WO2007108109A1 - 安定化されたポリオレフィン系樹脂およびポリオレフィン系樹脂の安定化方法 - Google Patents
安定化されたポリオレフィン系樹脂およびポリオレフィン系樹脂の安定化方法 Download PDFInfo
- Publication number
- WO2007108109A1 WO2007108109A1 PCT/JP2006/305626 JP2006305626W WO2007108109A1 WO 2007108109 A1 WO2007108109 A1 WO 2007108109A1 JP 2006305626 W JP2006305626 W JP 2006305626W WO 2007108109 A1 WO2007108109 A1 WO 2007108109A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyolefin resin
- polyolefin
- resin
- salt
- agricultural
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Definitions
- the present invention relates to a stabilized polyolefin resin and a polyolefin resin.
- the present invention relates to a method for stabilizing in-based resins.
- the present invention relates to a stabilized polyolefin resin and a method for stabilizing a polyolefin resin, which can be advantageously used as an agricultural polyolefin film.
- an antioxidant such as hindered phenol, phosphite, and thioether is mainly used for the purpose of improving heat resistance.
- UV absorbers such as benzazol, benzophenone, and benzoate are used, and hindered amine light stabilizers are used.
- polyolefin resin is its use as agricultural polyolefin film in the field of agricultural materials.
- an ultraviolet absorber is added for the purpose of improving the weather resistance
- the film absorbs ultraviolet rays and the growth of crops is not a little affected.
- the use of UV absorbers can be largely limited, and at present the method of adding hindered light stabilizers is the mainstream.
- Use of agricultural polyolefin film in agricultural houses fumigation treatment with sulfur is frequently performed, so that the surface of the agricultural polyolefin film in the house becomes acidic, and the stability of the polyolefin resin is significantly impaired. is there.
- resin degradation under acidic conditions caused by acid rain caused by air pollution is a problem.
- Acidification with ⁇ treatment and air pollution is considered s ⁇ 2 is due to generating of H 2 S_ ⁇ 3 and H 2 S_ ⁇ 4 in the presence of oxygen and water.
- the deterioration of the polyolefin resin may be caused by accelerated decomposition of the antioxidant due to contact with an acid, or when a hindered and light-based light stabilizer is used, the light stabilizer and the acid form a salt. This is thought to be due to performance degradation due to generation.
- Japanese Patent Application Laid-Open No. 8-48 8 2 2 proposes a polyolefin film having a weather resistance and a pesticide resistance, which contains a hindered domine and a metal oxide or hydroxide.
- a polyolefin resin that is satisfactory in stability in use under acidic conditions has not yet been obtained.
- Japanese Patent Application Laid-Open No. 7-166 247 discloses that an acidic phosphate ester gold salt is added to a polyolefin resin.
- This publication can provide sufficient weather resistance by using a hindered vane light stabilizer and a benzotriazole, benzophenone, or benzoate UV absorber.
- acidic phosphate ester metal salts By using acidic phosphate ester metal salts, the weather resistance can be maintained for a longer period of time. It is described that it can be made.
- this method requires the use of light stabilizers and UV absorbers, which are weather resistance improvers, and therefore the impact on the growth of agricultural products due to the presence of UV absorbers cannot be avoided. Even if it discloses that a phosphoric acid ester gold salt is added, there is no description in the publication regarding the stability when used under acidic conditions. Disclosure of the invention
- the present invention improves the stability in use under acidic conditions, and also affects the growth of crops when used as an agricultural polyolefin film. It is an object of the present invention to provide a polyolefin-based resin that does not give any odor.
- the present inventors have obtained excellent stability even when used under acidic conditions by blending a specific phosphate metal salt with a polyolefin resin.
- the inventors have found that a polyolefin resin exhibiting properties can be obtained.
- the present inventors have further improved the use of a hindered light stabilizer, which is a weather resistance improver, in addition to a specific phosphoric acid ester metal salt. It has been found that a polyolefin resin having high stability can be obtained.
- the present invention provides the following polyolefin resin and method for stabilizing a polyolefin resin.
- Polyolefin resin that is stabilized for use under acidic conditions which is made by blending Zn salt of stearyl phosphate ester as an acid stabilizer with a polyolefin resin that does not contain UV absorbers.
- a hindered light stabilizer is added as a weather resistance improver.
- polyolefin resins under acidic conditions including the addition of Zn salts of stearyl phosphate esters as antioxidant stabilizers to polyolefin resins that do not contain UV absorbers. To stabilize.
- the Zn salt of stearyl phosphate ester (also known as octadecyl phosphate ester) which is an acid stabilizer is preferably 0 with respect to 100 parts by mass of the polyolefin resin. 1 to 10 parts by mass
- the stearyl phosphate ester constituting the Zn salt of stearyl phosphate ester is represented by the following formula [I] or [II]
- stearyl phosphate esters can be obtained by reacting stearyl alcohol with anhydrous phosphoric acid to convert to phosphoric acid ester, and then by a general method such as neutralization reaction or metathesis reaction, etc. It can be.
- antioxidants generally used as a basic blend may be used for the polyolefin resin stabilized by the addition of the ⁇ ⁇ ⁇ ⁇ salt of stearyl phosphate.
- a light stabilizer or the like is added to further improve the weather resistance. There is no problem in adding it.
- Polyolefin resins useful in the present invention include homopolymers of olefins such as ethylene, propylene and butene, copolymers of two or more of these olefins, and these olefins. Examples include resins mainly composed of copolymers with vinyl compounds, etc.
- polyethylene for agricultural materials includes polyethylene, linear low density polyethylene, linear ethylene mono-alpha-olefin Examples thereof include a polymer, an ethylene monoacetate copolymer, etc., each having a single or a combination as a main component.
- hindered amine light stabilizers include bis (2,2,6,6—tetramethyl-4-piperidyl) sebacate, bis (1,2, 2, 6, 6 — Penyumethyl 4-seperidyl) Sebacate, Bis (1, 2, 2, 6, 6 — Pentamethyl 1-4-piperidyl) 1 2 _ (3, 5 — Di_t-butyl-4 —Hydroxybenzyl) _ 2 — n_Butylmalonate, Tetokis (2, 2, 6, 6, 6-Tetramethyl mono 4-piperidyl) , 2, 2, 6, 6 — Penyu methyl 4-piperidyl) _ 1, 2, 3, 4—butante tracarboxylate, mixed 2, 2, 6, 6 —tetramethyl-4-piperidyl tridecyl-1, 2, 3, 4—butante tracarboxylate, mixed 1, 2, 2, 6, 6 — Ntamechiru - 4 Piperi Jill / DOO Ride Shiru 1, 2, 3, 4 But
- the hindered and dominated light stabilizer is a olefin resin.
- the stabilizing effect is preferably used in an amount of 0.05 mass parts, particularly 0.1 mass parts, with respect to 100 mass parts. If the amount is less than 5 parts by mass, the stabilizing effect may not be sufficient, and if it exceeds 5 parts by weight, further improvement in the effect cannot be expected, which is economically disadvantageous.
- the film was molded at a temperature of 180 ° C. by an inflation film molding machine to obtain films each having a thickness of 100 m. .
- Ethylene monoacetate copolymer (Novatech E VA L V 4 30) (vinyl acetate content 15%) (manufactured by Nippon Polyethylene Co., Ltd.) 7 5%
- J P— 6 50 Tris (2, 4-di-t-butylphenyl) phosphite) (manufactured by Johoku Chemical Industry Co., Ltd.)
- Fumigation test Each evaluation film is used to cover a mini-house (bottom 80 cm x 15 O cm, height 6 O cm) installed in the test field of Tsurudo, Taniwahara Village, Ibaraki Prefecture Then, fumigation was performed for 1.5 hours by heating 5 g of sulfur on the hot plate installed inside the mini house.
- the frequency of fumigation is set to 1 week, and the exposed film is sampled every 3 months. The appearance of each film sample (the surface turns white and becomes brittle) is observed, and JISK In accordance with 6 7 8 1, the tensile elongation at break in the transverse direction was measured, and the fumigation resistance was evaluated according to the following criteria.
- the present invention can provide a polyolefin resin that is excellent in stability under use under acidic conditions and that does not affect the growth of crops when used as an agricultural polyolefin film. It can be used advantageously in industry.
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2006800538516A CN101400731A (zh) | 2006-03-15 | 2006-03-15 | 稳定化的聚烯烃类树脂和聚烯烃类树脂的稳定化方法 |
EP06729593A EP1995276A4 (en) | 2006-03-15 | 2006-03-15 | STABILIZED POLYOLEFIN RESIN AND METHOD FOR STABILIZING POLYOLEFIN RESIN |
PCT/JP2006/305626 WO2007108109A1 (ja) | 2006-03-15 | 2006-03-15 | 安定化されたポリオレフィン系樹脂およびポリオレフィン系樹脂の安定化方法 |
US12/281,228 US20090012216A1 (en) | 2006-03-15 | 2006-03-15 | Stabilized Polyolefin-Based Resin and Polyolefin-Based Resin Stabilization Process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2006/305626 WO2007108109A1 (ja) | 2006-03-15 | 2006-03-15 | 安定化されたポリオレフィン系樹脂およびポリオレフィン系樹脂の安定化方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007108109A1 true WO2007108109A1 (ja) | 2007-09-27 |
Family
ID=38522149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/305626 WO2007108109A1 (ja) | 2006-03-15 | 2006-03-15 | 安定化されたポリオレフィン系樹脂およびポリオレフィン系樹脂の安定化方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20090012216A1 (ja) |
EP (1) | EP1995276A4 (ja) |
CN (1) | CN101400731A (ja) |
WO (1) | WO2007108109A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63175072A (ja) | 1987-01-16 | 1988-07-19 | Mikado Kako Kk | 農業用フイルム |
JPH07163247A (ja) | 1993-12-14 | 1995-06-27 | Mitsubishi Chem Corp | 土壌被覆材 |
JPH0848822A (ja) | 1994-06-27 | 1996-02-20 | Ciba Geigy Ag | 改良された光安定性および有害生物防除剤耐性を有するポリオレフィンまたはオレフィンコポリマーフィルム |
JPH08176382A (ja) * | 1994-12-21 | 1996-07-09 | Asahi Denka Kogyo Kk | 農業用塩化ビニル系樹脂組成物 |
JPH09111018A (ja) * | 1995-10-19 | 1997-04-28 | Mitsubishi Chem Mkv Co | 農業用ポリオレフィン系樹脂フィルム |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63308052A (ja) * | 1987-06-10 | 1988-12-15 | Chisso Corp | 改質プロピレン系重合体組成物の製造方法 |
JPH0269540A (ja) * | 1988-09-05 | 1990-03-08 | Chisso Corp | 結晶性ポリオレフイン組成物 |
DE69201008T2 (de) * | 1991-05-10 | 1995-07-20 | Mitsubishi Chemical Mkv Comp | Thermoplastische Elastomerzusammensetzung. |
US5266331A (en) * | 1991-11-27 | 1993-11-30 | Euroceltique, S.A. | Controlled release oxycodone compositions |
US6887202B2 (en) * | 2000-06-01 | 2005-05-03 | Science Applications International Corporation | Systems and methods for monitoring health and delivering drugs transdermally |
US6961599B2 (en) * | 2001-01-09 | 2005-11-01 | Childrens Hospital Los Angeles | Identifying or measuring selected substances or toxins in a subject using resonant raman signals |
US20020103429A1 (en) * | 2001-01-30 | 2002-08-01 | Decharms R. Christopher | Methods for physiological monitoring, training, exercise and regulation |
US20070167853A1 (en) * | 2002-01-22 | 2007-07-19 | Melker Richard J | System and method for monitoring health using exhaled breath |
GB2384819A (en) * | 2002-02-02 | 2003-08-06 | New Holland | Vehicle door hinge with reinforcement |
US20040092809A1 (en) * | 2002-07-26 | 2004-05-13 | Neurion Inc. | Methods for measurement and analysis of brain activity |
US20080242947A1 (en) * | 2007-03-30 | 2008-10-02 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Configuring software for effective health monitoring or the like |
-
2006
- 2006-03-15 EP EP06729593A patent/EP1995276A4/en not_active Withdrawn
- 2006-03-15 US US12/281,228 patent/US20090012216A1/en not_active Abandoned
- 2006-03-15 WO PCT/JP2006/305626 patent/WO2007108109A1/ja active Application Filing
- 2006-03-15 CN CNA2006800538516A patent/CN101400731A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63175072A (ja) | 1987-01-16 | 1988-07-19 | Mikado Kako Kk | 農業用フイルム |
JPH07163247A (ja) | 1993-12-14 | 1995-06-27 | Mitsubishi Chem Corp | 土壌被覆材 |
JPH0848822A (ja) | 1994-06-27 | 1996-02-20 | Ciba Geigy Ag | 改良された光安定性および有害生物防除剤耐性を有するポリオレフィンまたはオレフィンコポリマーフィルム |
JPH08176382A (ja) * | 1994-12-21 | 1996-07-09 | Asahi Denka Kogyo Kk | 農業用塩化ビニル系樹脂組成物 |
JPH09111018A (ja) * | 1995-10-19 | 1997-04-28 | Mitsubishi Chem Mkv Co | 農業用ポリオレフィン系樹脂フィルム |
Non-Patent Citations (1)
Title |
---|
See also references of EP1995276A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP1995276A1 (en) | 2008-11-26 |
CN101400731A (zh) | 2009-04-01 |
EP1995276A4 (en) | 2009-09-09 |
US20090012216A1 (en) | 2009-01-08 |
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