CN104540895A - Aliphatic polyester resin composition and biodegradable film - Google Patents
Aliphatic polyester resin composition and biodegradable film Download PDFInfo
- Publication number
- CN104540895A CN104540895A CN201380042662.9A CN201380042662A CN104540895A CN 104540895 A CN104540895 A CN 104540895A CN 201380042662 A CN201380042662 A CN 201380042662A CN 104540895 A CN104540895 A CN 104540895A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- aliphatic polyester
- acid
- aliphatic
- resin composition
- 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.)
- Pending
Links
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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
-
- 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
- C08J2367/02—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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Provided is an aliphatic polyester resin composition which can be degraded to such an extent that a cultivation operation is not affected substantially before the start of the cultivation of following crops. The composition comprises an aliphatic polyester resin (A) and an aliphatic aromatic polyester resin (B) at a content ratio, (A):(B), of 1:1 to 4:1 (by weight), wherein the aliphatic polyester resin (A) comprises an aliphatic polyester resin (a1) that contains an adipic acid unit as a dicarboxylic acid unit and an aliphatic polyester resin (a2) that does not contain an adipic acid unit as a dicarboxylic acid unit at a content ratio, i.e., (a1):(a2), of 1:9 to 9:1 (by weight).
Description
Technical field
The aliphatic polyester resin composition that the present invention relates to biological degradability excellence and the biological degradability film employing this aliphatic polyester resin composition.
Background technology
As one of means solving recent waste problem etc., carrying out the research employing the material with biological degradability gradually in a large number.As the typical example of Biodegradable material, the aromatic-aliphatic copolymer polyester resin that the such aliphatic polyester resin of poly(lactic acid), poly butylene succinate, succinic acid-butanediol ester-tetramethylene adipate multipolymer, tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester's multipolymer are such can be enumerated, carried out various research.
But, when biological degradability film being formed film with inflation forming machine, not yet intensity can be had with practical level manufacture and the film of flexibility excellence.Up to now, carry out following research: by the low melting point polymer with biological degradability, mix the higher resin of fusing point such as polylactic acid resin, thus give flexibility and intensity, the described low melting point polymer with biological degradability is such as: with polyfunctional isocyanate to the aliphatic-aromatic polyester resin being carried out high molecular by the dicarboxylic acid component comprising hexanodioic acid and terephthalic acid and the aliphatic-aromatic polyester of diol component condensation that comprises BDO and obtain; By the aliphatic polyester resin of succsinic acid, BDO and the polycondensation of lactic acid Direct Dehydration; Or by 1, the polycondensation of the dicarboxylic acid of the polyvalent alcohol such as 4-butyleneglycol and succsinic acid, hexanodioic acid and so on and the aliphatic polyester resin obtained.But, even if mix poly(lactic acid) in the composition, still there is no expected such effect because lacking consistency yet.
Among above-mentioned, as by improving the consistency of biodegradable composition thus the biological degradability film making physical strength improve when not damaging flexibility, propose the film utilizing inflation processing machine following resin membranization to be obtained, described resin is: with polyfunctional isocyanate to the aliphatic-aromatic polyester resin being carried out high molecular by the dicarboxylic acid component comprising hexanodioic acid and terephthalic acid and the aliphatic-aromatic polyester of diol component condensation that comprises BDO and obtain; And, by the aliphatic polyester resin of succsinic acid, BDO and the polycondensation of lactic acid Direct Dehydration; Also and, there is the aromatic polyester resins (patent documentation 1) of biological degradability.
In addition, when biological degradability film being applied to the purposes such as agricultural use, until raise crop grows into a certain degree, in order to ground temperature being remained specified temperature and preventing weed growth, need film to have enough intensity not break to keep film, on the other hand, terminate at crop harvesting, when lower first phase arable farming starts, need before this time interim use film be degraded to a certain degree in soil.But such having can stand the intensity that uses as film for agricultural use and have the film that biodegradable characteristic occurs during suitable concurrently not yet to reach practical.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-227882 publication
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of aliphatic polyester resin composition and biological degradability film, its from the sowing, field planting of raise crop until during plant growth to a certain extent, there is the heat insulation function of ground temperature and have to prevent weed growth and required sufficient intensity, further, there is the biodegradation character that can be degraded to the degree in fact not hindering farming operation before the cultivation of the harvest home of raise crop, lower first phase crop starts.
For solving the means of problem
Present inventor conducts in-depth research, found that, following aliphatic polyester resin composition and the biological degradability film employing this aliphatic polyester resin composition can solve above-mentioned problem, thus complete the present invention, described aliphatic polyester resin composition comprises aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B) with specific ratio, described aliphatic polyester resin (A) contains: comprise the aliphatic polyester resin of hexanodioic acid unit as dicarboxylic acid units, do not comprise the aliphatic polyester resin of hexanodioic acid unit as dicarboxylic acid units.
That is, main idea of the present invention is as follows.
(1) a kind of aliphatic polyester resin composition, it comprises aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B), both compounding ratios are (A): (B)=1:1 ~ 4:1 (weight ratio)
Described aliphatic polyester resin (A) is containing following aliphatic polyester resin (a1) and following aliphatic polyester resin (a2), described aliphatic polyester resin (a1) comprises hexanodioic acid unit as dicarboxylic acid units, described aliphatic polyester resin (a2) does not comprise hexanodioic acid unit as dicarboxylic acid units, and the compounding ratio of described aliphatic polyester resin (a1) and aliphatic polyester resin (a2) is (a1): (a2)=1:9 ~ 9:1 (weight ratio).
(2) aliphatic polyester resin composition as described in (1), wherein, for the total weight part (100 weight part) of described aliphatic polyester resin (A) and described aliphatic-aromatic polyester resin (B), described aliphatic polyester resin composition contains the lactic acid polymer ester resin (C) of 3 ~ 20 weight parts.
(3) aliphatic polyester resin composition as described in (1) or (2), wherein, for the aliphatic polyester resin composition of 100 weight parts, described aliphatic polyester resin composition comprises the inorganic filling material of 0.05 ~ 1.0 weight part.
(4) a kind of biological degradability film, it is characterized in that, aliphatic polyester resin composition according to any one of (1) ~ (3) is formed, described biological degradability film was exposed to weathering tester after 100 hours, and the tension fracture elongation rate on the shaping direction (MD) of machinery maintains more than 40% relative to the tension fracture elongation rate before being exposed to weathering tester.
Invention effect
By the present invention, can provide a kind of biological degradability film, its formability, shock strength are excellent, and are exposed to weathering tester after 100 hours, and the tension fracture elongation rate on mechanical-moulded direction (MD) maintains the level of regulation.Therefore, a kind of biological degradability film can be provided by the present invention, its from the sowing, field planting of raise crop until during plant growth to a certain extent, there is the heat insulation function of ground temperature and have to prevent weed growth and required sufficient intensity, further, described film has the biological decomposition characteristic that can decompose the degree in fact not hindering farming operation before the cultivation of the harvest home of raise crop, lower first phase crop starts.
Embodiment
An embodiment of the invention are a kind of aliphatic polyester resin compositions, it comprises aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B), both compounding ratios are (A): (B)=1:1 ~ 4:1 (weight ratio), above-mentioned aliphatic polyester resin (A) is containing following aliphatic polyester resin (a1) and following aliphatic polyester resin (a2), described aliphatic polyester resin (a1) comprises hexanodioic acid unit as dicarboxylic acid units, described aliphatic polyester resin (a2) does not comprise hexanodioic acid unit as dicarboxylic acid units, the compounding ratio of described aliphatic polyester resin (a1) and aliphatic polyester resin (a2) is (a1): (a2)=1:9 ~ 9:1 (weight ratio).
aliphatic polyester resin (A)
Aliphatic polyester resin (A) contains: comprise hexanodioic acid unit as the aliphatic polyester resin (a1) of dicarboxylic acid units with do not comprise the aliphatic polyester resin (a2) of hexanodioic acid unit as dicarboxylic acid units.
In the present invention, the aliphatic polyester resin that aliphatic polyester resin (a1) and aliphatic polyester resin (a2) as the constituent of aliphatic polyester resin (A) they are preferably principal constituent with aliphatic diol unit and aliphatic dicarboxylic acid unit.Herein, " principal constituent " refers to, to form whole monomeric units of aliphatic polyester for benchmark (100 % by mole), aliphatic diol unit and aliphatic dicarboxylic acid unit are more than 70 % by mole, be preferably more than 80 % by mole, be more preferably more than 90 % by mole.
When specifically representing aliphatic polyester resin (a1) and aliphatic polyester resin (a2), it is such as comprising the resin of chain fatty race and/or ester ring type diol units that following formula (1) represents and the chain fatty race that following formula (2) represents and/or ester ring type dicarboxylic acid units.
－O－R
1－O－ (1)
(in formula (1), R
1represent the chain fatty race alkyl of divalent and/or the ester ring type alkyl of divalent.When carrying out copolymerization, in resin, two or more R can be comprised
1.)
－OC－R
2－CO－ (2)
(in formula (2), R
2represent the chain fatty race alkyl of divalent and/or the ester ring type alkyl of divalent.When carrying out copolymerization, in resin, two or more R can be comprised
2.)
It should be noted that, in above-mentioned formula (1), formula (2), " the chain fatty race alkyl of divalent and/or the ester ring type alkyl of divalent " refers to, also can comprise the chain fatty race alkyl of divalent and the ester ring type alkyl of divalent.In addition, hereinafter sometimes also by " chain fatty race and/or ester ring type " referred to as " aliphatics ".
Aliphatic polyester resin of the present invention (a1) and aliphatic polyester resin (a2) are following resins: wherein, as the diol units of above-mentioned formula (1), containing BDO unit as required composition.Be benchmark (100 % by mole) to form whole monomeric units of aliphatic polyester resin (a1) or aliphatic polyester resin (a2), 1, the content of 4-butyleneglycol unit is preferably 30 ~ 60 % by mole, is particularly preferably 40 ~ 50 % by mole.
As the diol units beyond BDO unit, be not particularly limited, but preferably carbonatoms is the aliphatic diol unit of 3 ~ 10, particularly preferably carbonatoms is the aliphatic diol unit of 4 ~ 6.Specifically, 1,3-propane diol, Isosorbide-5-Nitrae-hexane dimethanol etc. can be enumerated.There is provided the diol component of above-mentioned aliphatic diol unit also can use two or more.
Aliphatic polyester resin of the present invention (a1) and aliphatic polyester resin (a2) are following resin further: wherein, as dicarboxylic acid units, containing succsinic acid unit as required composition.
In addition, in aliphatic polyester resin (a1), as dicarboxylic acid units, comprise hexanodioic acid as required composition, be benchmark (100 % by mole) to form whole monomeric units of aliphatic polyester resin (a1), the content of hexanodioic acid unit is preferably 0.5 ~ 20 % by mole, more preferably 1 ~ 15 % by mole.It should be noted that, aliphatic polyester resin (a2) is not in fact containing hexanodioic acid unit.
As the dicarboxylic acid units except succsinic acid unit, hexanodioic acid unit, be not particularly limited, but the aliphatic dicarboxylic acid unit that carbonatoms is 2 ~ 10 is preferred, carbonatoms is the aliphatic dicarboxylic acid unit of 4 ~ 8 is particularly preferred.Specifically, suberic acid, sebacic acid, dodecanedioic acid etc. can be enumerated.There is provided the dicarboxylic acid component of above-mentioned aliphatic dicarboxylic acid unit also can use two or more.
And then aliphatic polyester resin of the present invention (a1) and aliphatic polyester resin (a2) also can contain aliphatic hydroxyl carboxylic acid.As the concrete example of aliphatic hydroxyl carboxylic acid providing aliphatic hydroxyl carboxylic acid, lactic acid, oxyacetic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6 hydroxycaproic acid, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-hydroxy isocaproic acid etc. or their lower alcohol or intramolecular ester can be enumerated.When there is optical isomer in them, can be any in D type optical isomer, L-type optical isomer or racemic modification, as form, can be any form in solid, liquid or the aqueous solution.Wherein particularly preferably be lactic acid or oxyacetic acid.These aliphatic hydroxyl carboxylic acids can be used alone, and also can use with the form of mixture of more than two kinds.
Be benchmark (100 % by mole) to form whole monomeric units of aliphatic polyester resin (a1) or aliphatic polyester resin (a2), the content of aliphatic hydroxyl carboxylic acid is preferably 0 ~ 30 % by mole, more preferably 0.01 ~ 20 % by mole, be particularly preferably 0.01 ~ 10 % by mole.
As the concrete example of such aliphatic polyester resin, Mitsubishi Chemical Ind's system " GSPla ", Showa electrician Inc. " Bionolle " etc. can be enumerated.
In the present invention, contain in aliphatic polyester resin (A): comprise hexanodioic acid unit as the aliphatic polyester (a1) of dicarboxylic acid units with do not comprise the aliphatic polyester (a2) of hexanodioic acid unit as dicarboxylic acid units, both compounding ratios (weight ratio) are preferably the scope of 1:9 ~ 9:1, be more preferably the scope of 1:6 ~ 6:1, more preferably the scope of 1:4 ~ 4:1.
As aliphatic polyester resin (A), use 2 kinds of aliphatic polyester resins as described above, and make them be the compounding ratio of specified range, thus, stably can keep the formability of film, the balancing performances such as the weathering resistance of film, biological degradability can be made better.By making aliphatic polyester resin (A) for such formation, especially, when for film for agricultural use etc., from the sowing, field planting of raise crop until during plant growth to a certain extent, have ground temperature heat insulation function and in order to prevent weed growth and required sufficient intensity, and the degree in fact not hindering farming operation can be degraded to before the cultivation of the harvest home of raise crop, lower first phase crop starts.
aliphatic-aromatic polyester resin (B)
The aliphatic-aromatic polyester resin (B) used in the present invention comprises aliphatic dicarboxylic acid unit, aromatic dicarboxylic acid unit and chain fatty race and/or ester ring type diol units, with the total amount of aliphatic dicarboxylic acid unit and aromatic dicarboxylic acid unit for benchmark (100 % by mole), the content of aromatic dicarboxylic acid unit is 5 ~ 60 % by mole.
Aliphatic-aromatic polyester resin (B) in the present invention, specifically, the resin of to be such as aromatic dicarboxylic acid unit that the aliphatic dicarboxylic acid unit that represents of aliphatic diol unit, the following formula (4) represented with following formula (3) and following formula (5) represent be required composition.
－O－R
3－O－ (3)
(in formula (3), R
3representing the chain fatty race alkyl of divalent and/or the ester ring type alkyl of divalent, when carrying out copolymerization, being not limited to a kind.)
－OC－R
4－CO－ (4)
(in formula (4), R
4represent Direct Bonding, or the chain fatty race alkyl of divalent and/or the ester ring type alkyl of divalent, when carrying out copolymerization, be not limited to a kind.)
－OC－R
5－CO－ (5)
(in formula (5), R
5representing the aromatic hydrocarbyl of divalent, when carrying out copolymerization, being not limited to a kind.)
The diol component of the diol units of formula (3) is provided, for carbonatoms is generally the diol component of 2 ~ 10, such as, ethylene glycol, 1,3-PD, BDO, 1,4 cyclohexane dimethanol etc. can be enumerated.Wherein, the glycol of preferred carbonatoms less than more than 24, more preferably ethylene glycol, BDO, particularly preferably BDO.
The dicarboxylic acid component of the dicarboxylic acid units of formula (4) is provided, for carbonatoms is generally the dicarboxylic acid component of less than more than 2 10, such as, succsinic acid, hexanodioic acid, suberic acid, sebacic acid, dodecanedioic acid etc. can be enumerated.Wherein, preferred succsinic acid or hexanodioic acid.
As the aromatic dicarboxylic acid composition of aromatic dicarboxylic acid unit providing formula (5), such as, terephthalic acid, m-phthalic acid, naphthalic acid etc. can be enumerated, wherein preferably terephthalic acid, m-phthalic acid, particularly preferably terephthalic acid.In addition, the aromatic dicarboxylic acid that the part can enumerating aromatic nucleus is replaced by sulfonate.It should be noted that, aliphatic dicarboxylic acid composition, aliphatic diol composition and aromatic dicarboxylic acid composition also can use two or more respectively.
In aliphatic-aromatic polyester resin (B) in the present invention, also aliphatic hydroxyl carboxylic acid can be contained.As the concrete example of aliphatic hydroxyl carboxylic acid providing aliphatic hydroxyl carboxylic acid, lactic acid, oxyacetic acid, 2-hydroxyl-butanic acid, 2-hydroxycaproic acid, 6 hydroxycaproic acid, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-hydroxy isocaproic acid or their mixture etc. can be enumerated.And then, also can be their lower alkyl esters or intramolecular ester.When there is optical isomer in them, can be any in D type optical isomer, L-type optical isomer or racemic modification, as form, can be any form in solid, liquid or the aqueous solution.Wherein preferably lactic acid or oxyacetic acid.These aliphatic hydroxyl carboxylic acids can be used alone, and also can use with the form of mixture of more than two kinds.
In the whole constituents forming aliphatic-aromatic polyester resin (B), the amount of this aliphatic hydroxyl carboxylic acid is preferably 0 ~ 30 % by mole, more preferably 0.01 ~ 20 % by mole.
For the melt flow rate (MFR) (MFR) of the aliphatic-aromatic polyester resin (B) in the present invention, 190 DEG C, measure under 2.16kg load time, be preferably 0.1 ~ 100g/10 minute, more preferably 0.1 ~ 50g/10 minute, is particularly preferably 0.1 ~ 30g/10 minute.
As the concrete example of such aliphatic-aromatic polyester resin (B), BASF AG's system " Ecoflex ", S-EnPol Inc. " EnPol " etc. can be enumerated.
In aliphatic polyester resin composition of the present invention, the compounding ratio (A) of aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B): (B) (weight ratio) is preferably 1:1 ~ 4:1, be more preferably 1:1 ~ 3.8:1, more preferably 1:1 ~ 2:1.
When with compounding ratio (A): when the mode that (B) is greater than 1:1 has coordinated aliphatic-aromatic polyester resin (B), the formability deteriorates of film, deterioration at the end of cultivation is insufficient, there is the possibility that film is wound around when utilizing machinery to process.In addition, when having coordinated aliphatic polyester resin (A) with the compounding ratio being greater than 4:1, the dura mater lacking flexibility may be formed.
lactic acid polymer ester resin (C)
In optimal way of the present invention, for the total weight part (100 weight part) of aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B), aliphatic polyester resin composition contains the lactic acid polymer ester resin (C) of preferably 3 ~ 20 weight parts, more preferably 3 ~ 15 weight parts, further preferred 5 ~ 10 weight parts.If the content of lactic acid polymer ester resin (C) is outside the scope of 3 ~ 20 weight parts, then reaches biodegradable period likely elongated, or shortage flexibility may be become.
For aliphatic polyester resin composition of the present invention, by coordinating aliphatic polyester resin (A), aliphatic-aromatic polyester resin (B) and lactic acid polymer ester resin (C) with certain amount, and there is above-mentioned biological degradability, thus, there is following performance: after cultivation terminates, before the cultivation of lower first phase crop starts, be degraded to the degree in fact not hindering and start the operation of cultivating.
In the present invention, as lactic acid polymer ester resin (C), the homopolymer or multipolymer etc. of Pfansteihl, D-ALPHA-Hydroxypropionic acid, DL-LACTIC ACID or their mixture, rac-Lactide etc. can be used.Lactic acid polymer ester resin (C) can be manufactured by the ring-opening polymerization etc. of their raw material by Direct Dehydration condensation or rac-Lactide, is not particularly limited for method for making.In addition, in the degree of character not damaging lactic acid polymer ester resin, also can copolymerization other hydroxycarboxylic acids, aliphatic polyol, aliphatic polybasic acids etc. except lactic acid.
As the concrete example of such lactic acid polymer ester resin, Nature Works Inc. " Ingeo Biopolymer ", Zhejiang Hai Zheng Biomatera Inc. system " REVODE " etc. can be enumerated.
In addition, lactic acid polymer ester resin (C) is not particularly limited, but preferred noncrystalline lactic acid polymer ester resin.
By using amorphous lactic acid polymer ester resin, thus lactic acid polymer ester resin (C) become good relative to the dispersiveness of aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B), can have evenly performance.
In addition, crystalline lactic acid polymer ester resin (C), compare with aliphatic-aromatic polyester resin (B) with aliphatic polyester resin (A), fusing point is higher, therefore, for the composition of the resin of mixing these (A), (B) and (C), the tendency that the scope that there is good condition of molding narrows, but by using amorphous lactic acid polymer ester resin (C), for the composition of the resin of mixing (A), (B) and (C), the scope of good condition of molding can be made to become wider.
inorganic filling material
In another optimal way of the present invention, above-mentioned aliphatic polyester resin composition contains inorganic filling material.In optimal way of the present invention, for the aliphatic polyester resin composition of 100 weight parts, inorganic filling material is with preferably 0.05 ~ 1.0 weight part, more preferably 0.1 ~ 0.9 weight part, preferably the amount of 0.2 ~ 0.8 weight part is involved further.Comprise inorganic filling material as described above, aliphatic polyester resin composition can be made to become the viscosity of appropriateness, better formability can be obtained.
As the inorganic filling material that can use in the present invention, silicon-dioxide, mica, talcum, titanium oxide, calcium carbonate, diatomite, malthacite, wilkinite, potassium titanate, zeolite, sepiolite, montmorillonite, kaolin, kaolinite, glass, Wingdale, charcoal, wollastonite can be enumerated, burn till the oxyhydroxide such as the silicate such as perlite, Calucium Silicate powder and water glass, aluminum oxide, magnesiumcarbonate, calcium hydroxide, iron carbonate, zinc oxide, ferric oxide, aluminum phosphate and barium sulfate etc., can be used alone a kind in them, also can be mixed with two or more.
other compositions
In aliphatic polyester resin composition of the present invention, existing known various additives can also be coordinated.As additive, such as, Nucleating Agent, antioxidant, anti-hard caking agent, slip(ping)agent, UV light absorber, photostabilizer, softening agent, thermo-stabilizer, tinting material, fire retardant, releasing agent, antistatic agent, antifogging agent, moistened surface activator can be enumerated, burn auxiliary, pigment, lubricant, dispersion agent, various tensio-active agent, anti hydrolysis agent etc.Can be used alone a kind in them, also can be mixed with two or more.Wherein, slip(ping)agent, anti-hard caking agent is particularly preferably coordinated.
As slip(ping)agent, unsaturated fatty acids acid amides, unsaturated fatty acids diamide that the unsaturated fatty acids that can to enumerate by carbonatoms be 6 ~ 30 is formed, preferred erucicamide, erucic acid diamide.
As anti-hard caking agent, can enumerate carbonatoms be 6 ~ 30 unsaturated fatty acid amide or saturated fatty acid diamide (such as stearic amide, stearic acid diamide), methylol amide, glycollic amide, native silicon dioxide, synthetic silica, synthetic zeolite, talcum etc.
As tinting material, the normally used tinting material such as carbon black, titanium oxide can be used.As tinting material, directly can use, also can be used as masterbatch and add.
As photostabilizer, such as, sebacic acid two (2 can be enumerated, 2, 6, 6-tetramethyl--4-piperidyl) ester, sebacic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, two (the 1-octyl group oxygen base-2 of sebacic acid, 2, 6, 6-tetramethyl--4-piperidyl) ester, 2-(3, 5-di-tert-butyl-hydroxy phenyl)-2-normal-butyl-propanedioic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, 2-(3, 5-di-tert-butyl-hydroxy phenyl)-2-normal-butyl-propanedioic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 2-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-2-normal-butyl-propanedioic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, 2-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-2-normal-butyl-propanedioic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 1, 2, 3, 4-BTCA four (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, 1, 2, 3, 4-BTCA four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, (mixed) 1 of mixing, 2, 3, 4-BTCA (2, 2, 6, 6-tetramethyl--4-piperidyl/tridecyl) ester, 1 of mixing, 2, 3, 4-BTCA (1, 2, 2, 6, 6-pentamethyl--4-piperidyl/tridecyl) ester, 1 of mixing, 2, 3, 4-BTCA { 2, 2, 6, 6-tetramethyl--4-piperidyl/β, β, β ', β '-tetramethyl--3, 9-(2, 4, 8, 10-tetra-oxaspiro [5.5] undecane) diethyl } ester, 1 of mixing, 2, 3, 4-BTCA { 1, 2, 2, 6, 6-pentamethyl--4-piperidyl/β, β, β ', β '-tetramethyl--3, 9-(2, 4, 8, 10-tetra-oxaspiro [5.5] undecane) diethyl } ester, 1, two (the 3-oxo-2 of 2-, 2, 6, 6-tetramethyl--4-piperidyl) ethane, 1-(3, 5-di-tert-butyl-hydroxy phenyl)-1, 1-two (2, 2, 6, 6-tetramethyl--4-piperidyl oxygen base carbonyl) pentane, poly-(1-oxygen base ethylidene (2, 2, 6, 6-tetramethyl--1, 4-piperidyl) oxygen base succinyl-), poly-(2-(1, 1, 4-trimethyl butyl imino-)-4, 6-triazine two base-(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-hexa-methylene-(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-), N, N '-bis-(3-aminopropyl) ethylene diamine-2, two (N-butyl-the N-(2 of 4-, 2, 6, 6-tetramethyl--4-piperidyl) amino)-6-chloro-1, 3, 5-triazine condenses and N-methyl compound thereof, succsinic acid and 1-(2-hydroxyethyl)-4-hydroxyl-2, 2, 6, the polycondensate of 6-tetramethyl piperidine, poly-[{ 6-((1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine 2, 4-bis-base } { (2, 2, 6, 6-tetramethyl--4-piperidyl) imino-} hexa-methylene { ((2, 2, 6, 6-tetramethyl--4-piperidyl) imino-}] etc.
As UV light absorber, in the UV light absorber such as benzophenone, benzotriazole category, salicylic acid, cyanoacrylate, preferred Benzotriazole Ultraviolet Stabilizer, specifically, 2-[5-chlorine (2H)-benzotriazole-2-base]-4-methyl 6-(tertiary butyl) phenol, 2-[2-hydroxyl-3 can be enumerated, two (α, the α-dimethylbenzyl) phenyl of 5-]-2H-benzotriazole, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-hexyl oxygen base-phenol.
As antioxidant, BHT can be exemplified, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 3,3 ', 3 ", 5,5 ', 5 "-six tertiary butyl-α, α ', α "-(sym-trimethylbenzene-2,4,6-tri-base) three-p-cresol, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-tri-[(the 4-tertiary butyl-3-hydroxyl-2,6-xylyl) methyl]-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, diethyl two [{ two (1,1-the dimethyl ethyl)-4-hydroxy phenyl of 3,5-} methyl] phosphonic acids (phosphonate) calcium, two (2,2 '-dihydroxyl-3,3 '-di-t-butyl-5,5 '-3,5-dimethylphenyl) ethane, N, N ' two [3-(3,5-the di-t-butyl)-4-hydroxy phenyl] propionic acid amide of-hexane-1,6-bis-base, the hindered phenol anti-oxidants such as Octadecane base 3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, tridecyl phosphite (phosphite), phenylbenzene decyl phosphorous acid ester, four (2,4-di-tert-butyl-phenyl) [1,1-biphenyl]-4,4 '-two base biphosphinate (phosphonite), two [two (1,1-the dimethyl ethyl)-6-aminomethyl phenyl of 2,4-] ethyl ester phosphorous acid, the phosphorus antioxidants such as two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, the lactone antioxidant such as the resultant of reaction of 3-hydroxyl-5,7-di-t-butyls-furans-2-ketone and dimethylbenzene, thiodipropionate dilauryl, the sulphur class antioxidants such as thio-2 acid distearyl ester and mixture of more than two kinds etc. in them.
As stablizer, fatty acid metal salt can be enumerated.As the fatty acid component of fatty acid metal salt, for have carboxyl, usually carbonatoms be the carboxylic acid of the chain of 6 ~ 30, can be straight-chain also can be branched, in addition, only can have saturated bond, also can have unsaturated link(age).As the concrete example of lipid acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, behenic acid, montanic acid, Zoomeric acid, oleic acid, eicosenoic acid, erucic acid, elaidic acid, anti-form-1 1-eicosenoic acid, anti-form-1 3-Decosahedaenoic acid, linolic acid, linolenic acid, ricinolic acid, erucic acid etc. can be enumerated.
On the other hand, as atoms metal, the atom of 1A, 2A, 2B and 3B race of preferred elements periodictable.As preferred example, sodium, potassium, calcium, magnesium, barium, aluminium, zinc etc. can be enumerated.
As fatty acid metal salt, such as, calcium stearate, Magnesium Stearate, barium stearate, aluminum stearate, Zinic stearas, calcium laurate, Magnesium monolaurate, Aluminum trilaurate, montanic acid sodium etc. can be enumerated.1 kind in them can be used, also may be combined with and use two or more.Wherein preferred calcium stearate, Magnesium Stearate, aluminum stearate, calcium laurate, Magnesium monolaurate and Aluminum trilaurate.
As dispersion agent, the ester wax such as montanin wax can be enumerated.
In addition, in aliphatic polyester resin composition of the present invention, in the scope not hindering effect of the present invention, Biodegradable resin and natural goods can be coordinated, such as, animal/plant material micropowder or their mixture such as polycaprolactone, polymeric amide, polyvinyl alcohol, cellulose ester etc., starch, Mierocrystalline cellulose, paper, wood powder, chitin (chitin) chitosan (chitosan) material, coconut shell flour, walnut shell flour.
biological degradability film
Another embodiment of the present invention is the biological degradability film formed by above-mentioned aliphatic polyester resin composition of the present invention.
For biological degradability film of the present invention, be exposed to the tension fracture elongation rate on the shaping direction (MD) of machinery of weathering tester after 100 hours, be preferably more than 40% relative to the tension fracture elongation rate of above-mentioned biological degradability film on the shaping direction (MD) of machinery before being exposed to weathering tester.Thus, during cultivating in the cultivation operation carried out out of doors, required intensity can be had within the period of about 3 ~ 6 months.
Herein, as weathering tester, sunlight weather resistance test case (sunshineweather meter) (such as, the sunlight weather resistance test case of SUGA trier Inc.) can be used.
In addition, as the exposure condition in weathering tester, JISA1415 can be used.
In addition, biological degradability film of the present invention shaping after the shock strength exposed in shock test at initial stage be preferably more than 3.0kgcm.Thus, required shock strength can be had in the cultivation operation carried out out of doors, when the cultivation initial stage carries out operation (utilizing the expansion etc. that machinery carries out).
In addition, the thickness of biological degradability film is preferably 5 μm ~ 50 μm, is more preferably 5 μm ~ 40 μm, more preferably 5 μm ~ 30 μm.When the thickness of biological degradability film is below 5 μm, the shaping of film becomes unstable, and when for evolutionary operation etc., intensity likely becomes insufficient.In addition, when thickness is greater than 50 μm, the degraded at the end of cultivation in soil likely becomes insufficient.
Form the compounding process of the aliphatic polyester resin composition of biological degradability film of the present invention, the ordinary method of the compounding process of resin combination can be used as.Specifically, can carry out dry type mixing with Henschel mixer, the fragment etc. of ribbon mixer to particle, powder, solid, the known melting mixing machine such as single screw extrusion machine or twin screw extruder, Banbury mixer, kneader, mixing roll that is supplied to is to carry out melting mixing.
As the method by aliphatic polyester resin composition forming process film forming, carry out with the extrusion moulding of casting roll (cast roll) cooling curing to use forcing machine with the film that T mould is extruded, to utilize inflation forming machine to carry out shaping method be suitable.
Embodiment
Below embodiments of the invention are described, but the present invention is not by any restriction of these embodiments.
[evaluation method]
(1) atmospheric exposure test method
Using SUGA trier Inc. sunlight weather resistance test case, according to the condition of JISA1415, Black panel temperature is set to 63 DEG C, exposing 100 hours by using the shaping film of inflation forming machine.
(2) measuring method of the elongation retention after atmospheric exposure test
Utilize according to the method for JISK6781, use the tensile testing machine of (strain) Shimadzu Seisakusho Ltd., carry out the tension test on mechanical-moulded direction (MD), by following calculating formula by distance between bench marks during sample breakage from calculating.
Elongation at break (%)=((distance between bench marks during fracture from the)-distance between bench marks of the initial stage (from))/distance between bench marks of the initial stage (from)) × 100
Tension test, carrying out carrying out before and after atmospheric exposure test, calculates elongation retention by following calculating formula.
Elongation retention (%)=(elongation after atmospheric exposure test)/(initial stage elongation) × 100
Metewand (exposing after the 100 hours) > of < elongation retention
◎: elongation retention is more than 60%
Zero: elongation retention is more than 40%, is less than 60%
△: elongation retention is more than 20%, is less than 40%
×: elongation retention is less than 20%
(3) formability
When using inflation forming machine shaping membrane, according to the benchmark of following record, evaluate the difference of the design temperature of the forcing machine for not adding the situation of lactic acid polymer ester (C).
◎: be less than 20 DEG C
More than zero: 20 DEG C
(4) shock strength is exposed
By with the shaping each film of inflation forming machine, making size is the test film of 100mm × 100mm, often kind of film production 4 test films, use the Toyo Seiki Inc. " puncture test machine (top uses the sphere head of 1 inch) " based on JIS P8134, read the amount (shock strength [kgcm]) of the energy required for rupture test sheet from scaleplate.Obtain the mean value of 4 measured test films.This value is judged according to the benchmark of following record.
◎: more than 5.0kgcm
○：3.0－5.0kg·cm
×: be less than 3.0kgcm
[raw material of use]
Aliphatic polyester (aliphatic polyester (a1)): Mitsubishi Chemical Ind's system " GSPlaFD99WN "
Aliphatic polyester (aliphatic polyester (a2)): Mitsubishi Chemical Ind's system " GSPlaFZ91PN "
Aliphatic-aromatic polyester: BASF AG's trade(brand)name " Ecoflex "
Lactic acid polymer ester: Nature Works company trade(brand)name " Ingeo Biopolymer2003D ", " IngeoBiopolymer 4060D "
Inorganic filling material (talcum): Japanese MISTRON company " MISTRON850JS "
[embodiment 1 ~ 6]
About inorganic filling material, use twin screw extruder melting mixing by prior with a certain amount of mixture mixed with aliphatic polyester, make masterbatch, respectively according to the cooperation recorded in table 1, be dry mixed with graininess, barrel and mold temperature set are become the melt temperature+40 DEG C of aliphatic polyester, use the inflation forming machine of MODERN Inc., the shaping film obtaining thick 18 μm (embodiments 1 ~ 5), 12 μm (embodiments 6).
Above-mentioned test method and metewand is utilized to evaluate the elongation retention after atmospheric exposure test and formability to the film obtained.The results are shown in table 1.
Confirm in addition: the film of embodiment 1 ~ 6 is all degraded to after 5 months in expansion and machinery can be utilized to carry out the degree processed, and is also degraded to the degree do not had problems in upper once cultivation before starting by the fragment of ploughing in soil.
[table 1]
The weight ratio of aliphatic polyester (a1) and aliphatic polyester (a2)
Embodiment 1:FD99WN (a1)/FZ91PN (a2)=9/1
Embodiment 2:FD99WN (a1)/FZ91PN (a2)=3/7
Embodiment 3:FD99WN (a1)/FZ91PN (a2)=9/1
Embodiment 4:FD99WN (a1)/FZ91PN (a2)=5/5
Embodiment 5:FD99WN (a1)/FZ91PN (a2)=8/2
Embodiment 6:FD99WN (a1)/FZ91PN (a2)=6/4
Comparative example 1:FD99WN (a1)/FZ91PN (a2)=0/0
Comparative example 2:FD99WN (a1)/FZ91PN (a2)=10/0
The thickness of embodiment 1 ~ 5 and comparative example 1 ~ 2 is 18 μm, the thickness of embodiment 6 is 12 μm.
As shown in Table 1, biological degradability film of the present invention not only formability is excellent, and is being exposed to weathering tester after 100 hours, and in mechanical-moulded direction, (MD) has good tension fracture elongation rate.Therefore, pass through the present invention, a kind of biological degradability film can be provided, its from the sowing, field planting of raise crop until during plant growth to a certain extent, there is the heat insulation function of ground temperature and have to prevent weed growth and required sufficient intensity, further, there is the biological decomposition characteristic that can decompose the degree in fact not hindering farming operation before the cultivation of the harvest home of raise crop, lower first phase crop starts.
Claims (4)
1. an aliphatic polyester resin composition, it comprises aliphatic polyester resin (A) and aliphatic-aromatic polyester resin (B), both compounding ratios are (A): (B)=1:1 ~ 4:1 (weight ratio)
Described aliphatic polyester resin (A) is containing following aliphatic polyester resin (a1) and following aliphatic polyester resin (a2), described aliphatic polyester resin (a1) comprises hexanodioic acid unit as dicarboxylic acid units, described aliphatic polyester resin (a2) does not comprise hexanodioic acid unit as dicarboxylic acid units, and the compounding ratio of described aliphatic polyester resin (a1) and described aliphatic polyester resin (a2) is (a1): (a2)=1:9 ~ 9:1 (weight ratio).
2. aliphatic polyester resin composition as claimed in claim 1, wherein, for the total weight part (100 weight part) of described aliphatic polyester resin (A) and described aliphatic-aromatic polyester resin (B), described aliphatic polyester resin composition contains the lactic acid polymer ester resin (C) of 3 ~ 20 weight parts.
3. aliphatic polyester resin composition as claimed in claim 1 or 2, wherein, for the aliphatic polyester resin composition of 100 weight parts, described aliphatic polyester resin composition comprises the inorganic filling material of 0.05 ~ 1.0 weight part.
4. a biological degradability film, it is characterized in that, aliphatic polyester resin composition according to any one of claims 1 to 3 is formed, described biological degradability film was exposed to weathering tester after 100 hours, and the tension fracture elongation rate on the shaping direction (MD) of machinery maintains more than 40% relative to the tension fracture elongation rate before being exposed to weathering tester.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012233943 | 2012-10-23 | ||
| JP2012-233943 | 2012-10-23 | ||
| PCT/JP2013/070778 WO2014064983A1 (en) | 2012-10-23 | 2013-07-31 | Aliphatic polyester resin composition and biodegradable film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104540895A true CN104540895A (en) | 2015-04-22 |
Family
ID=50544364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380042662.9A Pending CN104540895A (en) | 2012-10-23 | 2013-07-31 | Aliphatic polyester resin composition and biodegradable film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2014064983A1 (en) |
| CN (1) | CN104540895A (en) |
| WO (1) | WO2014064983A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115038329A (en) * | 2020-02-03 | 2022-09-09 | 日本甜菜制糖株式会社 | Seedling raising pot body with time stability and decomposition promoting method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003001704A (en) * | 2001-06-27 | 2003-01-08 | C I Kasei Co Ltd | Biodegradable film |
| JP2010253902A (en) * | 2009-04-28 | 2010-11-11 | Mkv Dream Co Ltd | Biodegradable laminated film for agriculture |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3387052B2 (en) * | 1999-10-05 | 2003-03-17 | 株式会社日本触媒 | Biodegradable polyester resin composition and its use |
| JP4247971B2 (en) * | 2003-05-28 | 2009-04-02 | シーアイ化成株式会社 | Biodegradable agricultural coating |
-
2013
- 2013-07-31 JP JP2014543166A patent/JPWO2014064983A1/en active Pending
- 2013-07-31 WO PCT/JP2013/070778 patent/WO2014064983A1/en active Application Filing
- 2013-07-31 CN CN201380042662.9A patent/CN104540895A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003001704A (en) * | 2001-06-27 | 2003-01-08 | C I Kasei Co Ltd | Biodegradable film |
| JP2010253902A (en) * | 2009-04-28 | 2010-11-11 | Mkv Dream Co Ltd | Biodegradable laminated film for agriculture |
Non-Patent Citations (1)
| Title |
|---|
| 翁云宣等: "《生物分解塑料与生物基塑料》", 31 July 2010, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115038329A (en) * | 2020-02-03 | 2022-09-09 | 日本甜菜制糖株式会社 | Seedling raising pot body with time stability and decomposition promoting method thereof |
| CN115038329B (en) * | 2020-02-03 | 2024-05-28 | 日本甜菜制糖株式会社 | Seedling raising pot with time stability and decomposition promoting method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014064983A1 (en) | 2014-05-01 |
| JPWO2014064983A1 (en) | 2016-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4585749B2 (en) | Carbodiimide composition with reduced yellowing, hydrolysis resistance stabilizer and thermoplastic resin composition | |
| ES2718635T3 (en) | Combinations of polymers with improved rheology and impact resistance without improved notch | |
| JP5958713B2 (en) | Poly (3-hydroxyalkanoate) resin composition | |
| US20200384745A1 (en) | Molded article, sheet and container, and tubular article, straw, cotton swab, and stick for balloons | |
| CN113631657B (en) | Polyhydroxyalkanoate-based resin composition, molded article thereof, and film or sheet | |
| JP4611214B2 (en) | Biodegradable resin composition | |
| CN104945861A (en) | Polyester resin composition | |
| JP2005082642A (en) | Hydrolysis resistance stabilizer for ester group-bearing resin and thermoplastic resin composition | |
| CN117795004A (en) | Biodegradable resin composition, biodegradable film and biodegradable mulch film each using the same | |
| JP4766019B2 (en) | Agricultural multi-film | |
| JP6056368B2 (en) | the film | |
| US20220073734A1 (en) | Use of an additive composition for the controlled accelerated decomposition of condensation polymers | |
| JP2020122131A (en) | Tubular body, straw, cotton swab, and baloon stick | |
| JP6908892B2 (en) | Polyamide resin composition containing a metal salt of a phenylphosphonic acid compound | |
| CN104540895A (en) | Aliphatic polyester resin composition and biodegradable film | |
| WO2020202813A1 (en) | Polyester resin composition, production method therefor, and molded body | |
| JP2013172678A (en) | Biodegradable mulch film | |
| JP2022104869A (en) | Materials for three-dimensional modeling with excellent biodegradability and their modeled products | |
| JP2006143829A (en) | Polylactic acid-based resin molding and method for producing the same | |
| JP5472502B2 (en) | Film containing polyester resin composition | |
| JP2016112013A (en) | Biodegradable film for agriculture | |
| JP2018139560A (en) | Biodegradable film for agriculture | |
| JP5218724B2 (en) | Film containing polyester resin composition | |
| JP2021055084A (en) | Film | |
| JP4980736B2 (en) | Monofilament made of aliphatic polyester resin and net comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150422 |