Classifications

• • 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
  • C08L1/08—Cellulose derivatives
  • C08L1/10—Esters of organic acids, i.e. acylates
• • 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
  • C08L1/08—Cellulose derivatives
  • C08L1/10—Esters of organic acids, i.e. acylates
  • C08L1/12—Cellulose acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to thermoplastic resin compositions.
• the present invention relates to thermoplastic resin compositions containing cellulose esters.
• cellulose esters have poor thermal meltability due to hydrogen bonding caused by hydroxyl groups remaining in the molecular chain.
• the lower the degree of cellulose ester substitution the higher the melting temperature tends to be.
• the degree of substitution of the cellulose ester is increased, the crystallinity of the cellulose ester increases, so that the solubility and meltability tend to decrease.
• plasticizers were added to cellulose esters to lower their melting temperatures to improve processability. There was a problem with processability into films and sheets.
• cellulose esters such as cellulose acetate are biodegradable and are known to be decomposed by activated sludge.
• biodegradable molded articles have been desired in various technical fields.
• Patent Document 1 describes at least one biodegradable resin selected from polylactic acid, cellulose acetate, polyvinyl alcohol, polycaprolactone, polybutylene succinate and polyethylene succinate, and a A biodegradable coating is disclosed which is characterized by containing an edible coloring agent.
• JP-A-2003-276094 Patent Document 2 describes polyvinyl alcohol and/or starch, polyethylene glycol, carboxymethyl cellulose, polyethylene succinate, polybutylene succinate, polybutylene succinate/adipate, polycaprolactone, acetic acid, A foam-molded product obtained by kneading and foam-molding an aqueous solution of a binder mixed with at least one component selected from cellulose and polylactic acid and a fibrous substance is disclosed.
• the biodegradable coating disclosed in Patent Document 1 is intended for use as ink, paint, etc., and cannot be applied to molded articles such as films.
• the molded body disclosed in Patent Document 2 is a porous body obtained by mixing a binder composed of a biodegradable polymer and a fibrous substance, and is not a technique applicable to molded articles such as films by melt molding.
• An object of the present disclosure is to provide a thermoplastic resin composition that is excellent in biodegradability and capable of obtaining melt-molded articles having good elongation.
• the thermoplastic resin composition of the present disclosure contains cellulose ester, polyester and plasticizer.
• the number average molecular weight of the plasticizer is 1000 or less.
• the amount of polyester is 120 parts by weight or less per 100 parts by weight of cellulose ester.
• the amount of plasticizer is less than 100 parts by weight per 100 parts by weight of cellulose ester.
• the total degree of substitution of the cellulose ester is preferably 2.1 or more and 2.6 or less.
• both the degree of substitution at the 2-position and the degree of substitution at the 3-position of the cellulose ester are greater than the degree of substitution at the 6-position.
• the plasticizer is one or more selected from citric acid esters, glycerin esters, adipate esters and polyethylene glycol esters.
• the polyester has, as a repeating structure, a structural unit obtained by dehydration condensation of a dicarboxylic acid and a diol.
• the proportion of structural units containing an aromatic ring may be 50% or less of all structural units.
• the dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid and terephthalic acid.
• the diol is selected from the group consisting of ethylene glycol, propylene glycol and butylene glycol.
• the polyester is selected from the group consisting of polybutylene succinate (PBS), poly(butylene succinate-co-butylene adipate) (PBSA) and polybutylene adipate terephthalate (PBAT).
• PBS polybutylene succinate
• PBSA poly(butylene succinate-co-butylene adipate)
• PBAT polybutylene adipate terephthalate
• the cellulose ester may be cellulose acetate.
• thermoplastic resin composition of the present disclosure a molded article having excellent biodegradability and good elongation can be obtained by melt molding.
• the thermoplastic resin composition of the present disclosure can be suitably used as a material for melt-molded products, injection-molded products, particularly thin-film-thick molded products such as films and sheets.
• X to Y indicating the range means “X or more and Y or less”. Also, unless otherwise noted, all test temperatures are room temperature (20°C ⁇ 5°C).
• thermoplastic resin composition includes a cellulose ester, a polyester, and a plasticizer.
• the number average molecular weight of the plasticizer is 1000 or less.
• the amount of polyester is no more than 120 parts by weight per 100 parts by weight of cellulose ester.
• the amount of plasticizer is less than 100 parts by weight per 100 parts by weight of cellulose ester.
• thermoplastic resin composition can be melt-molded in a relatively low temperature range by containing the plasticizer in the amount described above.
• the above-described amount of polyester imparts good extensibility to the molded article obtained.
• cellulose esters and polyesters have good biodegradability.
• a plasticizer having a number average molecular weight of 1000 or less does not inhibit the biodegradability of cellulose esters and polyesters.
• molded articles having excellent biodegradability and good elongation can be obtained. By melt-molding this resin composition as a material, a thin film, sheet, or the like can be obtained.
• Cellulose ester has an acyl group as a substituent.
• acyl groups include acetyl group, propionyl group, butyryl group, carboxyl group, carboxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, methyl group and the like.
• the substituent of the cellulose ester is preferably an acetyl group, a propionyl group, or a butyryl group, and more preferably an acetyl group.
• a cellulose ester may have two or more acyl groups.
• the cellulose ester may contain substituents other than acyl groups as long as the effects of the present disclosure are not impaired.
• cellulose esters contained in the thermoplastic resin composition of the present disclosure include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and the like.
• Cellulose acetate is preferred because a molded product having excellent strength can be obtained.
• the total substitution degree of cellulose ester is preferably 2.6 or less, more preferably 2.5 or less, more preferably 2.4 or less, and particularly preferably 2.3 or less.
• the total substitution degree of cellulose ester is preferably 1.9 or more, more preferably 2.0 or more, and particularly preferably 2.1 or more.
• a cellulose ester having a total degree of substitution of 1.9 or more and 2.6 or less is preferred.
• the total degree of substitution of the cellulose ester may be 1.9-2.5, 1.9-2.4, 1.9-2.3, 2.0-2. 6, may be from 2.0 to 2.5, may be from 2.0 to 2.4, may be from 2.0 to 2.3, may be from 2.1 to 2.6 may be from 2.1 to 2.5, may be from 2.1 to 2.4, or may be from 2.1 to 2.3.
• the degree of substitution at the 2-, 3-, and 6-positions of the cellulose ester contained in the resin composition of the present disclosure is not particularly limited, but from the viewpoint of improving biodegradability, the degree of substitution at the 2-position and the degree of Cellulose esters with a degree of substitution greater than the 6-position are preferred.
• the degree of substitution at the 2-, 3-, and 6-positions is the average number of substituents that substitute the hydrogen atoms of the hydroxyl groups at the 2-, 3-, and 6-positions of the cellulose repeating unit (glucopyranose unit). means.
• the 6-position substitution degree of this cellulose ester is preferably 0.8 or less, more preferably 0.75 or less, and even more preferably 0.7 or less.
• the 6-position substitution degree of the cellulose ester may be 0 or 0.1 or more.
• the degree of substitution of cellulose ester can be measured by the following method. For example, it can be measured by the NMR method according to the method of Tezuka (Carbonydr. Res. 273, 83 (1995)). That is, the free hydroxyl groups of the cellulose ester are acylated with a carboxylic acid anhydride in pyridine.
• the type of carboxylic acid anhydride used here should be selected according to the purpose of analysis. Acetic anhydride is good if necessary.
• the obtained sample is dissolved in deuterated chloroform and the 13 C-NMR spectrum is measured.
• the carbon signals of the acetyl group appear in the order of the 2nd, 3rd and 6th positions from the high magnetic field in the region of 169 ppm to 171 ppm.
• the signal of the carbonyl carbon of the propionyl group is from 172 ppm. They appear in the same order in the 174 ppm region.
• the viscosity-average degree of polymerization of the cellulose ester is not particularly limited, it is preferably 10 or more and 400 or less.
• a resin composition containing a cellulose ester having a viscosity-average degree of polymerization within this range is excellent in melt moldability.
• the viscosity average degree of polymerization is more preferably 15 or more and 300 or less, and further preferably 20 or more and 200 or less.
• the viscosity average degree of polymerization of cellulose ester may be 10 or more and 300 or less. It may be 10 or more and 200 or less, 15 or more and 400 or less, 15 or more and 200 or less, 20 or more and 400 or less, or 20 or more and 300 or less.
• the viscosity average degree of polymerization is determined based on the intrinsic viscosity ([ ⁇ ], unit: cm 3 /g) of cellulose ester.
• the intrinsic viscosity ([ ⁇ ], unit: cm 3 /g) is determined according to JIS-K-7367-1 and ISO1628-1. Specifically, a sample solution using dimethyl sulfoxide (DMSO) as a solvent is prepared, and the logarithmic relative viscosity at 25° C. measured using an Ubbelohde viscometer of size number 1C is divided by the concentration of the sample solution. Desired.
• DMSO dimethyl sulfoxide
• Viscosity average molecular weight (intrinsic viscosity [ ⁇ ]/0.171) (1/0.61)
• Viscosity average degree of polymerization (DPv) viscosity average molecular weight / (162.14 + 42.037 x DS)
• DS is the total degree of substitution of the cellulose ester described above.
• Weight average molecular weight of cellulose ester is not particularly limited, it is preferably 100,000 or more, more preferably 120,000 or more, from the viewpoint of obtaining molded articles having excellent tensile properties.
• the weight average molecular weight of the cellulose ester is preferably 1,500,000 or less, more preferably 1,200,000 or less, from the viewpoint of obtaining appropriate fluidity during melting.
• the weight average molecular weight of cellulose ester can be determined by a known method. Specifically, the weight average molecular weight of the cellulose ester is determined by performing size exclusion chromatography (GPC) measurement with the following equipment and conditions (GPC-light scattering method).
• GPC size exclusion chromatography
• the content of the cellulose ester in the thermoplastic resin composition of the present disclosure is preferably 30% by weight or more and 90% by weight or less with respect to the entire resin composition. From the viewpoint of obtaining a molded product with high strength, the content of the cellulose ester is more preferably 35% by weight or more. From the viewpoint of obtaining good elongation, the content of cellulose ester is more preferably 85% by weight or less.
• the content of cellulose ester in the resin composition of the present disclosure may be from 30 to 85 wt%, from 35 to 90 wt%, or from 35 to 85 wt%. When two or more cellulose esters are used in combination, the total amount is preferably adjusted within the numerical range described above.
• the polyester contained in the thermoplastic resin composition of the present disclosure is not particularly limited, and any polyester that exhibits biodegradability can be suitably used. It may be an aliphatic polyester or an aliphatic aromatic polyester. Further, from the viewpoint of the polymer structure, it may be a polyester having, as a repeating unit, a structural unit obtained by polycondensation of a hydroxycarboxylic acid, or a polyester having, as a repeating unit, a structural unit obtained by dehydration condensation of a dicarboxylic acid and a diol. There may be.
• polyesters having repeating units of structural units obtained by polycondensation of hydroxycarboxylic acid include polyglycolic acid, polylactic acid, poly( ⁇ -hydroxybutyric acid), poly( ⁇ -hydroxyvaleric acid), poly(lactic acid-co-glycol acid), poly( ⁇ -hydroxybutyric acid-co- ⁇ -hydroxyvaleric acid), poly( ⁇ -propiolactone), poly( ⁇ -caprolactone) and the like.
• polyesters having, as repeating units, structural units obtained by dehydration condensation of a dicarboxylic acid and a diol include polyethylene succinate, polybutylene succinate, poly(butylene succinate-co-butylene adipate), polybutylene adipate terephthalate, and the like. be. From the viewpoint of facilitating polymer designing, a polyester having, as a repeating unit, a structural unit obtained by dehydration condensation of a dicarboxylic acid and a diol is preferred.
• a polyester having, as a repeating unit, a structural unit obtained by dehydration condensation of a dicarboxylic acid and a diol is preferred. Since it is excellent in biodegradability and has a low environmental load, it is preferable that the proportion of structural units containing an aromatic ring is 50% or less, more preferably 45% or less, and 40% or less. More preferably, it may be 0%.
• Dicarboxylic acids selected from the group consisting of succinic acid, adipic acid and terephthalic acid are preferred.
• Diol components that make up polyester include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene propylene glycol, and butylene glycol. Diols selected from the group consisting of ethylene glycol, propylene glycol and butylene glycol are preferred.
• Polyesters selected from the group are preferred. Two or more polyesters may be used in combination. Other polyesters may be blended as long as the effects of the present disclosure are not impaired.
• the weight average molecular weight of the polyester is preferably 100,000 or more, more preferably 120,000 or more.
• the weight average molecular weight of the polyester is preferably 1,000,000 or less, more preferably 800,000 or less, from the viewpoint of easy kneading with cellulose ester.
• the weight average molecular weight of polyester is measured by the method described above for cellulose ester.
• the number of carbon atoms in the dicarboxylic acid component constituting the polyester is preferably 8 or less, more preferably 6 or less.
• the number of carbon atoms in the diol component constituting the polyester is preferably 8 or less, more preferably 6 or less.
• the amount of polyester is 120 parts by weight or less with respect to 100 parts by weight of cellulose ester, and from the viewpoint of obtaining high strength, the amount is 100 parts by weight or less. is preferred, and 80 parts by weight or less is more preferred. From the viewpoint of imparting good extensibility to the molded product, the amount of polyester is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and further preferably 10 parts by weight or more with respect to 100 parts by weight of cellulose. preferable.
• the amount of polyester relative to 100 parts by weight of cellulose ester may be greater than 0 and 120 parts by weight or less, may be greater than 0 and may be 100 parts by weight or less, may be greater than 0 and may be 80 parts by weight or less, may be from 3 to 120 parts by weight, may be from 3 to 100 parts by weight, may be from 3 to 80 parts by weight, may be from 5 to 120 parts by weight, may be from 5 to 100 parts by weight, It may be from 5 to 80 parts by weight, it may be from 10 to 120 parts by weight, it may be from 10 to 100 parts by weight, it may be from 10 to 80 parts by weight.
• the total amount is adjusted so as to fall within the range described above.
• the plasticizer contained in the thermoplastic resin composition of the present disclosure is a compound having a number average molecular weight of 1000 or less, and from the viewpoint that the effect of improving the plasticity of cellulose acetate is large, the number average molecular weight should be 800 or less. Preferably, 700 or less is more preferable. From the viewpoint of reducing bleeding from the resulting molded article, the number average molecular weight of the plasticizer is preferably 50 or more, more preferably 100 or more, and particularly preferably 200 or more. The number average molecular weight of the plasticizer is measured by the method described above for the cellulose ester.
• the type of the plasticizer contained in the thermoplastic resin composition of the present disclosure is not particularly limited as long as the number average molecular weight is 1000 or less, but a plasticizer that improves the plasticity of cellulose acetate is preferable, and cellulose acetate and polyester. Plasticizers that both improve plasticity are more preferred. Plasticizers selected from the group consisting of citric acid esters, glycerin esters, adipate esters and polyethylene glycol esters are preferred. Two or more plasticizers may be used in combination. It is also possible to further contain other plasticizers as long as the effects of the present disclosure are not impaired.
• citrate esters include acetyltriethyl citrate, acetyltributyl citrate, isodecyl citrate, isopropyl citrate, triethyl citrate, triethylhexyl citrate, and tributyl citrate.
• glycerin esters include triacetin, diacetin, monoacetin and the like.
• adipates include dimethyl adipate, dibutyl adipate, diisostearyl adipate, diisodecyl adipate, diisononyl adipate, diisobutyl adipate, diisopropyl adipate, diethylhexyl adipate, dioctyl adipate, and dioctyl adipate. dodecyl, dicapryl adipate, dihexyldecyl adipate and the like.
• polyethylene glycol esters include triethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol dipropionate, triethylene glycol dibenzoate, tetraethylene glycol diacetate and the like.
• the amount of the plasticizer is less than 100 parts by weight with respect to 100 parts by weight of the cellulose ester, and is preferably 90 parts by weight or less from the viewpoint of excellent shapeability. 80 parts by weight or less is more preferable. From the viewpoint of enabling uniform melting of cellulose ester and polyester, the amount of the plasticizer is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and 15 parts by weight with respect to 100 parts by weight of cellulose. The above are particularly preferred.
• the amount of the plasticizer relative to 100 parts by weight of the cellulose ester may be greater than 0 and less than 100 parts by weight, may be greater than 0 and may be 90 parts by weight or less, may be greater than 0 and may be 80 parts by weight or less. , may be 5 parts by weight or more and less than 100 parts by weight, may be 5 to 90 parts by weight, may be 5 to 80 parts by weight, may be 10 parts by weight or more but less than 100 parts by weight, may be 10 to 90 parts by weight 10 to 80 parts by weight, 15 to 100 parts by weight, 15 to 90 parts by weight, or 15 to 80 parts by weight. When two or more plasticizers are used in combination, the total amount is adjusted within the above range.
• thermoplastic resin composition of the present disclosure is obtained by melt-kneading a cellulose ester, a polyester, and a plasticizer having a number average molecular weight of 1000 or less in the aforementioned blending amounts.
• this resin composition is obtained by melt-kneading a cellulose ester and a plasticizer, and then melt-kneading the resulting melted mixture with the polyester.
• the cellulose ester and the plasticizer may be mixed and then melt-kneaded.
• the plasticizer and the cellulose ester are more uniformly blended into each other in a short period of time, and the obtained kneaded product is homogenized. This further facilitates melt-kneading with polyester.
• a known mixer such as a Henschel mixer can be used to mix the cellulose ester and the plasticizer. Either dry mixing or wet mixing may be used.
• the temperature in the mixer is preferably a temperature at which the cellulose ester does not melt, for example, 20°C or higher and lower than 200°C.
• An extruder such as a twin-screw extruder is used for melt-kneading the cellulose ester and the plasticizer, and melt-kneading the kneaded product of the cellulose ester and the plasticizer and the polyester.
• the kneading temperature (cylinder temperature) of the extruder is preferably 170° C. or higher and 230° C. or lower from the viewpoint of uniformity of the kneaded product and suppression of heat deterioration.
• the kneading temperature also referred to as cylinder temperature
• the kneaded material may be extruded into strands from a die attached to the tip of the twin-screw extruder, and then hot-cut into pellets. At this time, the die temperature may be about 220°C.
• the amount of polyester blended in the thermoplastic resin composition of the present disclosure is 120 parts by weight or less with respect to 100 parts by weight of cellulose ester. When blending two or more kinds of polyesters, the total amount is adjusted to 120 parts by weight or less.
• the amount of plasticizer blended in the thermoplastic resin composition of the present disclosure is less than 100 parts by weight with respect to 100 parts by weight of cellulose ester. When blending two or more plasticizers, the total amount is adjusted to less than 100 parts by weight.
• cellulose ester, polyester and plasticizer in the resin composition is preferably 90% by weight or more.
• thermoplastic resin composition of the present disclosure can be melt-molded at relatively low temperatures. Since the thermoplastic resin composition of the present disclosure has moderate fluidity when melted, it can be suitably applied to injection molding. Molded articles obtained using this thermoplastic resin composition have excellent biodegradability and good elongation properties, and therefore can be applied to the production of films or sheets by injection molding and melt film forming. Furthermore, it can be made into a thin film by stretching or inflation molding after melt extrusion.
• thermoplastic resin composition according to the present disclosure includes, for example, tableware, packaging containers, trays, agricultural materials, fishery materials, OA parts, construction materials, medical parts, home appliance parts, automotive parts, Japanese It can be suitably used as a material for miscellaneous goods, stationery, spectacle frames and the like.
• triacetin manufactured by Daicel, molecular weight 218.21
• a mixture of The obtained mixture is supplied to a twin-screw extruder (manufactured by Ikegai Co., Ltd., trade name "PCM30", cylinder temperature: 200 ° C., die temperature: 220 ° C.) and melt-kneaded, and then extruded into a strand. Pellets were obtained by hot cutting.
• thermoplastic resin composition of Example 1 was obtained by supplying to, melt-kneading and extruding.
• the blended polybutylene succinate was 22 parts by weight with respect to 100 parts by weight of cellulose acetate.
• Example 2 and Comparative Examples 1-4 Thermoplastic resin compositions of Example 2 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1, except that the compositions of cellulose acetate, triacetin and polybutylene succinate were as shown in Table 1 below. . In Comparative Example 2, cellulose acetate and polybutylene succinate did not melt uniformly.
• thermoplastic resin compositions of Example 1-2 and Comparative Example 1-4 were injection molded (cylinder temperature: 230°C, mold temperature: 50°C) to prepare a dumbbell-shaped test piece.
• the resin composition of Comparative Example 2 did not melt uniformly during molding, and could not be molded into a shape that conformed to the mold. Therefore, the following tensile test was not performed.
• a tensile test is performed in accordance with ISO527-1 (tensile speed 10 mm / min, grip 115 mm), and the breaking strength (unit: MPa), nominal strain at break (%) and elastic modulus (MPa) of Example 1-2 and Comparative Examples 1 and 3-4 were measured. The average of each of the 5 measurements is shown in Table 1 below.
• the resin composition described above can be applied to various fields using melt molding, injection molding, and melt film formation.

Landscapes

• 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)

Priority Applications (7)

Applications Claiming Priority (1)

Publications (1)

Family

ID=83227578

Family Applications (1)

Country Status (7)

Cited By (2)

Citations (9)

Family Cites Families (6)

• 2021
  • 2021-03-12 EP EP21929435.2A patent/EP4306592A4/en active Pending
  • 2021-03-12 JP JP2023505056A patent/JP7793596B2/ja active Active
  • 2021-03-12 CA CA3213125A patent/CA3213125A1/en active Pending
  • 2021-03-12 WO PCT/JP2021/010150 patent/WO2022190373A1/ja not_active Ceased
  • 2021-03-12 US US18/281,590 patent/US20240228753A1/en active Pending
  • 2021-03-12 CN CN202180095520.3A patent/CN116981728B/zh active Active
  • 2021-03-12 KR KR1020237034598A patent/KR102952699B1/ko active Active

Patent Citations (9)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events