydrotalcite, and prevents odor by adsorbing volatile organic solvent by adding hydrotalcite while suppressing thermal decomposition of vinyl chloride polymer. To do. Therefore, the addition of hydrotalcite alone is inferior in plasticity, thermal stability, and color resistance at the time of forming into a hose or flexible pool, or at the time of processing in the previous stage, and processing and molding itself are difficult. Yes, performance other than odor will be significantly inferior. In addition, since the odor cannot be improved without using a special vinyl chloride resin in the formulation disclosed in Patent Document 2, there is still a problem in terms of cost. Further, in the formulation disclosed in Patent Document 3 It was still insufficient as an improvement in odor.

  Then, the objective of this invention is providing the hose and flexible pool using the vinyl chloride resin composition for tap water contact with few odors.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by blending a phosphite compound having a specific structure into a vinyl chloride resin. The invention has been completed.

  That is, the tap water contact vinyl chloride resin composition of the present invention is characterized in that 0.01 to 10 parts by mass of (B) phosphite is contained with respect to 100 parts by mass of (A) vinyl chloride resin. Is.

（式（１）中、Ｒは置換または無置換の炭素数８〜１６のアルキル基を表す。）で表されるトリアルキルホスファイトであることが好ましい。さらにまた、本発明の樹脂組成物においては、前記一般式（１）で表されるトリアルキルホスファイトのアルキル基は、炭素数８〜１６の分岐のアルキル基であることが好ましい。また、本発明の樹脂組成物においては、前記一般式（１）で表されるトリアルキルホスファイトは、トリ（２−エチルヘキシル）ホスファイト、トリ（イソノニル）ホスファイト、トリ（イソデシル）ホスファイト、トリ（イソウンデシル）ホスファイトおよびトリ（イソドデシル）ホスファイトからなる群から選ばれるいずれか１つ以上であることが好ましい。本発明の樹脂組成物においては、さらに、酸化防止剤、可塑剤、金属系安定剤、β-ジケトン化合物、ハイドロタルサイト、紫外線吸収剤およびヒンダードアミン系光安定剤からなる群から選択される１種または２種以上が含有されてなることが好ましい。 In the resin composition of the present invention, the (B) phosphite is preferably produced using phosphorus trichloride as a raw material. Moreover, in the resin composition of this invention, it is preferable that a phenol is 0.1 mass% or less with respect to (B) phosphite as an impurity in said (B) phosphite. Furthermore, in the resin composition of the present invention, the (B) phosphite has the following general formula (1),

(In the formula (1), R represents a substituted or unsubstituted alkyl group having 8 to 16 carbon atoms) and is preferably a trialkyl phosphite. Furthermore, in the resin composition of the present invention, the alkyl group of the trialkyl phosphite represented by the general formula (1) is preferably a branched alkyl group having 8 to 16 carbon atoms. In the resin composition of the present invention, the trialkyl phosphite represented by the general formula (1) is tri (2-ethylhexyl) phosphite, tri (isononyl) phosphite, tri (isodecyl) phosphite, It is preferably any one or more selected from the group consisting of tri (isoundecyl) phosphite and tri (isododecyl) phosphite. In the resin composition of the present invention, one kind further selected from the group consisting of an antioxidant, a plasticizer, a metal stabilizer, a β-diketone compound, a hydrotalcite, an ultraviolet absorber, and a hindered amine light stabilizer. Or it is preferable that 2 or more types are contained.

  Moreover, the hose of the present invention is characterized in that the vinyl chloride resin composition for contacting tap water of the present invention is molded.

  Furthermore, the flexible pool of the present invention is characterized in that the vinyl chloride resin composition for contacting tap water of the present invention is formed.

  ADVANTAGE OF THE INVENTION According to this invention, the vinyl chloride resin composition for tap water contact with few odors, a hose using this, and a flexible pool can be provided.

Hereinafter, the present invention will be described in detail.
The vinyl chloride resin composition for contact with tap water of the present invention comprises (B) phosphite (hereinafter referred to as “(B)” with respect to 100 parts by mass of (A) vinyl chloride resin (hereinafter also referred to as “component (A)”). It is also referred to as “component”) 0.01 to 10 parts by mass. With such a composition, even if the molded article of the vinyl chloride resin composition comes into contact with water, the substance causing the odor does not elute into the water, and the odor can be prevented. Hereinafter, each component according to the resin composition of the present invention will be described in detail.

<(A) Vinyl chloride resin>
In the resin composition of the present invention, the component (A) is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride -Chlorine-containing resins such as maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their blends or their Chlorine-containing resins and other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene terpolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers Examples thereof include blends, blends with polyesters, block copolymers, graft copolymers, and the like. In the resin composition of this invention, (A) component may be used independently and may use 2 or more types together.

<(B) Phosphite>
In the resin composition of the present invention, the raw material of the component (B) is not particularly limited. For example, red phosphorus, yellow phosphorus, phosphorus trichloride, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triphenyl Phosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenyl phosphite, trimethyl phosphinate, triethyl phosphinate, tripropyl phosphinate, tributyl phosphinate, dimethyl methyl phosphonate, dimethyl ethyl phosphonate, trimethyl Examples include phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, and trimethylphosphine oxide. Methylphosphine, triphenylphosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenyl phosphite are preferred, phosphorus trichloride, triethyl phosphite, triphenyl phosphite are more preferred, phosphorus trichloride Triethyl phosphite is more preferred.

  In the component (B) used in the present invention, from the viewpoint of safety, phenol is preferably 0.1% by mass or less with respect to (B) phosphite as an impurity, and 0.05% by mass. The following is more preferable, 0.01% by mass or less is further preferable, and substantially 0% by mass is most preferable.

In the resin composition of the present invention, the component (B) is preferably a trialkyl phosphite represented by the following general formula (1). Here, in formula (1), R represents a substituted or unsubstituted alkyl group having 8 to 16 carbon atoms.

  Examples of the alkyl group having 8 to 16 carbon atoms include octyl group, isooctyl group (2-ethylhexyl group), nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, Examples thereof include an isotridecyl group, a tetradecyl group, an isotetradecyl group, a pentadecyl group, an isopentadecyl group, a hexadecyl group, and an isohexadecyl group.

  Among these, a branched alkyl group having 8 to 16 carbon atoms is preferable, a branched alkyl group having 8 to 14 carbon atoms is more preferable, and a branched alkyl group having 8 to 13 carbon atoms is preferable for thermal stability, workability, Most preferable from the viewpoint of coloring resistance, compatibility with resins, and odor improving properties. With branched alkyl groups having 7 or less carbon atoms, the (B) trialkyl phosphite represented by the general formula (1) sufficiently exhibits the effects of thermal stability, processability, color resistance, and odor improving properties. When the number of carbon atoms is 17 or more, the effects of thermal stability, processability, coloration resistance, compatibility with resins, and odor improving properties may not be sufficiently exhibited.

  Substituents include halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl Acyl groups such as acetyloxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl , Cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino Diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonyl Amino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylamino Substituted amino groups such as sulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; Hon'amido group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imido group, a carbamoyl group, a sulfonamido group and the like, these groups may be further substituted. Moreover, the carboxyl group and the sulfo group may form a salt.

  In the resin composition of the present invention, among the trialkyl phosphites represented by the general formula (1), tri (2-ethylhexyl) phosphite, tri (isononyl) phosphite, tri (isodecyl) phosphite, tri (Isoundecyl) phosphite and tri (isododecyl) phosphite are more preferable.

  The content of the component (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) vinyl chloride resin, from the viewpoint of improvement in thermal stability, processability, color resistance, and odor. 0.01-8 mass parts is preferable, 0.01-5 mass parts is more preferable, 0.01-3 mass parts is further more preferable, 0.01-1 mass part is especially preferable. If the content is less than 0.01 parts by mass, the thermal stability, coloring resistance, and odor may not be sufficiently improved. If the content exceeds 10 parts by mass, the thermal stability, workability, and odor improvement are reduced. There is a case. In the resin composition of this invention, (B) component may be used independently and may use 2 or more types together.

  The method for producing the component (B) used in the present invention is described in Organic Synthesis. Although it can manufacture by the well-known method of 1951,31,111 grade | etc., It is not specifically limited, For example, the method using a chloride, transesterification, etc. are mentioned. For example, it can be suitably produced by a direct esterification reaction in which phosphorus trichloride is reacted with an alcohol or a transesterification reaction between triphenyl phosphite and an alcohol. In the production, the raw materials can be charged all at once. However, when chloride is used, it is preferable from the viewpoint of reactivity to add phosphorus trichloride dropwise. Although reaction temperature is not specifically limited, 30-80 degreeC is preferable and 40 degreeC-70 degreeC is especially preferable. When chloride is used, the generated hydrogen chloride may be discharged out of the system, and it is used for neutralization and washing steps with hydroxides such as potassium hydroxide and sodium hydroxide, and amine compounds such as triethylamine and diethylphenylamine. May be processed.

  In the resin composition of the present invention, one or two selected from the group consisting of an antioxidant, a plasticizer, a metal stabilizer, a β-diketone compound, a hydrotalcite, an ultraviolet absorber, and a hindered amine light stabilizer. More than one species may be contained.

  In the resin composition of the present invention, examples of the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant. Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5- Ditertiary butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tertiarybutyl-m-cresol), 2-octylthio-4,6-di (3,5-ditertiarybutyl- 4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bi (4-Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,1-butylidenebis (2-methyl-4-hydroxy-5-tert-butylphenyl), 4,4′-butylidenebis (4 6-ditert-butylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3) -Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3 5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl ) Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy) -3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy} -1,1- Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionate] and the like.

  Preferably, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,1-butylidenebis (2-methyl-4-hydroxy-5-tert-butylphenyl), stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis [ 2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy} -1,1-dimethylethyl] -2,4,8 10-tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, and 1,1 -Butylidenebis (2-methyl-4-hydroxy-5-tert-butylphenyl), stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-ditert. Tributyl-4-hydroxyphenyl) propionate] methane is more preferred.

  Content of a phenolic antioxidant is 0.01-1 mass part with respect to 100 mass parts of (A) vinyl chloride resin, 0.01-0.8 mass part is preferable, 0.01-0 0.7 parts by mass is more preferable, and 0.01 to 0.5 parts by mass is still more preferable. If the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. If the content exceeds 1 part by mass, compatibility with the resin and product aesthetics may be impaired.

  Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic acid esters. Preferably, ditridecylthiodipropionate and pentaerythritol tetrakis (3-dodecylthiopropionate) are used.

  Content of sulfur type antioxidant is 0.01-1 mass part with respect to 100 mass parts of (A) vinyl chloride resin, 0.01-0.8 mass part is preferable, 0.01-0 0.7 parts by mass is more preferable, and 0.01 to 0.5 parts by mass is still more preferable. If the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. If the content exceeds 1 part by mass, compatibility with the resin and product aesthetics may be impaired. These phenol-based antioxidants and sulfur-based antioxidants may be used alone or in combination of two or more.

  Examples of the plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like; dioctyl adipate , Diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate and other adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl Phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate Phosphate plasticizers of ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, trimethylolpropane And dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid And a polyester plasticizer using monovalent alcohol, monocarboxylic acid (acetic acid, aromatic acid, etc.) as a stopper as needed; epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxy Epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized saff Wer oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearic acid stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxy Epoxy linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexylmethyl, epoxycyclohexanecarboxylate, etc., other tetrahydrophthalic acid plastics Agent, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biff Examples include enylene polycarboxylic acid plasticizers, aromatic acid ester plasticizers of polyhydric alcohols (such as tribenzoate of trimethylolpropane), and the like.

  Preferably, a phthalate plasticizer, an adipate plasticizer, a sebacic acid plasticizer, an epoxy plasticizer, and an aromatic acid ester plasticizer of a polyhydric alcohol are used. The content of the plasticizer is 10 to 90 parts by mass with respect to 100 parts by mass of the (A) vinyl chloride resin, and is preferably 10 to 85 parts by mass from the viewpoint of processability, handleability, product aesthetics, strength, and the like. 10-80 mass parts is more preferable, 20-80 mass parts is further more preferable, and 30-80 mass parts is still more preferable. If the content is less than 10 parts by mass, the processability may be insufficient, and if it exceeds 90 parts by mass, the handleability and strength may be inferior, or the product aesthetics may be impaired. These plasticizers may be used alone or in combination of two or more.

  Examples of the metal stabilizer include organic acid metal salts, and examples of the organic acid component of the organic acid metal salt include carboxylic acids, organic phosphoric acids, and phenols.

  Examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, octylic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12- Hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acid, coconut oil A mixture of the above naturally occurring acids such as fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-tert-octylsa Chill acid, naphthenic acid, and cyclohexane carboxylic acid. Among these, octylic acid, 2-ethylhexylic acid, neodecanoic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid, and benzoic acid are preferable.

  Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like. It is done.

  Examples of phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, and dodecylphenol.

  As the metal component of the organic acid metal salt, lithium (Li), sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), strontium (Sr), zinc (Zn), cesium (Cs), Examples include tin (Sn), barium (Ba), and aluminum (Al). Among these, Mg, Ca and Zn are preferable. The organic acid metal salt, which is a salt of the organic acid component and the metal component, can form a normal salt, an acidic salt, a basic salt, or an overbased salt by the combination thereof. You may use, and may use 2 or more types together. From the point of high compatibility with the resin and the stabilizing effect, stearic acid metal salt, lauric acid metal salt, oleic acid metal salt, ricinoleic acid metal salt, neodecanoic acid metal salt, 2-ethylhexylic acid metal salt, A benzoic acid metal salt is preferable, and the metal is preferably Ca, Zn or Mg.

  0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a metal type stabilizer, 0.01-8 mass parts is more preferable, and 0.01-5 mass parts is further. Preferably, 0.01-3 mass parts is especially preferable, and 0.01-1 mass part is the most preferable. If the content is less than 0.01 parts by mass, the thermal stability, workability, and color resistance may be insufficient. If the content exceeds 10 parts by mass, the thermal stability and color resistance may be reduced. . These metal stabilizers may be used alone or in combination of two or more.

  Examples of the β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylmethane, dicyclohexylcarbonylmethane, and benzoyl. Formylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, stearoylbenzoylmethane, bis (4-octylbenzoyl) methane, benzoyldiacetylmethane, 4-methoxybenzoylmethane, bis (4-carboxymethylbenzoyl) methane, 2- Carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, 3,6-dimethyl-2,4-di Carboxymethyl cyclohexane -1-carboxylate, 2-acetyl cyclohexanone, dimedone, 2-benzoyl-cyclohexane, and the like. Preferred examples include phenylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, stearoylbenzoylmethane, bis (4-octylbenzoyl) methane, and dibenzoylmethane, octylbenzoylmethane. Stearoylbenzoylmethane is more preferred.

  In the resin composition of the present invention, metal salts of these β-diketone compounds can also be used. Examples of the metal species that can provide the β-diketone metal salt include Li, Na, and K, Mg, Ca, Sr, Zn, Al, and the like. The content of the β-diketone compound is preferably 0.01-5 parts by mass, more preferably 0.01-4 parts by mass, and further 0.01-3 parts by mass with respect to 100 parts by mass of the component (A). Preferably, 0.01-2 mass parts is especially preferable. When the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content exceeds 5 parts by mass, compatibility with the resin, coloring resistance, and product aesthetics may be impaired. These β-diketone compounds may be used alone or in combination of two or more.

The hydrotalcite is, for example, a composite salt compound composed of Mg and / or alkali metal and aluminum or Zn, Mg and Al, as represented by the following general formula (2), and is obtained by dehydrating crystal water. There may be.
_{M x Mg y Al z CO 3} (OH) xp + 2y + 3z-2 · nH 2 O (2)
(Wherein M is an alkali metal or Zn, x is a number from 0 to 6, y is a number from 0 to 6, z is a number from 0.1 to 4, p is a valence of M, n Represents the number of water of crystallization from 0 to 100).

  The content of the hydrotalcite compound is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and further preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the component (A). Preferably, 0.01-2 mass parts is especially preferable. When the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content exceeds 5 parts by mass, compatibility with the resin, coloring resistance, and product aesthetics may be impaired. These hydrotalcites may be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2- 2-hydroxybenzophenones such as methacryloyloxyethoxyethoxy) benzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl- 5-methylphenyl) -5-chlorobenzotriazole, 2- 2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3) , 5-Dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-tri Gin, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxyethoxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (2- (2-ethylhexanoyloxy) ethyloxy) phenyl)- 4,6-diphenyl-1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2 2- (2-hydroxyphenyl) -1,3,5-triazines such as -hydroxy-3-methyl-4- (2-octanoyloxyethyl) phenyl) -1,3,5-triazine; Sylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4 -Benzoates such as hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substitution of 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide and the like Oxanilides; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, tetrakis (α-cyano-β, β-diphenylacryloyloxymethyl) ) Cyanoacrylates such as methane.

  0.01-5 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a ultraviolet absorber, 0.01-3 mass parts is more preferable, 0.01-2 mass parts is more preferable. 0.01 to 1 part by mass is particularly preferable. When the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content exceeds 5 parts by mass, compatibility with the resin, coloring resistance, and product aesthetics may be impaired. These ultraviolet absorbers may be used alone or in combination of two or more.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6 6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6 Ruphorino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine heavy Condensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 Yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl- 4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2 , 2,6,6-tetramethyl-4-piperidyl) amino-s-tria Gin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine -6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl] ) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine-4- Le) carbonate.

  The content of the hindered amine light stabilizer is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and 0.01 to 2 parts by mass with respect to 100 parts by mass of the component (A). More preferably, 0.01-1 mass part is especially preferable. When the content is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content exceeds 5 parts by mass, compatibility with the resin, coloring resistance, and product aesthetics may be impaired. These hindered amine light stabilizers may be used alone or in combination of two or more.

  The vinyl chloride resin composition for contacting tap water according to the present invention may further contain various additives such as zeolite compounds, polyols, and other inorganic compounds.

  The zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and typical examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Sites, sodalite aluminosilicates, clinobutyrolite, erionite, chabazite, etc., and water containing zeolitic water of these zeolite compounds (so-called zeolitic water) or anhydrous water except for crystallization water Any of the objects can be used. Although content of a zeolite compound can be mix | blended in the range which does not impair the effect of this invention, 0.01-5 mass parts is preferable.

  Examples of polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, glycerin, tris ( 2-hydroxyethyl) isocyanurate, sorbitol, mannitol, lactitol, trehalose and the like. Although content of polyol can be mix | blended in the range which does not impair the effect of this invention, 0.01-2 mass parts is preferable.

  Examples of other inorganic compounds include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like. Although content of another inorganic compound can be mix | blended in the range which does not impair the effect of this invention, 0.01-2 mass parts is preferable.

  In addition, the present invention further includes other additives as required, for example, fillers, colorants, crosslinking agents, antistatic agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, A glaze, a disinfectant, a metal deactivator, a release agent, a pigment, a processing aid, a light stabilizer other than a hindered amine, a foaming agent, and the like can be blended within a range that does not impair the effects of the present invention.

  The vinyl chloride resin composition for contact with tap water of the present invention can be prepared by a known production method. As the method for adjusting the vinyl chloride resin composition for contacting tap water of the present invention, the component (A), the component (B), and, if desired, an antioxidant, a plasticizer, a metal stabilizer, β-diketone One type or two or more types selected from the group consisting of compounds, hydrotalcite, UV absorbers and hindered amine light stabilizers, V-type blenders, ribbon blenders, Henschel mixers, rocking mixers, tumbler mixers, planetary A method of mixing with a mixer such as a mixer, a method of kneading with a kneader such as an extruder, mixing roll, Banbury mixer, mill mixer, kneader, or a combination of a mixer and a kneader, and mixing and kneading them. Methods and the like.

  The use of the polyvinyl chloride resin composition for contact with tap water of the present invention is not particularly limited, but it is preferably used for hoses, flexible pools, home outdoor baths, simple water storage tanks in emergency, agricultural sheets, etc. A flexible pool is more preferred, and a hose is even more preferred.

Next, the hose and flexible pool of the present invention will be described.
The hose and flexible pool of the present invention are formed by molding the vinyl chloride resin composition for contacting tap water of the present invention. The hose and flexible pool of the present invention are obtained after the resin composition of the present invention is formed into a hose by a known production method, for example, an extruder, or a sheet is formed by a T-die method or an inflation method. It can be molded into a flexible pool. The structure of the hose or sheet thus obtained, the thickness of the hose or sheet, etc. are arbitrarily set depending on the purpose of use, but from the viewpoint of the flexibility, flexibility, and odor improvement of the molded product, the thickness is 0.01-20 mm is preferable, and 0.01-15 mm is more preferable from the point of the odor improvement property of the water which contacts a molded article, and the odor improvement property from the molded article.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

<Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-6>
For the following formulation 1, the formulations described in Tables 1 and 2 below were dried up at 100 ° C. for 1 hour, and then kneaded with a lab plast mill under conditions of 140 ° C. × 50 rpm × 5 minutes. Thereafter, pressing was performed at 140 ° C. for 3 minutes to prepare a 2 mm thick sheet. In addition, the unit of the compounding quantity in a table | surface is a mass part.

<Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-6>
For the following formulation 2, the formulations described in Tables 3 and 4 below were dried up at 100 ° C. for 1 hour, and then kneaded in a lab plast mill under conditions of 140 ° C. × 50 rpm × 5 minutes. Thereafter, pressing was performed at 140 ° C. for 3 minutes to prepare a 2 mm thick sheet. In addition, the unit of the compounding quantity in a table | surface is a mass part.

<Odor evaluation>
30 g of the obtained sheet was weighed and completely immersed in a hypochlorous acid aqueous solution, and the odor over time at room temperature was 1 (no odor), 2 (almost no odor), 3 (with odor), 4 ( The odor was strong), and the evaluation was based on the numerical value of 5 (odor). The results are also shown in Tables 1-4.

<Evaluation of coloring resistance>
Color resistance (YI: Yellowness Index) was evaluated using the obtained sheet. In addition, it is a grade which is satisfactory if coloring resistance is 6.0 or less. The results are also shown in Tables 1-4.

<Formulation-1>
Polyvinyl chloride resin (degree of polymerization 1000) 100 parts by mass Phosphite See Tables 1 and 2 below Stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate
0.05 parts by mass Di-isononyl phthalate 70 parts by mass Epoxidized soybean oil 3 parts by mass Zinc oleate 0.45 parts by mass Barium oleate 0.55 parts by mass Dibenzoylmethane 0.05 parts by mass

＊１：トリ（２−エチルヘキシル）ホスファイト
＊２：トリ（イソデシル）ホスファイト
＊３：トリ（イソドデシル）ホスファイト
＊４：トリ（イソトリデシル）ホスファイト
比較化合物５

* 1: Tri (2-ethylhexyl) phosphite * 2: Tri (isodecyl) phosphite * 3: Tri (isododecyl) phosphite * 4: Tri (isotridecyl) phosphite Comparative compound 5

比較化合物１

比較化合物２

比較化合物３

比較化合物４

Comparative compound 1

Comparative compound 2

Comparative compound 3

Comparative compound 4

<Formulation-2>
Polyvinyl chloride resin (degree of polymerization 1000) 100 parts by weight Phosphite See Tables 3 and 4 below Di-isononyl phthalate 70 parts by weight Epoxidized soybean oil 3 parts by weight ADK STAB SP-2015 (manufactured by ADEKA Corporation, metal-based stabilizer) 1.5 parts by mass ADK STAB 1413 (light stabilizer made by ADEKA) 0.3 parts by mass ADK STAB LA-63P (light stabilizer made by ADEKA) 0.3 part by mass

  As shown in Comparative Examples 1-2 to 1-6 and 2-2 to 2-6 in Tables 1 to 4 above, when Comparative Compounds 1 to 5 are added, the odor tends to increase with time. became. Further, as shown in Comparative Examples 1-1 and 2-1, it was also found that the coloring resistance is remarkably lowered although there is no odor when the phosphite is not added. On the other hand, as shown in Examples 1-1 to 1-4 and 2-1 to 2-4, by using the trialkyl phosphite of the present invention, no odor is generated over time, and further, coloring resistance It became clear that the effect was excellent also in sex.

  Further, as shown in Examples 1-5 and 2-5, the odor is suppressed and the coloring resistance is reduced in the formulation of 0.1% or less with respect to the phosphite as an impurity in the trialkyl phosphite of the present invention. It became clear that the property was also good. That is, it has been clarified that the resin composition of the present invention and its molded product exhibit excellent effects in both odor and color resistance.

Claims (9)

  (A) A vinyl chloride resin composition for contacting tap water, wherein 0.01 to 10 parts by mass of (B) phosphite is contained with respect to 100 parts by mass of the vinyl chloride resin.   The vinyl chloride resin composition for contacting tap water according to claim 1, wherein the (B) phosphite is produced using phosphorus trichloride as a raw material.   The vinyl chloride resin composition for tap water contact according to claim 1 or 2, wherein phenol as an impurity in the (B) phosphite is 0.1% by mass or less with respect to the (B) phosphite. The (B) phosphite is represented by the following general formula (1),

(In formula (1), R represents a substituted or unsubstituted alkyl group having 8 to 16 carbon atoms.) The water supply according to any one of claims 1 to 3, which is a trialkyl phosphite represented by the formula (1). Vinyl chloride resin composition for water contact.   The vinyl chloride resin composition for tap water contact according to claim 4, wherein the alkyl group of the trialkyl phosphite represented by the general formula (1) is a branched alkyl group having 8 to 16 carbon atoms.   The trialkyl phosphites represented by the general formula (1) are tri (2-ethylhexyl) phosphite, tri (isononyl) phosphite, tri (isodecyl) phosphite, tri (isoundecyl) phosphite and tri (isododecyl). The vinyl chloride resin composition for contact with tap water according to any one of claims 1 to 5, wherein the composition is any one or more selected from the group consisting of phosphites.   Further, one or more selected from the group consisting of antioxidants, plasticizers, metal stabilizers, β-diketone compounds, hydrotalcite, ultraviolet absorbers and hindered amine light stabilizers are contained. The vinyl chloride resin composition for tap water contact according to any one of claims 1 to 6.   A hose formed by molding the tap water contact vinyl chloride resin composition according to any one of claims 1 to 7.   A flexible pool formed by molding the vinyl chloride resin composition for contact with tap water according to any one of claims 1 to 7.