JP2006008963A - Coating material and solution for dispersing photocatalyst - Google Patents
Coating material and solution for dispersing photocatalyst Download PDFInfo
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Images
Abstract
Description
本発明は、建築用の外装材や内装材、各種成形品、又は動植物等などの表面部などに塗布することにより、抗菌、防汚、脱臭、空気浄化などの作用を有するコーティング材及びそれに使用する光触媒分散用液剤に関する。The present invention is a coating material having antibacterial, antifouling, deodorizing, air purification, and other coating materials applied to a surface of a building exterior or interior material, various molded products, or animals and plants, etc. The present invention relates to a photocatalyst dispersion liquid.
二酸化チタンに代表される光触媒により抗菌・防汚・防臭作用を有することは従来から知られており、最近ではこれらの作用を利用した様々な材料が研究、開発されている。It has been conventionally known that the photocatalyst typified by titanium dioxide has antibacterial, antifouling and deodorizing actions, and recently various materials utilizing these actions have been researched and developed.
具体的には、二酸化チタンに紫外線を照射すると、空気中に含まれる水や酸素の分解が引き起こされて、その表面に活性酸素（ＯＨ−、Ｏ２−）が生成される。そして、この活性酸素の作用により、大気中の汚染物質を酸化分解したり、臭気成分を分解して脱臭したり、細菌を死滅させることができる。Specifically, when titanium dioxide is irradiated with ultraviolet rays, water and oxygen contained in the air are decomposed to generate active oxygen (OH − , O 2− ) on the surface. And by the action of this active oxygen, it is possible to oxidize and decompose pollutants in the atmosphere, to decompose odor components and deodorize them, or to kill bacteria.
しかし、二酸化チタンの光触媒機能は極めて強いため、その塗膜に触れる汚染物質が酸化分解されるだけでなく、コーティング材を塗布した基材をも酸化分解してしまい、基材が白亜化してボロボロになるいわゆるチョーキングを起こす。However, since the photocatalytic function of titanium dioxide is extremely strong, not only the contaminants that touch the coating film are oxidatively decomposed, but also the substrate coated with the coating material is oxidatively decomposed, and the substrate becomes chalky and worn out. Cause so-called choking.
このためコーティング材として使用する場合、従来は、光触媒の作用によって分解されにくい樹脂を塗膜形成要素として含む樹脂塗料に二酸化チタンを混合し、この樹脂塗料を用いて基材の表面をコーティングする方法、又は基材の表面に樹脂塗料を塗布し、次いでその樹脂塗料が硬化する前に、樹脂塗料の上に二酸化チタンを塗布する方法が挙げられる。For this reason, when used as a coating material, conventionally, titanium dioxide is mixed with a resin paint containing a resin that is difficult to be decomposed by the action of a photocatalyst as a coating film forming element, and the surface of the substrate is coated using this resin paint. Alternatively, there may be mentioned a method in which a resin paint is applied to the surface of the substrate and then titanium dioxide is applied on the resin paint before the resin paint is cured.
しかしながら、これらの方法では樹脂塗料が白濁したり、皮膜の中に二酸化チタンが埋没してしまい、十分な活性を示さないという欠点、又は工程が煩雑な上、均質で透明な塗膜が得られない欠点がある。さらに、光触媒を固定化する基材として、プラスチック成形体、フィルム、有機塗膜等の有機基材を用いた場合、上述した従来技術で得られる光触媒皮膜は光触媒作用により該有機基材を酸化分解し、有機基材表面部が分解すると、その上に存在している中間層、光触媒層ともに足場を失うため、脱落する。またそれにより、光触媒作用を利用した目的の機能（防汚性や、抗菌性、脱臭性など）が失われるだけでなく、表面光沢が低下したり、粉吹き状態になるなど、本来の外観特性や意匠性も失われてしまう。塗装工程においても材料費が嵩むだけでなく、通常の塗装に比して倍の手間と時間及び特殊な技術が必要となるという問題があった。However, in these methods, the resin paint becomes cloudy or titanium dioxide is buried in the film, and it does not show sufficient activity, or the process is complicated, and a uniform and transparent coating film can be obtained. There are no drawbacks. Furthermore, when an organic base material such as a plastic molded body, a film, or an organic coating film is used as a base material for immobilizing the photocatalyst, the photocatalyst film obtained by the above-described conventional technique oxidatively decomposes the organic base material by photocatalytic action. However, when the organic base material surface portion is decomposed, both the intermediate layer and the photocatalyst layer present on the organic base material lose their scaffolds and fall off. In addition, not only the intended function (antifouling property, antibacterial property, deodorizing property, etc.) using photocatalysis is lost, but also the original appearance characteristics such as surface gloss is lowered and powder is blown. And design will be lost. In the painting process, there is a problem that not only the material cost increases, but also labor and time that are twice as much as those of ordinary painting, and special techniques are required.
また、このように塗布しても、そのコーティング皮膜の寿命が短く、１〜２年で剥離してしまうため、頻繁に塗り直しをしなければならないという問題もあった。Moreover, even if it apply | coated in this way, since the lifetime of the coating film was short and it will peel in 1 to 2 years, there also existed a problem that it had to repaint frequently.
そして、コーティング被膜の欠点について発明者が研究した結果、光触媒粒子自体にはノンチョーキング処理が施されていないため、光触媒を分散させているエマルジョンが酸化されることが判明した。As a result of the inventor's research on the defects of the coating film, it was found that the emulsion in which the photocatalyst is dispersed is oxidized because the photocatalyst particles themselves are not subjected to non-choking treatment.
そこで本発明は、基材に直接塗布してもチョーキングを起こすことなく、また、寿命が極めて長いコーティング被膜を形成できるようにすることを技術的課題としている。Therefore, the present invention has a technical problem that a coating film having a very long life can be formed without causing choking even when directly applied to a substrate.
この課題を解決するために、本発明に係るコーティング材は、水を主成分とする溶液中にアルカリ解溶型親水性高分子材を分散させたエマルジョンを分散媒とし、これに光触媒を分散させたことを特徴とする。なお、この明細書において光触媒と言うときは、光吸収により空気中の水や酸素から活性酸素を生じさせ、その活性酸素により他物を酸化分解させる反応を惹き起こす物質を言うものとする。In order to solve this problem, the coating material according to the present invention uses, as a dispersion medium, an emulsion in which an alkaline desolvation type hydrophilic polymer material is dispersed in a water-based solution, and a photocatalyst is dispersed in the emulsion. It is characterized by that. In this specification, the photocatalyst refers to a substance that causes a reaction of generating active oxygen from water or oxygen in the air by light absorption and oxidatively decomposing other substances by the active oxygen.
本発明のコーティング材を基材に塗布して乾燥させると、光触媒と基材の間に耐酸性を有するアルカリ解溶型親水性高分子皮膜が介装されることとなるので物品表面の酸化が防止され、さらに、その皮膜自身が酸化されることがなく、コーティング皮膜が長持ちするという大変優れた効果を奏する。When the coating material of the present invention is applied to a substrate and dried, an alkali-dissolving hydrophilic polymer film having acid resistance is interposed between the photocatalyst and the substrate, so that the surface of the article is oxidized. Further, the coating film itself is not oxidized and the coating film lasts for a very long time.
本発明によるコーティング材を基材の表面に塗布すると、まず、光触媒はエマルジョンに分散された状態で塗着されたコーティング層が形成され、エマルジョンに含まれる水分の蒸発に伴ってコーティング層が表層側から肉やせを起こし、その表層に光触媒が露出されたコーティング皮膜が形成される。When the coating material according to the present invention is applied to the surface of the substrate, first, a coating layer is formed in which the photocatalyst is dispersed in the emulsion, and the coating layer is on the surface side as the water contained in the emulsion evaporates. A coating film is formed in which the photocatalyst is exposed on the surface layer.
そして、露出されている光触媒の表面に空気が触れると、光照射下において、その空気中に含まれる水や酸素から活性酸素が生成され、ここに付着した汚染物質は活性酸素の酸化作用により酸化分解され、雨水により洗い流される。また、空気中に含まれる臭気成分が触れると、これが酸化分解されて消臭され、さらに、細菌類が付着しても活性酸素の酸化作用により滅菌される。When air touches the exposed surface of the photocatalyst, active oxygen is generated from the water and oxygen contained in the air under light irradiation, and contaminants adhering thereto are oxidized by the oxidizing action of active oxygen. Disassembled and washed away with rainwater. Further, when an odor component contained in the air is touched, it is decomposed by oxidization and deodorized, and even if bacteria adhere, it is sterilized by the oxidizing action of active oxygen.
なお、本発明のコーティング材を用いたところ、基材の白亜化が生じなかったので、光触媒と基材表面の間にはアルカリ解溶型親水性高分子材の皮膜が形成されていると考えられる。すなわち、個々の光触媒粒子は基材表面に直接接触しないので、基材表面で活性酸素が生成されることがなく、基材表面の白亜化が防止される。In addition, when the coating material of the present invention was used, no chalking of the base material occurred. Therefore, it is considered that a film of an alkali-dissolving hydrophilic polymer material is formed between the photocatalyst and the base material surface. It is done. That is, since the individual photocatalyst particles do not directly contact the substrate surface, active oxygen is not generated on the substrate surface, and chalking of the substrate surface is prevented.
また、エマルジョンに含まれる水分が蒸発して形成されたアルカリ解溶型親水性高分子材の皮膜は耐酸性を有し、光触媒により生成された活性酸素により酸化されることがないので、コーティング皮膜が容易に剥離することもなく長持ちする。特に、アルカリ解溶型親水性高分子材として有機物が含有されている場合は、水分が蒸発したときに強固な樹脂皮膜が形成されるので、その後は風雨に曝されても溶け出すことがない。In addition, the film of the alkaline desolubilized hydrophilic polymer material formed by evaporation of the water contained in the emulsion has acid resistance and is not oxidized by active oxygen generated by the photocatalyst. Long-lasting without easily peeling off. In particular, when an organic substance is contained as an alkali-dissolving hydrophilic polymer material, a strong resin film is formed when moisture evaporates, so that it does not dissolve even when exposed to wind and rain thereafter. .
以下、本発明の実施の形態を図面に基づいて具体的に説明する。図１は本発明に係るコーティング材を示す説明図、図２は他の実施形態を示す説明図である。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is an explanatory view showing a coating material according to the present invention, and FIG. 2 is an explanatory view showing another embodiment.
本例のコーティング材１は、水を主成分とする溶掖２中にアルカリ解溶型親水性高分子材３を分散させたエマルジョン４を分散媒とし、これに光触媒となる粉末又は液状の二酸化チタン５が１０％程度の濃度で分散されて成る。The
エマルジョン４に使用される溶液２は、水を主成分とし、水だけを用いる場合であっても、また、水溶性添加剤等を溶解した水溶液を用いる場合であっても良い。The solution 2 used for the emulsion 4 may be a case where water is the main component and only water is used, or an aqueous solution in which a water-soluble additive or the like is dissolved may be used.
そして、この溶液２に分散されるアルカリ解溶型親水性高分子材３としては、アルカリ解溶型親水性有機高分子材３Ａ及びアルカリ解溶型親水性無機高分子材３Ｂのいずれか一方又は双方が用いられる。The alkali-dissolving hydrophilic polymer material 3 dispersed in the solution 2 is either one of the alkali-dissolving hydrophilic organic polymer material 3A and the alkali-dissolving hydrophilic inorganic polymer material 3B or Both are used.
アルカリ解溶型親水性有機高分子材３Ａとしては、カルボキシル基などの親水基を導入して水性化した水性ポリエステル樹脂の他、アクリル系樹脂やウレタン系樹脂など任意の有機高分子材を水性化して用いることができる。As the alkaline desolubilizing hydrophilic organic polymer material 3A, water-based aqueous polyester resin, which is made water-based by introducing hydrophilic groups such as carboxyl groups, and any organic polymer material such as acrylic resin and urethane resin can be made water-based. Can be used.
また、アルカリ解溶型親水性無機高分子材３Ｂとしては、海藻抽出物をはじめとする天然高分子の他、天然高分子誘導体、合成高分子等の一般に安定剤として用いられる物質を使用し得る。Further, as the alkali desolubilizing hydrophilic inorganic polymer material 3B, in addition to natural polymers such as seaweed extract, substances generally used as stabilizers such as natural polymer derivatives and synthetic polymers can be used. .
前記天然高分子には、植物系、微生物系、動物系のものがある。そして、植物系としては、寒天、カラギーナン、ファーセラン、アルギン酸などの海藻抽出物、ローカストビーンガム、グアーガム、タマリンドガムなどの種子粘質物、アラビアガム、トラガントガム、カラヤガムなどの樹脂様粘質物、ペクチン、アラビノガラクタンなどの植物粘質物（果実）、大豆タンパク、小麦タンパクなどの植物タンパク質、生澱粉などの澱粉質、大豆レシチンなどの脂質を使用し得る。The natural polymers include plant-based, microbial-based and animal-based ones. Plant systems include seaweed extracts such as agar, carrageenan, fercelan, alginic acid, seed mucilage such as locust bean gum, guar gum, tamarind gum, resinous mucilage such as gum arabic, tragacanth gum, karaya gum, pectin, arabi Plant mucilage (fruit) such as nogalactan, plant protein such as soybean protein and wheat protein, starch such as raw starch, and lipid such as soybean lecithin can be used.
また、微生物系としては、キサンタンガム、プルラン、デキストラン、動物物系としては、ゼラチン、カゼイン、アルブミンなどの動物タンパク質、卵黄レシチンなどの脂質を使用できる。In addition, xanthan gum, pullulan, dextran can be used as the microorganism system, and animal proteins such as gelatin, casein, and albumin, and lipids such as egg yolk lecithin can be used as the animal system.
さらに、前記天然高分子誘導体としては、リンサン澱粉、カルボキシルメチル化澱粉などの澱粉系、マイクロセルロース、ヒドロキシエチルセルロース、カルボキシルメチルセルロースなどのセルロース系を使用しうる。Furthermore, as the natural polymer derivative, starch systems such as phosphosan starch and carboxymethylated starch, and cellulose systems such as microcellulose, hydroxyethylcellulose, and carboxymethylcellulose can be used.
またさらに、前記合成高分子としては、ポリビニルアルコール、ポリビニルメチルエーテル、ポリアクリル酸、ポリエチレンオキサイド、ポリエチレングリコールなどを使用しうる。Furthermore, as the synthetic polymer, polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyethylene oxide, polyethylene glycol, or the like can be used.
表１はコーティング材１（１Ａ〜１Ｃ）に使用する光酸化触媒分散用液材となるエマルジョン４の組成例を示す。Table 1 shows a composition example of the emulsion 4 that is a liquid material for dispersing the photooxidation catalyst used for the coating material 1 (1A to 1C).
コーティング材１Ａのエマルジョン４は、５９％の水に添加剤として１０％のエチレングリコールモノターシャリーブチルエーテル（ＣＨ３Ｃ（ＣＨ３）２Ｏ・ＣＨ２ＣＨ２ＯＨ）を混合した溶液２に、アルカリ解溶型親水性有機高分子材３Ａである３０％の水性ポリエステル樹脂と、アルカリ解溶型親水性無機高分子材３Ｂである１％のカラギーナンを分散させた。Emulsion 4 of coating material 1A is obtained by adding alkaline solution to solution 2 in which 59% water is mixed with 10% ethylene glycol monotertiary butyl ether (CH 3 C (CH 3 ) 2 O.CH 2 CH 2 OH) as an additive. 30% water-based polyester resin, which is the desolubilized hydrophilic
コーティング材１Ｂのエマルジョン４は、６０％の水に添加剤として１０％のエチレングリコールモノターシャリーブチルエーテル（ＣＨ３Ｃ（ＣＨ３）２Ｏ・ＣＨ２ＣＨ２ＯＨ）を混合した溶液２に、アルカリ解溶型親水性有機高分子材３Ａである３０％の水性ポリエステル樹脂を分散させた。Emulsion 4 of coating material 1B is obtained by adding alkali 2 to solution 2 in which 10% ethylene glycol monotertiary butyl ether (CH 3 C (CH 3 ) 2 O.CH 2 CH 2 OH) is mixed as an additive with 60% water. A 30% aqueous polyester resin, which is the dissolution type hydrophilic organic polymer material 3A, was dispersed.
コーティング材１Ｃのエマルジョン４は、溶液２となる９８％の水に、アルカリ解溶型親水性無機高分子材３Ｂである２％のカラギーナンを分散させた。In the emulsion 4 of the coating material 1C, 2% carrageenan, which is the alkali desolubilized hydrophilic inorganic polymer material 3B, was dispersed in 98% of water used as the solution 2.
そして、各コーティング材１Ａ〜１Ｃは、これらのエマルジョン４を分散媒として、これに分散質として粉末又は液状の二酸化チタン５を１０％程度混入させ、十分に攪拌して分散させればよい。And each coating material 1A-1C should just disperse | distribute about 10% of powder or
以上が本発明に係るコーティング材とそれに用いる光酸化触媒用溶液の構成例であって、次にその作用について説明する。まず、アルカリ解溶型親水性高分子材３として、アルカリ解溶型親水性有機高分子材３Ａとアルカリ解溶型親水性無機高分子材３Ｂの双方を用いたコーティング材１Ａについて説明する。The above is a configuration example of the coating material according to the present invention and the photooxidation catalyst solution used therefor, and the operation thereof will be described next. First, a description will be given of a coating material 1A that uses both an alkali-dissolving hydrophilic organic polymer material 3A and an alkali-dissolving hydrophilic inorganic polymer material 3B as the alkali-dissolving hydrophilic polymer material 3.
コーティング材１Ａは、図１（ａ）に示すように、二酸化チタン５の周囲がアルカリ解溶型親水性無機高分子材３Ｂで覆われると共に、更に、その外側がアルカリ解溶型親水性有機高分子材３Ａで二層に覆われて親水コロイド粒子６を形成し、この親水コロイド粒子６が溶液２中に分散されているものと考えられる。As shown in FIG. 1A, the
このコーティング材１Ａを建造物の基材７に塗布すると、未乾燥状態では、二酸化チタン５の粒子がエマルジョン４内に分散されたコーティング層８が形成される。そして、時間が経つにつれてエマルジョン４に含まれる水分が徐々に蒸発すると同時に、アルカリ解溶型親水性高分子材３が固体化して、コーティング層８が肉やせを起こし、これに伴って、図１（ｂ）に示すように、コーティング層８の表層に二酸化チタン５の粒子が表層に露出した皮膜が形成される。When this coating material 1A is applied to the base material 7 of the building, a coating layer 8 in which particles of
したがって、このコーティング層８の表層に付着する汚染物質は、酸化能力の高い活性酸素により酸化分解され、抗菌、防汚、脱臭、空気浄化作用を発揮する。Therefore, contaminants adhering to the surface layer of the coating layer 8 are oxidatively decomposed by active oxygen having a high oxidizing ability, and exhibit antibacterial, antifouling, deodorizing, and air purification effects.
このとき、コーティング層８内に分散されている個々の二酸化チタン５の背面側には、アルカリ解溶型親水性高分子材３の皮膜が形成されており、二酸化チタン５が基材７に直接接触していないので、基材７で活性酸素が生成されることがない。したがって、基材７に酸化防止剤を塗布するまでもなく白亜化が防止される。At this time, a film of the alkali desolubilizing hydrophilic polymer material 3 is formed on the back side of each
また、エマルジョン４に含まれる水分が蒸発して形成されたアルカリ解溶型親水性高分子材３の皮膜は耐酸性を有し、光触媒により生成された活性酸素により酸化されることがないので、コーティング皮膜が１〜２年で容易に剥離することもなく長持ちする。特に、アルカリ解溶型親水性有機高分子材３Ａが含まれている場合は、水分が蒸発して強固な樹脂皮膜が形成された後は、風雨に曝されても溶け出すことがないので、屋外用のコーティング材として使用することができる。Further, the film of the alkali desolubilized hydrophilic polymer material 3 formed by evaporating the water contained in the emulsion 4 has acid resistance and is not oxidized by the active oxygen generated by the photocatalyst. The coating film lasts for 1-2 years without being easily peeled off. In particular, when the alkali-dissolving hydrophilic organic polymer material 3A is included, after the moisture evaporates and a strong resin film is formed, it does not melt even if exposed to wind and rain. It can be used as an outdoor coating material.
次いで、アルカリ解溶型親水性高分子材３として、アルカリ解溶型親水性有機高分子材３Ａ又はアルカリ解溶型親水性無機高分子材３Ｂのいずれか一方を用いたコーティング材１Ｂ、１Ｃについて説明する。Next, coating materials 1B and 1C using either the alkali desolubilized hydrophilic organic polymer material 3A or the alkali desolubilized hydrophilic inorganic polymer material 3B as the alkali desolubilized hydrophilic polymer material 3 explain.
コーティング材１Ｂ、１Ｃは、図２（ａ）に示すように、二酸化チタン５の周囲がアルカリ解溶型親水性有機高分子材３Ａ又はアルカリ解溶型親水性無機高分子材３Ｂで覆われて親水コロイド粒子を形成し、この親水コロイド粒子が溶液２中に分散されているものと考えられる。As shown in FIG. 2 (a), the coating materials 1B and 1C are covered with an alkali-dissolving hydrophilic organic polymer material 3A or an alkali-dissolving hydrophilic inorganic polymer material 3B. It is considered that hydrocolloid particles are formed and the hydrocolloid particles are dispersed in the solution 2.
このコーティング材１Ｂ、１Ｃを基材７に塗布すると、未乾燥状態では、二酸化チタン５の粒子がエマルジョン４内に分散されたコーティング層８が形成される。そして、時間が経つにつれてエマルジョン４に含まれる水分が徐々に蒸発すると同時に、アルカリ解溶型親水性高分子材３が固体化して、コーティング層８が肉やせを起こし、これに伴って、図２（ｂ）に示すように、コーティング層８の表層に二酸化チタン５の粒子が表層に露出した皮膜が形成される。When the coating materials 1B and 1C are applied to the substrate 7, a coating layer 8 in which particles of
この二酸化チタン５の光触媒機能により、空気中に含まれる水分Ｈ２Ｏや酸素Ｏ２から活性酸素ＯＨ−やＯ２ −を生成し、コーティング層８の表層に付着する汚染物質や空気中の臭気成分を酸化分解したり、細菌類を滅菌するセルフクリーニング作用有する点については前述と全く同様である。Due to the photocatalytic function of the
また、本例でもコーティング層８内に分散されている個々の二酸化チタン５の背面側には、アルカリ解溶型親水性高分子材３の皮膜が形成され、二酸化チタン５が基材７に直接接触していないので、基材７で活性酸素が生成されることがなく、したがって、基材７に酸化防止剤を塗布するまでもなく白亜化が防止される。Also in this example, a film of the alkali-dissolving hydrophilic polymer material 3 is formed on the back side of the
また、エマルジョン４に含まれる水分が蒸発して形成されたアルカリ解溶型親水性高分子材３Ａ又は３Ｂの皮膜は耐酸性を有するので、光触媒により生成された活性酸素により酸化されることがない。特に、有機高分子材３Ａの皮膜は強固で、風雨に曝されても溶け出すことがないので、屋外用のコーティング材として使用できる。In addition, since the film of the alkali-dissolving hydrophilic polymer material 3A or 3B formed by evaporation of water contained in the emulsion 4 has acid resistance, it is not oxidized by the active oxygen generated by the photocatalyst. . In particular, the film of the organic polymer material 3A is strong and does not melt even when exposed to wind and rain, so it can be used as an outdoor coating material.
なお、光触媒としては二酸化チタンに限るものではなく、太陽光や照明光の照射下において水や酸素から活性酸素を生成できるものであれば任意の物質を適用し得る。The photocatalyst is not limited to titanium dioxide, and any substance can be applied as long as it can generate active oxygen from water or oxygen under irradiation of sunlight or illumination light.
１ コーティング材
２ 溶液
３ アルカリ解溶型親水性高分子材
３Ａ アルカリ解溶型親水性有機高分子材
３Ｂ アルカリ解溶型親水性無機高分子材
４ エマルジョン
５ 二酸化チタン（光触媒）
６ コロイド粒子
７ 基材
８ コーティング層DESCRIPTION OF
6 Colloidal particles 7 Base material 8 Coating layer
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007141875A1 (en) * | 2006-06-09 | 2007-12-13 | Nippon Shokubai Co., Ltd. | Method of producing water-absorbing resin composition and water-absorbing resin composition |
| US8952116B2 (en) | 2009-09-29 | 2015-02-10 | Nippon Shokubai Co., Ltd. | Particulate water absorbent and process for production thereof |
| US9062140B2 (en) | 2005-04-07 | 2015-06-23 | Nippon Shokubai Co., Ltd. | Polyacrylic acid (salt) water-absorbent resin, production process thereof, and acrylic acid used in polymerization for production of water-absorbent resin |
| US9090718B2 (en) | 2006-03-24 | 2015-07-28 | Nippon Shokubai Co., Ltd. | Water-absorbing resin and method for manufacturing the same |
| US9926449B2 (en) | 2005-12-22 | 2018-03-27 | Nippon Shokubai Co., Ltd. | Water-absorbent resin composition, method of manufacturing the same, and absorbent article |
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2004
- 2004-06-21 JP JP2004210843A patent/JP2006008963A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9062140B2 (en) | 2005-04-07 | 2015-06-23 | Nippon Shokubai Co., Ltd. | Polyacrylic acid (salt) water-absorbent resin, production process thereof, and acrylic acid used in polymerization for production of water-absorbent resin |
| US9926449B2 (en) | 2005-12-22 | 2018-03-27 | Nippon Shokubai Co., Ltd. | Water-absorbent resin composition, method of manufacturing the same, and absorbent article |
| US10358558B2 (en) | 2005-12-22 | 2019-07-23 | Nippon Shokubai Co., Ltd. | Water-absorbent resin composition, method of manufacturing the same, and absorbent article |
| US9090718B2 (en) | 2006-03-24 | 2015-07-28 | Nippon Shokubai Co., Ltd. | Water-absorbing resin and method for manufacturing the same |
| WO2007141875A1 (en) * | 2006-06-09 | 2007-12-13 | Nippon Shokubai Co., Ltd. | Method of producing water-absorbing resin composition and water-absorbing resin composition |
| JPWO2007141875A1 (en) * | 2006-06-09 | 2009-10-15 | 株式会社日本触媒 | Method for producing water absorbent resin composition and water absorbent resin composition |
| JP5020637B2 (en) * | 2006-06-09 | 2012-09-05 | 株式会社日本触媒 | Method for producing water absorbent resin composition |
| US8952116B2 (en) | 2009-09-29 | 2015-02-10 | Nippon Shokubai Co., Ltd. | Particulate water absorbent and process for production thereof |
| US9775927B2 (en) | 2009-09-29 | 2017-10-03 | Nippon Shokubai Co., Ltd. | Particulate water absorbent and process for production thereof |
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