JP2009091499A - Fine gel particle of water-absorbing resin, and coated film and laminated product made from the same - Google Patents

Fine gel particle of water-absorbing resin, and coated film and laminated product made from the same Download PDF

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JP2009091499A
JP2009091499A JP2007265253A JP2007265253A JP2009091499A JP 2009091499 A JP2009091499 A JP 2009091499A JP 2007265253 A JP2007265253 A JP 2007265253A JP 2007265253 A JP2007265253 A JP 2007265253A JP 2009091499 A JP2009091499 A JP 2009091499A
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water
absorbent resin
absorbing resin
fine
gel
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JP5242983B2 (en
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Yuhei Funabiki
裕平 船引
Norihiro Sugihara
範洋 杉原
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Sumitomo Seika Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine gel particle of a water-absorbing resin capable of being dispersed in an aqueous medium stably, and to provide a coated film and a laminated product made from it. <P>SOLUTION: This fine gel particle of the water-absorbing resin is produced by grinding the gel of the water-absorbing resin of 80-100% swelling degree and has a mean particle size of 0.01-5 μm. The coated film and the laminated product is produced by use of it. Because the gel particle has a fine mean particle size of 0.01-5 μm as a swelled state of the water-absorbing resin, it is suitably used as a material to form a hydrophilic coating film, for a printing medium for an inkjet printer, an anti-fog coating, an anti-fouling coating, a treating agent for a moisture condensation proofing wall paper, a surface treating agent for an agriculture use vinyl film, a chemicals absorber for medical, an antistatic agent, a synthetic leather, an artificial leather, a water vapor permeable waterproofing material for a fiber coating, and an adhesive for earthenware, etc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、吸水性樹脂の微細ゲル粒子、ならびにそれにより得られるコーティング膜および積層体に関する。さらに詳しくは、インクジェットプリンター用記録媒体、防曇塗料、汚れ防止機能を有する塗料、結露防止壁紙用処理剤、農業用ビニルフィルムの表面処理剤、メディカル用薬液吸収体、帯電防止剤、合成皮革、人工皮革、繊維コーティング用透湿防水素材、陶器用粘着剤等に、親水性コーティング膜形成材料として好適に用いられる吸水性樹脂の微細ゲル粒子、ならびにそれにより得られるコーティング膜および積層体に関する。   The present invention relates to fine gel particles of a water absorbent resin, and a coating film and a laminate obtained thereby. More specifically, recording media for inkjet printers, antifogging paints, antifouling paints, anti-condensation wallpaper treatments, agricultural vinyl film surface treatments, medical chemical absorbers, antistatic agents, synthetic leather, The present invention relates to fine gel particles of a water-absorbent resin suitably used as a hydrophilic coating film forming material for artificial leather, moisture-permeable waterproof material for fiber coating, adhesive for ceramics, and the like, and a coating film and a laminate obtained thereby.

従来から、吸水性樹脂は、紙おむつ、生理用ナプキン等の衛生材料、ケーブル用止水材等の工業材料、土壌改質剤、結露防止剤、固化剤等の土木建築材料等に幅広く用いられている。   Conventionally, water-absorbing resins have been widely used in sanitary materials such as disposable diapers and sanitary napkins, industrial materials such as water-stopping materials for cables, civil engineering and building materials such as soil modifiers, anti-condensation agents, and solidifying agents. Yes.

近年、様々な基材に対して、くもり防止、汚れ防止、結露防止、帯電防止、透水防止、吸湿防止等の性能を付与するために、吸水性樹脂を溶媒に分散させたコーティング剤が検討されている。また、環境、安全性の観点から、水および/または親水性有機溶媒を用いたコーティング剤が特に望まれている。   In recent years, a coating agent in which a water-absorbing resin is dispersed in a solvent has been studied in order to impart various properties such as fogging prevention, dirt prevention, condensation prevention, antistatic, water permeation prevention, moisture absorption prevention, etc. ing. In addition, from the viewpoint of environment and safety, a coating agent using water and / or a hydrophilic organic solvent is particularly desired.

このようなコーティング剤に用いられる吸水性樹脂は、微細なものが好適に用いられる。微細な吸水性樹脂を得るには、吸水性樹脂を製造後、粉砕する方法が挙げられるが、多大な労力、時間を要し、経済的にも不利である。そこで、直接微細な吸水性樹脂を得る方法が提案されているが(特許文献1参照)、微細粉化した吸水性樹脂は、粉立ち、帯電等の安全面、ハンドリング面において問題がある。一方、上記の問題を解決するために、吸水性樹脂の製造時から水系の溶媒を用いて、直接、水系の吸水性樹脂分散液を得る方法が提案されている(特許文献2参照)。しかしながら、この方法では使用できるモノマーが限定されるため、様々な機能を付与した吸水性樹脂を有する分散液を製造することは難しい。   A fine water-absorbing resin used for such a coating agent is preferably used. In order to obtain a fine water-absorbent resin, a method of pulverizing the water-absorbent resin can be mentioned, but it requires a lot of labor and time, which is disadvantageous economically. Therefore, a method for directly obtaining a fine water-absorbing resin has been proposed (see Patent Document 1), but the finely powdered water-absorbing resin has problems in terms of safety such as dusting and charging, and handling. On the other hand, in order to solve the above problems, a method of directly obtaining an aqueous water-absorbent resin dispersion using an aqueous solvent has been proposed since the production of the water-absorbent resin (see Patent Document 2). However, since the monomers that can be used in this method are limited, it is difficult to produce a dispersion having a water-absorbing resin having various functions.

さらに、吸水性樹脂を膨潤させた状態で粉砕する方法として、吸水ポリマーを水中で膨潤した状態で粉砕する方法(特許文献3参照)、吸水性ゲルを水性溶媒により膨潤させて、機械的に粉砕させる方法(特許文献4参照)等が提案されている。しかしながら、これらの方法では粉砕時の吸水性樹脂の膨潤度が低く粉砕が不十分となり、微細な粒子径の吸水性ゲル粒子が得られない。   Furthermore, as a method of pulverizing the water-absorbing resin in a swollen state, a method of pulverizing the water-absorbing polymer in a swollen state in water (see Patent Document 3), a water-absorbing gel is swollen with an aqueous solvent and mechanically pulverized. A method (see Patent Document 4) is proposed. However, in these methods, the degree of swelling of the water-absorbent resin during pulverization is low and pulverization becomes insufficient, and water-absorbing gel particles having a fine particle diameter cannot be obtained.

このため、水性媒体に安定的に分散可能な、吸水性樹脂の微細ゲル粒子が望まれている。   For this reason, fine gel particles of a water-absorbing resin that can be stably dispersed in an aqueous medium are desired.

特開平05−178924号公報JP 05-178924 A 特開平11−228808号公報JP-A-11-228808 特開平06−207107号公報Japanese Patent Laid-Open No. 06-207107 特開平10−279693号公報JP-A-10-279893

本発明の目的は、水性媒体に安定的に分散可能な吸水性樹脂の微細ゲル粒子、ならびにそれにより得られるコーティング膜および積層体を提供することにある。   An object of the present invention is to provide fine gel particles of a water-absorbent resin that can be stably dispersed in an aqueous medium, and a coating film and a laminate obtained thereby.

すなわち本発明は、膨潤度が80〜100%の吸水性樹脂のゲルを粉砕することにより得られる、中位粒子径が0.01〜5μmの吸水性樹脂の微細ゲル粒子、ならびにそれにより得られるコーティング膜および積層体に関する。   That is, the present invention provides a water-absorbent resin fine gel particle having a median particle diameter of 0.01 to 5 μm obtained by pulverizing a gel of a water-absorbent resin having a degree of swelling of 80 to 100%, and is obtained thereby. The present invention relates to a coating film and a laminate.

本発明によれば、吸水性樹脂を水により特定の膨潤度に膨潤させた状態で粉砕するので、吸水性樹脂の微細粉化に、多大な労力や時間を要せず、粉立ち、帯電等の安全面、ハンドリング面における問題もなく、水性分散液に安定的に分散可能な、吸水性樹脂の微細ゲル粒子が得られる。   According to the present invention, the water-absorbing resin is pulverized in a state of being swollen to a specific degree of swelling with water, and therefore, fine powdering of the water-absorbing resin does not require much labor and time, and powdering, charging, etc. Thus, fine gel particles of a water-absorbent resin that can be stably dispersed in an aqueous dispersion without any problems in safety and handling are obtained.

本発明の中位粒子径が0.01〜5μmの吸水性樹脂の微細ゲル粒子は、膨潤度が80〜100%の吸水性樹脂のゲルを粉砕することにより得られる。   The water-absorbent resin fine gel particles having a median particle diameter of 0.01 to 5 μm of the present invention can be obtained by pulverizing a water-absorbent resin gel having a swelling degree of 80 to 100%.

吸水性樹脂としては、特に限定されず、例えば、澱粉−アクリロニトリルグラフト共重合体の加水分解物、澱粉−アクリル酸グラフト重合体の中和物、酢酸ビニル−アクリル酸エステル共重合体のケン化物、アクリル酸塩−ビニルアルコール共重合体およびその架橋物、無水マレイン酸グラフトポリビニルアルコール架橋物、架橋イソブチレン−無水マレイン酸共重合体、カルボキシメチルセルロースのアルカリ塩架橋物、α−ヒドロキシアクリル酸重合体の架橋物、ポリアクリル酸部分中和物、変性ポリアルキレンオキサイド、アミノ基含有エチレン性不飽和単量体重合物、スルホン酸基含有エチレン性不飽和単量体重合物等が挙げられる。   The water absorbent resin is not particularly limited, for example, a hydrolyzate of starch-acrylonitrile graft copolymer, a neutralized product of starch-acrylic acid graft polymer, a saponified product of vinyl acetate-acrylic ester copolymer, Acrylate-vinyl alcohol copolymer and its cross-linked product, maleic anhydride grafted polyvinyl alcohol cross-linked product, cross-linked isobutylene-maleic anhydride copolymer, carboxymethyl cellulose alkali salt cross-linked product, cross-linked α-hydroxyacrylic acid polymer Product, polyacrylic acid partial neutralized product, modified polyalkylene oxide, amino group-containing ethylenically unsaturated monomer polymer, sulfonic acid group-containing ethylenically unsaturated monomer polymer, and the like.

前記吸水性樹脂は、市販のものを用いることもでき、例えば、ポリアクリル酸部分中和物(住友精化株式会社の商品名「アクアキープSA60、10SH−P」);ノニオン型ポリアルキレンオキサイド系樹脂(住友精化株式会社の商品名「アクアコークTWB−P」);アクリル酸塩−ビニルアルコール共重合体(住友精化株式会社製)等が挙げられる。これらは、単独で使用してもよいし、2種以上を併用してもよい。   A commercially available product can be used as the water-absorbing resin. For example, a partially neutralized polyacrylic acid (trade name “Aquakeep SA60, 10SH-P” from Sumitomo Seika Co., Ltd.); nonionic polyalkylene oxide type Resin (trade name “Aqua Coke TWB-P” of Sumitomo Seika Co., Ltd.); acrylate-vinyl alcohol copolymer (manufactured by Sumitomo Seika Co., Ltd.) and the like. These may be used alone or in combination of two or more.

前記吸水性樹脂のイオン交換水に対する吸水能は、1〜1500g/gが好ましく、1〜1000g/gであることがより好ましい。吸水性樹脂のイオン交換水に対する吸水能が1g/g未満の場合、得られる吸水性樹脂粒子の水性分散液を用いてコーティング膜を形成したときに、充分な吸水能力が得られないおそれがある。また、吸水性樹脂のイオン交換水に対する吸水能が1500g/gを超える場合、使用できなくはないが、工業的に製造されていないため実用的ではない。なお、本発明においてイオン交換水に対する吸水能とは、後述の測定方法により求められた値である。   The water absorption capacity of the water absorbent resin with respect to ion-exchanged water is preferably 1-1500 g / g, and more preferably 1-1000 g / g. When the water absorption capacity of the water absorbent resin with respect to ion-exchanged water is less than 1 g / g, there is a possibility that sufficient water absorption capacity may not be obtained when a coating film is formed using an aqueous dispersion of the resulting water absorbent resin particles. . Moreover, when the water absorption capacity with respect to ion-exchange water of a water absorbing resin exceeds 1500 g / g, it cannot be used, but since it is not manufactured industrially, it is not practical. In addition, in this invention, the water absorption ability with respect to ion-exchange water is the value calculated | required by the below-mentioned measuring method.

本発明においては、吸水性樹脂を水により膨潤させ、膨潤度が80〜100%、好ましくは83〜100%となるように、膨潤状態の吸水性樹脂のゲルを調製する。膨潤度が80%未満の場合、吸水性樹脂が十分に膨潤できていないために粉砕不良となり、得られる吸水性樹脂のゲル粒子の中位粒子径が大きくなったり、不均一となる。   In the present invention, the water-absorbent resin is swollen with water, and the swollen water-absorbent resin gel is prepared so that the degree of swelling is 80 to 100%, preferably 83 to 100%. When the degree of swelling is less than 80%, the water-absorbent resin is not sufficiently swollen, resulting in poor pulverization, and the median particle size of the resulting water-absorbent resin gel particles becomes large or non-uniform.

本発明において、膨潤度とは、吸水性樹脂のゲルに含まれる吸水性樹脂単位質量あたりの水(g/g)の、後述の測定方法により求められた吸水性樹脂のイオン交換水に対する吸水能(g/g)に対する割合を意味する。詳しくは、次式により求められる。
[膨潤度(%)]=[ゲルに含まれる水(g)/吸水性樹脂(g)]
÷吸水能(g/g)×100
In the present invention, the degree of swelling refers to the water absorption capacity of water-absorbent resin per unit mass of water-absorbent resin contained in the gel of the water-absorbent resin to the ion-exchanged water of the water-absorbent resin determined by the measurement method described later It means the ratio to (g / g). Specifically, it is obtained by the following equation.
[Swelling degree (%)] = [Water (g) contained in gel / Water-absorbing resin (g)]
÷ water absorption capacity (g / g) x 100

なお、吸水性樹脂のゲルに含みきれない遊離水が存在する(吸水能以上の水が存在する)状態も、膨潤度100%である。   In addition, the state in which free water that cannot be contained in the gel of the water-absorbent resin exists (the presence of water having a water absorption capacity or more) is also 100% swelling.

吸水性樹脂を膨潤させる水としては、上水、工業用水、イオン交換水および蒸留水等の水が挙げられる。   Examples of the water that swells the water-absorbent resin include water such as clean water, industrial water, ion exchange water, and distilled water.

膨潤度が80〜100%の吸水性樹脂のゲルを粉砕する手段としては、水で膨潤させた吸水性樹脂に対して、強い剪断エネルギーを与えることが可能なものであれば特に限定されず、例えば、高速回転遠心放射型攪拌機、高速回転剪断型攪拌機、コロイドミル、メディア式分散機、高圧噴射式乳化分散機、超音波乳化分散機等の一般的な乳化機または粉砕機が挙げられる。これらの中でも、微小な粒子を得る手段として特に強い剪断エネルギーを与えることが可能な、フィルミックス(プライミクス株式会社製)、クレアミックス(エム・テックニック株式会社製)等の高速回転剪断型攪拌機;コロイドミル;ホモジナイザー(ニロ・ソアビ社製)、スターバースト(株式会社スギノマシン製)等の高圧噴射式乳化分散機が好適に用いられる。   The means for pulverizing the gel of the water-absorbent resin having a swelling degree of 80 to 100% is not particularly limited as long as it can give a strong shearing energy to the water-absorbent resin swollen with water. Examples thereof include general emulsifiers or pulverizers such as a high-speed rotary centrifugal radiation stirrer, a high-speed rotary shear stirrer, a colloid mill, a media-type disperser, a high-pressure jet emulsifier-disperser, and an ultrasonic emulsifier-disperser. Among these, a high-speed rotary shearing type stirrer such as Filmix (manufactured by Primix Co., Ltd.), Claremix (manufactured by M Technic Co., Ltd.) or the like capable of giving particularly strong shear energy as a means for obtaining fine particles; A colloid mill; a high-pressure jet type emulsifying disperser such as a homogenizer (manufactured by Niro Soabi) or starburst (manufactured by Sugino Machine Co., Ltd.) is preferably used.

粉砕する際の条件としては、使用する機械、機種、および、処理を行う膨潤した吸水性樹脂のゲルの状態により異なるため、一概には言えないが、例えば、高速回転剪断型攪拌機であれば、回転数:12000〜22000r/min、処理時間:5〜60分間;高圧噴射式乳化分散機であれば、加圧条件:50〜245MPa、処理数:1〜10pass等が挙げられる。   The conditions for pulverization vary depending on the machine used, the model, and the state of the swollen water-absorbent resin gel to be treated, so it cannot be generally stated, for example, if it is a high-speed rotary shear type stirrer, Rotational speed: 12000 to 22000 r / min, treatment time: 5 to 60 minutes; pressurization condition: 50 to 245 MPa, treatment number: 1 to 10 pass, etc., for a high-pressure injection type emulsifying disperser.

また、1度の粉砕で所望の中位粒子径を有する吸水性樹脂の微細ゲル粒子が得られない際は、2度以上の粉砕工程を経て、所望の中位粒子径を有する吸水性樹脂の微細ゲル粒子を得ることもできる。   When fine gel particles of a water-absorbing resin having a desired median particle size cannot be obtained by one pulverization, the water-absorbing resin having a desired median particle size is passed through two or more pulverization steps. Fine gel particles can also be obtained.

粉砕の際、粉砕効率を向上させる観点から、水に可溶な親水性有機溶媒を添加することができる。親水性有機溶媒としては、メタノール、エタノール、およびイソプロパノール等のアルコール類;アセトン、エチルメチルケトンおよびイソブチルメチルケトン等のケトン類;酢酸エチル、酢酸プロピル、および酢酸ブチル等のエステル類等が挙げられる。これら親水性有機溶媒は、単独で使用してもよいし、2種以上を併用してもよい。   In the pulverization, a hydrophilic organic solvent soluble in water can be added from the viewpoint of improving the pulverization efficiency. Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate. These hydrophilic organic solvents may be used alone or in combination of two or more.

本発明の吸水性樹脂の微細ゲル粒子には、吸水性樹脂の物性を損なわない範囲、かつ粉砕中および粉砕後の吸水性樹脂の微細ゲル粒子を水性媒体に安定的に分散させる目的で、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤等の界面活性剤を添加してもよい。   The fine gel particles of the water-absorbent resin of the present invention have an anion for the purpose of stably dispersing the fine gel particles of the water-absorbent resin in the aqueous medium during and after pulverization without impairing the physical properties of the water-absorbent resin. A surfactant such as a cationic surfactant, a nonionic surfactant, or a cationic surfactant may be added.

本発明の吸水性樹脂の微細ゲル粒子には、目的に応じて、成膜助剤、pH調製剤、増粘剤、防腐剤、防カビ剤、防藻剤、防蟻剤、紫外線吸収剤、酸化防止剤、消泡剤、可塑剤等の添加剤を添加してもよい。   Depending on the purpose, the fine gel particles of the water-absorbent resin of the present invention include a film forming aid, a pH adjuster, a thickener, an antiseptic, an antifungal agent, an algaeproofing agent, an antifungal agent, an ultraviolet absorber, You may add additives, such as antioxidant, an antifoamer, and a plasticizer.

前記界面活性剤および各種添加剤は、その使用する目的に応じて、粉砕前〜粉砕後の任意の工程において添加が可能である。   The surfactant and various additives can be added in any step before pulverization to after pulverization depending on the purpose of use.

本発明の吸水性樹脂の微細ゲル粒子は、別途、水や親水性有機溶媒を添加する方法、粉砕の際に吸水性樹脂を膨潤させるために用いて過剰となった水や親水性有機溶媒をろ過や留去(減圧留去を含む)等を行う方法により、所望の吸水性樹脂濃度に調整された吸水性樹脂の微細ゲル粒子の水性分散液とすることもできる。   The fine gel particles of the water-absorbent resin of the present invention are prepared by separately adding water or a hydrophilic organic solvent, excess water or a hydrophilic organic solvent used for swelling the water-absorbent resin during pulverization. It is also possible to obtain an aqueous dispersion of fine gel particles of a water absorbent resin adjusted to a desired water absorbent resin concentration by a method such as filtration or distillation (including distillation under reduced pressure).

本発明の吸水性樹脂の微細ゲル粒子の中位粒子径は、0.01〜5μm、好ましくは0.05〜5μmである。中位粒子径が0.01μm未満の場合、コーティング膜にした際に、膜強度が低くなりすぎて、破壊されやすくなる傾向がある。また、中位粒子径が5μmを超える場合、コーティング膜を形成したときに、不均一な皮膜を形成したり、ピンホールが発生しやすくなる傾向がある。なお、中位粒子径は、後述する測定方法によって測定したときの値である。   The median particle size of the fine gel particles of the water absorbent resin of the present invention is 0.01 to 5 μm, preferably 0.05 to 5 μm. When the median particle diameter is less than 0.01 μm, when a coating film is formed, the film strength tends to be too low and the film tends to be easily broken. When the median particle diameter exceeds 5 μm, when a coating film is formed, a non-uniform film tends to be formed or pinholes tend to occur. In addition, a median particle diameter is a value when it measures by the measuring method mentioned later.

本発明において、膨潤度が80〜100%の吸水性樹脂のゲルを粉砕することにより、中位粒子径が0.01〜5μmの吸水性樹脂の微細ゲル粒子が得られる理由は定かではないが、膨潤度が80〜100%であれば、粉砕の際に吸水性樹脂からはきだされた水や遊離水が、吸水性樹脂のゲルのまわりに存在し、粉砕時に吸水性樹脂が流動性を有する柔らかいゲル状態を保てるため、非常に微細な状態まで粉砕できると推察できる。   In the present invention, the reason why fine gel particles of a water-absorbing resin having a median particle diameter of 0.01 to 5 μm can be obtained by pulverizing a gel of a water-absorbing resin having a swelling degree of 80 to 100% is not clear. If the degree of swelling is 80 to 100%, water or free water discharged from the water-absorbent resin during pulverization exists around the gel of the water-absorbent resin, and the water-absorbent resin exhibits fluidity during pulverization. Since the soft gel state can be maintained, it can be inferred that it can be pulverized to a very fine state.

本発明においては、得られた吸水性樹脂の微細ゲル粒子を用い、例えば、基材上に塗布、乾燥することにより、基材上に吸水能を有する樹脂コーティング膜を形成することができ、さらにそのコーティング膜を有する積層体を提供することができる。   In the present invention, by using the fine gel particles of the obtained water-absorbing resin, for example, by applying and drying on the substrate, a resin coating film having a water-absorbing ability can be formed on the substrate. A laminate having the coating film can be provided.

吸水性樹脂の微細ゲル粒子を基材上に塗布する方法としては、特に限定されず、キャスティングヘッド法、ロールコート法、エアナイフコート法、グラビアロールコート法、ドクターロールコート法、ドクターナイフコート法、カーテンフローコート法、スプレー法、浸漬法、刷毛塗り法等の公知の塗布方法を採用することができる。   The method for applying fine gel particles of the water-absorbent resin on the substrate is not particularly limited, and is a casting head method, a roll coating method, an air knife coating method, a gravure roll coating method, a doctor roll coating method, a doctor knife coating method, Known coating methods such as curtain flow coating, spraying, dipping, and brushing can be employed.

前記方法により吸水性樹脂の微細ゲル粒子が塗布された基材を乾燥する方法としては、例えば、自然乾燥法、赤外線照射法、熱風乾燥法等が挙げられる。   Examples of the method for drying the substrate on which the fine gel particles of the water-absorbent resin are applied by the above method include a natural drying method, an infrared irradiation method, a hot air drying method, and the like.

また、本発明の吸水性樹脂の微細ゲル粒子は、スプレードライ等の方法により乾燥させることにより、均一な粒子径を有する微細粉化された吸水性樹脂を得ることも可能である。   The fine gel particles of the water-absorbent resin of the present invention can be dried by a method such as spray drying to obtain a finely powdered water-absorbent resin having a uniform particle size.

以下、実施例、比較例および参考例により本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example, a comparative example, and a reference example demonstrate this invention in detail, this invention is not limited to these Examples.

なお、実施例1〜3、比較例1〜2、および参考例1において、用いた吸水性樹脂のイオン交換水に対する吸水能、得られた吸水性樹脂の微細ゲル粒子の中位粒子径は、以下の手順により測定した。   In Examples 1 to 3, Comparative Examples 1 and 2, and Reference Example 1, the water absorption capacity of the used water absorbent resin with respect to ion-exchanged water, and the median particle diameter of the fine gel particles of the obtained water absorbent resin are The measurement was performed according to the following procedure.

(1)吸水性樹脂のイオン交換水に対する吸水能
1000gのイオン交換水を入れた1L容のビーカーに、吸水性樹脂0.5gを攪拌下で添加し、ママコが発生していないのを確認した後、30分間攪拌し続けた。その後、あらかじめ質量(Wa(g))を測定しておいた直径20cmの目開き38μmのJIS標準篩を用いて濾過し、篩を水平方向に対して30度傾けた状態で、30分間放置した。篩に付着している余分な水分をふき取った後、篩の質量(Wb(g))を測定し、次式により吸水能を算出した。
吸水能(g/g)=[Wb−Wa−0.5](g)÷0.5(g)
(1) Water-absorbing capacity of water-absorbing resin to ion-exchanged water 0.5 g of water-absorbing resin was added to a 1 L beaker containing 1000 g of ion-exchanged water under stirring, and it was confirmed that no mamako was generated. Thereafter, stirring was continued for 30 minutes. Then, it filtered using the JIS standard sieve of 38 micrometers of openings whose diameter (Wa (g)) was measured beforehand, and left for 30 minutes in the state which inclined the screen 30 degrees with respect to the horizontal direction. . After excess water adhering to the sieve was wiped off, the mass (Wb (g)) of the sieve was measured, and the water absorption capacity was calculated by the following formula.
Water absorption capacity (g / g) = [Wb−Wa−0.5] (g) ÷ 0.5 (g)

(2)中位粒子径
実施例1により得られた吸水性樹脂の微細ゲル粒子は、動的光散乱式粒子径測定装置(マルバーン社製、ゼータサイザーナノ)を用いて中位粒子径を測定した。また、実施例2,3により得られた吸水性樹脂の微細ゲル粒子、ならびに比較例2および参考例により得られた吸水性樹脂のゲル粒子は、レーザー回折式粒度分布測定装置(株式会社島津製作所製、SALD−2000)を用いて中位粒子径を測定した。
(2) Median particle size The fine gel particles of the water-absorbent resin obtained in Example 1 were measured for the median particle size using a dynamic light scattering particle size measurement device (Malvern, Zetasizer Nano). did. Further, the fine gel particles of the water absorbent resin obtained in Examples 2 and 3 and the gel particles of the water absorbent resin obtained in Comparative Example 2 and Reference Example were obtained by a laser diffraction particle size distribution measuring apparatus (Shimadzu Corporation). The median particle diameter was measured using SALD-2000).

[実施例1]
2L容のビーカーに水900gをとり、吸水性樹脂としてノニオン型ポリアルキレンオキサイド系樹脂(住友精化株式会社の商品名「アクアコークTWB−P」、乾燥時中位粒子径50μm、吸水能30g/g)30gを添加し、10分間攪拌混合することにより、吸水性樹脂の膨潤ゲルを調製した(膨潤度100%)。
[Example 1]
900 g of water was taken in a 2 liter beaker, and a nonionic polyalkylene oxide resin (trade name “Aqua Coke TWB-P” from Sumitomo Seika Co., Ltd., medium particle diameter when dried, 50 μm, water absorption capacity 30 g / g) A swelling gel of water-absorbent resin was prepared by adding 30 g and stirring and mixing for 10 minutes (swelling degree 100%).

吸水性樹脂の膨潤ゲルを、高圧ホモジナイザー(ニロ・ソアビ社の商品名「PANDA」、2K型)を用いて、150MPa/10passの条件で粉砕処理し、吸水性樹脂の微細ゲル粒子を得た。なお、得られた吸水性樹脂の微細ゲル粒子の中位粒子径は0.07μmであった。   The swelling gel of the water-absorbent resin was pulverized using a high-pressure homogenizer (trade name “PANDA”, model 2K, manufactured by Niro Soabi) under the condition of 150 MPa / 10 pass to obtain fine gel particles of the water-absorbent resin. In addition, the median particle diameter of the fine gel particles of the obtained water-absorbent resin was 0.07 μm.

[実施例2]
2L容のビーカーに水1040gをとり、吸水性樹脂としてアクリル酸塩−ビニルアルコール共重合体(住友精化株式会社製、乾燥時中位粒子径200μm、吸水能370g/g)2gを添加し、10分間攪拌混合することにより、吸水性樹脂の膨潤ゲルを調製した(膨潤度100%、遊離水あり)。
[Example 2]
Take 1040 g of water in a 2 L beaker and add 2 g of acrylate-vinyl alcohol copolymer (manufactured by Sumitomo Seika Co., Ltd., medium particle size at drying 200 μm, water absorption capacity 370 g / g) as a water absorbent resin, A swollen gel of a water-absorbent resin was prepared by stirring and mixing for 10 minutes (with a swelling degree of 100% and free water).

吸水性樹脂の膨潤ゲル(遊離水込み)を、クレアミックス(エム・テクニック株式会社の商品名「CLM−0.8型」)を用いて、15000r/min、5分間の条件で粉砕処理し、吸水性樹脂のゲル粒子を得た。なお、得られた吸水性樹脂のゲル粒子の中位粒子径は110μmであった。   The swelling gel (including free water) of the water-absorbent resin was pulverized under the conditions of 15000 r / min and 5 minutes using CLEARMIX (trade name “CLM-0.8 type” manufactured by M Technique Co., Ltd.) Gel particles of a water absorbent resin were obtained. In addition, the median particle diameter of the gel particles of the obtained water absorbent resin was 110 μm.

得られた吸水性樹脂のゲル粒子を、さらに高圧ホモジナイザー(ニロ・ソアビ社の商品名「PANDA」、2K型)を用いて、150MPa/10passの条件で更に粉砕処理し、吸水性樹脂の微細ゲル粒子を得た。なお、得られた吸水性樹脂の微細ゲル粒子の中位粒子径は4.5μmであった。   The obtained water-absorbent resin gel particles were further pulverized under a condition of 150 MPa / 10 pass using a high-pressure homogenizer (trade name “PANDA”, model 2K, manufactured by Niro Soavi Co., Ltd.) to obtain a fine gel of the water-absorbent resin. Particles were obtained. In addition, the median particle diameter of the fine gel particles of the obtained water absorbent resin was 4.5 μm.

[実施例3]
2L容のビーカーに水1020gをとり、吸水性樹脂としてアクリル酸塩−ビニルアルコール共重合体(住友精化株式会社製、乾燥時中位粒子径50μm、吸水能600g/g)2gを添加し、10分間攪拌混合することにより、吸水性樹脂の膨潤ゲルを調製した(膨潤度85%)。
[Example 3]
Take 1020 g of water in a 2 L beaker and add 2 g of acrylate-vinyl alcohol copolymer (manufactured by Sumitomo Seika Co., Ltd., medium particle size when dried, water absorption capacity 600 g / g) as a water-absorbing resin, A swollen gel of water-absorbent resin was prepared by stirring and mixing for 10 minutes (swelling degree 85%).

吸水性樹脂の膨潤ゲルを、高圧ホモジナイザー(ニロ・ソアビ社の商品名「PANDA」、2K型)を用いて、150MPa/10passの条件で粉砕処理し、吸水性樹脂の微細ゲル粒子を得た。なお、得られた吸水性樹脂の微細ゲル粒子の中位粒子径は2μmであった。   The swelling gel of the water-absorbent resin was pulverized under a condition of 150 MPa / 10 pass using a high-pressure homogenizer (trade name “PANDA”, model 2K, manufactured by Niro Soabi) to obtain fine gel particles of the water-absorbent resin. In addition, the median particle diameter of the fine gel particles of the obtained water absorbent resin was 2 μm.

[比較例1]
2L容のビーカーに水900gをとりに、吸水性樹脂としてノニオン型ポリアルキレンオキサイド系樹脂(住友精化株式会社の商品名「アクアコークTWB−P」、乾燥時中位粒子径50μm、吸水能30g/g)60gを添加し、10分間攪拌混合することにより、吸水性樹脂の膨潤ゲルを調製した(膨潤度50%)。
[Comparative Example 1]
Take 900g of water in a 2L beaker and use nonionic polyalkylene oxide resin (trade name "Aqua Coke TWB-P", Sumitomo Seika Co., Ltd. / G) A swelling gel of water-absorbent resin was prepared by adding 60 g and stirring and mixing for 10 minutes (swelling degree 50%).

吸水性樹脂の膨潤ゲルを、高圧ホモジナイザー(ニロ・ソアビ社の商品名「PANDA」、2K型)を用いて、150MPa/10passの条件で粉砕処理を行ったが、粉砕できなかった。   The swelling gel of the water-absorbent resin was pulverized under a condition of 150 MPa / 10 pass using a high-pressure homogenizer (trade name “PANDA”, model 2K, manufactured by Niro Soabi), but could not be pulverized.

また、吸水性樹脂の膨潤ゲルを、クレアミックス(エム・テクニック株式会社の商品名「CLM−0.8型」)を用いて、15000r/min、5分間の条件で粉砕処理を行ったが、粉砕できなかった。   In addition, the swelling gel of the water-absorbent resin was pulverized under the condition of 15000 r / min for 5 minutes using CLEARMIX (trade name “CLM-0.8 type” manufactured by M Technique Co., Ltd.) Could not be crushed.

[比較例2]
2L容のビーカーに水1095gをとり、吸水性樹脂としてアクリル酸塩−ビニルアルコール共重合体(住友精化株式会社製、乾燥時中位粒子径200μm、吸水能370g/g)4gを添加し、10分間攪拌混合することにより、吸水性樹脂の膨潤ゲルを調製した(膨潤度74%)。
[Comparative Example 2]
Take 1095 g of water in a 2 L beaker and add 4 g of acrylate-vinyl alcohol copolymer (manufactured by Sumitomo Seika Co., Ltd., medium particle diameter at drying 200 μm, water absorption capacity 370 g / g) as a water absorbent resin, A swollen gel of water-absorbent resin was prepared by stirring and mixing for 10 minutes (swelling degree 74%).

吸水性樹脂の膨潤ゲルを、クレアミックス(エム・テクニック株式会社の商品名「CL
M−0.8型」)を用いて、20000r/min、60分間の条件で粉砕処理し、吸水性樹脂のゲル粒子を得た。なお、得られた吸水性樹脂のゲル粒子の中位粒子径は20μmであった。
The swollen gel of the water-absorbent resin was applied to CLEARMIX (trade name “CL” of M Technique Co., Ltd.
M-0.8 type ") was pulverized under the conditions of 20000 r / min for 60 minutes to obtain water-absorbent resin gel particles. The median particle size of the gel particles of the obtained water absorbent resin was 20 μm.

[参考例1]
2L容のビーカーに水900gをとり、吸水性樹脂としてアクリル酸塩−ビニルアルコール共重合体(住友精化株式会社製、乾燥時中位粒子径50μm、吸水能600g/g)1gを添加し、10分間攪拌混合することにより、吸水性樹脂のゲル粒子を得た。なお、得られた吸水性樹脂のゲル粒子の中位粒子径は460μmであった。
[Reference Example 1]
900 g of water was taken into a 2 L beaker, and 1 g of an acrylate-vinyl alcohol copolymer (manufactured by Sumitomo Seika Co., Ltd., medium particle size when dried, water absorption capacity 600 g / g) was added as a water absorbent resin. By stirring and mixing for 10 minutes, gel particles of a water absorbent resin were obtained. In addition, the median particle diameter of the gel particles of the obtained water absorbent resin was 460 μm.

以下、実施例4〜6、比較例3および参考例2において、前記実施例1〜3で得られた吸水性樹脂の微細ゲル粒子、ならびに比較例2および参考例1で得られた吸水性樹脂のゲル粒子を用いて、コーティング膜を形成し、外観、膜厚、吸水能を以下の手順で測定した。   Hereinafter, in Examples 4 to 6, Comparative Example 3 and Reference Example 2, the fine gel particles of the water absorbent resin obtained in Examples 1 to 3 and the water absorbent resin obtained in Comparative Example 2 and Reference Example 1 were used. The gel particles were used to form a coating film, and the appearance, film thickness, and water absorption capacity were measured by the following procedure.

(3)外観
コーティング膜の表面の外観(ひび割れ等)を、目視で観察した。
(3) Appearance The appearance (cracking etc.) of the surface of the coating film was visually observed.

(4)膜厚
コーティング膜の膜厚は、分光法を用いた膜厚計(スペクトラコープ社製)を用いて測定した。
(4) Film thickness The film thickness of the coating film was measured using a film thickness meter (Spectra Corp.) using spectroscopy.

(5)コーティング膜のイオン交換水に対する吸水能
吸水性樹脂の微細ゲル粒子をコーティングしたガラス板(Wd(g))を、イオン交換水50gを入れたシャーレに浸漬し、30分間放置した。その後、ガラス板を取り出して余分な水分をふき取った後、吸水後のガラス板の質量(We(g))を測定し、次式により吸水能を算出した。ただし、Wc(g)は、コーティング前のガラス板の質量である。
吸水能(g/g)=[We−Wd](g)÷[Wd−Wc](g)
(5) Water absorption capacity of coating film for ion-exchanged water A glass plate (Wd (g)) coated with fine gel particles of a water-absorbing resin was immersed in a petri dish containing 50 g of ion-exchanged water and left for 30 minutes. Then, after taking out a glass plate and wiping off excess water | moisture content, the mass (We (g)) of the glass plate after water absorption was measured, and the water absorption ability was computed by following Formula. However, Wc (g) is the mass of the glass plate before coating.
Water absorption capacity (g / g) = [We−Wd] (g) ÷ [Wd−Wc] (g)

[実施例4]
ガラス板(35×100mm、厚さ2mm)の片面に、実施例1で得られた吸水性樹脂の微細ゲル粒子を、バーコーター(No.80)を用いて塗工し、120℃で5分間乾燥し、吸水性樹脂コーティング膜を形成した。得られたコーティング膜は、均質でひび割れは無く、膜厚は6μm、吸水能は25g/gであった。
[Example 4]
On one side of a glass plate (35 × 100 mm, thickness 2 mm), fine gel particles of the water-absorbent resin obtained in Example 1 were applied using a bar coater (No. 80), and 120 ° C. for 5 minutes. It dried and formed the water absorbing resin coating film. The obtained coating film was homogeneous and free of cracks, the film thickness was 6 μm, and the water absorption capacity was 25 g / g.

[実施例5]
ガラス板(35×100mm、厚さ2mm)の片面に、実施例2で得られた吸水性樹脂の微細ゲル粒子を、バーコーター(No.80)を用いて塗工し、120℃で5分間乾燥し、吸水性樹脂コーティング膜を形成した。得られたコーティング膜は、均質でひび割れは無く、膜厚は0.5μm、吸水能は300g/gであった。
[Example 5]
On one surface of a glass plate (35 × 100 mm, thickness 2 mm), fine gel particles of the water-absorbent resin obtained in Example 2 were applied using a bar coater (No. 80), and at 120 ° C. for 5 minutes. It dried and formed the water absorbing resin coating film. The obtained coating film was homogeneous and free of cracks, the film thickness was 0.5 μm, and the water absorption capacity was 300 g / g.

[実施例6]
ガラス板(35×100mm、厚さ2mm)の片面に、実施例3で得られた吸水性樹脂の微細ゲル粒子を、バーコーター(No.80)を用いて塗工し、120℃で5分間乾燥し、吸水性樹脂コーティング膜を形成した。得られたコーティング膜は、均質でひび割れは無く、膜厚は0.45μm、吸水能は500g/gであった。
[Example 6]
On one side of a glass plate (35 × 100 mm, thickness 2 mm), fine gel particles of the water-absorbent resin obtained in Example 3 were applied using a bar coater (No. 80), and 120 ° C. for 5 minutes. It dried and formed the water absorbing resin coating film. The obtained coating film was homogeneous and free of cracks, the film thickness was 0.45 μm, and the water absorption capacity was 500 g / g.

[比較例3]
ガラス板(35×100mm、厚さ2mm)の片面に、比較例2で得られた吸水性樹脂のゲル粒子を、バーコーター(No.80)を用いて塗工し、120℃で5分間乾燥し、吸水性樹脂コーティング膜を形成した。得られたコーティング膜は、不均一に乾燥粒子が分散し、ピンホールが発生した。
[Comparative Example 3]
The gel particles of the water-absorbent resin obtained in Comparative Example 2 were applied to one side of a glass plate (35 × 100 mm, thickness 2 mm) using a bar coater (No. 80) and dried at 120 ° C. for 5 minutes. Then, a water-absorbing resin coating film was formed. In the obtained coating film, dry particles were dispersed non-uniformly and pinholes were generated.

[参考例2]
ガラス板(35×100mm、厚さ2mm)の片面に、参考例1で得られた吸水性樹脂のゲル粒子を、刷毛を用いて塗工し、120℃で5分間乾燥したが、成膜せずに不均一に乾燥粒子が分散し、付着していた。
[Reference Example 2]
The water-absorbent resin gel particles obtained in Reference Example 1 were applied to one side of a glass plate (35 × 100 mm, thickness 2 mm) using a brush and dried at 120 ° C. for 5 minutes. The dried particles were dispersed and adhered non-uniformly.

実施例1〜3で得られた吸水性樹脂の微細ゲル粒子は、均質でひび割れが無く、良好な膜厚および吸水能を有するコーティングを付与できることがわかった。   It was found that the fine gel particles of the water-absorbent resin obtained in Examples 1 to 3 were uniform and free of cracks, and could provide a coating having a good film thickness and water absorption ability.

本発明の吸水性樹脂の微細ゲル粒子は、吸水性樹脂粒子が膨潤した状態として中位粒子径が0.01〜5μmと小さく、インクジェットプリンター用記録媒体、防曇塗料、汚れ防止機能を有する塗料、結露防止壁紙用処理剤、農業用ビニルフィルムの表面処理剤、メディカル用薬液吸収体、帯電防止剤、合成皮革、人工皮革、繊維コーティング用透湿防水素材、陶器用粘着剤等に、親水性コーティング膜形成材料として好適に用いられる。   The fine gel particles of the water-absorbent resin of the present invention have a median particle diameter as small as 0.01 to 5 μm in a swollen state of the water-absorbent resin particles, and have a recording medium for an ink jet printer, an antifogging paint, and a paint having a stain prevention function. , Anti-condensation wallpaper treatments, agricultural vinyl film surface treatments, medical chemical absorbers, antistatic agents, synthetic leather, artificial leather, moisture permeable waterproof materials for fiber coatings, adhesives for ceramics, etc. It is suitably used as a coating film forming material.

Claims (4)

膨潤度が80〜100%の吸水性樹脂のゲルを粉砕することにより得られる、中位粒子径が0.01〜5μmの吸水性樹脂の微細ゲル粒子。
膨潤度:吸水性樹脂のゲルに含まれる吸水性樹脂単位質量あたりの水(g/g)の、吸水性樹脂のイオン交換水に対する吸水能(g/g)に対する割合。
[膨潤度(%)]=[ゲルに含まれる水(g)/吸水性樹脂(g)]
÷吸水能(g/g)×100
Fine gel particles of a water-absorbing resin having a median particle diameter of 0.01 to 5 μm obtained by pulverizing a gel of a water-absorbing resin having a swelling degree of 80 to 100%.
Swelling degree: Ratio of water (g / g) per unit mass of water-absorbing resin contained in the gel of water-absorbing resin to water-absorbing capacity (g / g) with respect to ion-exchanged water of water-absorbing resin.
[Swelling degree (%)] = [Water (g) contained in gel / Water-absorbing resin (g)]
÷ water absorption capacity (g / g) x 100
吸水性樹脂のイオン交換水に対する吸水能が、1〜1500g/gである請求項1に記載の吸水性樹脂の微細ゲル粒子。   The water-absorbent resin fine gel particles according to claim 1, wherein the water-absorbent resin has a water absorption capacity of 1 to 1500 g / g with respect to ion-exchanged water. 請求項1または2に記載の吸水性樹脂の微細ゲル粒子をコーティングしてなるコーティング膜。   A coating film formed by coating the fine gel particles of the water-absorbent resin according to claim 1 or 2. 基材上に、請求項1または2に記載の吸水性樹脂の微細ゲル粒子がコーティングされていることを特徴とする積層体。   A laminate comprising the substrate coated with the fine gel particles of the water-absorbent resin according to claim 1 or 2.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017501278A (en) * 2013-12-20 2017-01-12 リライアンス インダストリーズ リミテッドReliance Industries Ltd. Water-absorbing polymer and process for its preparation
WO2018225267A1 (en) * 2017-06-09 2018-12-13 花王株式会社 Water absorbent sheet
WO2018225266A1 (en) * 2017-06-09 2018-12-13 花王株式会社 Water absorbent sheet

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57195124A (en) * 1981-05-26 1982-11-30 Rapuko Kk Preparation of dispersion of water-absorbing polymer
JPS60184540A (en) * 1984-03-02 1985-09-20 Fujikura Kasei Kk Composition containing powder of water-absorptive resin
JPH01172475A (en) * 1987-12-28 1989-07-07 Hoechst Gosei Kk Coating composition for forming rugged surface
JPH01252669A (en) * 1988-03-31 1989-10-09 Sumitomo Seika Chem Co Ltd Water-absorptive water-retentive material
JPH0576300A (en) * 1991-09-18 1993-03-30 Asahi Chem Ind Co Ltd Non-caloric additive for cooked rice
JPH09272806A (en) * 1996-04-05 1997-10-21 Sanyo Chem Ind Ltd Water absorbing resin dispersion
JPH10279693A (en) * 1997-04-03 1998-10-20 Fuji Xerox Co Ltd Production of water-absorbing gel particle
JPH11349687A (en) * 1998-04-07 1999-12-21 Nippon Shokubai Co Ltd Particulate water-containing gel polymer and preparation of water absorption resin
JP2004196709A (en) * 2002-12-18 2004-07-15 Shiseido Co Ltd Gel-like composition, flavoring agent, skin care preparation and cosmetic

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57195124A (en) * 1981-05-26 1982-11-30 Rapuko Kk Preparation of dispersion of water-absorbing polymer
JPS60184540A (en) * 1984-03-02 1985-09-20 Fujikura Kasei Kk Composition containing powder of water-absorptive resin
JPH01172475A (en) * 1987-12-28 1989-07-07 Hoechst Gosei Kk Coating composition for forming rugged surface
JPH01252669A (en) * 1988-03-31 1989-10-09 Sumitomo Seika Chem Co Ltd Water-absorptive water-retentive material
JPH0576300A (en) * 1991-09-18 1993-03-30 Asahi Chem Ind Co Ltd Non-caloric additive for cooked rice
JPH09272806A (en) * 1996-04-05 1997-10-21 Sanyo Chem Ind Ltd Water absorbing resin dispersion
JPH10279693A (en) * 1997-04-03 1998-10-20 Fuji Xerox Co Ltd Production of water-absorbing gel particle
JPH11349687A (en) * 1998-04-07 1999-12-21 Nippon Shokubai Co Ltd Particulate water-containing gel polymer and preparation of water absorption resin
JP2004196709A (en) * 2002-12-18 2004-07-15 Shiseido Co Ltd Gel-like composition, flavoring agent, skin care preparation and cosmetic

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017501278A (en) * 2013-12-20 2017-01-12 リライアンス インダストリーズ リミテッドReliance Industries Ltd. Water-absorbing polymer and process for its preparation
WO2018225267A1 (en) * 2017-06-09 2018-12-13 花王株式会社 Water absorbent sheet
WO2018225266A1 (en) * 2017-06-09 2018-12-13 花王株式会社 Water absorbent sheet
JPWO2018225267A1 (en) * 2017-06-09 2020-04-09 花王株式会社 Water absorbent sheet

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