EP3467176B1 - Structure de nanofibres constituée d'acide polyhydroxyalcanoïque et tissu non tissé - Google Patents

Structure de nanofibres constituée d'acide polyhydroxyalcanoïque et tissu non tissé Download PDF

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Publication number
EP3467176B1
EP3467176B1 EP16904579.6A EP16904579A EP3467176B1 EP 3467176 B1 EP3467176 B1 EP 3467176B1 EP 16904579 A EP16904579 A EP 16904579A EP 3467176 B1 EP3467176 B1 EP 3467176B1
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Prior art keywords
nanofiber structure
nanofiber
film
woven fabric
polyhydroxyalkanoic acid
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EP16904579.6A
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German (de)
English (en)
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EP3467176A1 (fr
EP3467176A4 (fr
Inventor
K. Sudesh KUMAR
Kozo Inoue
Kazuya Nitta
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Fuence Co Ltd
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Fuence Co Ltd
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/022—Moisture-responsive characteristics hydrophylic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/12—Physical properties biodegradable

Definitions

  • the present invention relates to a nanofiber structure constituted of polyhydroxyalkanoic acid, and a non-woven fabric, and more particularly, to a nanofiber structure constituted of polyhydroxyalkanoic acid having oil or organic solvent absorbency simultaneously with a property of being rapidly degraded by microorganisms and the like in the natural environment, and a non-woven fabric.
  • Non-woven fabric manufactured from various organic polymers has recently been expanded, and is used for various uses in various industries from textile industries (interlining field) to sanitary materials, medical materials, automobile interior materials, industrial materials (filter, wiping, etc.), civil engineering materials, agricultural materials, geotextiles (fiber sheet for soil reinforcement), environmental industries, and the like.
  • production of the non-woven fabric is predicted to continuously expand every year.
  • polypropylene (PP) non-woven fabric has a high growth rate, and a growth rate of nearly 10% is expected.
  • biodegradable polymer in a raw material of the non-woven fabric.
  • Resin products using a biodegradable organic polymer such as polylactic acid or polyhydroxyalkanoic acid have been already developed.
  • polyhydroxyalkanoic acid has been developed for a long time by domestic and foreign companies, costs of production and purification by microorganisms delay practicality.
  • Kaneka Corporation recently reported that commercialization of a resin product manufactured from polyhydroxyalkanoic acid is in progress. However, since the company aims to develop a so called, resin product, development in the non-woven fabric field as described above has not been made.
  • Non Patent Literature 1 Non Patent Literature 1
  • Non Patent Literature 2 “Manufacture of biodegradable plastic by microorganisms ( Microbiol. Cult. Coll.
  • Non Patent Literature 3 describes high-elasticity polyhydroxyalkanoate (PHA) porous fiber material and a preparation method thereof.
  • US 2015/0012018 describes medical devices containing dry spun non-wovens of poly-4-hydroxybutyrate and copolymers with aniosotropic properties.
  • US 2009/0162276 describes medical devices containing melt-blown non-wovens of poly-4-hydroxybutyrate and copolymers thereof.
  • a market size of a non-woven fabric in particular a polypropylene (PP) non-woven fabric is to increase by about 8% every year in the future, and is to reach about 30 billion US dollars in 2020.
  • the main uses thereof are sanitary goods such as diapers (for infants or the elderly), geotextiles, environmental pollutant treatments, automobile industries, furniture, and the like, and it is said that the uses are caused by growth in Asia-Pacific region which has a high population growth rate.
  • the inventors of the present application repeated study and speculation for solving the problems, and as a result, found a technique of making biodegradable polyhydroxyalkanoic acid into nanofiber and using the nanofiber as a nanofiber structure (such as non-woven fabric) having various characteristics.
  • An object of the present invention is to provide a nanofiber structure constituted of polyhydroxyalkanoic acid. Another object of the present invention is to develop the nanofiber structure as the non-woven fabric to solve the problems of the current synthetic resin non-woven fabric.
  • a nanofiber structure according to a first invention is a nanofiber structure constituted of polyhydroxyalkanoic acid (one or plural types) manufacturable by an electrospray deposition method, wherein the polyhydroxyalkanoic acid includes polyhydroxybutyrate as a main component, wherein the nanofiber structure is degraded by microorganisms in soil in a natural environment and wherein the nanofiber structure has a porosity of 50% or more.
  • the structure includes polyhydroxybutylate as a main component, and preferably, is blended with another polyhydroxyalkanoic acid (for example, a copolymer with polyhydroxyhexanoic acid).
  • another polyhydroxyalkanoic acid for example, a copolymer with polyhydroxyhexanoic acid.
  • the structure has high air permeability and a light weight by having higher porosity.
  • a nanofiber structure according to a second invention is characterized by having a fiber diameter of 1 ⁇ m or less.
  • a nanofiber structure according to a third invention is characterized by having water repellency, and a contact angle of pure water to a surface of the nanofiber structure is 100° or more.
  • a nanofiber structure according to a fourth invention is characterized by having oil absorbency.
  • a nanofiber structure according to a fifth invention is characterized by having organic solvent absorbency.
  • a nanofiber structure according to a sixth invention is characterized in that the surface of the nanofiber structure has hydrophilicity by surface modification by a plasma treatment, a corona discharge, electron beam irradiation, or laser irradiation.
  • the nanofiber structure may be used in sanitary products and the like by having hydrophilicity by surface modification.
  • a nanofiber structure according to a seventh invention is characterized by including an adsorbent material.
  • An adsorbent is for example, activated carbon, zeolite, or the like, and included in a nanofiber and on a surface of the nanofiber.
  • a nanofiber structure according to an eighth invention is characterized in that the nanofiber structure is partially fused to have a film shape.
  • the solution to the problem of the present invention is describedas ananofiber structure, however, the present invention may also be realized by a method of manufacturing a nanofiber structure which substantially corresponds to the solution, and it should be understood that the scope of the present invention also includes the method.
  • nanofiber structure film having characteristics of being flexible and having oil or organic solvent absorbency, simultaneously with being rapidly degraded by microorganisms in the natural environment so as not to cause an increase of CO 2 gas.
  • the nanofiber structure may be used as non-woven fabric in various industries.
  • a polyhydroxyalkanoic acid used in an exemplary embodiment of the present invention is a sample prepared by microbial culture and purification method, the patentee of which is University of Science-Malaysia to which one of the inventors of the present application belongs.
  • Nanofiber may be manufactured from the sample by an electrospray deposition (ESD) method.
  • ESD method electrospray deposition method
  • ESD electrospray device
  • Fig. 1 is a conceptual diagram representing a basic configuration of an electrospray deposition device.
  • a container (CNT) contains a sample solution (SL).
  • the sample solution (SL) is, for example, an organic polymer solution, a polymer solution, or the like.
  • the sample solution is a polyhydroxyalkanoic acid solution, that is, a polyhydroxyalkanoic acid solution.
  • the ESD method is a very complicated physical phenomenon and all of the processes are not explained, the ESD method is generally considered as being the following phenomenon.
  • the sample solution is contained in a thin capillary shaped nozzle (NZL), and voltage of thousands to tens of thousands of volts is applied to a target substrate (TS) (counter electrode) opposing thereto.
  • TS target substrate
  • TS target substrate
  • a strong electric field occurs by an electric field concentration effect, and microdroplets with charge on a liquid surface gather to form a cone (also called Taylor cone).
  • the sample solution from the tip destroys surface tension to become a jet.
  • the jet is strongly charged and becomes spray by a repulsion of electrostatic force (coulomb explosion).
  • the droplets formed by spray are very small so that the solvent is evaporated and dried within a short time to become fine nanoparticles or nanofiber.
  • the solvent may be deposited in a wet state which is not evaporated or dried.
  • the charged fine nanoparticles or nanofiber having a small diameter is pulled to the target substrate (TS) functioning as a counter electrode by electrostatic force.
  • a pattern to be deposited may be controlled by an insulator mask or an auxiliary electrode (not shown) .
  • the sample is not limited to a solution, and a dispersion solution is fine.
  • the sample solution in the container (CNT) applies extrusion pressure toward the nozzle (NZL) by an air pressure syringe pump, plunger, or the like (ejection means, not shown) .
  • the extrusion pressure is imparted by for example, a stepping motor and a screw feed mechanism (not shown) .
  • the sample solution (SL) to which the extrusion pressure is applied has increased internal pressure in the container (CNT) so as to be discharged from the tip of nozzle (NZL) .
  • an adjustment mechanism the stepping motor and the screw feed mechanism
  • the nozzle (NZL) is made of metal, and positive voltage is supplied from a high voltage power supply (HPS) through a conductor wire (WL).
  • HPS high voltage power supply
  • the negative side of the high voltage power supply (HPS) is connected to the target substrate (TS) (substrate to be a counter electrode).
  • nanofiber structure when the nanofiber structure is manufactured, it is preferred that non-woven fabric is placed on the target substrate (TS), and the nanofiber structure is deposited on the non-woven fabric.
  • various conditions such as voltage level, concentration of the sample solution, the kind of polyhydroxyalkanoic acid as a sample, the kind of solvent, and the like are adjusted to manufacture the nanofiber structure .
  • the sprayed material becomes fiber or droplets, and repeats division during scattering by repulsion due to charging to form nanofiber or nanoparticles. Since the sprayed material has a large surface area in a nano size, when the sprayed material comes into contact with the substrate, it is in an almost dried state.
  • the shape or size may be changed depending on the spray conditions, and for example, when a polymer solution is used, thick nanofiber is formed with a high molecular weight and a high concentration, and thin nanofiber or nanoparticles are formed with a low molecular weight and a low concentration.
  • various conditions such as voltage or a distance between the nozzle and the substrate and ambient temperature or humidity have an influence thereon.
  • various kinds of solvent-soluble polyhydroxyalkanoic acid are used as a sample to manufacture nanofiber under various conditions, and confirmation of water repellency, air permeability, hydrophilicity, and the like were carried out by the method described in the Example.
  • the electrospray deposition device another type of ESD device as well as the above-described device can be used.
  • a method using air current described in Japanese Patent No. 5491189 developed by the applicants, is preferred.
  • Fig. 2 is a photograph of a polyhydroxyalkanoic acid nanofiber film (PHA nanofiber structure) manufactured by an ESD device of Fig. 1 .
  • a chloroform solution including 10% by weight of polyhydroxyalkanoic acid (PHA) was used.
  • an ESD device ES-4000, manufactured by HUENS Co., LTD.
  • ES-4000 manufactured by HUENS Co., LTD.
  • a thickness of nanofiber film shown in the drawing was 20 ⁇ m. This nanofiber film is very thin, is a free-standing film in spite of the small fiber diameter, may be deposited on other non-woven fabric or film or incorporated into another member or instrument, and is very useful.
  • Fig. 3 is an electron microscope photograph (SEM photograph) of the PHA nanofiber structure shown in Fig. 2 .
  • the magnification of the photograph is 1000 times.
  • an average diameter of the nanofiber was about 1 ⁇ m.
  • the PHA nanofiber structure may be used as a filter using the porous property.
  • the nanofiber diameter, porosity, density, and the like are varied by changing various solution compositions or spray conditions according to the purpose, and are controllable.
  • Fig. 4 is a drawing representing biodegradability of the nanofiber film of Example 1.
  • the biodegradability of the nanofiber film (nanofiber structure) obtained in Example 1 by microorganisms and the like was studied by leaving the nanofiber filminsoil.
  • Fig. 4 (a) is a photograph immediately after placing the nanofiber film in soil.
  • Fig. 4(b) is a photograph after leaving the nanofiber film in Fig. 4(a) for 12 days as it is. As seen from the comparison of these photographs, the polyhydroxyalkanoic acid nanofiber film degrades quite rapidly in soil.
  • the nanofiber film may be used as a resource which does not increase gas causing global warming and may be permanently used.
  • Fig. 5 is a drawing representing water repellency of the nanofiber film of Example 1.
  • Fig. 5 is a photograph immediately after adding pure water dropwise by a pipette on the nanofiber film obtained in Example 1.
  • the dropped pure water (WD) remained on the film as a droplet, as shown in the photograph.
  • a value of 87.5-130.5° was obtained by measurement with 10 droplets, and the average was 113.7°.
  • the nanofiber film had water repellency.
  • Fig. 6 is a drawing representing oil-water separability and oil absorbency of the nanofiber film of Example 1.
  • the nanofiber film obtained in Example 1 was added to a container having a methylene blue solution and salad oil therein by pouring it from the above.
  • Fig. 6(a) is a photograph before the nanofiber film was added to the container.
  • the aqueous methylene blue solution and salad oil are mixed in a separated state.
  • Fig. 6 (b) is a photograph 1 minute after the nanofiber film was added to the container.
  • Fig. 6(b) it is observed that the nanofiber film floated on the aqueous methylene blue solution so that only the salad oil (OL) remained in the nanofiber film.
  • Fig. 6(c) is a photograph 10 minutes after the nanofiber film was added. As shown in the photograph of Fig. 6(c) , it is observed that the nanofiber film absorbed only the salad oil within 10 minutes, and absorbed all of the salad oil in the film, at the end. In addition, the nanofiber film did not absorb the aqueous methylene blue solution at all. That is, it was found that polyhydroxyalkanoic acid nanofiber film has a function of separating water and oil simultaneously with a function of selectively absorbing only oil.
  • Fig. 7 is a drawing representing organic solvent absorbency of the nanofiber film of Example 1.
  • Fig. 7(a) is a photograph before the nanofiber film obtained in Example 1 was added to the container having an aqueous methylene blue solution (MB) and hexane (HX).
  • MB aqueous methylene blue solution
  • HX hexane
  • Fig. 7(b) is a photograph 10 minutes after the nanofiber film was added to the container. As shown in the photograph of the drawing, it is observed that hexane (HX) was all absorbed in the nanofiber film within 10 minutes.
  • the nanofiber film Since the amount of the aqueous methylene blue solution (MB) was not changed, it was found that the nanofiber film selectively absorbed only hexane of the organic solvent and did not absorb water. That is, it was found that the nanofiber film represents excellent organic solvent absorbency.
  • MB aqueous methylene blue solution
  • Nanofiber film (nanofiber structure) partially having a film shape
  • Fig. 8 is an electron microscope photograph (SEM photograph) of the nanofiber film (nanofiber structure) in which the nanofiber film is partially fused to have a film shape. As shown in the drawing, it is observed that there is a film shape in the front side and a nanofiber film in the inside. This film shaped part is useful for improving strength of the film itself.
  • Fig. 9 is an electron microscope photograph (SEM photograph) of the nanofiber film including fine particles as an adsorbent material.
  • SEM photograph electron microscope photograph
  • activated carbon fine particles AC1 andAC2 as the adsorbent material are entangled with the nanofiber FBR1 and FBR2 and maintained.
  • the activated carbon fine particles may be in the nanofiber or on the surface of the nanofiber.
  • the adsorbent material effectively absorbs the components dissolved in the organic solvent (impurities or components to be separated) passing between the nanofiber films.
  • an adsorbent for example, activated carbon, zeolite, or the like can be selected depending on the use.
  • Biodegradable polyhydroxyalkanoic acid which is a raw material of the nanofiber film can be produced using a plant component of nature as a raw material. It is possible to suppress an increase in carbon dioxide gas by using the biodegradable polyhydroxyalkanoic acid to manufacture the nanofiber structure and widely use it for a non-woven fabric.
  • the polypropylene non-woven fabric which is the conventional product is flexible and strong and has good adhesion with other materials, and thus, has been used for various uses.
  • the polypropylene non-woven fabric has been used as an oil adsorbent material since the polypropylene non-woven fabric absorbs oil. It was found by an experiment that the polyhydroxyalkanoic acid or polyhydroxybutyric acid which is a material of the nanofiber structure according to an exemplary embodiment of the present invention absorbs an organic solvent and toxic organic compounds soluble in the solvent as well as oil.
  • contaminated goods can be filtered and absorbed to make clean water.
  • the nanofiber structure (nanofiber film) according to the present invention is expected to be used for various purposes mainly as a non-woven fabric.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Claims (8)

  1. Une structure de nanofibres formée d'acide polyhydroxyalcanoïque pouvant être fabriquée par un procédé de dépôt par électronébulisation, dans laquelle l'acide polyhydroxyalcanoïque comprend du polyhydroxybutyrate comme composant principal, dans laquelle la structure de nanofibres est dégradée par des micro-organismes dans le sol dans un environnement naturel, et dans laquelle la structure de nanofibres a une porosité de 50 % ou plus.
  2. La structure de nanofibres selon la revendication 1, dans laquelle la structure de nanofibres a un diamètre de fibre de 1 µm ou moins.
  3. La structure de nanofibres selon la revendication 1, dans laquelle la structure de nanofibres est hydrofuge, et un angle de contact de l'eau pure avec une surface de la structure de nanofibres est de 100° ou plus.
  4. La structure de nanofibres selon la revendication 1, dans laquelle la structure de nanofibres a une capacité d'absorption d'huile.
  5. La structure de nanofibres selon la revendication 1, dans laquelle la structure de nanofibres a une capacité d'absorption de solvant organique.
  6. La structure de nanofibres selon la revendication 1, dans laquelle la surface de la structure de nanofibres a un caractère hydrophile par modification de surface par traitement au plasma, décharge corona, irradiation par faisceau d'électrons, ou irradiation laser, ou similaire.
  7. La structure de nanofibres selon la revendication 1, comprenant en outre un matériau adsorbant.
  8. La structure de nanofibres selon la revendication 1, dans laquelle la structure de nanofibres est partiellement fusionnée pour avoir une forme de film.
EP16904579.6A 2016-06-07 2016-06-07 Structure de nanofibres constituée d'acide polyhydroxyalcanoïque et tissu non tissé Active EP3467176B1 (fr)

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PCT/JP2016/066904 WO2017212544A1 (fr) 2016-06-07 2016-06-07 Structure de nanofibres constituée d'acide polyhydroxyalcanoïque et tissu non tissé

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EP3467176A1 EP3467176A1 (fr) 2019-04-10
EP3467176A4 EP3467176A4 (fr) 2019-12-25
EP3467176B1 true EP3467176B1 (fr) 2021-08-18

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US (1) US20200181818A1 (fr)
EP (1) EP3467176B1 (fr)
JP (1) JP7199702B2 (fr)
KR (1) KR20190016073A (fr)
CN (1) CN109563660A (fr)
MY (1) MY191871A (fr)
WO (1) WO2017212544A1 (fr)

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JP6959280B2 (ja) * 2019-02-28 2021-11-02 花王株式会社 洗浄用部材及びその製造方法
KR102399859B1 (ko) * 2021-07-30 2022-05-19 씨제이제일제당(주) 생분해성 코팅 조성물, 이의 제조 방법 및 이를 이용한 생분해성 물품

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EP3467176A1 (fr) 2019-04-10
US20200181818A1 (en) 2020-06-11
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MY191871A (en) 2022-07-18
CN109563660A (zh) 2019-04-02
JP7199702B2 (ja) 2023-01-06
WO2017212544A1 (fr) 2017-12-14
EP3467176A4 (fr) 2019-12-25

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