WO2012153383A1 - Procédé de fabrication d'un comprimé - Google Patents

Procédé de fabrication d'un comprimé Download PDF

Info

Publication number
WO2012153383A1
WO2012153383A1 PCT/JP2011/060696 JP2011060696W WO2012153383A1 WO 2012153383 A1 WO2012153383 A1 WO 2012153383A1 JP 2011060696 W JP2011060696 W JP 2011060696W WO 2012153383 A1 WO2012153383 A1 WO 2012153383A1
Authority
WO
WIPO (PCT)
Prior art keywords
tablet
granulated product
mixture
bed granulator
fluidized bed
Prior art date
Application number
PCT/JP2011/060696
Other languages
English (en)
Japanese (ja)
Inventor
小星　重治
吉本　博
Original Assignee
株式会社ホットアルバム炭酸泉タブレット
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ホットアルバム炭酸泉タブレット filed Critical 株式会社ホットアルバム炭酸泉タブレット
Priority to PCT/JP2011/060696 priority Critical patent/WO2012153383A1/fr
Priority to JP2012097342A priority patent/JP2012236817A/ja
Priority to JP2012107272A priority patent/JP6000630B2/ja
Publication of WO2012153383A1 publication Critical patent/WO2012153383A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets

Definitions

  • the present invention relates to a method for producing a tablet, which is a foamable composition that has good long-term storage stability as a commercial product and quickly dissolves while foaming carbon dioxide in water.
  • Molding a mixture containing carbonate or bicarbonate and an organic acid by tableting or the like to form an effervescent composition is a cleaning agent, bath agent, bath water cleaner, pool disinfectant It is applied to such products.
  • These products have the advantage of quickly dissolving while generating carbon dioxide when they react with water, and at the same time increase the commercial value because they give consumers a comfortable feeling of use. In particular, in bath preparations, the blood circulation promoting effect of the generated carbon dioxide gas is actively used.
  • Patent Document 1 a method has been proposed in which the salt of carbonate and sodium sulfate is adjusted in advance and the organic acid is adjusted to this.
  • PEG polyethylene glycol
  • Patent Document 2 A method of embedding a foaming component in PEG has been proposed (Patent Document 2).
  • an object of the present invention is to maintain the shape of the tablet even if it is transported under the condition that citric acid is used as an organic acid, which has a fatigue recovery action and has a blood smoothing effect that creates a clean blood vessel.
  • citric acid is used as an organic acid
  • the present invention for solving the above problems has the following configuration. 1.
  • a and a mechanical fluidized bed granulator that does not substantially use air as a stirring action the powder temperature of the mixture of sodium bicarbonate and polyethylene glycol is raised to 60 to 65 ° C., and then cooled.
  • a granulated product obtained by using a mechanical fluidized bed granulator that does not substantially use air as a stirring action raising the powder temperature of a mixture of citric acid and polyethylene glycol to 60 to 65 ° C., and then cooling.
  • a and a mechanical fluidized bed granulator that does not substantially use air as a stirring action the powder temperature of the mixture of sodium bicarbonate and polyethylene glycol is raised to 60 to 65 ° C., and then cooled.
  • Citric acid decomposes the lactic acid that is sometimes produced, and it has the effect of recovering from fatigue, and it helps blood function and discharges waste products.
  • the effect of the present invention becomes more remarkable by specifying the mixing ratio of the granulated products A and B.
  • the mechanical fluidized bed granulator which does not substantially use air as the stirring action used in the present invention is a mixing in which a chamfered shovel is arranged in a horizontal drum to cause centrifugal diffusion and vortex action to flow three-dimensionally.
  • a chamfered shovel is arranged in a horizontal drum to cause centrifugal diffusion and vortex action to flow three-dimensionally.
  • the volume ratio of the powder to be filled is particularly preferably 40% or more and 80% or less in view of the effects of the present invention.
  • the granulator is preferably provided with a vacuum pump for reducing the pressure.
  • a granulator for tableting for example, one using air disclosed in Patent Document 3 for stirring action is known.
  • This granulator has so-called wet fracture granulation and stirring granulation.
  • the basic technology is granulation for tableting, which is a structure in which powder is suspended by air and granulated.
  • the granulated granule is porous, and when this granule is tableted, the hardness is increased and the granulation is performed at high speed. There is merit that can be tableted. That is, it is an extremely excellent technique for coding, and since it is a porous granule, it is easy to obtain hardness and has good solubility.
  • this technique can form a good tablet with an organic acid, for example, succinic acid or fumaric acid.
  • an organic acid for example, succinic acid or fumaric acid.
  • the technique is as follows. It turns out that there are drawbacks and inconveniences. That is, since it is made to flow with air, moisture cannot be completely removed, and the running cost is greatly increased. Moreover, it is difficult to completely remove moisture from the air. Even if the air contains a small amount of moisture, when it is flowed, citric acid and sodium bicarbonate absorb moisture during granulation with a large amount of moisture in the air. As a result, it became clear that various problems occur not only during production but also during storage and distribution of products.
  • the mechanical fluidized bed granulator which does not substantially use air as the stirring action used in the present invention is made to flow mechanically using blades called excavators without flowing with air.
  • the mechanical fluidized bed granulator which does not substantially use air as the stirring action used in the present invention is made to flow mechanically using blades called excavators without flowing with air.
  • the inventors of the present invention have also studied various techniques prior to the air-stirring fluidized bed granulator described in Patent Document 3 above. That is, for example, a Henschel granulator (wet breaking granulator) that does not use air is known, but this cannot be flowed, and the granule size distribution of the granules to be produced is wide, so that tableting is possible. This requires a process such as classification, which takes time and is disadvantageous in terms of cost. Moreover, the granule was high in density, and therefore could not give hardness, and was cracked or shattered by the impact of the transportation level. In addition, the present inventors have found out that it is difficult to apply to citric acid among organic acids because it has a high density and is difficult to dissolve and foam, resulting in lumps and precipitation. .
  • the powder temperature in the present invention is provided with a thermocouple for measuring the powder temperature in the can of a mechanical fluidized bed granulator that does not substantially use air as a stirring action, and is measured and displayed.
  • This powder temperature can be controlled by flowing hot water from a hot water tank that can control the temperature to the jacket, and cold water (about 5 ° C) prepared in advance for cooling and lowering the powder temperature in a short time. It is preferable that the tank can be switched.
  • the powder temperature of the present invention is preferably 60 ° C. or higher and 65 ° C. or lower for achieving the effects of the present invention. If the temperature is lower than 60 ° C, a part of the PEG melts due to the friction of the powder, and the granulation proceeds. However, it takes time and the efficiency is poor. Therefore, even if the surface is solidified, the inside does not solidify easily, and it takes time to cool down and the production efficiency is poor.
  • the PEG used in the present invention is preferably one having an average molecular weight of 4000 to 8000 because the effects of the present invention are exhibited.
  • PEG having an average molecular weight of about 6000 is most preferred from the viewpoint of improvement in molding stability, wrinkle adhesion resistance, capping, and tablet molding speed by a compression molding tableting machine such as a rotary tableting machine.
  • the ratio of PEG to 100 parts by mass of citric acid in the granulated product A is 1 to 20 parts by mass, preferably 2 to 10 parts by mass.
  • the ratio of PEG is less than the above amount, quality stability and tabletability
  • the ratio of PEG is larger than the above-mentioned amount, it is inferior in terms of quality stability and manufacturing cost.
  • the ratio of PEG in the granulated product B is 1 to 20 parts by mass, preferably 2 to 10 parts by mass per 100 parts by mass of sodium hydrogen carbonate.
  • the ratio of PEG is less than the above amount, quality stability and tableting
  • the ratio of PEG is larger than the above-mentioned amount, it is inferior in terms of quality stability and production cost.
  • the granulated product B is sodium hydrogen carbonate alone and does not contain PEG, there is a drawback that carbon dioxide gas is spontaneously generated and disintegrated after about 2 months at room temperature after the product after tableting.
  • the granulated product B may contain sodium carbonate together with sodium hydrogen carbonate.
  • sodium carbonate include decahydrate, monohydrate and anhydrous salt.
  • An anhydrous salt is preferred for performance. That is, by using anhydrous sodium carbonate in an amount of 1/10 to 1/30 of the amount of sodium hydrogen carbonate in operation 11 in the examples described later, sample No. The effect equivalent to 14 was obtained. Further, this sample No. As shown in FIG. 14, the effect of the present invention was better exhibited by using spraying with ethanol together.
  • the ratio of the granulated product B to the granulated product A is particularly preferably 1 to 4 to 1 to 6 parts by mass for obtaining the effects of the present invention.
  • a mold release agent can be used, and as this mold release agent, n-hexane sulfonate sodium and n-octane sulfonate sodium are preferable for achieving the effects of the present invention.
  • sodium n-octane sulfonate is most preferable for stably and continuously molding the tablet according to the present invention at a high speed.
  • Ethanol is preferably 99% ethyl alcohol as a raw material, using a zeolite membrane manufactured by Mitsui Engineering & Shipbuilding Co., Ltd. to produce 99.9% ethyl alcohol, and using this is preferable for achieving the effects of the present invention.
  • the ratio of ethanol to 100 parts by mass of citric acid in the granulated product A is 0.05 to 5 parts by mass, preferably 0.1 to 1 part by mass. If the ethanol ratio is less than the above amount, quality stability On the other hand, when the ratio of ethanol is larger than the above amount, it is inferior in terms of quality stability and production cost.
  • the ratio of ethanol in the granulated product B is 0.05 to 5 parts by mass, preferably 0.1 to 1 part by mass per 100 parts by mass of citric acid. If the ethanol ratio is less than the above amount, the quality is stable. When the ratio of ethanol is larger than the above amount, the quality stability and production cost are inferior.
  • the granulated product A includes fragrances, pigments, surfactants and the like.
  • the granulated product B includes sodium carbonate, fragrances, pigments, surfactants and the like.
  • the mixing ratio of the granulated product A and the granulated product B is 1: 2 to 1:10, preferably 1: 4 to 1: 6, and if it is outside this range, the effects of the present invention can be obtained. (Refer to sample Nos. 8, 9, and 11 in the examples described later).
  • a known compression molding machine can be used without any particular limitation.
  • a hydraulic press machine, a single shot tableting machine, a rotary tableting machine, a briquetting machine, etc. can be used. .
  • Example 1 Preparation of Comparative Tablet A The following operation was performed using a fluidized bed granulator GPCG-300CT manufactured by Powerex. (Operation 1) Preparation of comparative granule A 390 kg of anhydrous citric acid and PEG # 6000, 20 kg were added to a Porex fluidized bed granulator GPCG-300CT installed in a granulation chamber air-conditioned at 23 ° C. and 60%. Then, the powder is flowed with flowing air set at 65 ° C. When the powder temperature reaches 65 ° C., the flowing air is set at 15 ° C. and the powder is cooled. When the powder temperature reached about 35 ° C., the granulation was finished, the powder was discharged into an airtight container, stored, and granules A were obtained.
  • Comparative Tablet B The following operation was performed using a fluidized bed granulator GPCG-300CT manufactured by Powerex. (Operation 6) Preparation of Comparative Granule C Charged with 390 kg of anhydrous citric acid and PEG # 6000, 20 kg into a Porex fluidized bed granulator GPCG-300CT installed in a granulation chamber conditioned at 60 ° C. at 23 ° C. Then, the powder is flowed with flowing air set at 65 ° C. When the powder temperature reaches 65 ° C., the flowing air is set at 15 ° C. and the powder is cooled. When the powder temperature reached about 35 ° C., the granulation was finished, the powder was discharged into an airtight container, stored, and granules C were obtained.
  • Preparation of tablet according to the present invention (Operation 10) Preparation of granule A2 Matsudaka Giken-made Readyge Mixer VT1200 installed in a granulation chamber air-conditioned at 23 ° C. and 60% (a horizontal excavator in a horizontal drum and It has a vacuum pump for depressurization, and has a chopper for preventing granulated granules from becoming coarse particles during cooling, and it can be controlled by flowing hot water from a hot water tank that can control the temperature to the jacket. In addition, in order to cool and lower the powder temperature in a short time, it has a configuration in which cold water (about 5 ° C.) can be switched to a cold water tank prepared in advance.
  • the hot water at about 65 ° C. was circulated and heated while stirring at 115 rpm.
  • PEG # 6000, 20 Kg was added.
  • the powder temperature reached 65 ° C. the hot water in the jacket was replaced with water at a water temperature of 15 ° C., and the pressure was reduced to 10 Torr. Cooled down.
  • the powder temperature reached about 35 ° C. the powder was discharged from the bottom outlet and stored in an airtight container to obtain granules A2.
  • Foam test The volume change of the aluminum barrier bag before and after storage at 45 ° C. was measured. In addition, if it is 5 ml or less, it will be practical and there is no problem as a commercial product.
  • Dissolution test One tablet was placed in 1000 ml of water kept at 40 ° C., and the state until the tablet was dissolved was observed and evaluated according to the following criteria.
  • the present invention has no problem that tablets containing citric acid and sodium hydrogen carbonate are disintegrated even when transported, that is, the shape of the tablets can be maintained, and carbon dioxide gas due to storage can be maintained. There is no occurrence and it can be seen that the tablet is completely dissolved in use.
  • the storage period was extended to 20 days, it was confirmed that the samples other than the present invention ruptured the aluminum barrier bag.
  • Example 2 In Table 2, the ratio of the granule B2 to the granule A2 was changed in the operation 12 of the sample 3 of Example 1, and the subsequent operation was performed in the same manner to prepare a sample, and the evaluation results were summarized. Sample No. 1 and 3 are also shown.
  • Example 3 (Operation 15) Preparation of ethanol 99.9% ethyl alcohol (hereinafter referred to as ethanol) was prepared from commercially available 99% ethyl alcohol using a zeolite membrane manufactured by Mitsui Engineering & Shipbuilding. Table 3 shows the sample No. of Example 1. In the operations 10 and 11 of 3, after the introduction of PEG # 6000, the ethanol prepared in the operation 15 is sprayed at an amount of 0.3 parts by mass per 100 parts by mass of citric acid at a rate of 200 ml / min. Thereafter, the same operation was performed to prepare granules. Others were prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 3. Sample No. 1 and 3 are also shown.
  • Example 4 Sample No. 1 in Example 1 In the preparation of No. 3, only the following operations were performed, and the others were the same. That is, in operation 11, anhydrous sodium carbonate was added in an amount of 1/10 or 1/30 of the amount of sodium bicarbonate. As for the evaluation results, the sample No. It was equivalent to 14.
  • foamed compositions as solid materials such as cleaning agents, bath agents, bath water cleaners, and pool disinfectants.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention s'attaque au problème consistant à proposer un procédé de fabrication d'un comprimé qui utilise de l'acide citrique, conserve la forme de comprimé de celui-ci même lorsqu'il est transporté, ne génère pas de dioxyde de carbone gazeux lorsqu'il est stocké, et se dissout complètement dans l'eau lorsqu'il est utilisé. La solution à ce problème est un procédé de fabrication dans lequel une substance sous forme de granulés (A) obtenue, à l'aide d'un granulateur mécanique à lit fluidisé qui n'est sensiblement pas utilisé pour une agitation d'air, par augmentation de la température d'une poudre qui est un mélange d'acide citrique et de polyéthylène glycol à 60-65°C, puis refroidissement, et une substance sous forme de granulés (B) obtenue, à l'aide d'un granulateur mécanique à lit fluidisé qui n'est sensiblement pas utilisé pour une agitation d'air, par augmentation de la température d'une poudre qui est un mélange d'hydrogéno carbonate de sodium et de polyéthylène glycol à 60-65°C, puis refroidissement, sont mélangés d'une manière telle que le rapport de la seconde substance sous forme de granulés (B) par rapport à la première substance sous forme de granulés (A) est 1 :2-1 :10, puis le mélange est moulé par compression en un comprimé.
PCT/JP2011/060696 2011-05-10 2011-05-10 Procédé de fabrication d'un comprimé WO2012153383A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/JP2011/060696 WO2012153383A1 (fr) 2011-05-10 2011-05-10 Procédé de fabrication d'un comprimé
JP2012097342A JP2012236817A (ja) 2011-05-10 2012-04-23 錠剤の製造方法
JP2012107272A JP6000630B2 (ja) 2011-05-10 2012-05-09 錠剤の製造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2011/060696 WO2012153383A1 (fr) 2011-05-10 2011-05-10 Procédé de fabrication d'un comprimé

Publications (1)

Publication Number Publication Date
WO2012153383A1 true WO2012153383A1 (fr) 2012-11-15

Family

ID=47138886

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/060696 WO2012153383A1 (fr) 2011-05-10 2011-05-10 Procédé de fabrication d'un comprimé

Country Status (1)

Country Link
WO (1) WO2012153383A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013180048A1 (fr) * 2012-05-28 2013-12-05 株式会社ホットアルバム炭酸泉タブレット Procédé de fabrication d'un comprimé et comprimé
JP2013245218A (ja) * 2012-10-10 2013-12-09 Hot Album Tansansen Tablet Inc 錠剤の製造方法及び錠剤
JP2014005268A (ja) * 2012-05-28 2014-01-16 Hot Album Tansansen Tablet Inc 固形浴剤、ミネラル汚れ洗浄法及び皮膚又は毛髪の美容法
CN112195565A (zh) * 2020-09-27 2021-01-08 上海纳米技术及应用国家工程研究中心有限公司 用于室内空气调湿的静电纺丝多层纳米纤维膜的制备方法及产品和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61176519A (ja) * 1985-01-30 1986-08-08 Kao Corp 錠剤の製造方法
WO2001052820A1 (fr) * 2000-01-17 2001-07-26 Kyowa Hakko Kogyo Co., Ltd. Pastille a effet moussant, pastille d'addition pour le bain a effet moussant, pastille detergente de lavage a effet moussant, pastille a effet moussant pour administration orale et procedes de production de ces pastilles
JP2002275051A (ja) * 2001-01-12 2002-09-25 Kansai Koso Kk 固体化粧料
JP2011021004A (ja) * 2009-06-16 2011-02-03 Kao Corp 発泡性粉末入浴剤組成物の製造方法
JP2011105615A (ja) * 2009-11-13 2011-06-02 Ando Masahiro 錠剤の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61176519A (ja) * 1985-01-30 1986-08-08 Kao Corp 錠剤の製造方法
WO2001052820A1 (fr) * 2000-01-17 2001-07-26 Kyowa Hakko Kogyo Co., Ltd. Pastille a effet moussant, pastille d'addition pour le bain a effet moussant, pastille detergente de lavage a effet moussant, pastille a effet moussant pour administration orale et procedes de production de ces pastilles
JP2002275051A (ja) * 2001-01-12 2002-09-25 Kansai Koso Kk 固体化粧料
JP2011021004A (ja) * 2009-06-16 2011-02-03 Kao Corp 発泡性粉末入浴剤組成物の製造方法
JP2011105615A (ja) * 2009-11-13 2011-06-02 Ando Masahiro 錠剤の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013180048A1 (fr) * 2012-05-28 2013-12-05 株式会社ホットアルバム炭酸泉タブレット Procédé de fabrication d'un comprimé et comprimé
JP2014005268A (ja) * 2012-05-28 2014-01-16 Hot Album Tansansen Tablet Inc 固形浴剤、ミネラル汚れ洗浄法及び皮膚又は毛髪の美容法
JP2014005266A (ja) * 2012-05-28 2014-01-16 Hot Album Tansansen Tablet Inc 錠剤の製造方法及び錠剤
JP2013245218A (ja) * 2012-10-10 2013-12-09 Hot Album Tansansen Tablet Inc 錠剤の製造方法及び錠剤
CN112195565A (zh) * 2020-09-27 2021-01-08 上海纳米技术及应用国家工程研究中心有限公司 用于室内空气调湿的静电纺丝多层纳米纤维膜的制备方法及产品和应用

Similar Documents

Publication Publication Date Title
JP5017516B2 (ja) 錠剤の製造方法
JP2011105615A5 (fr)
EP1220883A1 (fr) Produit de bain moussant et effervescent
WO2005074948A1 (fr) Formulation solide pour dialyse et procede de fabrication de ladite formulation
WO2012153383A1 (fr) Procédé de fabrication d'un comprimé
JP5877778B2 (ja) 錠剤の製造方法及び錠剤
JP2014005266A5 (fr)
JP5588490B2 (ja) 錠剤の製造方法及び錠剤
JPS61176519A (ja) 錠剤の製造方法
JPS6289616A (ja) 錠剤の製造方法
JP5987162B2 (ja) ブリケット型入浴剤
JP2012236817A (ja) 錠剤の製造方法
JP2013245218A5 (fr)
JPH07187998A (ja) 錠剤の製造方法
JP6000630B2 (ja) 錠剤の製造方法
JPH02145522A (ja) ペースト状人工腎臓潅流用剤及びその製造方法
JP4561978B2 (ja) 固形透析用剤およびその製造方法
JP6776020B2 (ja) 粒状皮膚洗浄料組成物の製造方法
JP2001276597A (ja) 造粒粉体及びその製造方法及び圧縮成形固形物
JP5727193B2 (ja) 圧縮成形浴用剤
JP2986810B2 (ja) 透析用剤及びその製造方法
JP6830647B2 (ja) 発泡性成形浴用剤
JP7391032B2 (ja) ジクロロイソシアヌル酸ナトリウムを含有する発泡錠
JP7398775B2 (ja) 発泡性成形浴用剤
JP7313856B2 (ja) キセノンウルトラファインバブル発生剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11865391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11865391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP