CN1246385C - Biodegradable resin composition with controlled biodegradation rate film and agricutlural mulch film - Google Patents
Biodegradable resin composition with controlled biodegradation rate film and agricutlural mulch film Download PDFInfo
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- CN1246385C CN1246385C CNB028014766A CN02801476A CN1246385C CN 1246385 C CN1246385 C CN 1246385C CN B028014766 A CNB028014766 A CN B028014766A CN 02801476 A CN02801476 A CN 02801476A CN 1246385 C CN1246385 C CN 1246385C
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- Prior art keywords
- aliphatic polyester
- weight parts
- acid
- biodegradable
- biodegradation rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000006065 biodegradation reaction Methods 0.000 title claims abstract description 46
- 239000002362 mulch Substances 0.000 title claims abstract description 25
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- 239000011342 resin composition Substances 0.000 title abstract description 4
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- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims description 43
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 33
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- 239000000463 material Substances 0.000 claims description 21
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 11
- 150000002596 lactones Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000071 blow moulding Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
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- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JWJGFXCGGDFFHW-UHFFFAOYSA-N dibutyl benzene-1,2-dicarboxylate;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC JWJGFXCGGDFFHW-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A thermoplastic resin composition comprising an aliphatic polyester (A) and a polylactic acid polymer (B), the amount of the polylactic acid polymer (B) being 1 to 20 parts by weight, excluding 20 parts by weight, per 100 parts by weight of the sum of both. The composition gives a biodegradable film having a controlled biodegradation rate, in particular, a biodegradable agricultural mulch film, which is suitable for practical use.
Description
Technical field
The present invention relates to biodegradable resin combination, biodegradable book film and Farm mulch that biodegradation rate is controlled.
Background technology
In recent years, along with environmental problem more and more is subjected to people's attention, the commodity that the consumed energy of exploitation in the manufacturing processed is few, the commodity that can be used as resource reutilization and commodity free from environmental pollution, particularly there is the cry of commodity of biodegradable characteristic more and more higher.These commodity environmental problem behave gaze at now, all come into one's own at all areas, wherein, have the exploitation of the commodity of biodegradable characteristic in enterprise, office, also discussing actively.These exploitations relate to the many aspects of expecting each stage of finished product from former.
Definition according to biodegradable plastic research association, biodegradable resin is meant " though with general plastics same rerum natura is arranged in using; in case discarded, be decomposed by means of the activity of the microorganism in the physical environment, finally be broken down into the plastics of water and carbonic acid gas ".Now, as general biodegradable resin, can list that 1. Monsanto Company produces the polymkeric substance of microorganisms of バ イ オ Port one Le and so on, 2. the PCA of DAICEL chemical industry Co., Ltd. production is the polymkeric substance that derives from natural product of " セ Le グ リ one Application " (cellulose acetate) and so on, 3. Showa Highpolymer Co., Ltd " PVC オ ノ one レ " that produce, the PHB system " セ Le グ リ one Application " (caprolactone is the mixed stocker of resin and condensed type vibrin) that DAICEL chemical industry Co., Ltd. produces belongs to the polymkeric substance of chemosynthesis of " レ イ シ ア " (all being trade(brand)name in " ") and so on of Mitsui Chemicals, Inc's production of polymer in poly lactic acid series.This wherein develops the most active is the polymkeric substance of chemosynthesis, but these stages all also under development, in the maintenance biological degradability, satisfies the material of physics value required value aspect practical and we can say do not have.
Biodegradable resin now as the purposes in the test comprise agricultural with film, compost bag, give birth to the formed body etc. of the book of refuse bag, bottle and so on, but mainly be to be used for the book film.
For example, the spy opens flat 8-259823 communique and discloses and use the biological degradability mulch film that the macromolecular material of biodegradation character is arranged, particularly contain the polymkeric substance of lactic acid units.But, adopt the mulch film of this technology, as main body, too hard as Farm mulch with poly(lactic acid), biodegradation rate is too slow in addition, is not the controlled material of rerum natura.
Te Kaiping 9-111107 communique disclose biodegradable resin book film or the sheet material, the particularly content of biodegradable fatty polyester that obtain at the aliphatic polyester below 0 ℃ from polymer in poly lactic acid series and vitrifying transition point (Tg) with respect to polylactic acid polymer 100 weight parts, be that the thermoforming of 7～60 weight parts is with film or sheet material.But what adopt this technology also is based on poly(lactic acid), with top described identical, is not the material that biodegradation rate is controlled.
Te Kaiping 9-272794 communique discloses by polymer in poly lactic acid series and the book film of other aliphatic polyesters with 75: 25～20: 80 part by weight mixing gained, and it is that the tension spring rate is at 250Kg/mm
2Below, light penetration is at the biodegradable book film more than 65%.But, adopting the book film of this technology, its poly lactic acid series incorporation accounts for 20 parts more than the weight part in 100 weight part gross weights, therefore, lack under the flexibility, particularly situation, flexibility is not made the such problem in field that requires more with regard to having occurred to be used for as the book film.
For example, Te Kaiping 11-222528 communique discloses the improved biological degradability book of a kind of like this fragility film, its polymer in poly lactic acid series is 80: 20～20: 80 (weight) with the ratio of the content of other aliphatic polyesters, this film is characterised in that the conversion heat of fusion Δ Hml of the polymer in poly lactic acid series when the book film is heated up is below 35J/g.But, adopt the film of this technology also to exist the content of polylactic acid polymer in 100 weight part gross weights, to account for more than 20 weight parts thereby lack the problem of flexibility.
Particularly along with the effect of biological degradability Farm mulch is familiar with by people in recent years gradually, such mulch film is also being come into market.As the characteristic of biological degradability Farm mulch, the operability when requiring laying plastic down on the farm, after laying preserve moisture and heat retaining property, disguise and plant growth etc. to the two the good balance of performance of the desired performance of general Farm mulch of using general plastics and the distinctive biodegradation rate of biodegradable resin, biological degradability.But the biological degradability Farm mulch that begins to occur on the market can fully satisfy the existence hardly of above-mentioned two side's performance requriementss now.
If pay attention to the film properties as general plastics, biological degradability will be not enough, and if pay attention to biological degradability, general property will be not enough.To fully satisfy this two sides performance requriements, also need further discussion.
Requirement has the mulch film, particularly biological degradability Farm mulch that a kind of biodegradation rate can be controlled, rerum natura can satisfy the practicability needs again fully.
In order to solve this problem, the present inventor has carried out deep research, found that, in the film physical properties excellent but add lactic acid polymer in the specified range in the fast aliphatic polyester of biodegradation rate, just can when keeping the film rerum natura, control biological degradability and shape collapse speed, thereby finish the present invention.
Disclosure of an invention
Promptly, the 1st aspect of the present invention is, the biodegradable resin combination that provides a kind of biodegradation rate to be controlled, it is characterized in that, it is made up of aliphatic polyester (A) and polymer in poly lactic acid series (B), in both sums is 100 weight parts, the content of polymer in poly lactic acid series (B) more than 1 weight part, discontented 20 weight parts.
The 2nd aspect of the present invention be, the resin combination that provides the described biodegradation rate in the 1st aspect of the present invention with following characteristics to be controlled: described aliphatic polyester (A) is the aliphatic polyester (A ') with structure that the polycondensation by dibasic alcohol and dicarboxylic acid obtains.
The 3rd aspect of the present invention is, the resin combination that provides the described biodegradation rate in the 2nd aspect of the present invention with following characteristics to be controlled: described aliphatic polyester (A ') is to have by 1, the aliphatic polyester (A (BG-S)) of the polycondensation of 4-butyleneglycol and succsinic acid and the structure that obtains and/or have by 1, the polycondensation of 4-butyleneglycol and succsinic acid and hexanodioic acid and the aliphatic polyester (A (BG-S/A)) of the structure that obtains.
The 4th aspect of the present invention is, the resin combination that provides the described biodegradation rate in the 3rd aspect of the present invention with following characteristics to be controlled: is 100 weight parts in aliphatic polyester (A (BG-S)) with aliphatic polyester (A (BG-S/A)) sum, and (A (BG-S) accounts for 90～30 weight parts to aliphatic polyester.
The 5th aspect of the present invention be, the resin combination that provides the described biodegradation rate in the 1st aspect of the present invention with following characteristics to be controlled: described aliphatic polyester (A) is the aliphatic polyester (A ") with the structure that obtains by lactone ring opening polymerization.
The 6th aspect of the present invention be, the resin combination that provides the described biodegradation rate in the 5th aspect of the present invention with following characteristics to be controlled: (A ") is the caprolactone based polymer (A (CL)) that the 6-caprolactone ring-opening polymerization is obtained to described aliphatic polyester.
The 7th aspect of the present invention is that the resin combination that the described biodegradation rate in any aspect is controlled in the 1st to 6 aspect of the present invention with following characteristics is provided: described aliphatic polyester (A) is aliphatic polyester (A ') and the aliphatic polyester (mixture of A ").
The 8th aspect of the present invention is, the resin combination that provides the described biodegradation rate in the 7th aspect of the present invention with following characteristics to be controlled: (A ") sum is 100 weight parts, and aliphatic polyester (A ') accounts for 90～30 weight parts in aliphatic polyester (A ') and aliphatic polyester.
The 9th aspect of the present invention is, the resin combination that provides the described biodegradation rate in the 7th aspect of the present invention with following characteristics to be controlled: in aliphatic polyester (A (BG-S)), aliphatic polyester (A (BG-S/A)) and caprolactone based polymer (A (CL)) sum is 100 weight parts, aliphatic polyester (A (BG-S)) accounts for 90～30 weight parts, (A (BG-S/A)) accounts for 5～65 weight parts, and caprolactone system (A (CL)) accounts for 5～65 weight parts.
The 10th aspect of the present invention is, the resin combination that the described biodegradation rate in any aspect is controlled in the 1st to the 9th aspect of the present invention with following characteristics is provided, promptly, its biodegradation rate is controlled in following level: in according to the test of the biological degradability after the cultivation in urban sewage mud of JIS K6950 regulation, decomposed in 28 days more than 60%.
The 11st aspect of the present invention is, the resin combination that the described biodegradation rate in any aspect is controlled in the 1st to the 10th aspect of the present invention with following characteristics is provided, promptly, its biodegradation rate is controlled in following level: in according to the test of the biological degradability after the cultivation in urban sewage mud of JIS K6950 regulation, in 28 days, decompose more than 60%, and, when being configured as the book film, film is die-cut into No. 2 dumbbell shaped sheet materials of JISK7113, imbed gardening with in the soil, under the condition of 28 ℃ * 99%RH, bury 60 hours underground, bury underground before and bury underground after tension test, before burying underground, the extensibility of TD direction, buries the back underground more than 200% more than 300%.
The 12nd aspect of the present invention is, the biodegradable film that provides a kind of biodegradation rate to be controlled, it is characterized in that the biodegradable resin combination that it is controlled by the biodegradation rate with any aspect record in the present invention the 1st to the 11st aspect carries out film blow molding, T shape mould extrusion molding or calendaring molding and obtains.
The 13rd aspect of the present invention is that the biodegradable Farm mulch that provides a kind of biodegradation rate to be controlled is characterized in that, the biodegradable film that the biodegradation rate that it uses the present invention the 12nd aspect to put down in writing is controlled.
The best mode that carries out an invention
Below the present invention is elaborated.
To the polyester (A) that uses among the present invention, there is no particular limitation, but be preferably, and its melting point has thermoplasticity more than 60 ℃.
As aliphatic polyester (A), can list aliphatic polyester (A ') and have the aliphatic polyester of the structure that obtains by lactone ring opening polymerization or with the polycondensation of the corresponding hydroxycarboxylic acid of described lactone that (A ") does not comprise polymer in poly lactic acid series described later (B) with structure that the polycondensation by aliphatic dicarboxylic acid and aliphatic diol obtains.
As aliphatic polyester (A '), can list from succsinic acid and 1,4-succinyl and the vibrin (A (BG-S)) that obtains, from succsinic acid, hexanodioic acid and 1,4-butyleneglycol and the vibrin (A (BG-S/A)) that obtains, from succsinic acid and glycol and the vibrin (A (EG-S)) that obtains, from oxalic acid and neopentyl glycol and the vibrin (A (NPG-O)) that obtains, from oxalic acid and 1,4-butyleneglycol and the vibrin (A (BG-O)) that obtains are from oxalic acid and glycol and vibrin (A (EG-O)) that obtains etc.Preferably have by 1 the aliphatic polyester (A (BG-S)) of the polycondensation of 4-butyleneglycol and succsinic acid and the structure that obtains and by 1, the polycondensation of 4-butyleneglycol and succsinic acid, hexanodioic acid and the aliphatic polyester (A (BG-S/A)) of the structure that obtains.Their independent uses are also passable, mix to use also can.
(A ") can enumerate the lactone polymer that obtains by interior polyisocyanate polyaddition as aliphatic polyester.As described lactone, its representational example has 6-caprolactone, δ-caprolactone; 4-methyl caprolactone, 3,5,5-trimethylammonium caprolactone, 3,3, various methylated caprolactones such as 5-trimethylammonium caprolactone; Beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, δ-Wu Neizhi, β-valerolactone, Beta-methyl-δ-Wu Neizhi, lactone ring opening polymerization such as oenantholacton and the material that obtains, the hydroxycarboxylic acid beyond material that obtains with the polycondensation of the corresponding hydroxycarboxylic acid of above-mentioned lactone and the lactic acid, oxyacetic acid for example, hydroxy new pentane acid, hydroxycaproic acid etc. or their cyclic ester, and the cyclic dimer ester of glycollide and so on for example.The material that can be to use these two or more raw materials, obtain by ring-opening polymerization or polycondensation.(A "), the caprolactone based polymer (A (CL)) that the 6-caprolactone ring-opening polymerization is obtained can obtain using satisfactorily as aliphatic polyester.In addition, as caprolactone based polymer (A (CL)), except the independent ring-opening polymerization polymer of caprolactone, also comprise the caprolactone monomer unit that contains 80 weight % above (preferably more than the 90 weight %), all the other are the unitary multipolymers of other internal ester monomers.
The preferable weight-average molecular weight of these aliphatic polyesters (A),, it is desirable to more than 120,000, below 200,000 below 250,000 usually more than 100,000 more than 40,000.
In the present invention, can with above-mentioned vibrin (A ') more than 2 kinds, (A ") more than 2 kinds or (A ') and (A ") each more than one mix and use.
Use that the example of above-mentioned vibrin (A ') is the mixture of above-mentioned aliphatic polyester (A (BG-S)) and aliphatic polyester (A (BG-S/A)) more than 2 kinds, their ratio is, 100 weight parts with respect to both sums, aliphatic polyester (A (BG-S)) is for surpassing 0 weight part, 100 weight parts less than, ideal is 90～30 weight parts, and special ideal is 70～50 weight parts.
In addition, with vibrin (A ') and (example that A ") mix to use is, with respect to 100 weight parts of both sums, vibrin (A ') be less than 100 weight parts to above 0 weight part, ideal is 90～30 weight parts.
As above-mentioned (A ') and (each a kind example that mixes use of A "); can enumerate the mixture of aliphatic polyester (A (BG-S)) and caprolactone based polymer (A (CL)); its ratio of mixture is; with respect to 100 weight parts of both sums; aliphatic polyester (A (BG-S)) is less than 100 weight parts to surpassing 0 weight part; ideal is 90～30 weight parts, and better is 70～50 weight parts.As other examples, can enumerate the mixture of aliphatic polyester (A (BG-S/A)) and caprolactone based polymer (A (CL)), their ratio of mixture is identical with the mixture of aliphatic polyester (A (BG-S)) and caprolactone based polymer (A (CL)).
As above-mentioned (A ') 2 kinds and (a kind of example that mixes use of A "); can enumerate the mixture of aliphatic polyester (A (BG-S)) and aliphatic polyester (A (BG-S/A)) and caprolactone based polymer (A (CL)); their ratio of mixture is; with respect to 100 weight parts of three's sum; aliphatic polyester (A (BG-S)) is 90～30 weight parts; (A (BG-S/A)) is 5～65 weight parts, caprolactone based polymer (A (CL)) is 5～65 weight parts.Ideal is that aliphatic polyester (A (BG-S)) is 70～30 weight parts, and (A (BG-S/A)) is 10～60 weight parts, and caprolactone based polymer (A (CL)) is 10～60 weight parts.
In addition, as the aliphatic polyester resin (A) that uses in the present invention, can use with the chain extension agent reaction of a small amount of diisocyanate cpd, bicyclic oxygen compound and so on, molecular chain in contain the aliphatic polyester resin of amino-formate bond, bicyclic oxygen compound residue.The aliphatic polyester resin that contains amino-formate bond is preferably to have carried out the above-mentioned aliphatic polyester resin that polymer quantizes with the aliphatic diisocyanate compound.
As the aliphatic diisocyanate compound, can list hexamethylene diisocyanate, lysinediisocyanate methyl esters { OCN-(CH
2)
4-CH (CH (NCO) (COOCH
3), trimethylammonium hexamethylene diisocyanate etc., wherein, hexamethylene diisocyanate is more satisfactory.The preferable weight-average molecular weight of aliphatic polyester resin that contains amino-formate bond is more than 40,000, and more than 100,000 below 250,000, more satisfactory is more than 120,000, below 200,000 usually.
The polymer in poly lactic acid series that uses in the present invention (B) is with L-, D-and the DL-lactic acid units polymkeric substance as main component.As polymer in poly lactic acid series (B), can be the multipolymer of independent polymkeric substance, L-and the D-lactic acid of L-or D-lactic acid, also can be to contain a small amount of unitary multipolymer of other hydroxycarboxylic acids as copolymer composition.As other hydroxycarboxylic acids of copolymer composition, can enumerate oxyacetic acid, hydroxycaproic acid etc.The copolymerization ratio of lactic acid and described other hydroxycarboxylic acids is 100: 0 moles～80: 20 moles.
In addition, these independent polymkeric substance and multipolymer are identical with above-mentioned aliphatic polyester resin, and it is also passable to contain a spot of chain extension agent residue.
As the polymerization process of polymer in poly lactic acid series (B), can use the polycondensation method, known method such as ring-opening polymerization method.For example, legal with polycondensation, with the polymerization of dewatering of L-lactic acid or D-lactic acid or their mixture, can access the poly(lactic acid) of any composition.In addition, in ring-opening polymerization method (rac-Lactide method), can when using polymerization to adjust agent, use selected catalyzer as required, by obtaining polymer in poly lactic acid series (B) for the rac-Lactide of lactic acid cyclic dimer.The ideal range of the weight-average molecular weight of the polymer in poly lactic acid series that uses among the present invention (B) is 60,000～700,000, and better is 80,000～400,000, and special ideal is 100,000～300,000.Molecular weight is too little, almost just loses practical rerum naturas such as its mechanical characteristics, thermotolerance, and molecular weight is too big, and then melt viscosity will be excessive, and shaping processability is poor.
The blending ratio of aliphatic polyester resin (A) and polymer in poly lactic acid series (B) is added required biodegradation rate according to the molecular weight of each resin and melt flow characteristics and is decided, with respect to (A) and (B) 100 weight parts of sum, (B) be necessary for that 1 weight part is above, 20 weight parts less than, ideal is 2～15 weight parts, and special ideal is the scope of 5～10 weight parts.In this case, if (B) be discontented with 1 weight part, the effect that delays biodegradation rate just can not occur.And if more than 20 weight parts, as the rerum natura of Farm mulch, particularly flexibility is just not enough.
As required, can add other biodegradable resins in the controlled biological degradability Farm mulch of biodegradation rate of the present invention.
As other biodegradable resins, can use synthetic and/or natural polymer.
As synthetic macromolecule, can enumerate polymeric amide, polyesteramide, Biodegradable cellulose ester, polypeptide, polyvinyl alcohol, their mixture in addition.
As Biodegradable cellulose ester, can enumerate organic acid acetic such as cellulose acetate, cellulose butylate, cellulose propionate; Nitrocellulose, sulfate cellulose, inorganic acid esters such as phosphorylated cotton; Cellulose acetate butyrate, cellulose acetate phthalate, mixed esters such as nitric acid cellulose acetate.These cellulose ester can use in independent or two or more mixing.Organic acid acetic in them, particularly acetic ester is more satisfactory.
In addition, as polypeptide, can enumerate polyamino acid such as gathering methyl paddy ammonia and polymeric amide etc.
As polyesteramide, can enumerate by 6-caprolactone and ε-Ji Neixianan synthetic resin etc.
As synthetic macromolecule, can use the weight-average molecular weight that records (being converted into polystyrene standard) with GPC more than 40,000, more than 100,000 below 250,000, gratifying is the material below 2000,000 more than 120,000 usually.
As natural polymer, can enumerate starch, Mierocrystalline cellulose, paper, paper pulp, cotton, fiber crops, hair, thin,tough silk, leather, carrageenin, chitin, chitosan, natural straight chain shape polyester based resin, perhaps their mixture.
As above-mentioned starch, can enumerate birth starch, starch producing and their mixture.
Give birth to starch and can list W-Gum, yam starch, sweet potato starch, wheat starch, tapioca (flour), sago starch, edible tapioca (flour), rice starch, beans starch, amylum marantae, fern starch, lotus starch, water chestnut starch.Starch producing can list the starch (Alpha-starch, classification amylose starch, wet heat treatment starch etc.) of physically modified, enzymically modified starch (hydrolysis dextrin, enzyme decomposes dextrin, amylose starch etc.), decomposition treated starch (acid treated starches, hypochlorous acid acidifying starch, dialdehyde starch etc.), chemically modified starch derivative (esterification starch, etherification starch, cationic starch, cross-linking starch etc.).
In the above-mentioned starch, esterification starch can list the acetic acid esterification starch, succinic acid esterification starch, nitric acid esterification starch, organic phosphate starch, urea organic phosphate starch, xanthogenic acid esterification starch, etheric acid esterification starch etc.; Etherification starch can list the allyl etherification starch, methyl-etherified starch, carboxymethylation ether, hydroxyethyl etherificate starch, hydroxypropyl etherificate starch etc.; Cationic starch can list the reactant of starch and 2-diethyl monochloroethane, starch and 2, the reactant of 3-epoxypropyl trimethylammonium chloride ammonium etc.; Cross-linking starch can list formaldehyde crosslinking starch, epichlorohydrin cross-linked starch, phosphoric acid crosslinked starch, propenal cross-linking starch etc.
As required, in the biodegradable resin combination that biodegradation rate of the present invention is controlled, can add resin additive.
As resin additive, can list softening agent, thermo-stabilizer, lubricant, adhesion prevents agent, nucleator, photolysis agent, biodegradation promotor, antioxidant, light (ultraviolet ray) stablizer, antistatic agent, fire retardant, levelling agent, sterilant, deodorizer, filling agent, tinting material, perhaps their mixture.
As softening agent, can list fatty group dibasic acid, phthalic ester, the hydroxyl polycarboxylic acid, polyester is a softening agent, fatty acid ester, epoxy resin softening agent, and their mixture.Specifically, have edicarboxylic acid two (2-ethylhexyl) (DOP), phthalic acid dibutyl phthalate (DBP), phthalic acid two isodecyl ester phthalic acid esters such as (DIDP), hexanodioic acid two (2-ethylhexyl), diisodecyl adipate adipic acid esters such as (DIDA), nonane diacid two (2-ethylhexyl) hydroxyl polycarboxylic acid's esters such as azelate, acetyl tributyl citrate three (2-ethylhexyl), tributyl acetylcitrate such as (DOZ), polyester such as polypropylene glycol adipic acid ester are softening agent, they can use separately, also can mix use more than two kinds.
According to different purposes, the addition of these softening agent is different, and in general, with respect to 100 weight parts of aliphatic polyester (A) and polymer in poly lactic acid series (B) sum, softening agent is 3～30 weight parts, and more satisfactory is 5～15 weight parts.If discontented 3 weight parts, then elongation at break and shock strength reduce, and if above 30 weight parts, then have the situation that breaking tenacity and shock strength reduce.
Thermo-stabilizer as using among the present invention has the aliphatic carboxylate.In the aliphatic carboxylic acid, particularly the aliphatic hydroxyl carboxylic acid is desirable.As the aliphatic hydroxyl carboxylic acid, the material that occurring in natures such as lactic acid, hydroxyl butyric acid exist is for well.
The example of salt has the salt of sodium, calcium, aluminium, barium, magnesium, manganese, iron, zinc, lead, silver, copper etc.They can use separately, also can mix use more than two kinds.
With respect to 100 weight parts of aliphatic polyester (A) and polymer in poly lactic acid series (B) sum, addition is in the scope of 0.5～10 weight part.In above-mentioned scope, use thermo-stabilizer, the effect that has the difference of shock strength (Ai Zuoshi impact value) enhancing, elongation at break, breaking tenacity, shock strength to reduce.
As the lubricant that uses among the present invention, can generally be used as the material of internal lubricant, exterior lubricant, for example, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, hydroxy fatty acid, fatty acid amide, alkane difatty acid acid amides, aliphatic ketone, lipid acid low-carbon-ester, polyol esters of fatty acids, fatty acid polyglycol ester, fatty alcohol, polyvalent alcohol, polyoxyethylene glycol, polyglycerol, metallic soap, modified siloxane or their mixture.Preferred fat acid esters, hydrocarbon resin etc.
When selecting lubricant, need select the lubricant of melting point under it according to the melting point of lactone resin and other biological degradation property resin.For example, consider the melting point of aliphatic polyester resin,, will select the fatty acid amide below 160 ℃ as fatty acid amide.
With respect to 100 weight parts of aliphatic polyester (A) and polymer in poly lactic acid series (B) sum, the addition of lubricant is 0.05～5 weight part.If discontented 0.05 weight part, effect are just not enough, and if surpass 5 weight parts, then can not twisting cohesion to cylinder, rerum natura also descends to some extent.
As lubricant, from antipollution viewpoint, with safe and be good at second distearyl acid acid amides, stearic amide, amine hydroxybenzene, the erucicamide of FDA (FDA (Food and Drug Adminstration)) registration.
Above-mentioned photolysis agent can list for example bitter almond oil camphor class, benzoin alkylether class, benzophenone, 4, benzophenone and its derivatives such as 4-two (dimethylamino) benzophenone, phenyl methyl ketone, α, the phenyl methyl ketone and the derivative thereof of α-diethoxy phenyl methyl ketone etc., quinones, the thioxanthene ketone, phthalocyanines etc. close excitation material; The sensitizing agent of anatase-type titanium oxide, the plain multipolymer of ethene-carbon monoxide, aromatic ketone and metal-salt etc.These photolysis agents can use separately, also can share more than 2 kinds.
Above-mentioned biodegradation promotor comprises that for example alcohol acid (for example, carbonatomss such as oxyacetic acid, lactic acid, citric acid, tartrate, oxysuccinic acid are the alcohol acid about 2～6), organic acid such as saturated dicarboxylic acid (for example, carbonatomss such as oxalic acid, propanedioic acid, succsinic acid, succinyl oxide, pentanedioic acid are rudimentary saturated dicarboxylic acid about 1～4 etc.); These organic acids and carbonatoms are the lower alkyl esters of the alcohol about 1～4.Biodegradation promotor comprises that carbonatomss such as citric acid, tartrate, oxysuccinic acid are organic acid about 2～6 and Exocarpium cocois (Cocos nucifera L) activated carbon etc. preferably.These biodegradation promotor can be used separately, also can use simultaneously more than 2 kinds.
As above-mentioned light (ultraviolet ray) stablizer, preferable example has that poly-({ 6-(1,1,3, the 3-tetramethyl butyl) imino--1,3,5-triazine-2,4-two bases } { (2,2,6, the 6-tetramethyl-4-piperidyl) imino-} hexa-methylene { 2,2,6, the 6-tetramethyl-4-piperidyl) imino-}), it is poly-that ({ 6-(1,1, the 3-tri-methyl-amyl) imino--1,3,5-triazines-2,4-two bases } { (N-methyl-2,2,6, the 6-tetramethyl-4-piperidyl) imino-} eight methylene radical { (N-methyl-2,2,6, the 6-tetramethyl-4-piperidyl) imino-}), 2,2,6,6-tetramethyl-piperidyl-4 benzoic acid ester, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, 1,3,8-three azepines, 7,7,9,9-tetramethyl--3-n-octyl spiral shell (4,5) decane-2, the 4-diketone, 1,2,2,4-four (4-ketonic oxygen base-2,2,6, the 6-tetramethyl piperidine)-hindered amines such as amine are photostabilizer (HALS), 2-(2H-benzotriazole-2-yl)-p-cresol, 2-(2H-benzotriazole-2-yl)-4,6-two (1-methyl isophthalic acid-styroyl) phenol, 2 benzotriazole-2-base-4, the 6-DI-tert-butylphenol compounds, 2-(5-chlorine (2H)-benzotriazole-2-yl)-benzotriazoles such as 4-methyl-6-tert butyl phenol are UV light absorber, three azines are UV light absorber, the benzophenone series UV light absorber, benzoic ether is a UV light absorber.With respect to 100 weight parts of aliphatic polyester (A) and polymer in poly lactic acid series (B) sum, the incorporation of these stablizers is 0.01～1.0 weight part, preferably in the scope of 0.05～0.5 weight part.
As filling agent (comprising extender), can list various filling agents, for example, the organic additives such as particle (also claiming organic filling agent) of inorganic additives (also claiming inorganic filling agent) such as lime carbonate, mica, Calucium Silicate powder, talcum powder, SiO 2 powder (anhydride), white carbon (hydrate), asbestos, potter's clay (burning till), medical stone, various titanium oxide, glass fibre and natural material.
Because by adding filling agent, can further improve biological degradability, melt strength (viscosity) becomes big simultaneously, so the drawing-off can prevent melt-shaping the time improves the plasticity of vacuum forming, inflation shaping, blow molding etc.
The addition of filling agent is, the weight ratio of filling agent/[aliphatic polyester (A) and polymer in poly lactic acid series (B) sum] is 5～50/95～50, is 10～45/90～55 preferably, better is 20～40/80～60, and good especially is 25～35/75～65.
If the amount of filling agent is excessive, then resin can blow powder, and if too small, have tangible drawing-off, constriction, in uneven thickness, bonding generation when then being shaped.
As the SiO 2 powder of inorganic additives, can be with the silicon-dioxide of damp process manufacturing or the silicon-dioxide that makes by the pyrohydrolysis of silicon tetrachloride in oxyhydrogen flame, but particle diameter will be below 50nm.
The example of organic additive have diameter below 50 μ m by micro mist particle made of paper.The addition of organic additive is identical with inorganic additives.
The example of extender has wood powder, glass balloon etc.The addition of extender is identical with inorganic addition.
The example of tinting material has various known inorganic and organic colorants such as carbon black etc.
In addition, in the scope that does not influence effect of the present invention, it is also passable to add above-mentioned other biological degradation property resin, in addition, rerum natura with adjustment shaping processability, other book films and sheet material is a purpose, also can add softening agent, fluidity amendment, lubricant, strengthening agent, can also add inorganic is heat preserving agent, fluorescent agent etc.
Biodegradable resin constituent provided by the invention, the rate of decomposition after cultivating in the urban sewage standard mud of JIS K6950 regulation surpasses 60%, surpasses 80% preferably.In addition, biological degradability book film provided by the invention can replace existing polyethylene and other polyenes.
The biological degradability evaluation method of sample has use according to the method for the active sludge of JIS K6950, by being embedded in the soil, soaking in seawater or in the rivers and creeks, being embedded in and various methodologies such as estimating in the compost, but in following examples, there is the JIS K6950 of correlationship to carry out according to the decomposability that is considered to in general field.
In the present invention, described " biodegradation rate is controlled " is meant " biological degradability and shape disintegration rate are controlled ", " originally keep finely during use; after discarded; according to above-mentioned biological degradability test; be decomposed more than 60% in 28 days as the necessary rerum natura of goods (tensile strength for example; tension extensibility; mechanical properties such as tension spring rate), preferably, be decomposed more than 80%, and under the situation that is configured as the book film, put into gardening with soil according to the book film that JIS K7113 is die-cut into No. 2 dumbbell plates, under the condition of 28 ℃ * 99%RH, bury 60 hours underground, before burying underground and the tension test after burying underground.The extensibility of TD direction is more than 300% before burying underground, is preferably more than 400%, is more preferably more than 500%, buries the back underground more than 200%, is preferably more than 300%, is more preferably more than 400% ".
As aliphatic polyester resin, lactone is the method for mixing of resin, polylactic acid based resin and other additives etc., general method can access reasonable use, specifically, material resin particle and powder, solid shred etc. can be carried out by Henschel stirrer, ribbon blender that single shaft is mixed, offered to dry type, 2 known melting mixing machines such as forcing machine, Banbury mixer, kneading machine, mixing roll carry out fusion and mix.
After fusion was mixed, directly, perhaps being preferably and making the postforming of pill shape was the biological degradability mulch film.As manufacturing process, there is no particular limitation, can use existing method.Can list blow-moulding process, T shape mould extrusion molding method, calendaring molding method etc. particularly, be blow-moulding process, T shape mould extrusion molding method preferably.
The possibility of utilizing on the industry
The thermoplastic resin composition that uses biodegradation rate of the present invention to be controlled can obtain the shaping thing that biodegradation rate is controlled, particularly biological degradability mulch film, the biological degradability Farm mulch of more specifically saying so, and practical value is big.
Embodiment
＜embodiment 1-6, comparative example 1-3 〉
Below, by embodiment the present invention is carried out specific description, but the present invention is not limited to this.
Following represented be the ellipsis that uses in the raw material that uses among the embodiment and the following table 1.
The aliphatic polyester (A) of #1001:Bionolle#1001[aliphatic dicarboxylic acid-aliphatic diol system, Showa Highpolymer Co., Ltd's product].
The aliphatic polyester (A (BG-S/A)) of #3001:Bionolle#3001[aliphatic dicarboxylic acid-aliphatic diol system, Showa Highpolymer Co., Ltd produces].
PH7: セ Le グ リ one Application PH7[caprolactone based polymer (A (CL)), DAICEL chemical industry Co., Ltd. produces]
ラ Network テ ィ one 9400:[polymer in poly lactic acid series (B), Shimadzu Corporation produces] (mixture)
To under following extrusion condition, carry out by the blended resin of prescription shown in the table 1 with two forcing machines the blended resin compound, granulation.Used resin raw material is in advance through super-dry (50 ℃ * more than 10 hours).In addition, when mixing respectively, use the level land tumbler.
＜extrusion condition 〉
C1 (under the magazine): 100 ℃, C2:180 ℃, C3:200 ℃, C4:200 ℃, C5:200 ℃, C6:210 ℃, C7:210 ℃, AD (pressing mold front): 210 ℃, D (pressing mold): 200 ℃.
1～7 the numbering of C is to begin to increase to the pressing mold direction under the magazine of C1.The numbering of book membranization operation too.
The resin that magazine is supplied with by from C1 (under the magazine) after D (pressing mold) extrudes, cut with dicing machine.
(film forming)
Use obtains the book film by the grain sheet that aforesaid method obtains with following film blowing molding condition.
＜film blowing molding condition 〉
C1 (under the magazine): 100 ℃, C2:150 ℃, C3:160 ℃, C4:160 ℃, C5:160 ℃, C6:160 ℃, AD (pressing mold front): 160 ℃, 1:200 ℃ of D (pressing mold), 2:150 ℃ of D (pressing mold).
The grain sheet that magazine is supplied with is extruded to D (pressing mold) from C1 (under the magazine), locates upwards to be extruded at D (pressing mold), expand into cylindricly by air pressure, becomes the book film.
The book film pulls speed: 17.0～22.0m/min
Flanging is wide: 2.0mm
The book film is wide: 1350mm
Book film thickness: 20 μ m
Use the resin particle sheet and the book film shaping thing that obtain like this, carry out various evaluation shown below, its result is illustrated in the table 2.
(split hand)
To engrave cut channel on the widely used polyethylene book film (blow molding) as general book film now, be felt as benchmark (10 are divided into full marks) with it with what hand was torn, the sensation when the book film that obtains is above torn with hand is estimated with 10 fens full marks.
At this moment judging criterion is, passes to the waveform of on hand resistance, cracking mode (having or not rectilinearity), cracking face etc. when tearing with hand, except simple intensity, tearing property carried out comprehensive sensory evaluation.
The sensory evaluation benchmark is as follows.
◎: the cracking face becomes waveform, oblique segmentation in addition, and tearing resistance is big.
Zero: the cracking face is in line, and a little waveform is also arranged, but tearing resistance is big.
*: the cracking face is in line, and tearing resistance is little.
* *: ratio * tearing resistance is little, easily spreads in the crack.(tear strength)
Sample: each book film cut growth (MD direction) 100mm, the wide 25mm that will be obtained by aforesaid method at an end of width, from the centre, engrave the cut channel of 30mm, along its length as sample.
Sample is placed in the thermostatic constant wet chamber of 23 ℃ * 50%RH, carries out damping in 24 hours and handle, use for measuring.
＜tear strength condition determination 〉
Sample length (distances between anchor clamps): 30mm
Use machine: OLIENTEC company product, trade(brand)name RTA-500
Load cell: 5kgf, 20%
Pinblock speed: 500mm/ branch
Test number (TN): n=3 time, the result represents with its mean value.
The metewand of sensory evaluation is as follows.
◎: tear strength is big, oblique segmentation, and the cracking face has fluctuating.
Zero: tear strength is big, the cracking face linearly, the cracking face has fluctuating.
*: tear strength is little, and the cracking face is in line.
* *: tear strength is very little, and the cracking face is in line, and the fluctuating of cracking face does not almost have.
(tear test)
According to JIS K7113, will be cut into the dumbbell shaped sheet material No. 2 by each book film that aforesaid method obtains, carry out tension test.The book film is die-cut to carry out from MD, TD both direction.
Sample is placed in the thermostatic constant wet chamber of 23 ℃ * 50%RH, carries out damping in 24 hours and handle, use for measuring.Condition determination is as follows.
＜tension test condition determination 〉
Sample length (distances between anchor clamps): 80mm
Use machine: OLIENTEC company product, trade(brand)name RTA-500
Load cell: 10kgf, 40%
Pinblock speed: 500mm/ branch
Test number (TN): n=3 time, the result represents with its mean value.
(biological degradability)
According to simple and easy resolution test (JIS K6950) biodegrade evaluation of using active sludge.
Use Himeji city standard active sludge, measure the biological degradability (weight %) behind trial period on the 28th.The biological degradability numerical value that obtains by above-mentioned test the usefulness below 60% *, usefulness zero, the 80% usefulness ◎ more than 60% represents.
(shape disintegration rate)
According to JIS K7113, to be cut into No. 2 the dumbbell shaped sheet material by each film that aforesaid method obtains, put it into gardening soil (ェ Application セ Le company product, the soil (home gardening compost) of plantation flower and vegetables) in, under the condition of 28 ℃ * 99%RH, bury 60 hours underground, to before burying underground and the film after burying underground carry out above-mentioned tension test, the tension elongation at break degree of TD direction relatively.In addition, the film after above-mentioned the burying underground also claims the film after decomposition rate is estimated.
Table 1
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 1 | 2 | 3 | ||
| #1001 | Weight part | 95 | 90 | 85 | 70 | 70 | 50 | 80 | 50 | 50 |
| #3001 | Weight part | 20 | 20 | 30 | ||||||
| PH7 | Weight part | 20 | 20 | |||||||
| ラ ケ テ イ 1 | Weight part | 5 | 10 | 15 | 10 | 10 | 10 | 20 | 20 | 50 |
| The split hand sense | 10 stages were estimated sensory evaluation | 6 ○ | 6 ○ | 5 ○ | 8 ◎ | 8 ◎ | 8 ◎ | 3 × | 3 × | 1 × |
| Tear strength (MD direction) | G/20 μ m sensory evaluation | 110 ○ | 100 ○ | 90 ○ | 380 ◎ | 420 ◎ | 430 ◎ | 50 × | 60 × | 60 × |
| The tension experiment, (MD direction) tension breaking stress tension elongation at break degree, (TD direction) tension breaking stress tension elongation at break degree | kgf/cm 2 ％ kgf/cm 2The % sensory evaluation | 430 300 360 400 ○ | 450 280 350 320 ○ | 470 260 340 300 ○ | 380 360 310 690 ◎ | 390 350 310 670 ◎ | 360 400 320 800 ◎ | 480 180 420 120 × | 450 210 380 150 × | 710 10 560 15 × |
| Shaping processability | The sense organ valency of knowing clearly | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | × |
| The biodegradation rate biological degradability | The % sensory evaluation | 80 ◎ | 78 ○ | 68 ○ | 85 ◎ | 84 ◎ | 88 ◎ | 54 × | 62 × | 31 × |
| The shape disintegration rate | Sensory evaluation | 260 ○ | 220 ○ | 190 ○ | 510 ◎ | 490 ◎ | 520 ◎ | 50 × | 65 × | 15 ×× |
Though comparative example 3 is the systems of having added the polymer in poly lactic acid series (B) of 50 weight %, perhaps is the reason that contains the poly(lactic acid) of a large amount of shortage flexibilities, obtained in the result who all is not suitable for use in film aspect shaping processability, the film initial stage rerum natura.In addition, aspect biological degradability, also obtained the result that decomposition rate when polylactic acid polymer (B) addition is 50 weight % overflows, is not suitable for the purposes such as Farm mulch that the short period of time uses very much.
In addition, though comparative example 1 and 2 is the systems that the addition of polymer in poly lactic acid series reduced to 20 weight %, even but like this, aspect the elongation at break degree (the particularly elongation at break degree of TD direction) of MD direction, its film performance can not be satisfactory, extremely is not suitable for purposes such as mulch film.Though the tension elongation at break degree conservation rate height of the TD direction after decomposition rate is estimated is because the initial stage extensibility is not enough, so can not become practical film.
By comparison, embodiment 1 and 2 is that the addition of polymer in poly lactic acid series (B) is the system of 5 and 10 weight parts.Shaping processability is also no problem, and the elongation at break degree after film shaped (the particularly elongation at break degree of TD direction) improves greatly.It is about 300% that the raising of the elongation at break degree of TD direction surpasses, and practicality will show.The elongation at break degree of the TD direction after the decomposition rate evaluation of this sample also keeps finely.
Embodiment 4 and 5 and 6 has mixed the softish polyester as the polyester composition except that polymer in poly lactic acid series (B) (promptly, mixing use multiple aliphatic polyester (A) in specified range) system, thus, the tremendous rising of elongation at break degree of its TD direction, and, the also tremendous rising of tear strength.The gained film has reached the numerical value requirement of the practical rerum natura of Farm mulch etc. fully.In addition, the elongation at break degree of the TD direction after the decomposition rate evaluation also keeps finely.
According to the above, affirmation can provide the Biodegradable resin composition that biodegradation rate is controlled, the Biodegradable film (particularly biological degradability Farm mulch) that biological degradability speed was controlled and had practical rerum natura.
Claims (12)
1. biodegradable film that biodegradation rate is controlled, it carries out film blow molding, T shape mould extrusion molding or calendaring molding by the biodegradable resin combination that biodegradation rate is controlled and obtains, the biodegradable resin combination that described biodegradation rate is controlled is made up of aliphatic polyester (A) and polymer in poly lactic acid series (B), in both sums is 100 weight parts, the content of polymer in poly lactic acid series (B) more than 1 weight part, discontented 20 weight parts.
2. biodegradable film according to claim 1 is characterized in that, described aliphatic polyester (A) is the aliphatic polyester (A ') with structure that the polycondensation by dibasic alcohol and dicarboxylic acid obtains.
3. biodegradable film according to claim 2, it is characterized in that, described aliphatic polyester (A ') is to have by 1, the aliphatic polyester (A (BG-S)) of the polycondensation of 4-butyleneglycol and succsinic acid and the structure that obtains and/or have by 1, the polycondensation of 4-butyleneglycol and succsinic acid and hexanodioic acid and the aliphatic polyester (A (BG-S/A)) of the structure that obtains.
4. biodegradable film according to claim 3 is characterized in that, is 100 weight parts in aliphatic polyester (A (BG-S)) with aliphatic polyester (A (BG-S/A)) sum, and (A (BG-S) accounts for 90～30 weight parts to aliphatic polyester.
5. biodegradable film according to claim 1 is characterized in that, described aliphatic polyester (A) is the aliphatic polyester (A ") with the structure that obtains by lactone ring opening polymerization.
6. biodegradable film according to claim 5 is characterized in that, (A ") is the caprolactone based polymer (A (CL)) that the 6-caprolactone ring-opening polymerization is obtained to described aliphatic polyester.
7. according to each described biodegradable film among the claim 1-5, it is characterized in that described aliphatic polyester (A) is aliphatic polyester (A ') and the aliphatic polyester (mixture of A ").
8. biodegradable film according to claim 7 is characterized in that, (A ") sum is 100 weight parts, and aliphatic polyester (A ') accounts for 90～30 weight parts in aliphatic polyester (A ') and aliphatic polyester.
9. biodegradable film according to claim 7, it is characterized in that, in aliphatic polyester (A (BG-S)), aliphatic polyester (A (BG-S/A)) and caprolactone based polymer (A (CL)) sum is 100 weight parts, aliphatic polyester (A (BG-S)) accounts for 90～30 weight parts, (A (BG-S/A)) accounts for 5～65 weight parts, and caprolactone system (A (CL)) accounts for 5～65 weight parts.
10. biodegradable film according to claim 1, it is characterized in that, its biodegradation rate is controlled in following level: in according to the test of the biological degradability after the cultivation in urban sewage mud of JIS K6950 regulation, decomposed in 28 days more than 60%.
11. biodegradable film according to claim 1, it is characterized in that, its biodegradation rate is controlled in following level: in according to the test of the biological degradability after the cultivation in urban sewage mud of JIS K6950 regulation, in 28 days, decompose more than 60%, and, when being configured as the book film, film is die-cut into No. 2 dumbbell shaped sheet materials of JISK7113, imbed gardening with in the soil, under the condition of 28 ℃ * 99%RH, bury 60 hours underground, bury underground before and bury underground after tension test, the extensibility of TD direction bury underground before more than 300%, bury underground the back more than 200%.
12. the biodegradable Farm mulch that biodegradation rate is controlled is characterized in that, it uses each described biodegradable film among the claim 1-11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP153121/2001 | 2001-05-22 | ||
| JP153121/01 | 2001-05-22 | ||
| JP2001153121 | 2001-05-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1462296A CN1462296A (en) | 2003-12-17 |
| CN1246385C true CN1246385C (en) | 2006-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB028014766A Expired - Fee Related CN1246385C (en) | 2001-05-22 | 2002-05-21 | Biodegradable resin composition with controlled biodegradation rate film and agricutlural mulch film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4127648B2 (en) |
| KR (1) | KR20030011358A (en) |
| CN (1) | CN1246385C (en) |
| HK (1) | HK1060894A1 (en) |
| WO (1) | WO2002094935A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1525482A (en) * | 2003-02-25 | 2004-09-01 | 英保达股份有限公司 | Multimedia playing device with multiple functions integrated |
| US7718718B2 (en) * | 2003-03-28 | 2010-05-18 | Toray Industries, Inc. | Polylactic acid resin composition, process for producing the same, biaxially stretched polylactic acid film, and molded articles thereof |
| JP2005002165A (en) * | 2003-06-10 | 2005-01-06 | Daicel Chem Ind Ltd | Biodegradable resin composition, agricultural mulching film and method for inhibiting biodegradability |
| JP4493993B2 (en) * | 2003-11-28 | 2010-06-30 | ダイセル化学工業株式会社 | Biodegradable polyester resin composition, molded article and agricultural multi-film |
| JP2006096863A (en) * | 2004-09-29 | 2006-04-13 | Daicel Chem Ind Ltd | Film of aliphatic polyester resin composition and its application |
| WO2007073109A1 (en) * | 2005-12-23 | 2007-06-28 | Wan Pyo Hong | Biodegradable resin composition and plastic product made thereof |
| KR20070107427A (en) * | 2006-05-03 | 2007-11-07 | 위더스케미칼 주식회사 | Biodegradable heat-shinkable film and production method therof |
| KR100812824B1 (en) * | 2006-09-27 | 2008-03-12 | 주식회사 제닉 | Biocompatible low toxicity film using chitosan and polyethylene glycol |
| IES20080565A2 (en) * | 2007-07-11 | 2009-01-21 | Russell Walsh | Improvements relating to compostable bags |
| CN101967236A (en) * | 2010-11-04 | 2011-02-09 | 天津市东南恒生医用科技有限公司 | Phthalate plasticizer and application thereof in biodegradable material |
| JP5935565B2 (en) * | 2012-07-23 | 2016-06-15 | 三菱化学株式会社 | Resin composition and molded product formed by molding the resin composition |
| JP5978827B2 (en) * | 2012-07-23 | 2016-08-24 | 三菱化学株式会社 | Resin composition and molded product formed by molding the resin composition |
| WO2018182543A2 (en) * | 2017-03-29 | 2018-10-04 | Scg Packaging Public Company Limited | Soil covering material having structural layers |
| DE202017107116U1 (en) * | 2017-04-05 | 2018-01-11 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable film |
| CN110105731A (en) * | 2019-05-08 | 2019-08-09 | 九江智达环能科技有限公司 | A kind of polymer material capable of being fast degraded and preparation method thereof |
| CN118139926A (en) * | 2021-10-22 | 2024-06-04 | 株式会社可乐丽 | Resin composition |
| WO2023229209A1 (en) | 2022-05-21 | 2023-11-30 | 에코밴스 주식회사 | Biodegradable molded product and biodegradable polyester resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3415017B2 (en) * | 1997-12-15 | 2003-06-09 | ワイケイケイ株式会社 | Biodegradable resin fastener molded product |
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- 2002-05-21 WO PCT/JP2002/004908 patent/WO2002094935A1/en active Application Filing
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| Publication number | Publication date |
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| CN1462296A (en) | 2003-12-17 |
| KR20030011358A (en) | 2003-02-07 |
| JPWO2002094935A1 (en) | 2004-09-09 |
| WO2002094935A1 (en) | 2002-11-28 |
| JP4127648B2 (en) | 2008-07-30 |
| HK1060894A1 (en) | 2004-08-27 |
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