JP2012025789A - Warm-keeping agent for polyolefin-based resin, and agricultural film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a warm-keeping agent for a polyolefin-based resin with which a polyolefin-based resin excellent in warm-keeping property can be obtained, and the polyolefin-based resin in which deterioration hardly occurs even if a pipe in contact with it is further heat-accumulated, can be obtained by adding it to the polyolefin-based resin as a warm-keeping property improver; and an agricultural film using it.SOLUTION: The warm-keeping agent for the polyolefin-based resin includes a perchlorate ion type hydrotalcite compound, and further, the polyolefin-based resin composition containing the warm-keeping agent is especially used for agricultural films.

Description

The present invention relates to a heat-retaining agent for polyolefin resin that is excellent in heat retention by being added to a polyolefin resin, and hardly deteriorates even when a pipe that is in contact with heat is stored, and an agricultural film using the same. .

In recent years, agricultural films used for greenhouse cultivation, such as crop houses and tunnel houses, transmit sunlight through the house or tunnel house with high transmittance in the daytime, while infrared rays radiated from the ground or plants at night. There is a demand for characteristics such as preventing absorption of light from the house or tunnel house due to absorption or reflection.

In the agricultural film, the use of a heat insulating agent (infrared absorbing agent) has been proposed for the purpose of absorbing infrared rays radiated at night and improving the heat retaining effect. (For example, Japanese Patent Publication No. Sho 62-031744 and Japanese Patent Laid-Open Publication No. Sho 63-149148) It is known that inorganic substances such as hydrotalcites having particularly high infrared absorption ability and high transparency are well-balanced substances. .

However, if a large amount of inorganic material such as hydrotalcite is added to the polyolefin-based resin, it is possible to impart the required heat retention to the film. There was a big problem that the sun rays hit the pipe mainly used as the aggregate of the heat, the pipe stored heat, the part in contact with the pipe was easily deteriorated or hardened and was torn.
Therefore, researches using many stabilizers, ultraviolet absorbers, etc. have been conducted for improving pipe deterioration. However, at present, sufficient pipe deterioration improving agents have not been obtained. As a pipe deterioration improving method, it has been proposed to mix a phosphite compound and an organic phosphate metal salt (Japanese Patent Laid-Open No. 7-179700), but the improvement by the heat insulating agent as in the present invention is not specified at all.
JP 7-179700 A

An object of the present invention is a polyolefin-based resin heat insulating agent, a polyolefin-based resin molded using the resin has excellent heat-retaining properties, and the polyolefin-based resin hardly deteriorates even if the contacting pipe stores heat. It is providing the heat insulating agent for polyolefin resin from which resin is obtained, and the agricultural film using the same.

As a result of intensive investigation of a polyolefin resin heat-retaining agent in order to overcome the problems of the prior art, the present inventor has to use a perchlorate ion type hydrotalcite compound or other hydrotalcite compound in combination with it. Thus, it has been found that it has a special effect as a heat insulating agent. The present invention has been made based on such findings.

In other words, the present invention is used as a heat retention improver that is excellent in heat retention when added to a polyolefin resin, and can be obtained as a polyolefin resin that is less likely to deteriorate even when the pipes in contact with it store heat. A novel insulation for polyolefin-based resins containing the perchlorate ion-type hydrotalcite compound or the perchlorate ion-type hydrotalcite compound and one or more of the other hydrotalcite compounds described in 1. An agent is provided.
Moreover, the agricultural film as described in 5-8 is provided.
1 A heat-retaining agent added to a polyolefin-based resin, characterized by containing a perchlorate ion-type hydrotalcite compound. 2 A heat-retaining agent for a polyolefin-based resin 2 A perchlorate ion-type hydrotalcite compound Following formula (1)
(In the formula, 3 <x <10, 0 ≦ y <1, 0.1 <z ≦ 1, 0 <m <10, 0.5 ≦ n ≦ 20, where mH ₂ O is interlayer water, nH ₂ O indicates free water.)
1. Polyolefin resin heat-retaining agent according to 1, wherein the polyolefin resin heat-retaining agent according to 1, which contains one or more hydrotalcite compounds excluding perchlorate ion-type hydrotalcite compounds, Agriculture using the heat insulating agent for polyolefin resins according to 2, which contains one or more of hydrotalcite compounds excluding chlorate ion type hydrotalcite compounds, according to 51 The polyolefin fat retaining agent described in the agricultural film 84 using the polyolefin resin insulating agent described in the agricultural film 73 using the polyolefin resin insulating agent described in the insulating film 62 is used. Agricultural film The present invention is described in detail below.

The heat insulating agent for polyolefin resin according to the present invention is a perchlorate ion type hydrotalcite compound, and preferably a compound represented by the following formula (1).
(In the formula, 3 <x <10, 0 ≦ y <1, 0.1 <z ≦ 1, 0 <m <10, 0.5 ≦ n ≦ 20, where mH ₂ O is interlayer water, nH ₂ O indicates free water.)

As the hydrotalcite compound in combination with a perchlorate ion type hydrotalcite compound of the present invention, DHT-4A as a representative example _{(Mg 4.5 Al 2 (OH)} 12 (CO 3) · 3.5H ₂ O), Alkamizer-2 (Mg ₄ Al ₂ (OH) ₁₂ CO ₃ ), Alkamizer 1, Alkamizer ₄ , Alkamizer 7 (all manufactured by Kyowa Chemical Industry Co., Ltd.) HT-7 (Mg _3.5 Zn _0.5 Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O), HT-1, HT-P (all manufactured by Kyowa Chemical Industry Co., Ltd.), NAOX-33, NAOX-71, NAOX-54, NAOX-57, NAOX- 55, NAOX-56, NAOX-72, OPTIMA-LSA, OPTIMA-XT, MAGGOLD, MAGCLEAR, NAOX-19, NAOX-19T, NAOX-81, NAOX-91 (all of which are Toda Kogyo Co., Ltd.).

The amount of the heat insulating agent of the present invention added to the polyolefin resin is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to the polyolefin resin. If the amount is less than 1 part by weight, a sufficient heat retention effect is not observed, and if it exceeds 50 parts by weight, the translucency and mechanical strength of the agricultural film are lowered.

Examples of the polyolefin-based resin in the present invention include α-olefin homopolymers, copolymers with different monomers mainly composed of α-olefins, α-olefins such as conjugated dienes and nonconjugated dienes. Examples include copolymers with unsaturated compounds, acrylic acid, methacrylic acid, vinyl acetate, etc., for example, high density, low density or linear low density polyethylene, polypropylene, ethylene-propylene copolymer ethylene-butene copolymer Examples thereof include a copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-acrylic acid copolymer.

The polyolefin resin composition containing the heat retention agent of the present invention includes other additives, stabilizers, antioxidants, infrared absorbers, lubricants, and antifogging agents that are usually used as additives for polyolefin resin compositions. Various additives such as fillers, colorants and processing aids are used in combination

Stabilizers include carboxylic acid or phenolic metal salts, organotin sulfur-containing compounds, organic phosphorus compounds, phosphorous acid or phosphoric acid compounds, organic phosphorus-containing metal salts, inorganic metal compounds, pure organic compound stabilization aids, oxidation Examples thereof include an inhibitor, an ultraviolet absorber, and a light stabilizer.

Examples of carboxylic acids of the above carboxylic acids or metal salts of phenols include acetic acid, propionic acid, butanoic acid, 2-methylpropionic acid, pentanoic acid, 3-methylbutanoic acid, hexanoic acid, 2,2-dimethylpropanoic acid, 2 -Butenoic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, palmic acid, myristic acid, stearic acid, isostearic acid, behenic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidic acid, elca A mixture of natural fatty acids such as acids, 12-hydroxystearic acid, 12-ketostearic acid, phenylstearic acid, montanic acid, acetoacetic acid, tallow fatty acid, coconut oil fatty acid, pearl fatty acid, tung oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, Benzoic acid, P-tert-butylbenzoic acid, dimethylbenzoic acid, Tylbenzoic acid, dimethylhydroxybenzoic acid, toluic acid, acetoxybenzoic acid, propylbenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, salicylic acid, P-tert-octylsalicylic acid, thioglycolic acid, mercaptopropion Monovalent carboxylic acids such as acids, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, adiline acid, suberic acid, fumaric acid , Monoester compounds of divalent carboxylic acids such as citraconic acid, metaconic acid, itaconic acid and oxyphthalic acid, diester compounds of trivalent carboxylic acids such as hemimellitic acid and trimellitic acid, and pyromellitic acid, merophanic acid and pyromellitic acid Triesterification of tetravalent carboxylic acid Goods and the like. Examples of the phenolic compounds phenol, cresol, cyclohexyl phenol, nonylphenol, decyl phenol. Examples of the metal bonded to the carboxylic acid or the phenol compound include lithium, sodium, potassium, calcium, barium, strontium, magnesium, aluminum, zinc, cadmium, cesium, tin, and organic tin.

Examples of organotin sulfur-containing compounds include mono (or di) methyltin tris (or di) (isooctyl thioglycolate), mono (or di) butyl (isooctyl thioglycolate), and mono (or di) octyl tin tris. (Or di) (isooctyl thioglycolate), mono (or di) methyl tin tris (or bis) (2-mercaptoethyl oleate), mono (or di) alkyl (C1-12) tin sulfide, mono (or di) ) (Butylcarboxyethyl) tin tris (or bis) (isooctyl thioglycolate), mono (or di) alkyl (C1-12) tin oxide, mono (or di) alkyl (C1-12) tin (β-mercapto) Propionate), mono (or di) alkyl (C1-12) tin (thioglycolate), mono (or di) alkyl (C1-12) And tri (or di) mercaptoethanol and the like.

Examples of organic phosphorus compounds include dioctyl monoxylyl phosphate, diphenyl monoxylyl phosphate, ditolyl monoxylyl phosphate, di-t-butylphenyl monoxylyl phosphate, didodecyl mono-di-t-butylphenyl phosphate, dibenzyl mono-di-t -Butylphenyl phosphate, di-octylphenyl mono-di-t-butylphenyl phosphate, ditridecyl monodinonyl phenyl phosphate, ditolyl monodinonyl phenyl phosphate, dinonylphenyl monodinonyl phenyl phosphate, monotridecyl dixylyl phosphate, Monophenyl dixylyl phosphate, monotolyl dixylyl phosphate, monononylphenyl dixylyl phosphate, monododecyl di-di-t-butyl pheny Phosphate, monobenzyl di-di-t-butylphenyl phosphate, monooctylphenyl di-di-t-butylphenyl phosphate, monooctyldidinonylphenyl phosphate, monophenyldidinonylphenyl phosphate, mono-t-butylphenyldidinonylphenyl phosphate, etc. Can give.

Examples of phosphorous acid or phosphoric acid compounds include triphenyl phosphite, tri (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tri (2-ethylhexyl) phosphite, tri (nonylphenyl) phosphite, Tri (octylphenyl) phosphite, tri (cyclohexylphenyl) phosphite, tricyclohexylphosphite, tri (decyl) thiophosphite, triisodecylthiophosphite, phenyl di (2-ethylhexyl) phosphite, phenyl diisodecyl Phosphite, Phenyl dicyclohexyl phosphite, Phenyl diisooctyl phosphite, Phenyl di (tridecyl) phosphite, Phenyl dicyclohexyl phosphite, Diphenyl isooctyl Phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl. (Tridecyl) thiophosphite, nonylphenyl di (tridecyl) phosphite, phenyl p-tert- Butyl dodecyl phosphite, tetra (tridecyl) .4,4'-isopropylidene-diphenyl diphosphite, tetra (tridecyl) .4,4'-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite Tetraisooctyl • 4,4′-thiobis (2-tert-butyl-5-methylphenol) diphosphite, tetra (nonylphenyl) poly (propyleneoxy) isopropyldiphosphite, tetra (tridecyl) ) Propyleneoxypropyl diphosphite, tetra (tridecyl) .4,4'-isopropylidene-di (cyclohexyl) diphosphite, penta (nonylphenyl) .bis [poly (propyleneoxy) isopropyl] triphosphite, hepta (nonylphenyl) Tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, hepta (nonylphenyl) Tetrakis (4,4'-isopropylidene-diphenyl) pentaphosphite, deca (nonylphenyl) heptakis (propyleneoxyisopropyl) octaphos Phyto, decaphenyl hepta (propyleneoxyisopropyl) octaphosphite, di (butoxycarboethyl) 2,2'-dimethylene-trimethylenedithiophosphite, di (isooctoxy) Cicarbomethyl), 2,2'-dimethylene-trimethylenedithiophosphite, tetra (lauryl) ethylenedithiophosphite, tetra (lauryl) hexamethylenedithiophosphite, tetra (lauryl) 2,2'-oxydiethylenedithio Phosphite, penta (dodecyl) .di (hexamethylene) trithiophosphite, tetra (phenyl) .4,4'-isopropylidene-dicyclohexyldiphosphite, tetra (mixed alkyl (C12-C15)). 4,4 ' -Isopropylidene-diphenyl diphosphite, 2-tert-butyl-4- [1- (3-tert-butyl-4-hydroxyphenyl) isopropyl] phenyl di (p-nonylphenyl) phosphite, 4,4 ' -Butylidene-bis (3-methyl-6-t rt-butylphenyl) -di (tridecyl) diphenyl diphosphite, distearyl 2,2-dimethylene-trimethylene diphosphite, tricyclohexylphenyl phosphite, hexa (tridecyl) .4,4'.4 "-(1 , 1,3-butanetriyl) -tris (2-tert-butyl-5-methylphenyl) triphosphite, tri (dodecyl) thiophosphite, decaphenyl hepta (propyleneoxyisopropyl) octaphosphite, dibutyl penta (2 , 2-dimethylene-trimethylene) diphosphite, dioctyl penta (2,2-dimethylene-trimethylene) diphosphite, didecyl (2,2-dimethylene-trimethylene) diphosphite and the like.

Examples of the inorganic metal compound used as the stabilizer include zeolite compounds having a silicate condensation acid structure, hydrotalcite compounds, lithium-containing composite hydroxides, and the like.

Examples of the pure organic compound stabilization aid include 4-cyclopentene-1,3-dione, 4-methylcyclohexane-1,3-dione, 2-phenylcyclohexane-1,3-dione, 2,2-dimethylcyclohexane- 1,3,5-trione, 2-benzylcyclohexane-1,3-dione, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, 1,4-bis (2,6- Dioxocyclohexyl) -2-butene, bis (4-butylbenzoyl) methane, benzoyl-acetylmethane, 4-methoxybenzoyl-hexanoylmethane, benzoyl-acetyl-octylmethane, tribenzoylmethane, dehydroacetic acid, dehydropropionylacetic acid, 2- (2-Cyclohexen-1-yl) Chlorohexane-1,3-dione, caproyl acetylmethane, benzoyl diacetylmethane, cyclohexylcarbonyl acetylmethane, cyclohexylcarbonyl benzoylmethane, benzoyltetralone, acetyltetralone, bis (cyclohexylcarbonyl) methane, dibenzoylmethane, Β- such as acetylacetone, butanoylacetone, stearoylacetone, lauroylacetone, benzoyl-phenylacetylmethane, benzoylformylmethane, benzoyl-palmitoylmethane, hexadecanoyl-formylmethane, isovaleryl-cyclohexylcarbonylmethane, cyclohexylcarbonyl-acetyl-ethylmethane Diketone compounds, and these β-diketone compounds and lithium, sodium, potassium, Metal salts with gnesium, calcium, strontium, barium, aluminum, zinc, tin, organic tin, polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, sorbitol, trehalol, and tris (2-hydroxy And ethyl) isocyanurate.

Antioxidants are phenolic antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-methyl-4-isopropylphenol, 2,6- Di-tert-butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxyphenyl) propane, bis (5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2,5-di- tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,1-bis (3-tert- Til-4-hydroxy-5-methylphenyl) butane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) methane, 2,6-bis (2-hydroxy-3-tert-butyl-5- Methylbenzyl) -4-methylphenol, bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) sulfide, bis (3-tert-butyl-5-ethyl-2-hydroxyphenyl) methane, bis (3 , 5-Di-tert-butyl-4-hydroxyphenyl) methane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis [ 3,3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid] glycol ester, bis 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-di-methylphenyl) ) -2-methylpropane, 4-methoxyphenol, cyclohexylphenol, p-phenylphenol, catechol, hydroquinone, 4-tert-butylcarecol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol 2,4,5-trihydroxybutyrophenone, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanate, 1,3,5-tri-methyl-2,4,6-tris (3 5-Di-tert-butyl-4-hydroxybenzyl) benze 1,6-bis [2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxymethyl] methane, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] sulfide, n -Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionylamino] hexane, 2, 6-Bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methylphenol Bis (S- (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) thioterephthalate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxyethyl] isocyanurate, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, sulfur-based antioxidants such as bis (dodecyloxycarbonylethyl) sulfide, bis ( Tridecyloxycarbonylethyl) sulfide, bis (tetradecyloxycarbonylethyl) sulfide, bis (hexadecyloxycarbonylethyl) sulfide, bis (2-hexadecyloxycarbonyl-1-methyl-ethyl) sulfide, dodecyloxycarbonylethyl. Hexadecyloxycarbonylethyl sulfide, 3,3′-thiodipropionic acid, pentaerythritol tetra (3-dodecylthiopropionate), and UV absorbers are salicylates (phenyl salicylate, 4-tert-butylphenyl salicylate, 4 -Tert-octylphenyl salicylate, bisphenol A disalicylate, 2-isopropyl-methyl-cyclohexyl salicylate, 1,7,7-trimethylbicyclo [2,21] -2-heptyl salicylate, monoglycol salicylate, etc.).

UV absorbers include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3' , 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy -3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy- '-Tert-butyl-5'-methacryloxyethyl phenyl) -5-chloro -, and the like benzotriazole. The benzophenone series includes 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, 2-hydroxy -4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2 -Hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,4-dihydroxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-n-octylbenzophenone, 2 2'-dihydroxy-4,4'-dimethoxy benzophenone, and the like 2,4,5-trihydroxy benzophenone.

The light stabilizer is 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine, 4-benzoyloxy-2,2, 6,6-tetramethylpiperidine, 4-dodecylsuccinimide-2,2,6,6-tetramethylpiperidine, 1- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl-4- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy-2,2,6,6-tetramethylpiperidine, 4,4′-sebacoyldioxy-bis (2,2,6,6- Tetramethylpiperidine), 4,4'-sebacoyldioxy-bis (1,2,2,6,6-pentamethylpiperidine), 4,4 '-(3,5-di-t rt-butyl-4-hydroxybenzyl) -butylmalonyldioxy-bis (1,2,2,6,6-pentamethylpiperidine), 4,4′-hexamethylenediimino-bis (2,2,6, 6-tetramethylpiperidine), 4,4 ', 4 ", 47-1,2,3,4-butanetetracarbonyltetraoxy-tetra (2,2,6,6-tetramethylpiperidine), 4,4' , 4 ", 4" '-1,2,3,4-butanetetracarbonyltetraoxy-tetra (1,2,2,6,6-pentamethylpiperidine), 4,4'-(ditridecyloxycarbonyl) Butanedicarbonyldioxy) -bis (2,2,6,6-tetramethylpiperidine), tris [2-hydroxy-3- (2,2,6,6-tetramethyl-4-piperidylamino) propyl] Sosocyanurate, poly [ethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino-hexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino], poly [1- Ethylene-2,2,6,6-tetramethyl-4-piperidyl-malonyloxy], poly {(4-morpholino-1,3,5-triazine-2,6-diyl) [(2,2,6 6-tetramethyl-4-piperidyl) imino-hexamethylene-bis (2,2,6,6-tetramethyl-4-piperidyl) imino]}, 1,5,8,12-tetrakis [2,4-bis (Butyl (2,2,6,6-tetramethyl-4-piperidyl) amino) -6-1,3,5-triazinyl] -1,5,8,12-tetraazadodecane, 4,4 ', 4 ″ -Nitrilotori (methylene carbonate) Rubonyloxy) -tris (2,2,6,6-tetramethyl-4-piperidine), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- 2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like. be able to. The addition amount of the light stabilizer is 0.01 to 2 parts by weight, preferably 0.02 to 1 part by weight per 100 parts by weight of the polyolefin resin.

Infrared absorbers are magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium sulfate, aluminum sulfate, lithium phosphate , Calcium phosphate, magnesium silicate, calcium silicate, aluminum silicate, calcium aluminate, magnesium aluminate, sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, kaolin, clay, talc, mica, zeolite, lithium aluminum composite hydroxide Aluminum / lithium / magnesium composite carbonate compounds, aluminum / lithium / magnesium composite silicate compounds, magnesium / aluminum / silicon composite water Products, magnesium aluminum silicon composite sulfate compounds, magnesium aluminum silicon composite carbonate compound, and the like. These may be obtained by dehydrating crystal water.

Examples of the antifogging agent include sorbitan monostearate, sorbitan monobehenate, glycerin monopalmitate, diglycerin monostearate, polyethylene glycol monopalmitate and the like.

Examples of the lubricant include paraffin wax, stearic acid, methylene bis stearamide, cetyl alcohol and the like.

The polyolefin resin composition in which the above-mentioned heat retaining agent is blended can be made into an agricultural film by forming into a film by a method such as inflation processing, calendar processing, T-die processing and the like according to a conventional method.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited by this.

Synthesis Example 1 DHT-4A (registered trademark) (manufactured by Kyowa Chemical Industry Co., Ltd.) (Mg _4.5 Al ₂ (OH) ₁₂ (CO ₃ ) · 3.5H ₂ O) 507 g (1 mol) as a hydrotalcite compound ) Was added dropwise and mixed thoroughly with 201.2 g (2.0 mol) of perchloric acid diluted with 134 g of water. Karl Fischer moisture titration (water vaporization method) (vaporization temperature: 105 ° C.)
As a result of measuring moisture according to JIS K0068), the following formula containing 16.5% (6.9 mol of free water) of water was obtained.
The heat insulating agent of the present invention which is a perchlorate ion type hydrotalcite represented by [Mg _4.5 Al ₂ (OH) ₁₂ (ClO ₄ ) ₂ · 3.5H ₂ O] · 6.9H ₂ O is obtained. It was.

DHT-4A Synthetic Example 2 hydrotalcite compound (registered trademark) (manufactured by Kyowa Chemical Industry Co., _{Ltd.) (Mg 4.5 Al 2 (OH} ) 12 (CO 3) · 3.5H 2 O) 507g (1 mole ) Was added dropwise and mixed thoroughly with 53.5 g (0.5 mol) of perchloric acid diluted with 33.5 g of water. Karl Fischer moisture titration (water vaporization method) (vaporization temperature: 105 ° C.)
As a result of measuring moisture according to JIS K0068), the following formula containing 5.1% (1.6 mol of free water) of water
[Mg _4.5 Al ₂ (OH) ₁₂ (CO ₃ ) _0.75 (ClO ₄ ) _0.5 · 3.5H ₂ O] Perchlorate ion type hydrotalcite represented by 1.6H ₂ O A certain heat-retaining agent of the present invention was obtained.

Synthesis Example 3 HT-7 (R) as a hydrotalcite compound (manufactured by Sakai Chemical Industry Co., _{Ltd.) (Mg 3.5 Zn 0.5 Al 2} (OH) 12 (CO 3) · 3H 2 O) 490g ( 1 mol), 201.2 g (2.0 mol) of perchloric acid diluted with 134 g of water was added dropwise and mixed well. Karl Fischer moisture titration (water vaporization method) (vaporization temperature: 105 ° C.)
As a result of measuring moisture according to JIS K0068), the following formula containing 18.5% (6.6 mol of free water) of water was obtained.
The _{[Mg 3.5 Zn 0.5 Al 2 (} OH) 12 (ClO 4) 2 · 3H 2 O] insulation agent 6.6H present invention that are perchlorate ion type hydrotalcite represented by ₂ O Obtained.

Synthesis Example 4 50 g of perchlorate ion type hydrotalcite of Synthesis Example 2 and Alkamizer 2 (registered trademark) (manufactured by Kyowa Chemical Industry Co., Ltd.) (Mg ₄ Al ₂ (OH) ₁₂ CO) as a hydrotalcite compound ₃ ) 50 g was mixed to obtain the heat insulating agent of the present invention of perchlorate ion type hydrotalcite of Synthesis Example 2, 50% by weight, Alkamizer 2, 50% by weight.

Synthesis Example 5 50 g of perchlorate ion-type hydrotalcite of Synthesis Example 2 was used as a hydrotalcite compound as HT-7 (registered trademark) (Sakai Chemical Industry Co., Ltd.) (Mg _3.5 Zn _0.5 Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O) were mixed to obtain the heat insulating agent of the present invention of perchlorate ion type hydrotalcite of Synthesis Example 2, 50 wt%, HT-7 50 wt%.

Synthesis Example 6 Perchlorate ion hydrotalcite of Synthesis Example 2 was mixed with 50 g of DHT-4A (registered trademark) (Kyowa Chemical Industry Co., Ltd.) as a hydrotalcite compound to 50 g of perchlorate ion of Synthesis Example 2. A type of thermal talcite, 50% by weight, and 50% by weight of DHT-4A were obtained.

Synthesis Example 7 Perchlorate ion hydrotalcite of Synthesis Example 2 was mixed with 90 g of DHT-4A (registered trademark) (Kyowa Chemical Industry Co., Ltd.) as a hydrotalcite compound in 10 g, and the perchlorate ion of Synthesis Example 2 was synthesized. A type of hydrotalcite, 10% by weight, and DHT-4A 90% by weight were obtained.

Example In order to see the effect of the heat-retaining agent of the present invention, a sheet having a thickness of 0.075 mm was prepared by melt-kneading for 5 minutes with an 8-inch roll set to 180 ° C. with the following composition, A heat storage deterioration test film was obtained. In addition, the implemented evaluation method followed the following method. The results are shown in Table 1.
Thermal insulation test Each film was measured for infrared absorption using FT-IR8700 (Shimadzu Corporation), and the absorption area of the film without the heat retention agent for absorption at 400 to 2000 cm ⁻¹ was used as a reference value (0%). Absorption area increase rate was expressed as a heat retention index. Pipe degradation test showing that the higher the thermal insulation index is, the better the thermal insulation was. The pipe used in the agricultural house was brought into contact with each film and placed in an oven at 100 ° C., and the degradation was confirmed over time. In addition, the evaluation criteria are 10 levels, 10 represents a state in which there is almost no deterioration, and coloring increases as the numerical value decreases.

[Combination]
EVA resin 100 parts by weight Stearic acid 0.3 parts by weight Sorbitan palmitate 1.5 parts by weight UV absorber (* 1) 0.1 parts by weight Phenol-based antioxidant (* 2) 0.2 parts by weight * 1 Seesorb 703
* 2 Tominox TT

* Sample 1 DHT-4A (Kyowa Chemical Industry Co., Ltd. hydrotalcite compound)
* Sample 2 HT-7 (hydrotalcite compound manufactured by Sakai Chemical Industry Co., Ltd.)
* Sample 3 DHT-4A 50% by weight, Alkamizer 2 (Kyowa Chemical Industry Co., Ltd. hydrotalcite compound) 50% by weight

As is clear from Table 1, the heat-retaining agent of the present invention is a polyolefin-based resin that is excellent in heat-retaining agent when added to a polyolefin-based resin as a heat-retaining agent, and is less susceptible to deterioration even when the contacting pipes store heat. A resin is obtained.

Claims (8)

A heat insulating agent added to a polyolefin resin and containing a perchlorate ion-type hydrotalcite compound, a heat insulating agent for a polyolefin resin The perchlorate ion type hydrotalcite compound is represented by the following formula (1)
(In the formula, 3 <x <10, 0 ≦ y <1, 0.1 <z ≦ 1, 0 <m <10, 0.5 ≦ n ≦ 20, where mH ₂ O is interlayer water, nH ₂ O indicates free water.)
The heat-retaining agent for polyolefin resin according to claim 1 The heat insulating agent for polyolefin resin according to claim 1, comprising one or more hydrotalcite compounds excluding perchlorate ion type hydrotalcite compounds. The heat insulating agent for polyolefin resin according to claim 2, comprising one or more hydrotalcite compounds excluding perchlorate ion type hydrotalcite compounds. Agricultural film using the heat insulating agent for polyolefin resin according to claim 1 Agricultural film using the heat insulating agent for polyolefin resin according to claim 2 Agricultural film using the heat insulating agent for polyolefin resin according to claim 3 Agricultural film using the polyolefin resin heat-retaining agent according to claim 4