WO2012121296A1 - Composition de particules de résine polyester aliphatique biodégradable, et procédé de fabrication de celle-ci - Google Patents

Composition de particules de résine polyester aliphatique biodégradable, et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2012121296A1
WO2012121296A1 PCT/JP2012/055842 JP2012055842W WO2012121296A1 WO 2012121296 A1 WO2012121296 A1 WO 2012121296A1 JP 2012055842 W JP2012055842 W JP 2012055842W WO 2012121296 A1 WO2012121296 A1 WO 2012121296A1
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polyester resin
aliphatic polyester
biodegradable aliphatic
pga
average particle
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Japanese (ja)
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山▲崎▼昌博
佐藤浩幸
阿部俊輔
三枝孝拓
来原なな子
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Kureha Corp
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Kureha Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/124—Treatment for improving the free-flowing characteristics
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/16—Biodegradable polymers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/013—Additives applied to the surface of polymers or polymer particles
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a biodegradable aliphatic polyester resin granule composition containing a biodegradable aliphatic polyester resin granule excellent in an antiblocking effect and a method for producing the same.
  • Aliphatic polyester resins such as polyglycolic acid resin (hereinafter sometimes referred to as “PGA”) and polylactic acid resin (hereinafter sometimes referred to as “PLA”) are microorganisms that exist in nature such as soil and sea. Or since it is decomposed
  • PGA polyglycolic acid resin
  • PVA polylactic acid resin
  • biodegradable aliphatic polyester resin examples include PLA composed of lactic acid repeating units, PGA composed of glycolic acid repeating units, lactone polyester resins such as poly- ⁇ -caprolactone, polyhydroxybutyrate polyester resins, and co-polymers thereof.
  • a polymer for example, a copolymer comprising a glycolic acid repeating unit and a lactic acid repeating unit (hereinafter sometimes referred to as “PGLA”) is known.
  • PGA has excellent degradability, mechanical properties such as heat resistance and tensile strength, and gas barrier properties particularly when used as a film or sheet. For this reason, PGA is expected to be used as agricultural materials, various packaging (container) materials and medical polymer materials, and has been developed for use alone or in combination with other resin materials.
  • Methods for producing products from biodegradable aliphatic polyester resins such as PGA include extrusion molding, injection molding, compression molding, injection compression molding, transfer molding, cast molding, blow molding, stretched film molding, inflation Melt molding and other molding methods such as film molding, laminate molding, calendar molding, foam molding, RIM molding, FRP molding, powder molding or paste molding are employed.
  • the biodegradable aliphatic polyester resin pellets used as a molding raw material for melt molding are melted in a strand form by blending various additives into the biodegradable aliphatic polyester resin using, for example, a twin screw extruder.
  • the average particle diameter obtained by extrusion and cutting into a predetermined size is about several mm.
  • a biodegradable aliphatic polyester resin granule prepared in a predetermined size and shape according to the application is used as the powder of the biodegradable aliphatic polyester resin used as a molding raw material for powder molding or paste molding.
  • biodegradable aliphatic polyester resin granules such as PGA are focused on the properties of each resin such as heat resistance and mechanical properties, as well as its degradability, and paints, coating agents, inks, toners, agricultural chemicals, It is expected to be used as a raw material or additive in fields such as medicine, cosmetics, mining, and well drilling.
  • a biodegradable aliphatic polyester resin granule to be applied to these fields a granule having particle characteristics such as a particle size, a particle size distribution, and a particle shape that meet the purpose is required.
  • a bit attached to the tip of the drill advances through the well while rotating the rocks of the formation while rotating, and carries the broken rocks to the surface.
  • bentonite, mica, slaked lime, carboxy, etc. are used for the purpose of reducing friction between the drill and the wall, cooling bits, carrying out crushed rocks, etc.
  • a slurry-like drilling dispersion liquid (hereinafter sometimes referred to as “well fluid”) in which granular materials such as methylcellulose and silicone resin are dispersed in a liquid carrier such as water or an organic solvent is used.
  • the dispersion for excavation uses the above granular material as water, or a diol or triol such as ethylene glycol, propylene glycol, glycerol, or trimethylene glycol; glyceryl triacetate (triacetin), glyceryl tripropionate (tripropionine), or glyceryl tributyrate.
  • Liquid carriers selected from organic solvents such as glycerol esters such as (tributyrin); polyglycols such as polyethylene glycol; and the like, anti-sludge agents, specific gravity agents, dispersants, surfactants, viscosity modifiers, thickeners, etc. It is used by dispersing with additives.
  • the granular material used for the excavation dispersion liquid has fluidity, heat resistance, chemical stability, mechanical properties, and other properties so as not to hinder excavation work. It is necessary to be able to discharge the dispersion and safely dispose of it, and there is a need for a granular composition and particle characteristics that satisfy these requirements.
  • Biodegradable aliphatic polyester resin granules such as PGA have fluidity, heat resistance, and other properties that do not interfere with excavation work, and are also biodegradable and hydrolyzable, making disposal easy. Therefore, it is expected to be used as a dispersion liquid for excavation. Accordingly, there is a need for a biodegradable aliphatic polyester resin granule composition containing biodegradable aliphatic polyester resin granules that are optimal for a drilling dispersion in terms of granule composition and particle characteristics.
  • a biodegradable aliphatic polyester resin granule As a biodegradable aliphatic polyester resin granule, a granule excellent in handleability and storage stability is required.
  • a granular material having a small particle size has poor handleability, increased hygroscopicity, increased surface area, and has a large influence on the decomposition rate, which is superior to biodegradable aliphatic polyester resins.
  • Patent Document 1 discloses a method for producing a polylactic acid resin powder in which a chip or block made of PLA resin is cooled to a low temperature of ⁇ 50 to ⁇ 180 ° C., impact pulverized and classified.
  • Patent Document 2 discloses biodegradability in which an organic solvent solution of a biodegradable aliphatic polyester resin and aromatic hydrocarbons are mixed at a temperature of less than 60 ° C., and the precipitated solid is separated into solid and liquid.
  • a method for producing a powdered polyester resin is disclosed, and in the examples, Mw 145,000 PLA, Mw 10.0 million polybutylene succinate, and Mw 17.2 million PLA and polybutylene succinate Coalescence is used as a raw material.
  • PLA and a solvent a mixture of dimethyl adipate, dimethyl glutarate, and dimethyl succinate (DBE (registered trademark), manufactured by DuPont) have a dissolution temperature of 140.
  • PLA particles having an average primary particle size of 250 nm or less, or, as Production Example 4, using PGA and a solvent (bis (2-methoxyethyl) ether) PGA particles having an average primary particle size of 150 nm or less obtained by setting the temperature to 150 ° C. and the cooling temperature to ⁇ 35 ° C. are disclosed.
  • biodegradable aliphatic polyester resins such as PGA and PLA can be stored and used until they are used in products for the above-mentioned applications, even after obtaining granular materials having particle characteristics suitable for applications.
  • the granular material sometimes aggregates (blocks).
  • blocks When blocking of the granular material occurs, the handleability of the granular material deteriorates, and the average particle diameter, particle size distribution, and shape of the granular material manufactured so as to be suitable for the application are lost, and the desired characteristics are lost. May not be able to demonstrate.
  • the biodegradable aliphatic polyester resin granule is likely to be blocked when a load is applied in a temperature environment near its glass transition temperature (Tg: about 40 ° C.
  • the granular materials may be exposed to high temperatures near Tg or higher, so effective anti-blocking measures for biodegradable aliphatic polyester resin granular materials can be taken. It was sought after.
  • the composition of the anti-blocking agent is limited in the use of the biodegradable aliphatic polyester resin granule, and for example, the anti-blocking agent is used after the well drilling operation or after the well drilling operation is completed. Consideration has arisen that there is a possibility of adversely affecting the discharge and disposal, and further improvement has been demanded.
  • An object of the present invention is to provide a biodegradable aliphatic polyester resin granular composition such as PGA or PLA, which has an excellent anti-blocking effect, and a method for producing the same.
  • biodegradable aliphatic polyester resin granules In order to solve the above-described problems, the present inventors have generated blocking of granules of biodegradable aliphatic polyester resin (hereinafter sometimes simply referred to as “biodegradable aliphatic polyester resin granules”).
  • biodegradable aliphatic polyester resin granules obtained by the so-called impact pulverization method melt and soften the surface of the granular material due to the shearing force during pulverization. I found that the ratio was growing.
  • a biodegradable aliphatic polyester resin granule composition obtained by adding an antiblocking agent to biodegradable aliphatic polyester resin granules having an average particle diameter of 0.01 to 1000 ⁇ m. Is provided.
  • biodegradable aliphatic polyester resin granular compositions (1) to (6) are provided as embodiments.
  • F1 A cylindrical shape obtained by molding the granular composition under molding conditions in which a load of 100 gf / cm 2 is applied for 24 hours at a glass transition temperature of the biodegradable aliphatic polyester resin of ⁇ 5 ° C. or higher. Normal fracture stress of tablets; However, the biodegradable aliphatic polyester resin granular composition satisfying the formula F1 ⁇ 1000 gf / cm 2 .
  • biodegradable aliphatic polyester resin granular composition wherein the biodegradable aliphatic polyester resin is a polyglycolic acid resin.
  • the said biodegradable aliphatic polyester resin granular material composition whose antiblocking agent is an organic substance containing an organic substance, especially a biodegradable aliphatic polyester resin.
  • an antiblocking agent is added to the granules of the biodegradable aliphatic polyester resin having an average particle size of 0.01 to 1000 ⁇ m, and the biodegradable aliphatic polyester resin is at 0 ° C. or higher.
  • a biodegradable aliphatic polyester resin granule composition obtained by adding an antiblocking agent to biodegradable aliphatic polyester resin granules having an average particle size of 0.01 to 1000 ⁇ m.
  • an antiblocking agent is added to the granules of biodegradable aliphatic polyester resin having an average particle size of 0.01 to 1000 ⁇ m, and the biodegradable aliphatic polyester resin is at 0 ° C. or higher.
  • the biodegradable aliphatic polyester resin granular composition can be easily produced.
  • the biodegradable aliphatic polyester resin constituting the biodegradable aliphatic polyester resin granule of the present invention contains glycolide (GL) that is a bimolecular cyclic ester of glycolic acid and glycolic acid.
  • GL glycolide
  • Glycolic acid, lactic acid and lactic acid containing lactide which is a bimolecular cyclic ester of lactic acid, ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactones (eg, ⁇ -propiolactone, ⁇ -butyrolactone, pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.), carbonates (eg trimethylene carbonate, etc.), ethers (eg 1,3-dioxane, etc.) ), Cyclic monomers such as ether esters (such as dioxanone); -Hydroxycarboxylic acids such as hydroxypropanoic acid, 4-hydroxybutanoic acid and 6-hydroxycaproic acid or alkyl esters thereof; aliphatic diols such as ethylene glycol and 1,4-butan
  • PLA such as L-lactic acid homopolymer, D-lactic acid homopolymer, copolymer having 50% by mass or more of repeating units of L-lactic acid or D-lactic acid, a mixture thereof, and the like; glycolic acid Homopolymers of the above, copolymers having a glycolic acid repeating unit of 50% by mass or more, PGA such as a mixture thereof; and further, a mixture of PLA and PGA is preferable.
  • PGA excellent in decomposability, heat resistance, mechanical properties and the like.
  • biodegradable aliphatic polyester resins can be synthesized, for example, by dehydration polycondensation of ⁇ -hydroxycarboxylic acids such as glycolic acid and lactic acid known per se.
  • a method of synthesizing a bimolecular cyclic ester of ⁇ -hydroxycarboxylic acid and subjecting the cyclic ester to ring-opening polymerization is employed.
  • PLA is obtained by ring-opening polymerization of lactide, which is a bimolecular cyclic ester of lactic acid.
  • PGA is obtained by ring-opening polymerization of glycolide, which is a bimolecular cyclic ester of glycolic acid.
  • PLA can be synthesized by the above-mentioned method, and commercially available products include, for example, “Lacia (registered trademark)” (Mitsui, Inc.) such as Lacia H-100, H-280, H-400, and H-440.
  • “Ingeo (registered trademark)” manufactured by Nature Works
  • "Eco-plastic U'z series” such as S-17 (manufactured by Toyota Motor Corporation), "Vairo Indiana (registered trademark)” (manufactured by Toyobo Co., Ltd.), etc.
  • S-17 manufactured by Toyota Motor Corporation
  • Vairo autoimmune (registered trademark)” manufactured by Toyobo Co., Ltd.
  • etc. are compatible with strength and flexibility, and heat resistance From the viewpoint of, it is preferably selected.
  • PGA an example of a biodegradable aliphatic polyester resin.
  • PLA and other biodegradable aliphatic polyester resins also take a form for carrying out the invention according to PGA. be able to.
  • PGA Polyglycolic acid resin
  • a PGA copolymer containing 50% by mass or more of the glycolic acid repeating unit is included. .
  • Examples of comonomers that give a PGA copolymer together with glycolic acid monomers such as glycolide include ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactides, lactones, carbonates, ethers.
  • the glycolic acid repeating unit in the PGA of the present invention is 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more. And most preferably a substantially PGA homopolymer of 99% by weight or more. If the proportion of glycolic acid repeating units is too small, the strength and degradability expected for PGA will be poor.
  • the repeating unit other than the glycolic acid repeating unit is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less. Most preferably, it is used in a proportion of 1% by mass or less, and may not contain any repeating unit other than the glycolic acid repeating unit.
  • the PGA in the present invention is preferably a PGA obtained by polymerizing 50 to 100% by mass of glycolide and 50 to 0% by mass of the other comonomer described above in order to efficiently produce a desired high molecular weight polymer.
  • the other comonomer may be a cyclic monomer between two molecules, or may be a mixture of both instead of the cyclic monomer, but in order to obtain the PGA granular material targeted by the present invention, the cyclic monomer Is preferred.
  • PGA obtained by ring-opening polymerization of 50 to 100% by mass of glycolide and 50 to 0% by mass of other cyclic monomers will be described in detail.
  • glycolide that forms PGA by ring-opening polymerization is a bimolecular cyclic ester of glycolic acid, which is a kind of hydroxycarboxylic acid.
  • the manufacturing method of glycolide is not specifically limited, Generally, it can obtain by thermally depolymerizing a glycolic acid oligomer.
  • a depolymerization method for glycolic acid oligomers for example, a melt depolymerization method, a solid phase depolymerization method, a solution depolymerization method, etc. can be adopted, and glycolide obtained as a cyclic condensate of chloroacetate should also be used. Can do.
  • glycolide containing glycolic acid can be used up to 20% by mass of the glycolide amount.
  • the PGA in the present invention may be formed by ring-opening polymerization of only glycolide, but may be formed by simultaneously ring-opening polymerization using another cyclic monomer as a copolymerization component.
  • the proportion of glycolide is 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass. % Or more, and most preferably 99% by mass or more of a substantially PGA homopolymer.
  • hydroxycarboxylic acids include L-lactic acid, D-lactic acid, ⁇ -hydroxybutyric acid, ⁇ -hydroxyisobutyric acid, ⁇ - Hydroxyvaleric acid, ⁇ -hydroxycaproic acid, ⁇ -hydroxyisocaproic acid, ⁇ -hydroxyheptanoic acid, ⁇ -hydroxyoctanoic acid, ⁇ -hydroxydecanoic acid, ⁇ -hydroxymyristic acid, ⁇ -hydroxystearic acid, and these Examples include alkyl-substituted products.
  • Another particularly preferable cyclic monomer is lactide, which is a bimolecular cyclic ester of lactic acid, and may be any of L-form, D-form, racemate, and a mixture thereof.
  • the other cyclic monomer is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass. Used in the following proportions.
  • the melting point (crystal melting point) of PGA (copolymer) is lowered to lower the processing temperature, or the crystallization speed is controlled to control the extrusion processability and stretching. Workability can be improved.
  • the ring-opening polymerization or ring-opening copolymerization of glycolide (hereinafter sometimes collectively referred to as “ring-opening (co) polymerization”) is preferably carried out in the presence of a small amount of a catalyst.
  • the catalyst is not particularly limited.
  • a tin-based compound such as tin halide (for example, tin dichloride, tin tetrachloride) and organic carboxylate (for example, tin octoate such as tin 2-ethylhexanoate).
  • Titanium compounds such as alkoxy titanates; aluminum compounds such as alkoxy aluminum; zirconium compounds such as zirconium acetylacetone; antimony compounds such as antimony halide and antimony oxide;
  • the amount of the catalyst used is preferably about 1 to 1000 ppm, more preferably about 3 to 300 ppm in terms of mass ratio with respect to the cyclic ester.
  • Ring-opening (co) polymerization of glycolide uses alcohols such as lauryl alcohol as a higher alcohol and protic compounds such as water as molecular weight regulators in order to control physical properties such as melt viscosity and molecular weight of the produced PGA.
  • Alcohols such as lauryl alcohol as a higher alcohol
  • protic compounds such as water as molecular weight regulators in order to control physical properties such as melt viscosity and molecular weight of the produced PGA.
  • Glycolide usually contains trace amounts of water and hydroxycarboxylic acid compounds composed of glycolic acid and linear glycolic acid oligomers as impurities, and these compounds also act on the polymerization reaction.
  • the concentration of these impurities is quantified as a molar concentration by, for example, neutralization titration of carboxylic acids present in these compounds, and alcohols and water are added as protic compounds according to the target molecular weight,
  • the molecular weight of the produced PGA can be adjusted by controlling the molar concentration of the active compound with respect to glycolide.
  • the ring-opening (co) polymerization of glycolide may be bulk polymerization or solution polymerization, but in many cases, bulk polymerization is employed.
  • bulk polymerization equipment for bulk polymerization, such as an extruder type, a vertical type with paddle blades, a vertical type with helical ribbon blades, a horizontal type such as an extruder type and a kneader type, an ampoule type, a plate type and a tubular type.
  • the device can be selected as appropriate.
  • various reaction tanks can be used for solution polymerization.
  • the polymerization temperature can be appropriately set according to the purpose within a range from 120 ° C. to 300 ° C. which is a substantial polymerization start temperature.
  • the polymerization temperature is preferably 130 to 270 ° C., more preferably 140 to 260 ° C., and particularly preferably 150 to 250 ° C. If the polymerization temperature is too low, the molecular weight distribution of the produced PGA tends to be wide. If the polymerization temperature is too high, the produced PGA is susceptible to thermal decomposition.
  • the polymerization time is in the range of 3 minutes to 50 hours, preferably 5 minutes to 30 hours. If the polymerization time is too short, the polymerization does not proceed sufficiently and a predetermined weight average molecular weight cannot be realized. If the polymerization time is too long, the produced PGA tends to be colored.
  • Solid phase polymerization means an operation of heat treatment while maintaining a solid state by heating at a temperature lower than the melting point of PGA.
  • the solid phase polymerization is preferably performed for 1 to 100 hours, more preferably 2 to 50 hours, particularly preferably 3 to 30 hours.
  • the weight average molecular weight (Mw) of PGA contained in the biodegradable aliphatic polyester resin granule composition of the present invention is usually preferably within the range of 5 to 1.5 million, more preferably 6 to 1.3 million, Preferably, one in the range of 7 to 1.1 million, particularly preferably in the range of 100,000 to 1,000,000 is selected.
  • the weight average molecular weight (Mw) of PGA is determined by a gel permeation chromatography (GPC) apparatus.
  • the weight average molecular weight (Mw) of PLA contained in the granular composition of the present invention is preferably in the range of 5 to 1,200,000, more preferably 6 to 1,000,000, still more preferably 70 to 800,000.
  • the crystal melting point (Tm) of PGA contained in the biodegradable aliphatic polyester resin granular composition of the present invention is usually from 197 to 245 ° C., and the weight average molecular weight (Mw), molecular weight distribution, types of copolymer components and It can be adjusted by the content ratio or the like.
  • the crystal melting point (Tm) of PGA is preferably 200 to 240 ° C, more preferably 205 to 235 ° C, and particularly preferably 210 to 230 ° C.
  • the crystal melting point (Tm) of a homopolymer of PGA is usually about 220 ° C. If the crystal melting point (Tm) is too low, the heat resistance and strength may be insufficient.
  • the crystal melting point (Tm) of PGA was determined in a nitrogen atmosphere using a differential scanning calorimeter (DSC). Specifically, the sample PGA was heated to about 280 ° C., held at this temperature for 2 minutes, and then rapidly cooled with liquid nitrogen (about 100 ° C./minute) to obtain an amorphous sample in a nitrogen atmosphere. In the middle, it means the temperature of the endothermic peak accompanying crystal melting detected in the process of reheating at around 20 ° C./min from around room temperature. When a plurality of endothermic peaks are observed, the peak having the largest endothermic peak area is defined as the crystalline melting point (Tm).
  • DSC differential scanning calorimeter
  • the crystal melting point (Tm) of PLA contained in the granular composition of the present invention is preferably in the range of 145 to 185 ° C., more preferably 150 to 180 ° C., and still more preferably 155 to 175 ° C.
  • the crystalline PLA is not limited to this.
  • the glass transition temperature (Tg) of PGA contained in the biodegradable aliphatic polyester resin granular composition of the present invention is usually 25 to 60 ° C., preferably 30 to 55 ° C., more preferably 32 to 52 ° C., Particularly preferred is 35 to 50 ° C.
  • the glass transition temperature (Tg) of PGA can be adjusted by the weight average molecular weight (Mw), the molecular weight distribution, the type and content ratio of the copolymerization component, and the like.
  • the glass transition temperature (Tg) of PGA was determined in a nitrogen atmosphere using a differential scanning calorimeter (DSC), similarly to the measurement of the crystal melting point (Tm).
  • the sample PGA is heated to about 280 ° C., held at this temperature for 2 minutes, and then rapidly cooled with liquid nitrogen (about 100 ° C./min), and then an amorphous sample obtained by differential scanning is used.
  • Secondary transition region corresponding to transition region from glass state to rubber state when reheating from near room temperature to 100 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere using a calorimeter (DSC)
  • DSC calorimeter
  • the intermediate point between the start temperature and the end temperature of the secondary transition of the calorific value in the glass is the glass transition temperature (Tg) (hereinafter sometimes referred to as “intermediate glass transition temperature”).
  • the glass transition temperature (Tg) is too low, the surface and internal crystallinity of the PGA granules may be lowered due to heat generated by the pulverization process described later, and the granules may be easily blocked.
  • the glass transition temperature (Tg) is too high, the decomposability at the time of actual use becomes insufficient, and the required function may not be exhibited.
  • the glass transition temperature (Tg) of PLA contained in the granular composition of the present invention is preferably in the range of 45 to 75 ° C, more preferably 50 to 70 ° C, and still more preferably 55 to 65 ° C.
  • Biodegradable aliphatic polyester resin granules having an average particle size of 0.01 to 1000 ⁇ m The biodegradable aliphatic polyester resin granules forming the biodegradable aliphatic polyester resin granules of the present invention have an average particle size It is a biodegradable aliphatic polyester resin granule having a diameter (50% D) of 0.01 to 1000 ⁇ m.
  • the biodegradable aliphatic polyester resin granule in the present invention is a granule mainly composed of the biodegradable aliphatic polyester resin, preferably a PLA granule or a PGA granule, particularly preferably a PGA granule. Is the body.
  • the biodegradable aliphatic polyester resin which is a main component such as PGA or PLA
  • the biodegradable aliphatic polyester resin granule may further contain other biodegradable materials as long as it does not contradict the purpose of the present invention.
  • polyglycols such as polyethylene glycol and polypropylene glycol
  • other resins such as modified polyvinyl alcohol, polyurethane and polyamides such as poly L-lysine
  • plasticizers antioxidants
  • end-capping agents Additions usually added such as heat stabilizers, light stabilizers, UV absorbers, lubricants, mold release agents, colorants, crystallization accelerators, hydrogen ion concentration regulators, antistatic agents, reinforcing fiber fillers, etc. If necessary, the agent may be blended by melt blending or direct mixing into resin granules.
  • the compounding amount of these additives and the like is usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and 5 parts by mass or less or 1 part by mass or less with respect to 100 parts by mass of PGA.
  • the amount may be fine.
  • the average particle diameter (50% D) of the biodegradable aliphatic polyester resin granules such as PGA granules in the present invention is a granule dispersion obtained by dispersing the biodegradable aliphatic polyester resin granules in ion-exchanged water.
  • the liquid means a value represented by a particle size at which the cumulative mass from the small particle size side becomes 50% using the particle size distribution of the granular material measured and determined using a laser diffraction particle size distribution measuring device. .
  • the average particle diameter (50% D) of the biodegradable aliphatic polyester resin granules in the present invention is preferably 0.1 to 800 ⁇ m, more preferably 1 to 600 ⁇ m, still more preferably 5 to 500 ⁇ m, and particularly preferably 10 to The range is 400 ⁇ m. If the average particle size (50% D) is too small, the handleability and storage stability of the granular material will be poor. If the average particle size (50% D) is too large, for example, when applied to well fluids, the ability to prevent lost mud during well drilling will be insufficient, and the production fluid recovery efficiency will be due to clogging of the screen. It is not preferable because it may cause a decrease in the temperature.
  • the fluidity of the biodegradable aliphatic polyester resin granules such as PGA granules is good, and the handleability and storage stability of the granules are good.
  • excavation work of the well and the subsequent discharge of the well fluid can be performed efficiently.
  • the production method of the biodegradable aliphatic polyester resin granules such as PGA granules in the present invention is not particularly limited as long as the average particle diameter (50% D) is in the range of 0.01 to 1000 ⁇ m.
  • the average particle diameter (50% D) is in the range of 0.01 to 1000 ⁇ m.
  • it was obtained from a polymer having a shape such as powder or flakes collected after the polymerization reaction for producing a biodegradable aliphatic polyester resin such as PGA, preferably by washing and classification as required. It may be a thing.
  • the recovered biodegradable aliphatic polyester resin may be obtained by mechanically pulverizing or pulverizing and classifying as necessary.
  • particles obtained by coagulation or precipitation from an organic solvent solution or dispersion of a biodegradable aliphatic polyester resin or particles of powdered biodegradable aliphatic polyester resin particles may be used.
  • the pulverization method is preferably employed, and the granule obtained by the impact pulverization method can be classified as desired and used as a raw material for the biodegradable aliphatic polyester resin granule composition of the present invention.
  • the biodegradable aliphatic polyester resin granules such as PGA granules are obtained by removing the biodegradable aliphatic polyester resin having a shape such as powder or flakes collected after the polymerization reaction from ⁇ 100 ° C. It can be produced by pulverizing at a temperature in the range of the glass transition temperature (Tg) of the degradable aliphatic polyester resin.
  • Tg glass transition temperature
  • the pulverization temperature varies depending on the type of biodegradable aliphatic polyester resin, but is preferably in the range of ⁇ 50 to 40 ° C., more preferably ⁇ 40 to 35 ° C., and still more preferably ⁇ 35 to 30 ° C.
  • a hydrolyzable resin leads to a decrease in storage stability due to condensation and an increase in pulverization cost.
  • the treatment temperature is too high, the surface of the biodegradable aliphatic polyester resin granules is softened or melted, and the surface properties of the biodegradable aliphatic polyester resin granules are not controlled, and the antiblocking agent described later Even if it adds, there exists a possibility that sufficient antiblocking effect may not be acquired, or a biodegradable aliphatic polyester resin granular material may aggregate depending on the case. Furthermore, adhesion of the resin to the apparatus due to melting may cause a significant reduction in grinding efficiency.
  • the biodegradable aliphatic polyester resin By crushing the biodegradable aliphatic polyester resin, which is a raw material resin, in this temperature range, the biodegradable aliphatic polyester resin is pulverized in a state of low-temperature embrittlement. It is easy to obtain biodegradable aliphatic polyester resin granules such as PGA granules having an average particle diameter (50% D) of 0.01 to 1000 ⁇ m, without causing modification and with controlled fluctuation of crystallization characteristics. Can do.
  • the biodegradable aliphatic polyester resin granules of the present invention may be prepared by classification so that the average particle size (50% D) is 0.01 to 1000 ⁇ m.
  • An apparatus for pulverizing a biodegradable aliphatic polyester resin such as PGA as a raw material resin by an impact pulverization method at a temperature between ⁇ 100 ° C. and the glass transition temperature (Tg) of the biodegradable aliphatic polyester resin is a jet.
  • a mill, a blade mill, a hammer mill, a pin mill, etc. can be used, but an apparatus having both a cooling unit and a pulverizing unit with an ultra-low temperature refrigerant such as liquid nitrogen, and more preferably a particle size adjusting unit is preferable. It is preferable to use a pin mill that can obtain particles having a desired particle size and shape by adjusting the clearance and rotation speed of the disk pin.
  • the time for pulverizing the biodegradable aliphatic polyester resin, which is a raw material resin, from ⁇ 100 ° C. to the glass transition temperature (Tg) of the biodegradable aliphatic polyester resin depends on the treatment temperature at which impact pulverization is performed. However, it is usually in the range of 10 seconds to 20 minutes, preferably 20 seconds to 15 minutes, more preferably 30 seconds to 10 minutes, and particularly preferably 45 seconds to 5 minutes. Moreover, if it is in the said range, you may repeat a grinding
  • an average particle size (50% D) is 0.01 to 1000 ⁇ m. It is particularly limited as long as it is added to the aliphatic polyester resin granules, can adhere to the granules, or can be interposed between the granules, and can exert an anti-blocking effect on the granules.
  • the anti-blocking agent may be an inorganic substance or an organic substance, and may be in the form of granules, powders, granules, flat plates, fibers, needles, etc., or in the form of liquid, fluid or wax.
  • the antiblocking agent a substance that dissolves or decomposes in a liquid carrier such as water or a substance that does not dissolve or decompose in a liquid carrier such as water can be used.
  • a liquid carrier such as water
  • a substance that does not dissolve or decompose in a liquid carrier such as water
  • Inorganic substances include magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony or titanium metal oxides, hydroxides, sulfates, carbonates or silicic acids. Examples thereof include salts and chlorides of metals such as sodium, potassium, magnesium, calcium or zinc.
  • silica gel aluminum oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide, lead oxide, diatomaceous earth, bentonite, zeolite, aluminosilicate, talc, white carbon, mica, Glass fiber, glass powder, glass beads, clay, wollastonite, iron oxide, antimony oxide, titanium oxide, silicon dioxide, lithopone, pumice powder, aluminum sulfate, zirconium silicate, barium carbonate, dolomite, disulfide Examples thereof include inorganic particles containing molybdenum, iron sand, carbon black, graphite, and metal halides such as sodium chloride and potassium chloride.
  • the average particle size of the inorganic particles is determined by the adhesion to the biodegradable aliphatic polyester resin granules, the intervening performance between the granules, and further, for example, the biodegradable fat From the viewpoint of fluidity of the well fluid containing the group polyester resin granular composition, ease of discharge, etc., it is preferably 0.5 to 1000 ⁇ m, more preferably 1 to 800 ⁇ m, and still more preferably 2 to 600 ⁇ m.
  • the method for measuring the average particle size of the inorganic particles is the same as the method for measuring the average particle size of the biodegradable aliphatic polyester resin granules.
  • the antiblocking agent is a metal halide such as sodium chloride or potassium chloride
  • it is not necessarily limited to the above average particle diameter, but is preferably 1000 ⁇ m or less from the viewpoint of an antiblocking effect.
  • the average particle size of the inorganic antiblocking agent with respect to the average particle size of the biodegradable aliphatic polyester resin granules is preferably 0.000625 to 10,000, more preferably 0.00167 to 800, and still more preferably 0.005. A ratio range of ⁇ 60.
  • Organic substances that can be used as anti-blocking agents include polymethyl methacrylate resin, polystyrene resin, nylon resin, melamine resin, benzoguanamine resin, phenol resin, urea resin, silicone resin, acrylate resin, other biodegradable aliphatics
  • Polymer particles such as polyester resin; solid materials such as cellulose powder, nitrocellulose powder, wood powder, waste paper powder, rice husk powder, and starch; hydrocarbon waxes such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and polyethylene wax
  • Fatty acid-based waxes such as stearic acid; fatty acid amide-based waxes such as stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide, oleic acid amide, esylic acid amide; Ester waxes such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids and fatty acid polyglycol esters; alcohol waxe
  • the biodegradable aliphatic polyester resin granule composition of the present invention contains PGA granule as a main component, amorphous or crystalline polylactic acid (PLA) or polyhydroxyalkanoate resin (PHA) , Aliphatic polyesters such as polybutylene succinate resin (PBS), copolymer polyesters of aliphatic esters and aromatic esters such as “Biomax (registered trademark)” manufactured by DuPont, and polyester amides that are copolymers of polyester and polyamide Are preferred.
  • PBS polybutylene succinate resin
  • Biomax registered trademark
  • the biodegradable aliphatic polyester resin granule composition of the present invention contains PLA granule as a main component, polyglycolic acid (PGA), polyhydroxyalkanoate resin (PHA), polybutylene succinate Particles of an aliphatic polyester such as a resin (PBS), a copolymerized polyester of an aliphatic ester and an aromatic ester such as “Biomax (registered trademark)” manufactured by DuPont, and a polyesteramide that is a copolymer of a polyester and a polyamide are preferred.
  • the polymer particles containing these other biodegradable aliphatic polyester resins may be those having a modified surface by increasing the crystallinity of the particle surface or by performing a crosslinking treatment.
  • the average particle size of the particle is determined by the adhesion to the biodegradable aliphatic polyester resin granules and the intervening performance between the granules, for example, the flow of well fluid From the viewpoint of the property and ease of discharge, the thickness is preferably 1 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, still more preferably 10 to 100 ⁇ m.
  • the method for measuring the average particle size of the polymer particles is the same as the method for measuring the average particle size of the biodegradable aliphatic polyester resin granules described above.
  • the average particle size of the organic antiblocking agent with respect to the average particle size of the biodegradable aliphatic polyester resin granules is preferably 0.00125 to 2000, more preferably 0.0083 to 150, and still more preferably 0.025.
  • the average particle size of the antiblocking agent with respect to the average particle size of the biodegradable aliphatic polyester resin granules is preferably 0.00125 to 10,000, more preferably 0.005 to 2000, and particularly preferably 0.025 to 800.
  • the ratio range is preferably 0.00125 to 10,000, more preferably 0.005 to 2000, and particularly preferably 0.025 to 800.
  • Biodegradable Aliphatic Polyester Resin Granule Composition The biodegradable aliphatic polyester resin granule composition of the present invention has the above-mentioned average particle diameter (50% D) of 0.01 to 1000 ⁇ m.
  • the above-mentioned antiblocking agent is added to the polyester resin granules.
  • the antiblocking agent may be substantially uniformly attached to the surface of the biodegradable aliphatic polyester resin granule, or may be partially included or impregnated inside.
  • a thin film may be formed on the surface of the biodegradable aliphatic polyester resin granule, but without entering the inside or the surface of the granule, a plurality of biodegradable aliphatic polyester resin granules are simply formed. It may be interposed between them to prevent aggregation of the granular material. In short, it is only necessary that the surfaces of the biodegradable aliphatic polyester resin granules are prevented from sticking to each other and agglomerating by the presence of the anti-blocking agent, and the biodegradable aliphatic polyester resin granules.
  • the addition amount of the anti-blocking agent is not particularly limited as long as the anti-blocking effect can be exhibited. However, in order to enhance the effect of preventing aggregation and the effect of eliminating aggregation of the biodegradable aliphatic polyester resin granules, The amount is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 14 parts by weight, still more preferably 0.1 to 13 parts by weight, particularly preferably 100 parts by weight of the degradable aliphatic polyester resin granules.
  • the addition amount of the antiblocking agent is extremely small, the effect of preventing aggregation and the effect of eliminating aggregation of the biodegradable aliphatic polyester resin granules cannot be obtained sufficiently. If the amount of the antiblocking agent added is too large, various adverse effects due to the remaining antiblocking agent may occur. For example, the resulting biodegradable aliphatic polyester resin granular composition is dispersed in a liquid carrier. There is a risk that the fluidity of the well fluid will be insufficient, and that the excavation dispersion liquid will be discharged and discarded at the end of excavation work simply and inexpensively.
  • the biodegradable aliphatic polyester resin granular composition of the present invention is obtained by adding 100 gf / cm 2 of the granular composition at a glass transition temperature (Tg) of the biodegradable aliphatic polyester resin ⁇ 5 ° C. or higher.
  • Tg glass transition temperature
  • F1 vertical fracture stress
  • the vertical fracture stress (F1) is more preferably 950 gf / cm 2 or less, more preferably 900 gf, in order to further enhance the effect of preventing aggregation and the effect of eliminating aggregation of the biodegradable aliphatic polyester resin granules. / Cm 2 or less, particularly preferably 850 gf / cm 2 or less.
  • F1 exceeds 1000 gf / cm 2 , the anti-blocking effect by the anti-blocking agent during storage or transfer of the biodegradable aliphatic polyester resin granule composition is not sufficient, and the biodegradable aliphatic polyester resin granule Occurrence of blocking cannot be suppressed, and the aggregated state may not be resolved.
  • the lower limit of the vertical fracture stress (F1) is not particularly limited, as viewed from the amount in the range of anti-blocking agent, is usually 30 gf / cm 2, it may be about 50gf / cm 2, 100gf / cm 2 of about It may be a thing.
  • the biodegradable aliphatic polyester resin granular composition of the present invention is a columnar tablet formed by molding the above-mentioned vertical fracture stress (F1) and the above-mentioned granular material to which no antiblocking agent is added, under the above molding conditions.
  • the vertical fracture stress (F0) satisfies the formula) F1 / F0 ⁇ 0.95, that is, when F1 / F0 is 0.95 or less, the effect of preventing aggregation of the biodegradable aliphatic polyester resin granules, This is preferable because the effect of eliminating aggregation is further increased.
  • F1 / F0 is more preferably 0.9 or less, still more preferably 0.8 or less, and particularly preferably 0.6 or less.
  • F1 / F0 exceeds 0.95, the anti-blocking effect of the granular material due to the anti-blocking agent during storage or transfer of the biodegradable polyester resin granular composition is not sufficient, and the occurrence of blocking cannot be suppressed, In addition, the aggregation state may not be resolved.
  • the lower limit value of F1 / F0 is not particularly limited, but is usually 0.01 and may be about 0.05.
  • the anti-blocking effect is particularly high. This is preferable.
  • the vertical breaking stress of the biodegradable aliphatic polyester resin granule composition or the biodegradable aliphatic polyester resin granule is 1 cm in cross-sectional area prepared from the sample of the biodegradable aliphatic polyester resin granule composition or granule.
  • the predetermined temperature of the glass transition temperature (Tg) ⁇ 5 ° C. or higher is preferably a specific temperature within the range of Tg ⁇ 4 ° C. or higher, more preferably Tg ⁇ 3 ° C. or higher, and further preferably Tg ⁇ 2 ° C. or higher.
  • the temperature is usually set within a range of 120 ° C. or lower, preferably 110 ° C. or lower, more preferably 100 ° C. or lower.
  • the biodegradable aliphatic polyester resin granule composition of the present invention contains, for example, water, a liquid carrier selected from organic solvents such as ethylene glycol and propylene glycol, a dispersant, a surfactant, a viscosity modifier, an increase agent. It can be dispersed with additives such as a sticking agent and used as a well fluid.
  • Well fluids are drilling wells that extract oil, natural gas, hot springs, etc.
  • a bit attached to the tip of the drill rotates and breaks the rocks in the formation while digging the wells. When carrying out, it is used for the purpose of reducing friction between the drill and the mine wall, cooling the bit, carrying out crushed rocks, etc., and preventing collapse of the mine wall formed by excavation.
  • the biodegradable aliphatic polyester resin granule composition of the present invention contains a biodegradable aliphatic polyester resin such as PGA that is biodegradable, which facilitates disposal, and in some cases, a special disposal operation. Is no longer necessary. Moreover, disposal can be facilitated by hydrolyzing the biodegradable aliphatic polyester resin using an acidic compound or an alkaline compound.
  • the method for producing the biodegradable aliphatic polyester resin granule composition of the present invention is such that the average particle diameter (50% D) is 0.01 to 1000 ⁇ m.
  • the said antiblocking agent can be added with respect to a certain biodegradable aliphatic polyester resin granule and a biodegradable aliphatic polyester resin granule composition can be obtained, it is not limited, but average particle diameter (50 % D) 0.01 to 1000 ⁇ m of biodegradable aliphatic polyester resin granules, an antiblocking agent is added, and the glass transition temperature (Tg) -5 of the biodegradable aliphatic polyester resin is 0 ° C. or higher. It can be easily produced by stirring and mixing at a temperature in the range of 0 ° C. or lower for 5 minutes to 2 hours.
  • the temperature at which stirring and mixing are performed is more preferably in the range of 3 ° C. or more and Tg ⁇ 8 ° C. or less, more preferably 5 ° C. or more and Tg ⁇ 10 ° C. or less. If the temperature for stirring and mixing is too low, the antiblocking agent may not adhere sufficiently to the surface of the biodegradable aliphatic polyester resin granules, or may not be effectively interposed between the biodegradable aliphatic polyester resin granules. There is a risk. If the temperature at which stirring and mixing are performed is too high, aggregation (blocking) of the biodegradable aliphatic polyester resin particles may occur due to heat generated by stirring and mixing, or once generated aggregation may not be easily resolved. There is a risk.
  • the time for stirring and mixing depends on the predetermined temperature at which stirring and mixing are performed, but is usually 5 minutes to 2 hours, preferably 10 minutes to 1 hour 30 minutes, more preferably 15 minutes to 1 hour, and still more preferably 20 minutes. ⁇ 50 minutes. If the time for stirring and mixing is too short, the anti-blocking agent may not be sufficiently dispersed, and the anti-blocking effect of the biodegradable aliphatic polyester resin granules may not be obtained. If the time for stirring and mixing is too long, each component is unevenly distributed due to density difference and particle size distribution difference between the anti-blocking agent and the biodegradable polyester resin granular material, resulting in non-uniformity, and the expected anti-blocking effect It may not be obtained.
  • the atmosphere for stirring and mixing is not particularly limited, and may be performed in dry air at normal pressure, but may be performed in an inert gas atmosphere such as nitrogen gas or helium gas, and may be slightly used for degassing. It may be a reduced pressure environment. However, if stirring and mixing is performed in a humid atmosphere, the biodegradable aliphatic polyester resin granules may be aggregated (blocking) or the aggregate once generated may not be easily eliminated. It is preferable to perform in an atmosphere of preferably 80% or less, more preferably 65% or less, and still more preferably 50% or less.
  • the apparatus used for stirring and mixing is not particularly limited as long as it can mix the biodegradable aliphatic polyester resin granules and the antiblocking agent, and a normal powder mixing apparatus, Although a kneading device such as a Henschel mixer can be used, the device that gives excessive shearing force causes aggregation (blocking) of the biodegradable aliphatic polyester resin granules, and once generated aggregation easily resolves. This is not preferable because it may disappear.
  • the measuring method of the physical property or characteristic of the biodegradable aliphatic polyester resin granular material in an Example and a comparative example is as follows.
  • the weight average molecular weight (Mw) of the biodegradable aliphatic polyester resin was 10 ml by dissolving 10 mg of the sample in hexafluoroisopropanol (HFIP) in which sodium trifluoroacetate was dissolved at a concentration of 5 mM, and then the membrane filter. To obtain a sample solution, 10 ⁇ l of this sample solution was injected into a gel permeation chromatography (GPC) apparatus, and the molecular weight was measured under the following measurement conditions.
  • HFIP hexafluoroisopropanol
  • Glass transition temperature (Tg) A 10 mg sample of a biodegradable aliphatic polyester resin was heated to about 280 ° C. using a differential scanning calorimeter (DSC; TC-15 manufactured by METTLER TOLEDO), held at this temperature for 2 minutes, and then liquid nitrogen. The intermediate point when an amorphous sample obtained by rapid cooling (approximately 100 ° C./min) by reheating from a temperature near room temperature to 100 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere. The glass transition temperature was defined as the glass transition temperature (Tg).
  • Average particle size (50% D) The average particle size (50% D) was determined by using a laser diffraction particle size distribution measuring apparatus (SALAD-3000S manufactured by Shimadzu Corporation) for a granular dispersion in which biodegradable aliphatic polyester resin granules were dispersed in ion-exchanged water. ) was used as the average particle size (50% D). The particle size at which the cumulative mass from the small particle size side was 50% was determined from the particle size distribution obtained using
  • the vertical fracture stress was determined by using a cylindrical tablet with a cross-sectional area of 1 cm 2 prepared from a biodegradable aliphatic polyester resin granular composition or a granular sample at a speed of 1 mm / min using STA-1150 manufactured by ORIENTEC.
  • the sample passes through the mesh of the sieve and can be taken out as a granular material.
  • C When the above sieve is manually sieved for about 1 minute, it is observed that agglomerates of granular materials are partially present on the upper surface of the sieve. Aggregates remain.
  • the contents were transferred to an apparatus equipped with a metal (SUS304) tube having an inner diameter of 28 mm.
  • a heat medium oil at 170 ° C. was circulated through the main body and held for 7 hours to obtain a PGA lump.
  • This lump was pulverized by a pulverizer.
  • the obtained PGA pulverized product was put into a dryer in which dry air was blown, and dried at a temperature of 120 ° C. for 12 hours.
  • the obtained PGA dry pulverized product was melt-extruded using a twin-screw extruder (“TEM-41SS” manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 200 to 270 ° C. and a die temperature of 230 ° C. to have a diameter of about 2.8 mm.
  • PGA pellets were obtained.
  • the PGA pellets were put in a dryer in which dry nitrogen was blown, and heat treated at 170 ° C. for 17 hours to obtain PGA pellets A.
  • the weight average molecular weight was 180,000, and the glass transition temperature (Tg) was 40 ° C.
  • N, N-2,6-diisopropylphenylcarbodiimide (trade name “DIPC”) is 0.3 mass% with respect to PGLLA, and mono and distearyl acid to the obtained PGLLA dry pulverized product.
  • PGLLA pellet C was obtained in the same manner as in Preparation Example 1 except that an approximately equimolar mixture of phosphate (“ADK STAB AX-71”) was added in an amount of 300 ppm with respect to PGLLA.
  • the weight average molecular weight was 231,000, and the glass transition temperature (Tg) was 42 ° C.
  • Preparation Example 4 Production of PGLLA pellet D As in Preparation Example 3, except that 375 kg of glycolide, 125 kg of L-lactide and 1700 g of n-dodecyl alcohol were added to a sealable SUS container. PGLLA pellet D was obtained. The weight average molecular weight was 255,000, and the glass transition temperature (Tg) was 44 ° C.
  • Preparation Example 5 Production of PGLLA pellet E As in Preparation Example 3, except that 260 kg of glycolide and 240 kg of L-lactide and 1700 g of n-dodecyl alcohol were added to a sealable SUS container. PGLLA pellet E was obtained. The weight average molecular weight was 246,000, and the glass transition temperature (Tg) was 45 ° C.
  • Example 1 [Production of Biodegradable Aliphatic Polyester Resin Granule Composition]
  • the PGA pellet A prepared in Preparation Example 1 was cooled with liquid nitrogen using a pin mill capable of cooling with liquid nitrogen at the time of pulverization (“Ultrafine pulverized pin mill: Contraplex series”), the pulverization temperature After pulverization (cooling pulverization) for 2 minutes under conditions of 7.5 ° C. and a peripheral speed of 187 m / sec, the mixture was passed through a sieve having an aperture of 106 ⁇ m (150 mesh), and PGA granules passed through the sieve under the sieve were collected.
  • the average particle diameter (50% D) of the recovered PGA granules was 49 ⁇ m.
  • Example 2 Except that PGA pellet B prepared in Preparation Example 2 was used in place of PGA pellet A, cooling and pulverization were performed in the same manner as in Example 1 to obtain granules having an average particle size (50% D) of 78 ⁇ m. It was collected. Using 100 parts by mass of the obtained PGA granular material, a granular material composition was obtained in the same manner as in Example 1. The obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 1 except that the tablet molding temperature was 70 ° C. Table 1 shows the composition and characteristics of the granular composition.
  • Example 3 Except that the PGLLA pellet C prepared in Preparation Example 3 was used in place of the PGA pellet A, cooling pulverization was carried out in the same manner as in Example 1 to obtain granules having an average particle diameter (50% D) of 89 ⁇ m. It was collected. Using 100 parts by mass of the obtained PGLLA granular material, a granular material composition was obtained in the same manner as in Example 1. The obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 1 except that the tablet molding temperature was 80 ° C. Table 1 shows the composition and characteristics of the granular composition.
  • Example 4 Except that the PGLLA pellet D prepared in Preparation Example 4 was used instead of the PGA pellet A, cooling pulverization was performed in the same manner as in Example 1 to obtain a granule having an average particle size (50% D) of 102 ⁇ m. It was collected. Using 100 parts by mass of the obtained PGLLA granular material, a granular material composition was obtained in the same manner as in Example 1. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 5 Using PGLLA pellet E prepared in Preparation Example 5 instead of PGA pellet A, cooling and pulverizing, and cooling and pulverizing in the same manner as Example 1 except that it was passed through a sieve having an opening of 150 ⁇ m (100 mesh). Granules having an average particle diameter (50% D) of 131 ⁇ m were recovered. Using 100 parts by mass of the obtained PGLLA granular material, a granular material composition was obtained in the same manner as in Example 1. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 6 Except that the PGLLA pellet F prepared in Preparation Example 6 was used in place of the PGA pellet A, cooling pulverization was performed in the same manner as in Example 1 to obtain a granule having an average particle size (50% D) of 94 ⁇ m. It was collected. Using 100 parts by mass of the obtained PGLLA granular material, a granular material composition was obtained in the same manner as in Example 1. The obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 1 except that the tablet molding temperature was 45 ° C. Table 1 shows the composition and characteristics of the granular composition.
  • Example 2 In the same manner as in Example 2, a PGA granule was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle size (50% D) of 5 ⁇ m, the obtained granular material was subjected to a vertical fracture stress test (tablet molding temperature of 70 ° C.) in the same manner as in Example 2. And the simple handling property evaluation test was done. Table 1 shows the characteristics of the granular material.
  • Example 3 In the same manner as in Example 3, a PGLLA granular material was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle diameter (50% D) of 5 ⁇ m, the obtained granular material was subjected to a vertical fracture stress test (tablet molding temperature of 80 ° C.) in the same manner as in Example 3. And the simple handling property evaluation test was done. Table 1 shows the characteristics of the granular material.
  • Example 5 In the same manner as in Example 5, a PGLLA granular material was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle size (50% D) of 5 ⁇ m, the obtained granular material was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) in the same manner as in Example 5. And the simple handling property evaluation test was done. Table 1 shows the characteristics of the granular material.
  • Example 6 In the same manner as in Example 6, a PGLLA granular material was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle diameter (50% D) of 5 ⁇ m, the obtained granular material was subjected to a vertical fracture stress test (tablet molding temperature of 45 ° C.) in the same manner as in Example 6. And the simple handling property evaluation test was done. Table 1 shows the characteristics of the granular material.
  • Example 7 In the same manner as in Example 2, a PGA granule was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle diameter (50% D) of 5 ⁇ m, the obtained granular material was the same as in Example 2 except that the tablet molding temperature was 40 ° C. A vertical fracture stress test and a simple handling property evaluation test were conducted. Table 1 shows the characteristics of the granular material.
  • Example 7 Instead of 5 parts by mass of CaCO 3 having an average particle diameter (50% D) of 5 ⁇ m, 5 parts by mass of talc (MICRO ACE P-6 manufactured by Nippon Talc Co., Ltd.) having an average particle diameter (50% D) of 4 ⁇ m Except having used, it carried out similarly to Example 2, and obtained the granular material composition.
  • the obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 2 except that the tablet molding temperature was changed to 40 ° C. Table 1 shows the composition and characteristics of the granular composition.
  • Example 8 instead of 5 parts by mass of talc having an average particle size (50% D) of 4 ⁇ m, in the same manner as in Example 7, except that 5 parts by mass of potassium chloride (Kanto Chemical Co., Ltd. reagent grade) was used. A granular composition was obtained. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 9 Instead of 5 parts by mass of talc having an average particle diameter (50% D) of 4 ⁇ m, 5 parts by mass of graphite (SP-270 manufactured by Nippon Graphite Co., Ltd.) having an average particle diameter (50% D) of 3 ⁇ m was used. Except for, a granular composition was obtained in the same manner as in Example 7. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 10 Instead of 5 parts by mass of talc having an average particle diameter (50% D) of 4 ⁇ m, 5 parts by mass of graphite (SP-10 manufactured by Nippon Graphite Co., Ltd.) having an average particle diameter (50% D) of 12 ⁇ m was used. Except for, a granular composition was obtained in the same manner as in Example 7. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 11 Instead of using 5 parts by mass of talc having an average particle size (50% D) of 4 ⁇ m, 5 parts by mass of bentonite (Telgel manufactured by Ternite Co., Ltd.) having an average particle size (50% D) of 4 ⁇ m was used. In the same manner as in Example 7, a granular composition was obtained. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 12 Instead of 5 parts by mass of talc having an average particle diameter (50% D) of 4 ⁇ m, 5 parts by mass of SiO 2 (EGB731) having an average particle diameter (50% D) of 24.3 ⁇ m is used. Except that, a granular composition was obtained in the same manner as in Example 7. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 13 Instead of 5 parts by mass of talc having an average particle size (50% D) of 4 ⁇ m, 5 parts by mass of SiO 2 (Potters Barotini Co., Ltd. GB153T) having an average particle size (50% D) of 545 ⁇ m was used. Except for, a granular composition was obtained in the same manner as in Example 7. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • Example 14 Instead of 5 parts by mass of talc having an average particle diameter (50% D) of 4 ⁇ m, 10 parts by mass of PLLA (Ingeo (registered trademark) 7000D manufactured by Nature Works) having an average particle diameter (50% D) of 86 ⁇ m was used. Except having used, it carried out similarly to Example 7, and obtained the granular material composition. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • PLLA Ingeo (registered trademark) 7000D manufactured by Nature Works
  • Example 15 Instead of 5 parts by mass of talc having an average particle size (50% D) of 4 ⁇ m, a polyhydroxyalkanoate resin having an average particle size (50% D) of 59 ⁇ m (Mirel (registered trademark) P4001 manufactured by Telles) 10 Except having used the mass part, it carried out similarly to Example 7, and obtained the granular material composition.
  • the obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test. Table 1 shows the composition and characteristics of the granular composition.
  • the granule compositions of Examples 1 to 15 in which various antiblocking agents were added to PGA granules or PGLLA granules having an average particle size (50% D) of 49 to 131 ⁇ m The result of the simple handling property evaluation test was SB evaluation, and the handleability was good. Further, the granular compositions of Examples 1 to 15 having good handleability were molded at a temperature of 40 to 80 ° C. included in the temperature range of the glass transition temperature (Tg) of the PGA or PGLLA of ⁇ 5 ° C. or higher.
  • vertical fracture stress of cylindrical tablets (F1) is a 67 ⁇ 870gf / cm 2, it was found that shows the 1000 gf / cm 2 or less a small value.
  • the granule compositions of Examples 1 to 15 have the above-mentioned vertical fracture stress (F1) and the formula of the vertical fracture stress (F0) of a cylindrical tablet formed from a granule to which no antiblocking agent is added) F1 It was found that / F0 is 0.05 to 0.62, and shows a small value of 0.95 or less.
  • the granular compositions of Examples 9 to 13 have a very low vertical fracture stress (F1) of about 100 gf / cm 2 and the above formula) F1 / F0 of 0.1 or less. Therefore, the result of the simple handling property evaluation test was S evaluation, and the handleability was very good. Therefore, the granular compositions of Examples 1 to 15 do not contain blocked granular bodies, or even if blocking occurs once, the blocked state is very easily broken and has excellent particle characteristics. It turns out that it is obtained.
  • Example 16 A granular composition was prepared in the same manner as in Example 2 except that 0.5 part by mass of CaCO 3 was used instead of 5 parts by mass of CaCO 3 having an average particle size (50% D) of 5 ⁇ m. Obtained. The obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 2 except that the tablet molding temperature was 40 ° C. Table 2 shows the composition and characteristics of the granular composition.
  • Example 17 A granular composition was prepared in the same manner as in Example 16 except that 1 part by mass of CaCO 3 was used instead of 0.5 part by mass of CaCO 3 having an average particle size (50% D) of 5 ⁇ m. Obtained. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test in the same manner as in Example 16. Table 2 shows the composition and characteristics of the granular composition.
  • Example 18 A granular composition was prepared in the same manner as in Example 16 except that 10 parts by mass of CaCO 3 was used instead of 0.5 parts by mass of CaCO 3 having an average particle diameter (50% D) of 5 ⁇ m. Obtained. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test in the same manner as in Example 16. Table 2 shows the composition and characteristics of the granular composition.
  • Example 19 After cooling and pulverizing the PGA pellet B prepared in Preparation Example 2 in the same manner as in Example 2, it was passed through a sieve having an opening of 106 ⁇ m (150 mesh), and the granular material that passed through the sieve under the sieve was collected. Classification was carried out through a sieve having an opening of 20 ⁇ m (500 mesh), and PGA granules having an average particle diameter (50% D) of 10 ⁇ m were recovered. Next, a granular material composition was obtained in the same manner as in Example 2 with respect to 100 parts by mass of the obtained PGA granular material. The obtained granular composition was subjected to a vertical fracture stress test and a simple handling property evaluation test in the same manner as in Example 2 except that the tablet molding temperature was 40 ° C. Table 2 shows the composition and characteristics of the granular composition.
  • Example 20 The PGA pellet B prepared in Preparation Example 2 is put into a hammer mill (“POLYMIX, PX-MFC90D” manufactured by KINEMATIC AG) together with twice the amount of dry ice, and the pulverization temperature is 5 ° C. and the rotational speed is 6000 rpm for 1 minute. After pulverization, the sieve was passed through a sieve having an opening of 350 ⁇ m (40 mesh), and the granular material that passed through the sieve under the sieve was recovered. The average particle size (50% D) of the recovered PGA granules was 350 ⁇ m. A granule composition was obtained in the same manner as in Example 2 with respect to 100 parts by mass of the obtained PGA granule. The obtained granular composition was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) and a simple handling property evaluation test in the same manner as in Example 19. Table 2 shows the composition and characteristics of the granular composition.
  • Example 8 In the same manner as in Example 19, a PGA granule was obtained. Without adding 5 parts by mass of CaCO 3 having an average particle size (50% D) of 5 ⁇ m, the obtained granular material was subjected to a vertical fracture stress test (tablet molding temperature 40 ° C.) in the same manner as in Example 19. And the simple handling property evaluation test was done. Table 2 shows the characteristics of the granules.
  • the PGA granule compositions of Examples 16 to 20 in which an antiblocking agent was added to the PGA granule having an average particle size (50% D) of 10 to 350 ⁇ m were subjected to a simple handling property evaluation test. The result was A or B evaluation, and the handleability was good.
  • the granular compositions of Examples 16 to 20 having good handleability are cylindrical tablet tablets molded at a temperature of 40 ° C. included in the glass transition temperature (Tg) ⁇ 5 ° C. or more of the PGA.
  • vertical fracture stress (F1) is a 360 ⁇ 947gf / cm 2, it was indicative of 1000 gf / cm 2 or less a small value.
  • the granular compositions of Examples 16 to 20 have a formula (F1 and F0) F1 / F0 of 0.35 to 0.68 and a small value of 0.95 or less. I understood that. From this, the granule compositions of Examples 16 to 20 do not contain a blocked granule, or have excellent particle characteristics that the blocking state is extremely easily broken even if blocking once occurs. It was found to be a body composition.
  • a biodegradable aliphatic polyester resin granule composition obtained by adding an antiblocking agent to biodegradable aliphatic polyester resin granules having an average particle size of 0.01 to 1000 ⁇ m.
  • an antiblocking agent is added to the biodegradable aliphatic polyester resin granules having an average particle size (50% D) of 0.01 to 1000 ⁇ m, and the biodegradability is 0 ° C. or higher.
  • Tg glass transition temperature

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une composition de particules de résine polyester aliphatique biodégradable constituée, de préférence, par adjonction d'un agent anti-bloquant à des particules de résine polyester aliphatique biodégradable dont le diamètre moyen est de 0,01 à 1000µm. De préférence, la tension de rupture verticale (F1) d'une pastille de forme cylindrique dans laquelle ladite composition de particules est formée sous des conditions de formation telles qu'une charge de 100gf/cm2 constitue une charge pour 24 heures à une température comprise dans une plage supérieure ou égale à la température de transition vitreuse de ladite résine -5°C, est inférieure ou égale à 1000gf/cm2; et/ou la tension de rupture verticale (F0) de la pastille de forme cylindrique dans laquelle lesdites particules sont formées sous lesdites conditions, est telle que F1/F0≦0,95. En outre, l'invention concerne le procédé de fabrication de ladite composition de particules.
PCT/JP2012/055842 2011-03-08 2012-03-07 Composition de particules de résine polyester aliphatique biodégradable, et procédé de fabrication de celle-ci Ceased WO2012121296A1 (fr)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2014109347A1 (fr) * 2013-01-11 2014-07-17 株式会社クレハ Article solidifié et moulé par extrusion d'acide poly-l-lactique, son procédé de production et ses applications d'utilisation
JP2018009107A (ja) * 2016-07-14 2018-01-18 株式会社カネカ 脂肪族ポリエステル樹脂組成物の製造方法
EP3315553A4 (fr) * 2015-06-29 2019-03-06 Toray Industries, Inc. Mélange de poudre de résine de polyester
JP2019530791A (ja) * 2016-09-08 2019-10-24 シェーファー・カーク・ゲーエムベーハー・ウント・コンパニー・カーゲーＳｃｈａｅｆｅｒ Ｋａｌｋ Ｇｍｂｈ ＆ Ｃｏ． Ｋｇ 微細構造粒子を有するカルシウム塩含有複合粉末
US11441008B2 (en) 2016-09-08 2022-09-13 Schaefer Kalk Gmbh & Co. Kg Composite powder containing calcium carbonate and having microstructured particles
CN115298243A (zh) * 2020-04-06 2022-11-04 帝人株式会社 脂肪族聚酯的制造方法、脂肪族聚酯树脂和脂肪族聚酯树脂组合物
US11548998B2 (en) 2016-09-08 2023-01-10 Schaefer Kalk Gmbh & Co. Kg Inhibiting calcium carbonate additive
US11760874B2 (en) 2016-09-08 2023-09-19 Schaefer Kalk Gmbh & Co. Kg Composite powder containing calcium carbonate and having microstructured particles having inhibiting calcium carbonate

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JPS63186776A (ja) * 1987-01-28 1988-08-02 Nippon Paint Co Ltd 粉体塗料の製造方法
JP2007197602A (ja) * 2006-01-27 2007-08-09 Asahi Kasei Chemicals Corp 生分解性樹脂粉体及びその製造方法
JP2009263663A (ja) * 2008-03-31 2009-11-12 Sanyo Chem Ind Ltd ガラスチョップドストランドマット用バインダー

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JPS5038123B2 (fr) * 1972-06-01 1975-12-08
JPS63186776A (ja) * 1987-01-28 1988-08-02 Nippon Paint Co Ltd 粉体塗料の製造方法
JP2007197602A (ja) * 2006-01-27 2007-08-09 Asahi Kasei Chemicals Corp 生分解性樹脂粉体及びその製造方法
JP2009263663A (ja) * 2008-03-31 2009-11-12 Sanyo Chem Ind Ltd ガラスチョップドストランドマット用バインダー

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014109347A1 (fr) * 2013-01-11 2014-07-17 株式会社クレハ Article solidifié et moulé par extrusion d'acide poly-l-lactique, son procédé de production et ses applications d'utilisation
JPWO2014109347A1 (ja) * 2013-01-11 2017-01-19 株式会社クレハ ポリ−ｌ−乳酸固化押出成形物及びその製造方法並びにその応用
US10072476B2 (en) 2013-01-11 2018-09-11 Kureha Corporation Poly-L-lactic acid solid-state extrusion molded article, method for producing the same, and use applications of the same
EP3315553A4 (fr) * 2015-06-29 2019-03-06 Toray Industries, Inc. Mélange de poudre de résine de polyester
JP2018009107A (ja) * 2016-07-14 2018-01-18 株式会社カネカ 脂肪族ポリエステル樹脂組成物の製造方法
JP2019530791A (ja) * 2016-09-08 2019-10-24 シェーファー・カーク・ゲーエムベーハー・ウント・コンパニー・カーゲーＳｃｈａｅｆｅｒ Ｋａｌｋ Ｇｍｂｈ ＆ Ｃｏ． Ｋｇ 微細構造粒子を有するカルシウム塩含有複合粉末
US11352491B2 (en) 2016-09-08 2022-06-07 Schaefer Kalk Gmbh & Co. Kg Calcium-salt-containing composite powder having microstructured particles
US11441008B2 (en) 2016-09-08 2022-09-13 Schaefer Kalk Gmbh & Co. Kg Composite powder containing calcium carbonate and having microstructured particles
US11548998B2 (en) 2016-09-08 2023-01-10 Schaefer Kalk Gmbh & Co. Kg Inhibiting calcium carbonate additive
US11760874B2 (en) 2016-09-08 2023-09-19 Schaefer Kalk Gmbh & Co. Kg Composite powder containing calcium carbonate and having microstructured particles having inhibiting calcium carbonate
CN115298243A (zh) * 2020-04-06 2022-11-04 帝人株式会社 脂肪族聚酯的制造方法、脂肪族聚酯树脂和脂肪族聚酯树脂组合物
CN115298243B (zh) * 2020-04-06 2023-12-12 帝人株式会社 脂肪族聚酯的制造方法、脂肪族聚酯树脂和脂肪族聚酯树脂组合物

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