Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

Definitions

• the present invention relates to a water-based resin composition, a water-based paint, and an article coated with the water-based paint.
• acrylic resins have been widely used for paints, inks, adhesives, synthetic leathers, and the like, due to their excellent weather resistance, flexibility, strength, adhesiveness, and the like.
• base resin for paint applications, in the fields of automobiles, home appliances, building materials, etc., it is used as a base resin for paints that coat various base materials (e.g., metals, wood, paper, plastics). resin has been developed.
• plastic molded products for example, products made from olefin resins such as polyethylene and polypropylene are widely used due to their light weight and ease of molding.
• olefin resins such as polyethylene and polypropylene
• polyethylene and polypropylene have very low polarity, there is a problem that acrylic resin cannot exhibit sufficient adhesion.
• the problem to be solved by the present invention is to provide a water-based resin composition, a paint, and an article coated with the paint, which is excellent in storage stability and capable of obtaining a coating film with excellent adhesion to various substrates. is.
• aqueous resin composition containing a specific polypropylene, a polypropylene-modified acrylic resin which is a reaction product of an unsaturated monomer mixture, and an aqueous medium.
• the inventors found that a coating film having excellent storage stability and excellent adhesion to various substrates can be obtained, and completed the invention.
• the present invention provides an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer and the polypropylene-modified acrylic resin has an acid value of 20 to 80 mgKOH/g.
• the aqueous resin composition of the present invention has excellent storage stability and can obtain a coating film having excellent adhesion to various substrates. It can be suitably used as a paint for coating various articles such as housings for equipment; housings for home electric appliances such as televisions, refrigerators, washing machines, and air conditioners; automobile bumpers, and interior materials for various vehicles such as automobiles and railway vehicles. .
• the aqueous resin composition of the present invention is an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer, and the acid value of the polypropylene-modified acrylic resin is 20 to 80 mgKOH/g.
• polypropylene (A) will be explained. It is important that this polypropylene (A) is a homopolymer, so that a coating film with excellent adhesion to various substrates can be obtained. In addition, polypropylene (A) can be used alone or in combination of two or more.
• the weight average molecular weight of the polypropylene (A) is preferably from 15,000 to 200,000, more preferably from 20,000 to 80,000, because the adhesion to the substrate is further improved.
• the melting point of the propylene (A) is preferably 40 to 120°C, more preferably 40 to 90°C, because the adhesion to the substrate is further improved.
• This unsaturated monomer mixture (B) contains the unsaturated monomer (b1) having a carboxyl group as an essential component.
• Examples of the unsaturated monomer (b1) having a carboxyl group include (meth)acrylic acid, crotonic acid, ⁇ -carboxyethyl (meth)acrylate, ⁇ -carboxy-polycaprolactone mono(meth)acrylate, 2- Unsaturated monocarboxylic acids such as (meth)acryloyloxyethyl succinate and 2-(meth)acryloyloxyethylhexahydrophthalic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; A half ester etc. are mentioned. Among these, (meth)acrylic acid is preferred because of its superior dispersibility in water. These unsaturated monomers (b1) can be used alone or in combination of two or more.
• (meth)acrylic acid refers to one or both of methacrylic acid and acrylic acid
• (meth)acrylate refers to one or both of methacrylate and acrylate
• (meth) ) “acryloyl group” refers to one or both of a methacryloyl group and an acryloyl group.
• the unsaturated monomer mixture (B) contains the unsaturated monomer (b1) as an essential component, and other unsaturated monomers (b2) include, for example, methyl (meta) Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth) Acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate Acrylate, tridecyl (meth)acrylate, cetyl (meth)
• the unsaturated monomer (b1) in the unsaturated monomer mixture (B) is preferably 2 to 40% by mass, and 5 to 20% by mass, because it further improves water dispersibility and storage stability. more preferred.
• the unsaturated monomer (b2) in the unsaturated monomer mixture (B) is the balance of 100% by mass minus the usage ratio of the unsaturated monomer (b1), but the amount of the unsaturated monomer (b2) is the remainder of 100% by mass.
• n-octyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl ( Alkyl (meth)acrylates having an alkyl group having 6 to 12 carbon atoms such as meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate; styrene, ⁇ - It is more preferable to contain at least one monomer selected from the group consisting of styrene compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene in an amount of 5% by mass or more.
• the polypropylene-modified acrylic resin is preferably a reaction product obtained by polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A).
• a method for obtaining the polypropylene-modified acrylic resin a method of radically polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A) and a solvent is preferable because it is simple.
• the above radical polymerization method is a method of dissolving each raw material monomer in a solvent and performing a polymerization reaction in the presence of a polymerization initiator.
• solvents that can be used at this time include aromatic hydrocarbon compounds such as toluene and xylene; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• Ester compounds such as ethyl acetate, n-butyl acetate, isobutyl acetate and propylene glycol monomethyl ether acetate; Alcohol compounds such as n-butanol, isopropyl alcohol and cyclohexanol; Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Glycol compounds such as diethylene glycol dimethyl ether; aliphatic hydrocarbon compounds such as heptane, hexane, octane, and mineral terpene; Among these, it is preferable to use a water-miscible organic solvent because it can be used as it is as an aqueous medium contained in the aqueous resin composition of the present invention. These solvents can be used alone or in combination of two or more.
• polymerization initiator examples include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; 1,1-bis(tert-butylperoxy)-3, 3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(4,4-di tert-butylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-amylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-hexylperoxycyclohexyl)propane, 2 , 2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-dic
• the mass ratio (A/B) of the polypropylene (A) and the unsaturated monomer mixture (B) is 10/90 to 70, since the substrate adhesion of the resulting coating film is further improved. /40 is preferred, and 20/80 to 50/50 is more preferred.
• the acid value of the polypropylene-modified acrylic resin is preferably in the range of 20 to 80 mgKOH/g, 25 to 65 mgKOH/ A range of g is more preferred.
• the acid value of the resin of the present invention is a calculated value obtained from the raw material composition.
• the weight average molecular weight of the polypropylene-modified acrylic resin is preferably from 7,000 to 150,000, more preferably from 10,000 to 60,000, because the adhesion to the substrate of the obtained coating film is further improved.
• the molecular weight dispersity (weight average molecular weight/number average molecular weight) of the polypropylene-modified acrylic resin is preferably 5 to 20, since the obtained coating film has better adhesion to the substrate.
• the average molecular weight of the present invention is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
• aqueous medium examples include water, hydrophilic organic solvents, and mixtures thereof.
• hydrophilic organic solvent a water-miscible organic solvent that is miscible with water without separating is preferable, and among them, an organic solvent having a solubility in water (number of grams of organic solvent dissolved in 100 g of water) of 3 g or more at 25° C. is preferable. .
• water-miscible organic solvents include alcohol solvents such as methanol, ethanol, propanol, butanol, 3-methoxybutanol, and 3-methyl-3-methoxybutanol; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol monomethyl; Ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, prop
• the aqueous resin composition of the present invention contains a polypropylene-modified acrylic resin and an aqueous medium, it is preferable that the polypropylene-modified acrylic resin obtained by the above method is dissolved or dispersed in an aqueous medium. is more preferred.
• Examples of the basic compound include monoalkanolamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N,N-dimethylethanolamine and 2-aminoethanol, and diethanolamine. , diisopropanolamine, dibutanolamine and other organic amines; ammonia, sodium hydroxide, potassium hydroxide and other inorganic basic compounds; tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. and quaternary ammonium hydroxide. Among these, it is preferable to use organic amines and ammonia (aqueous ammonia may be used). These basic compounds can be used alone or in combination of two or more.
• the neutralization rate of the carboxyl groups possessed by the polypropylene-modified acrylic resin is in the range of 50 to 100%. Amount is preferred.
• the paint of the present invention contains the aqueous resin composition of the present invention, and other ingredients such as an antifoaming agent, a viscosity modifier, a light stabilizer, a weather stabilizer, a heat stabilizer, and an ultraviolet absorber. , antioxidants, leveling agents, pigment dispersants, and other additives may be used. Pigments such as titanium oxide, calcium carbonate, aluminum powder, copper powder, mica powder, iron oxide, carbon black, phthalocyanine blue, toluidine red, perylene, quinacridone, and benzidine yellow can also be used.
• Examples of the coating method of the paint of the present invention include spray, applicator, bar coater, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, A method such as screen printing can be used.
• a method of forming a coating film after coating a method of drying in the range of normal temperature to 120° C. can be mentioned.
• the paint of the present invention has high adhesion to plastic substrates, it can be suitably used as a paint for coating various plastic molded articles.
• the housing of electronic equipment such as mobile phones, smartphones, tablet terminals, personal computers, digital cameras, and game consoles; the housing of home appliances such as televisions, refrigerators, washing machines, and air conditioners; Examples include interior materials for various vehicles.
• Measuring device high-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8 mm I.D.
• Example 1 Production of aqueous resin composition (1)
• polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S600", melting point 80 ° C., weight average molecular weight 75,000; hereinafter abbreviated as "polypropylene (A-1)”
• polypropylene (A-1) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
• a mixed liquid consisting of 29.5 g of MMA, 50 g of St, 40.5 g of BA, 4.6 g of CHMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, and further 3 hours. Stirred.
• a water dispersion step the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution.
• Example 2 Production of aqueous resin composition (2)
• 150 g of toluene and 90 g of polypropylene (A-1) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
• a mixed liquid consisting of 10 g of MMA, 40 g of St, 24 g of CHMA, 20 g of SLMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, followed by stirring for 3 hours.
• a water dispersion step the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution.
• Example 3 Production of aqueous resin composition (3)
• 80 g of toluene, polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S400", melting point 80 ° C., weight average molecular weight 45,000; hereinafter abbreviated as "polypropylene (A-2)”
• polypropylene (A-2) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
• A-2 polypropylene
• a mixture of 25 g of St, 24 g of CHMA, 20 g of SLMA, 12 g of maleic anhydride, and 5.2 g of ABN-E was added dropwise over 4 hours, followed by stirring for 3 hours.
• the above reaction liquid was cooled to 75° C., and 200 g of methylcyclohexane, 400 g of isopropyl alcohol, 28 g of triethylamine and 440 g of water were successively added to obtain a water-dispersed particle solution.
• Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (3) as an aqueous dispersion having a solid content concentration of 25% by mass.
• Example 4 Production of aqueous resin composition (4)
• 225 g of butyl acetate and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
• A-2 polypropylene
• a mixture of 50 g of MMA, 10 g of St, 68 g of EA, 11.2 g of AA and 8.5 g of PO was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
• the above reaction solution is cooled to 75° C., and 180 g of methylcyclohexane, 510 g of isopropyl alcohol, 13.9 g of N,N-dimethylethanolamine, and 510 g of water are successively added to obtain a water-dispersed particle solution.
• Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (4) as an aqueous dispersion having a solid content concentration of 27% by mass.
• Example 5 Production of aqueous resin composition (5)
• 270 g of butyl acetate and 90 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
• A-2 polypropylene
• a mixture of 5.4 g of MMA, 42.5 g of EA, 48.6 g of IBXMA, 11.5 g of AA and 4 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
• the above reaction solution was cooled to 75° C., and 190 g of methylcyclohexane, 400 g of isopropyl alcohol, 14.2 g of N,N-dimethylethanolamine, and 540 g of water were successively added to obtain a water-dispersed particle solution.
• Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (5) as an aqueous dispersion having a solid content concentration of 26% by mass.
• Example 6 Production of aqueous resin composition (6)
• polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S901", melting point 80 ° C., weight average molecular weight 130,000; hereinafter abbreviated as "polypropylene (A-3)”
• A-3 weight average molecular weight 130,000
• a mixed liquid consisting of 15 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
• the above reaction liquid is cooled to 75 ° C., N,N-dimethylethanolamine 3.7 g and water 380 g are sequentially added to form a water dispersion with a solid content concentration of 30% by mass.
• a composition (6) was obtained.
• Example 7 Production of aqueous resin composition (7)
• 70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
• a mixed liquid consisting of 35 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 8 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
• Example 8 Production of aqueous resin composition (8)
• 250 g of toluene and 18 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
• A-2 polypropylene
• a mixture of 29.5 g of MMA, 47 g of St, 25.5 g of BA, 64.6 g of CHMA, 11 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
• the reaction solution was cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 13.6 g of N,N-dimethylethanolamine, and 440 g of water were successively added to obtain a water-dispersed particle solution.
• aqueous resin composition (R1) 70 g of butyrocellosolve and 30 g of a polypropylene copolymer (manufactured by Evonik "Bestplast 750", propylene/ethylene/1-butene copolymer, melting point 107° C.) were added to a four-necked flask with a capacity of 2 L, and an inert gas atmosphere was added. The temperature was raised to 140° C. below.
• a mixed liquid consisting of 15.0 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours. did.
• a water dispersion step the above reaction solution is cooled to 75 ° C., and 3.7 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass.
• a composition (R1) was obtained.
• Tables 1 and 2 show the compositions and evaluation results of the aqueous resin compositions (1) to (8) obtained above.
• Table 3 shows the compositions and evaluation results of the comparative aqueous resin compositions (R1) to (R3) obtained above.
• Example 9 Preparation and evaluation of water-based paint (1)
• aqueous resin composition (1) obtained above 0.2 g of BYK-348 (manufactured by BYK Chemie) as a leveling agent and 0.1 g of SN Deformer 777 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent are added, and the mixture is stirred for 15 minutes. Stirred. Next, the mixture was diluted with deionized water until the paint viscosity reached 12 seconds using a viscosity cup NK-2 (manufactured by Anest Iwata Co., Ltd.) to obtain water-based paint (1).
• BYK-348 manufactured by BYK Chemie
• SN Deformer 777 manufactured by San Nopco Co., Ltd.
• Example 10 to 16 Preparation and evaluation of water-based paints (2) to (8)
• Water-based paints (2) to (8) were prepared in the same manner as in Example 9, except that the water-based resin composition (1) was changed to the water-based resin compositions (2) to (8), and substrate adhesion was evaluated.
• the aqueous resin composition of the present invention has excellent storage stability, and that the resulting coating film has excellent adhesion to various substrates.
• Comparative Example 1 is an example in which the homopolymer of polypropylene, which is an essential component of the present invention, was not used. Adhesion to was insufficient.
• Comparative Example 2 is an example in which the acid value of the polypropylene-modified acrylic resin is greater than the upper limit of the present invention of 80 mgKOH/g, but the resulting coating film is based on a polypropylene base and an acrylonitrile-butadiene-styrene copolymer base. , the adhesion to the nylon substrate was insufficient.
• Comparative Example 3 is an example in which the acid value of the polypropylene-modified acrylic resin is less than 20 mgKOH/g, which is the lower limit of the present invention. Adhesion was insufficient.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=83396899

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (4)

Family Cites Families (1)

• 2022
  • 2022-02-08 TW TW111104613A patent/TW202300585A/zh unknown
  • 2022-03-03 WO PCT/JP2022/009015 patent/WO2022202172A1/ja not_active Ceased
  • 2022-03-03 JP JP2023508875A patent/JP7364115B2/ja active Active
  • 2022-03-03 CN CN202280011576.0A patent/CN116724085A/zh active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events