JP2006124502A - Stabilizer for halogen-containing resin, and halogen-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stabilizer for a halogen-containing resin capable of obtaining the halogen-containing resin composition excellent in properties such as weather resistance, heat resistance, thermal stability, processability, transparency, blowing property suppression, etc., and the halogen-containing resin composition containing the stabilizer for the halogen-containing resin. <P>SOLUTION: This stabilizer for the halogen-containing resin consists of zinc oxide particles having 0.01-0.05 μm mean particle diameter. The halogen-containing resin composition is characterized by preferably containing the zinc oxide particles having 0.01-0.05 μm mean particle diameter and the halogen-containing resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a stabilizer for a halogen-containing resin and a halogen-containing resin composition.

Halogen-containing resins such as vinyl chloride resins are used in a wide range of fields such as sheets, films, electric / electronic parts, automobile parts, machine parts, building members, and miscellaneous goods. Various additives are widely added to such halogen-containing resins in order to improve various physical properties such as heat resistance during molding, workability, electrical insulation, mechanical properties, and weather resistance. Has been done.

Examples of applications that require improvement of the physical properties of the halogen-containing resin by using such additives include, for example, atypical building materials for housing, agricultural films, coating films for steel plates and plywood, canvas, curing The net etc. can be mentioned. In these applications, properties such as heat resistance, weather resistance, transparency, thermal stability, workability, and squeeze suppression are required depending on the purpose, and various additives are used.

For example, a halogen-containing resin such as a hard vinyl chloride resin used for atypical building materials such as a window frame in a house is particularly required to have weather resistance, heat resistance, thermal stability, and workability. Conventionally, lead stabilizers have been used as stabilizers for imparting such properties. However, in recent years, lead-free stabilizers have been studied from the viewpoint of environmental problems, and stabilizers composed of hydrotalcite and an organic acid zinc such as zinc stearate are known. Such a lead-free stabilizer is problematic in that it is inferior in heat resistance and weather resistance as compared with the conventional lead stabilizer. For this reason, it is desired to provide a stabilizer for a halogen-containing resin having excellent heat resistance and weather resistance without using a lead compound.

Furthermore, for example, agricultural sheets used for house (greenhouse), tunnel cultivation, etc .; coating films for steel plates and plywood; canvas; curing nets, etc. of soft vinyl chloride resins used for applications requiring transparency In such a halogen-containing resin, it is necessary to impart various properties such as heat resistance and weather resistance while maintaining transparency.

Also, in such applications, various additives such as plasticizers are usually used, but those additives leak out to the surface from the resin after a few years have passed since molding. The phenomenon is often seen. When such a ballooning phenomenon occurs, for example, when an agricultural vinyl chloride film is used for covering a house, a tunnel or the like, dust tends to adhere to the surface, leading to a decrease in light transmittance, and adversely affecting crop growth. Etc. arises.

On the other hand, it is known that zinc oxide is used as an additive to a halogen-containing resin, and is usually used as a white pigment, a flame retardant aid, and an ultraviolet absorber (for example, Patent Document 1). However, as an additive to the halogen-containing resin, zinc oxide having an average particle size of 0.1 μm or more is used, and it is known that fine zinc oxide particles are used as an additive to the halogen-containing resin. Not.

JP 2003-411147 A

In view of the above, the present invention provides a halogen-containing resin stabilization capable of obtaining a halogen-containing resin composition having excellent properties such as weather resistance, heat resistance, thermal stability, processability, transparency, and suppression of deflation. It is an object of the present invention to provide a halogen-containing resin composition comprising an agent and the halogen-containing resin stabilizer.

The present invention is a stabilizer for a halogen-containing resin characterized by comprising zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm.
The present invention is also a halogen-containing resin composition comprising zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm and a halogen-containing resin.

The zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm are preferably in a proportion of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the halogen-containing resin.
The halogen-containing resin composition further includes a hydrotalcite compound, a polyhydric alcohol compound, an organic acid calcium salt, an organic acid zinc salt, an organic phosphate metal salt, a β-diketone, and a metal salt of β-diketone. It preferably contains at least one selected component.

The halogen-containing resin composition further comprises a plasticizer, a lubricant, a stabilizer other than the zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm, a surfactant, an antifoggant, an ultraviolet absorber, a hindered amine. It is preferable to contain at least one component selected from the group consisting of a system light stabilizer, a filler, an antioxidant, an antistatic agent and a colorant.

This invention is also a housing unusual building material characterized by consisting of the halogen-containing resin composition mentioned above.
This invention is also an agricultural sheet | seat characterized by consisting of the halogen-containing resin composition mentioned above.
The present invention is also a coating film comprising the halogen-containing resin composition described above.
The present invention is described in detail below.

The present invention is a stabilizer for halogen-containing resins. The halogen-containing resin is not particularly limited, and can be used for a resin containing fluorine, chlorine, bromine, or iodine, but can be preferably used particularly for a resin containing chlorine. The resin containing chlorine is not particularly limited. For example, polyvinyl chloride; ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer, polyvinylidene chloride, chlorine And resins such as modified polyolefins. It can also be applied to mixtures with other resins that are compatible with the halogen-containing resin. As said other resin, a polyester resin, an epoxy resin, an acrylic resin, a urethane resin, an acrylonitrile-butadiene-styrene copolymer etc. can be mentioned, for example. The average degree of polymerization of the halogen-containing resin is not particularly limited, and can be applied to a resin in the range of 600 to 3000, preferably 700 to 2500, for example. The halogen-containing resin can be produced by a known method such as a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method.

The stabilizer for halogen-containing resin of the present invention comprises zinc oxide particles having an average particle size of 0.01 to 0.05 μm (hereinafter referred to as “fine zinc oxide particles”). Zinc oxide changes its properties by making the particle size minute. For this reason, when the fine zinc oxide particles are used, various excellent effects that cannot be obtained when zinc oxide particles having a large average particle diameter are used are obtained.

The average particle diameter is a primary particle diameter defined by a constant direction diameter (so-called FERET diameter) in a field of view of 100,000 times that of a transmission electron micrograph. When the average particle size is smaller than 0.01 μm, it is difficult to produce industrially, and when the average particle size is larger than 0.05 μm, heat resistance, weather resistance, transparency, etc. are added when added to a halogen-containing resin. The property is inferior. The fine zinc oxide particles are known particles for additives and cosmetics for polyester resins and polycarbonate resins. For example, the fine zinc oxide particles can be used as a metal soap at a temperature equal to or higher than the melting point of the metal soap disclosed in Japanese Patent Application Laid-Open No. 2003-411147. By mixing with zinc oxide particles, it can be produced by a method for producing fine zinc oxide particles coated with metal soap. Commercially available fine zinc oxide particles can be used, and are not particularly limited, and examples thereof include “Nanofine W-1” (trade name) manufactured by Sakai Chemical Industry Co., Ltd. Can do.

Although the said fine zinc oxide particle changes with uses, it is preferable to add in the ratio of 0.01-1.0 mass part with respect to 100 mass parts of said halogen-containing resin. If it is less than 0.01 parts by mass, the heat resistance and weather resistance may be insufficient, and if it exceeds 1.0 parts by mass, there may be a problem of a decrease in heat resistance. The lower limit is more preferably 0.05 parts by mass. The upper limit is more preferably 0.5 parts by mass.

The present invention is also a halogen-containing resin composition containing the fine zinc oxide particles and the halogen-containing resin. The fine zinc oxide particles and halogen-containing resin used in the halogen-containing resin composition of the present invention are each as described above, and the mixing ratio thereof is also preferably in the above-mentioned range.

The halogen-containing resin composition of the present invention may contain any additive in combination with the fine zinc oxide particles. The optional additives are preferably selected and used in accordance with the purpose of use. When the halogen-containing resin composition contains a vinyl chloride resin, it may be a hard vinyl chloride resin or a soft vinyl chloride resin.

For example, in a halogen-containing resin composition that requires the same high level of heat resistance, weather resistance, and workability as when a lead-based stabilizer is used, such as atypical building materials for houses, Use at least one component selected from the group consisting of a hydrotalcite compound, a polyhydric alcohol compound, an organic acid calcium salt, an organic acid zinc salt, an organic phosphate metal salt, a β-diketone, and a β-diketone metal salt It is preferable. By using together the said component, it can be set as the halogen-containing resin composition which has higher level heat resistance, a weather resistance, and workability.

The hydrotalcite compound has the following general formula (1):
^{_{M 2+ 1-x M 3+ x}} (OH) 2 A n- x / n · mH 2 O (1)
(In the formula, M ²⁺ represents Mg ²⁺ , Zn ²⁺ , Fe ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ .
In the formula, M ³⁺ represents Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ .
^{Wherein, A _{n-is, OH -, CO 3 2-,}} SO 4 2-, NO 3 -, Cl - represent.
In the formula, x is 0 <x <0.33. )
It is a compound represented by these. There are no particular restrictions regarding the hydrotalcite compound, for _{example, Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O Mg 4.5 Al 2 (OH) 13 CO 3 · 3.5H 2 O Mg 4.5 Examples include Al ₂ (OH) ₁₃ CO ₃ Mg _3.5 Zn _1.0 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O. A commercial item can also be used as said hydrotalcite compound. It does not specifically limit as a commercial item, For example, Alkamizer 1, Alkamizer 2, Alkamizer 3, Alkamizer 4, Alkamizer 5, DHT-4A (all manufactured by Kyowa Chemical Industry Co., Ltd.), Hydrotalcite HT-1 (Manufactured by Sakai Chemical Industry Co., Ltd.). The hydrotalcite compound is known as a stabilizer for halogen-containing resins, and when used in combination with fine zinc oxide particles, further excellent thermal stability can be obtained.

The hydrotalcite compound is preferably contained in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, with respect to 100 parts by mass of the halogen-containing resin. If it is less than 0.01 part by mass, the effect of improving the thermal stability is not sufficient, and if it exceeds 10 parts by mass, there is a possibility that problems such as a decrease in transparency and coloring during processing may occur.

The polyhydric alcohol compound is a compound having two or more hydroxyl groups in one molecule. The polyhydric alcohol is not particularly limited, and examples thereof include dipentaerythritol, dipentaerythritol partial ester, pentaerythritol, mannitol, sorbitol, and ditrimethylolpropane. Although the said polyhydric alcohol is well-known as a stabilizer of halogen-containing resin, heat resistance improves remarkably by using together with a fine zinc oxide particle.

The polyhydric alcohol compound is preferably contained in an amount of 0.01 to 10 parts by mass, and more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the halogen-containing resin. If it is less than 0.01 part by mass, the heat resistance is insufficient, and if it exceeds 10 parts by mass, there is a possibility of causing problems such as a decrease in transparency and coloring during processing.

The organic acid calcium salt is not particularly limited, and examples thereof include aliphatic calcium salts such as calcium stearate and calcium salts of aromatic carboxylic acids such as calcium para-t-butylbenzoate. It is preferable to contain 0.05-5 mass parts with respect to 100 mass parts of halogen-containing resin, and, as for the said organic acid calcium salt, it is still more preferable to contain 0.1-2 mass parts. If it is less than 0.05 part by mass, the heat resistance is not sufficient, and if it exceeds 5 parts by mass, there is a possibility of causing a problem of coloring during processing.

Although it does not specifically limit as said organic acid zinc salt, The zinc salt of C12-C20 saturated fatty acid or unsaturated fatty acid generally called metal soap is preferable. Although the said organic acid zinc salt is well-known as a stabilizer of halogen containing resin, it can be set as the halogen containing resin composition which has a more excellent effect by using the said compound together with the said fine zinc oxide particle. Examples of the organic acid zinc salt include zinc stearate, zinc palmitate, zinc myristate, zinc laurate, zinc octylate, and zinc behenate.

It is preferable to contain 0.05-5 mass parts with respect to 100 mass parts of halogen-containing resin, and, as for the said organic acid zinc salt, it is still more preferable to contain 0.1-2 mass parts. If the amount is less than 0.05 parts by mass, the heat resistance and weather resistance may not be sufficiently improved. If the amount exceeds 5 parts by mass, the processability may be deteriorated due to lubricity. In particular, when a large amount of fatty acid zinc is blended in order to improve thermal stability and weather resistance, there is often a problem that processability deteriorates, but in the present invention, it is used in combination with fine zinc oxide particles. Thus, the amount of fatty acid zinc used can be reduced, and the heat resistance and weather resistance can be improved without causing problems in workability.

It does not specifically limit as said organophosphate metal salt, For example, a stearyl zinc phosphate, a stearyl calcium phosphate, etc. can be mentioned. The organophosphate metal salt is preferably contained in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the halogen-containing resin. If it is less than 0.05 parts by mass, the heat resistance is not sufficient, and if it exceeds 5 parts by mass, there is a possibility that problems of deterioration of workability due to lubricity and coloring during processing may occur.

The β-diketone or a metal salt thereof is not particularly limited as long as it is a compound that can be used as a stabilizer for a halogen-containing resin. For example, dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, benzoylacetone, Examples include dibenzoylmethane zinc and stearoylbenzoylmethane zinc.

The β-diketone or a metal salt thereof is preferably contained in an amount of 0.005 to 1.0 part by mass, and more preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the halogen-containing resin. If it is less than 0.005 parts by mass, the heat resistance and weather resistance may not be sufficiently improved. If it exceeds 1.0 parts by mass, there may be a problem of poor weather resistance.

In addition to the above components, the halogen-containing resin composition of the present invention further includes a plasticizer, a lubricant, a stabilizer other than the fine zinc oxide particles, a surfactant, an antifoggant, an ultraviolet absorber, a hindered amine light stabilizer. Other additives usually used in halogen-containing resins such as an agent, a filler, an antioxidant, an antistatic agent, and a colorant may be used in combination.

As the halogen-containing resin composition used for atypical building materials of a house, a halogen-containing resin composition containing a vinyl chloride resin, fine zinc oxide particles, a hydrotalcite compound and / or a polyhydric alcohol compound, and an organic acid zinc salt ( I) or a halogen-containing resin composition containing vinyl chloride resin, fine zinc oxide particles, hydrotalcite compound and / or polyhydric alcohol compound, organic acid zinc, and metal salt of β-diketone and / or β-diketone The product (II) is particularly preferable from the viewpoint of excellent heat resistance and weather resistance. In particular, at the time of hot melt molding such as injection molding and extrusion molding, it is possible to suppress the decrease in resin physical properties due to heat to the same level as that of lead-based stabilizers, so that the amount of lead used can be reduced.

This invention is also the unusual building material of the house which consists of the said halogen-containing resin composition. The atypical building material has good moldability, excellent thermal stability and weather resistance without using a lead compound.

When the halogen-containing resin composition of the present invention is used for applications requiring transparency, such as agricultural sheets used for house (greenhouse) and tunnel cultivation; coating films for steel plates and plywood; canvas; It is necessary to impart various properties such as heat resistance and weather resistance while maintaining transparency. In the above-mentioned use, the halogen-containing resin composition is preferably a soft vinyl chloride resin. In addition, in these applications, various additives are often used in combination, so that the additive properties may cause a decrease in physical properties due to the bleed phenomenon that leaks to the surface, and the bleed phenomenon may be reduced. It has been demanded.

In the halogen-containing resin composition used in applications requiring transparency as described above, for example, plasticizers, lubricants, stabilizers other than the fine zinc oxide particles, surfactants, antifogging agents, ultraviolet absorption An agent, a hindered amine light stabilizer, a filler, an antioxidant, an antistatic agent, and at least one additive selected from the group consisting of a coloring agent may be used in combination. When the fine zinc oxide particles are used in combination with these additives, there is an effect that the brewing effect is reduced.

The plasticizer is not particularly limited, and examples thereof include phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, and diisodecyl phthalate; isophthalic acid derivatives such as diisooctyl phthalate; -Adipic acid derivatives such as butyl adipate and dioctyl adipate; Maleic acid derivatives such as di-n-butyl malate; Citric acid derivatives such as tri-n-butyl citrate; Itaconic acid derivatives such as monobutyl itaconate; Oleic acid derivatives; ricinoleic acid derivatives such as glycerin monoricinoleate; epoxy plasticizers; triisopropylphenyl phosphate, isodecyldiphenyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, Li ethyl phosphate, trioctyl phosphate, can be mentioned tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate organic phosphate plasticizers such like. Examples of the epoxy plasticizer include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxy resins. The addition amount of the plasticizer is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the halogen-containing resin.

The lubricant is not particularly limited, and examples thereof include fatty acids such as stearic acid, palmitic acid, 12-hydroxystearic acid, and behenic acid, and fatty acid amides such as stearic acid amide, palmitic acid amide, oleic acid amide, and ethylenebisstearic acid amide. And fatty acid esters such as butyl stearate, butyl palmitate and octyl stearate, polyethylene wax, liquid paraffin, natural paraffin, synthetic paraffin, solid higher alcohol, glycerin fatty acid ester and the like. The said lubricant can be used individually or in combination of 2 or more types. It is preferable to contain the said lubricant in the ratio of 0.5-7.0 mass parts with respect to 100 mass parts of halogen-containing resin, and it is more preferable that it is a ratio of 1.0-5.0 mass parts.

Stabilizers other than the fine zinc oxide particles are not particularly limited. For example, metal soap stabilizers such as calcium stearate, cadmium stearate, barium stearate, aluminum stearate, magnesium stearate; Ba-Zn series , Ca-Zn-based, Ca-Zn-Ba-based, Ba-Mg-Al-based, Cd-Ba-based, Cd-Ba-Zn-based, Cd-Ba-Pb-based stabilizers; zinc stearyl phosphate, calcium stearyl phosphate, etc. Organophosphate metal salts of the above; chelating agents such as organic phosphites; polyol compounds such as pentaerythritol and trimethylolpropane. These stabilizers can be used alone or in combination of two or more. The addition amount of the stabilizer other than the fine zinc oxide particles is preferably 0.5 to 7.0 parts by mass, and 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the halogen-containing resin. It is preferable.

The surfactant is not particularly limited, and examples thereof include nonionic surfactants, fluorine surfactants, and silicone surfactants.

The nonionic surfactant is not particularly limited, and examples thereof include a polyhydric alcohol partial ester compound composed of a polyhydric alcohol and higher fatty acids. The polyhydric alcohol partial ester-based compound is not particularly limited. For example, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate sorbitan / glycerin condensate and higher fatty acid ester, sorbitan / alkylene glycol Sorbitan surfactants such as esters of condensates and higher fatty acids; glycerol monolaurate, glycerol monostearate, diglycerol monostearate, diglycerol monolaurate, diglycerol monopalmitate, triglycerol monostearate, Glycerin surfactants such as tridiglycerin monostearate; polyethylene glycol monostearate, polyethylene glycol monopalmitate, polyethylene glycol alkyl phenyl ether, etc. Ethylene glycol surfactants; Trimethylolpropane surfactants such as trimethylolpropane monostearate; Pentaerythritol surfactants such as pentaerythritol monopalmitate, pentaerythritol monostearate, dipentaerythritol monostearate Or these isomers.

The silicone-based surfactant is not particularly limited, and examples thereof include polyether-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, and the like. Generally, at least 0.01% by mass, Preferably, it has a solubility in water of at least 0.1% by mass and has the ability to reduce the surface tension of water at 25 ° C. to 35 dyn / cm or less, particularly 30 dyn / cm or less.

A commercially available product may be used as the silicone surfactant. Examples of commercially available silicone surfactants include KF-354 (manufactured by Shin-Etsu Chemical), SH-3746 (manufactured by Dow Corning Toray), TSF-4445 (manufactured by Toshiba Silicone), and the like.

As the surfactant, the above-described surfactants may be used alone, or two or more kinds may be used in appropriate combination. As addition amount of the said surfactant, it is preferable that it is 0.01-2 mass parts with respect to 100 mass parts of halogen-containing resin, and it is more preferable that it is 0.02-1.9 mass parts.

The anti-fogging agent is not particularly limited, and examples thereof include a high molecular or low molecular fluorine-containing surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group, and is generally at least 0.001% by mass, Preferably, it has a solubility in water of at least 0.01% by mass and has the ability to reduce the surface tension of water at 25 ° C. to 35 dyn / cm or less, preferably 30 dyn / cm or less. The perfluoroalkyl group may have an oxygen atom in its carbon chain. Commercially available anti-fogging agents that can be used in the resin composition of the present invention include, for example, Unidyne DS-401, Unidyne DS-403, Unidyne DS-451 (manufactured by Daikin Industries, Ltd.), MegaFuck F-142D. , MegaFuck F-177 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Fluorad FC-170, Fluorad FC-176, Fluorad FC-430 (above, manufactured by Sumitomo 3M), Surflon S-141, Surflon S-145 , Surflon S-381, Surflon S-382, Surflon S-393 (manufactured by Asahi Glass Co., Ltd.) and the like.

When it contains the said anti-fogging agent, it is preferable to contain in the ratio of 1 mass part or less with respect to 100 mass parts of said halogen-containing resin, and it is more preferable that it is a ratio of 0.01-0.7 mass part. .

The ultraviolet absorber is not particularly limited, and those usually blended with halogen-containing resins can be used. For example, various ultraviolet absorbers such as benzotriazole, benzophenone, salicylic acid, hydroquinone, and cyanoacrylate An agent can be mentioned. In particular, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and salicylic acid ultraviolet absorbers are more preferable.

The benzotriazole-based ultraviolet absorber is not particularly limited, and examples thereof include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-amyl-5′-isobutylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-isobutyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2 ′ Proxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] can be exemplified benzotriazole.

The benzophenone-based ultraviolet absorber is not particularly limited. For example, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy- 4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. be able to.

The salicylic acid-based ultraviolet absorber is not particularly limited, and examples thereof include phenyl salicylate and paraoctylphenyl salicylate.

The said ultraviolet absorber can be used individually or in combination of 2 or more types. The blending amount is preferably in the range of 3.0 parts by mass or less, more preferably 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the halogen-containing resin.

The hindered amine light stabilizer is not particularly limited, and examples thereof include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (1,2,2,6,6,- Pentamethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, poly {[6- (1,1,3) , 3-Tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyl [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2, 6,6-tetramethyl-4-piperidyl) imino]}, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2 , 6,6 Pentamethyl-4-piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis (2-hydroxy-1, 1-dimethylethyl) -2,4,8,10 tetraspiro [5,5] undecane and an ester of butanetetracarboxylic acid. The above light stabilizers may be used alone or in combination of two or more. The hindered amine light stabilizer is preferably contained at a ratio of 0.01 to 2.0 parts by mass, more preferably 0.03 to 1.0 part by mass with respect to 100 parts by mass of the halogen-containing resin.

The filler is not particularly limited, and examples thereof include silica, talc, diatomaceous earth, ferrites, aluminum hydroxide, calcium sulfate, calcium silicate, calcium hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, barium sulfate, and kaolin. Clay, mica, alumina, calcium carbonate, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate, hydrotalcites, fiber and powder such as glass or carbon or metal, glass sphere, graphite, lithium-aluminum composite Examples thereof include hydroxide salts and lithium-magnesium-aluminum composite hydroxide salts. The said filler is used in order to suppress the stickiness at the time of setting it as a film, or to maintain heat retention. The said filler may be used independently and may be used in combination of 2 or more type. It is preferable to contain the said filler in the ratio of 0.05-7.0 mass parts with respect to 100 mass parts of halogen-containing resin, and 0.1-5.0 mass parts is more preferable. In addition, when shape | molding and using a halogen-containing resin composition in a film form, it is preferable to select a kind and compounding quantity suitably according to the thickness of the film obtained.

It does not specifically limit as said antioxidant, For example, a phenolic antioxidant and sulfur type antioxidant can be mentioned. The phenolic antioxidant is not particularly limited, and examples thereof include 2,6-di-butyl-4-methylphenol-2,2-methylenebis (6-tert-butyl-4-ethylphenol). The sulfur-based antioxidant is not particularly limited, and examples thereof include dilauryl thiodipropionate. The said antioxidant may be used individually or in combination of 2 or more types.

The antistatic agent is not particularly limited, and examples thereof include polyoxyethylene alkylamine, polyglycol ether, and sodium p-styrenesulfonate.

The colorant is not particularly limited, and examples thereof include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, permanent red, quinacridone, and the like. These colorants can also be used alone or in combination of two or more.
The halogen-containing resin composition of the present invention may be used in combination with additives other than those described above.

The method of mixing the above components is not particularly limited. For example, the halogen-containing resin is weighed with the necessary components and various additives that can be blended as necessary, and a ribbon blender, a Banbury mixer, a super mixer. In addition, it can be carried out by charging and kneading in a known blender or mixer.

The halogen-containing resin composition of the present invention can be used after being formed into a film shape.
The method for molding a chlorine-containing resin film comprising the halogen-containing resin composition of the present invention is not particularly limited. For example, the resin composition mixed by the above method is formed by a known method such as a calendering method or an extrusion molding method. And the like.

The present invention is also an agricultural sheet comprising the halogen-containing resin composition. The agricultural sheet is a sheet used for a house, a tunnel-grown house, a tunnel, or the like. The present invention is also a coated melt sheet. The covering sheet is a sheet for covering the surface of a steel plate or plywood to protect the surface, and even if it is bonded to the steel plate or plywood to form a laminate, it is physically integrated. It may be installed on a steel plate or a plywood without being made into. In addition, the halogen-containing resin composition can be used for canvas, curing nets, and the like.

Since the stabilizer for halogen-containing resin of the present invention is as described above, it is excellent in properties such as weather resistance, heat resistance, thermal stability, workability, transparency, and suppression of whipping. A halogen-containing resin composition can be obtained. The halogen-containing resin composition of the present invention has excellent properties such as weather resistance, heat resistance, thermal stability, processability, transparency, and suppression of whipping.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples. In the examples, “parts” means “parts by mass” unless otherwise specified.

Examples 1-7, Comparative Examples 1-7
Each additive shown in Table 1 is blended in a proportion shown in Table 1 with respect to 100 parts by mass of a polyvinyl chloride resin (degree of polymerization 1000), kneaded for 5 minutes with a 160 ° C. roll, and then at a 170 ° C. press. A sheet having a thickness of 1 mm was prepared. The prepared sheet was evaluated according to the following evaluation criteria. The results are shown in Table 1 (Examples) and Table 2 (Comparative Examples). In addition, what was shown below was used for each component in Table 1 and Table 2.
* 1: Vigot 10 manufactured by Shiroishi Kogyo Co., Ltd.
* 2: SC-P manufactured by Sakai Chemical Co., Ltd.
* 3: SZ-P manufactured by Sakai Chemical Co., Ltd.
* 4: Rhodia dibenzoylmethane * 4: Guangei Chemical Dipentalit 300
* 6: Two types of zinc oxide manufactured by Sakai Chemical Co., Ltd. (average particle size 0.6 μm)
* 7: Nano Fine W-1 manufactured by Sakai Chemical Industry Co., Ltd. (average particle size: 0.02 μm)
* 8: Anomoto Fine Techno Plenizer ST-210
* 9: Hydrotalcite HT-1 (trade name) manufactured by Sakai Chemical

Reference example 1
As a reference example, a sheet was prepared in the same manner as in Example 1 using a lead-based stabilizer.

<Evaluation method>
(Heat resistance) The above sheet was pressed with a 180 ° C. press for 10 minutes, and the discoloration of the obtained sheet was evaluated based on the following criteria.
A: No discoloration of the sheet is observed.
○: Some discoloration is observed.
X: Significant discoloration was observed.

(Weather resistance) The product was exposed with a metal weather meter manufactured by Daipura Wintes, and the change in surface gloss was evaluated based on the following criteria. The test conditions were irradiation, humidification, and rest cycle (Light 8 hours, 63 ° C., humidity 70%, light intensity 80 mW / cm ² , Dew 8 hours, 55 ° C., humidity 90%, Rest 8 hours, 30 ° C. , Humidity 98%).
A: No change in gloss is observed.
○: Gloss slightly decreased.
X: The gloss was almost lost.

(Processability) Using 68 g of the compound mixed at the blending ratios in Tables 1 and 2, evaluation was performed under the conditions of 170 ° C. and 50 rpm with Toyo Seiki Lab Plast Mill, and evaluation was performed based on the following criteria. Here, the cohesiveness means the degree of ease of gelation when a compound, which is a powder mixture, is heated and kneaded with a plast mill.
A: The unity is very fast.
○: The unity is fast.
X: The unity property is slow.

From the results in Table 1 above, the resin composition containing fine zinc oxide having an average particle size of 0.02 μm in the halogen-containing resin has heat resistance and weather resistance without impairing conventional performance (workability, etc.). It is clear that it can be improved significantly. Its physical properties are almost the same as when a lead-based stabilizer is used.

Examples 8-14, Comparative Examples 8-11
The raw materials having the composition shown in Table 3 were mixed for 10 minutes with a super mixer, then kneaded with a test roll at 175 ° C., and formed into a 0.1 mm agricultural vinyl chloride resin film. The obtained film was evaluated for the blowing property, accelerated weather resistance, film transparency, and plate-out by the following methods. The results are shown in Table 3.

[Test method]
(1) Draft properties The film obtained was immersed in water at 40 ° C. for 24 hours, and then the speech bubble on the film surface when left at 23 ° C. for 2 hours was visually evaluated.
◎ ・ ・ ・ No speech bubbles are recognized ○ ・ ・ ・ Slightly speech bubbles are observed △… Speech bubbles are recognized × ・ ・ ・ Many speech bubbles are recognized XX ・ ・ ・ Small speech bubbles are recognized

(2) Accelerated weather resistance The obtained film was subjected to an accelerated weather resistance tester (trade name “Daipura Metal Weather”, manufactured by Daipura Wintes Co., Ltd.), and the deterioration change of the film appearance after 100 hours was visually evaluated. The test conditions were irradiation, humidification, and rest cycle (Light 8 hours, 63 ° C., humidity 70%, light intensity 80 mW / cm ² , Dew 8 hours, 55 ° C., humidity 90%, Rest 8 hours, 30 ° C. , Humidity 98%).
◎ ・ ・ ・ No browning is observed ○ ・ ・ ・ Slight browning is observed △ ・ ・ ・ Browning is observed × ・ ・ ・ Many browning is observed XX ・ ・ ・ Blanting is observed on the entire surface

(3) Film transparency The turbidity of the obtained film was measured with a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NDH-300A”) to evaluate the transparency.
◎ ... Turbidity 0 to less than 5% ○ ... Turbidity 5 to less than 10% Δ ... Turbidity 10 to less than 15% × ... Turbidity 15 to less than 20% XX… Turbidity 20% or more

(4) Plate-out 80 g of the obtained film was kneaded with a test roll at 185 ° C., and the amount of generated plate-out was observed.
◎ ・ ・ ・ Not recognized ○ ・ ・ ・ Slightly recognized △ ・ ・ ・ Allowed × ・ ・ ・ Almost recognized XX ・ ・ ・ Remarkably increased

From the results shown in Table 3, it is clear that the films of the examples have excellent properties in terms of suppression of bleeding, weather resistance, and processability while maintaining the transparency of the film. It is clear from these properties that they are suitable for use in agricultural sheets.

Examples 15-20, Comparative Examples 12-14
The vinyl chloride resin composition having the composition shown in Table 4 was mixed with a super mixer for 10 minutes, kneaded with a test roll at 175 ° C., and then molded into a 0.15 mm semi-rigid vinyl chloride resin film. Accelerated weather resistance, film transparency, and plate-out were evaluated in the same manner as in 8-14 and Comparative Examples 8-11. The results are shown in Table 4.

From the results of Table 4, it is clear that the films of the examples have excellent properties in weather resistance and processability while maintaining the transparency of the film. It is apparent that these properties are suitable for use in coating films.

The halogen-containing resin composition of the present invention is not particularly limited in application, and can be used in various applications. The main applications include, for example, atypical building materials for houses, agricultural sheets used for house (greenhouse), tunnel cultivation, etc .; films for covering steel plates and plywood; canvas; curing nets and the like. Moreover, it can shape | mold and use for various forms, such as a film, a fiber, a molded object, according to a use.

Claims (8)

A stabilizer for halogen-containing resin, comprising zinc oxide particles having an average particle diameter of 0.01 to 0.05 µm. A halogen-containing resin composition comprising zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm and a halogen-containing resin. The halogen-containing resin composition according to claim 2, wherein the zinc oxide particles having an average particle diameter of 0.01 to 0.05 µm are in a ratio of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the halogen-containing resin. Further, at least one component selected from the group consisting of a hydrotalcite compound, a polyhydric alcohol compound, an organic acid calcium salt, an organic acid zinc salt, an organic phosphate metal salt, a β-diketone, and a metal salt of β-diketone. The halogen-containing resin composition according to claim 2 or 3, which is contained. Furthermore, plasticizers, lubricants, stabilizers other than zinc oxide particles having an average particle diameter of 0.01 to 0.05 μm, surfactants, antifogging agents, ultraviolet absorbers, hindered amine light stabilizers, fillers, The halogen-containing resin composition according to claim 2, 3 or 4, comprising at least one component selected from the group consisting of an antioxidant, an antistatic agent and a colorant. A housing unusual building material comprising the halogen-containing resin composition according to claim 2, 3 or 4. An agricultural sheet comprising the halogen-containing resin composition according to claim 2, 3 or 5. A coating film comprising the halogen-containing resin composition according to claim 2, 3 or 5.