WO2007132591A1

WO2007132591A1 - Mixture, thermal stabilizer using the mixture, and halogen-containing resin composition

Info

Publication number: WO2007132591A1
Application number: PCT/JP2007/055436
Authority: WO
Inventors: Masashi Harada; Yosuke Ishima; Keiichi Odagiri; Akihiro Maruyama; Yasuhiro Kishimoto
Original assignee: Adeka Corporation
Priority date: 2006-05-12
Filing date: 2007-03-16
Publication date: 2007-11-22
Also published as: JP2007302833A

Abstract

Disclosed is a halogen-containing resin composition comprising a mixture which can be produced by melting pentaerythritol, dipentaerythritol and a pentaerythritol condensation product in the form of a trimer or more under heating. In the mixture, the sum total of the contents of pentaerythritol and dipentaerythritol is 20 to 80% by mass and the content of the pentaerythritol condensation product is 20 to 80% by mass both relative to the total amount of the mixture (wherein the sum total of the contents of pentaerythritol, dipentaerythritol and the pentaerythritol condensation product is 100% by mass).

Description

Specification

Mixture, heat stabilizer using the same, and halogen-containing resin composition

Technical field

The present invention relates to a mixture that can be used as a heat stabilizer, a heat stabilizer using the same, and a halogen-containing resin composition containing the heat stabilizer, and more specifically, a halogen excellent in heat resistance and coloring resistance. A resin composition is provided.

[0002] Among halogen-containing resins, vinyl chloride resins are difficult to stabilize against light and heat, and are known to cause decomposition mainly due to dehalogenated hydrogen during thermoforming and product use. ing. Therefore, various stabilizers such as metal salts of organic acids, organic tin compounds, organic phosphate compounds, epoxy compounds, β-diketone compounds, antioxidants, and UV absorbers are added to improve the stability of the vinyl chloride resin. Attempts have been made to improve.

[0003] In recent years, the use of harmful heavy metals such as lead and cadmium has been avoided due to toxicity problems, and therefore, barium zinc-based composite stabilizers tend to be used. More recently, replacement with a less toxic calcium zinc system or a composite system of calcium magnesium zinc system is desired. However, the performance of heat stabilizers is not sufficient with these system stabilizers alone.

[0004] In addition, the salty resin resin can be easily adjusted in hardness by using a plasticizer, so that it can be used in various applications such as agricultural sheets and building materials such as window frames. However, a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing only a small amount of plasticizer is exposed to high temperature and high pressure during processing, and molded. Since high performance is required for the thermal stability of products, higher performance stabilization aids are required.

[0005] Therefore, for the purpose of improving the thermal stability of these various stabilizers, pentaerythritol condensates such as bentaerythritol and dipentaerythritol or tripentaerythritol (hereinafter referred to as these) are used as stabilizing aids. This compound is sometimes referred to as “pentaerythritol compound.” It has been reported that) is added to a vinyl chloride resin in combination with a stabilizer (Patent Documents 1 and 2). However, the above pentaerythritol compound is heat resistant. However, since the melting point of the pentaerythritol compound is higher than the processing temperature of the vinyl chloride resin, it is not compatible with the salted resin resin. Therefore, the vinyl chloride system containing the pentaerythritol compound is poor. In a product obtained by molding and processing a resin composition (halogen-containing resin composition), plate-out due to poor dispersion of pentaerythritol compound may appear.

[0006] As a method for improving the above-mentioned dispersion failure, a method of pulverizing has been proposed (Patent Document 3), and pentaerythritol compound is pulverized to a particle size of 35 μm or less. Therefore, the above problem has a problem that the powder energy required for the fine powder that can be improved is large and the cost is high.

[0007] As another method, a method for improving the dispersibility of dipentaerythritol by melting a mixture of ditrimethylolpropane and dipentaerythritol has been disclosed (Patent Document 4). However, since ditrimethylolpropane does not have an effect as a stabilizing aid, dipentaerythritol, which is the original active ingredient, is reduced in such a mixture, and is used in a large amount in order to achieve the desired performance. There is a need. However, if it is used in a large amount, there are problems that the physical property value of the molded product obtained by the molding process is lowered, and the plate-out appears on the surface.

[0008] In addition, a mixed ester obtained by esterification of pentaerythritol with stearic acid, adipic acid, or the like, or a partial ester obtained by esterification of pentaerythritol with a linear saturated fatty acid is converted into a halogen-containing resin. (Patent Document 5 and Patent Document 6) have been disclosed, respectively, but since pentaerythritol, which is the original active ingredient, is reduced in the same manner as described above, it is not satisfactory as a stabilizing aid. I got it.

Patent Document 1: Japanese Patent Laid-Open No. 6-248142

Patent Document 2: JP-A-8-143704

Patent Document 3: Japanese Patent Laid-Open No. 10-7859

Patent Document 4: Japanese Patent Laid-Open No. 9_268286

Patent Document 5: JP-A-11-222545

Patent Document 6: JP-A-7_97495

Disclosure of the invention Problems to be solved by the invention

[0010] As described above, although various investigations have been made so far, a plasticizer containing only a small amount, or a case where it is not compounded at all, or a case where it is dripping, lead or a cadmium stabilizer. In the case of a formulation that does not use No. 1, a compound having a sufficient effect as a stabilizing aid with respect to thermal stability and coloring resistance has not been obtained.

[0011] Accordingly, an object of the present invention is to provide a halogen-containing resin composition that exhibits sufficient thermal stability and color resistance even when blended without using a lead or cadmium stabilizer by improving the stabilizing aid. Is to provide.

[0012] As a result of extensive investigations, the present inventors have obtained a mixture obtained by heating and melting pentaerythritol, dipentaerythritol, and a pentaerythritol condensate of a trimer or more, which is configured in a specific ratio. The present inventors have found that a halogen-containing resin composition using can achieve the above object, and has completed the present invention.

Means for solving the problem

[0013] That is, the present invention relates to a mixture obtained by heating and melting pentaerythritol, dipentaerythritol, and a pentamer erythritol condensate of a trimer or more, and the total amount of the pentaerythritol and dipentaerythritol. the sum of the content of erythritol is 20 to 80 mass ^_0/0, 3 content of dimer or more pentaerythritol condensate is mixed compound is 20 to 80 mass%. (However, the sum of the contents of pentaerythritol, dipentaerythritol, and a penta-erythritol condensate of trimer or higher is 100% by mass).

[0014] In addition, the present invention achieves the above object by providing a heat stabilizer containing the above mixture.

[0015] Further, the present invention achieves the above object by providing a halogen-containing resin composition containing the above mixture.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the mixture of the present invention, a heat stabilizer using the same, and a halogen-containing resin composition will be described in detail.

The mixture of the present invention comprises pentaerythritol, dipentaerythritol and a trimer or more. It is obtained by heating and melting a pentaerythritol condensate.

In the mixture, the total content of the pentaerythritol and the dipentaerythritol is 20 to 80% by mass with respect to the total amount of the mixture, and the content of the pentaerythritol condensate of the trimer or more is 20 to 20% by mass. a 80 weight ^_0/0, the sum of the content of pentaerythritol, Jipentae Risuritoru and trimer or more pentaerythritol condensate is 100% by weight.

[0017] When the sum of the content of pentaerythritol and dipentaerythritol is less than 20% by mass or more than 80% by mass with respect to the total amount of the above mixture, the mixture may be subjected to heat-melt treatment. The effect of the present invention in which the melting point is high cannot be obtained.

[0018] Examples of the pentaerythritol condensate having a trimer or higher include tripentaerythritol, tetrapentaerythritol, pentapentaerythritol, hexapentaerythritol, and the like.

[0019] In addition, when the content of the pentaerythritol condensate of the trimer or more is less than 20% by mass or more than 80% by mass with respect to the total amount of the mixture, the mixture is subjected to heat-melt treatment. Even if it goes, the effect of the present invention in which the melting point of the mixture is high cannot be obtained.

[0020] In the present invention, the total content of pentaerythritol and dipentaerythritol and the content of the pentaerythritol condensate of trimer or more are 30% by mass to 30% by mass relative to the total amount of the mixture. Mixtures that satisfy the conditions in the range of 70% by weight are particularly preferably used.

[0021] The heat-melting treatment in the present invention involves melting a mixture of pentaerythritol, dipentaerythritol, and a penta-erythritol condensate of trimer or higher until it becomes transparent while stirring at 230 ° C, and after cooling and solidification. By pulverization, a mixture of 150 mesh pass (particle size of 100 μm or less) is obtained.

The mixture of the present invention preferably has a melting point of 200 ° C or lower, more preferably a melting point of 185 ° C or lower.

[0022] The heat stabilizer of the present invention contains the above mixture.

The heat stabilizer of the present invention may contain other additives in addition to the above mixture. Other supplementary caro When the agent is contained, the content of the mixture of the present invention in the heat stabilizer is preferably from:! To 70% by mass, more preferably from! To 50% by mass. Examples of other additives that can be blended in the heat stabilizer of the present invention include additives that can be blended in the halogen-containing resin composition described later.

[0023] The halogen-containing resin composition of the present invention contains the above mixture.

The halogen-containing resin composition of the present invention preferably contains the above-mentioned mixture in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the halogen-containing resin. It is particularly preferable to contain part by mass.

[0024] Furthermore, in the present invention, at least one or more selected from β-diketone compounds, compounds, id mouth talcite compounds, and fatty acid zinc can be suitably used for the halogen-containing resin composition. .

[0025] The halogen-containing resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and is not limited to polychlorinated butyl, chlorinated polychlorinated vinyl. , Poly (vinyl chloride), chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride propylene copolymer, salt vinyl chloride-styrene copolymer, vinyl chloride isobutylene Copolymer, vinyl chloride-salt vinylidene chloride copolymer, vinyl chloride-styrene maleic anhydride terpolymer, salted butyl-styrene-attaloniloyl copolymer, butyl chloride-butadiene copolymer, salt 匕Vinyl-isoprene copolymer, butyl chloride monochlorinated propylene copolymer, butyl chloride-vinylidene chloride-butyl acetate terpolymer, salt Bulle-maleic acid ester copolymer, chlorinated butyl methacrylate ester copolymer, chlorinated butyl copolymer, nitrile copolymer, vinyl chloride-various vinyl ether copolymers and other chlorine-containing resins, and their blends Alternatively, other chlorine-free synthetic resins such as the above-mentioned rhogen-containing resins, acrylonitrile-styrene copolymers, ethylene-butyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, polyesters, polyolefins Further, it may be a blend with polyamide, polycarbonate or the like, or alloy.

[0026] In the halogen-containing resin composition of the present invention, addition of at least one β-diketone compound can suppress product coloring due to molding. preferable.

[0027] Examples of the β-diketone compound include acetylylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethyl, lauroylacetylmethane, nonremiacetylacetylmethane, stearoylbenzoate. Methyl methane, stearoyl acetyl methane, phenyl acetyl acetyl methane, dicyclohexyl carbonyl methane, benzoylformole methane, benzoyl acetyl methane, dibenzoyl methane, octyl benzoyl methane, bis (4-octyl) Benzoinole) methane, benzoyldiacetyl methane, 4-methoxybenzoylbenzoylmethane, bis (4 carboxymethylbenzoinole) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, Acetate acetate, cycloto San 1, 3-dione, 3, 6-dimethyl-2, hexane 1 carboxymethyl phosphate methyl to 4 Jiokishishikuro, cyclohexanone to 2 Asechirushikuro, dimedone, hexane and the like to the 2-base Nzoirushikuro. These compounds may be metal salts. The metal species that can provide the metal salt of the above-mentioned diketone compound include Group Ia metals such as lithium, sodium and potassium; Group Ila metals such as magnesium, calcium, strontium and barium; Anoleminium, tin, alkyl tin and the like can be mentioned.

Among these β-diketone compounds, it is preferable to use dibenzoylmethane, stearoyl benzoinolemethane, acetylethylacetone metal salt, or calcium acetylethylacetonate because a product with suppressed coloring can be obtained.

[0028] The amount of the β-diketone compound used is 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the halogen-containing resin.

[0029] In addition, in the halogen-containing resin composition of the present invention, it is preferable to add at least one kind of a no- and ido-talcite compound because heat resistance can be improved.

[0030] As the Hyde mouth talcite compound, for example, magnesium and aluminum, or a double salt compound composed of zinc, magnesium and aluminum is preferably used, and the Hyde mouth talcite compound dehydrated crystal water. It may be a thing.

[0031] The above-mentioned hydride talcide compound may be a natural product or a synthetic product, and can be used without being limited by the crystal structure, crystal particle diameter, etc. of hydride talcite. It is. In addition, the above-mentioned Hyde Tarusai compound has its surface coated with stearic acid. Higher fatty acid metal salts such as higher fatty acid and alkali metal oleate, organic sulfonic acid metal salts such as alkali metal dodecylbenzene sulfonate, higher fatty acid amides, higher fatty acid esters or waxes may be used.

[0032] The above-mentioned Hyde mouth talcite may be commercially available. For example, Al Power Mizer 1, Al Carmizer 2, Al Power Mizer 4, Al Power Mizer 5, Al Power Mizer 7, DHT -4A (manufactured by Kyowa Chemical Co., Ltd.). Among these, Al force mizer 1 and DHT-4A can be suitably used.

[0033] The Hyde mouth talcite compound is used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the halogen-containing resin. If the above-mentioned hard mouth talcite compound is less than 0.001 part by mass, the effect of addition is hardly observed, and if it exceeds 10 parts by mass, the effect does not increase and the color resistance may be lowered.

[0034] The halogen-containing resin composition of the present invention is preferable because a product excellent in coloring resistance can be obtained by further blending at least one organic acid zinc salt.

[0035] Examples of the organic acid zinc salt include zinc salts of carboxylic acids, organic phosphoric acids, or phenols. Here, examples of the carboxylic acid include caproic acid, caplinoleic acid, pelargonic acid, 2-ethylhexylic acid, force puric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid. , Isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylenostearic acid, ricinolelic acid, linolenolic acid, linolenic acid, oleic acid, arachic acid, behenic acid, erucic acid , Brassicic acid and similar acids and tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids and other naturally occurring mixtures of the above acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, Isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5_tertiary octylsalicylic acid, Putian acid, hexanoic force carboxylic acid cyclohex the like. Examples of the organic phosphoric acid include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (noelphenyl) phosphoric acid, phosphonic acid nourphenyl ester, and phosphonic acid stearyl ester. Etc. Examples of the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like. It is done. The organic acid zinc salt may be any of a normal salt, an acidic salt, a basic salt, an overbased salt, and the like.

[0036] The amount of the organic acid zinc salt used is 0.

001-10 parts by mass, preferably 0.05-5 parts by mass.

[0037] In addition, an organic acid metal salt other than an organic acid zinc salt can be used for the halogen-containing resin of the present invention. Examples of the organic acid metal salt include metal (Li, Na, K, Ca, Mg, Ba, Sr, Cd, Al) salts of carboxylic acids, organic phosphoric acids or phenols. Here, examples of the carboxylic acid, organic phosphoric acid, and phenol include those exemplified as those used in the organic acid zinc salt. These organic acid metal salts may be any of normal salts, acidic salts, basic salts, overbased salts, and the like. Among these organic acid metal salts, it is particularly preferable to use organic acid salts of non-heavy metals (Li, Na, K, Ca, Mg, Al) because a low-toxic composition is obtained. It is preferable to use a calcium acid salt and the organic acid zinc salt in combination because a composition having excellent heat resistance and coloration resistance can be obtained in spite of low toxicity.

[0038] The amount of the organic acid metal salt used is 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[0039] Further, the halogen-containing resin composition of the present invention further includes additives that are usually used as necessary, for example, plasticizers, organic phosphite compounds, phenol-based or sulfur-based antioxidants, epoxy A compound, an ultraviolet absorber, a hindered amine light stabilizer, a foaming agent, a filler, a polyol compound, and the like can also be blended.

[0040] Examples of the plasticizer include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate, dioctyl adipate, diisononyl adipate, di (butyl diglycol) adipate and the like. Phosphate plasticizers such as adipate plastic lj, tricresyl phosphate, polyester plasticizer, chlorinated paraffin plasticizer, trimellitate plasticizer, pyromellitate plasticizer, biphenyl tetracarboxylate plasticizer, etc. Is mentioned.

[0041] Examples of the organic phosphite compound include triphenyl phosphite and tris (2, 4

—Ditertiarybutylphenyl) phosphite, Tris (nonylphenyl) phosphite, Tris (Dino (Yulphenyl) phosphite, tris (mono- and di-mixed nourphenyl) phosphite, diphenylenoresid phosphite, 2,2'-methylenebis (4,6-ditertiarybutylphenolino) octinole phosphite, diphenyldecylphos Phytite, phenyldiisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilaurinoretrie Thiophosphite, bis (neopentyl glycol) · 1,4-cyclohexane dimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2, 6 ditert-butyl-4 Methylphenyl) pentaeryth Torujihosufu Ait, distearyl pentaerythritol phosphite, phenylene Lou 4, 4 '- Isopuropiri Denji phenol' pentaerythritol phosphite, tetra (C ~ mixed alkyl)

12 15

4, 4 Isopropylidene diphenyl diphosphite, hydrogenated 4, 4 '-Isopropylidene diphenol polyphosphite, bis (octylphenyl)' bis [4,4'- η-butylidenebis (2 tert-butyl-5-methylphenol) ] 1, 6 Hexanediol 'diphosphite, tetratridecyl · 4,4'-butylidenebis (2 tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) · 1, 1, 3-tris (2-methyl) —5-tert-butyl-4-hydroxyphenyl) butane.triphosphite, 9, 10-dihydride 9-oxa 10-phosphenanthrene 10-oxide, 2-butyl 2-ethylpropylpropanediol 2, 4, 6_tri-tert-butylphenol monophosphite.

Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl _ρ_creso-monole, 2,6-diphenyl_4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl_4— Hydroxyphenyl) propionate, distearyl (3,5-ditertiary butinole_4-hydroxybenzyl) phosphonate, thiojetylene bis [(3,5-ditertiary butinole_4-hydroxyphenyl) propionate], 4, 4'-thiobis (6-tert-butyl _m_ cresol), 2-octylthio-1,4-6-di (3,5-ditert-butyl _4-hydroxyphenoxy) s-triazine, 2, 2'- Methylenebis (4-methyl-6-tert-butylphenol), bis [3,3_bis (4-hydroxy-1-tertiarybutylphenyl) butyric acid] glyconeol esterol, 4, 4, monobutylidenebis (6 — Tert-butyl _m_cresol), 2, 2'-ethylidenebis (4,6-ditertiarybutylphenol), 1,1,3-tris (2-methyl 4 —Hydroxy mono-5_tertiary butylphenyl) butane, bis [2_tertiary butyl_4 methyl mono 6- (2-hydroxy mono-3_tertiary butyl_5_methylbenzyl) phenyl] terephthalate, 1, 3, 5 _Tris (2, 6-dimethyl _ 3-hydroxy-l-4 tert-butylbenzyl) isocyanurate, 1, 3, 5-tris (3,5-di-tert-butyl _4-hydroxybenzyl) isocyanurate, 1, 3 , 5-tris (3,5-ditertiary butynole _4-hydroxybenzyl) _ 2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditertiarybutyl _4-hydroxyphenyl) Nore) bropionyloxychetyl] isocyanurate, tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, 2-tertiarybutyl-4-methyl-6- (2 Atari Royloxy 3 Third Thilu-5 methylbenzyl) phenol, 3, 9 bis [1,1-dimethinole 2 hydroxyethinole] -2, 4, 8, 10 Tetraxosaspiro [5,5] undecane bis [one (3-tert-butyl-4-hydroxy-) 5-butylphenol) propionate], triethylene glycol bis [j3 (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

[0043] Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristinorestearinole and distearyl esters of thiodipropionic acid and pentaerythritol tetra (β-dodecyl). And β-alkyl mercaptopropionic esters of polyols such as mercaptopropionate).

[0044] Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxi cocoa flower oil, and the like. Oil, epoxy methyl stearate, monobutynore, _2-ethylhexyl, monostearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxy amadi oil fatty acid ester, Examples thereof include bisphenol and diglycidyl ether, bullcyclohexene gepoxide, dicyclohexene gepoxide, 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate, and the like. In addition, when using an epoxy compound that is also used as a plasticizer such as epoxy soybean oil, in order to prevent a decrease in rigidity, do not use more than 25 parts by mass with the plasticizer. To.

[0045] Examples of the ultraviolet absorber include 2, 4-dihydroxybenzophenone, 2 hydro 2-hydroxybenzophenones such as xyl _4—methoxybenzophenone, 2-hydroxy _4—otatoxybenzophenone, 5, 5, monomethylenebis (2-hydroxy _4-methoxybenzophenone); 2- (2— Hydroxy-5_methylphenyl) benzotriazole, 2_ (2-hydroxy-5_tertiaryoctylphenyl) benzotriazole, 2_ (2-hydroxy-1,3,5-ditert-butylphenyl) _5_clobenzobenzotriazole, 2_ (2-hydroxy-1-tertiary butyl-5-methylphenyl) _5_ clobenzobenzotriazole, 2_ (2-hydroxy-1,5-dicumylphenyl) benzotriazole, 2, 2'-methylenebis (4-th Polyethylene of 3-otatilu-6 benzotriazolyl) phenol, 2- (2 hydroxy-3 tert-butyl-5 carboxyphenyl) benzotriazole 2- (2-hydroxyphenenole) benzotriazoles such as lenglycol esters; phenyl salicylates, resorcinol monobenzoate, 2,4 ditertiary butylphenol 3,5 ditertiary butyl-4-hydroxybenzoate, Benzoates such as oxadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate; 2 ethyl 2 'ethoxyoxanilide, 2 ethoxy 4' substituted oxanilides such as dodecyloxazanilide; ethyl α-cyano β, β-diphenyl allylate And cyanoacrylates such as methyl 2 cyano 3-methyl 3- (ρ-methoxyphenyl) acrylate.

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, 2, 2, 6, 6-tetramethylolate. _4—piperidino lenzoate, bis (2, 2, 6, 6—tetramethinole _4—piperidyl) sebacate, bis (1, 2, 2, 6, 6 _pentamethyl _4-piperidyl) sebacate, tetrakis (2, 2, 6 , 6-Tetramethyl _4-piperidyl) butanetetracarboxylate, tetrakis (1, 2, 2, 6, 6 _pentamethyl _4-piperidyl) butanetetracarboxylate, bis (1, 2, 2, 6, 6 _pentamethyl _4— Piperidyl) 'di (tridecinole) _ 1, 2, 3, 4_butanetetra force norevoxylate, bis (1, 2, 2, 6, 6 _pentamethinole _4—piperidyl) _ 2_butyl _ 2_ (3, 5—di Third Butyl _4-hydroxybenzylene) malonate, 1 _ (2-hydroxyethyl) -1,2,2,6,6-tetramethyl _4-piberidinol ジェ Jetyl polycondensate of succinate, 1,6 _bis (2, 2 , 6, 6-tetraethyl _4-piperidylamino) hexane / dibromoethane polycondensate, 1, 6 bis (2, 2, 6, 6 tetra Methyl _4—piperidylamino) hexane / 2, 4—Dichloro mouth 6 morpholino s—Triazine polycondensate, 1, 6 _bis (2, 2, 6, 6-tetramethyl _4—piperidylamino) ) Hexane Z2, 4—Dichloro mouth 6 _Tertioctylamino _s—Triazine polycondensate, 1, 5, 8, 12 —Tetrakis [2,4_bis (N-butyl _N_ (2, 2, 6, 6-tetramethyl _4-piperidinole) amino) 1 s-triazine 6-yl] 1, 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-Triazine-6-yl] -1, 1, 5, 8, 12-tetraazadodecane, 1, 6 , 11-Tris [2,4-bis (N-butyl N- (2, 2, 6, 6 tetramethyl-4-piperidyl) amino) -s triazine-6-ylamino] undecane, 1, 6, 11- Squirrel [2, 4- bis (N-butyl N- (1, 2, 2, 6, 6-pentamethyl-one 4-piperidyl) Amino) Single s- triazine 6- Iruamino] Hindadamin compounds such Undekan like.

[0047] Examples of the foaming agent include azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, jetylazodicarboxylate, diisopropyl azodicarboxylate, azobis (hexahydrobenzene). Azonitrile), N, N 'dinitro pentamethylenetetramine, N, Ν'-dimethyl-1-N, Ν'-dinitroterephthalamine, and other nitroso foaming agents, benzenesulfonylhydrazide, ρ toluenesulfonyl Hydrazides such as hydrazide, 3, 3'-disulfone hydrazide phenyl sulfone, toluene disulfonyl hydrazone, thiobis (benzenesulfonyl hydrazide), toluene ether sulfonyl azide, toluenesulfonyl semicarbazide, ρ, ρ'-bis (benzenesulfonyl hydrazide) ether Series blowing agent, ρ-t Examples include strong rubazide foaming agents such as ruenesulfonyl semicarbazide and 4,4'-oxybiz (sulfonyl semi-strength rubazide), triazine foaming agents such as trihydrazinotriazine and 1,3_bis (ο-biphenyltriazine), etc. It is done.

[0048] Examples of the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, and water. Aluminum oxide, sodium aluminate, sodium talcite, calcium calcite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, tanolec, clay, bengara, asbestos, antimony trioxide, etc. . [0049] The polyol compound may be a force containing a pentaerythritol compound or other polyol compounds. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2_propanediol, 1,3_propanediol, 1,2_butanediole, 1,3_butanediole, 1,4_butanediole, 1,6_ Low molecular weight polyol compounds such as xanthdiol, hydrogenated bisphenol A, glycerin, trimethylolpropane, 1,2,6_hexanetriol, diglycerin, dextrose, sorbitol, sucrose; alkylene oxide is added to the low molecular weight polyol compound Examples include the added Polio-Ruich compound.

[0050] In addition, other stabilizing aids can be added to the halogen-containing resin composition of the present invention. Examples of strong stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, keihic acid, p-tert-butylbenzoic acid, zeolite, perchlorate and the like.

[0051] In addition, the halogen-containing resin composition of the present invention includes a crosslinking agent, an antistatic agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a lubricant, a flame retardant, and an antifogging agent as necessary. , Fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, and the like. The amount of each of the various additives used is the halogen-containing resin composition of the present invention. However, the total content is preferably 100 parts by mass or less based on 100 parts by mass of the halogen-containing resin.

[0052] Further, the halogen-containing resin composition of the present invention can be used without being limited to a processing method, and includes, for example, a calendar process, a roll process, an extrusion molding process, an injection molding process method, It can be suitably used for melt casting, pressure molding, powder molding, and the like.

[0053] In the halogen-containing resin composition of the present invention, building materials such as wall materials, floor materials, window frames, wallpaper, etc .; automotive interior materials; wire covering materials; agricultural materials; food packaging materials; paints; It can be suitably used as miscellaneous goods such as pipes, sheets, and toys.

Example

[0054] Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. It is not limited by the embodiments.

[0055] [Example 1 1:! To 1 1 3, Comparative Example 1 1:! To 1 1 2]

The mixture of pentaerythritol, dipentaerythritol and a pentamer erythritol condensate of trimer or more shown in Table 1 is melted by heating at 230 ° C until it becomes transparent, cooled and solidified, and then pulverized to 150 mesh pass. A mixture having a particle size of 100 xm or less was obtained. Using this, the following tests were conducted and the results are shown in Table 1.

[0056] (Measuring melting point)

Regarding the melting point of the mixtures listed in Table 1, using a differential scanning calorimeter (Thermoplus TG812 0; manufactured by Rigaku Corporation) under a nitrogen atmosphere (20 ml / min) up to 300 ° C at 10 ° C / min And the temperature at which the melting peak begins was determined.

[0057] [Table 1]

* 1) PE: Pentaerythritol

* 2) DiPE: Dipentaerythritol

* 3) Poly-PE: Trimer or higher pentaerythritol condensate

[0058] [Example 2— :! to 2-3, Comparative Example 2— :! to 2-6]

Polychlorinated bur resin (degree of polymerization 1000) 100 parts by mass, Ido, talcite (Al force Mizer 1; manufactured by Kyowa Chemical Industry Co., Ltd.) 0.5 part by mass, calcium stearate 0.5 part by mass, stearin A halogen-containing resin composition was obtained by blending 1 part by mass of zinc oxide with 0.8 parts by mass of the mixture shown in Table 2 in addition to the powerful standard composition.

The mixture described in Examples and Comparative Examples 2— :! to 2-3 was heated and melted in the same manner as in Example 1-1, whereas Comparative Examples 2 — 4 to 2 The mixture of _6 is a mixture that has not been heated and melted. In addition, the mixture of Comparative Example 2_5 was finely pulverized, and the force S used for evaluation was 200 mesh pass (particle size of about 75 μΐη or less), and the other mixture was 100 mesh pass (particle size of about 150 What was μΐη or less) was used for evaluation. About these halogen-containing resin compositions, the evaluation shown below was carried out and the results were It is shown in Table 2.

[0059] (Dynamic thermal stability)

The halogen-containing resin composition is put into a lab plast mill (30C150 type; manufactured by Toyo Seiki Co., Ltd., 190 ° C, 50rpm, 65g / 60cc), and the resin is obtained by kneading the powerful halogen-containing resin composition. The decomposition time until decomposition and the kneading torque increased was measured.

[0060] (Plate-out resistance)

About the halogen-containing resin composition, it was put into a twin screw extruder, and the resin kneaded at an extrusion temperature of 180 ° C and a screw rotation speed of 20 rpm was immediately formed into a sheet shape having a width of 20 mm and a thickness of 2 mm with a roll processing machine. The size of the plate-out was evaluated by visually observing the surface of the strong sheet (evaluation criteria; ○: no deposit, Δ: slight deposit, X: large deposit).

[0061] (Static thermal stability)

The halogen-containing resin composition is put into a roll cage heated to 190 ° C., roll-kneaded for 3 minutes to form a sheet with a thickness of 0.5 mm, and the sheet is cut to a length of 20 mm. A strip-shaped test piece 10 mm wide was produced.

The powerful strip-shaped test piece was placed in an oven at 190 ° C and removed every 15 minutes, and the time for the strip-shaped test piece to partially blacken was confirmed.

[0062] [Table 2]

* 1) PE pentaerythri 1 ^ 1

* 2) DiPE: Dipen evening erythritol

* 3) Poly-PE: Pen erythritol condensate of trimer or higher

* 4) The mixture of Comparative Example 2-5 is 200 mesh pass (particle size is less than 75 m)

[0063] From Table 1, the sum of the contents of pentaerythritol and dipentaerythritol or the content of the pentaerythritol condensate is 20% by mass to 80% by mass with respect to the total amount of the mixture. In the case of an out-of-range mixture, the melting point of the mixture is high (Comparative Example 1-11 and Comparative Example 1-1-2) even when the melting treatment is performed. From Table 2, a halogen-containing resin composition containing such a mixture Example 2-2 and Comparative Example 2-3) have the problems of low dynamic thermal stability and static thermal stability and plate out on the surface.

Also, from Comparative Example 2-5, the problem of plate-out can be improved by pulverizing pentaerythritol compound, but the effect on dynamic thermal stability and static thermal stability is small. It is clear.

Then, even if the sum of the contents of pentaerythritol and dipentaerythritol and the content of the pentaerythritol condensate are both within the range of 20% by mass to 80% by mass with respect to the total amount of the mixture, the mixture subjected to the melting treatment Otherwise, a halogen-containing resin composition containing such a mixture cannot provide satisfactory performance (Comparative Examples 2-6).

[0064] On the other hand, a halogen-containing resin composition containing a melt-treated mixture in which the sum of the contents of pentaerythritol and dipentaerythritol and the content of the pentaerythritol condensate of the present invention are both 20% by mass to 80% by mass. It is clear that the product (Example 2— :! to 2-3) exhibits excellent effects in terms of dynamic thermal stability, plate-out resistance and static thermal stability.

[0065] As described above, the present invention relates to a mixture obtained by subjecting a melt-treated mixture in which the sum of the contents of pentaerythritol and dipentaerythritol and the content of the pentaerythritol condensate are both in the range of 20% by mass to 80% by mass. By containing it in the contained resin composition, it exhibits excellent effects in terms of dynamic thermal stability, plate-out resistance and static thermal stability.

Industrial applicability

[0066] According to the halogen-containing resin composition of the present invention, particularly when only a small amount of a plasticizer is blended or when it is not blended, excellent thermal stability and color resistance without using a heavy metal stabilizer. Is shown. Therefore, the halogen-containing resin composition of the present invention can be suitably used particularly for a building material application in which no plasticizer is used.

Claims

The scope of the claims

[1] A mixture obtained by heating and melting pentaerythritol, dipentaerythritol and a pentamer erythritol condensate of a trimer or more, wherein the sum of the contents of pentaerythritol and dipentaerythritol is relative to the total amount of the mixture. 20 to 80 weight ^_0/0, the mixture content of the trimer or more pentaerythritol condensate is 20 to 80 mass ^_0/0. (However, the sum of the contents of pentaerythritol, dipentaerythritol and pentaerythritol condensate of trimer or higher is 100% by mass.)

[2] A heat stabilizer containing the mixture according to claim 1.

[3] A halogen-containing resin composition containing the mixture according to claim 1.

[4] The halogen-containing resin composition according to claim 3, which contains 0.05 to 10 parts by mass of the above mixture with respect to 100 parts by mass of the halogen-containing resin.

[5] The halogen-containing resin composition according to claim 3 or 4, further comprising at least one selected from a β-diketone compound, a hydrated talcite compound and a fatty acid zinc.