CN118591591A - Thermoplastic resin composition for agricultural materials and agricultural materials - Google Patents
Thermoplastic resin composition for agricultural materials and agricultural materials Download PDFInfo
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- CN118591591A CN118591591A CN202380017627.5A CN202380017627A CN118591591A CN 118591591 A CN118591591 A CN 118591591A CN 202380017627 A CN202380017627 A CN 202380017627A CN 118591591 A CN118591591 A CN 118591591A
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- resin composition
- mass
- thermoplastic resin
- parts
- agricultural materials
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- 239000011342 resin composition Substances 0.000 title claims abstract description 151
- 239000012773 agricultural material Substances 0.000 title claims abstract description 111
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 81
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- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 46
- 235000019698 starch Nutrition 0.000 claims abstract description 45
- 239000008107 starch Substances 0.000 claims abstract description 44
- 239000004645 polyester resin Substances 0.000 claims abstract description 39
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 29
- 229920001225 polyester resin Polymers 0.000 claims abstract description 22
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- -1 carbodiimide compounds Chemical class 0.000 claims description 50
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
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- 239000002245 particle Substances 0.000 claims description 20
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- 239000000155 melt Substances 0.000 claims description 14
- 238000000071 blow moulding Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 10
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- 238000002844 melting Methods 0.000 claims description 7
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- IDVWLLCLTVBSCS-UHFFFAOYSA-N n,n'-ditert-butylmethanediimine Chemical compound CC(C)(C)N=C=NC(C)(C)C IDVWLLCLTVBSCS-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 101710108497 p-hydroxybenzoate hydroxylase Proteins 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 description 1
- 229920000739 poly(3-hydroxycarboxylic acid) polymer Polymers 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/02—Receptacles, e.g. flower-pots or boxes; Glasses for cultivating flowers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- 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
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Cultivation Receptacles Or Flower-Pots, Or Pots For Seedlings (AREA)
Abstract
The invention discloses a thermoplastic resin composition for agricultural materials and an agricultural material formed by using the thermoplastic resin composition for agricultural materials, wherein the thermoplastic resin composition for agricultural materials comprises starch, biodegradable resin and viscosity regulator, the content of plasticizer in the thermoplastic resin composition for agricultural materials is 0to 5 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials, and the biodegradable resin comprises aliphatic polyester resin and aliphatic aromatic polyester resin.
Description
Technical Field
The invention relates to a thermoplastic resin composition for agricultural materials and the agricultural materials.
Background
Plastics are easily molded and processed, and therefore are used in a wide variety of fields such as electric/electronic equipment parts, automobile parts, medical parts, food containers, etc., and depending on the application, the plastic molded products are given physical properties such as strength or functionality. In the field of agricultural materials, it is used for applications requiring the assurance of water resistance and strength.
Examples of agricultural materials include: agricultural mulching film used for the purpose of raising the ground temperature or heat preservation and pest control; and a seedling raising basin as one of special containers for raising seedlings.
As a solution to alleviate the recent waste problem and the recovery work of agricultural materials, there are agricultural materials using biodegradable materials, which do not need to be recovered and can be degraded in the ground (in the soil) after use.
Patent document 1 describes a film which has a high tear strength, good biodegradability, formability, heat shrinkability, transparency, a high modulus of elasticity, and is less likely to wrinkle by containing an aliphatic polyester resin, an aromatic aliphatic polyester resin, starch, and a polyol in a specific mass ratio.
In the film, an aliphatic polyester resin and an aromatic aliphatic polyester resin are used as biodegradable materials, and the content of the polyhydric alcohol is adjusted, so that the plasticizing of starch is performed and the physical properties of the resin composition such as tear strength and tensile elastic modulus are improved.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-26538
Disclosure of Invention
Problems to be solved by the invention
Since starch has no thermoplasticity and a low thermal degradation temperature, modification of the resin composition is achieved by adding a plasticizer such as a polyol, but if the plasticizer is contained in the resin composition, there is a possibility that: the surface of the molded article obtained is adhered, and the releasability between the mold of the molding machine and the resin composition and the lubricity of separating the molded article from each other during molding are reduced, which affects the molding of the resin composition.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a thermoplastic resin composition for agricultural materials which can produce a molded article having suppressed surface blocking and which has good biodegradability and moldability, and an agricultural material comprising the thermoplastic resin composition for agricultural materials.
Technical means for solving the problems
As a result of diligent studies to solve the above problems, the present inventors have found a thermoplastic resin composition for agricultural materials having the following structure, and have completed the present invention.
That is, an embodiment of the present invention is as follows.
1 > A thermoplastic resin composition for agricultural materials, comprising starch, a biodegradable resin and a viscosity modifier, wherein the content of the plasticizer is 0 to 5 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials, the biodegradable resin comprises an aliphatic polyester-based resin and an aliphatic aromatic polyester-based resin, the total content of the aliphatic polyester-based resin and the aliphatic aromatic polyester-based resin is 80 parts by mass or more based on 100 parts by mass of the biodegradable resin, the content of the starch is 5 to 60 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials, the content of the biodegradable resin is 35 to 94.5 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials, the viscosity modifier is a viscosity modifier for increasing the melt tension of the thermoplastic resin composition for agricultural materials, the viscosity modifier comprises a thermoplastic resin selected from the group consisting of a carbodiimide compound, an oxazoline compound, a silica compound, a cellulose compound and a cellulose anhydride compound, and at least 0.01 to 5 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials, and the content of the thermoplastic resin is 0.01 to 0 part by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
The thermoplastic resin composition for agricultural materials according to < 2 > to < 1 >, wherein the starch is contained in an amount of 10 to 30 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
The thermoplastic resin composition for agricultural materials according to < 3 > to < 1 > or < 2 >, wherein the average particle size of the starch is 5 μm to 50. Mu.m.
The thermoplastic resin composition for agricultural materials according to any one of < 1 > - < 3 >, wherein the viscosity modifier comprises at least one selected from the group consisting of cellulose fibers and carbodiimide compounds.
The thermoplastic resin composition for agricultural materials according to any one of < 1 > - < 4 >, wherein the content ratio (parts by mass) of the aliphatic polyester resin to the aliphatic aromatic polyester resin is 1 to 3:1.
The thermoplastic resin composition for agricultural materials according to any one of < 1 > - < 5 >, wherein the melt viscosity at the shear rate 243s -1 is 1000 Pa.s or more and less than 5000 Pa.s at a temperature of the melting point of the biodegradable resin (B) or more and the melting point +40 ℃ or less.
The thermoplastic resin composition for agricultural materials according to any one of < 1 > - < 6 > for blow molding or vacuum forming.
The thermoplastic resin composition for agricultural materials according to any one of < 1 > - < 7 > for use in a nursery pot.
< 9 > An agricultural material, formed using the thermoplastic resin composition for agricultural material according to any one of the above < 1 > - < 8 >.
The agricultural materials are the seedling raising basin, and the agricultural materials are more than 10 and less than 9.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, there can be provided a thermoplastic resin composition for agricultural materials which can produce a molded article having suppressed surface blocking and which has biodegradability and good moldability, and an agricultural material comprising the thermoplastic resin composition for agricultural materials.
Detailed Description
Thermoplastic resin composition for agricultural Material
The thermoplastic resin composition for agricultural materials of the present embodiment is characterized by comprising starch, a biodegradable resin and a viscosity modifier, and by being free of plasticizers. By adjusting the starch and the viscosity modifier to specific contents and not containing a plasticizer, the obtained resin composition has good moldability, can be biodegradable, and can inhibit adhesion of the surface of a molded article.
In the present disclosure, "thermoplastic resin composition for agricultural materials" is sometimes referred to as "resin composition", starch "is also referred to as" starch (a) ", biodegradable resin is also referred to as" biodegradable resin (B) ", viscosity modifier is also referred to as" viscosity modifier (C) ", and plasticizer is also referred to as" plasticizer (D) ".
The degradation step of the resin composition is roughly divided into two parts.
The first stage is to lower the molecular weight of a resin constituting an agricultural material (pot for raising seedlings, agricultural mulch film, etc.) as a molded article of the resin composition by hydrolysis or oxidative degradation.
In turn, the second stage is the monolithic degradation of agricultural materials comprising low molecular weight resins by microorganisms in the soil.
Since the low molecular weight of the resin is also performed during the period of preserving or using agricultural materials, the hydrolysis control in the first stage becomes important. As a factor of hydrolysis, crystallinity of the resin is exemplified. Since the amorphous region is more easily hydrolyzed than the crystalline region, the hydrolysis can be suppressed by improving the crystallinity.
In general, when an additive or the like is added to a thermoplastic resin composition, the particles become crystal nuclei, and the formation of crystals (nucleation effect) can be promoted, so that the crystallinity is improved, and a hydrolysis-suppressing effect can be obtained.
Since the thermoplastic resin composition for agricultural materials according to the present embodiment contains the starch (a) that promotes biodegradability and the viscosity regulator (C) that increases melt tension in specific amounts, the biodegradation rate of the agricultural materials containing the resin composition can be regulated. For example, it is desirable that the agricultural materials are inhibited from degrading and maintaining their shape at least during the cultivation of the seedlings, that is, for about four months, and that the agricultural materials are degraded by microorganisms in the soil to be able to penetrate the soil after about one year exceeding the cultivation period of the seedlings.
The present embodiment will be described in detail below.
(Starch (A))
Starch (a) is a substance that promotes the action (biodegradability) of various microorganisms present in soil or water. The starch (a) is not particularly limited, and commonly available starches can be used. Examples include: corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, etc. Among them, when cornstarch having a uniform particle diameter of about 20 μm is used, it is preferable to homogenize the thickness of the agricultural material comprising the resin composition (to reduce the surface irregularities) and to suppress the occurrence of thin portions, as a result of which breakage of the agricultural material can be suppressed. These may be used singly or in combination of two or more.
The starch (a) is a component capable of adjusting the biodegradation rate, and the content thereof is preferably 5 to 60 parts by mass, or 10 to 50 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass, based on 100 parts by mass of the resin composition. If the content of the starch (a) is 5 parts by mass or more, biodegradation can be promoted, and if it is 60 parts by mass or less, the content of the biodegradable resin (B) can be ensured, thereby ensuring moldability.
In addition, the average particle diameter of the starch (A) is preferably 5 μm to 50. Mu.m, and may be 10 μm to 50. Mu.m, from the viewpoint of moldability. When the average particle diameter of the starch (a) is within the above range, the dispersibility of the starch (a) in the biodegradable resin (B) can be made compatible with the smoothness of the surface of the molded article.
In particular, in the blow molding in which the resin is directly placed in a mold and air is supplied, the average particle diameter of the starch (a) in the resin composition is preferably in the above range in order to contribute to the moldability.
The average particle diameter of the starch (a) can be obtained, for example, by observing the particles of the starch (a) with a scanning electron microscope, randomly observing 100 particles, measuring the distance between the farthest two points of the outer shape of each particle based on the length of the micrometer mark on the screen, and averaging.
(Biodegradable resin (B))
The biodegradable resin (B) is a substance that is degraded by the action of various microorganisms present in soil or water. The biodegradable resin (B) is not particularly limited, and a generally available biodegradable resin can be used. Examples thereof include polycaprolactone, aliphatic polyester resins, aliphatic aromatic polyester resins, and the like. These biodegradable resins may be used singly or in combination of two or more.
Among these, aliphatic polyester resins or aliphatic aromatic polyester resins are preferable from the viewpoints of biodegradability and moldability.
In the case of using an aliphatic polyester resin and an aliphatic aromatic polyester resin in combination as the biodegradable resin, the content of the aliphatic polyester resin is preferably not less than the content of the aliphatic aromatic polyester resin. By mixing an aliphatic polyester resin as a base resin and an aliphatic aromatic polyester resin having ductility and formability, the formability of the resin composition and the strength of agricultural materials as a formed product thereof can be ensured. The content ratio (parts by mass) of the aliphatic polyester resin and the aliphatic aromatic polyester resin is preferably, for example, 1 to 4:1, more preferably 1 to 3:1, and more preferably 1 to 2:1, particularly preferably 1 to 1.65:1, more preferably 1 to 1.57:1, may be 1.5 to 2:1.
Examples of the aliphatic polyester resin include aliphatic polyesters obtained by polycondensation reaction of aliphatic diols and aliphatic dicarboxylic acids, and polylactic acids obtained by polycondensation of lactic acid. Examples of the aliphatic diol include: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol. These may be used alone or as a mixture of these. Among them, 1, 4-butanediol is preferably used. Examples of the aliphatic dicarboxylic acid include: oxalic acid, succinic acid, glutaric acid (glutaric acid), adipic acid, sebacic acid, suberic acid, dodecanedioic acid, derivatives of these, i.e. anhydrides, can also be used. Among them, succinic acid or succinic anhydride, or a mixture of these with adipic acid is preferable.
Specifically, there may be mentioned: polybutylene succinate (Polybutylene succinate, PBS) obtained from 1,4 butanediol and succinic acid (for example, "BioPBS" (trade name) manufactured by mitsubishi chemical company (Mitsubishi Chemical Corporation, MCC) biochemistry (Biochem)), polybutylene succinate adipate (Polybutylene Succinate Adipate, PBSA) obtained by copolymerizing adipic acid on PBS, and the like.
Examples of the aliphatic aromatic polyester resin include a copolymer containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and/or alicyclic diol unit. The diol component providing the diol unit is a component having a carbon number of usually 2 to 10, and examples thereof include: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, and the like. Among them, a diol having 2 to 4 carbon atoms is preferable, ethylene glycol and 1, 4-butanediol are more preferable, and 1, 4-butanediol is still more preferable. The dicarboxylic acid component providing the dicarboxylic acid unit is a component having usually 2 to 10 carbon atoms, and examples thereof include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like. Among them, succinic acid or adipic acid is preferable. Examples of the aromatic dicarboxylic acid component providing the aromatic dicarboxylic acid unit include terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Among them, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable.
Specifically, there may be mentioned: polybutylene terephthalate adipate (Polybutylene ADIPATE TEREPHTHALATE, PBAT) which is a copolymer of 1, 4-butanediol, adipic acid and terephthalic acid (for example, "ico Filler s (Ecoflex)" (trade name) manufactured by BASF) company).
The biodegradable resin (B) may be in the form of a combination of the aliphatic polyester resin and/or the aliphatic aromatic polyester resin and other biodegradable resins. Examples of the other biodegradable resin include: poly (3-hydroxyalkanoate) of aliphatic polyester copolymer obtained from hydroxyalkanoic acid and polycarboxylic acid (wherein poly (3-hydroxybutyrate-co-3-hydroxycaproate) (poly-3-hydroxybutyrate-co-3-hydroxyhexanoate, PHBH) (for example, "ornielex (AONILEX)" (trade name) manufactured by Kaneka corporation), polylactic acid (polylactic acid, PLA) (for example, "Le Wode (REVODE)" (trade name) manufactured by haeman biological materials corporation, and "leygorski (Ingeo)" (trade name) manufactured by naqigaku (nature works)) are disclosed.
The content of the biodegradable resin (B) may be 35 to 95 parts by mass, more preferably 35 to 94.99 parts by mass, still more preferably 35 to 94.5 parts by mass, and still more preferably 39 to 90 parts by mass, based on 100 parts by mass of the resin composition. The content of the biodegradable resin (B) is within the above range, whereby the processability and moldability of the resin composition can be achieved. The total content of the aliphatic polyester resin and/or the aliphatic aromatic polyester resin is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, based on 100 parts by mass of the biodegradable resin (B).
(Viscosity modifier (C))
The viscosity modifier (C) is a substance that adjusts the viscosity of the resin composition to improve moldability, and increases the melt tension of the resin composition, which is an index of moldability. The viscosity modifier (C) is not particularly limited, and generally available ones can be used. Examples include: carbodiimide compounds, oxazoline compounds, epoxy compounds, acid anhydride compounds, cellulose fibers, silica-based fillers, and the like.
The melt tension of the resin composition can be increased by using a polyfunctional compound as the viscosity modifier (C) and forming a crosslinked structure with the biodegradable resin (B). Examples of the polyfunctional compound include a polyfunctional carbodiimide compound, a polyfunctional oxazoline compound, an epoxy compound, and an acid anhydride compound. The multifunctional carbodiimide compound may be a monomer or a polymer having two or more carbodiimide groups, but is preferably a polymer having two or more carbodiimide groups.
The melt tension of the resin composition can be increased by introducing a reactive group into the biodegradable resin (B) using a reactive compound as the viscosity modifier (C) and forming a crosslinked structure starting from the reactive group. Examples of the reactive compound include a carbodiimide compound, an oxazoline compound, an epoxy compound, and an acid anhydride compound. It is preferable to use a cyclic carbodiimide as the carbodiimide compound. The cyclic carbodiimide compound is a compound having a carbodiimide group on the ring of an aliphatic ring or an aromatic ring.
The use of the filler as the viscosity modifier (C) increases the solid content of the resin composition and thickens the same, thereby increasing the melt tension of the resin composition. The filler may be any of an organic filler and an inorganic filler, and examples thereof include cellulose fibers and silica fillers.
In a preferred embodiment, compounds described in the positive list of green plastics may be used, for example, cellulose microfibrils (cellulose microfibril, CMF) as cellulose fibers, carbodiimide compounds (carbodiimide, CDI) and the like may be used. The cellulose microfibrils are cellulose fibers of a relatively large size obtained by reducing a defibration step of cellulose obtained by subjecting pulp to treatment with hot water or the like, and after the pulp is hydrolyzed and embrittled, defibrating the pulp by a pulverizing method such as a high-pressure homogenizer. By containing cellulose microfibrils and a carbodiimide compound, the viscosity of the resin composition is increased, and strength can be ensured.
That is, if the cellulose microfibrils are contained in the resin composition, the strength of the resin composition increases due to the filler effect of the cellulose microfibrils. In addition, the silica-based filler has a filler effect similar to that of cellulose microfibrils, and thus increases the strength of the resin composition similar to that of cellulose microfibrils. In the molding of the resin composition containing at least one of the cellulose microfibrils and the silica-based filler as the viscosity modifier (C), for example, blow molding or the like may be used.
If the carbodiimide compound is contained in the resin composition, the resin reacts with the carbodiimide compound to increase the molecular weight of the resin, and therefore, it takes time until the molecular weight of the resin becomes small, and the biodegradation rate becomes slow. Therefore, in the case of agricultural materials requiring the strength of the resin composition, it is preferable to contain a carbodiimide compound as the viscosity modifier (C). In addition, the oxazoline compound, the epoxy compound, and the acid anhydride compound have reactivity with the resin, respectively, similarly to the carbodiimide compound, and therefore, the strength of the resin composition can be improved, respectively. The resin composition containing at least one of a carbodiimide compound, an oxazoline compound, an epoxy compound, and an acid anhydride compound can be molded, for example, using vacuum molding.
Examples of the carbodiimide compound include: polycarbodiimide compounds such as "Carbodilite (Carbodilite) HMV-15CA (trade name)", manufactured by Nisshink chemical company; diisopropylcarbon diimine (II) diisopropylcarbodiimide dimethyl carbodiimide monocarbodiimides such as diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide and di-t-butylcarbodiimide; and cyclic carbodiimide compounds such as "Ka Lu Baoji Sta (Carbosista) TCC-NP (trade name)", manufactured by Di person Co., ltd. These compounds may be used alone or in combination.
As the oxazoline compound, for example, "Ebolos (Epocros) RA-45" (trade name), "Ebolos (Epocros) RPS-1005" (trade name) manufactured by Japanese catalyst Co., ltd. These compounds may be used alone or in combination.
Examples of the epoxy compound include: epoxy-acrylic compound (manufactured by BASF corporation, "Zhuang Keli (Joncryl) ADR-4468" (trade name), manufactured by BASF corporation, "Zhuang Keli (Joncryl) ADR-4400" (trade name), manufactured by east Asia Synthesis Co., ltd., "A Lu Hong (Arufon) UG-4040" (trade name), manufactured by east Asia Synthesis Co., ltd., "A Lu Hong (Arufon) UG-4070" (trade name)), and the like. These compounds may be used alone or in combination.
Examples of the acid anhydride compound include: styrene maleic anhydride compound (pamehold HOLLAND) manufactured by pamehold brand company, "Xibaode (XIBOND) 120" (trade name), "Xibaode (XIBOND) 140" (trade name), "Xibaode (XIBOND) 160" (trade name), "Xibaode (XIBOND) 180" (trade name), "Xibaode (XIBOND) 200" (trade name), "Xibaode (XIBOND) 220" (trade name), "Xibaode (XIBOND) 250" (trade name), "Xibaode (XIBOND) 280" (trade name), "Xibaode (XIRAN) 1000" (trade name), "Xilan (XIRAN) 2000" (trade name), "Xilan (XIRAN) 2500" (trade name), "Xilan (XIRAN) 3000" (trade name), "Xilan (XIRAN) 4000" (trade name), "Xibaode (XIRAN) 6000" (trade name), "Xilan (XIRAN) 0" (trade name), "Xilan (XIRAN) and so on. These compounds may be used alone or in combination.
Examples of the silica-based filler include: silica filler (Japanese Ai Luoxi mol (Aerosil) manufactured by the company GmbH) 'Ai Luoxi mol (Aerosil) 130' (trade name), 'Ai Luoxi mol (Aerosil) 150' (trade name), 'Ai Luoxi mol (Aerosil) 200' (trade name), 'Ai Luoxi mol (Aerosil) 300' (trade name), 'Ai Luoxi mol (Aerosil) RX 200' (trade name), 'Ai Luoxi mol (Aerosil) RY 200' (trade name), 'Nipsil) SS-50B' (trade name), 'Nipsil) SS-50F' (trade name), 'Nipsil) K-500' (trade name), 'Nipsil) G-300' (trade name), and the like. These compounds may be used alone or in combination.
In order to make the viscosity of the resin composition appropriate, the content of the viscosity modifier (C) is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, and may be 0.01 to 1 part by mass or 0.1 to 0.8 part by mass based on 100 parts by mass of the resin composition.
Further, since the cellulose fibers contribute to high viscosity and high strength of the resin composition, if the content of the cellulose fibers contained in the resin composition is large, fluidity and processability of the resin composition may be lowered, and moldability of the resin composition may be lowered. Therefore, when the cellulose fiber is contained in the resin composition, the content of the cellulose fiber is preferably 0 part by mass or more and less than 1.5 parts by mass, more preferably 0.01 part by mass to 1.4 parts by mass, still more preferably 0.01 part by mass to 1.2 parts by mass, and still more preferably 0.01 part by mass to 1 part by mass, based on 100 parts by mass of the resin composition. When the content of the cellulose fiber is within the above range, fluidity and processability of the resin composition can be ensured, and the reduction in moldability of the resin composition can be suppressed.
(Plasticizer (D))
The thermoplastic resin composition for agricultural materials of the present embodiment does not contain a plasticizer (D) which is generally used for plasticizing the starch (a). In the present specification, "not containing the plasticizer (D)" means that the plasticizer (D) is substantially not contained, specifically, the content of the plasticizer (D) is 0 to 5 parts by mass based on 100 parts by mass of the resin composition.
Examples of the plasticizer (D) include alcohols which are organic compounds having a hydroxyl group. Specifically, glycerin, monoglyceride, ethylene glycol, and diethylene glycol are examples.
When the plasticizer (D) is 5 parts by mass or less relative to 100 parts by mass of the resin composition, good moldability can be achieved while suppressing surface blocking of the obtained molded article. The content of the plasticizer (D) is preferably 0 to 2 parts by mass, more preferably 0 to 1 part by mass, and even more preferably 0 part by mass (excluding) based on 100 parts by mass of the resin composition, from the viewpoints of blocking inhibition and moldability.
(Other Components)
The resin composition may optionally contain other components such as other additives (excluding the plasticizer (D)) as required. Examples of other additives include: dispersants, lubricants (higher fatty acid metal salts, waxes, etc.), hydrotalcite, surfactants, antistatic agents, flame retardants, antioxidants, ultraviolet absorbers, fillers, pigments, etc. The choice of other optional components and the amounts thereof are not particularly limited as long as they are within a range that can solve the problems of the embodiment of the present invention. Multiple additives may also be used in combination. The resin composition may contain a part of a resin other than the biodegradable resin within a range that does not hinder the effect of the embodiment of the present invention.
The resin composition is colored with a pigment, whereby a molded article having excellent heat insulating effect or a molded article which is easily recognized can be produced. The pigment is not particularly limited, and a generally available pigment can be used, but from the viewpoint of natural environment, a pigment substantially free of cadmium, lead, chromium, arsenic, mercury, copper, selenium, nickel, molybdenum, and fluorine is preferable.
For example, when the resin composition contains a pigment, a dispersant for dispersing the pigment is preferably used in combination, and as the dispersant, a fatty acid metal salt is exemplified. The fatty acid component of the fatty acid metal salt is preferably a linear carboxylic acid having 6 to 30 carbon atoms, and may be linear or branched, or may have only a saturated bond or an unsaturated bond.
Examples of fatty acids include: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, montanic acid, and the like.
The metal is preferably an element of the first, second, twelfth or thirteenth group, and more preferably an element of the first or second group. Specific examples thereof include sodium, potassium, calcium, magnesium, and barium.
Examples of fatty acid metal salts include: calcium stearate, magnesium stearate, barium stearate, calcium laurate, magnesium laurate, sodium montanate, and the like. One kind of these may be used, or two or more kinds may be used in combination. Among them, calcium stearate, magnesium stearate, calcium laurate, and magnesium laurate are preferable.
(Workability)
In the thermoplastic resin composition for agricultural materials, regarding processability at extrusion, strand breakage occurs 5 times or less, and may be 1 to 5 times, preferably, strand breakage does not occur at the time of continuous production for 1 hour.
(Melt viscosity)
In the thermoplastic resin composition for agricultural materials, japanese industrial standard (Japanese Industrial Standards, JIS) K7199 in terms of strength of the obtained molded article and fluidity and moldability of the resin composition: the melt viscosity at the shear rate 243s -1 in 1999 is preferably 1000pa·s or more and less than 5000pa·s, more preferably 1500pa·s or more and less than 4500pa·s at a temperature of the melting point of the biodegradable resin (B) or more and the melting point +40 ℃ or less.
(Use)
The thermoplastic resin composition for agricultural materials of the present embodiment can be used for various agricultural materials. In particular, the resin composition may be suitable for use as a nursery pot. The seedling pot is a pot for cultivating seedlings in a container until the seedlings grow to a certain degree, and is not directly planted in a field. Since the molded article using the resin composition of the present embodiment is suitably biodegradable in soil, seedlings can be directly transplanted into soil in a seedling pot without taking out the seedlings from the seedling pot after the seedlings grow.
Method of manufacturing
The resin composition of the present embodiment can be produced by kneading the starch (a) and the viscosity modifier (C) at a temperature at which the biodegradable resin (B) melts. Specifically, for example, the biodegradable resin (B), the starch (a), and the viscosity modifier (C) may be added, and various additives may be added as needed, and the mixture may be mixed and melt-kneaded by a batch kneader, a roll mill, a super mixer, a high-speed mixer, a ball mill, a sand mill, an attritor, an internal mixer (Banbury mixer), or the like, to prepare a granular, powdery, granular, or bead-like resin composition. In view of the high kneading force and the easiness of the subsequent molding process, it is preferable to use a single-screw extruder or a twin-screw extruder to prepare pellets.
The resin composition may be used in the form of a master batch or a composite.
In the case of the master batch, after the master batch is produced, for example, the master batch may be formulated as a base resin for agricultural materials using the same biodegradable resin (B) as that used in the production of the master batch as a diluent resin, thereby producing the agricultural materials. The content of the master batch is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the biodegradable resin (B) as the main resin.
The biodegradable resin (B) used as the diluent resin in this case may be the same as or different from the one used in the production of the master batch, but is preferably the same biodegradable resin because the thermoplastic resin composition has excellent compatibility with the resin.
In the case of a composite, the composite may be used directly after the composite is manufactured, by which method an agricultural asset is manufactured.
< Agricultural Material >)
The agricultural material of the present embodiment can be obtained by molding the thermoplastic resin composition for agricultural material. Examples of agricultural materials include seedling pots, agricultural mulching films, containers, and agricultural nets.
(Seedling pot)
The nursery pot is a container used for the purpose. The method of molding the seedling pot is not particularly limited, and suitable examples thereof include blow molding in which a heated and plasticized resin composition is extruded and directly introduced into a mold without cooling and solidifying the resin composition and air is supplied, and vacuum molding in which a sheet or film of the heated and plasticized resin composition is placed on the mold and vacuum-sucked from the inside of the mold to perform molding.
The seedling pot containing the resin composition can be biodegraded after being buried in soil, so that the natural environment is not destroyed, and the labor for taking out seedlings from the seedling pot and spreading the planted seedlings can be reduced. The seedling pot is not degraded during the cultivation period of the seedling, namely about 4 months, and can be well cultivated. In addition, the seedling raising pot has strength suitable for seedling raising use, so that the operation is easy, and the proper shape can be maintained during seedling raising.
(Agricultural mulch film)
Agricultural mulch (mulching film)) is a film that covers the roots of crops. The method for molding a film from the resin composition is not particularly limited, and a method of extrusion molding in which a film extruded in a T-die using an extruder is cooled and solidified by a casting roll, or molding by an inflation molding machine is suitable.
Blow molding and vacuum Forming
Since the melt tension of the resin composition is increased by the viscosity modifier (C), the resin composition can be prevented from being pulled down (the resin after the preform cannot withstand its own weight and sags down in the gravity direction).
In the case of blow molding, the molded article can be suppressed from becoming thinner and lighter. The resin composition of the present embodiment may be blow molded, and for example, when 2 seedling raising pots 3 of one group are continuously produced by a direct blow molding machine, the difference between the weight of each seedling raising pot of the first group and the weight of each seedling raising pot of the third group may be set to be less than 30% with respect to the weight of each seedling raising pot of the first group. The weight of each pot may be 0.7g or more and less than 0.8g, preferably 0.8g or more and less than 0.9g, more preferably 0.9g or more. By using the resin composition, blow moldability can be obtained.
For example, in the case where the molded article is a seedling pot, the seedling pot preferably does not flex as long as the seedling pot has strength enough to stand alone. By using the resin composition, a seedling pot ensuring strength can be obtained.
In the case of vacuum forming, occurrence of defective appearance due to sagging such as wrinkles caused by deflection of the sheet can be suppressed. For example, even if there is an appearance defect caused by sagging in the molded article, the vacuum molding may be performed using the resin composition, and the appearance defect is preferably small, and more preferably no appearance defect. By using the resin composition, a vacuum formed article can be obtained.
For example, in the case where the molded article is a nursery pot, when 1kg of soil is put into the nursery pot and dropped from a height of 5m, the nursery pot may be damaged by 3 or less out of 10, or 1 to 3 out of 10, preferably 1 or no damage is caused. By using the resin composition, a seedling pot ensuring strength can be obtained.
(Adhesion of molded article)
The dynamic friction coefficient μd in JIS K7125 of the surface of a molded article molded using the resin composition may be 0.3 or more and less than 0.5, and preferably less than 0.3, as long as it is less than 0.5. By using the resin composition, a molded article having suppressed blocking can be obtained.
(Biodegradation rate)
When a molded article molded from the resin composition is buried in the ground for 6 months, the molded article is degraded and perforated everywhere, and it is preferable that the molded article is degraded and scattered. By using the resin composition, a molded article having a properly adjusted biodegradation rate can be obtained.
According to the present embodiment, the thermoplastic resin composition for agricultural materials contains a specific amount of starch (a) that promotes biodegradability and a viscosity regulator (C) that increases melt tension, and does not contain a plasticizer (D), and therefore, an agricultural material excellent in biodegradability and moldability and suppressed in surface blocking can be obtained.
Embodiments of the present invention include various embodiments and the like not described herein. For example, the following related aspects are included.
[1] A thermoplastic resin composition for agricultural materials comprising starch (A), a biodegradable resin (B) and a viscosity modifier (C) and not comprising a plasticizer (D), the content of the starch (A) is 5 to 60 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials, and the content of the viscosity regulator (C) is 0.01 to 1 part by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
[2] The thermoplastic resin composition for agricultural materials according to [1], wherein the content of the starch (A) is 10 to 30 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
[3] The thermoplastic resin composition for agricultural materials according to [1] or [2], wherein the average particle diameter of the starch (A) is 5 μm to 50. Mu.m.
[4] The thermoplastic resin composition for agricultural materials according to any one of [1] to [3], wherein the viscosity modifier (C) comprises at least one selected from the group consisting of cellulose fibers and carbodiimide compounds.
[5] The thermoplastic resin composition for agricultural materials according to any one of [1] to [4], wherein the biodegradable resin (B) comprises an aliphatic polyester-based resin and an aliphatic aromatic polyester-based resin, and the content of the aliphatic polyester-based resin is not less than the content of the aliphatic aromatic polyester-based resin.
[6] The thermoplastic resin composition for agricultural materials according to any one of [1] to [5], wherein the melt viscosity at the shear rate 243s -1 is 1000 Pa.s or more and less than 5000 Pa.s at a temperature of the biodegradable resin (B) or more and the melting point +40 ℃ or less.
[7] The thermoplastic resin composition for agricultural materials according to any one of [1] to [6], which is used for blow molding or vacuum molding.
[8] The thermoplastic resin composition for agricultural materials according to any one of [1] to [7], which is used for a seedling pot.
[9] An agricultural material comprising the thermoplastic resin composition for agricultural materials according to [1] to [7 ].
[10] The agricultural material according to [9], which is a seedling pot.
In the present specification, the numerical range indicated by "to" is a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value of the numerical range in one stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range in another stage.
The present invention is associated with the subject matter of japanese patent application No. 2022-053396 filed on 3 months 29 of 2022, the entire disclosure of which is incorporated herein by reference.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the experimental examples and comparative examples, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.
The amounts in the tables are expressed in parts by mass. In addition, blank columns in the table indicate undeployed.
The method for measuring the average particle size of starch is as follows.
< Measurement of average particle diameter >)
The starch particles were observed at a field magnification of 100 times by using a scanning electron microscope (Scanning Electron Microscope, SEM) manufactured by hitachi corporation, 100 particles were randomly observed, and the distance between the farthest two points of the outer shape of each particle was measured based on the length of the micrometer mark on the screen, and the average was obtained.
Next, materials used in the thermoplastic resin composition for agricultural materials are listed below.
(Starch (A))
A-1: kaimes tower (CHEMISTAR) 420 (starch derived from corn, average particle size 15 μm, manufactured by Grignard high (GLICO) nutrient food Co., ltd.)
A-2: kaimes tower (CHEMISTAR) 310 (starch derived from cassava, average particle size: 50 μm, manufactured by Grignard high (GLICO) nutrient food Co., ltd.)
A-3: FP (starch from potato, average particle size: 100 μm, manufactured by Grignard high (GLICO) nutrient food company)
(Biodegradable resin (B))
B-1: bioPBS FZ91 (aliphatic polyester resin: PBS resin manufactured by Mitsubishi chemical company (Mitsubishi Chemical Corporation, MCC) of Thailand Petroleum administration (Petroleum Authority of Thailand, PTT)) biochemistry (Biochem)
B-2: ico Filler s (Ecoflex) C1200 (aliphatic aromatic polyester resin manufactured by Basf Co., ltd.: PBAT resin)
B-3: yigao (Ingeo) Biopolymer 6252D (aliphatic polyester resin: PLA resin manufactured by Naqi Wake (Nature works) Co.)
(Viscosity modifier (C))
C-1: KC Fulaaceae (Flock) W-50 (cellulose microfibrils, average fibre length: 50 μm)
C-2: carbotilite HMV-15CA (polycarbodiimide Compound manufactured by Nisshink chemical Co., ltd.)
C-3: ka Lu Baoji Sta (Carbosista) TCC-NP (cyclic carbodiimide Compound manufactured by Di people Co., ltd.)
C-4: zhuang Keli (Joncryl) ADR-4468 (manufactured by Basf Co., ltd.), epoxy-acrylic compound
C-5: sibaode (XIBOND) 220 (styrene maleic anhydride Compound manufactured by Parmehalland (Palmer Holland) Inc.)
C-6: ebolos (Epocros) RA-45 (oxazoline Compound manufactured by Japanese catalyst Co., ltd.)
C-7: ai Luoxi mol (Aerosil) 200 (manufactured by Japanese Ai Luoxi mol (Aerosil) Co., ltd.) silica filler
C-8: niphil (Nipsil) SS-50 (silica filler manufactured by Tosoh-silica Co., ltd.)
(Plasticizer (D))
D: DG (manufactured by daily oil company, polyol, glycerol)
Production of thermoplastic resin composition for agricultural Material
Experimental example 1
(Production of thermoplastic resin composition (Compound) for agricultural Material)
5 Parts by mass of (A-1) as starch (A), 94.5 parts by mass of (B-1) as biodegradable resin (B) and 0.5 part by mass of (C-1) as viscosity modifier (C) were mixed, and extruded at 190℃by a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) to obtain a thermoplastic resin composition for agricultural materials.
(Manufacture of seedling pot)
The obtained thermoplastic resin composition for agricultural materials is subjected to blow molding or vacuum molding, thereby obtaining a seedling pot.
[ Experimental example 2 to Experimental example 35, comparative example 1 to comparative example 5]
Thermoplastic resin compositions for agricultural materials and nursery pots were obtained in the same manner as in experimental example 1, except that the materials and the amounts (parts by mass) were changed as shown in table 1, respectively. In addition, experimental examples 1 to 13 are examples including only one of the aliphatic polyester resin (B-1 or B-3) and the aliphatic aromatic polyester resin (B-2) as a biodegradable resin, and can be regarded as reference examples, unlike experimental examples in which the aliphatic polyester resin (B-1 or B-3) and the aliphatic aromatic polyester resin (B-2) are used as biodegradable resins.
TABLE 1
The thermoplastic resin compositions for agricultural materials and seedling pots obtained in the experimental examples and comparative examples were evaluated according to the following criteria. The evaluation results are shown in table 1.
< Evaluation of processability >)
Processability during extrusion of the thermoplastic resin composition for agricultural materials was evaluated. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
And (2) the following steps: strand breakage does not occur when the production is continued for 1 hour.
Delta: strand breakage occurred 1 to 5 times in 1 hour of continuous production.
X: more than 6 strand breaks occurred at 1 hour of continuous production.
< Melt viscosity evaluation >
According to JIS K7199:1999 the melt viscosity of the thermoplastic resin composition for agricultural materials at a shear rate of 243s -1 was measured at 150 ℃. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
O: the melt viscosity is more than 1500 Pa.s
Delta: melt viscosity of 1000 Pa.s to less than 1500 Pa.s
X: melt viscosity of less than 1000 Pa.s
< Evaluation of blow Forming Property >
2 Seedling raising pots of 1 group were continuously produced at 150℃by a direct blow molding machine (manufactured by Protecan (placon Co., ltd.), and the difference between the weight of each seedling raising pot of the first group and the weight of each seedling raising pot of the third group (weight difference) and the weight of each seedling raising pot were evaluated as formability at the time of production. In this evaluation, the term "blow-moldable" means that the weight difference is less than 30% with respect to the weight of each seedling pot of the first group. The evaluation criteria are described below, and "excellent", "o" and "Δ" are practically applicable.
[ Evaluation criterion ]
And (3) the following materials: can be blow molded, and the weight of each seedling raising basin is more than 0.9g
O: can be blow molded, and the weight of each seedling raising basin is more than 0.8g and less than 0.9g
Delta: can be blow molded, and the weight of each seedling raising basin is more than 0.7g and less than 0.8g
X: cannot be blow molded
< Evaluation of vacuum formability >)
A sheet of 30cm in the longitudinal direction, 30cm in the transverse direction, and 0.45mm in thickness was molded at 180℃by a T-die molding machine. The molded sheet was heated to 110℃and the seedling pot was molded by a vacuum molding machine, and the moldability at the time of production was evaluated. The evaluation criteria are described below, and "excellent", "o" and "Δ" are practically applicable.
[ Evaluation criterion ]
And (3) the following materials: can be formed in vacuum, and has no appearance defect caused by sagging.
O: can be formed in vacuum, and has a few bad appearance parts caused by sagging.
Delta: the vacuum forming can be performed, and defective appearance caused by sagging can be confirmed in the nursery pot.
X: vacuum forming is impossible.
< Formed article Strength evaluation >
The strength of the pot for raising seedlings produced at the time of evaluating the blow moldability was evaluated. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
O: the seedling raising basin is free-standing without flexing.
Delta: the seedling raising basin flexes but is free-standing.
X: the seedling pot cannot bear the dead weight and cannot stand alone.
< Formed article brittleness evaluation >
1Kg of soil was placed in each of 10 seedling pots prepared at the time of evaluation of vacuum formability and dropped from a height of 5m, whereby the brittleness of the seedling pot was evaluated. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
O: 1 seedling pot out of 10 was also undamaged.
Delta: 1 to 3 out of 10 were damaged.
X: more than 4 out of 10 were damaged.
< Evaluation of adhesion of molded article >
The adhesion of the seedling pot was evaluated by measuring the dynamic friction coefficient of the side surface of the seedling pot produced at the time of evaluating the blow moldability according to JIS K7125. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
O: coefficient of dynamic friction [ mu ] D of less than 0.3
Delta: a dynamic friction coefficient [ mu ] D of 0.3 or more and less than 0.5
X: a dynamic friction coefficient [ mu ] D of 0.5 or more
< Evaluation of biodegradation Rate >)
The seedling pot prepared at the time of evaluation of blow molding was buried under the ground, and after 6 months, the biodegradability was evaluated by digging. The evaluation criteria are as follows, and o and Δ are practically usable.
[ Evaluation criterion ]
O: the seedling pot is degraded to be scattered
Delta: the seedling raising basin is degraded and perforated everywhere
X: seedling pot preservation prototype
From the above results, it was confirmed that the resin compositions and the pot for seedlings in examples 1 to 35 were environmentally friendly, and were biodegradable, and the adhesion on the surface was suppressed, and the moldability was also excellent.
Claims (10)
1. A thermoplastic resin composition for agricultural materials, comprising starch, a biodegradable resin and a viscosity modifier, wherein the content of the plasticizer in the thermoplastic resin composition for agricultural materials is 0 to 5 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials,
The biodegradable resin comprises an aliphatic polyester resin and an aliphatic aromatic polyester resin, wherein the total content of the aliphatic polyester resin and the aliphatic aromatic polyester resin is 80 parts by mass or more based on 100 parts by mass of the biodegradable resin,
The starch content is 5 to 60 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials,
The content of the biodegradable resin is 35 to 94.5 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials,
The viscosity modifier is a viscosity modifier for increasing the melt tension of the thermoplastic resin composition for agricultural materials,
The viscosity modifier comprises at least one selected from the group consisting of carbodiimide compounds, oxazoline compounds, epoxy compounds, acid anhydride compounds, cellulose fibers and silica-based fillers,
The content of the viscosity modifier is 0.01 to 3 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials,
The content of the cellulose fiber is 0 parts by mass or more and less than 1.5 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials,
The content of the aliphatic polyester resin is not less than the content of the aliphatic aromatic polyester resin.
2. The thermoplastic resin composition for agricultural materials according to claim 1, wherein the content of the starch is 10 to 30 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
3. The thermoplastic resin composition for agricultural materials according to claim 1 or 2, wherein the average particle diameter of the starch is 5 μm to 50 μm.
4. The thermoplastic resin composition for an agricultural material according to any one of claims 1 to 3, wherein the viscosity modifier comprises at least one selected from the group consisting of cellulose fibers and a carbodiimide compound.
5. The thermoplastic resin composition for agricultural materials according to any one of claims 1 to 4, wherein the content ratio (parts by mass) of the aliphatic polyester-based resin to the aliphatic aromatic polyester-based resin is 1 to 3:1.
6. The thermoplastic resin composition for agricultural materials according to any one of claims 1 to 5, wherein a melt viscosity at a shear rate 243s -1 is 1000 Pa-s or more and less than 5000 Pa-s at a temperature of a melting point of the biodegradable resin or more and a melting point +40 ℃ or less.
7. The thermoplastic resin composition for agricultural materials according to any one of claims 1 to 6, which is used for blow molding or vacuum forming.
8. The thermoplastic resin composition for agricultural materials according to any one of claims 1 to 7, which is used for a nursery pot.
9. An agricultural material formed using the thermoplastic resin composition for agricultural material according to any one of claims 1 to 8.
10. The agricultural material of claim 9, which is a nursery pot.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-053396 | 2022-03-29 | ||
| JP2022053396A JP7232367B1 (en) | 2022-03-29 | 2022-03-29 | Thermoplastic resin composition for agricultural materials and agricultural materials |
| PCT/JP2023/005361 WO2023188943A1 (en) | 2022-03-29 | 2023-02-16 | Thermoplastic resin composition for agricultural materials, and agricultural material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118591591A true CN118591591A (en) | 2024-09-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202380017627.5A Pending CN118591591A (en) | 2022-03-29 | 2023-02-16 | Thermoplastic resin composition for agricultural materials and agricultural materials |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7232367B1 (en) |
| CN (1) | CN118591591A (en) |
| WO (1) | WO2023188943A1 (en) |
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| JP4414415B2 (en) * | 2006-07-19 | 2010-02-10 | 昭和高分子株式会社 | Biodegradable resin composition and biodegradable film |
| EP2380932B1 (en) * | 2008-12-26 | 2018-03-14 | Mitsubishi Chemical Corporation | Resin composition, film, bag product and production process of resin composition |
| IT1396597B1 (en) * | 2009-11-05 | 2012-12-14 | Novamont Spa | BIODEGRADABLE POLYESTER MIXTURES |
| JP2012031329A (en) * | 2010-08-02 | 2012-02-16 | Mitsubishi Chemicals Corp | Biodegradable resin composition and molded article obtained by molding the composition |
| CN203666067U (en) * | 2013-11-27 | 2014-06-25 | 山东农业大学 | Strip-segmenting agricultural plastic mulching film with different degradation functions |
| CN105273376B (en) * | 2014-08-29 | 2017-08-15 | 陈再荣 | A kind of biodegradation material and preparation method thereof and purposes |
| JP7360450B2 (en) * | 2019-03-29 | 2023-10-12 | 株式会社カネカ | Method for producing polyester resin composition |
| WO2021193219A1 (en) * | 2020-03-27 | 2021-09-30 | 株式会社カネカ | Manufacturing method for thermoplastic resin composition, manufacturing method for shaped body, and film |
-
2022
- 2022-03-29 JP JP2022053396A patent/JP7232367B1/en active Active
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2023
- 2023-02-16 CN CN202380017627.5A patent/CN118591591A/en active Pending
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| Publication number | Publication date |
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| JP2023146286A (en) | 2023-10-12 |
| WO2023188943A1 (en) | 2023-10-05 |
| JP7232367B1 (en) | 2023-03-02 |
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