CN1227235A - Resin composition and film having layer of the same - Google Patents
Resin composition and film having layer of the same Download PDFInfo
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- CN1227235A CN1227235A CN98126958A CN98126958A CN1227235A CN 1227235 A CN1227235 A CN 1227235A CN 98126958 A CN98126958 A CN 98126958A CN 98126958 A CN98126958 A CN 98126958A CN 1227235 A CN1227235 A CN 1227235A
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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Abstract
The invention disclosed a resin composition excellent in heat resistance, weather- resistance, transparency and processability by making the composition include a polyolefin based resin, basic aluminum carbonates and hindered amine compounds. the films made from the composition is excellent for agricultural.
Description
The present invention relates to polyolefin resin composition of thermotolerance, weathering resistance, the transparency, excellent processability and uses thereof.
In recent years, automotive material, material of construction, agricultural are leaping increase with material etc. in the requirement of the resin of outdoor application.
As the agricultural material, can be set forth in the agricultural film that is used to cover facilities such as house, air channel in the horticultural facility.As the agricultural film, can use polychloroethylene film, polyolefin resin film (for example, polyethylene film, ethylene/vinyl acetate copolymerization film) etc. now usually.Wherein, be difficult for making dirty, the polyolefin resin film of less generation toxic gas generally is used for horticultural facility during in light weight, burning.
On the one hand, because agricultural film is in outdoor application, so if the basic resin weathering resistance of film is bad, because of the reaction of resin oxidative degradation, rerum naturas such as the elongation retention of film or tensile strength in use reduce, and make the film variation.Therefore in order to improve weathering resistance, advised in polyolefin resin, cooperating the resin combination of various weathering resistance additives such as antioxidant, UV light absorber.In the weathering resistance additive, steric hindrance amine stablizer, as disclosed among open clear 59-86645 of communique of Japanese Patent and the open flat 2-167350 of communique of Japanese Patent, can significantly improve the weathering resistance of polyolefin resin with a small amount of additive, simultaneously can keep effect for a long time, the gloss and the tonal variation that can significantly suppress the polyolefin resin film are ideal so use.
In the open clear 56-41254 of communique of Japanese Patent, disclose that to contain the bulky amine compounds and surface-area is arranged be 10m
2The thermoplastic resin membrane at the polarity inorganic micro powder end that/g is above also discloses in the open clear 63-175072 of communique of Japanese Patent and has contained thermoplastic resin, the agricultural film of bulky amine compounds and hydrotalcite-based compound.
Yet, can not fully keep mechanical and physical performance with this film being exposed under the environment such as agricultural chemicals and acid rain, also have, because the variable color that poor heat stability causes or be attended by to add and bubble man-hour, weathering resistance is very not good.
Present inventors further investigate in order to address the above problem, and the result has developed thermotolerance and the good polyolefin resin composition of weathering resistance, and the result has finished the present invention.
It is the resin combination of feature that one of invention of the application provides to comprise polyolefin resin, Aluminum Carbonate Basic salt or a positive aminated compounds.Said composition also can contain UV light absorber.
Two of the application's invention provides the film with layer that one deck at least forms by above-mentioned resin combination.This film contains antifogging agent or anti-turbid dose, perhaps antifogging agent and anti-turbid dose.In addition, film of the present invention can have anti-turbid property overlay film.
Another invention of the application provides the purposes of film of the present invention as film for agricultural use.
Another invention of the application provides the use of film of the present invention in agricultural usefulness facility.
This accompanying drawing is the x-ray diffraction pattern of carbonate aluminum,basic salt (SW).
Be used for carbonate aluminum,basic salt of the present invention by aluminum ion, carbonic acid ion and at least a cation composition except that aluminum ion.As aluminum ions positively charged ion, also can enumerate alkalimetal ion, alkaline-earth metal ion, ammonium ion, transition metal ion etc., wherein sodium ion, potassium ion, ammonium ion are preferred.As the example of described carbonate aluminum,basic can list the salt in the open flat 09-279131 of communique of Japanese Patent, put down in writing and following document 1. 2. in the salt of example.These carbonate aluminum,basic salt can use a kind of, also can use two kinds or more than.The manufacture method of carbonate aluminum,basic is not particularly limited, and can list the method for putting down in writing among the open flat 09-279131 of communique of Japanese Patent particularly.
Aluminum ion in the carbonate aluminum,basic salt and other cationic mol ratios (aluminum ion/positively charged ion) are generally 0.3/1～2/1, and be preferred 0.5/1～1.5/1, and more preferably 0.9/1～1.2/1.
In addition, aluminum ion and carbonic acid ionic mol ratio (Al/CO
3) be 0.3/1～2/1, preferred 0.8/1～1.5/1, more preferably 1/1～1.3/1.
Specifically, can enumerate aluminium carbonate sodium (Na
2OAl
2O
32CO
3NH
2O (n＞o)), aluminium carbonate potassium (K
2OAl
2O
32CO
3NH
2O (n＞0)) etc. (reference literature: document is Comprehensive inorganicchemistry 1., the 12nd volume, the 1045th page, 1973 publication distribution, Pergamon Press Ltd, document is Acomprehensive treatise on inorganic and theoretical chemistry 2., the 15th volume, 358-359 page or leaf, nineteen sixty publication distribution, Longman, Green and Co Ltd).
Carbonate aluminum,basic salt can contain water, water ratio is preferably 10 weight % or following, more preferably 5 weight % or following, preferred especially 3 weight % or following, water ratio is measured according to the JISK0067 method usually, specifically, water ratio can be used as at 180 ℃ of weight decrements that heated 2 hours down and tries to achieve.
The median size of carbonate aluminum,basic salt is usually at 5 μ m or following, preferred 0.05-3 μ m, more preferably 0.1～1 μ m.When resin combination of the present invention was used to need the purposes of heigh clarity, the specific refractory power that the specific refractory power of this carbonate aluminum,basic salt approaches employed polyolefin resin was an ideal.Usually, the specific refractory power of the carbonate aluminum,basic salt of measuring with the method for JISK0062 record, preferred 1.47～1.55, more preferably 1.48-1.54, preferred especially 1.49-1.53.
The content of resin combination neutral and alkali aluminium carbonate salt of the present invention is preferably the 0.03-200 weight part with respect to 100 parts of weight part polyolefin resins.When this resin combination being used for agricultural with the situation of the coating film of facility etc., consider from the film transparency and intensity aspect, the use level of carbonate aluminum,basic salt is preferably 35 weight parts or following with respect to 100 weight part polyolefin resins, more preferably 20 weight parts or following, preferred especially 15 weight parts or following.
In order to improve the dispersiveness of carbonate aluminum,basic salt in resin combination, can carry out surface treatment to carbonate aluminum,basic salt with dispersion agent.As dispersion agent, the stearic acid of can giving an example.Hexadecanoic acid.Senior lipid acid such as lauric acid, metallic soaps such as the calcium salt of higher fatty acid, zinc salt, magnesium salts, barium salt, sodium salt, phosphoric acid ester, silane coupling agent, aluminium class coupling agent, zirconium class coupling agent, paraffin etc.Surface treatment method adopts and to make dispersion agent evenly the method attached to the surface of carbonate aluminum,basic salt is just passable, for example, can enumerate a carbonate aluminum,basic salt and join and make slurry in the appropriate solvent, with this slurry and dispersion agent be mixed together, stirring method.
Be used for bulky amine compounds of the present invention, can enumerate the compound that for example has in the structural formula of the flat 8-73667 record of the open communique of Japanese Patent, concrete specifiable trade(brand)name has チ ヌ PVC Application 622-LD, キ マ Application-Block 944-LD. チ ヌ PVC Application 123 (above by the manufacturing of チ バ ヌ ペ シ ャ Le テ ィ ケ ミ カ Le ズ company), ホ ス PVC Application N30, VP Sanduvor PR-31 (above by the manufacturing of name Network リ ァ Application ト company), サ ィ セ ソ-プ uv3526 (manufacturing of サ ィ ラ Star Network company) etc.The stablizer that contains the bulky amine compounds can exemplify composition (trade(brand)name チ ヌ ピ Application 492, the チ ヌ PVC Application of putting down in writing among the open clear 63-286448 of communique of Japanese Patent 494; チ バ ス ペ シ ヤ Le テ ィ ケ ミ カ Le ズ company makes).The bulky amine compounds can use separately, also can more than two kinds and use.
Steric hindrance aminated compounds content is with respect to preferred 0.02 weight part of 100 weight part polyolefin resins in the resin combination of the present invention.In order to suppress bloom, preferred 5 weight parts or following, more preferably 0.1-2 weight part.
As the polyolefin resin in resin combination of the present invention, can enumerate for example alpha-olefin homo such as polyethylene, polypropylene; Ethene-alpha-olefin copolymers such as ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-4 methyl 1 pentene copolymer, ethene-hexene copolymer, ethylene-octene copolymer; Ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-vinyl acetate-methylmethacrylate copolymer; Ionic resin etc. be main composition and monomeric multipolymer not of the same race with alpha-olefin.When resin combination of the present invention is used for agricultural film, from the transparency, weathering resistance, preferably polyethylene is considered in aspects such as price, ethene-alpha-olefin copolymer and Vinyl Acetate Monomer content are at 30 weight % or following ethylene-vinyl acetate copolymer.
Use so-called single-minded site catalyst such as transition metal complex compound catalyzer such as palladium, nickel and metallocenes, under solvent existed or be solvent-free, the ethene-alpha-olefin copolymer of the alpha-olefin gained of polymerising ethylene and C3-18 was preferred the use under gas phase-solid phase, liquid phase-solid phase or even liquid-phase condition.Usually polymerization temperature is about 30 ℃-Yue 300 ℃, and polymerization pressure is a normal atmosphere to about 3,000kg/cm
2For example be recorded in the metalloscene catalyst composition among the open flat 6-9724 of communique of Japanese Patent, the open flat 6-136195 of communique of Japanese Patent, the open flat 6-136196 of communique of Japanese Patent, the open flat 6-207057 of communique of Japanese Patent, in the presence of so-called class of metallocenes catalyst for olefines polymerizing, make ethene and C
3-18Alpha-olefin copolymer close the ethylene that obtains and can preferably use in the present invention.
In order to improve the weathering resistance of resin combination more, resin combination of the present invention can also contain at least a UV light absorber.Can enumerate three benzophenone class UV light absorber, benzodiazole UV light absorber, benzoates UV light absorber, cyanoacrylate UV light absorber etc. as such UV light absorber.When containing UV light absorber, its consumption is the preferred 0.05-1 weight part of 0.01-3 weight part scope from improving the weathering resistance effect and suppressing the bloom aspect and consider with respect to 100 weight part polyolefin resins.
Resin combination of the present invention can comprise the complex hydroxide of lithium aluminum complex hydroxide, hydrotalcite-based compound etc.; Metal oxides such as magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, titanium oxide; Oxyhydroxide such as lithium hydroxide, magnesium hydroxide, calcium hydroxide, aluminium hydroxide; Carbonate such as magnesiumcarbonate, lime carbonate; Sulfateses such as vitriolate of tartar, sal epsom, calcium sulfate, zinc sulfate, Tai-Ace S 150; Trilithium phosphate, sodium phosphate, potassiumphosphate, calcium phosphate, zirconium phosphate phosphoric acid salts such as (for example being disclosed in the H type zirconium phosphate among the open flat 8-67774 of communique of Japanese Patent); Silicates such as Magnesium Silicate q-agent, Calucium Silicate powder, pure aluminium silicate, titanium silicate; Aluminate class such as sodium aluminate, potassium aluminate, calcium aluminate; Aluminum silicates such as sodium aluminium silicate, aluminum potassium silicate, calcium aluminosilicate; Clay minerals such as kaolin, clay, talcum; The mineral compound of more than one in other composite oxides etc.
As hydrotalcite-based compound is the compound that formula I is represented under the usefulness:
M
2+ 1-xAl
3+ x(OH
-)
2(A
1 n-)
x/n·mH
2O????(Ⅰ)
(M in the formula
2+Be divalent-metal ion, A
1 N-Be n valency negatively charged ion, x, m and n satisfy the condition of 0＜x＜0.5,0≤m≤2,1≤n≤3).Can enumerate Mg
2+, Ca
2+, Zn
2+Deng as M
2+N valency negatively charged ion is not had special the qualification, can enumerate for example Cl
-, Br
-, I
-, NO
3 -, ClO
4 -, SO
4 2-, CO
3 2-, SiO
3 2-, HPO
4 3-, HBO
4 3-, PO
4 3-, Fe (CN)
6 3-, Fe (CN)
6 4-, CH
3COO-, C
6H
4(OH) COO-, (COO)
2 2-, negatively charged ion such as terephthaldehyde's acid ion, naphthene sulfonic acid ion and be recorded in multi-silicate ion and Tripyrophosphoric acid ion among the open flat 8-217912 of communique of Japanese Patent.Specifically can use for example natural water talcum and the such synthetic hydrotalcite of picture ァ Le カ マ ィ ザ-DHT-4A (trade(brand)name, the manufacturing of consonance chemical industry).
As the lithium aluminum complex hydroxide, can enumerate the following formula II compound that for example is recorded among the open flat 5-179052 of communique of Japanese Patent:
Li
+(Al
3+)
2(OH
-)
6·(A
2 n-)
1/n·mH
2O????(Ⅱ?)
(in the formula, A
2 N-Be n valency negatively charged ion, m and n satisfy the condition of 0≤m≤3,1≤n≤3).As n valency negatively charged ion, do not limit especially, for example can enumerate and compd A in formula I
1 N-Identical negatively charged ion.
As the complex hydroxide except that above-mentioned two kinds, can enumerate for example to contain being selected among alkaline-earth metal, transition metal, Zn and the Si at least a element and containing Li and Al, and have the compound of hydroxyl.In alkaline-earth metal, preferably magnesium, calcium.In addition, in transition metal, preferred divalence or ferric iron, cobalt, nickel, manganese, wherein more preferably iron.The mol ratio of Al and Li (Al/Li) is generally 1.5/1-2.5/1, preferred 1.8/1-2.5/1.
The element mol ratio (a) that is selected among alkaline-earth metal, transition metal, Zn and the Si is generally 0＜a＜1.5 for 1 mole of lithium, preferred 0.1≤a≤1.4, more preferably 0.2≤a≤1.2.Anionicsite beyond the above-mentioned complex hydroxide hydroxyl can be enumerated for example multi-silicate ions such as disilicic acid ion, ring silicic acid ion, different silicic acid ion, page or leaf silicic acid ion, net silicic acid ion; Inorganic acid ions such as carbonic acid ion, halogen ion, sulfate ion, sulfurous acid ion, nitrate ion, nitrite ion, phosphate ion, phosphorous acid ion, ortho phosphorous acid ion, Tripyrophosphoric acid ion, aluminic acid ion, silicic acid ion, high chloro acid ion, borate ion; Fe (CN)
6 3-, Fe (CN)
6 4-Deng negatively charged ion transition-metal coordination body; Organic acid ions such as acetic acid ion, phenylformic acid ion, formate ion, terephthaldehyde's acid ion, alkylsulphonic acid ion etc., wherein, preferred carbonic acid ion, halogen ion, sulfate ion, phosphate ion, Tripyrophosphoric acid ion, silicic acid ion, multi-silicate ion, high chloro acid ion, preferred especially carbonic acid ion, Tripyrophosphoric acid ion, silicic acid ion, multi-silicate ion.
Object lesson as this complex hydroxide, can enumerate and contain Al, Li, Mg, and the complex hydroxide of the about 2.3/1/0.28 of Al/Li/Mg=(mol ratio) (trade(brand)name: LMA, Fuji chemical industry make) and contain Al, Li, Si, and the complex hydroxide of Al/Li/Si=about 2/1/1.2 (mol ratio) (trade(brand)name: Off ヅ レ イ Application LS, Fuji's chemical industry manufacturing).
The complex hydroxide preferred example is to be recorded in compound that the following formula III among the WO97/00828 represents and the compound that disclosed formula IV is down represented in the open flat 8-217912 of communique of Japanese Patent:
[(Li
+ (1-x)M
2+ x)(Al
3+)
2(OH
-)
6]
2(Si
yO
(2y+1) 2-)
(1+x)·mH
2O????(Ⅲ)
(in the formula, M
2+Be divalent-metal ion, m, x and y satisfy 0≤m＜5,0≤x＜1,2≤y≤4 conditions), [(Li
+ (1-x)M
2+ x) (Al
3+)
2(OH
-)
6]
2(A
N-)
2 (1+x)/nMH
2O (IV)
(in the formula, M
2+Be divalent-metal ion, A
N-Be n valency negatively charged ion, m, x and n satisfy 0≤m＜5,0.01≤x＜1,1≤n≤3 conditions).In formula III and (IV), as M
2+Mg can give an example
2+, Ca
2+, Zn
2+Deng.
Resin combination of the present invention can contain at least a infrared absorbent.Can enumerate as described infrared absorbent, for example organic class infrared absorbent such as polyoxymethylene, polyvinyl alcohol and derivative, ethylene-vinyl alcohol copolymer etc.
Resin combination of the present invention can contain at least a antifogging agent.As antifogging agent, can enumerate for example have perfluoroalkyl, the fluorine cpd of ω-hydrogenation fluoro-alkyl (particularly fluorochemical surfactant), and contain silicon compounds (particularly silicon-containing surfactant) of alkylsiloxane base etc.Trade(brand)name ュ ニ ダ ィ Application DS-403, DS-406, DS-401 (making) etc. can be enumerated as the object lesson of fluorochemical surfactant, trade(brand)name SH-3746 (eastern レ ダ ゥ コ-ニ Application グ シ リ コ Application Co., Ltd. makes) can be enumerated as silicon-containing surfactant by ダ イ キ Application ェ industry.
Resin combination of the present invention can contain at least a anti-turbid dose.This anti-turbid dose have at room temperature be solid-state also have be in a liquid state.
As solid-state anti-turbid dose, can enumerate nonionogenic tenside, for example the sorbitan-fatty acid ester class tensio-active agent of sorbitan monostearate, the soft ester acid esters of sorbitan list, sorbitan list montanate etc.; Glycerol fatty acid ester class tensio-active agents such as glycerine list palmitate, Zerol, two Stearic diglycerides, triglycerin monostearate, the two montanates of four glycerine, polyethylene glycols tensio-active agents such as polyethyleneglycol palmitate, polyethylene glycol mono stearate; The epoxide affixture of alkylphenol; Sorbitan/glycerol condensate and organic acid ester; The hard esteramides of polyoxyethylene (2 moles), polyoxyethylene (2 moles) laurylamide, polyoxyethylene alkyl amine compounds such as polyoxyethylene (4 moles) stearylamide, polyoxyethylene (2 moles) stearylamide monostearate, polyoxyethylene (2 moles) stearylamide SUNSOFT Q-182S, polyoxyethylene (mole) stearylamide monostearate, polyoxyethylene (4 moles) Stearyl Amine SUNSOFT Q-182S, polyoxyethylene (8 moles) stearylamide monostearate, polyoxyethylene (2 moles) stearylamide list n-docosane acid esters, the fatty acid ester of polyoxyethylene alkyl amine compounds such as polyoxyethylene (2 moles) laurylamide stearate, the amine tensio-active agent of the resin acid acid acid amides of polyoxyethylene alkyl amine compounds such as polyoxyethylene (2 moles) stearic amide etc. etc.
As anti-turbid dose of liquid state, can enumerate for example glycerols fatty acid esters such as glyceryl monooleate, two glyceryl monooleates, two glycerine sesquioleate, four glyceryl monooleates, sesquialter glyceryl monooleate, sesquialter triolein, four trioleins, four glyceryl monolaurates, sesquialter glyceryl monolaurate; Sorbitan class fatty acid esters such as sorbitan monooleate, sorbitan dioleate.
Resin combination of the present invention can further comprise photostabilizer beyond paraffin, oxidation inhibitor, static inhibitor, the positive amine in position, lubricant, pigment, anti-algae agent etc.
Resin combination of the present invention for example can be by following method manufacturing.Mix in the polyolefin resin and carbonate aluminum,basic salt, the bulky amine compounds of mixing specified amount with the mixed milling machine, and mix other additive as required.As the mixed milling machine, for example can use mixing machine or habitual devices such as single screw rod or twin screw extruder in propeller type kneading machine, super mixing machine, the spot uncle.The gained resin combination can suitably be used for extrusion molding, injection molded, blow molding etc.Resin combination of the present invention in particular can be preferred for making has at least one deck by the cambial film of this resin combination.
Resin combination of the present invention can be supplied with forming technology after diluting with polyolefin resin.At this moment, the resin combination before the dilution is commonly referred to masterbatch.
Film of the present invention can be the individual layer that is formed by resin combination of the present invention, also can be two layers or the above laminate film that is formed by resin combination of the present invention.Film of the present invention also can be more than the one deck that forms by resin combination of the present invention layer with by resin of the present invention one deck of forming of material or above laminate film in addition.The layer structure of stacked film do not limit especially, but examples example is as two kinds two layers, two kinds three layers, three kinds three layers, three kinds five layers etc.The layer that is formed by resin combination of the present invention is preferably by the middle layer of three layers or the above laminate film that forms.Film of the present invention is when the situation of the laminate film that is in the layer that material forms except that resin combination of the present invention, and the layer that material forms beyond the resin combination of the present invention is usually by resin formation.
Film of the present invention can be with resin combination of the present invention and is also used other material as required, and conventional process manufacturings such as employing is extruded, coextrusion, fusion coating method, extruding layer platen press, three laminatings form.
As being used for resin combination layer of the present invention, can enumerate for example alpha-olefin homo such as polyethylene, polypropylene with outer field resin; Ethene-alpha-olefin copolymers such as ethylene-propylene copolymer, ethene-butene-1-multipolymer, ethene-4 methyl 1 pentene copolymer, ethene-hexene copolymer, ethylene-octene copolymer; Alpha-olefins such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-vinyl acetate, methylmethacrylate copolymer, ion of bonding polymkeric substance resin are the monomeric multipolymer not of the same race of main composition.Wherein, when laminate film of the present invention is used for agriculture situation, from the transparency, weathering resistance, consideration in price, preferably using polyethylene, ethene-alpha-olefin copolymer, Vinyl Acetate Monomer content is 30 weight % or following ethylene-vinyl acetate copolymer.
As hereinbefore, film of the present invention can comprise mineral compound such as at least a complex hydroxide, metal oxide, oxyhydroxide, carbonate, Sulfates, phosphoric acid salt, silicates, aluminate class, aluminum silicate, clay mineral, composite oxides.Owing to add this mineral compound, improved the heat retaining property of film.
These mineral compound can be contained in any one deck in the film of the present invention, but preferably be contained in the layer of resin combination of the present invention, its content is with respect to 100 weight part polyolefin resins, preferred 0.03-150 weight part, more preferably 0.03-30 weight part, preferred especially 0.03-15 weight part.
As hereinbefore, film of the present invention can contain at least a infrared absorbent.
As hereinbefore, film of the present invention can contain at least a antifogging agent.
When film of the present invention contained the antifogging agent situation, its content is the 0.01-3 weight % of all weight of film preferably, more preferably 0.02-2 weight %, especially preferably 0.05-0.5 weight %.
In film of the present invention, as hereinbefore, can contain at least a anti-turbid dose.Separate out with the aspect of the film transparency toward film surface and to consider from suppressing anti-turbid dose, preferably will at room temperature be in a liquid state and be anti-turbid dose of solid-state use together.When film of the present invention contained anti-turbid dose situation, its content preferably accounted for all 0.1-4 weight % of film, more preferably 1.5-4 weight %, especially preferably 2.2-2.8 weight %.
Film of the present invention has anti-turbid property overlay film at the one side surface at least.Film with anti-turbid property overlay film can keep its anti-turbid property for a long time.This anti-turbid property overlay film, for example can enumerate, be recorded in the clear 49-32668 of Japanese patent gazette, what the clear 50-11348 of Japanese patent gazette etc. located is the inorganic oxide sol coat film of representative with colloid silica and aluminium colloidal sol, be recorded in Japanese patent gazette clear 6345432, the clear 63-45711 of Japanese patent gazette, the clear 64-2158 of Japanese patent gazette number, the coat film of inorganic oxide sol that the open flat 3-207643 of communique of Japanese Patent etc. locates and organic oxygen compound (tensio-active agent and resin etc.) etc., with the tensio-active agent is the liquid coat film of major ingredient, with hydrophilic resin (for example, polyvinyl alcohol, polyose, polyacrylic acid etc.) be the film etc. of major ingredient.Film-forming methods of these anti-turbid property overlay films can be cladding processes, make anti-turbid property overlay film after, this overlay film can be laminated into laminate film.Anti-turbid property overlay film can be individual layer or two layers or more than.
The moulding method of available normal use, for example can use rolling process, extrude the film shaped method of T pattern, film plastic uptake formed film method etc. made film of the present invention.Consider from the film strength aspect film thickness be 0.01mm or above be ideal; Consider from aspects such as film following process and overwrite jobs, film thickness be 0.3mm or following be ideal.Better film thickness is in the 0.03-0.25mm scope.
Above-mentioned film can be suitable as agricultural film, is especially suitable for use as the coating film of agriculturals such as house and air channel with facility.
By the resin combination thermotolerance that the present invention obtains, weathering resistance, transparent good can be used for agricultural material, household appliances, automotive material, material of construction etc.Especially, use this resin combination film, when coating film that is used as agricultural house, air channel and ground coating film situation, its weathering resistance is very good, is effective material aspect horticultural facility.Film of the present invention is compared with coating film with existing agricultural under conditions such as contact light, agricultural chemicals, also has excellent weather resistance.Further, resin combination of the present invention even above-mentioned performance variation and the colour-change brought thus also reduce seldom under the continuous molding processing conditions, and is shaped that to add the foaming in man-hour few, and the processing stability that is shaped for a long time is good.
Below represent the embodiment of the invention, but the present invention is not limited by these.
Test method in embodiment and the comparative example is as follows.[heat stability test]
Thick 1mm test piece is placed under gear baking oven, the 180 ℃ of air atmospheres, estimated its degree of staining every 1 hour, estimate in order to standard down.
Zero: compare with A-stage, painted hardly
△: compare with A-stage, be little yellow or light brown
*: compare with A-stage, be yellow or brown
* *: compared with A-stage, is Vandyke brown [atmospheric exposure test (1)]
Thick 1mm test piece ァ イ ス-パ-UV tstr-SUV-W11 (manufacturing of ァ イ グ ラ Off イ Star Network ス Co., Ltd.) 60 ℃ of wind pushing temperatures, was placed 24 hours under the relative humidity 32%RH condition.Estimate this test piece degree of staining, in order to following standard evaluation.
Zero: compare with A-stage, painted hardly
△: compare with A-stage, be little yellow or light brown
*: compare with A-stage, be yellow or brown
* *: compared with A-stage, is Vandyke brown [atmospheric exposure test (2)]
Thick 1mm test piece is suspended on being equipped with in the 500ml vial that 50ml concentration is the 6% sulfurous acid aqueous solution of sealing, at room temperature placed 4 hours.In ァ イ ス-パ-UV tstr-SUV-W11 (manufacturing of ァ イ グ ラ Off イ Star Network ス Co., Ltd.),, place this test piece 24 hours under the relative humidity 32%RH condition 60 ℃ of wind pushing temperatures.Estimate the degree of staining of this test piece, estimate with following benchmark.
Zero: compare with A-stage, painted hardly
△: compare with A-stage, be little yellow or light brown
*: compare with A-stage, be yellow or brown
* *: compared with A-stage, is Vandyke brown [transparency is measured]
According to JISK7105, measure total light transmittance and HAZE with the haze gauger that ス ガ trier is made.The HAZA value is more little, and the expression transparency is good more.
Embodiment 1-3
With resin as shown in table 1, carbonate aluminum,basic salt (constituent ratio Al/Na=1/1, Al/CO
3=1.2/1), bulky amine compounds and other additives made pellet with the forcing machine granulation with mixing roll in the spot uncle after under 140 ℃ mixing 5 minutes.With the injection molded method this pellet is made the thin slice of thick 1mm, carry out the mensuration of heat stability test and atmospheric exposure test (1), (2).The result is as shown in table 1, and thermostability and weathering resistance are good.The details of employed carbonate aluminum,basic salt is shown in Table 3.Comparative example 1-3
Remove with hydrotalcite (trade(brand)name: DHT:4A; Consonance chemical industrial company makes) replace carrying out the test identical beyond the carbonate aluminum,basic salt with embodiment 1-3.The thermostability and the thermotolerance of gained resin combination are as shown in table 1, and it is poor comparing with embodiment 1-3 resin combination.The details of used hydrotalcite is shown in Table 3.Embodiment 4-6
Resin as shown in table 2, carbonate aluminum,basic salt, bulky amine compounds were made pellet with the forcing machine granulation with mixing roll in the spot uncle after under 140 ℃ mixing 5 minutes.With the injection molded method this pellet is made thick 1mm thin slice, carry out thermal stability determination.The thermostability of gained resin combination is as shown in table 2 to be good.Comparative example 7-9
Remove with hydrotalcite (trade(brand)name: DHT-4A, the manufacturing of consonance chemical industry) and in addition, carry out the test identical with embodiment 4-6.Gained resin combination thermostability is as shown in table 2, and it is poor comparing with embodiment 4-6 resin combination.Reference example 1
In 83.9 parts by weight of ethylene-vinyl acetate copolymer (trade(brand)name: ェ バ テ-ト H2031; Sumitomo Chemical is made) in, add 13 weight part carbonate aluminum,basic salt, 0.3 weight part bulky amine compounds A (trade(brand)name: チ ヌ PVC Application 622; チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ manufacturing), 0.3 weight part bulky amine compounds B (trade(brand)name: キ マ ソ-Block 944-LD; チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ manufacturing), 0.1 weight part UV light absorber (trade(brand)name: ス ミ ソ-Block 130; The Sumitomo Chemical manufacturing), 0.1 weight part oxidation inhibitor (trade(brand)name: イ Le ガ ノ Star Network ス 1010; チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ manufacturing), 1.4 weight part list glycerol monostearates, 0.6 weight part, two glycerol SUNSOFT Q-182S, 0.2 weight part stearic amide (lubricant), 0.1 weight part fluorochemical surfactant (antifogging agent) (trade(brand)name: DS-403, the industry of ダ イ キ Application are made); with Banbury 150 ℃ the time after mixing 5 minutes; use the tablets press granulation, make the resin combination pellet.This resin combination 1. as resin combination.Then, in 96.9 parts by weight of ethylene/vinyl acetate copolymer (trade(brand)name: ェ パ テ-ト D2011; Sumitomo Chemical is made) in; add 0.6 weight part bulky amine compounds A; 0.1 weight part UV light absorber, 0.1 weight part oxidation inhibitor, 1.4 weight part list glycerol monostearates, 0.6 weight part, two glycerol SUNSOFT Q-182S, 0.2 weight part stearic amide, 0.1 weight part fluorochemical surfactant; with Banbury 150 ℃ the time after mixing 5 minutes; use the tablets press granulation, make the resin combination pellet.This resin combination 2. as resin combination.With above-mentioned two kinds of pellets, 1. form the middle layer by the manufacturing of film blow-moulding machine by resin combination, and by internal layer that 2. forms at the stacked resin combination in its both sides and the outer thick 0.1mm laminate film (middle layer 0.06mm, each 0.02mm of ectonexine) that forms.When making this laminate film, material is non-foaming.This laminate film weathering resistance, anti-turbid property, transparent good can be suitable as agricultural film.Reference example 2
In 86 parts by weight of ethylene/vinyl acetate copolymer (trade(brand)name: ェ バ テ-ト H2031; Sumitomo Chemical is made) middle 13 weight part carbonate aluminum,basic salt, 0.6 weight part bulky amine compounds B, 0.1 weight part UV light absorber, 0.1 weight part oxidation inhibitor, the 0.2 weight part stearic amide (lubricant) of adding; with Banbury 140 ℃ the time after mixing 5 minutes; use the tablets press granulation, make the resin combination pellet.With this resin combination 3. as resin combination.Then, in 96.3 parts by weight of ethylene/vinyl acetate copolymer (trade(brand)name: ェ バ テ-ト D2011; Sumitomo Chemical is made) in; add 3.0 weight part carbonate aluminum,basic salt, 0.3 weight part bulky amine compounds A, 0.3 weight part position sun aminated compounds B, 0.1 weight part antioxidant; with Banbury 140 ℃ the time after mixing 5 minutes; use the tablets press granulation, make the resin combination pellet.This resin combination 4. as resin combination.Further, in 96 weight part new LDPE (film grade)s (trade(brand)name: ス ミ カ セ Application F208-0; Sumitomo Chemical is made) middle 3.0 weight part carbonate aluminum,basic salt, 0.3 weight part bulky amine compounds A, 0.3 weight part bulky amine compounds B, 0.1 weight part UV light absorber, 0.1 weight part oxidation inhibitor, the 0.2 weight part stearic amide of adding; with Banbury 140 ℃ the time after mixing 5 minutes; use the tablets press granulation, make the resin combination pellet.5. this resin combination is used as resin combination.Can make the middle layer that is 3. formed by resin combination with these three kinds of pellets by the film blow-moulding machine, the internal layer that 4. stacked resin combination forms on one side, middle layer reaches the skin that 5. forms at the stacked resin combination in another side, middle layer and the thick 0.1mm laminate film (middle layer 0.06mm, internal layer 0.02mm, outer 0.02mm) that constitutes.To be coated with バ-コ- with the anti-turbid dose of coating liquid A that 4/3/0.1/75/25 weight ratio blended ス ノ-テ Star Network ス 30, カ ヤ Network リ Le レ ジ Application H300, ェ ピ Network ロ Application 860, water and ethanol constitute at the laminar surface place that 4. resin combination forms, make the solid composition become about 1g/m
2, carry out drying again, also can obtain having anti-turbid property film.The weathering resistance of these films, anti-turbid property, the transparency etc. are good, are suitable as agricultural film.ス ノ-テ Star Network ス 30 is trade(brand)names of the colloid silica of daily output chemical industry manufacturing.カ ヤ Network リ Le レ ジ Application H300 is the trade(brand)name of the acrylic latex of Japanese gunpowder industry manufacturing.ェ ピ Network ロ Application 860 is trade(brand)names of the dihydroxyphenyl propane type epoxy compounds of big Japanese ink chemical industry manufacturing.Reference example 3
Except reference example 2 resin combinations 4., 5. in 85 weight % of resin replace to the commercially available ethylene/hexene multipolymer of metalloscene catalyst polymeric (trade(brand)name: ス ミ カ セ Application EFV403; Density 0.919g/10 branch, MFR:4g/10 branch) in addition, adopt the method identical to make laminate film with reference example 2.This laminate film adhesion inhibiting properties, weathering resistance, the transparency etc. are good, are suitable for use as agricultural film.Further, if carry out Corona discharge Treatment on the one side of this laminate film, synthetic anti-turbid dose of coating liquid B below the coating makes the about 0.1g/m of solid composition thickness thereon
2, at room temperature dry then, just can make anti-turbid property and the good laminate film of antifog property.Anti-turbid property coating liquid B is alumina sol (the daily output chemistry is made, trade(brand)name ァ Le ミ Na ゾ Le 520, solid composition 20%), the colloid silica (trade(brand)name: ス ノ-テ Star Network ス 20 with the 1.6/0.4/0.08/0.08 weight ratio; The daily output chemistry is made; Solid composition: 20%).Sodium dodecylbenzene sulfonate (trade(brand)name: ネ オ ペ レ Star Network ス F25; Flower king system), Sodium decanoic acid (Na カ テ イ テ ス Network system) thin up makes.
Table 1
| Resin combination | Thermostability | Weathering resistance | ||||||||||
| Resin (weight part) | HALS (weight part) | UVA (weight part) | AO agent (weight part) | TGMS (weight part) | Mineral compound (weight part) | 1 hour | 2 hours | 3 hours | 5 hours | ???(1) | ???(2) | |
| Embodiment 1 | ?A1(100) | ????0.1 | ???SW(10) | ??○ | ??○ | ???○ | ?○～△ | ???○ | ???○ | |||
| Embodiment 2 | ?A1(100) | ????0.1 | ????0.1 | ???SW(10) | ??○ | ??○ | ???○ | ?○～△ | ???○ | ???○ | ||
| Embodiment 3 | ?A1(100) | ????0.1 | ????0.1 | ????2.5 | ???SW(10) | ??○ | ??○ | ???○ | ?○～△ | ???○ | ???○ | |
| Comparative example 1 | ?A1(100) | ????0.1 | ?DHT-4A(10) | ○～△ | ??△ | △～× | ??×× | ???○ | ???△ | |||
| Comparative example 2 | ?A1(100) | ????0.1 | ????0.1 | ?DHT-4A(10) | ??△ | ??△ | △～× | ??×× | ???○ | ???△ | ||
| Comparative example 3 | ?A1(100) | ????0.1 | ????0.1 | ????2.5 | ?DHT-4A(10) | ??△ | ??△ | △～× | ?△～× | ???○ | ???△ | |
(notes)
A1: ethylene/vinyl acetate copolymer (trade(brand)name: ェ バ テ-ト H2031; Sumitomo Chemical system; Vinyl Acetate Monomer content: 19wt%;
The MFR:1.5g/10 branch)
HALS: bulky amine compounds (trade(brand)name: キ マ ソ-Block 944-LD; チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ system)
UVA: UV light absorber; Trade(brand)name: ス ミ ソ-Block 130; Sumitomo Chemical system
AO agent: oxidation inhibitor: trade(brand)name: イ Le ガ ノ Star Network ス 1010; チ バ ス ペ シ ヤ Le テ イ-ケ ミ カ Le ズ system
TGMS: four glycerol monostearate (trade(brand)names: MS-310; This medicine of slope system)
SW: carbonate aluminum,basic salt (constituent ratio: Al/Na=1/1, Al/CO
3=1.2/1; Shui swamp chemical industry system)
DHT-4A (trade(brand)name): Ha イ De ロ Le サ イ ト; Consonance chemical industry system
Table 2
| Resin combination | Thermostability | ||||||
| Resin (weight part) | HALS (weight part) | Mineral compound (weight part) | 1 | 2 hours | 3 hours | 5 hours | |
| Embodiment 4 | ?A2(100) | ????0.1 | ???SW(2) | ??○ | ?○～△ | ○～△ | ○～△ |
| Embodiment 5 | ?A2(100) | ????0.1 | ???SW(10) | ??○ | ?○～△ | ○～△ | ○～△ |
| Embodiment 6 | ?A2(100) | ????0.1 | ???SW(20) | ??○ | ?○～△ | ○～△ | ○～△ |
| Comparative example 4 | ?A2(100) | ????0.1 | ??DHT-4A(2) | ??○ | ?○～△ | ??△ | △～× |
| Comparative example 5 | ?A2(100) | ????0.1 | ??DHT-4A(10) | ??○ | ?○～△ | ??△ | ??× |
| Comparative example 6 | ?A2(100) | ????0.1 | ??DHT-4A(20) | ??○ | ?○～△ | ??Δ | ??× |
(notes)
A2: new LDPE (film grade) (trade(brand)name: ス ミ カ セ Application F208-0; Sumitomo Chemical system; The MFR:1.5g/10 branch)
Table 3
| DHT-4A (ハイドロルサイト) | SW carbonate aluminum,basic salt | |
| Chemical constitution | MgO:36.5 Al 2O 3:18.6 CO 2: 8.3 moisture etc.: 36.6 | Na 2O:21.0 Al 2O 3:36.2 CO 2: 25.8 moisture etc.: 17.0 |
| Moisture (%) 110 ℃, 2 hours | 0.7 | ?0.9 |
| Heat-flash decrement (%) 180 ℃, 2 hours | 4.2 | ?2.7 |
| Specific refractory power | 1.51 | ?1.51 |
| Median size (μ m) | 0.28 | ?1.1 |
(notes)
Median size is that the 1g test portion is disperseed in 50ml ethanol, and is fixed with laser diffraction formula size-grade distribution instrumentation.
Claims (14)
1, a kind of resin combination is characterized in that containing polyolefin resin, carbonate aluminum,basic salt and bulky amine compound.
2, according to the described resin combination of claim 1, wherein the carbonate aluminum,basic salts contg is the 0.03-200 weight part with respect to 100 weight part polyolefin resins.
3, according to claim 1 or 2 described resin combinations, wherein the bulky amine kind compound content is the 0.02-5 weight part with respect to 100 weight part polyolefin resins.
4, according to any one described resin combination among the claim 1-3, wherein the specific refractory power of carbonate aluminum,basic salt is in the 1.48-1.53 scope.
5, according to any one described resin combination among the claim 1-4, wherein further contain UV light absorber.
6, according to the described resin combination of claim 5, wherein the ultraviolet radiation absorption agent content is the 0.01-3 weight part with respect to 100 weight part polyolefin resins.
7, a kind of have a film that one deck is at least formed by any one described resin combination among the claim 1-6.
8, also contain anti-turbid dose according to the described film of claim 7.
9, according to the described film of claim 7, also contain antifogging agent.
10, according to the described film of claim 8, wherein anti-turbid dose of consumption is 0.1-4 weight % in the film.
11, according to the described film of claim 9, wherein the antifogging agent consumption is 0.01-3 weight % in the film.
12,, has anti-turbid property overlay film according to any one described film among the claim 7-11.
13, any one described film is used as the purposes of agricultural with film among the claim 7-12.
14, the purposes of any one described film in agricultural usefulness is arranged among the claim 7-12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP352909/97 | 1997-12-22 | ||
| JP35290997 | 1997-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1227235A true CN1227235A (en) | 1999-09-01 |
Family
ID=18427288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126958A Pending CN1227235A (en) | 1997-12-22 | 1998-12-21 | Resin composition and film having layer of the same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR19990063163A (en) |
| CN (1) | CN1227235A (en) |
| ES (1) | ES2163960B1 (en) |
| FR (1) | FR2772775A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2893032A1 (en) * | 2005-11-04 | 2007-05-11 | Dgtec Soc Par Actions Simplifi | Polymer, useful in e.g. deprived dwelling, comprises e.g. carbonates of aluminum, yttrium and zinc and oxalates of magnesium, calcium, yttrium and zinc |
| KR100716586B1 (en) * | 2005-11-16 | 2007-05-09 | 부경대학교 산학협력단 | Method for processing of polyethylene for agriculture film having antifogging |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0429731A1 (en) * | 1989-12-01 | 1991-06-05 | At Plastics Inc. | Composition for use in films |
| WO1995019391A1 (en) * | 1994-01-14 | 1995-07-20 | Exxon Chemical Patents Inc. | Gas fade resistant ultraviolet additive formulations for polyethylene |
| IT1269953B (en) * | 1994-06-27 | 1997-04-16 | Ciba Geigy Spa | POLYOLEFIN FILMS OR OLEFINE COPOLYMERS WITH IMPROVED LIGHT STABILITY AND INSECTICIDE RESISTANCE |
| ES2134083B1 (en) * | 1994-12-09 | 2000-05-01 | Sumitomo Chemical Co | COVER POLYOLEFIN RESIN FILM AND METHOD FOR PLANT CULTIVATION. |
-
1998
- 1998-12-17 KR KR1019980055766A patent/KR19990063163A/en not_active Application Discontinuation
- 1998-12-21 FR FR9816114A patent/FR2772775A1/en not_active Withdrawn
- 1998-12-21 CN CN98126958A patent/CN1227235A/en active Pending
- 1998-12-21 ES ES009802658A patent/ES2163960B1/en not_active Withdrawn - After Issue
Also Published As
| Publication number | Publication date |
|---|---|
| FR2772775A1 (en) | 1999-06-25 |
| ES2163960B1 (en) | 2003-05-01 |
| ES2163960A1 (en) | 2002-02-01 |
| KR19990063163A (en) | 1999-07-26 |
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