JP5825888B2 - Water-absorbent resin composition, absorber and absorbent article - Google Patents

Water-absorbent resin composition, absorber and absorbent article Download PDF

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JP5825888B2
JP5825888B2 JP2011149387A JP2011149387A JP5825888B2 JP 5825888 B2 JP5825888 B2 JP 5825888B2 JP 2011149387 A JP2011149387 A JP 2011149387A JP 2011149387 A JP2011149387 A JP 2011149387A JP 5825888 B2 JP5825888 B2 JP 5825888B2
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absorbent resin
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潤一 鷹取
潤一 鷹取
昌良 半田
昌良 半田
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Sumitomo Seika Chemicals Co Ltd
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本発明は、抗菌、消臭性能に優れ、安全に取り扱うことができ、かつゲル安定性に優れた吸水性樹脂組成物に関する。また、本発明は、該吸水性樹脂組成物を用いて製造される吸収体、及び、該吸収体を用いて製造される吸収性物品に関する。   The present invention relates to a water-absorbent resin composition that is excellent in antibacterial and deodorizing performance, can be handled safely, and has excellent gel stability. Moreover, this invention relates to the absorber manufactured using this water absorbent resin composition, and the absorbent article manufactured using this absorber.

従来、吸水性樹脂は、紙おむつ、生理用ナプキン、失禁パッド等の衛生材料、ペット用の尿吸収材料、パッキング材等の土木建築用資材、ドリップ吸収剤、保冷材等の食品鮮度保持用材料、土壌用保水材等の農園芸用物品等の種々の分野で使用されている。
衛生材料である紙おむつ等に代表される吸収性物品は、体液等の液体を吸収する吸収体が、体に接する側に配された柔軟な液体透過性の表面シート(トップシート)と、表面シートの反対側に配された液体不透過性の背面シート(バックシート)とにより保持された構造を有する。通常、吸収体は、吸水性樹脂と親水性繊維との混合物からなる。
吸収性物品においては、体液、特に人尿を吸収した際に、不快な臭いを発生することが問題となっている。これらの臭いは、皮膚及び消化管に存在しているバクテリアが、尿素、タンパク質等の体液の成分を分解する酵素を生産し、体液の成分がその酵素により分解されることによって発生する腐敗臭であると考えられる。
Conventionally, water-absorbing resins have been used for sanitary materials such as disposable diapers, sanitary napkins, incontinence pads, urine absorbing materials for pets, civil engineering and building materials such as packing materials, food freshness-keeping materials such as drip absorbents and cold insulation materials, It is used in various fields such as agricultural and horticultural articles such as soil water retention materials.
Absorbent articles represented by sanitary materials such as disposable diapers are a flexible liquid-permeable surface sheet (top sheet) in which an absorbent that absorbs liquid such as body fluid is disposed on the side in contact with the body, and a surface sheet And a liquid impervious back sheet (back sheet) disposed on the opposite side. Usually, an absorber consists of a mixture of a water absorbing resin and a hydrophilic fiber.
In the absorbent article, there is a problem that an unpleasant odor is generated when a body fluid, particularly human urine is absorbed. These odors are rotting odors that are produced when bacteria present in the skin and digestive tract produce enzymes that break down components of body fluids such as urea and proteins, and the components of body fluids are decomposed by the enzymes. It is believed that there is.

これらの臭いの発生を抑制するために、活性炭、ゼオライト等の臭気成分吸着剤を混合した吸収体(例えば、特許文献1、2参照)や、上記バクテリアを殺菌し、経時的な腐敗臭の増加を防ぐ、銀、銅、亜鉛等の抗菌性金属を無機化合物に担持させた無機系抗菌剤と吸水性樹脂とからなる組成物が提案されている(例えば、特許文献3参照)。臭いの発生を抑制する他の手段として、第4級アンモニウム塩等の殺菌剤と吸水性樹脂とからなる吸水剤(例えば、特許文献4参照)等が提案されている。   In order to suppress the generation of these odors, absorbents mixed with odorous component adsorbents such as activated carbon and zeolite (see, for example, Patent Documents 1 and 2) and the above bacteria are sterilized, and the rot odor increases over time. A composition comprising an inorganic antibacterial agent in which an antibacterial metal such as silver, copper or zinc is supported on an inorganic compound and a water-absorbing resin has been proposed (for example, see Patent Document 3). As another means for suppressing the generation of odor, a water absorbent (for example, see Patent Document 4) composed of a sterilizing agent such as a quaternary ammonium salt and a water absorbent resin has been proposed.

また、臭いの発生を抑制するために、抗菌性を有するホスホニウム塩モノマー成分と、該ホスホニウム塩モノマー成分と共重合可能でかつ重合後に高吸水性樹脂となり得るモノマー成分とを架橋重合させた抗菌性高吸水性樹脂が提案されている(例えば、特許文献5参照)。   In addition, in order to suppress the generation of odor, antibacterial properties obtained by crosslinking and polymerizing a phosphonium salt monomer component having antibacterial properties and a monomer component that can be copolymerized with the phosphonium salt monomer component and become a superabsorbent resin after polymerization. A highly water-absorbent resin has been proposed (see, for example, Patent Document 5).

一方、人尿中には吸水性樹脂を劣化させるいくつかの因子が含まれており、吸水性樹脂が人尿を吸収すると、ゲルの劣化(強度が低下したり、ゲルが分解したりすること)が生じる。ゲルが劣化することで、ゲルの間の隙間が塞がれ、その結果、液体の浸透が妨げられるゲルブロッキングが生じ、液体の拡散性が悪くなり、吸収性物品に使用したときに人尿が漏れる原因となる。またゲルの分解によりゲルの可溶成分が溶出した場合には、かぶれなどの原因となる。
さらに、紙おむつ等の吸収性物品は、夜間の使用のように長時間着用することも多いため、人尿を吸収した後も長時間にわたってゲル安定性を発揮する吸水性樹脂が要求されている。
On the other hand, human urine contains several factors that degrade the water-absorbent resin. When the water-absorbent resin absorbs human urine, the gel deteriorates (the strength decreases or the gel decomposes). ) Occurs. As the gel deteriorates, gaps between the gels are blocked, resulting in gel blocking that prevents liquid penetration, resulting in poor liquid diffusivity, and human urine when used in absorbent articles. Cause leakage. Moreover, when the soluble component of a gel elutes by decomposition | disassembly of a gel, it causes a rash.
Furthermore, since absorbent articles such as paper diapers are often worn for a long time, such as nighttime use, a water-absorbing resin that exhibits gel stability for a long time after absorbing human urine is required.

特開2001−037805号公報JP 2001-037805 A 特表平11−512946号公報Japanese National Patent Publication No. 11-512946 特表2001−505237号公報JP-T-2001-505237 特開2000−079159号公報Japanese Unexamined Patent Publication No. 2000-079159 特開平8−092020号公報JP-A-8-092020

特許文献1〜3に開示されている臭気成分吸着剤や無機系抗菌剤は、吸水性樹脂との親和性に劣るため、紙おむつ等の吸収性物品を製造する際に吸着剤や抗菌剤が発塵し、製造の際の作業環境が悪化するという問題がある。また、特許文献4に開示されている第4級アンモニウム塩等の殺菌剤と吸水性樹脂とからなる吸水剤は、殺菌剤が、皮膚、粘膜と接触することによる炎症を引き起こす可能性がある。特許文献5に開示されている抗菌性高吸水性樹脂には、抗菌性を有するモノマー成分が高価であるため、経済的でないという欠点がある。また、これらの特許文献においては、吸水性樹脂組成物のゲル安定性は、考慮されていない。   The odor component adsorbents and inorganic antibacterial agents disclosed in Patent Documents 1 to 3 are inferior in affinity with the water-absorbent resin, and therefore adsorbents and antibacterial agents are generated when manufacturing absorbent articles such as disposable diapers. There is a problem that the working environment during production deteriorates due to dust. In addition, the water-absorbing agent comprising a bactericidal agent such as a quaternary ammonium salt and a water-absorbing resin disclosed in Patent Document 4 may cause inflammation due to contact of the bactericidal agent with the skin and mucous membrane. The antibacterial highly water-absorbent resin disclosed in Patent Document 5 has a disadvantage that it is not economical because the monomer component having antibacterial properties is expensive. Moreover, in these patent documents, the gel stability of the water-absorbent resin composition is not considered.

本発明は、抗菌、消臭性能に優れ、安全に取り扱うことができ、かつゲル安定性に優れた吸水性樹脂組成物を提供することを目的とする。また、本発明は、該吸水性樹脂組成物を用いて製造される吸収体、及び、該吸収体を用いて製造される吸収性物品を提供することを目的とする。   An object of the present invention is to provide a water-absorbent resin composition that is excellent in antibacterial and deodorizing performance, can be handled safely, and has excellent gel stability. Moreover, an object of this invention is to provide the absorber manufactured using this water absorbent resin composition, and the absorbent article manufactured using this absorber.

本発明は、吸水性樹脂とキク科植物抽出物とを含有する吸水性樹脂組成物であって、前記キク科植物抽出物の含有量が、吸水性樹脂100質量部に対して0.005〜5質量部である、吸水性樹脂組成物である。 The present invention is a water absorbent resin composition containing a water absorbent resin and an Asteraceae plant extract , wherein the content of the Asteraceae plant extract is 0.005 to 100 parts by mass of the water absorbent resin. It is a water-absorbent resin composition that is 5 parts by mass .

本発明にかかる吸水性樹脂組成物は、抗菌、消臭性能に優れ、安全性が高く発塵の問題のないキク科植物抽出物を含有するため、抗菌、消臭性能に優れ、安全に取り扱うことができ、かつゲル安定性に優れる。   The water-absorbent resin composition according to the present invention has an excellent antibacterial and deodorizing performance, and has a high safety and no problem of dust generation. And has excellent gel stability.

本発明にかかる吸水性樹脂組成物は、吸水性樹脂とキク科植物抽出物とを含有する。   The water-absorbing resin composition according to the present invention contains a water-absorbing resin and an Asteraceae plant extract.

上記吸水性樹脂としては、例えば、アクリル酸部分中和物重合体の架橋物、デンプン−アクリル酸塩グラフト共重合体の架橋物、ビニルアルコール−アクリル酸塩共重合体の架橋物、無水マレイン酸グラフトポリビニルアルコールの架橋物、架橋イソブチレン−無水マレイン酸共重合体、酢酸ビニル−アクリル酸エステル共重合体のケン化物等が挙げられる。これらの吸水性樹脂のなかでも、大量の液体を吸収すると共に、多少の荷重をかけても吸収した液体を分子内に保持しうることから、アクリル酸部分中和物重合体の架橋物が好ましい。   Examples of the water-absorbing resin include a crosslinked product of partially neutralized acrylic acid polymer, a crosslinked product of starch-acrylate graft copolymer, a crosslinked product of vinyl alcohol-acrylate copolymer, and maleic anhydride. Examples include a grafted product of grafted polyvinyl alcohol, a crosslinked isobutylene-maleic anhydride copolymer, a saponified product of vinyl acetate-acrylic acid ester copolymer, and the like. Among these water-absorbing resins, a cross-linked product of a partially neutralized acrylic acid polymer is preferable because it absorbs a large amount of liquid and can retain the absorbed liquid in the molecule even under some load. .

上記吸水性樹脂の製造方法は特に限定されず、例えば、逆相懸濁重合法、水溶液重合法等が挙げられる。   The manufacturing method of the said water absorbing resin is not specifically limited, For example, the reverse phase suspension polymerization method, the aqueous solution polymerization method, etc. are mentioned.

上記キク科植物としては、キク(イエギク)、アルニカ、エチナシ、カミツレ、カワラヨモギ、ステビア、セイヨウウスユキソウ、セイヨウノコギリソウ、トウキンセンカ、フキタンポポ、マリーゴールド、ヤーコン等が挙げられる。これらのキク科植物の中でも、抗菌性や安全性、また吸水性樹脂組成物のゲル安定性に効果があることから、ステビア、トウキンセンカ及びフキタンポポが好ましい。   Examples of the Asteraceae plants include chrysanthemum (iegiku), arnica, pear, chamomile, kawara mugwort, stevia, sorghum, yarrow, eucalyptus, marigold, and yacon. Among these asteraceae plants, stevia, milk moth and dandelion are preferred because they are effective in antibacterial properties and safety, and gel stability of the water-absorbent resin composition.

抽出物の原料として用いられる植物の部位は、特に制限はなく、葉、茎、花、蕾、根、種子、果実、果皮、果核、地上部、全草又はこれらの混合物が挙げられる。これらの中でも、特に葉や花を用いることが好ましい。原料は、生のまま抽出に供してもよいが、抽出効率の観点から、乾燥や粉砕等の処理を行ったものが好ましい。   The part of the plant used as the raw material of the extract is not particularly limited, and examples thereof include leaves, stems, flowers, buds, roots, seeds, fruits, peels, fruit nuclei, above-ground parts, whole grasses, or a mixture thereof. Among these, it is particularly preferable to use leaves and flowers. The raw material may be subjected to extraction as it is, but from the viewpoint of extraction efficiency, a material subjected to treatment such as drying and pulverization is preferable.

キク科植物抽出物は、植物の抽出に一般に用いられる方法により抽出したものを使用してもよいし、市販品を用いてもよい。   As the Asteraceae plant extract, one extracted by a method generally used for plant extraction may be used, or a commercially available product may be used.

上記キク科植物から抽出物を取り出す方法としては、例えば、原料を抽出溶媒に浸漬して行う方法が挙げられる。この場合、抽出効率を上げるため攪拌を行ったり、抽出溶媒中でホモジナイズしてもよい。抽出溶媒としては、水、親水性有機溶媒又はこれらの混合溶媒を用いることができる。親水性有機溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール等の低級アルコール;1,3−ブチレングリコール、プロピレングリコール、グリセリン等の多価アルコール;アセトン、メチルエチルケトン等のケトン類;ジエチルエーテル、ジプロピルエーテル等のエーテル類;酢酸エチル、酢酸ブチル等のエステル類等が用いられる。抽出温度としては、5℃程度から抽出溶媒の沸点以下の温度が好ましい。抽出時間は、原料、抽出溶媒の種類や抽出温度によって異なるが、4時間〜14日程度が好ましい。   Examples of the method for taking out the extract from the Asteraceae plant include a method in which the raw material is immersed in an extraction solvent. In this case, stirring may be performed to increase extraction efficiency, or homogenization may be performed in an extraction solvent. As the extraction solvent, water, a hydrophilic organic solvent, or a mixed solvent thereof can be used. Examples of the hydrophilic organic solvent include lower alcohols such as methanol, ethanol, propanol and isopropanol; polyhydric alcohols such as 1,3-butylene glycol, propylene glycol and glycerin; ketones such as acetone and methyl ethyl ketone; diethyl ether and dipropyl ether. Ethers such as ethyl ester and esters such as ethyl acetate and butyl acetate are used. The extraction temperature is preferably about 5 ° C. to the boiling point of the extraction solvent. The extraction time varies depending on the type of raw material, extraction solvent, and extraction temperature, but is preferably about 4 hours to 14 days.

上記キク科植物抽出物の使用量は、上記吸水性樹脂100質量部に対して0.005〜5質量部であることが好ましい。吸水性樹脂組成物として充分な抗菌消臭性を発現させ、また得られる吸水性樹脂組成物のゲル安定性の観点から、0.005質量部以上が好ましく、抗菌消臭性能に関する費用対効果と、キク科植物抽出物自身の臭気を抑制する観点から、5質量部以下が好ましい。上記キク科植物抽出物の使用量は、0.05〜3質量部であることがより好ましく、0.1〜2質量部であることが更に好ましい。   The amount of the Asteraceae plant extract used is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the water absorbent resin. From the viewpoint of exhibiting sufficient antibacterial deodorization properties as a water absorbent resin composition and gel stability of the resulting water absorbent resin composition, 0.005 parts by mass or more is preferable, From the viewpoint of suppressing the odor of the Asteraceae plant extract itself, 5 parts by mass or less is preferable. As for the usage-amount of the said Asteraceae plant extract, it is more preferable that it is 0.05-3 mass parts, and it is still more preferable that it is 0.1-2 mass parts.

本発明にかかる吸水性樹脂組成物は、例えば、以下の(a)〜(c)の方法で製造することができるが、本発明にかかる吸水性樹脂組成物はこれらの方法により製造されたものに限定されない。
(a)吸水性樹脂に、キク科植物抽出物を直接噴霧混合する方法。
(b)吸水性樹脂に、キク科植物抽出物の水溶液あるいはアルコール溶液を噴霧混合し、乾燥する方法。
(c)吸水性樹脂を膨潤させない溶媒中に、吸水性樹脂とキク科植物抽出物とを添加し、攪拌混合後、溶媒を除去する方法。
なお、本発明に用いられるキク科植物抽出物は、発塵を抑制する観点から、液状であることが好ましい。
The water absorbent resin composition according to the present invention can be produced, for example, by the following methods (a) to (c). The water absorbent resin composition according to the present invention is produced by these methods. It is not limited to.
(A) A method in which a asteraceae plant extract is directly spray mixed with a water-absorbent resin.
(B) A method in which a water-absorbent resin is spray-mixed with an aqueous solution or an alcohol solution of an Asteraceae plant extract and dried.
(C) A method of adding a water-absorbent resin and a asteraceae plant extract to a solvent that does not swell the water-absorbent resin, and removing the solvent after stirring and mixing.
In addition, it is preferable that the Asteraceae plant extract used for this invention is a liquid form from a viewpoint of suppressing dust generation.

本発明にかかる吸水性樹脂組成物と親水性繊維とを含有する吸収体もまた、本発明の1つである。   The absorber containing the water-absorbent resin composition according to the present invention and hydrophilic fibers is also one aspect of the present invention.

上記親水性繊維としては、例えば、セルロース繊維、人工セルロース繊維、親水化処理された合成繊維等が挙げられる。   Examples of the hydrophilic fiber include cellulose fiber, artificial cellulose fiber, and hydrophilic synthetic fiber.

本発明にかかる吸収体の好適な態様としては、例えば、本発明にかかる吸水性樹脂組成物と親水性繊維とを均一な組成となるように混合することによって得られる混合分散体、2枚の層状の親水性繊維の間に吸水性樹脂組成物が挟まれたサンドイッチ構造体等が挙げられる。   As a preferable aspect of the absorbent body according to the present invention, for example, a mixed dispersion obtained by mixing the water-absorbent resin composition according to the present invention and the hydrophilic fiber so as to have a uniform composition, Examples include a sandwich structure in which a water-absorbent resin composition is sandwiched between layered hydrophilic fibers.

本発明にかかる吸収体には、吸収体の形態保持性を高めるために、熱融着性合成繊維、ホットメルト接着剤、接着性エマルジョン等の接着性バインダーを添加してもよい。   To the absorbent body according to the present invention, an adhesive binder such as a heat-fusible synthetic fiber, a hot melt adhesive, or an adhesive emulsion may be added in order to improve the shape retention of the absorbent body.

液体透過性シートと液体不透過性シートとの間に本発明にかかる吸収体が保持されている吸収性物品もまた、本発明の1つである。   An absorbent article in which the absorbent according to the present invention is held between the liquid permeable sheet and the liquid impermeable sheet is also one aspect of the present invention.

上記液体透過性シートとしては、例えば、ポリエチレン、ポリプロピレン、ポリエステル等の繊維からなる、エアスルー型、スパンボンド型、ケミカルボンド型、ニードルパンチ型等の不織布が挙げられる。   Examples of the liquid permeable sheet include air-through type, spun bond type, chemical bond type, needle punch type nonwoven fabrics made of fibers such as polyethylene, polypropylene, and polyester.

上記液体不透過性シートとしては、例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等の樹脂からなる合成樹脂フィルム等が挙げられる。   Examples of the liquid impermeable sheet include synthetic resin films made of resins such as polyethylene, polypropylene, and polyvinyl chloride.

本発明にかかる吸収性物品は、例えば、紙おむつ、生理用ナプキンや失禁パッド等の衛生材料、ペット用の尿吸収材料、パッキング材等の土木建築用資材、ドリップ吸収剤、保冷材等の食品鮮度保持用材料、土壌用保水材等の農園芸用物品等に好適に用いられる。   Absorbent articles according to the present invention include, for example, sanitary materials such as disposable diapers, sanitary napkins and incontinence pads, urine absorbent materials for pets, civil engineering and building materials such as packing materials, food freshness such as drip absorbents and cold insulation materials. It is suitably used for agricultural and horticultural articles such as holding materials and soil water retaining materials.

以下に、本発明を合成例、製造例、実施例及び比較例に基づいてさらに詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。   Hereinafter, the present invention will be described in more detail based on synthesis examples, production examples, examples, and comparative examples, but the present invention is not limited only to such examples.

[合成例]
攪拌機、2段パドル翼、還流冷却器、滴下ロート及び窒素ガス導入管を備えた2L容の丸底円筒型セパラブルフラスコを準備した。このフラスコにn−ヘプタン280gをとり、ショ糖ステアリン酸エステル(三菱化学フーズ(株)、リョートーシュガーエステルS−370)0.83gを添加し、撹拌しながら80℃まで昇温してショ糖ステアリン酸エステルを溶解した後、50℃まで冷却した。
一方、500mL容の三角フラスコに80質量%のアクリル酸水溶液92g(1.02モル)をとり、外部より冷却しつつ、21質量%の水酸化ナトリウム水溶液146.0gを滴下して75モル%の中和を行った後、ラジカル重合開始剤として過硫酸カリウム0.074g(0.27ミリモル)、内部架橋剤としてN,N’−メチレンビスアクリルアミド9.2mg(0.06ミリモル)を加えて溶解し、第1段目の単量体水溶液を調製した。
前記の第1段目の単量体水溶液の全量を、前記セパブルフラスコに添加して、系内を窒素で充分に置換した後、フラスコを70℃の水浴に浸漬して昇温し、第1段目の重合を30分間行い、第1段目の反応混合物を得た。
一方、別の500mL容の三角フラスコに80質量%のアクリル酸水溶液128.8g(1.43モル)をとり、外部より冷却しつつ、27質量%の水酸化ナトリウム水溶液159.0gを滴下して75モル%の中和を行った後、ラジカル重合開始剤として過硫酸カリウム0.10g(0.37ミリモル)、内部架橋剤としてN,N’−メチレンビスアクリルアミド12.9mg(0.08ミリモル)を加えて溶解して、第2段目の単量体水溶液を調製した。
前記第1段目の反応混合物を25℃に冷却し、同温度の前記第2段目の単量体水溶液を系内に添加し、30分間吸収させると同時に系内を窒素で充分に置換した後、再度、フラスコを70℃の水浴に浸漬して昇温し、第2段目の重合を30分間行った。
第2段目の重合後、125℃の油浴で反応混合物を昇温し、n−ヘプタンと水との共沸蒸留によりn−ヘプタンを還流しながら222gの水を系外へ抜き出した後、エチレングリコールジグリシジルエーテルの2質量%水溶液3.98g(0.46ミリモル)を添加し、80℃で2時間、後架橋反応を行った。その後、125℃の油浴で反応混合物を昇温し、n−ヘプタンを蒸発させて乾燥することによって、吸水性樹脂225.4gを得た。
[Synthesis example]
A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. To this flask, 280 g of n-heptane was taken, 0.83 g of sucrose stearate ester (Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370) was added, and the temperature was raised to 80 ° C. with stirring to sucrose. After the stearic acid ester was dissolved, it was cooled to 50 ° C.
On the other hand, 92 g (1.02 mol) of 80% by mass acrylic acid aqueous solution was placed in a 500 mL Erlenmeyer flask, and 146.0 g of 21% by mass sodium hydroxide aqueous solution was added dropwise while cooling from the outside. After neutralization, 0.074 g (0.27 mmol) of potassium persulfate as a radical polymerization initiator and 9.2 mg (0.06 mmol) of N, N′-methylenebisacrylamide as an internal crosslinking agent were added and dissolved. The first stage monomer aqueous solution was prepared.
After adding the total amount of the first stage monomer aqueous solution to the separable flask and sufficiently replacing the system with nitrogen, the flask was immersed in a 70 ° C. water bath and heated. The first stage polymerization was carried out for 30 minutes to obtain a first stage reaction mixture.
On the other hand, 128.8 g (1.43 mol) of an 80% by weight acrylic acid aqueous solution was placed in another 500 mL Erlenmeyer flask, and 159.0 g of a 27% by weight sodium hydroxide aqueous solution was dropped while cooling from the outside. After neutralization of 75 mol%, 0.10 g (0.37 mmol) of potassium persulfate as a radical polymerization initiator and 12.9 mg (0.08 mmol) of N, N′-methylenebisacrylamide as an internal crosslinking agent Was added and dissolved to prepare a second-stage monomer aqueous solution.
The first-stage reaction mixture was cooled to 25 ° C., and the second-stage monomer aqueous solution at the same temperature was added to the system and absorbed for 30 minutes. At the same time, the system was sufficiently replaced with nitrogen. Thereafter, the flask was again immersed in a 70 ° C. water bath and the temperature was raised, and the second stage polymerization was carried out for 30 minutes.
After polymerization in the second stage, the reaction mixture was heated in an oil bath at 125 ° C., and 222 g of water was extracted out of the system while refluxing n-heptane by azeotropic distillation of n-heptane and water. 3.98 g (0.46 mmol) of a 2% by weight aqueous solution of ethylene glycol diglycidyl ether was added, and a post-crosslinking reaction was performed at 80 ° C. for 2 hours. Thereafter, the reaction mixture was heated in a 125 ° C. oil bath, and n-heptane was evaporated and dried to obtain 225.4 g of a water absorbent resin.

[製造例1]
キク科植物のトウキンセンカの花200gを乾燥、粉砕し、50容量%エタノール水溶液1L中にて、20℃で3日間攪拌抽出した後、濾過して濾液を得た。濾液を減圧下濃縮し、十分に乾燥した後、50容量%エタノール水溶液を用いて溶解し、1質量%トウキンセンカ抽出液を得た。
[Production Example 1]
200 g of flowers of the asteraceae, Asteraceae, were dried and pulverized, extracted with stirring in 1 L of 50% by volume ethanol aqueous solution at 20 ° C. for 3 days, and then filtered to obtain a filtrate. The filtrate was concentrated under reduced pressure, sufficiently dried, and then dissolved using a 50% by volume ethanol aqueous solution to obtain a 1% by weight milk scented extract.

[製造例2]
キク科植物のトウキンセンカの花500gを乾燥、粉砕し、70容量%エタノール水溶液3L中にて、20℃で7日間静置抽出した後、濾過して濾液を得た。濾液を減圧下濃縮し、十分に乾燥した後、50容量%エタノール水溶液を用いて溶解し、5質量%トウキンセンカ抽出液を得た。
[Production Example 2]
500 g of Asteraceae flower, Asteraceae, was dried and pulverized, and extracted by standing in 3 L of 70% by volume ethanol aqueous solution at 20 ° C. for 7 days, followed by filtration to obtain a filtrate. The filtrate was concentrated under reduced pressure, sufficiently dried, and then dissolved using a 50% by volume ethanol aqueous solution to obtain a 5% by weight milk sesame extract.

[製造例3]
キク科植物としてフキタンポポの花200gを使用した以外は製造例1と同様にして、2質量%フキタンポポ抽出液を得た。
[Production Example 3]
A 2% by weight dandelion extract was obtained in the same manner as in Production Example 1 except that 200 g of dandelion flowers were used as the Asteraceae plants.

[製造例4]
キク科植物のステビアの葉200gを乾燥、粉砕し、温水(50℃)1L中にて5時間攪拌抽出した後、濾過して濾液及び濾物を得た。濾物を再度、温水(50℃)1L中にて5時間攪拌抽出した後、濾過して、得られた濾液を先の操作で得られた濾液と混合した。この液を減圧下濃縮し、十分に乾燥した後、50容量%エタノール水溶液を用いて溶解し、1質量%ステビア抽出液を得た。
[Production Example 4]
200 g of Stevia leaves of the Asteraceae plant were dried, pulverized, extracted with stirring in 1 L of warm water (50 ° C.) for 5 hours, and then filtered to obtain a filtrate and a filtrate. The filtrate was again extracted by stirring in 1 L of warm water (50 ° C.) for 5 hours, filtered, and the obtained filtrate was mixed with the filtrate obtained in the previous operation. This solution was concentrated under reduced pressure, sufficiently dried, and then dissolved using a 50% by volume ethanol aqueous solution to obtain a 1% by mass stevia extract.

[実施例1]
合成例で得られた吸水性樹脂20gに、キク科植物抽出物として、製造例1で得られたトウキンセンカ抽出液(1質量%)20gを充分に混合した。次いで、この混合物を100℃の油浴で30分間加熱してエタノール及び水を留去し、吸水性樹脂組成物20.2gを得た。
[Example 1]
To 20 g of the water-absorbent resin obtained in the synthesis example, 20 g of the milk sesame extract (1% by mass) obtained in Production Example 1 was sufficiently mixed as an Asteraceae plant extract. Next, this mixture was heated in an oil bath at 100 ° C. for 30 minutes to distill off ethanol and water to obtain 20.2 g of a water absorbent resin composition.

[実施例2]
合成例で得られた吸水性樹脂20gに、キク科植物抽出物として、製造例1で得られたトウキンセンカ抽出液(1質量%)0.6gを直接噴霧し、充分に混合した。次いで、この混合物を100℃の油浴で30分間加熱してエタノール及び水を留去し、吸水性樹脂組成物20.0gを得た。
[Example 2]
20 g of the water-absorbent resin obtained in the synthesis example was directly sprayed with 0.6 g of the milk sesame extract (1% by mass) obtained in Production Example 1 as an Asteraceae plant extract and mixed well. Subsequently, this mixture was heated in an oil bath at 100 ° C. for 30 minutes to distill off ethanol and water to obtain 20.0 g of a water absorbent resin composition.

[実施例3]
キク科植物抽出物として、製造例2で得られたトウキンセンカ抽出液(5質量%)を16g用いた以外は、実施例1と同様にして吸水性樹脂組成物20.7gを得た。
[Example 3]
As the Asteraceae plant extract, 20.7 g of a water-absorbent resin composition was obtained in the same manner as in Example 1 except that 16 g of the milk moth extract (5% by mass) obtained in Production Example 2 was used.

[実施例4]
キク科植物抽出物として、製造例3で得られたフキタンポポ抽出液(2質量%)を15g用いた以外は、実施例1と同様にして吸水性樹脂組成物20.3gを得た。
[Example 4]
As an Asteraceae plant extract, 20.3 g of a water-absorbent resin composition was obtained in the same manner as in Example 1 except that 15 g of the dandelion extract (2% by mass) obtained in Production Example 3 was used.

[実施例5]
キク科植物抽出物として、製造例4で得られたステビア抽出液(1質量%)を6g用いた以外は、実施例2と同様にして吸水性樹脂組成物20.0gを得た。
[Example 5]
As a compositae plant extract, 20.0 g of a water-absorbent resin composition was obtained in the same manner as in Example 2, except that 6 g of the stevia extract (1% by mass) obtained in Production Example 4 was used.

[実施例6]
合成例で得られた吸水性樹脂50gに、キク科植物抽出物として、製造例1で得られたトウキンセンカ抽出液(1質量%)0.2gを直接噴霧し、充分に混合した。次いで、この混合物を100℃の油浴で30分間加熱してエタノール及び水を留去し、吸水性樹脂組成物50.0gを得た。ただし、実施例6は、参考例である。
[Example 6]
50 g of the water-absorbent resin obtained in the synthesis example was directly sprayed with 0.2 g of the milk sesame extract (1% by mass) obtained in Production Example 1 as an Asteraceae plant extract and mixed well. Next, this mixture was heated in an oil bath at 100 ° C. for 30 minutes to distill off ethanol and water to obtain 50.0 g of a water absorbent resin composition. However, Example 6 is a reference example.

[実施例7]
キク科植物抽出物として、製造例2で得られたトウキンセンカ抽出液(5質量%)を24g用いた以外は、実施例1と同様にして吸水性樹脂組成物21.1gを得た。ただし、実施例7は、参考例である。
[Example 7]
As an Asteraceae plant extract, 21.1 g of a water-absorbent resin composition was obtained in the same manner as in Example 1, except that 24 g of the milk sesame extract (5% by mass) obtained in Production Example 2 was used. However, Example 7 is a reference example.

[比較例1]
合成例で得られた吸水性樹脂20gを、そのまま用いた。
[Comparative Example 1]
20 g of the water absorbent resin obtained in the synthesis example was used as it was.

実施例により得られた吸水性樹脂組成物及び比較例の吸水性樹脂の人尿吸収時のゲル安定性、及び吸収体の臭気官能試験を以下の方法により行った。   The gel stability at the time of human urine absorption of the water-absorbent resin composition obtained in the examples and the water-absorbent resin of the comparative example, and the odor sensory test of the absorber were performed by the following methods.

<人尿吸収時のゲル安定性>
成人男性から採取した人尿39gを100mLビーカーに分取し、吸水性樹脂組成物又は吸水性樹脂1gを添加して、人尿吸収ゲルを作成した。この人尿吸収ゲルを40℃の恒温槽内に入れ、24時間後のゲル安定性について、以下の評価基準に従って評価した。結果を表1に示した。
A:ゲルの弾力性があり、強く押してもつぶれない。
B:ゲルの弾力性はあるが、強く押すとつぶれる。
C:ゲルの形状はあるが、軽くつまむとつぶれる。
D:ゲルの形状が崩れている。
<Gel stability during human urine absorption>
39 g of human urine collected from an adult male was collected in a 100 mL beaker, and 1 g of a water absorbent resin composition or a water absorbent resin was added to prepare a human urine absorbing gel. This human urine absorbing gel was placed in a constant temperature bath at 40 ° C., and the gel stability after 24 hours was evaluated according to the following evaluation criteria. The results are shown in Table 1.
A: The elasticity of the gel is not crushed even when pressed strongly.
B: The gel is elastic, but when pressed hard, it collapses.
C: Although there is a gel shape, it is crushed when lightly pinched.
D: The shape of the gel is broken.

<吸収体の臭気官能試験>
(a)吸収体の作製
吸水性樹脂組成物または吸水性樹脂1gと解砕パルプ1gをブレンドしたものを、空気抄造によって直径5cmのティッシュ上に形成させ、同じ大きさのティッシュ上に重ねた後、145kPaの荷重を30秒間施して吸収体を作製した。
<Odor sensory test of absorber>
(A) Preparation of Absorber After a water absorbent resin composition or a blend of 1 g of a water absorbent resin and 1 g of pulverized pulp is formed on a tissue having a diameter of 5 cm by air-making and stacked on a tissue of the same size An absorber was manufactured by applying a load of 145 kPa for 30 seconds.

(b)臭気官能試験
100mLマイヤーフラスコに新鮮な人尿50mLを入れ、尿素0.25g、使用済みおむつから採取したパルプ1gを加え、溶液を24時間放置し発酵尿を作製した。次いで、新鮮な人尿と上記発酵尿を9:1(質量比)の割合で混合することにより、試験液を調製した(新鮮な人尿は無菌なため、発酵尿を混合しないと充分な臭気が発生しない)。
上記(a)で得られた吸収体を250mLガラス瓶に入れた後、上記試験液30gを添加して吸収体を膨潤させた。試験液を添加後、直ちに密封し、40℃で24時間保存した。保存後、5人のパネラー(A〜E)に、250mLガラス瓶中の臭気を、規定基準の「6段階臭気強度表示法」に準じて下記の基準により判定してもらい、その平均値で評価した。結果を表1に示した。
5:強烈な臭い
4:強い臭い
3:楽に認識できる臭い
2:何の臭いか分かる弱い臭い
1:やっと感知できる臭い
0:無臭
(B) Odor sensory test 50 mL of fresh human urine was placed in a 100 mL Meyer flask, 0.25 g of urea and 1 g of pulp collected from used diapers were added, and the solution was allowed to stand for 24 hours to prepare fermented urine. Next, a test solution was prepared by mixing fresh human urine and the above fermented urine at a ratio of 9: 1 (mass ratio) (fresh human urine is sterile, so sufficient odor is required if fermented urine is not mixed) Does not occur).
After putting the absorber obtained in the above (a) into a 250 mL glass bottle, 30 g of the test solution was added to swell the absorber. After adding the test solution, it was immediately sealed and stored at 40 ° C. for 24 hours. After storage, five panelists (A to E) were asked to determine the odor in the 250 mL glass bottle according to the following criteria in accordance with the “standard 6-level odor intensity display method” of the standard criteria, and evaluated with the average value. . The results are shown in Table 1.
5: Strong odor 4: Strong odor 3: Easily recognizable odor 2: Weak odor that understands what kind of odor 1: Slightly detectable odor 0: No odor

Figure 0005825888
Figure 0005825888

表1中のキク科植物抽出物の使用量の数値は、吸水性樹脂100質量部に対する値(質量部)である。
表1から明らかなように、実施例1〜7の吸水性樹脂組成物は、比較例1の吸水性樹脂組成物と比較して、人尿吸収時のゲル安定性に優れ、臭気の抑制にも優れていることがわかる。また実施例6の場合、キク科植物抽出物の量が少ないため、人尿吸収時のゲル安定性が悪くなる傾向にあり、また人尿の不快な臭気の抑制効果が少ない。実施例7の場合、人尿の不快な臭気等は抑制されるが、キク科植物抽出物が多いため、キク科植物抽出物そのものの臭気が強くなる傾向にある。
一方、比較例1においては、キク科植物抽出物が混合されていないため、人尿吸収時のゲル安定性が低く、人尿の不快な臭気の抑制ができない。
The numerical value of the usage-amount of the Asteraceae plant extract in Table 1 is a value (parts by mass) with respect to 100 parts by mass of the water absorbent resin.
As is clear from Table 1, the water-absorbent resin compositions of Examples 1 to 7 are superior to the water-absorbent resin composition of Comparative Example 1 in terms of gel stability during human urine absorption, and to suppress odors. It turns out that it is excellent. In the case of Example 6, since the amount of the Asteraceae plant extract is small, the gel stability at the time of human urine absorption tends to be poor, and the effect of suppressing the unpleasant odor of human urine is small. In the case of Example 7, the unpleasant odor of human urine is suppressed, but the odor of the Asteraceae plant extract itself tends to be strong because there are many Asteraceae plant extracts.
On the other hand, in the comparative example 1, since the Asteraceae plant extract is not mixed, gel stability at the time of human urine absorption is low, and unpleasant odor of human urine cannot be suppressed.

本発明によれば、抗菌、消臭性能に優れ、安全に取り扱うことができ、かつゲル安定性に優れた吸水性樹脂組成物を提供することができる。また、本発明によれば、該吸水性樹脂組成物を用いて製造される吸収体、及び、該吸収体を用いて製造される吸収性物品を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, it is excellent in antibacterial and deodorizing performance, can be handled safely, and can provide the water absorbing resin composition excellent in gel stability. Moreover, according to this invention, the absorber manufactured using this water absorbent resin composition and the absorbent article manufactured using this absorber can be provided.

Claims (3)

吸水性樹脂とキク科植物抽出物とを含有する吸水性樹脂組成物であって、前記キク科植物抽出物の含有量が、吸水性樹脂100質量部に対して0.005〜5質量部である、吸水性樹脂組成物A water absorbent resin composition comprising a water absorbent resin and an Asteraceae plant extract , wherein the content of the Asteraceae plant extract is 0.005 to 5 parts by mass with respect to 100 parts by mass of the water absorbent resin. A water absorbent resin composition . 請求項1記載の吸水性樹脂組成物と親水性繊維とを含有する吸収体。 Absorber containing a water absorbent resin composition according to claim 1 Symbol placement and the hydrophilic fiber. 液体透過性シートと液体不透過性シートの間に請求項記載の吸収体が保持されている吸収性物品。 An absorbent article in which the absorbent body according to claim 2 is held between a liquid-permeable sheet and a liquid-impermeable sheet.
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