JP2006070177A - Mixed solvent and liquid state stabilizer composition of chlorine-containing resin by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mixed solvent excellent in dissolution property, without having problems such as precipitation and separation, also having a high boiling point and low volatility, improved with printability, and without vaporizing an organic substance having a high volatility from the stabilizer contained in the chlorine-containing resin so as not to induce the deterioration of living environment by the vaporized organic substance. <P>SOLUTION: This mixed solvent used in the liquid state stabilizer composition of the chlorine-containing resin consisting of 1 kind or ≥2 kinds of a metal salt of a carboxylic acid or an alkylphenol and 1 kind or ≥2 kinds of phosphorous acid ester compound, and consisting of (c-1) 1 kind or ≥2 kinds selected from glycol ether-based solvents having ≥250°C boiling point and (c-2) 1 kind or ≥2 kinds selected from aromatic, aliphatic, alicyclic hydrocarbon-based solvents having ≥250°C boiling point is provided by having the mixing ratio of the mixed solvent by (c-1):(c-2)=(5:95)-(95:5) in weight ratio. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a mixed solvent used in a liquid stabilizer composition of a chlorine-containing resin. In particular, the present invention relates to a liquid stabilizer composition which is a mixed solvent having excellent solubility and low volatility, and further using this solvent to obtain a chlorine-containing resin composition having excellent printability.

  Chlorine-containing resins such as polyvinyl chloride have various excellent properties, but if they are thermoformed, they have the disadvantage of causing decomposition with dehydrochlorination and coloring the molded product, thereby reducing the commercial value. . In order to improve this, it has been widely practiced to add various stabilizers to improve the thermal stability of chlorine-containing resins. Examples of such stabilizers include lead-based, organotin-based, and barium. -There are composite metal soap systems such as zinc and calcium-zinc.

  These chlorine-containing resin composition products such as polyvinyl chloride include water and sewage pipes, rain gutters, and window frames that are hard chlorine-containing resin compositions, and automobiles that are semi-hard and soft chlorine-containing resin compositions. There are films and sheets for interior materials, instrument panels, wire covering materials, wallpaper, packaging materials, floor materials, building materials, etc., and these are various processes such as extrusion molding, injection molding, calendar molding, paste coating, dipping, powder slush molding, etc. It is commercialized by the method.

  Examples of the stabilizer include barium-zinc-based, calcium-zinc-based metal carboxylates and phenolates, organic metal salts such as sodium, potassium, magnesium, aluminum, cadmium, lead, and organic tin compounds, and inorganic salts. , Inorganic metal compounds, hydrotalcites, zeolites, polyhydric alcohols, polyhydric alcohol esters, organic phosphite compounds, β-diketones, antioxidants, ultraviolet absorbers, light stabilizers or There are combinations of epoxy compounds.

  Among these stabilizers, liquid stabilizers have been widely used in view of workability, dispersibility, and processing efficiency. However, in recent years, it is called sick house syndrome, and the volatilization of organic substances that may harm the environment and health into the room is regarded as a problem. Causes of sick house syndrome include wallpaper, flooring, indoor building materials, furniture, fittings, etc., and adhesives and paints used in them for formalin, aromatic solvents, and other highly volatile organic substances that volatilize the room. If the resident inhales, it is said to cause symptoms such as headache and nausea.

  There is concern about the generation of highly volatile organic substances from stabilizers contained in chlorine-containing resin products such as vinyl chloride resins. Actually, for the liquid stabilizer, an aromatic solvent or aliphatic hydrocarbon solvent having excellent solubility and a relatively low boiling point, or glycol and glycol ether alcohols have been used.

  Conventionally, various phosphite compounds have been used to improve the thermal stability of chlorine-containing resins. Among them, a phosphite compound containing a phenol residue has been widely used because of its excellent performance. These phosphite compounds, especially phosphite compounds containing phenol residues, are hydrolyzed by the effects of chlorine gas and moisture generated during processing of chlorine-containing resin products, and atmospheric moisture exposed after processing. It is known that phenol is liberated easily. This liberated phenol is problematic because it easily volatilizes and has a strong odor. In order to solve these problems, there is an increasing demand to use various high-boiling solvents, trialkyl phosphite compounds that do not contain easily volatile phenol residues, and the like.

  Certainly, this high-boiling solvent is excellent in terms of volatility, but on the other hand, this has low solubility of the stabilizer composition and has problems such as precipitation and separation. Further, this trialkyl phosphite compound has good volatility like the high boiling point solvent, but has a phenomenon that printability is deteriorated. In order to solve these problems, a high boiling point solvent excellent in solubility of the liquid stabilizer composition is desired, and at the same time, means for improving the printability has been demanded.

  The present invention provides a mixed solvent used in a liquid stabilizer composition having excellent solubility, no problems such as precipitation and separation, high boiling point and low volatility, and improved printability. Thus, a highly volatile organic substance is not volatilized from the stabilizer contained in the chlorine-containing resin composition, and the volatilized organic substance does not cause deterioration of the living environment.

This invention is a mixed solvent (c) comprising (c-1) and (c-2) used in a liquid stabilizer composition of a chlorine-containing resin comprising the following (a) and (b): A mixed solvent used for a liquid stabilizer composition of a chlorine-containing resin in which the mixing ratio of the mixed solvent is (c-1) :( c-2) = 5: 95 to 95: 5 in terms of weight ratio. However,
(A) is one or more of carboxylic acid or alkylphenol metal salts, (b) is one or more of phosphite compounds represented by the following general formula (1), (c-1 ) Is one or more selected from glycol ethers represented by the following general formula (2) having a boiling point of 250 ° C. or higher, and (c-2) is aromatic or aliphatic having a boiling point of 250 ° C. or higher. , One or more selected from hydrocarbon solvents such as alicyclics.

(Claim 1) The (c-1) is tetraethylene glycol monobutyl ether. The mixed solvent used in the liquid stabilizer composition for a chlorine-containing resin according to claim 1, (Claim 2), (c-2) ) Is an aromatic solvent, the mixed solvent used in the liquid stabilizer composition for chlorine-containing resin according to claim 1 (claim 3), wherein the general formula (2) represented by (c-1) is tetra The mixed solvent (Claim 4) or any one of Claims 1 to 4, which is ethylene glycol monobutyl ether and (c-2) is used in a liquid stabilizer composition of a chlorine-containing resin which is an aromatic solvent. A chlorine-containing resin liquid stabilizer composition using a mixed solvent comprising any of the above compositions (Claim 5), the chlorine-containing resin liquid stabilizer composition of Claim 5, and the following general formula (3): The salicylphosphite compound (d) .05～10 liquid stabilizer composition of the chlorine-containing resin obtained by wt% mixed.

(Claim 6), a liquid stabilizer composition of a chlorine-containing resin in which the salicyl phosphite compound represented by the general formula (3) according to claim 6 is salicyl-normal octyl phosphite (Claim 7), It is a chlorine containing resin composition (Claim 8) formed by adding any one of the liquid stabilizer compositions of 5-7.

  Since the mixed solvent used for the liquid stabilizer composition of the chlorine-containing resin of the present invention has low volatility, it can improve the volatility of the organic substance from the chlorine-containing resin composition, and The solubility is excellent, and the printability of the chlorine-containing resin composition can be improved by adding a salicyl phosphite compound to the liquid stabilizer composition using this mixed solvent.

  The metal of the metal salt of (a) carboxylic acid or alkylphenol described in claim 1 is calcium, barium, magnesium, zinc, potassium, lithium, or sodium. Examples of the organic acid residue include carboxylic acid and alkylphenol as shown below. Carboxylic acid is formic acid, acetic acid, propionic acid, normal octylic acid, 2-ethylhexylic acid, neodecanoic acid, oleic acid, isostearic acid, stearic acid, lauric acid, ricinoleic acid, castor oleic acid, benzoic acid, para tertiary butyl benzoate There are acids, toluic acid and the like. Examples of alkylphenols include nonylphenol, dodecylphenol, and tertiary butylphenol.

  These metal salts of carboxylic acids and alkylphenols may be acidic salts or neutral salts, and may be basic salts or overbased salts. These salts may be partially substituted with carbonates.

Examples of the alcohol of the phosphite compound represented by (b) of the present invention include tridecyl alcohol, isodecyl alcohol, lauryl alcohol, stearyl alcohol, and C ₁₂ -C ₁₅ mixed alcohol. These may be one kind or a mixture of two or more kinds.

  Typical examples of the liquid glycol ether solvent having a boiling point of 250 ° C. or higher represented by (c-1) used in the mixed solvent of the present invention include tetraethylene glycol monobutyl ether, triethylene glycol monobutyl ether, pentaethylene glycol. Examples include monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoethyl ether.

As the hydrocarbon solvent having a boiling point of 250 ° C. or higher represented by (c-2) of the present invention, aromatic, aliphatic, alicyclic and the like can be used. Aromatics include mono-di-trialkylbenzenes, diphenylalkanes, alkylnaphthalenes and the like. These alkyl groups are C _{4 to} C ₁₃ , and alkanes are C _{2 to} C ₁₅ linear or branched. Examples of the aliphatic hydrocarbon include tetradecane, pentadecane, and hexadecane.

  There are single or mixed commercial products corresponding to the above-mentioned solvents. For example, liquid paraffin No. 100-S (trade name of Sanko Chemical Co., Ltd.), Pansolv H (trade name of Mitsubishi Kasei Co., Ltd.), Alkene L (new) Nippon Petrochemical Co., Ltd. trade name), Cactus Solvent P-220 (Nikko Petrochemical Co., Ltd. trade name), Nisseki Hyzol SAS-296 (Shin Nippon Petrochemical Co., Ltd. trade name), naphthtechlite NV-280 (Trade name of Sankyo Oil Chemical Co., Ltd.).

  Examples of the salicyl phosphite compound represented by (d) of the present invention include salicyl-n-octyl phosphite, salicyl chlorophosphite, salicyl hydrogen phosphite, salicyl-2-ethylhexyl phosphite, salicyl-4-methylbenzyl. Examples thereof include phosphite, salicyl-cyclohexyl phosphite, salicyl-2-ethylhexanoyl phosphite, salicyl-benzoyl phosphite, salicyl-pt-butylbenzoyl phosphite.

  In addition to the components (a), (b), (c), and (d) as liquid stabilizer compositions for chlorine-containing resins in the present invention, the following are usually used for chlorine-containing resin compositions as necessary. The compounds shown can be added. Moreover, a solvent, alcohol, etc. can be further added as needed.

  The above solvents can be used as necessary, and include hydrocarbon-based, aliphatic-based, aromatic-based, alicyclic-based, or mixed solvents thereof. For example, in addition to kerosene, Exol D-40, D-80 (exxon mobile (trade name)), liquid paraffin type liquid paraffin No. 30 (trade name of Sanko Chemical Industry Co., Ltd.), Christol # 70, # 100, # 355 (trade name of Esso Co., Ltd.), Isopar E, H, L and M (Esso Co., Ltd.) which are petroleum odorless solvents Trade name), Solvesso # 100, # 150 which is an aromatic mixed solvent, or Swazol 1000, 1500 (trade name of Maruzen Petroleum Co., Ltd.).

Moreover, the said alcohol solvent can be used as needed, 2-ethyl- hexanol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, methoxybutanol, isooctyl alcohol, benzyl alcohol, ethyl glycol, methyl diglycol, butyl diglycol, dibutyl glycol, alcohols or glycols or glycol ethers, such as mixed alcohols C ₁₂ -C _15, and the like.

  Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, and chloride. Vinyl-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl, cycloalkyl or arylmaleimide copolymer Polymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer Polymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester Alcohol copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - urethane copolymer, polyvinylidene chloride, chlorinated polyethylene, and the like chlorinated polypropylene. There is no particular limitation on the shape of the resin and the polymerization / production method.

  The chlorine-containing resin composition includes the following plasticizers, organometallic salts, organotin compounds, initial colorants, organic phosphites, organophosphates, antioxidants, epoxy compounds, polyhydric alcohols or This organic acid ester, UV absorber, light stabilizer, other metal deactivators such as antistatic agent, antifogging agent, rust inhibitor, antifungal agent, antibacterial agent, bactericidal agent, low molecular acrylic acid Inorganic salts or inorganic metal compounds such as plate oligomers such as ester oligomers, mold release agents, viscosity reducing agents, surfactants, optical brighteners, foaming agents, acrylic cell regulators, processing aids, lubricants, Pigments, fillers such as calcium carbonate and clay, flame retardants, surface treatment agents, cross-linking agents, reinforcing agents and the like can be appropriately used depending on the purpose.

Examples of the plasticizer include phthalate plasticizers such as di-2-ethylhexyl phthalate, dibutyl phthalate, diisodecyl phthalate, di-mixed-alkyl (C _9-11 ) phthalate, diheptyl phthalate, diisononyl phthalate, and di-2. -Adipate plasticizers such as ethylhexyl adipate, diisononyl adipate, diisobutyl adipate, diisodecyl adipate, tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, tributyl trimellitate, etc. Trimellitic plasticizers, sebacate plasticizers such as di-2-ethylhexyl sebacate, dibutyl sebacate, and citrate plastics such as tributyl acetylcitrate and triethyl acetylcitrate Glycerin acetic acid fatty acid ester plasticizers such as glycerin diacetomonolaurate, other phosphate plasticizers, polyester plasticizers, chlorinated paraffinic plasticizers, pyromellitate plasticizers, epoxy plasticizers and the like.

  Examples of the metal of the organic metal salt include sodium, potassium, lithium, magnesium, calcium, barium, zinc, and aluminum. Examples of organic acid residues include carboxylic acids as shown below, phenols and alkylphenols. The carboxylic acid is a saturated or unsaturated aliphatic carboxylic acid having 1 to 22 carbon atoms, a cyclic or heterocyclic carboxylic acid having 7 to 16 carbon atoms, a hydroxy acid or alkoxy acid having 2 to 10 carbon atoms, for example , Formic acid, acetic acid, propionic acid, caprylic acid, octylic acid, 2-ethylhexylic acid, neodecanoic acid, isodecanoic acid, lauric acid, stearic acid, myristic acid, palmitic acid, behenic acid, epoxidized stearic acid, isostearic acid, 12- Hydroxystearic acid, 12-ketostearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, glycolic acid, lactic acid, hydroacrylic acid, α-oxyacetic acid, glyceric acid, malic acid, tartaric acid, citric acid, thioglycolic acid , Mercaptopropionic acid, lauryl mercaptopropionic acid, benzoic acid Para tertiary butyl benzoic acid, toluic acid, dimethyl benzoic acid, aminobenzoic acid, salicylic acid, amino acid, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid, thiodipropionic acid. Examples of phenol and alkylphenol include phenol, nonylphenol, dodecylphenol, tertiary butylphenol, octylphenol, isoaminophenol, cresol, xylenol and the like.

  These metal salt compound of carboxylic acid and metal salt compound of alkylphenol may be acidic salt or neutral salt, and may be basic salt, carbonate salt or overbased salt. The amount of these organic metal salts added is 0.001 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin. These metal salts can be used alone or in combination.

  Examples of the organic tin-based compound include dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dibutyltin dilaurate, dibutyltin distearate, dioctyltin dioleate, dioctyltin dilaurate, Dioctyltin distearate, dioctyltin bis (oleyl malate), dibutyltin bis (stearylmalate), dibutyltin malate polymer, dioctyltin malate polymer, dioctyltin bis (butylmalate), dibutyltin-β-mercaptopropionate Dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (2-ethylhexylmercaptoacetate), dibutyltin (2-ethylhexyl mercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), dibutyltin bis (isooctylmercaptoacetate), dioctyltin bis (isooctylmercaptoacetate), dioctyltin bis (2-ethylhexyl) Mercaptoacetate), dimethyltin bis (isooctylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), monooctyltin tris (isooctylmercaptopropionate), and the like. Moreover, the addition amount of these organotin compounds is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

  A β-diketone compound or a sulfolene compound can be used as the initial coloring inhibitor. β-diketone compounds include, for example, dehydroacetic acid, cyclohexane-1,3-dione, 2-benzoylcyclopentanone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, acetyl stearoylmethane, benzoylacetone, palmitoylbenzoylmethane, stearoylbenzoylmethane, Dibenzoylmethane, tribenzoylmethane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoylmethane), 4-chlorobenzoyl-benzoylmethane, benzoyltrifluoroacetone, palmitoyltetralone, stearoyltetralone, and benzoyltetralone Etc.

  The β-diketone compound may be a metal complex salt, and examples of the metal constituting the complex salt include sodium, calcium, barium, and zinc. The addition amount of these initial coloring inhibitors is 0.0005 to 10 parts by weight, preferably 0.001 to 5 parts by weight, with respect to 100 parts by weight of the chlorine-containing resin. These initial coloring inhibitors can be used alone or in combination.

In the organic phosphite, one or more organic groups of the trialkyl phosphite, triaryl phosphite, alkylaryl phosphite, bisphenol-A-phosphite, polyhydric alcohol phosphite, ester residue are hydrogen atoms. Represented by substituted acid phosphites and the like, such as triphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite, triisotridecyl phosphite, triisodecyl thiophosphite, tribenzyl Phosphite, trinonylphenyl phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, diisodecylpentaerythritol diphosphite, teto Phenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, trilauryl phosphite, distearyl pentaerythritol diphosphite, tri-2,4-di-t-butylphenyl phosphite, 2,4- Di-t-butylphenyl diisodecyl phosphite, tributoxyethyl phosphite, 4,4′-isopropylidene diphenylalkyl (C ₁₂ -C ₁₅ ) diphosphite, pepquitas (dipropylene glycol) triphosphite, 4,4′-butylidenebis ( 3-methyl-6-tert-butyl-di-tridecyl phosphite) and the like.

  Acid phosphites in which one or two of the organic residues in the above phosphite are substituted with hydrogen atoms are also effective, for example, diphenyl acid phosphite, monophenyl acid phosphite, diisooctyl acid phosphite. Phyto, monoisooctyl acid phosphite, ditridecyl acid phosphite, dibenzyl acid phosphite, dinonylphenyl acid phosphite and the like.

Moreover, the said organic phosphate ester compound, for example, nonylphenyl polyoxyethylene (5-55) phosphoric acid, tridecyl polyoxyethylene (4-10) phosphoric acid, etc. are used as a processing aid. In addition, metal adducts of organophosphates such as magnesium, calcium, barium or zinc salts of mono-dimixed isooctyl phosphate, magnesium, calcium, barium or zinc salts of mono-dimixed isotridecyl phosphate are thermally stabilized. Each is useful as an auxiliary.

  Acid phosphates in which one or two of the organic residues in the organophosphate are substituted by hydrogen atoms are also effective. For example, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, stearyl acid phosphate and so on. In addition, there are metal salts of these acid phosphates, such as magnesium, calcium, barium or zinc salts.

  Examples of the antioxidant include hindered phenols such as alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, and polyalkylated phenol esters, such as butylated hydroxytoluene, 4-hydroxymethyl-2. , 6-di-t-butylphenol, 4,4'-dihydroxy-2,2'-diphenylpropane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6 -T-butyl-3-methylphenol), tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane. Examples of the sulfur-containing alkanoic acid alkyl ester include dilauryl thiopropionic acid ester and distearyl thiopropionic acid ester.

  The epoxy compound is an epoxidized unsaturated oil, epoxidized unsaturated fatty acid ester, epoxycyclohexane derivative or epichlorohydrin derivative, such as epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized safflower. Oils, epoxidized linseed oil fatty acid butyl, epoxidized butyl stearate, isooctyl, alkyl esters such as 2-ethylhexyl, and metal salts such as calcium and zinc, 3- (2-xenoxy) -1,2-epoxypropane, Epoxy hexahydrophthalic acid di-2-ethylhexyl, epoxy polybutadiene, bisphenol-A-diglycidyl ether, and the like.

  Other stabilizing aids include polyhydric alcohols such as mono and dipentaerythritol, mannitol, sorbitol, ester compounds of this polyhydric alcohol and carboxylic acids, amino acids or rosins such as pentaerythritol stearate, adipic acid. Pentaerythritol, dipentaerythritol pyrrolidonecarboxylate, pentaerythritol glutamate, wood rosin pentaerythritol, wood rosin pentaerythritol maleate, and wood rosin glycerol ester. Further, benzotriazole compounds such as 1,2,3-benzotriazole and tolyltriazole which are nitrogen-containing compounds, metal salts such as zinc, copper and cobalt, thiazole compounds such as 2-mercaptobenzothiazole, and These metal salts such as zinc, copper and cobalt, ester compounds of β-aminocrotonic acid and 1,3 or 1,4-butanediol, 1,2-dipropylene glycol, thiodiethylene glycol, lauryl alcohol, and the like, and Tris (2-hydroxylethyl) isocyanate, tris (mercaptoethyl) isocyanurate compound.

  Examples of the ultraviolet absorber include benzotriazole and benzophenone, and examples of the benzotriazole include 2 (5-methyl-2-hydroxyphenyl) benzotriazole and 2 (3,5-di-t -Butyl-2-hydroxylphenyl) -5-chlorobenzotriazole, benzotriazole compounds such as 2 (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, and dimethyl-1- (2- Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate. Examples of the benzophenone series include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, and 2,2′-dihydroxy-4,4′dimethoxy-benzophenone. 2-hydroxy-4-n-octoxy-benzophenone.

  Examples of the light stabilizer include poly [{6- (1,1,3,3-tetramethylbutyl) imino} imino-1,3,5-triazine-2,4-diyl] {2, 2,6,6-tetramethyl-4-piperidyl} imino}] and the like.

  The inorganic salt or inorganic metal compound is, for example, sodium, potassium, magnesium, calcium, barium, zinc, aluminum or tin, and an oxide, hydroxide, silicate, borate of these metals, Sulfates, perchlorates, phosphites, phosphates, basic carbonates, basic phosphates and the like. These compounds may be double salts, anhydrides or hydrates having water of crystallization, and may take the form of a mixture. Moreover, a complex compound with a polyhydric alcohol etc. may be sufficient.

  Typical examples of these compounds include hydrotalcites represented by the following formula (3), calcium-containing hydroxides represented by the following formula (4), calcium oxide, magnesium oxide, zinc oxide, and oxidation. Silicon, aluminum oxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, sodium silicate, calcium silicate, zinc silicate, aluminum silicate, potassium silicate-aluminum, sodium borate, potassium borate , Aluminum borate, aluminum sulfate 18 hydrate, aluminum sulfate-sodium 12 hydrate, sodium phosphate, sodium pyrophosphate, magnesium phosphate, calcium phosphate, calcium orthophosphate, zinc orthophosphate, sodium-substituted type A zeolite, calcium Replacement type A Zeolite, magnesium substituted A type zeolite, wollastonite acids, tobermorite such and the like.

M (1-X) Alx ( OH) 2 Ax / n · mH 2 O (3)
(Wherein M represents Mg and / or Zn, A represents CO ₃ and / or ClO ₄ , x represents a range of 0 <x <0.5, and m represents a range of 0 ≦ m <3). Hydrotalcite.

Ca (1-X) Mx (OH) ₂ (4)
(Wherein M represents Mg and Al, and x represents a range of 0.005 <x <0.5).

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example-1
300 g of Stabilizer component-A shown in Table 1 below was prepared by using the mixed solvents 1 to 9 shown in Table 2 and stirring at 80 ° C. in the proportion of Table 3 while stirring. The solubility at that time, and then the long-term storage stability immediately after setting the liquid temperature to 5 ° C. and one month later were evaluated. The results are shown in Table 3.

  As an evaluation method, the solubility is 3 stages A, B, and C. A is good (it became a transparent liquid easily within 10 minutes), B is acceptable (it took 10 minutes or more to become a transparent liquid). , C is impossible (dissolves and does not become a transparent liquid but separates, precipitates and becomes turbid), and the storage stability is 4 stages a, b, c, d, and a is good (the transparent liquid remains in the initial state) B) is acceptable (slightly opaque), c is impossible (precipitation / separation occurred), and d is impossible (solidified). In this evaluation, C, c, and d were inferior as products and could not be commodities.

Example-2
Stabilizer component-B shown in Table 4 below was prepared by heating and dissolving at 80 ° C. in the proportion of Table 5 using the mixed solvents 1, 3, and 5 shown in Table 2, and then cooled to a liquid temperature of 5 Table 5 shows the solubility and long-term storage stability when the temperature reached ° C.

  As an evaluation method, the solubility is 3 stages A, B, and C. A is good (it became a transparent liquid easily within 10 minutes), B is acceptable (it took 10 minutes or more to become a transparent liquid). , C is impossible (dissolves and does not become a transparent liquid but separates, precipitates and becomes turbid), and the storage stability is 4 stages a, b, c, d, and a is good (the transparent liquid remains in the initial state) B) is acceptable (slightly opaque), c is impossible (precipitation / separation occurred), and d is impossible (solidified). In this evaluation, C, c, and d were inferior as products and could not be commodities.

Example-3
Stabilizer components A to G shown in Table 6 and phosphite shown in Table 7 and mixed solvent 4 shown in Table 2 were used to dissolve by heating at 80 ° C. The printability was confirmed with the formulation described in No. 8.

  The compounding agents shown in Table 8 were mixed and kneaded with an 8-inch roll at 170 ° C. for 3 minutes to prepare a test sheet having a thickness of 0.4 mm. The obtained sheet was cut into 30 mm × 100 mm and changed with time in a constant temperature and humidity chamber at 70 ° C. and 90%. This was extracted after a lapse of 1 week, coated with ink (cyclohexanone vinyl ink) on the sheet surface, dried and then applied with a cellophane tape from above to peel it off at once. At this time, the amount of paint adhered to the cellophane tape was evaluated. The evaluation method was made into five stages, 1 was completely peeled off, and 5 was not peeled off at all. In this evaluation, 2 or less was inferior as a product and could not be a product.

  Details of the compounding materials used in the above examples are as shown below.

Polyvinyl chloride resin: Shin-Etsu Chemical Co., Ltd. product TK-1000
Dioctyl phthalate (DOP): Taoka Chemical Co., Ltd. product DOP
Epoxidized soybean oil: CECA (France) product ECEPOX PB3
* 1 Tominox TT: Ap Corporation Corporation Tetrakis [methylene-3- (3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane * 2 Tetraethylene glycol monobutyl ether: Kyowa Oil Chemical Co., Ltd.
Product Butisenol 40
* 3 Triethylene glycol: Mitsubishi Chemical Corporation * 4 Polyethylene glycol: Daiichi Kogyo Seiyaku Co., Ltd. PEG-
200
* 5 Mono-, di- and trialkylbenzene mixed solvent: Mitsubishi Chemical Corporation Pansolv H
* 6 Liquid paraffin: Sanko Chemical Co., Ltd. Liquid paraffin No.100-S
* 7 Petroleum hydrocarbons (aliphatic, alicyclic): Products of Sankyo Oil Chemical Co., Ltd.
NAFTECH LIGHT NV-280
* 8 Overbased Ba dodecyl phenol carbonate complex: OMG
Product PLASTISTTAB # 2106
* 9 Diphenyldecyl phosphite: Crompton product WD
PDP
* 10 Tris (tridecyl) phosphite: Johoku Chemical Industry Co., Ltd. J
P-333E
* 11 Tridecyl phosphite: Crompton product W-TDP
* 12 Salicyl-n-octyl phosphite: AP My Corporation product * 13 Tris (isooctyl) phosphite: Crompton product W
-TIOP
* 14 W-439: Crompton product Tetra-alkyl (C ₁₂
-C _{15)-4,4'-isopropylidene} diphenyl diphosphite ※ 15 PB3: atofina CECA product epoxidized soybean oil ※ 16 xylene: Nikko Petrochemicals Co. Product Cactus Solvent X-
A
As can be seen from the results of Comparative Examples 3 to 7 in Table 3, the solubility or long-term storage stability was poor when tetraethylene glycol monobutyl ether and other solvents were used alone.

  As can be seen from the results of Examples 1 to 7 in Table 3 and Examples 10 to 12 in Table 5, it is dissolved by mixing tetraethylene glycol monobutyl ether with an aromatic solvent or an aliphatic or aliphatic / aromatic solvent. It is clear that the property and long-term storage were improved.

  As can be seen from the examples in Table 8, if a stabilizer prepared by changing the phenol-containing phosphite to a trialkyl phosphite is added to the vinyl chloride resin, the printability deteriorates, but salicyl phosphite is added thereto. As a result, it was found that it was greatly improved.

Example-4
The samples shown in Table 9 below were tested for volatility.
Regarding the volatility of the mixed solvent, the volatility was evaluated as it was, and for the phosphite, the volatility of phenol and alcohol, which are decomposition products, was a problem. A 10 g sample was placed in a glass evaporating dish having a diameter of 9 cm and left in a gear oven at 40 ° C. for 1 day and 3 days. After taking out, it left to stand in a desiccator for 1 hour, and volatilization loss was measured.

  In the evaluation, the volatilization weight loss was less than 20% by weight, and the volatility was judged to be low volatility. The results were as shown in Table 9. As is apparent from Table 9, it can be seen that the mixed solvent of the present invention is also excellent in terms of low volatility.

Claims (8)

A mixed solvent (c) comprising (c-1) and (c-2) used in a liquid stabilizer composition of a chlorine-containing resin comprising the following (a) and (b), The mixed solvent used for the liquid stabilizer composition of the chlorine containing resin whose mixing ratio is (c-1) :( c-2) = 5: 95-95: 5 by weight ratio.
However,
(A) is one or more of carboxylic acid or alkylphenol metal salts, (b) is one or more of phosphite compounds represented by the following general formula (1), (c-1 ) Is one or more selected from glycol ethers represented by the following general formula (2) having a boiling point of 250 ° C. or higher, and (c-2) is aromatic or aliphatic having a boiling point of 250 ° C. or higher. , One or more selected from hydrocarbon solvents such as alicyclics.

  The mixed solvent used in the liquid stabilizer composition for a chlorine-containing resin according to claim 1, wherein (c-1) is tetraethylene glycol monobutyl ether.   The mixed solvent used in the liquid stabilizer composition for a chlorine-containing resin according to claim 1, wherein (c-2) is an aromatic solvent.   The liquid stabilizer composition for chlorine-containing resin according to claim 1, wherein the general formula (2) represented by (c-1) is tetraethylene glycol monobutyl ether, and (c-2) is an aromatic solvent. Mixed solvent used for products.   The liquid stabilizer composition of the chlorine containing resin using the mixed solvent which consists of a composition in any one of Claims 1-4. Liquid stability of a chlorine-containing resin obtained by mixing 0.05 to 10% by weight of the salicyl phosphite compound (d) represented by the following general formula (3) with the liquid stabilizer composition of chlorine-containing resin of claim 5 Agent composition.

  A liquid stabilizer composition of a chlorine-containing resin, wherein the salicyl phosphite compound represented by the general formula (3) according to claim 6 is salicyl-normal octyl phosphite.   The chlorine containing resin composition formed by adding the liquid stabilizer composition in any one of Claims 5-7.