JP2002146337A - Infrared light absorber and agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an IR light absorber which has a light IR light-absorbing ability, exhibits good dispersibility, when compounded with a resin, has a refractive index near to that of the resin, has excellent heat retainability and tranparency, when formed into a film, and has excellent acid resistance and productivity, to provide a resin composition containing the IR light absorber, and to provide an agricultural film. SOLUTION: This IR light absorber characterized by containing a composite hydroxide salt represented by the formula] [Al2Li(1-x)M2+(x+y)(OH)(6+2y)]2(SO4)z1 (CO3)z2(OH)z3.mH2O (I) [M2+ is a divalent metal; (m), (x), (y), (z1), (z2), and (z3) are contained in the ranges of 0<=(m)<5, 0<=(x)<=0.5, 0<=(y)<= 0.5, (z1)>0, (z)>0, (z3)>=0, (z1)+(z2)+(z3)/2=1+(x)] as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I) [Al ₂ Li _(1-x) M ²⁺ _{(x + y)} (OH) _{(6 + 2y)} ] ₂ (SO ₄ ) _z1 (CO ₃ ) _z2 (OH) _z3 · mH ₂ O (I) (wherein, M ²⁺ is a divalent metal, m, x, y, z1, z2,
z3 is 0 ≦ m <5, 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.
5, z1> 0, z2> 0, z3 ≧ 0, z1 + z2 + z3
/ 2 = 1 + x) as an active ingredient, and an agricultural film formed by blending the resin with a resin and molding the same. The infrared absorbent comprising the composite hydroxide salt of the present invention has a high infrared absorption ability, is excellent in dispersibility with a resin, and has a refractive index close to that of the resin, and has good acid resistance and good productivity. It is easy to mix with resin, easy to process with resin, and when formed into a film, has excellent heat retention, transparency, and pesticide resistance, and is suitable as an agricultural film.

[0002]

2. Description of the Related Art Agricultural films used in greenhouse cultivation such as houses and tunnels allow sunlight to pass efficiently with high transmittance in the daytime, while absorbing and reflecting infrared rays radiated from the ground and plants at nighttime. It is required to have such characteristics that it is not released out of a house or a tunnel. The range where the emissivity of infrared rays emitted from the ground or plants is large is 5 to 25 μm
Is known. 5-25 μm for agricultural film, especially 10 μm with maximum emissivity
It is necessary to be able to absorb infrared rays of a nearby wavelength. Conventionally, the above-mentioned agricultural films include, as infrared absorbers, magnesium carbonate, magnesium silicate, silicon dioxide, aluminum oxide, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, phosphate, silica, and the like. Acid salts, hydrotalcites and the like have been used. However, the above-mentioned conventional inorganic powders each have advantages and disadvantages, and there is no one that sufficiently satisfies the above-mentioned various physical properties. For example, silicon dioxide, aluminum silicate, etc. have excellent infrared absorbing ability, but have problems in refractive index, dispersibility, etc., and as a result, the translucency of the film is impaired, so it is not suitable as an agricultural film It was something. Further, hydrotalcites are relatively excellent in dispersibility, refractive index and the like, but are not sufficiently satisfactory in infrared absorption ability. Further, Japanese Patent Application Laid-Open No. 7-300313 discloses a technique of using a lithium aluminum composite hydroxide salt as a heat insulator for agricultural films. This hydroxide salt has a defect that the refractive index is 1.55, which is far from the value of about 1.50 of the polyolefin resin, so that the transparency is not good. Furthermore, various attempts have been made to increase the heat retention performance by inserting a silica component or a phosphoric acid component between the layers, but these ions are inferior in ion exchange ability with other acids, and are resistant to pesticides and the like. In terms of sex, higher performance was demanded. Further, there has been a demand for a more productive heat insulating agent to be incorporated into agricultural films.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a high infrared absorbing ability, a good dispersibility when blended with a resin, a refractive index close to the refractive index of the resin, and a heat retaining property when formed into a film. It is an object of the present invention to provide an infrared absorber excellent in transparency, excellent in acid resistance and productivity, a resin composition containing the infrared absorber, and an agricultural film.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the following formula (I) [Al ₂ Li _(1-x) M ²⁺ _{(x + y)} ( OH) _{(6 + 2y)} ] ₂ (SO ₄ ) _z1 (CO ₃ ) _z2 (OH) _z3 · mH ₂ O (I) (wherein, M ²⁺ is a divalent metal, m, x, y, z1 , Z2,
z3 is 0 ≦ m <5, 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.
5, z1> 0, z2> 0, z3 ≧ 0, z1 + z2 + z3
/ 2 = 1 + x) as an active ingredient, and is a basic composite having a giant site-structured aluminum hydroxide octahedral layer as a basic skeleton. The present inventors have found that a hydroxide salt can solve the above problems, and have reached the present invention. That is, the present invention is an infrared absorbent characterized by containing a complex hydroxide salt represented by the above formula (I) [hereinafter referred to as compound (I)] as an active ingredient. Compound (I) of the present invention
Is a basic structure in which lithium ions and divalent metal ions are inserted into vacancies (vacant) of an aluminum hydroxide octahedral layer having a gibbsite structure, and a basic structure in which an anion is introduced into an intermediate layer thereof is defined as a basic structure (y = 0). Further, it is a composite hydroxide salt obtained by compounding a hydroxide of a divalent metal with this basic structure (when 0 <y <1). The divalent metal is not particularly limited, but is easily introduced, is white, and satisfies transparency when blended into a film.
And the like are more preferable.

The infrared absorbent of the present invention, that is, the infrared absorbent containing the above compound (I) as an active ingredient, is used in the case of being blended into a film such as an agricultural film.
Fine particles having high dispersibility and having relatively developed crystals are preferred. Therefore, the average secondary particle diameter is preferably 3 μm or less, more preferably 1.5 μm or less. The BET specific surface area is preferably 50 m ² / g or less, more preferably 20 m ² / g or less.

[0006] Sulfate ions between layers have a function of expanding the layers to make the refractive index close to that of the polyolefin resin, and carbonate ions and hydroxide ions have a function of reacting with other acid ions to impart acid resistance. it seems to do. Among them, those in which sulfate ions, carbonate ions, and hydroxide ions are all present are more desirable from the viewpoint of acid resistance and transparency. Hereinafter, the production method of the compound (I) of the present invention will be described in detail with reference to a specific example where M ²⁺ is Mg.

The carbonate ion type lithium aluminum magnesium composite hydroxide salt used as a starting material for producing the compound (I) of the present invention is produced by the following method. Specifically, heat treatment of lithium carbonate and magnesium carbonate such as magnesium carbonate or basic magnesium carbonate in an aqueous medium of aluminum hydroxide, or adding magnesium chloride, magnesium sulfate, magnesium nitrate, etc. It can be produced by adding at least one selected from water-soluble magnesium and magnesium hydroxide and subjecting to heat treatment.

In this case, the amount of lithium carbonate and magnesium carbonate or basic magnesium carbonate used is [Li / Al ₂ O _{3] based on} the Al ₂ O ₃ content of aluminum hydroxide.
₃ (molar ratio)] + [MgO / Al ₂ O ₃ (molar ratio)] = 1
However, the lithium component may be excessively charged.

The temperature range of the heat treatment is preferably from room temperature to
A suitable temperature up to 200 ° C., more preferably 9 ° C.
The temperature is 0 to 160 ° C, particularly preferably 110 to 160 ° C. If the treatment temperature is lower than room temperature, the degree of crystallization is undesirably low.

Next, sulfuric acid is added to the slurry of the carbonated lithium-aluminum-magnesium composite hydroxide salt obtained above to acidify the liquid once, and then the liquid is transferred to the alkali side again with an alkali solution such as caustic soda. To give the compound (I) of the present invention.

The concentration of the sulfuric acid to be added is not particularly limited, but it is preferable that the concentration is not more than 20% by weight in view of preventing the crystal from collapsing. The amount of sulfuric acid added is pH
It is preferable to add until pH 3.0 to pH 6.0, and more preferably pH 4.0 to pH 5.0.

Although the alkali solution is not particularly limited, caustic soda of 25% by weight or less is preferable in view of industrialization. Further, the addition of the alkaline solution is performed at pH 7.0 to pH 1
It is preferable to add until 2.0, more preferably pH 9.0 to pH 11.0.

The desired compound is obtained by washing the above compound with water. The ratio of interlayer ions can also be controlled by washing with an appropriate concentration of sodium hydroxide, sodium carbonate or sodium bicarbonate.

The infrared absorbing agent of the present invention can be made more excellent in dispersibility by performing a surface treatment with a coating agent. As a coating agent, for example,
One or more selected from higher fatty acids, higher fatty acid salts, esters of higher fatty acid alcohols and phosphoric acid, waxes, nonionic surfactants, cationic surfactants or coupling agents, preferably Examples include higher fatty acids, higher fatty acid salts, phosphate esters of higher fatty acid alcohols, nonionic surfactants, cationic surfactants, and coupling agents.

The higher fatty acids include, for example, lauric acid, palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, and linoleic acid. The higher fatty acid salts include, for example, sodium salts of the above-mentioned higher fatty acids, Potassium salts and the like can be mentioned. Phosphate esters of higher fatty acid alcohols, for example, alkyl ether phosphoric acid such as lauryl ether phosphoric acid, stearyl ether phosphoric acid, oleyl ether phosphoric acid, dialkyl ether phosphoric acid, alkyl phenyl ether phosphoric acid,
Examples thereof include dialkylphenyl ether phosphates and the like, and alkyl ether phosphates such as sodium oleyl ether phosphate and potassium stearyl ether phosphate.

Examples of the nonionic surfactant include, for example,
Palm oil fatty acid monoethanolamide, alkylolamides such as lauric acid diethanolamide, polyoxyalkylphenyl ethers such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether,
Polyethylene glycol fatty acid esters such as polyethylene glycol distearate, sorbitan monocaprate, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan distearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxy Examples thereof include ethylene sorbite fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, and glycol ethers.

As the cationic surfactant, for example,
Alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide and stearyltrimethylammonium chloride; and alkyldimethylbenzylammonium salts such as stearyldimethylbenzylammonium chloride, benzalkonium chloride and lauryldimethylbenzylammonium chloride. it can.

Examples of the amphoteric surfactant include alkyl betaines such as coconut oil alkyl betaine, alkylamide betaines such as lauryl dimethylaminoacetic acid betaine, and midazolines such as Z-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolyme betaine. And glycines such as polyoctylpolyaminoethylglycine.

Examples of the coupling agent include a silane coupling agent, an aluminum coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like.

One or more of the above coating agents can be used simultaneously. The amount of the coating agent added is 0.1 to 10% by weight, preferably in the range of 0.5 to 6% by weight. If it is less than 0.1% by weight, dispersibility is poor, and if it is more than 10% by weight, the effect is sufficient, but it is not economically advantageous. The surface treatment can be facilitated by a wet method or a dry method according to a conventional method.

A second aspect of the present invention is a resin composition, an agricultural film, and a method for producing the same, which contain the infrared absorbent of the present invention. The agricultural film of the present invention can be manufactured by the method described below. First, the resin and the infrared absorbent of the present invention are charged into a mixer such as a ribbon blender, a Banbury mixer, a super mixer, a Henschel mixer, etc., according to a conventional method, and after mixing, an extruder, a Banbury mixer, a pressure kneader, etc. And a resin composition is prepared by melt-kneading.

The amount of the infrared absorber used is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the resin. If the amount is less than 1 part by weight, infrared rays cannot be sufficiently absorbed, and if the amount exceeds 50 parts by weight, the translucency and mechanical strength of the agricultural film decrease.

As the resin, polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride, halogenated polyethylene, halogenated polypropylene, or vinyl chloride-vinyl acetate, vinyl chloride-ethylene, vinyl chloride-propylene, vinyl chloride- Styrene, vinyl chloride-isobutylene, vinyl chloride-vinylidene chloride, vinyl chloride-styrene-acrylonitrile, vinyl chloride-butadiene, vinyl chloride-chlorinated propylene, vinyl chloride-vinylidene chloride-vinyl acetate, vinyl chloride-maleate, vinyl chloride -Methacrylic acid esters, copolymers comprising a combination of vinyl chloride-acrylonitrile and the like, or polymers or copolymers of olefins such as ethylene, propylene, butene-1, and vinyl acetate of olefins, for example, LLPE, polyethylene LDPE etc., polypropylene, ethylene - propylene copolymer,
Ethylene-α-olefin copolymers such as ethylene-butene-1 copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-acryl Acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-
Examples thereof include a vinyl acetate-methyl methacrylate copolymer and an ionomer resin. Among them, polyethylene, ethylene, ethylene-α-olefin copolymer, and ethylene-vinyl acetate copolymer having a vinyl acetate content of 25% by weight or less are more preferable in view of transparency, weather resistance, and price.

The resin composition obtained by the above-mentioned mixing, melting and kneading may be subjected to a conventional method such as inflation processing,
By forming the film by a method such as calendering and T-die processing, a film such as an agricultural film can be obtained.

Further, a laminated film having at least one film using the resin composition containing the infrared absorbent of the present invention can be formed. Specifically, a multilayer film can be formed by providing another resin layer on one or both surfaces thereof. Such a multilayer film can be produced by a conventional method, for example, a lamination method such as dry lamination and heat lamination, or a co-extrusion method such as T-die co-extrusion and inflation co-extrusion.

In the production of the agricultural film of the present invention, if necessary, various conventional additives for resins, for example, plasticizers, lubricants, light stabilizers, antioxidants, antistatic agents, pigments, ultraviolet absorbers, antifogging agents Agents, anti-fog agents, heat stabilizers, anti-blocking agents, dyes or warming agents and the like can be added.

Examples of the plasticizer include low-molecular-weight polyhydric alcohol plasticizers such as glycerin, ethylene glycol, triethylene glycol and sorbitol; phthalate plasticizers such as dioctyl phthalate (DOP) and dimethyl phthalate; and phosphate esters. Plasticizers, paraffin plasticizers, and wax plasticizers. Among these, polyhydric alcohols also have an antifogging effect on the film.

Examples of the lubricant include fatty acids such as stearic acid, oleic acid and palmitic acid, and metal salts thereof.
Examples include fatty acid amides derived from fatty acids, waxes such as polyethylene wax, liquid paraffin, esters such as glycerin fatty acid esters, and higher alcohols.

Examples of the light stabilizer include hindered amine compounds, cresols, melamines, benzoic acid and the like.

Examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4
-Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl) -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- Hydroxylphenyl) propionate, bis
(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-
Di-tert-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (1,2,2,
6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, tetra (2,2,6,6-tetramethyl-
4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis
(2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis {1,1-dimethyl-2- [tris (2,2,6,6- Tetramethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxy] ethyl {-2,4,8,10-tetrooxaspiro [5,5] undecane, 3,9-bis {1,1-dimethyl-2- [tris (1,2,2,6, 6-
Pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl {-2,4,8,10-
Tetraoxaspiro [5,5] undecane, 1,5,8,1
2-tetrakis 4,6-bis [N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino] -1,3,
5-triazin-2-yl} -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-
Dichloro-s-triazine / N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate, and the like. . The amount of the light stabilizer to be added is preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the resin.

Examples of the antioxidant include phenol-based, phosphorus-based, and sulfur-based antioxidants.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-
Di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-te
rt-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-te
rt-butyl-4-hydroxyphenyl) propionic amide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-
tert-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-tert-butylphenol, bis [3,3
-Bis (4-hydroxy-3-tert-butylphenyl)
Butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,
2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4
-Hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-tert-butyl-5-methylbenzyl) phenyl]
Terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-) Hydroxybenzyl) isocyanurate,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert- Butyl-
4-hydroxyphenyl) propionyloxyethyl]
Isocyanurate, tetrakis [methylene-3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-
6- (2-acryloyloxy-3-tert-butyl-5
-Methylbenzyl) phenol, 3,9-bis @ 1,1
-Dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-
Butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the phosphorus-based antioxidants include trisnonylphenyl phosphite and tris (2,4-di-
tert-butylphenyl) phosphite, tris [2-te
rt-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) 5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, Monodecyldiphenyl phosphite, mono (dinonylphenyl) bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-te
rt-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (C12-16 mixed alkyl) -4, 4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphos Fight, Tetrakis (2,4
-Di-tert-butylphenyl) biphenylenediphosphonite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (octyl) phosphite and the like.

Examples of the sulfur-based antioxidants include dialkyldithiopropionates such as dilauryl, dimyristyl and distearyl of thiodipropionic acid and β-polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). -Alkyl mercaptopropionates. The amount of the antioxidant is preferably about 0.01 to 3%.

Examples of the antistatic agent include polyoxyethylene-alkylamine, polyglycol ether, nonionic activator and cationic activator.

As the pigment, those having high permeability are preferable.

Examples of the ultraviolet absorber include benzophenone type, benzotriazole type, salicylate type, substituted oxalinides and cyanoacrylates.

As the benzophenone type, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
And 2-hydroxybenzophenones such as -methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone).

As benzotriazoles, for example,
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
tert-butylphenyl) benzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2 '-Methylenebis (4
2- (2'-hydroxyphenyl) benzotriazoles such as -tert-octyl-6-benzotriazole) phenol.

Examples of salicylates include, for example,
Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl- Benzoates such as 4-hydroxybenzoate can be mentioned.

The substituted oxalinides include, for example, 2
And substituted oxalinides such as -ethyl-2'-ethoxyoxalinide and 2-ethoxy-4'-dodecyloxanilide.

As the cyanoacrylates, for example,
Examples thereof include cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

As the antifogging agent, a nonionic, anionic or cationic surfactant can be suitably used. Specifically, sorbitan monostearate, sorbitan monopalmylate, sorbitan fatty acid esters such as sorbitan monobehenate, glycerin monolaurate, glycerin monostearate, glycerin monopalmite,
Polyglycol surfactants such as diglycerin dilaurate, diglycerin distearate, diglycerin monopalmite, glycerin fatty acid esters such as triglycerin monostearate, polyethylene glycol surfactants such as polyethylene glycol monostearate, And their alkylene oxide adducts, polyoxyalkylene ethers, esters with organic acids such as sorbitans and glycerins, and the like.

As the antimist agent, a fluorine antimist agent or a silicone antimist agent which is commonly used in conventional olefin resin films for agricultural use can be blended. For example, a low molecular weight or high molecular weight containing a perfluoroalkyl group or a perfluoroalkenyl group,
Have a solubility in water of at least 0.01% by weight,
The surface tension of water is 35 dyn / cm or less, preferably 3
Those having the ability to reduce the concentration to 0 dyn / cm or less are preferable. Further, the perfluoroalkyl group may have an oxygen atom interposed in its carbon chain.

Examples of the fluorine-based antimist agent include commercially available products Unidyne DS-401, Unidyne DS-403, Unidyne DS-451 (all manufactured by Daikin Industries, Ltd.) and Megafac F-177 (all manufactured by Dainippon Ink. Chemical Industry Co., Ltd.), Florard FC-170, Florard FC-176, Florard FC
-430 (all manufactured by Sumitomo 3M Limited), Surflon S-14
1, Surflon S-145, Surflon S-381, Surflon S-382, Surflon S-393 (all manufactured by Asahi Glass Co., Ltd.) and the like.

Examples of the silicone antifog include polyether-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil,
Amino-modified silicone oils and the like are preferred, and those which generally have a solubility in water of at least 0.1% by weight and a capability of reducing the surface tension of water at 25 ° C. to 35 dyn / cm or less are preferable. Examples of commercially available silicone surfactants include KF-354 (manufactured by Shin-Etsu Chemical Co., Ltd.) and SH-374.
6 (Toray Dow Corning), TSF-4445 (manufactured by Toshiba Silicone Co., Ltd.) and the like. About 0.1% to 5% of the compounding amount of the antifog is preferably used for 100 parts by weight of the resin.

Examples of the heat stabilizer include tin-based, lead-based, calcium-zinc-based, barium-zinc-based and other complex metal fatty acid-based stabilizers, etc., which are blended in a vinyl chloride-based resin.

Further, other heat insulators such as magnesium carbonate, magnesium silicate, silicon dioxide, aluminum oxide, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, phosphate,
Silicates, hydrotalcites and the like can also be used as long as the transparency of the film is not impaired.

One or more of the above-mentioned various additives may be appropriately selected and blended. The compounding amount is preferably in a range that does not degrade the properties of the film, and there is no particular limitation as long as it is within this range.

The agricultural film of the present invention comprises: 1) resin 10
Agricultural film, characterized in that 1 to 50 parts by weight of the composite hydroxide salt of the present invention is mixed with 0 part by weight, 2) resin 1
Agricultural film characterized in that 1 to 50 parts by weight of the composite hydroxide salt of the present invention and 0.02 to 5 parts by weight of a hindered amine-based light stabilizer are added to 00 parts by weight, and 3)
To 100 parts by weight of the resin, 1 to 50 of the composite hydroxide salt of the present invention is used.
Parts by weight and an agricultural film characterized by mixing 0.02 to 5 parts by weight of an antifogging agent, 4) 100 parts by weight of a resin,
1 to 50 parts by weight of the composite hydroxide salt of the present invention and 0.0
2 to 5 parts by weight of an agricultural film. Further, this agricultural film can be used as a multilayer film, and the composite hydroxide salt of the present invention may be used in any of the middle layer, the exterior, and the inner layer. Further, the agricultural film of the present invention can be used as a long-term film by coating with an antifogging agent or the like.

[0051]

【Example】

Example 1 214.0 g of aluminum hydroxide powder containing 65% by weight as Al ₂ O ₃ and magnesium carbonate 1 containing 42.0% by weight of MgO
0.5 g, 1.7 g of magnesium hydroxide having a concentration of 66.0% by weight as MgO, and lithium carbonate 53.8
g was added to water to obtain a slurry having a total volume of 3 liters (hereinafter, L). This slurry was 140 ° C. in a 5 L autoclave.
Heat treatment was performed for 4 hours. After the heat treatment, 8% by weight sulfuric acid was added to the slurry cooled to 70 ° C. until the pH reached 4.0. Next, 25% caustic soda was added to adjust the pH to pH 11 to pH 11
Was adjusted. While maintaining the pH-adjusted slurry at 55 ° C., 1,150 mL of a 1% solution of a sodium salt of stearic acid phosphate was added to perform surface treatment. Next, this slurry was filtered with a Nutsche and washed with water 15 times the amount of the product. After washing, it was dried at about 110 ° C. for 20 hours, pulverized in a mortar, and sieved with a 100-mesh sieve. When the obtained white powder was subjected to chemical analysis, [Al ₂ Li _0.92 Mg _0.10 (OH) _6.04 ] ₂
The composition was (SO ₄ ) _0.86 (CO ₃ ) _0.10 (OH) _0.24 3.2 H ₂ O.
The BET specific surface area is 8.0 m ² / g, and the average particle size is
It was 1.1 μm.

Example 2 The surface-treated slurry obtained in the same manner as in Example 1 was filtered with a Nutsche, washed with a 0.15N NaOH solution 35 times the product amount, and further 30 times the product amount. Washed with water. After washing, about 140 ° C
For 20 hours, crushed in a mortar and sieved with a 100 mesh sieve. When the obtained white powder was subjected to chemical analysis, [A
l ₂ Li _0.93 Mg _0.10 (OH) _6.06 ] ₂ (SO ₄ ) _0.56 (CO ₃ ) _0.22 (OH) _0.58
The composition was 1.7H ₂ O. The BET specific surface area is
9.0 m ² / g, average particle size was 1.1 μm.

Example 3 The surface-treated slurry obtained in the same manner as in Example 1 was filtered with a Nutsche, washed with a 0.01 M Na ₂ CO ₃ solution 10 times the amount of the product, and further washed with the amount of the product. Washed 30 times with water. After washing, about 140
C. for 20 hours, crushed in a mortar, and sieved through a 100 mesh screen. Chemical analysis of the resulting white powder [A
l ₂ Li _0.93 Mg _0.10 (OH) _6.06 ] ₂ (SO ₄ ) _0.49 (CO ₃ ) _0.58 1.6H ₂ O
The composition was as follows. The BET specific surface area is 8.6 m ² /
g, the average particle size was 1.2 μm.

Example 4 Water was added to 214.0 g of aluminum hydroxide powder containing 65% by weight as Al ₂ O ₃ and 53.8 g of lithium carbonate to prepare a slurry having a total volume of 3 L. This slurry was 140 ° C. in a 5 L autoclave.
Heat treatment was performed for 12 hours. After the heat treatment, 8% by weight sulfuric acid was added to the slurry cooled to 70 ° C. until the pH reached 4.0. Next, 25% caustic soda was added to adjust the pH to pH 11 to pH 11
Was adjusted. While maintaining the pH-adjusted slurry at 55 ° C., 970 mL of a 1% solution of sodium stearate was added to perform surface treatment. Next, this slurry was filtered with a Nutsche, and washed with water 30 times the amount of the product. After washing, about 1
It was dried at 60 ° C. for 20 hours, crushed in a mortar, and sieved with a 100 mesh sieve. When the obtained white powder was subjected to chemical analysis, [Al ₂ Li _1.00 (OH) ₆ ] ₂ (SO ₄ ) _0.70 (CO ₃ ) _0.18 (OH) _0.24 0.
The composition was 77H ₂ O. The BET specific surface area is 5.
9 m ² / g, the average particle size was 1.3 μm.

Example 5 An agricultural film was prepared using the composite hydroxide salt obtained in Example 1, and the effect was confirmed. 10 parts by weight of the composite hydroxide salt obtained in Example 1 was added to 100 parts by weight of EVA resin (PES-400, manufactured by Nippon Unicar), kneaded in a roll at 150 ° C., and pressed to form a 0.1 mm agricultural product. A film was obtained. The transparency and heat retaining effect of this agricultural film were measured. The heat retention was evaluated by a heat retention index measured by the following method. The infrared absorption of the obtained film is 20 cm in the range of 2,000 to 400 cm ^-1.
Each ^-1 was measured and corrected to a thickness of 0.1 mm to obtain a corrected extinction coefficient for each wave number. 15 ° C corresponding to each wave number in the corrected extinction coefficient
Was multiplied by the black body relative radiant energy to calculate the black body relative radiant energy absorption rate. The black body relative radiant energy absorptivity of each wave number was integrated, and the value was divided by the total black body relative radiant energy of 2,000 to 400 cm ^-1 to obtain a heat retention index. The higher the heat retention index, the higher the heat retention effect. The transparency was evaluated by measuring the total light transmittance and the haze value (cloudiness) using a spectrophotometer (manufactured by JASCO Corporation) and evaluating the values.
As the total light transmittance is closer to 100, the visible light transmittance of the film is better, and as the haze value (cloudiness) is smaller, it means that the haze is smaller. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Example 6 Using the composite hydroxide salt obtained in Example 2, a 0.1 mm agricultural film was prepared in the same manner as in Example 5, and the transparency and the heat retaining effect were measured. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Example 7 Using the composite hydroxide salt obtained in Example 3, a 0.1 mm agricultural film was prepared in the same manner as in Example 5, and the transparency and the heat retaining effect were measured. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Example 8 Using the composite hydroxide salt obtained in Example 4, a 0.1 mm agricultural film was prepared in the same manner as in Example 5, and the transparency and the heat retaining effect were measured. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Comparative Example 1 A 0.1 mm agricultural film was prepared in the same manner as in Example 5 using a commercially available heat insulating agent DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.), and the transparency and the heat insulating effect were measured. did. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Comparative Example 2 A 0.1 mm agricultural film was prepared in the same manner as in Example 5 using a commercially available heat insulating agent Mizukarak (manufactured by Mizusawa Chemical Industry Co., Ltd.), and the transparency and the heat insulating effect were measured. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

Comparative Example 3 Commercially available heat insulator Fujilein LS
(A) Example 5 using [Fuji Chemical Industry Co., Ltd.]
Similarly, a 0.1 mm agricultural film was prepared, and the transparency and the heat retaining effect were measured. Table 1 shows the heat retention index, total light transmittance, and haze value of this film.

[0063]

[Table 1]

Example 9 Ethylene-vinyl acetate copolymer (vinyl acetate content: 14% by weight, density: 0.92 g / cm
³ ) The compound 1 obtained in Example 1 was used as an infrared absorber.
0.0% by weight, hindered amine compound as light stabilizer (trade name: Tinuvin 622-LD, manufactured by Ciba-Gaiky)
0.5% by weight, antioxidant (trade name Irganox 10
10, manufactured by Ciba-Gaikey) 0.2% by weight, monoglycerin monostearate 1.0% by weight as an antifogging agent, 1.0% by weight of diglycerin distearate, Unidyne DS-401 (manufactured by Daikin Industries) as an antifog agent 0.1% by weight and 0.2% by weight of stearamide as a lubricant were added to make the total amount 100% by weight, and 13% using a Banbury mixer.
After kneading at 0 ° C. for 5 minutes, the mixture was granulated by a granulator to obtain a composition pellet. This is designated as resin composition A. Next, a composition pellet B was prepared in the same manner except that no infrared absorber was added.
I got Using a resin composition A as an intermediate layer and a resin composition B as both outer layers, a film having a film thickness of 0.1 mm (intermediate layer 0.06 mm, both outer layers 0.02 mm) was prepared using an inflation film forming machine.

Example 10 Example 2 as an infrared absorbent
A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that the compound obtained in the above was used.

Example 11 Example 3 as an infrared absorbent
A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that the compound obtained in the above was used.

Example 12 Example 4 as an infrared absorbent
A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that the compound obtained in the above was used.

Comparative Example 4 Commercial product DH as infrared absorber
A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that T-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) was used.

Comparative Example 5 A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that a commercial product Mizukarac (manufactured by Mizusawa Chemical Industry Co., Ltd.) was used as the infrared absorbing agent.

Comparative Example 6 A film having a film thickness of 0.1 mm was prepared in the same manner as in Example 9 except that a commercial product, Fujilein LS (A) (manufactured by Fuji Chemical Industry Co., Ltd.) was used as the infrared absorbing agent. .

The films obtained in the above Examples 9 to 12 and Comparative Examples 4 to 6 were stretched for 8 months from April to November 1999, and exposed to weather (Nakashinagawa-gun, Toyama Prefecture) under weathering conditions. The properties, antifogging property and dewproofing property were evaluated according to the following methods. As for the weather resistance, discoloration (yellowing, browning) and abnormal change of the film were visually confirmed. In addition, a tensile elongation test was performed in accordance with JIS K 6781, and the residual rate of elongation (%) was determined.
If the residual ratio is 90% or more, it is determined that the battery does not deteriorate.

The anti-fogging property was visually confirmed by looking at the entire film and forming droplets.

As for the anti-dew property, the entire film was checked to see if there was any dew on the film.

As a result, all of the agricultural films obtained by the methods of Examples and Comparative Examples of the present invention had weather resistance (discoloration,
No deterioration of the film is observed. ), No cloudiness (no droplets formed), no dew-proofing (no dew formation is observed at all).

The following operation was performed to evaluate acid resistance (pesticide resistance). The films obtained in Examples 9 to 12 and Comparative Examples 4 to 6 were allowed to stand in a sealed container in which sulfur was fumigated for about 1 hour. This sulfur fumigation film is
For 8 months from April to November 999, it was exposed outdoors (Nakashinagawa-gun, Toyama Prefecture) to observe the surface condition. The evaluation criteria were as follows, and the results after 8 months of outdoor exposure are shown in Table 2. A: Almost no change in appearance was observed. ；: Some changes in appearance such as coloring, cracking, and tearing are observed. Δ: Appearance changes such as coloring, cracks, tears, etc. are considerably recognized. ×: Cracks are observed over the entire surface.

[0076]

[Table 2]

[0077]

According to the present invention, the compound of the formula (I) [Al ₂ Li _(1-x) M ²⁺ _{(x + y)} (OH) _{(6 + 2y)} ] ₂ (SO ₄ ) _z1 (CO ₃ ) _z2 (OH) _z3 mH ₂ O (I) (wherein, M ²⁺ is a divalent metal, m, x, y, z1, z2,
z3 is 0 ≦ m <5, 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.
5, z1> 0, z2> 0, z3 ≧ 0, z1 + z2 + z3
/ 2 = 1 + x) as an active ingredient, and an agricultural film formed by blending the resin with a resin and molding the same. Was completed. The infrared absorbent comprising the composite hydroxide salt of the present invention has a high infrared absorption ability, is excellent in dispersibility with a resin, and has a refractive index close to that of the resin, and has good acid resistance and good productivity. It is easy to mix with resin, easy to process with resin, and when formed into a film, has excellent heat retention, transparency, and pesticide resistance, and is useful as an agricultural film.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2B024 DA04 DB01 EA01 2B029 EB02 EB16 EC09 EC14 EC17 EC18 EC20 4D075 CA39 DA04 DB31 DC50 EC02 EC35 4F100 AK01B AT00A CA30B

Claims (9)

[Claims] (1) Formula (I) [Al ₂ Li _(1-x) M ²⁺ _{(x + y)} (OH) _{(6 + 2y)} ] ₂ (SO ₄ ) _z1 (CO ₃ ) _z2 (OH) _z3 MH ₂ O (I) (wherein, M ²⁺ is a divalent metal, m, x, y, z1, z2,
z3 is 0 ≦ m <5, 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.
5, z1> 0, z2> 0, z3 ≧ 0, z1 + z2 + z3
/ 2 = 1 + x) as an active ingredient. 2. The composite hydroxide salt according to claim 1, wherein the complex hydroxide salt is a higher fatty acid, a higher fatty acid salt, an ester of a higher fatty alcohol and phosphoric acid, a wax, a nonionic surfactant,
An infrared absorber coated with one or more selected from a cationic surfactant and a coupling agent. 3. An agricultural film formed by blending 1 to 50 parts by weight of the composite hydroxide salt according to claim 1 or 100 parts by weight with respect to 100 parts by weight of the resin. 4. A resin composition is prepared by mixing 1 to 50 parts by weight of the composite hydroxide salt according to claim 1 and 0.02 to 5 parts by weight of a hindered amine light stabilizer with respect to 100 parts by weight of the resin. An agricultural film characterized by the above-mentioned. 5. A resin obtained by mixing 1 to 50 parts by weight of the composite hydroxide salt according to claim 1 and 0.02 to 5 parts by weight of an antifogging agent with respect to 100 parts by weight of a resin. Characteristic agricultural film. 6. A resin obtained by mixing 1 to 50 parts by weight of the composite hydroxide salt according to claim 1 and 0.02 to 5 parts by weight of an antifog with respect to 100 parts by weight of a resin. Characteristic agricultural film. 7. A resin composition containing the infrared absorbent according to claim 1 or 2. 8. A laminated film having at least one film using the resin composition containing the infrared absorbent according to claim 1 or 2. 9. An agricultural film comprising the laminated film according to claim 8.