JP6805042B2 - Cartridge for water purifier and water purifier for softening - Google Patents
Cartridge for water purifier and water purifier for softening Download PDFInfo
- Publication number
- JP6805042B2 JP6805042B2 JP2017062335A JP2017062335A JP6805042B2 JP 6805042 B2 JP6805042 B2 JP 6805042B2 JP 2017062335 A JP2017062335 A JP 2017062335A JP 2017062335 A JP2017062335 A JP 2017062335A JP 6805042 B2 JP6805042 B2 JP 6805042B2
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- exchange resin
- water purifier
- cartridge
- softening
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 90
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 71
- 239000003729 cation exchange resin Substances 0.000 claims description 71
- 239000002253 acid Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 239000008399 tap water Substances 0.000 claims description 32
- 235000020679 tap water Nutrition 0.000 claims description 32
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010828 elution Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、水道水を浄化する共に軟化する軟化用浄水器及びそれに用いられる浄水器用カートリッジに関する。 The present invention relates to a water purifier for softening that purifies and softens tap water and a cartridge for a water purifier used therein.
軟水の効能として、（ａ）お茶やコーヒーの味をまろやかにする、（ｂ）調理器具等のスケール発生を防止する、（ｃ）石鹸の泡立ちが良くなる、（ｄ）グラス等容器へのウォーターマーク発生を抑制する等がある。このため、従来から、軟化機能を有する浄水器が広く利用されている。 The effects of soft water include (a) mellowing the taste of tea and coffee, (b) preventing scale generation in cooking utensils, (c) improving the foaming of soap, and (d) water in containers such as glasses. There are measures such as suppressing the generation of marks. For this reason, water purifiers having a softening function have been widely used conventionally.
水の軟化方法としては、（１）カチオン交換樹脂を用いる方法、（２）ＮＦ（Ｎａｎｏｆｉｌｔｒａｔｉｏｎ；ナノろ過）又はＲＯ（Ｒｅｖｅｒｓｅ Ｏｓｍｏｓｉｓ；逆浸透）膜を用いる方法、（３）アルカリ剤を添加することにより沈澱したものを除去する方法などがある。これらの中で、エネルギー効率や装置の維持管理面から、上記（１）のカチオン交換樹脂を用いる方法が優れている。 As a method for softening water, (1) a method using a cation exchange resin, (2) a method using an NF (Nanofiltration; nanofiltration) or RO (Reverse Osmosis) membrane, and (3) adding an alkaline agent. There is a method of removing the sedimented material. Among these, the method using the cation exchange resin described in (1) above is excellent from the viewpoint of energy efficiency and maintenance of the apparatus.
軟化用浄水器として、カチオン交換樹脂を用いる方法を選択した場合、硬度除去性能が重要視されることはもちろんのこと、カチオン交換樹脂自体からの不純物の溶出により、処理水品質を損なわないことも重要である。 When a method using a cation exchange resin is selected as the water purifier for softening, not only the hardness removal performance is emphasized, but also the quality of treated water is not impaired by the elution of impurities from the cation exchange resin itself. is important.
カチオン交換樹脂自体からの溶出物対策としては、例えば、特開平７−２０４６３１号公報（特許文献１）に、カチオン交換樹脂と活性炭を混合した浄水器が開示されている。 As a countermeasure against elution from the cation exchange resin itself, for example, Japanese Patent Application Laid-Open No. 7-204631 (Patent Document 1) discloses a water purifier in which a cation exchange resin and activated carbon are mixed.
しかし、引用文献１の浄水器であってもなお、カチオン交換樹脂からの溶出物の溶出が起こることがあるとの問題、特に一定時間静置後、通水再開初期の軟化水への溶出物の溶出量が多いとの問題があった。 However, even with the water purifier of Cited Document 1, there is a problem that eluate from the cation exchange resin may elute, especially eluate to softened water at the initial stage of resumption of water flow after standing for a certain period of time. There was a problem that the amount of elution was large.
従って、本発明の目的は、カチオン交換樹脂からの溶出物の溶出を低減することができる浄水器用カートリッジ及びそれが用いられている軟化用浄水器を提供することにある。 Therefore, an object of the present invention is to provide a water purifier cartridge capable of reducing elution of eluate from a cation exchange resin and a water purifier for softening in which the cartridge is used.
本発明者らは、上記課題を解決すべく、鋭意検討を行った結果、（１）塩形の強酸性カチオン交換樹脂と粒状活性炭を混合すれば、強酸性カチオン交換樹脂の溶出物の浄水器出口からの溶出を抑制することは可能だが、その混合状態によって、溶出量が異なること、（２）特に、一定時間静置（浸漬）後、通水再開初期の溶出物の溶出量を抑えるには、混合層最下部の混合状態が、均一又は活性炭リッチであることが重要であり、混合層最下部の混合状態が、強酸性カチオン交換樹脂リッチの場合、粒状活性炭での溶出物の除去が不十分となること、（３）塩形の強酸性カチオン交換樹脂の均一係数及び調和平均径等の塩形の強酸性カチオン交換樹脂の物性を特定の範囲に規定することにより、混合層最下部の混合状態を均一又は活性炭リッチにできるため、一定時間静置（浸漬）後、通水再開初期の溶出物の溶出量を低減できることを、見出した。更に、本発明者らは、粒状活性炭の粒度分布、真密度、均一度等の物性を特定の範囲に規定することにより、上記効果が高まることを見出した。 As a result of diligent studies to solve the above problems, the present inventors have (1) mixed a salt-type strongly acidic cation exchange resin with granular activated carbon to purify the eluate of the strongly acidic cation exchange resin. It is possible to suppress elution from the outlet, but the amount of elution differs depending on the mixed state. (2) In particular, to suppress the amount of elution at the initial stage of resuming water flow after standing (immersing) for a certain period of time. It is important that the mixed state at the bottom of the mixed layer is uniform or rich in activated carbon, and when the mixed state at the bottom of the mixed layer is rich in strongly acidic cation exchange resin, the eluate can be removed with granular activated carbon. Insufficiency, (3) By defining the physical properties of the salt-type strongly acidic cation exchange resin such as the uniformity coefficient and harmonized average diameter of the salt-type strongly acidic cation exchange resin within a specific range, the bottom of the mixed layer It has been found that the elution amount of the eluate at the initial stage of resuming water flow can be reduced after standing (immersing) for a certain period of time because the mixed state of the above can be made uniform or rich in activated carbon. Furthermore, the present inventors have found that the above effects are enhanced by defining physical properties such as particle size distribution, true density, and uniformity of granular activated carbon within a specific range.
すなわち、本発明（１）は、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材と、
を有し、
該軟化処理材が、均一係数が１．００〜１．２０であり、且つ、調和平均径が５００〜７００μｍである塩形の強酸性カチオン交換樹脂と、粒状活性炭と、の混合物からなること、
を特徴とする浄水器用カートリッジを提供するものである。
That is, the present invention (1) includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
The softening material filled in the filling area of the softening material in the cartridge container,
Have,
The softening material comprises a mixture of a salt-type strong acid cation exchange resin having a uniformity coefficient of 1.00 to 1.20 and a harmonic mean diameter of 500 to 700 μm, and granular activated carbon.
It is intended to provide a cartridge for a water purifier characterized by.
また、本発明（２）は、前記粒状活性炭は、体積基準の粒度分布において、０．１８０〜２．３６ｍｍの範囲に９０％以上が存在し、真密度が１．８〜２．３ｇ／ｍＬであり、且つ、均一係数が１．２〜１．８である活性炭であることを特徴とする（１）の浄水器用カートリッジを提供するものである。 Further, in the present invention (2), 90% or more of the granular activated carbon is present in the range of 0.180 to 2.36 mm in the volume-based particle size distribution, and the true density is 1.8 to 2.3 g / mL. The present invention provides the cartridge for a water purifier according to (1), which is an activated carbon having a uniformity coefficient of 1.2 to 1.8.
また、本発明（３）は、前記塩形の強酸性カチオン交換樹脂の真密度が、１．２０〜１．４０ｇ／ｍＬであることを特徴とする（１）又は（２）いずれかの浄水器用カートリッジを提供するものである。 Further, the present invention (3) is characterized in that the true density of the salt-type strongly acidic cation exchange resin is 1.20 to 1.40 g / mL, and the purified water according to either (1) or (2). It provides a dexterous cartridge.
また、本発明（４）は、前記粒状活性炭に対する前記塩形の強酸性カチオン交換樹脂の混合比（塩形の強酸性カチオン交換樹脂／粒状活性炭）が、体積基準で、１〜２０であることを特徴とする（１）〜（３）いずれかの浄水器用カートリッジを提供するものである。 Further, in the present invention (4), the mixing ratio of the salt-type strong acid cation exchange resin to the granular activated carbon (salt-type strong acid cation exchange resin / granular activated carbon) is 1 to 20 on a volume basis. (1) to (3) for providing a cartridge for a water purifier.
また、本発明（５）は、（１）〜（４）いずれかの浄水器用カートリッジと、
該浄水器用カートリッジを収納する筐体と、
を有することを特徴とする軟化用浄水器を提供するものである。
Further, the present invention (5) includes a cartridge for a water purifier according to any one of (1) to (4).
A housing for storing the water purifier cartridge and
It provides a water purifier for softening, which is characterized by having.
本発明によれば、カチオン交換樹脂からの溶出物の溶出を低減することができる浄水器用カートリッジ及びそれが用いられている軟化用浄水器を提供することができる。 According to the present invention, it is possible to provide a water purifier cartridge capable of reducing elution of eluate from a cation exchange resin and a water purifier for softening in which the cartridge is used.
本発明の浄水器用カートリッジは、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材と、
を有し、
該軟化処理材が、均一係数が１．００〜１．２０であり、且つ、調和平均径が５００〜７００μｍである塩形の強酸性カチオン交換樹脂と、粒状活性炭と、の混合物からなること、
を特徴とする浄水器用カートリッジである。
The cartridge for a water purifier of the present invention includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
The softening material filled in the filling area of the softening material in the cartridge container,
Have,
The softening material comprises a mixture of a salt-type strong acid cation exchange resin having a uniformity coefficient of 1.00 to 1.20 and a harmonic mean diameter of 500 to 700 μm, and granular activated carbon.
It is a cartridge for a water purifier characterized by.
本発明の浄水器用カートリッジは、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、カートリッジ容器内の軟化処理材の充填領域に充填されて軟化処理材と、を有する。そして、本発明の浄水器用カートリッジは、水道水の供給口と、軟化用浄水器の筐体内に形成されている水道水の供給経路とが繋がり、且つ、軟化水の排出口と、軟化用浄水器の筐体内に形成されている軟化水の排出経路とが繋がるように、軟化用浄水器の筐体内に設置される。 The cartridge for a water purifier of the present invention has a cartridge container in which a tap water supply port and a softened water discharge port are formed, and a softening treatment material filled in a filling region of the softening treatment material in the cartridge container. In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier are connected, and the softening water discharge port and the softening water purification water are connected. It is installed in the housing of the softening water purifier so as to be connected to the discharge path of the softened water formed in the housing of the vessel.
本発明の浄水器用カートリッジに係る軟化処理材は、塩形の強酸性カチオン交換樹脂と、粒状活性炭と、の混合物により構成されている。軟化処理材は、本発明の浄水器用カートリッジのカートリッジ容器内の軟化処理材の充填領域に充填されて、軟化処理材層を形成している。 The softening material according to the cartridge for a water purifier of the present invention is composed of a mixture of a salt-type strong acid cation exchange resin and granular activated carbon. The softening material is filled in the filling region of the softening material in the cartridge container of the cartridge for a water purifier of the present invention to form a softening material layer.
本発明の浄水器用カートリッジに係る塩形の強酸性カチオン交換樹脂は、均一係数が１．００〜１．２０であり、且つ、調和平均径が５００〜７００μｍである塩形の強酸性カチオン交換樹脂である。 The salt-type strong acid cation exchange resin according to the cartridge for a water purifier of the present invention has a uniformity coefficient of 1.00 to 1.20 and a harmonic mean diameter of 500 to 700 μm. Is.
塩形の強酸性カチオン交換樹脂の基体は、スチレン−ジビニルベンゼン共重合体である。塩形の強酸性カチオン交換樹脂の基体を形成する樹脂材は、一定時間水中で静置されると、例えば、夜間に軟化浄水器が使用されないために、夜間軟化処理材の充填領域に満たされた水道水中に浸漬されると、溶出物を溶出する。 The substrate of the salt-type strong acid cation exchange resin is a styrene-divinylbenzene copolymer. When the resin material forming the substrate of the salt-shaped strong acid cation exchange resin is allowed to stand in water for a certain period of time, for example, since the softening water purifier is not used at night, the filling area of the night softening treatment material is filled. When immersed in tap water, the eluate is eluted.
塩形の強酸性カチオン交換樹脂のカチオン交換基は、スルホン酸基である。また、塩形の強酸性カチオン樹脂の塩形は、Ｎａ形、Ｋ形、又はＬｉ形であり、Ｎａ形、Ｋ形が好ましい。 The cation exchange group of the salt-type strong acid cation exchange resin is a sulfonic acid group. The salt form of the salt-type strongly acidic cationic resin is Na-type, K-type, or Li-type, and Na-type or K-type is preferable.
塩形の強酸性カチオン交換樹脂としては、例えば、ダウケミカル製のアンバージェット１２２０Ｎａ、住化ケムテックス製のイマックＨＰ１２２０Ｎａが挙げられる。また、塩形の強酸性カチオン交換樹脂としては、強酸性カチオン交換樹脂であるダウエックス製のアンバージェット１０２０Ｈ等を、Ｎａ形、Ｋ形、Ｌｉ形に変換したものでもよい。 Examples of the salt-type strong acid cation exchange resin include Amberjet 1220Na manufactured by Dow Chemical and Immac HP1220Na manufactured by Sumika Chemtex. Further, as the salt-type strong acid cation exchange resin, a strong acid cation exchange resin such as Dowex's Amber Jet 1020H may be converted into a Na type, a K type, or a Li type.
塩形の強酸性カチオン交換樹脂の均一係数は、１．００〜１．２０、好ましくは１．００〜１．１５、特に好ましくは１．００〜１．１０である。塩形の強酸性カチオン交換樹脂の均一係数が、上記範囲であることにより、溶出物の溶出量を少なくすることができる。なお、均一係数の測定方法であるが、先ず、レーザー回折散乱法粒度分布測定装置による粒度分布測定により、粒子の大きさを測定して、分布を作図し、得られる分布図より、ふるい残留百分率累計値（体積基準）が９０％及び４０％に対応するふるいの目開き（ｍｍ）を算出する。次いで、４０％に対応する目開き（ｍｍ）に対する９０％に対応する目開き（ｍｍ）の比を計算して、得られる値を均一係数とする。均一係数が小さいほど、粒子が均一であることを示す。 The uniformity coefficient of the salt-type strongly acidic cation exchange resin is 1.00 to 1.20, preferably 1.00 to 1.15, and particularly preferably 1.00 to 1.10. When the uniformity coefficient of the salt-type strongly acidic cation exchange resin is within the above range, the elution amount of the eluate can be reduced. Regarding the method for measuring the uniformity coefficient, first, the particle size is measured by the particle size distribution measurement device using the laser diffraction / scattering method particle size distribution measuring device, the distribution is plotted, and the sieve residual percentage is obtained from the obtained distribution map. Calculate the mesh size (mm) of the sieve corresponding to the cumulative value (volume basis) of 90% and 40%. Next, the ratio of the opening (mm) corresponding to 90% to the opening (mm) corresponding to 40% is calculated, and the obtained value is used as the uniformity coefficient. The smaller the uniformity coefficient, the more uniform the particles.
塩形の強酸性カチオン交換樹脂の調和平均径は、５００〜７００μｍ、好ましくは５５０〜７００μｍ、特に好ましくは５５０〜６５０μｍである。塩形の強酸性カチオン交換樹脂の調和平均径が、上記範囲であることにより、溶出物の溶出量を少なくすることができる。 The harmonic mean diameter of the salt-type strong acid cation exchange resin is 500 to 700 μm, preferably 550 to 700 μm, and particularly preferably 550 to 650 μm. When the harmonic mean diameter of the salt-type strongly acidic cation exchange resin is within the above range, the amount of eluate elution can be reduced.
塩形の強酸性カチオン交換樹脂の真密度は、好ましくは１．２０〜１．４０ｇ／ｍＬ、特に好ましくは１．２５〜１．３５ｇ／ｍＬである。塩形の強酸性カチオン交換樹脂の真密度が、上記範囲にあることにより、溶出物の溶出量を少なくすることができる。塩形の強酸性カチオン交換樹脂の真密度が、上記範囲外だと、塩形の強酸性カチオン交換樹脂と粒状活性炭の混合性が悪くなる。特に、塩形の強酸性カチオン交換樹脂の真密度が、上記範囲を超えると、最下層に存在する塩形の強酸性カチオン交換樹脂の混合比率が大きくなり過ぎるので、溶出物の溶出量を少なくすることができない。 The true density of the salt-type strong acid cation exchange resin is preferably 1.20 to 1.40 g / mL, particularly preferably 1.25 to 1.35 g / mL. When the true density of the salt-type strongly acidic cation exchange resin is within the above range, the elution amount of the eluate can be reduced. If the true density of the salt-type strong acid cation exchange resin is out of the above range, the miscibility of the salt-type strong acid cation exchange resin and the granular activated carbon becomes poor. In particular, when the true density of the salt-type strong acid cation exchange resin exceeds the above range, the mixing ratio of the salt-type strong acid cation exchange resin existing in the lowermost layer becomes too large, so that the elution amount of the eluate is small. Can not do it.
本発明の浄水器用カートリッジに係る粒状活性炭は、球形又は不定形の粒状の活性炭である。粒状活性炭としては、木粉系、ヤシガラ系、フェノール樹脂系、石油コークス系、石炭コークス系、ピッチ系等の原料が賦活された材料が挙げられる。粒状活性炭としては、例えば、フタムラ社製の太閤活性炭ＣＷ４８０ＰＧＲ、ＣＮ４８０Ｇや、クラレ製のクラレコールＧＷ−Ｂ等が挙げられる。 The granular activated carbon according to the cartridge for a water purifier of the present invention is a spherical or amorphous granular activated carbon. Examples of the granular activated carbon include materials in which raw materials such as wood flour, coconut husk, phenolic resin, petroleum coke, coal coke, and pitch are activated. Examples of the granular activated carbon include Taiko activated carbon CW480PGR and CN480G manufactured by Futamura, and Kuraraycol GW-B manufactured by Kuraray.
粒状活性炭は、体積基準の粒度分布において、０．１８０〜２．３６ｍｍの範囲に９０％以上存在しているものが好ましく、０．１８０〜２．３６ｍｍの範囲に９５％以上存在しているものが特に好ましい。粒状活性炭の粒度分布が上記範囲にあることにより、溶出物の溶出量を少なくすることができる。粒状活性炭の粒度分布が、上記範囲外だと、塩形の強酸性カチオン交換樹脂と粒状活性炭の混合性が悪くなる。特に、粒状活性炭の粒度分布が、上記範囲未満だと、最下層に存在する塩形の強酸性カチオン交換樹脂の混合比率が大きくなり過ぎるので、溶出物の溶出量を少なくすることができない。 The granular activated carbon preferably has 90% or more in the range of 0.180 to 2.36 mm, and 95% or more in the range of 0.180 to 2.36 mm in the volume-based particle size distribution. Is particularly preferable. When the particle size distribution of the granular activated carbon is within the above range, the elution amount of the eluate can be reduced. If the particle size distribution of the granular activated carbon is out of the above range, the miscibility of the salt-type strongly acidic cation exchange resin and the granular activated carbon becomes poor. In particular, if the particle size distribution of the granular activated carbon is less than the above range, the mixing ratio of the salt-type strong acid cation exchange resin existing in the lowermost layer becomes too large, so that the elution amount of the eluate cannot be reduced.
粒状活性炭の真密度は、好ましくは１．８〜２．３ｇ／ｍＬ、特に好ましくは１．９〜２．３ｇ／ｍＬである。活性炭の真密度が、上記範囲にあることにより、溶出物の溶出量を少なくする効果が高まる。 The true density of the granular activated carbon is preferably 1.8 to 2.3 g / mL, particularly preferably 1.9 to 2.3 g / mL. When the true density of the activated carbon is in the above range, the effect of reducing the elution amount of the eluate is enhanced.
粒状活性炭の比表面積は、好ましくは６００〜１８００ｍ２／ｇ、特に好ましくは８００〜１８００ｍ２／ｇである。また、粒状活性炭の全細孔容積は、好ましくは０．４〜１．４ｍＬ／ｇ、特に好ましくは０．６〜１．４ｍＬ／ｇである。 The specific surface area of the granular activated carbon is preferably 600 to 1800 m 2 / g, particularly preferably 800 to 1800 m 2 / g. The total pore volume of the granular activated carbon is preferably 0.4 to 1.4 mL / g, particularly preferably 0.6 to 1.4 mL / g.
軟化処理材中、粒状活性炭に対する塩形の強酸性カチオン交換樹脂の混合比（塩形の強酸性カチオン交換樹脂／粒状活性炭）は、体積基準で、１〜２０であることが好ましく、５〜１０であることが特に好ましい。軟化処理材中、粒状活性炭に対する塩形の強酸性カチオン交換樹脂の混合比（塩形の強酸性カチオン交換樹脂／粒状活性炭）が、上記範囲にあることにより、溶出物の溶出量を少なくする効果が高くなる。 The mixing ratio of the salt-type strong acid cation exchange resin to the granular activated carbon (salt-type strong acid cation exchange resin / granular activated carbon) in the softened material is preferably 1 to 20 on a volume basis, and 5 to 10 Is particularly preferable. The effect of reducing the elution amount of the eluate when the mixing ratio of the salt-type strong acid cation exchange resin to the granular activated carbon (salt-type strong acid cation exchange resin / granular activated carbon) in the softened material is within the above range. Will be higher.
本発明の浄水器用カートリッジは、水道水の供給口と、本発明の軟化用浄水器の筐体内に形成されている水道水の供給経路とが繋がり、且つ、軟化水の排出口と、本発明の軟化用浄水器の筐体内に形成されている軟化水の排出経路とが繋がるように、本発明の軟化用浄水器の筐体内に設置される。 In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier of the present invention are connected, and the softened water discharge port and the present invention It is installed in the housing of the water purifier for softening of the present invention so as to be connected to the discharge path of the softened water formed in the housing of the water purifier for softening.
そして、水道水が、本発明の軟化浄水器内に供給され、本発明の軟化用浄水器の筐体内の水道水の供給経路を経て、軟化処理材の充填領域内に供給されて、軟化処理材層に通液される。水道水が、軟化処理材層に通過するときに、軟化処理材により、水道水中の硬度成分であるＣａイオンが、軟化処理材の塩形の強酸性カチオン交換樹脂のＮａイオン、Ｋイオン又はＬｉイオンに交換されて、水道水が軟化されると共に、軟化処理材中の粒状活性炭により、水道水中の塩素分、有機物等が除去されて、水道水が浄化される。軟化及び浄化された処理水は、本発明の軟化浄水器の筐体内の軟化水の排出経路を経て、本発明の軟化用浄水器の外に排出され、軟化水として使用される。 Then, tap water is supplied into the softening water purifier of the present invention, is supplied into the filling region of the softening treatment material via the tap water supply path in the housing of the softening water purifier of the present invention, and is softened. The liquid is passed through the material layer. When tap water passes through the softening treatment material layer, the softening treatment material causes Ca ions, which are hardness components in tap water, to be Na ions, K ions or Li of the salt-type strongly acidic cation exchange resin of the softening treatment material. The tap water is softened by being exchanged with ions, and the granular activated charcoal in the softening treatment material removes chlorine and organic substances in the tap water to purify the tap water. The softened and purified treated water is discharged to the outside of the softening water purifier of the present invention through a discharge path of the softened water in the housing of the softened water purifier of the present invention, and is used as softened water.
カチオン交換樹脂と水道水が接触したときに、カチオン交換樹脂から水道水への溶出物の溶出が起こる。そして、カチオン交換樹脂と水道水との接触時間が短ければ、水道水中の溶出物の濃度は非常に低いので、問題とならない。一方、カチオン交換樹脂と水道水との接触時間が長くなると、水道水中の溶出物の濃度が高くなってしまう。 When the cation exchange resin comes into contact with tap water, elution of the eluate from the cation exchange resin into tap water occurs. If the contact time between the cation exchange resin and tap water is short, the concentration of the eluate in tap water is very low, so that there is no problem. On the other hand, if the contact time between the cation exchange resin and tap water is long, the concentration of the eluate in tap water becomes high.
ここで、カチオン交換樹脂が充填されている軟化用浄水器が、一定時間使用されないまま静置されると、例えば、夜間に使用されないままであると、浄水器用カートリッジの軟化処理材の充填領域内で、充填領域内に滞留している水道水に、軟化処理材が一定時間浸漬された状態が続く。つまり、軟化浄水器が、一定時間使用されないまま静置されているときは、水道水とカチオン交換樹脂とが長時間接触している。そのため、水道水の通水を再開した直後の軟化水中の溶出物の濃度が高くなってしまう。 Here, if the softening water purifier filled with the cation exchange resin is left unused for a certain period of time, for example, if it is left unused at night, it is within the filling region of the softening material of the water purifier cartridge. Then, the softened material is immersed in the tap water staying in the filling region for a certain period of time. That is, when the softened water purifier is left unused for a certain period of time, the tap water and the cation exchange resin are in contact with each other for a long time. Therefore, the concentration of the eluate in the softened water immediately after the resumption of tap water flow becomes high.
それに対して、本発明の軟化用浄水器が、一定時間使用されないまま静置されると、例えば、夜間に使用されないままであると、本発明の浄水器用カートリッジの軟化処理材の充填領域内で、充填領域内に滞留している水道水に、軟化処理材が一定時間浸漬された状態が続き、水道水とカチオン交換樹脂とが長時間接触したとしても、本発明の浄水器用カートリッジでは、本発明に規定の物性値を有する塩形の強酸性カチオン交換樹脂と粒状活性炭とが混合されている軟化処理材を用いることにより、あるいは、本発明に規定の物性値を有する塩形の強酸性カチオン交換樹脂と本発明に規定の物性値を有する粒状活性炭とが混合されている軟化処理材が用いることにより、上記のような、一定時間使用されないまま静置された後の通液再開直後の軟化水中の溶出物の濃度を低くすることができる。 On the other hand, if the water purifier for softening of the present invention is left unused for a certain period of time, for example, if it is left unused at night, within the filling region of the softening treatment material of the cartridge for the water purifier of the present invention. Even if the softened material is continuously immersed in the tap water staying in the filling region for a certain period of time and the tap water and the cation exchange resin come into contact with each other for a long time, the cartridge for the water purifier of the present invention is used. By using a softened material in which a salt-type strongly acidic cation exchange resin having the physical properties specified in the present invention and granular activated carbon are mixed, or by using a salt-shaped strong acidic cation having the physical properties specified in the present invention. By using a softening treatment material in which a replacement resin and granular activated carbon having the specified physical properties of the present invention are mixed, the softening immediately after resuming liquid flow after being left unused for a certain period of time as described above. The concentration of eluates in water can be reduced.
本発明の軟化用浄水器は、本発明の浄水器用カートリッジと、本発明の浄水器用カートリッジを収納する筐体と、を有することを特徴とする軟化用浄水器である。 The water purifier for softening of the present invention is a water purifier for softening, which comprises a cartridge for the water purifier of the present invention and a housing for accommodating the cartridge for the water purifier of the present invention.
本発明の軟化用浄水器により処理される被処理水は、水道水である。 The water to be treated by the water purifier for softening of the present invention is tap water.
以下、本発明を実施例に基づき詳細に説明する。ただし、本発明は、以下の実施例に制限されるものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.
（実施例１）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、均一係数１．１３、調和平均径６１０μｍ、真密度１．２７ｇ／ｍＬのＮａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）を９００ｍＬと、体積基準の粒度分布で、０．１８０〜２．３６ｍｍの範囲に９９％存在し、真密度１．９ｇ／ｍＬ、均一係数１．５、比表面積１４００ｍ２／ｇ、全細孔容積０．６ｍＬ／ｇの粒状活性炭（太閤活性炭ＣＷ４８０ＰＧＲ、フタムラ化学社製）を１００ｍＬとを混合したものを充填し、カートリッジを作製した。
次いで、そのカートリッジ内に、水温２３℃の水道水をＳＶ６０ＢＶ／ｈｒで１５分間通水を行った。その後、カーリッジ内に水道水が溜まった状態で、２３℃の調節した室内にて、２４時間放置した。
２４時間放置後、再び、水温２３℃の水道水をＳＶ６０ＢＶ／ｈｒで１分間通水し、その間の処理水を採取した。次いで、処理水のＴＯＣ（全有機炭素）濃度を分析した。その結果を表１に示す。
(Example 1)
Na-type strongly acidic cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) with a uniformity coefficient of 1.13, a harmonized average diameter of 610 μm, and a true density of 1.27 g / mL in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. With a volume-based particle size distribution of 900 mL, 99% is present in the range of 0.180 to 2.36 mm, true density 1.9 g / mL, uniformity coefficient 1.5, specific surface area 1400 m 2 / g, total pores. A cartridge was prepared by filling a mixture of granular activated carbon (Taiko activated carbon CW480PGR, manufactured by Futamura Chemical Co., Ltd.) having a volume of 0.6 mL / g with 100 mL.
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the carriage, it was left for 24 hours in a room adjusted at 23 ° C.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the TOC (total organic carbon) concentration of the treated water was analyzed. The results are shown in Table 1.
＜強酸性カチオン交換樹脂の均一係数の測定方法、強酸性カチオン交換樹脂の調和平均径の測定方法、粒状活性炭の粒度分布の測定方法、粒状活性炭の均一係数の測定方法＞
ベックマンコールター社製のレーザー回折散乱法粒度分布測定装置（商品名：ＬＳ １３ ３２０（湿式システム））を用いて測定した。
<Measuring method of uniform coefficient of strong acid cation exchange resin, measuring method of harmonic average diameter of strongly acidic cation exchange resin, measuring method of particle size distribution of granular activated carbon, measuring method of uniform coefficient of granular activated carbon>
The measurement was performed using a laser diffraction / scattering method particle size distribution measuring device (trade name: LS 13 320 (wet system)) manufactured by Beckman Coulter.
＜強酸性カチオン交換樹脂の真密度の測定方法＞
ＪＩＳＺ８８０７：２０１２「固体の密度及び比重の測定方法」に準拠して実施した。
<Measuring method of true density of strong acid cation exchange resin>
It was carried out in accordance with JISZ8807: 2012 "Measuring method of density and specific gravity of solid".
＜粒状活性炭の真密度の測定方法＞
ＪＩＳＺ８８０７：２０１２「固体の密度及び比重の測定方法」に準拠して実施した。
<Measuring method of true density of granular activated carbon>
It was carried out in accordance with JISZ8807: 2012 "Measuring method of density and specific gravity of solid".
（比較例１）
Ｎａ形強酸性カチオン交換樹脂として、均一係数が１．４５、調和平均径が６１０μｍ、真密度が１．２７ｇ／ｍＬのＮａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）を用いること以外は、実施例１と同様に行った。その結果を表１に示す。
(Comparative Example 1)
As the Na-type strong acid cation exchange resin, a Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) having a uniformity coefficient of 1.45, a harmonic mean diameter of 610 μm, and a true density of 1.27 g / mL is used. Except for the above, the same procedure as in Example 1 was carried out. The results are shown in Table 1.
（実施例２）
Ｎａ形強酸性カチオン交換樹脂として、均一係数が１．０５、調和平均径が６１０μｍ、真密度が１．２７ｇ／ｍＬのＮａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製のものを粒径調整したもの）を用いること以外は、実施例１と同様に行った。
(Example 2)
As a Na-type strong acid cation exchange resin, a Na-type strong acid cation exchange resin having a uniformity coefficient of 1.05, a harmonic mean diameter of 610 μm, and a true density of 1.27 g / mL (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) is used. The same procedure as in Example 1 was carried out except that the particle size was adjusted).
（実施例３）
Ｎａ形強酸性カチオン交換樹脂として、均一係数が１．１３、調和平均径が６４０μｍ、真密度が１．２７ｇ／ｍＬのＮａ形強酸性カチオン交換樹脂（アンバージェット １０２０Ｈ、ダウケミカル社製のものをＮａ形に変換したもの）を用いること以外は、実施例１と同様に行った。
(Example 3)
As a Na-type strong acid cation exchange resin, a Na-type strong acid cation exchange resin (Amberjet 1020H, manufactured by Dow Chemical Co., Ltd.) having a uniformity coefficient of 1.13, a harmonic mean diameter of 640 μm, and a true density of 1.27 g / mL is used. It was carried out in the same manner as in Example 1 except that the Na form was used.
（実施例４）
体積基準の粒度分布で、０．１８０〜２．３６ｍｍの範囲に９８％存在し、真密度２．０ｇ／ｍＬ、均一係数１．７、比表面積１１００ｍ２／ｇ、全細孔容積０．８ｍＬ／ｇの粒状活性炭（ダイヤホープＭＳ１０、カルゴンカーボンジャパン社製）を用いること以外は、実施例１と同様に行った。
(Example 4)
In the volume-based particle size distribution, 98% is present in the range of 0.180 to 2.36 mm, true density 2.0 g / mL, uniformity coefficient 1.7, specific surface area 1100 m 2 / g, total pore volume 0.8 mL. The procedure was the same as in Example 1 except that / g of granular activated carbon (Diahope MS10, manufactured by Calgon Carbon Japan Co., Ltd.) was used.
（比較例２）
Ｎａ形強酸性カチオン交換樹脂として、均一係数が１．１３、調和平均径が７１０μｍ、真密度が１．２７ｇ／ｍＬのＮａ形強酸性カチオン交換樹脂（アンバーライト ２００ＣＴＮａ、ダウケミカル社製のものを粒径調整したもの）を用いること以外は、実施例１と同様に行った。
(Comparative Example 2)
As a Na-type strong acid cation exchange resin, a Na-type strong acid cation exchange resin having a uniformity coefficient of 1.13, a harmonic mean diameter of 710 μm, and a true density of 1.27 g / mL (Amberlite 200CTNa, manufactured by Dow Chemical Co., Ltd.) is used. The same procedure as in Example 1 was carried out except that the particle size was adjusted).
カチオン交換樹脂の均一係数及び調和平均径が、本発明に規定の範囲にある実施例１〜４は、通水再開後のＴＯＣが低く、カチオン交換樹脂からの溶出物の溶出が低減されていた。一方、カチオン交換樹脂の均一係数が、本発明の規定の範囲から外れている比較例１、及び調和平均径が、本発明の規定の範囲から外れている比較例２は、いずれも、通水再開後のＴＯＣが、実施例１〜４に比べ高く、カチオン交換樹脂からの溶出物の溶出の低減が十分でなかった。 In Examples 1 to 4 in which the uniformity coefficient and the harmonic mean diameter of the cation exchange resin were within the ranges specified in the present invention, the TOC after resumption of water flow was low, and the elution of the eluate from the cation exchange resin was reduced. .. On the other hand, in Comparative Example 1 in which the uniformity coefficient of the cation exchange resin is out of the specified range of the present invention, and Comparative Example 2 in which the harmonic mean diameter is out of the specified range of the present invention, water flow is performed. The TOC after resumption was higher than in Examples 1 to 4, and the elution of the eluate from the cation exchange resin was not sufficiently reduced.
Claims (3)
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材とを有し、
該軟化処理材が、真密度が１．２０〜１．４０ｇ／ｍＬであり、均一係数が１．００〜１．２０であり、且つ、調和平均径が５００〜７００μｍである塩形の強酸性カチオン交換樹脂と、体積基準の粒度分布において、０．１８０〜２．３６ｍｍの範囲に９０％以上が存在し、真密度が１．８〜２．３ｇ／ｍＬであり、且つ、均一係数が１．２〜１．８である粒状活性炭と、の混合物からなること、
を特徴とする浄水器用カートリッジ。 A cartridge container in which a tap water supply port and a softened water discharge port are formed,
It has a softening material that is filled in the filling area of the softening material in the cartridge container.
The softened material is a salt-type strongly acidic material having a true density of 1.20 to 1.40 g / mL, a uniformity coefficient of 1.00 to 1.20, and a harmonic mean diameter of 500 to 700 μm. In the cation exchange resin and the volume-based particle size distribution, 90% or more is present in the range of 0.180 to 2.36 mm, the true density is 1.8 to 2.3 g / mL, and the uniformity coefficient is 1. Consisting of a mixture of granular activated carbon of .2-1.8 ,
A cartridge for a water purifier that features.
該浄水器用カートリッジを収納する筐体と、
を有することを特徴とする軟化用浄水器。 The water purifier cartridge according to claim 1 or 2 ,
A housing for storing the water purifier cartridge and
A water purifier for softening, which is characterized by having.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017062335A JP6805042B2 (en) | 2017-03-28 | 2017-03-28 | Cartridge for water purifier and water purifier for softening |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017062335A JP6805042B2 (en) | 2017-03-28 | 2017-03-28 | Cartridge for water purifier and water purifier for softening |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018164867A JP2018164867A (en) | 2018-10-25 |
| JP6805042B2 true JP6805042B2 (en) | 2020-12-23 |
Family
ID=63922345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017062335A Active JP6805042B2 (en) | 2017-03-28 | 2017-03-28 | Cartridge for water purifier and water purifier for softening |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6805042B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59193185A (en) * | 1982-12-28 | 1984-11-01 | Yokohamashi | Simple water filter for use at time of disaster |
| JP5375842B2 (en) * | 2011-01-28 | 2013-12-25 | 三浦工業株式会社 | Ion exchanger |
| AU2012352341B2 (en) * | 2011-12-13 | 2016-12-08 | Ecolab Usa Inc. | Acid regeneration of ion exchange resins for industrial applications |
| JP6207446B2 (en) * | 2014-03-28 | 2017-10-04 | オルガノ株式会社 | Water purifier cartridge and water purifier |
| JP6444083B2 (en) * | 2014-07-23 | 2018-12-26 | オルガノ株式会社 | Water purifier cartridge and water purifier |
-
2017
- 2017-03-28 JP JP2017062335A patent/JP6805042B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018164867A (en) | 2018-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5550067B2 (en) | Method and apparatus for enrichment of magnesium ions in water | |
| JP4934177B2 (en) | Water purification apparatus and method | |
| EP3580179B1 (en) | A method for producing ultrapure water | |
| CN103553235B (en) | A kind of tap water purifying filter core | |
| CN105293794A (en) | Device for producing pharmaceutical water | |
| JP6907514B2 (en) | Ultrapure water production system and ultrapure water production method | |
| JP4467488B2 (en) | Condensate demineralization method and condensate demineralization apparatus | |
| JP2017200670A (en) | Activated carbon molded body and water purification cartridge | |
| JP6805042B2 (en) | Cartridge for water purifier and water purifier for softening | |
| JP5729062B2 (en) | Water treatment method and water treatment system | |
| JP6444083B2 (en) | Water purifier cartridge and water purifier | |
| JP4943377B2 (en) | Condensate demineralization method and condensate demineralization apparatus | |
| JP6207445B2 (en) | Water purifier cartridge and water purifier | |
| JP6983582B2 (en) | Cartridge for water purifier and water purifier for softening | |
| JP2015003283A (en) | Water purification filter | |
| JP6805043B2 (en) | Cartridge for water purifier and water purifier for softening | |
| EP2539282B1 (en) | Device and method for water treatment | |
| JP2007117997A (en) | Membrane filtration system and membrane filtration method | |
| JP4943376B2 (en) | Condensate demineralization method and condensate demineralization apparatus | |
| JP2009279519A (en) | Condensate demineralization method and condensate demineralizer | |
| TWM558250U (en) | Brewing water treatment system | |
| JP6337933B2 (en) | Water quality management system and operation method of water quality management system | |
| JP4383091B2 (en) | Condensate desalination method and apparatus | |
| RU2205692C2 (en) | Ion-exchange treatment method for organics-containing water involving countercurrent regeneration of ion-exchange materials | |
| KR100613365B1 (en) | Ion-purifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191213 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200827 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200915 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20201106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201201 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201203 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6805042 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |