JP2006192368A - Film-like water absorption material, its production method and water absorption article - Google Patents
Film-like water absorption material, its production method and water absorption article Download PDFInfo
- Publication number
- JP2006192368A JP2006192368A JP2005006592A JP2005006592A JP2006192368A JP 2006192368 A JP2006192368 A JP 2006192368A JP 2005006592 A JP2005006592 A JP 2005006592A JP 2005006592 A JP2005006592 A JP 2005006592A JP 2006192368 A JP2006192368 A JP 2006192368A
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- Prior art keywords
- water
- film
- absorbing material
- salt
- cellulose derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 57
- 229920002678 cellulose Polymers 0.000 claims abstract description 48
- 239000001913 cellulose Substances 0.000 claims abstract description 48
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000011358 absorbing material Substances 0.000 claims description 76
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 36
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 36
- -1 aluminum ions Chemical class 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 18
- 150000001718 carbodiimides Chemical class 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 14
- 239000002504 physiological saline solution Substances 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002250 absorbent Substances 0.000 claims description 11
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 10
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
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- 239000000243 solution Substances 0.000 abstract description 8
- 239000011780 sodium chloride Substances 0.000 abstract description 7
- 239000000499 gel Substances 0.000 description 52
- 239000008279 sol Substances 0.000 description 16
- 241001122767 Theaceae Species 0.000 description 14
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- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 7
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- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 6
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 2
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Landscapes
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Abstract
Description
本発明は、優れた生分解性、優れた吸水性能とゲル強度を有するフィルム状吸水材及びその製造方法並びにそれを含む吸水性物品に関する。 The present invention relates to a film-like water-absorbing material having excellent biodegradability, excellent water-absorbing performance and gel strength, a method for producing the same, and a water-absorbing article including the same.
吸水材は、自重の数十倍から数千倍の水を吸水できる樹脂であり、例えばアクリル系吸水材などが知られている。これらの吸水材は、その高い吸水性から広く使い捨て衛生用品に使用されている。しかし、これまでの吸水材は生分解性がなく、それを含む衛生用品の処理方法に問題があった。 The water-absorbing material is a resin that can absorb water several tens to several thousand times its own weight. For example, an acrylic water-absorbing material is known. These water-absorbing materials are widely used for disposable sanitary products because of their high water absorption. However, conventional water-absorbing materials are not biodegradable, and there has been a problem in the method for treating sanitary products containing them.
生分解性を有する吸水材としては、例えばポリエチレンオキシド架橋体（例えば、特許文献１参照）、ポリビニルアルコール架橋体（例えば、特許文献２参照）、カルボキシメチルセルロース架橋体（例えば、特許文献３〜１０参照）、アルギン酸架橋体（例えば、特許文献１１参照）、澱粉架橋体（例えば、特許文献１２参照）、ポリアミノ酸架橋体（例えば、特許文献１３〜１７参照）、ガラクトマンナン金属イオン架橋体（例えば、特許文献１８〜２０参照）などが知られている。しかしいずれの吸水材も、アクリル系吸水材などの非生分解性のものに比べると、十分な性能を有しているとはいい難い。 Examples of the water-absorbing material having biodegradability include a crosslinked polyethylene oxide (see, for example, Patent Document 1), a crosslinked polyvinyl alcohol (see, for example, Patent Document 2), and a crosslinked carboxymethyl cellulose (see, for example, Patent Documents 3 to 10). ), Alginic acid crosslinked body (for example, see Patent Document 11), starch crosslinked body (for example, see Patent Document 12), polyamino acid crosslinked body (for example, see Patent Documents 13 to 17), galactomannan metal ion crosslinked body (for example, Patent Documents 18 to 20) are known. However, it is difficult to say that any water-absorbing material has sufficient performance as compared with non-biodegradable materials such as acrylic water-absorbing materials.
また、生分解性、非生分解性に関わらず、これらの吸水材はそのほとんどが粒状であり、成形性に乏しいため、特に生鮮食品の鮮度保持材、生理用品、紙おむつ、使い捨て雑巾、ペーパータオルなどの高い吸水能が要求される製品の素材として使用する場合、パルプ等ではさみ、多層構造にして使用しているのが現状である。しかし、これらの組成物は粒状吸水材がバインダー樹脂等内に分散しているために、必ずしも吸水材の吸水能が完全に発現されることは難しく、またバインダー樹脂等によって嵩高くなり、見かけほどの吸水能を示さなかった。したがって、実質上優れた吸水能を有するフィルムが強く望まれていた。 Regardless of biodegradability or non-biodegradability, most of these water-absorbing materials are granular and have poor moldability. Especially, freshness-keeping materials for fresh foods, sanitary products, disposable diapers, disposable cloths, paper towels, etc. When used as a raw material for products that require a high water-absorbing capacity, it is currently used in a multi-layered structure, sandwiched between pulp and the like. However, since these compositions absorb the particulate water-absorbing material in the binder resin or the like, it is not always possible to fully exhibit the water-absorbing capacity of the water-absorbing material, and the bulk of the water-absorbing material becomes bulky. The water absorption ability was not shown. Accordingly, there has been a strong demand for a film having substantially excellent water absorption ability.
吸水性フィルムとしては、熱可塑性吸水樹脂を含む親水性樹脂からなる吸水性フィルム（例えば、特許文献２１参照）、架橋ポリアルキレンオキシド樹脂とエチレン−ビニルアルコール共重合体とエチレン−酢酸ビニル共重合体を特定の割合で含む樹脂組成物からなる吸水性フィルム（例えば、特許文献２２参照）、架橋ポリアスパラギン酸を含有してなる吸水性フィルム（例えば、特許文献２３参照）、ポリエーテル・エステル・アミドブロック共重合体と吸水剤粒子からなる混合物を成形して得られる吸水性フィルム（例えば、特許文献２４参照）等が知られているが、生分解性、吸水性、製造コストのいずれもを満足させるものはない。 Examples of the water-absorbing film include a water-absorbing film made of a hydrophilic resin including a thermoplastic water-absorbing resin (see, for example, Patent Document 21), a crosslinked polyalkylene oxide resin, an ethylene-vinyl alcohol copolymer, and an ethylene-vinyl acetate copolymer. A water-absorbing film comprising a resin composition containing a specific proportion (for example, see Patent Document 22), a water-absorbing film containing a crosslinked polyaspartic acid (for example, see Patent Document 23), polyether ester amide A water-absorbing film obtained by molding a mixture comprising a block copolymer and water-absorbing agent particles (see, for example, Patent Document 24) is known, but satisfies all of biodegradability, water-absorbing properties, and production costs. There is nothing to do.
従来、カルボキシメチルセルロースは、水溶液にして捺染糊剤、経糸サイジング剤、あるいは各種増粘安定剤等に使用されてきたが、フィルムはもとより吸水性フィルムとしての利用は、吸水性能、ゲル強度、製造上の問題等から進んでいない。 Conventionally, carboxymethyl cellulose has been used as an aqueous solution for printing pastes, warp sizing agents, various thickening stabilizers, etc., but as a water-absorbing film as well as films, water absorption performance, gel strength, and production It is not progressing because of problems.
また、フィルムの物性向上のためにカルボキシメチルセルロースなどのセルロース誘導体をアルミニウム等の金属で架橋して得られるフィルムの製造方法がいくつか提案されている。例えば、カルボキシメチルセルロースの水溶液を調製し、この水溶液を平面上に流展したのち、半凝固状態とし、次いで水溶性金属塩溶液と接触させ、イオン交換することを特徴とする非水溶性カルボキシメチルセルロースフィルムの製造方法（例えば、特許文献２５参照）、１種以上のアニオン性水溶性高分子及びアルミニウムを含む無機塩を含有する水溶液を、有機酸又は無機酸により酸性化した後にフィルムを得るフィルムの製造方法（例えば、特許文献２６参照）等が提案されている。 In addition, several methods for producing a film obtained by crosslinking a cellulose derivative such as carboxymethyl cellulose with a metal such as aluminum have been proposed in order to improve the physical properties of the film. For example, a water-insoluble carboxymethylcellulose film characterized in that an aqueous solution of carboxymethylcellulose is prepared, the aqueous solution is flowed on a flat surface, made into a semi-solidified state, then contacted with a water-soluble metal salt solution, and ion exchanged (See, for example, Patent Document 25) Production of a film obtained by acidifying an aqueous solution containing one or more anionic water-soluble polymers and an inorganic salt containing aluminum with an organic acid or an inorganic acid A method (for example, see Patent Document 26) has been proposed.
しかし、通常、フィルム作成のためにカルボキシメチルセルロース等の水溶性高分子の水溶液にカリミョウバン等の多価金属塩を直接添加すると水溶液が即座にゲル化してしまうため、基板上に流延することができない。また、上記の特許文献２５の方法では半凝固状態物の表面からアルミニウムイオンが浸透するため、内部まで均一に架橋されにくく、むらが生じやすい。さらに、上記の特許文献２６の方法では、アルカリ性のフィルム原液を酸性浴に浸漬する際に基板側とフィルム原液表面側で不均一性が生じたり、フィルム原液が酸性浴に流れでるなどし、得られるフィルム厚が一定しないなどといった製造上の問題があった。 However, usually, when a polyvalent metal salt such as potassium alum is added directly to an aqueous solution of a water-soluble polymer such as carboxymethylcellulose for film production, the aqueous solution will immediately gel, and may be cast on a substrate. Can not. Further, in the method of Patent Document 25 described above, since aluminum ions permeate from the surface of the semi-solidified material, it is difficult to uniformly cross-link to the inside, and unevenness is likely to occur. Furthermore, in the method of Patent Document 26 described above, when the alkaline film stock solution is immersed in the acid bath, nonuniformity occurs between the substrate side and the film stock solution surface side, or the film stock solution flows into the acid bath. There was a problem in manufacturing such as the film thickness to be obtained was not constant.
また、本発明者らはガラクトマンナン又はその誘導体と多価金属イオンからなるフィルム状吸水材が、生分解性があり、吸水性能、ゲル強度が優れていることを報告した（例えば、特許文献２７参照）。 In addition, the present inventors have reported that a film-like water-absorbing material comprising galactomannan or a derivative thereof and a polyvalent metal ion is biodegradable and has excellent water-absorbing performance and gel strength (for example, Patent Document 27). reference).
特許文献２７の技術は極めて有意義なものであるが、なおも改善の余地が有り、特にゲル強度と製造方法の改善が望まれていた。ゲル強度が３,０００×１０-7N／ｍｍ2以下だと液体を吸水後、ゲルは時間と共に強度を失い、同時にゲル表面及び内部がべとつくようになってしまう。その結果、例えば、衛生用品の装着時間が長くなるに連れて保液性が低下し、液洩れの増加、装着感の悪化等を引き起こす問題を生じている。
一般に用いられる吸水材に求められる性能としては、一価以上のカチオンを含む尿、血液、経血、汗等の体液、さらに泥水、海水、河川水などの環境中の液体を大量に、かつ速やかに吸収し、保液することが要求される。 The performance required for commonly used water-absorbing materials includes urine, blood, menstrual blood, sweat, and other body fluids containing monovalent or higher cations, as well as a large amount of environmental fluids such as mud, seawater, and river water. It is required to absorb and retain liquid.
生分解性、非生分解性に関わらず、上記した吸水材はそのほとんどが粒状であり、これまれフィルム状吸水材としては、優れた吸水性能とゲル強度を有するものはなく、特に生分解性のものが強く望まれていた。 Regardless of biodegradability and non-biodegradability, most of the above water-absorbing materials are granular, and rarely film-like water-absorbing materials have excellent water-absorbing performance and gel strength, especially biodegradable. Things were strongly desired.
本発明の目的は、上記のような従来の問題点を解決し、生分解性を有し、吸水性能に優れ、製造コストの安価なフィルム状吸水材及びその製造方法並びにそれを含む吸水性物品を提供することにある。 An object of the present invention is to solve the conventional problems as described above, have a biodegradability, have excellent water absorption performance, and have a low manufacturing cost, a film-like water absorbing material, a method for producing the same, and a water absorbent article including the same. Is to provide.
本発明者らは、上記課題を解決するため鋭意検討した結果、セルロース誘導体もしくはその塩を特定の方法で架橋することによって、生分解性を有し、且つ優れた吸収性能及びゲル強度を併せ持ったフィルム状吸水材を安価に製造できることを見出し、本発明に到達した。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have biodegradability by combining a cellulose derivative or a salt thereof with a specific method, and have both excellent absorption performance and gel strength. The present inventors have found that a film-like water-absorbing material can be produced at low cost and have reached the present invention.
本発明は第一に、セルロース誘導体もしくはその塩を、架橋剤で架橋して形成してなるフィルム状吸水材であって、０．９％−生理食塩水に対する吸水量が自重の１０倍以上であり、かつ、該水溶液を自重の２０倍吸水した状態におけるゲル強度が３０００×１０-7N／ｍｍ2以上であることを特徴とするフィルム状吸水材を提供する。 A first aspect of the present invention is a film-like water-absorbing material formed by cross-linking a cellulose derivative or a salt thereof with a cross-linking agent, and the water absorption amount relative to 0.9% -physiological saline is 10 times or more of its own weight. And a film-like water-absorbing material characterized by having a gel strength of 3000 × 10 −7 N / mm 2 or more when the aqueous solution absorbs 20 times its own weight.
架橋剤は、アルミニウムイオン、鉄イオン、チタニウムイオンからなる群から選ばれる1種以上の多価金属イオンであることが好ましく、さらに、カルボジイミドを含むことがより好ましい。セルロース誘導体もしくはその塩として、カルボキシメチルセルロース塩（以下、ＣＭＣと略記する）、好ましくはカルボキシメチルセルロースアルカリ金属塩、特にカルボキシメチルセルロースナトリウム塩を用い、且つ架橋剤である多価金属イオンとして、アルミニウムイオンを用いるものが特に好ましい。アルミニウムイオン含有量は、セルロース誘導体もしくはその塩重量１ｋｇ当たり１〜１０００ミリモルであるのが好ましい。また、架橋剤であるカルボジイミドとしては、水溶性カルボジイミドが好ましい。水溶性カルボジイミド含有量は、セルロース誘導体もしくはその塩１００質量部に対して０．００１〜１０質量部であるのが好ましい。ＣＭＣを用いる場合、そのエーテル置換度（ＤＳ）が０．３〜２．８であり、且つその１質量％水溶液の粘度が１０ｍＰａ・ｓ〜２００００ｍＰａ・ｓであるのが好ましい。 The crosslinking agent is preferably one or more polyvalent metal ions selected from the group consisting of aluminum ions, iron ions, and titanium ions, and more preferably includes carbodiimide. Carboxymethylcellulose salt (hereinafter abbreviated as CMC), preferably carboxymethylcellulose alkali metal salt, particularly carboxymethylcellulose sodium salt is used as the cellulose derivative or salt thereof, and aluminum ion is used as the polyvalent metal ion that is a crosslinking agent. Those are particularly preferred. The aluminum ion content is preferably 1 to 1000 mmol per kg of the cellulose derivative or salt thereof. Moreover, as a carbodiimide which is a crosslinking agent, water-soluble carbodiimide is preferable. The water-soluble carbodiimide content is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative or a salt thereof. When CMC is used, the ether substitution degree (DS) is preferably 0.3 to 2.8, and the viscosity of the 1% by mass aqueous solution is preferably 10 mPa · s to 20000 mPa · s.
また、本発明は第二に、
ａ）セルロース誘導体もしくはその塩を含む乾燥フィルムに、多価金属イオンを含む水溶液を接触させ、水に対する膨潤度が１〜５０ｇ／ｇ（乾燥フィルム）の範囲で膨潤させると同時にセルロース誘導体もしくはその塩を架橋させる工程、
ｂ）得られたフィルムゲルを乾燥する工程、
を含む本発明のフィルム状吸水材の製造方法を提供する。
In addition, the present invention secondly,
a) An aqueous solution containing a polyvalent metal ion is brought into contact with a dry film containing a cellulose derivative or a salt thereof, and the cellulose derivative or a salt thereof is simultaneously swelled with a swelling degree with respect to water in the range of 1 to 50 g / g (dry film). Cross-linking the
b) drying the obtained film gel;
The manufacturing method of the film-form water absorbing material of this invention containing this is provided.
本発明の上記フィルム状吸水材の製造方法において、工程ａ）に用いる乾燥フィルムは、ｃ）水にセルロース誘導体もしくはその塩を、添加後の混合液に対して固形分濃度０．１〜２０質量％となるように添加し、セルロース誘導体もしくはその塩を水で膨潤させる工程、ｄ）得られたセルロース誘導体もしくはその塩のゾルを基板上に流延する工程、
ｅ）流延したゾルを乾燥する工程、により得られる乾燥フィルムであるのが好ましい。さらに、工程ｃ）に用いる水に、カルボジイミドを添加し、且つ、ｐＨを１．０〜７．０に調整する工程を含むのが好ましい。また、工程ｃ）に用いる水に、可塑剤としてグリセリンを添加するのが好ましい。
In the method for producing a film-shaped water-absorbing material of the present invention, the dry film used in step a) is c) a cellulose derivative or a salt thereof in water, and a solid content concentration of 0.1 to 20 mass with respect to the mixed liquid after addition. A step of swelling the cellulose derivative or a salt thereof with water, and d) casting a sol of the obtained cellulose derivative or a salt thereof on a substrate,
e) A dry film obtained by drying the cast sol is preferred. Further, it is preferable to include a step of adding carbodiimide to the water used in step c) and adjusting the pH to 1.0 to 7.0. It is also preferred to add glycerin as a plasticizer to the water used in step c).
また、本発明は第三に、本発明によるフィルム状吸水材を含んでなることを特徴とする吸水性物品を提供する。 Thirdly, the present invention provides a water-absorbing article comprising the film-like water-absorbing material according to the present invention.
（用語の定義）
［０．９％−生理食塩水に対する吸水量］
吸水量の測定は、ティーバッグ法にて０．９質量％塩化ナトリウム水溶液を用いて行う。すなわち、２５５メッシュのナイロン製ティーバッグに吸水材１ｇを入れ、１Ｌの０．９質量％塩化ナトリウム水溶液にティーバッグを６０分間浸し、ティーバッグを引き上げ、１０分間水切りを行った後、その重量を測定する。吸水材の吸水量は、６０分間水に浸した吸水材が入っていないティーバッグの重量をブランクとし、吸水して膨潤した吸水材が入ったティーバッグの重量から、膨潤前の吸水材の重量とブランクの重量を減じた値を、膨潤前の吸水材の重量で除した値を吸水量（ｇ／ｇ吸水材）とする。
(Definition of terms)
[0.9%-water absorption with respect to physiological saline]
The water absorption is measured using a 0.9% by mass sodium chloride aqueous solution by the tea bag method. That is, 1 g of a water absorbing material is put into a 255 mesh nylon tea bag, the tea bag is immersed in 1 L of 0.9 mass% sodium chloride aqueous solution for 60 minutes, the tea bag is pulled up, drained for 10 minutes, taking measurement. The water absorption amount of the water absorbent material is the weight of the tea bag without water absorbent material soaked in water for 60 minutes, and the weight of the water absorbent material before swelling from the weight of the tea bag containing the water absorbent material swollen after absorbing water And the value obtained by dividing the weight of the blank by the weight of the water-absorbing material before swelling is defined as the water-absorbing amount (g / g water-absorbing material).
［ゲル強度］
０．９％−生理食塩水を２０倍吸水時でのゲル強度の測定は、フィルム状吸水材に２０倍量の０．９質量％塩化ナトリウム水溶液を吸水させ、サイエンティフィク社のレオメトリックＳＲ−５０００を用いて１Ｈｚ、室温にて粘弾性Ｇ＊を測定し、その数値をゲル強度とする。
[Gel strength]
Measurement of gel strength when 0.9% of physiological saline is absorbed 20 times is carried out by absorbing 20 mass of 0.9% by mass sodium chloride aqueous solution into a film-like water absorbing material, and Rheometric SR of Scientific Co., Ltd. The viscoelasticity G * is measured at 1 Hz and room temperature using -5000, and the numerical value is taken as the gel strength.
本発明の吸水材は、生分解性、且つ優れた吸水性能を有し、安全性の高いフィルム状吸水材であり、効率良く低コストで製造できるものである。本発明の吸水材は、化粧用パック材、医療用手当材、創傷被覆材、生理用品や紙おむつ等の衛生材料分野をはじめとして、動物用屎尿処理材、飼料添加剤、農園芸用分野、鮮度保持等の食品分野、結露防止や保冷材等の産業分野等、吸水や保水を必要とする種々の用途に好適に利用できる。 The water-absorbing material of the present invention is a film-like water-absorbing material having biodegradability and excellent water-absorbing performance and high safety, and can be produced efficiently and at low cost. The water-absorbing material of the present invention includes animal packs, medical dressings, wound dressings, sanitary materials such as sanitary products and paper diapers, animal manure treatment materials, feed additives, agricultural and horticultural fields, freshness It can be suitably used for various applications that require water absorption or water retention, such as food fields such as holding, and industrial fields such as condensation prevention and cold insulation materials.
以下、本発明を詳細に説明する。
本発明でいう「フィルム状吸水材」とは、膜厚が０．２ｍｍより薄いものを呼び、膜厚の下限は限定的ではないが、十分な吸水性と乾燥時のフィルム強度を有するためには１μｍ以上とするのが好ましい。フィルムの表面積や幅は目的に応じて適宜選択すればよい。一般的には、フィルムは平滑で均一な厚みを有するものであるが、所望により、エンボス状等の平坦でない構造をとるものであってもよい。また、平面ではない３次元的な構造を取ったものでもよい。例えば、レンズ状とか、そりを持つものでもよい。本発明におけるフィルム状の吸水材は、その表面を加工してもよく、また、必要に応じて穴を空けたり、切り込み、ひびをいれてもよく、破砕してフレーク状としてもよい。
Hereinafter, the present invention will be described in detail.
The “film-like water-absorbing material” as used in the present invention refers to a film having a film thickness of less than 0.2 mm, and the lower limit of the film thickness is not limited, but has sufficient water absorption and film strength during drying. Is preferably 1 μm or more. What is necessary is just to select the surface area and width of a film suitably according to the objective. In general, the film has a smooth and uniform thickness, but may have an uneven structure such as an embossed shape, if desired. Moreover, what took the three-dimensional structure which is not a plane may be used. For example, it may have a lens shape or a sled. The film-like water-absorbing material in the present invention may be processed on its surface, or may be perforated, cut or cracked as necessary, and may be crushed into a flake shape.
本発明において原料として用いられるセルロース誘導体もしくはその塩は、セルロースの有する水酸基をエーテル化したセルロースエーテル類およびその塩であって、吸水特性を与えるものであれば特に限定されるものではない。 The cellulose derivative or salt thereof used as a raw material in the present invention is not particularly limited as long as it is a cellulose ether or a salt thereof obtained by etherifying a hydroxyl group of cellulose and gives water absorption characteristics.
本発明で用いられるセルロース誘導体もしくはその塩としては、例えば、カルボキシメチルセルロース、カルボキシメチルヒドロキシエチルセルロース、カルボキシエチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、メチルセルロース等および、これらのナトリウム塩、カリウム塩等のアルカリ金属塩が挙げられる。これらは、単独で使用してもよく、また、二種類以上を適宜混合して使用してもよいが、コスト、性能面から、カルボキシメチルセルロースのアルカリ金属塩、即ち、カルボキシメチルセルロース塩（以下、ＣＭＣという。）が好ましい。これはリンターパルプや木材パルプなどのセルロースをイソプロピルアルコール等の有機溶媒と水との混合溶媒中でアルカリ金属水酸化物存在下にクロロ酢酸等のエーテル化剤を反応させることにより得ることができる。 Examples of the cellulose derivative or salt thereof used in the present invention include carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose and the like, and alkalis such as sodium salts and potassium salts thereof. Metal salts are mentioned. These may be used singly or may be used in combination of two or more, but from the viewpoint of cost and performance, an alkali metal salt of carboxymethyl cellulose, that is, carboxymethyl cellulose salt (hereinafter referred to as CMC). Is preferred). This can be obtained by reacting cellulose such as linter pulp or wood pulp with an etherifying agent such as chloroacetic acid in the presence of an alkali metal hydroxide in a mixed solvent of an organic solvent such as isopropyl alcohol and water.
セルロース誘導体もしくはその塩の分子量としては、５万〜１５０万が好ましく、２０万〜８０万がさらに好ましい。
ＣＭＣとしては、カルボキシメチルセルロースのアルカリ金属塩であって、カルボキシル基による水酸基の置換度、即ち、エーテル置換度（ＤＳ）が０．３〜２．８の範囲内のものが好ましく、０．５〜１．０の範囲内のものが特に好ましい。ＤＳが０．３未満ではＣＭＣの溶解性が低いため、均一なゾルが得られない。逆にＤＳが２．８を超えると、アルミニウムイオン等による架橋が分子内で進行し、均一なゲルが得られない場合が生じる。
The molecular weight of the cellulose derivative or salt thereof is preferably 50,000 to 1,500,000, more preferably 200,000 to 800,000.
CMC is an alkali metal salt of carboxymethyl cellulose, preferably having a hydroxyl group substitution degree with a carboxyl group, that is, an ether substitution degree (DS) in the range of 0.3 to 2.8, 0.5 to 2.8 Those within the range of 1.0 are particularly preferred. If DS is less than 0.3, the solubility of CMC is low, so a uniform sol cannot be obtained. On the other hand, when DS exceeds 2.8, crosslinking with aluminum ions or the like proceeds in the molecule, and a uniform gel may not be obtained.
また、ＣＭＣとしては、１質量％水溶液とした時に粘度が１０ｍＰａ・ｓ〜２００００ｍＰａ・ｓの範囲内にあるものが好ましい。１０ｍＰａ・ｓ未満の場合はアルミニウムイオン等で架橋しても強度のあるゲルを形成しないので不適当である。２００００ｍＰａ・ｓを超えると粘性が非常に高くなるため、攪拌等の作業性が著しく悪化し、均一なフィルムが得られない。さらに、その高い粘性のために基板上に流延することができない場合があるので、好ましくない。 Moreover, as CMC, what has a viscosity in the range of 10 mPa * s-20000 mPa * s when it is set as 1 mass% aqueous solution is preferable. When the viscosity is less than 10 mPa · s, a strong gel is not formed even when crosslinked with aluminum ions or the like. When the viscosity exceeds 20000 mPa · s, the viscosity becomes very high, so that workability such as stirring is significantly deteriorated and a uniform film cannot be obtained. Furthermore, it may not be possible to cast on a substrate due to its high viscosity, which is not preferable.
本発明においては、必要に応じて、グアガム、ローカストビーンガム、タラガム、カシアガム、カラギーナン、アルギン酸、キサンタンガム、寒天、ペクチン、タラガントガム、プルラン、ジェランガム、タマリンドシードガム、カードラン、アラビアガム、グルコマンナン、デンプン、セルロース、キチン、キトサン、ヒアルロン酸又はこれらの誘導体などのセルロース誘導体もしくはその塩以外の天然多糖類を混合してもよい。これらを混合する割合としては、多糖類の組み合わせ等にもよるが、セルロース誘導体もしくはその塩１００質量部に対し１〜１００質量部の範囲内、より好ましくは１０〜５０質量部の範囲内とすればよい。 In the present invention, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, alginic acid, xanthan gum, agar, pectin, tarragant gum, pullulan, gellan gum, tamarind seed gum, curdlan, gum arabic, glucomannan, starch Natural polysaccharides other than cellulose derivatives such as cellulose, chitin, chitosan, hyaluronic acid or derivatives thereof or salts thereof may be mixed. The ratio of mixing them depends on the combination of polysaccharides, but is within the range of 1 to 100 parts by mass, more preferably within the range of 10 to 50 parts by mass with respect to 100 parts by mass of the cellulose derivative or salt thereof. That's fine.
以下、本発明を、本発明のフィルム状吸水材の製造方法に言及して説明する。
工程ａ）は、セルロース誘導体もしくはその塩を含む乾燥フィルムに、多価金属イオンを含む水溶液を接触させ、水に対する膨潤度が１〜５０ｇ／ｇ（乾燥フィルム）の範囲で膨潤させると同時にセルロース誘導体もしくはその塩を架橋させる工程である。
Hereinafter, the present invention will be described with reference to the method for producing a film-like water-absorbing material of the present invention.
In step a), an aqueous solution containing a polyvalent metal ion is brought into contact with a dry film containing a cellulose derivative or a salt thereof, and the cellulose derivative is swollen in the range of 1 to 50 g / g (dry film) with respect to water. Or it is the process of bridge | crosslinking the salt.
本発明の工程ａ）で用いられるセルロース誘導体もしくはその塩からなる乾燥フィルムは、水に膨潤し、折り曲げられる程度の柔軟性があれば、特に限定されない。 The dry film made of the cellulose derivative or salt thereof used in step a) of the present invention is not particularly limited as long as it is flexible enough to swell and bend in water.
本発明の工程ａ）で用いられる多価金属イオンとしては、セルロース誘導体もしくはその塩の有する官能基（即ち、水酸基、カルボキシル基）と架橋を形成し得る多価金属イオンがあれば、特に限定されない。例えば、アルミニウムイオン、鉄イオン、チタニウムイオン、カルシウムイオン、バリウムイオン、銅イオン、クロムイオン、鉛イオン、スズイオン、銀イオン等の多価金属イオンが例示されるが、安全性、性能、価格からアルミニウムイオン、鉄イオン、チタニウムイオンが好ましく、これらの中でも、特にアルミニウムイオンが好ましい。架橋剤として、これらからなる群の１種だけを使用してもよいが、２種以上を使用してもよい。 The polyvalent metal ion used in step a) of the present invention is not particularly limited as long as there is a polyvalent metal ion capable of forming a crosslink with the functional group (that is, hydroxyl group, carboxyl group) of the cellulose derivative or salt thereof. . For example, multivalent metal ions such as aluminum ion, iron ion, titanium ion, calcium ion, barium ion, copper ion, chromium ion, lead ion, tin ion, silver ion are exemplified, but aluminum is used for safety, performance and price. Ions, iron ions, and titanium ions are preferred, and among these, aluminum ions are particularly preferred. As the cross-linking agent, only one of these groups may be used, but two or more may be used.
多価金属イオンの形態（化合物の形態）としては特に限定されず、二価以上の金属イオンまたはセルロース誘導体もしくはその塩の有する官能基と反応しうる官能基を２個以上有する化合物であれば特に制限されないが、好ましくは親水性、より好ましくは水溶性の金属塩である。例えば、酢酸アルミニウム、硫酸アルミニウム、硝酸アルミニウム、硫酸アルミニウムカリウム（カリミョウバン）、塩化アルミニウム、などのアルミニウム塩、塩化第一鉄、塩化第二鉄、硫酸二鉄などの鉄塩、その他無機または有機のバリウム塩、カルシウム塩、チタン酸塩などが例示される。 The form of the polyvalent metal ion (form of the compound) is not particularly limited as long as it is a compound having two or more functional groups capable of reacting with a functional group of a divalent or higher-valent metal ion or cellulose derivative or salt thereof. Although not limited, it is preferably a hydrophilic, more preferably a water-soluble metal salt. For example, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum nitrate, potassium aluminum sulfate (potash alum), aluminum chloride, iron salts such as ferrous chloride, ferric chloride, ferric sulfate, and other inorganic or organic Examples include barium salts, calcium salts, titanates and the like.
工程ａ）で調製される水溶液中の多価金属イオンの濃度としては、セルロース誘導体もしくはその塩１ｋｇ当たり金属原子に換算して１〜１０００ミリモルが好ましく、より好ましくは１０〜６００ミリモル、特に好ましくは５０〜２５０ミリモルである。１ミリモル未満では、十分に架橋できず、非常にゲル強度の弱いフィルム状吸水材になってしまう。一方、１０００ミリモルを超えると吸水量が低下するため好ましくない。 The concentration of polyvalent metal ions in the aqueous solution prepared in step a) is preferably 1 to 1000 mmol, more preferably 10 to 600 mmol, particularly preferably in terms of metal atoms per kg of cellulose derivative or salt thereof. 50-250 mmol. If it is less than 1 millimolar, it cannot be sufficiently crosslinked, resulting in a film-like water-absorbing material with very low gel strength. On the other hand, if it exceeds 1000 mmol, the amount of water absorption is unfavorable.
工程ａ）における乾燥フィルムに多価金属イオンを含む水溶液を接触させる際の方法としては、均一に添加できれば特に限定されず、例えばスプレーで均一に噴霧したり、散布してもよいし、予め計算された量の水溶液をコーターによって塗工してもよく、浴に浸漬してもよい。また、水溶液は親水性揮発性有機溶媒が混合されていてもかまわない。 The method for bringing the aqueous solution containing polyvalent metal ions into contact with the dry film in step a) is not particularly limited as long as it can be uniformly added. For example, it may be sprayed uniformly or sprayed, or may be calculated in advance. The applied amount of aqueous solution may be applied by a coater or immersed in a bath. The aqueous solution may be mixed with a hydrophilic volatile organic solvent.
ここで使用する親水性揮発性有機溶媒は特に制限されないが、例えばメチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、ノルマルブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール等の低級アルコール類、アセトン、メチルエチルケトン等のケトン類、ジオキサン、テトラヒドロフラン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、ジメチルスルホキシド等のスルホキシド類等を挙げることができるが、コストや安全性の面からメタノール、エタノール、イソプロピルアルコールなどの低級アルコール類が好ましい。 The hydrophilic volatile organic solvent used here is not particularly limited, but examples thereof include lower alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, and t-butyl alcohol, acetone, and methyl ethyl ketone. Ketones such as dioxane, tetrahydrofuran, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, etc., but from the viewpoint of cost and safety, methanol, ethanol, isopropyl Lower alcohols such as alcohol are preferred.
工程ａ）における乾燥フィルムを多価金属イオンを含む水溶液で膨潤させるときの膨潤度としては、乾燥フィルム重量に対して水が１〜５０ｇ／ｇ（乾燥フィルム）が好ましく、５〜２０ｇ／ｇ（乾燥フィルム）がより好ましい。１ｇ／ｇ（乾燥フィルム）以下では均一な架橋が十分に進まず、ゲル強度の弱いフィルム状吸水材となるので、好ましくない。５０ｇ／ｇ（乾燥フィルム）を超えると乾燥する際に時間がかかり、エネルギーコストもかかるため好ましくない。 As swelling degree when the dry film in the step a) is swollen with an aqueous solution containing polyvalent metal ions, water is preferably 1 to 50 g / g (dry film) with respect to the dry film weight, and 5 to 20 g / g ( Dry film) is more preferred. If it is 1 g / g (dry film) or less, uniform crosslinking does not proceed sufficiently and a film-like water-absorbing material with low gel strength is obtained, which is not preferable. If it exceeds 50 g / g (dry film), it takes time to dry and energy costs are also undesirable, which is not preferable.
工程ｂ）は、工程ａ）で得られたフィルムゲルを乾燥する工程である。
工程ｂ）において乾燥に供するゲルのｐＨは３．０〜９．０が好ましく、ｐＨ４．０〜７．０がさらに好ましい。このため、ｐＨがこの範囲外にある場合は、適宜水酸化ナトリウムや塩酸などを添加してゲルｐＨを調整すればよい。
Step b) is a step of drying the film gel obtained in step a).
The pH of the gel subjected to drying in step b) is preferably from 3.0 to 9.0, more preferably from 4.0 to 7.0. For this reason, when the pH is outside this range, the gel pH may be adjusted by appropriately adding sodium hydroxide, hydrochloric acid or the like.
工程ｂ）における乾燥方法としては、乾燥後の吸水性能、ゲル強度を低下させるような方法であればいかなる乾燥方法でも限定されず、例えば常温乾燥、加熱乾燥や凍結乾燥、減圧乾燥、真空乾燥が挙げられる。好ましくは経済的な３０〜１００℃での加熱乾燥である。乾燥方法や乾燥温度、固形物の含水量などにもよるが、乾燥時間は１秒間〜６時間が好ましく、１０秒間〜１時間がより好ましい。乾燥の程度としては、乾燥後のフィルムの含水率が１５％以下であることが好ましく、より好ましくは１０％以下であり、５％以下が特に好ましい。 The drying method in step b) is not limited to any drying method as long as it reduces the water absorption performance after drying and the gel strength. For example, room temperature drying, heat drying, freeze drying, vacuum drying, and vacuum drying may be used. Can be mentioned. The economical drying at 30 to 100 ° C. is preferable. The drying time is preferably 1 second to 6 hours, more preferably 10 seconds to 1 hour, although it depends on the drying method, the drying temperature, the water content of the solid, and the like. As the degree of drying, the moisture content of the film after drying is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.
以下、上記工程ａ）に用いる乾燥フィルムの好ましい製造方法について説明するが、工程ａ）に用いる乾燥フィルムの製造方法はこれらに限定されない。
まず、工程ｃ）は、水にセルロース誘導体もしくはその塩を、添加後の混合液に対して固形分濃度０．１〜２０質量％となるように添加し、セルロース誘導体もしくはその塩を水で膨潤させる工程である。
Hereinafter, although the preferable manufacturing method of the dry film used for the said process a) is demonstrated, the manufacturing method of the dry film used for process a) is not limited to these.
First, in step c), a cellulose derivative or a salt thereof is added to water so that the solid content concentration is 0.1 to 20% by mass with respect to the mixed solution after the addition, and the cellulose derivative or a salt thereof is swollen with water. It is a process to make.
工程ｃ）において水にセルロース誘導体もしくはその塩を添加する量としては、固形分濃度がセルロース誘導体もしくはその塩の添加後の全質量に対して１〜２０質量％であることが好ましく、２〜１０質量％がより好ましい。１質量％未満では製造コストの上昇を招くため好ましくない。２０質量％を超えるとその高い粘性のために基板上に流延することができない場合があるだけでなく、吸水量が低下するため、好ましくない。 The amount of the cellulose derivative or salt thereof added to water in step c) is preferably 1 to 20% by mass with respect to the total mass after addition of the cellulose derivative or salt thereof. The mass% is more preferable. If it is less than 1% by mass, the production cost is increased, which is not preferable. If it exceeds 20% by mass, not only is it sometimes impossible to cast on the substrate due to its high viscosity, but also the amount of water absorption decreases, which is not preferable.
工程ｃ）を行う際の温度は特に限定されないが、均一なゾルを得るためにも５〜１００℃が好ましく、２０〜５０℃がさらに好ましい。 Although the temperature at the time of performing step c) is not particularly limited, it is preferably 5 to 100 ° C. and more preferably 20 to 50 ° C. in order to obtain a uniform sol.
次いで、工程ｄ）は、前記工程ｃ）で得られたセルロース誘導体もしくはその塩のゾルを基板上に流延する工程である。
ｄ）工程のセルロース誘導体もしくはその塩のゾルを基板上に流延する方法としては、膜厚の均一なフィルムが得られれば、特に限定されないが、既存のキャスト装置を用いて基板上に均一に流延すればよい。キャストに使用される基材としては、特に限定されないが、一般的にはガラス板、プラスチック板、金属板、紙等が挙げられる。離型性を必要とする場合は、ガラス板、テフロン板、金属板、またはシリコンコート処理されたプラスチック（ＰＥＴ、ＰＰ等）板等が好ましい。
Next, step d) is a step of casting the cellulose derivative or its salt sol obtained in step c) on a substrate.
The method of casting the sol of the cellulose derivative or salt thereof in step d) on the substrate is not particularly limited as long as a film having a uniform film thickness can be obtained, but uniformly on the substrate using an existing casting apparatus. Just cast. Although it does not specifically limit as a base material used for casting, Generally, a glass plate, a plastic plate, a metal plate, paper etc. are mentioned. When releasability is required, a glass plate, a Teflon plate, a metal plate, or a plastic (PET, PP, etc.) plate treated with silicon coating is preferable.
工程ｅ）は、工程ｄ）で流延したゾルを乾燥する工程である。
工程ｅ）において、前記工程ｄ）で流延されたゾルを乾燥する方法としては、吸水性能、ゲル強度を低下させるような方法でなければいかなる乾燥方法でも限定されるものではないが、例えば常温乾燥、加熱乾燥や凍結乾燥、減圧乾燥、真空乾燥が挙げられる。好ましくは経済的な３０〜１００℃での加熱乾燥である。乾燥方法や乾燥温度、固形物の含水量などにもよるが、乾燥時間は１秒間〜６時間が好ましく、１０秒間〜１時間がより好ましい。乾燥の程度としては、乾燥後のフィルムの含水率が１５％以下であることが好ましく、より好ましくは１０％以下であり、５％以下が特に好ましい。
Step e) is a step of drying the sol cast in step d).
In step e), the method for drying the sol cast in step d) is not limited to any drying method as long as it does not reduce water absorption performance and gel strength. Examples include drying, heat drying, freeze drying, reduced pressure drying, and vacuum drying. The economical drying at 30 to 100 ° C. is preferable. The drying time is preferably 1 second to 6 hours, more preferably 10 seconds to 1 hour, although it depends on the drying method, the drying temperature, the water content of the solid, and the like. As the degree of drying, the moisture content of the film after drying is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.
以上説明した本発明の吸水材の製造方法においては、工程ｃ）の水にカルボジイミドを添加し、且つ、ｐＨ１．０〜７．０に調整する工程をさらに含むことが好ましい。
本発明の工程ｃ）で水に添加されるカルボジイミドとしては、セルロース誘導体もしくはその塩の有する官能基（カルボキシル基、水酸基など）と架橋を形成し得るカルボジイミドであれば、特に限定されないが、水溶性カルボジイミドを用いるのが好ましい。
In the manufacturing method of the water absorbing material of this invention demonstrated above, it is preferable to further include the process of adding carbodiimide to the water of process c), and adjusting pH to 1.0-7.0.
The carbodiimide added to water in step c) of the present invention is not particularly limited as long as it is a carbodiimide capable of forming a crosslink with a functional group (carboxyl group, hydroxyl group, etc.) possessed by a cellulose derivative or a salt thereof. It is preferable to use carbodiimide.
水溶性カルボジイミドとしては、Ｎ−エチル−Ｎ’−（３−ジメチルアミノプロピル）カルボジイミド等のモノカルボジイミド類のほか、分子鎖中に２個以上のカルボジイミド基を持つカルボジイミド等が挙げられる。２個以上のカルボジイミド基を持つカルボジイミドとしては、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネート等の有機ジイソシアネートを合成原料としたポリカルボジイミドの重合末端であるイソシアネート基を活性水素化合物で末端封止した変性ポリカルボジイミド等が挙げられる。なお、活性水素化合物としては脂肪族、芳香族又は脂環族であって−ＯＨ基、＝ＮＨ基、−ＮＨ２基、−ＣＯＯＨ基、−ＳＨ基、エポキシ基を有する化合物、具体的には、メタノール、エタノール、シクロヘキサノール、ポリエチレングリコール、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコールモノメチルエーテル、ジエチルアミン、ジシクロヘキシルアミン、シクロヘキシルアミン、ブチルアミン、コハク酸、シクロヘキサン酸、安息香酸、エチルメルカプタン、チオフェノール等を例示することができ、これらの中では、水溶性付与の面からポリエチレングリコール、ポリエチレングリコールモノメチルエーテルが好ましい。 Examples of the water-soluble carbodiimide include monocarbodiimides such as N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide, and carbodiimide having two or more carbodiimide groups in the molecular chain. As carbodiimide having two or more carbodiimide groups, an isocyanate group which is a polymerization end of polycarbodiimide using an organic diisocyanate such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate as a synthetic raw material is end-capped with an active hydrogen compound. Modified polycarbodiimide and the like. The active hydrogen compound is an aliphatic, aromatic or alicyclic compound having an —OH group, ═NH group, —NH 2 group, —COOH group, —SH group or epoxy group, specifically , Methanol, ethanol, cyclohexanol, polyethylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, diethylamine, dicyclohexylamine, cyclohexylamine, butylamine, succinic acid, cyclohexane acid, benzoic acid, ethyl mercaptan, thiophenol, etc. Among these, polyethylene glycol and polyethylene glycol monomethyl ether are preferable from the viewpoint of imparting water solubility.
また、上記の活性水素化合物でポリカルボジイミドの重合度を制御するとき、水への溶解性の面から変性ポリカルボジイミドの重合度は１０以下のものが好ましい。
本発明において添加される水溶性カルボジイミドは、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド メチオジド、１−シクロヘキシル−３−（２−モルホリニル−４−エチル）カルボジイミド、１−シクロヘキシル−３−（２−モルホリノエチル）カルボジイミド等が好適である。
When the polymerization degree of polycarbodiimide is controlled with the above active hydrogen compound, the polymerization degree of the modified polycarbodiimide is preferably 10 or less from the viewpoint of solubility in water.
The water-soluble carbodiimide added in the present invention is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methiodide, 1-cyclohexyl-3- (2 -Morpholinyl-4-ethyl) carbodiimide, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide and the like are preferable.
水溶性カルボジイミドは、２種以上を添加することができる。水溶性カルボジイミドの添加量はセルロース誘導体もしくはその塩１００質量部に対し０．００１〜１０質量部が好ましく、０．１〜５質量部がより好ましい。上記の範囲内で水溶性カルボジイミドを用いることにより、さらにゲル強度を向上させることができる。 Two or more water-soluble carbodiimides can be added. 0.001-10 mass parts is preferable with respect to 100 mass parts of cellulose derivatives or its salt, and, as for the addition amount of water-soluble carbodiimide, 0.1-5 mass parts is more preferable. By using water-soluble carbodiimide within the above range, the gel strength can be further improved.
水溶性カルボジイミドの添加量が０．００１質量部未満では、ゲル強度を向上させる効果が得られない。また、１０質量部より多い場合には、セルロース誘導体もしくはその塩のゾルの流動性が高くなり基板に流延しづらくなるばかりか、原料コストも上がるため好ましくない。 When the addition amount of the water-soluble carbodiimide is less than 0.001 part by mass, the effect of improving the gel strength cannot be obtained. On the other hand, when the amount is more than 10 parts by mass, the fluidity of the sol of the cellulose derivative or a salt thereof becomes high, and it becomes difficult to cast the sol on the substrate.
また、工程ｃ）の水にグリセリン等の可塑剤を添加するのが好ましい。添加する可塑剤としてはグリセリンの他には生分解性を有する可塑剤であれば特に限定されないが、例えば、ソルビトール、ラクチトール、マルチトール、エリスリトール、ペンタエリスリトール、マンニトール、イズロン酸、アジピン酸ジイソノニル、ガラクタル酸、α−ガラクツロン酸、グルカル酸、β−グルクロン酸、グルコン酸、グルロン酸、２−デオキシグルコン酸、マンヌロン酸−６，３−ラクトン、α−ガラクトサミン塩酸塩、α−マンノサミン塩酸塩、ムラミン酸、コンドロイチン−４−硫酸塩、コンドロイチン−６−硫酸塩、ヒアルロン酸などが挙げられ、グリセリンを含めたこれらのうちの１種以上を混合して使用してもよい。これら可塑剤は、セルロース誘導体もしくはその塩１００質量部に対し、０．１〜７０質量部を添加することが好ましく、１〜２０質量部がより好ましい。かかる可塑剤の添加により、得られるフィルムに柔軟性を付与することができる。 It is also preferable to add a plasticizer such as glycerin to the water in step c). The plasticizer to be added is not particularly limited as long as it is a biodegradable plasticizer in addition to glycerin. Acid, α-galacturonic acid, glucaric acid, β-glucuronic acid, gluconic acid, guluronic acid, 2-deoxygluconic acid, mannuronic acid-6,3-lactone, α-galactosamine hydrochloride, α-mannosamine hydrochloride, muramic acid , Chondroitin-4-sulfate, chondroitin-6-sulfate, hyaluronic acid and the like, and one or more of these including glycerin may be used in combination. These plasticizers are preferably added in an amount of 0.1 to 70 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the cellulose derivative or salt thereof. By adding such a plasticizer, flexibility can be imparted to the resulting film.
また乾燥時のフィルムのヒビワレを防止する観点でトレハロースをセルロース誘導体もしくはその塩１００質量部に対し、０．０１〜１０質量部を添加することが好ましく、０．１〜５質量部がさらに好ましい０．０１質量部未満での添加ではヒビワレを防止する効果がほとんどみられず、１０質量部以上の添加では保湿性が高くなりすぎてフィルムが常に付着性を有するような状態となるので取り扱いがたく好ましくない。 Moreover, it is preferable to add 0.01-10 mass parts with respect to 100 mass parts of cellulose derivatives or its salt from the viewpoint of preventing the crack of the film at the time of drying, and 0.1-5 mass parts is still more preferable 0 Addition of less than 0.01 parts by weight hardly shows the effect of preventing cracking, and addition of 10 parts by weight or more makes the film always sticky because the moisture retention becomes too high. It is not preferable.
工程ｃ）において、水に所望によりカルボジイミド、可塑剤を添加して得られた水溶液は好ましくは、ｐＨ１．０〜７．０、さらに好ましくは、ｐＨ２．０〜４．０に調整する。水溶液のｐＨがこの範囲外にある場合は、ｐＨ調整剤を添加してｐＨを調整すればよい。本発明で用いるｐＨ調整剤としては、水溶液のｐＨを１．０〜７．０に調整できるものであれば特に限定されるものではなく、一般によく知られている酸性、塩基性試薬を用いればよい。ｐＨ値を下げる場合には、塩酸、硫酸、硝酸、炭酸、リン酸、酢酸等があり、ｐＨ値を上げる場合には、アルカリ金属、アルカリ土類金属、アンモニウムイオンの水酸化物・炭酸塩・リン酸塩などが例示される。具体的には、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ニカリウム、アンモニア水などが挙げられ、安価であることから水酸化ナトリウム、水酸化カリウムが好ましい。水溶液のｐＨが１．０未満の場合、セルロース誘導体もしくはその塩を含む多糖類が酸により加水分解され、低分子化し、ゲル強度が低下する場合があるので好ましくない。水溶液のｐＨが７．０以上の場合、ゲル強度が低下するため好ましくない。 In step c), the aqueous solution obtained by optionally adding carbodiimide and a plasticizer to water is preferably adjusted to pH 1.0 to 7.0, more preferably pH 2.0 to 4.0. If the pH of the aqueous solution is outside this range, a pH adjuster may be added to adjust the pH. The pH adjuster used in the present invention is not particularly limited as long as the pH of the aqueous solution can be adjusted to 1.0 to 7.0, and generally known acidic and basic reagents are used. Good. When lowering the pH value, there are hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, acetic acid, etc., when raising the pH value, alkali metal, alkaline earth metal, ammonium ion hydroxide, carbonate, Examples thereof include phosphates. Specifically, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate Sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, aqueous ammonia and the like, and sodium hydroxide and potassium hydroxide are preferred because they are inexpensive. When the pH of the aqueous solution is less than 1.0, a polysaccharide containing a cellulose derivative or a salt thereof is hydrolyzed with an acid, resulting in a low molecular weight, which is not preferable. When the pH of the aqueous solution is 7.0 or higher, the gel strength is not preferable.
本発明のフィルム状吸水材の製造方法では、さらに、必要に応じて、消臭剤、香料、各種の無機粉末、顔料、染料、抗菌剤、発泡剤、親水性短繊維、可塑剤、粘着剤、肥料、酸化剤、還元剤、水、塩類等を工程ａ）〜ｃ）において適宜添加し、これによりフィルム状吸水材に種々の機能を付与してもよい。 In the method for producing a film-like water-absorbing material of the present invention, if necessary, a deodorant, a fragrance, various inorganic powders, a pigment, a dye, an antibacterial agent, a foaming agent, a hydrophilic short fiber, a plasticizer, and an adhesive. Fertilizers, oxidizing agents, reducing agents, water, salts and the like may be appropriately added in steps a) to c), thereby imparting various functions to the film-like water-absorbing material.
ここで用いられる無機粉末としては、水性液体等に対して不活性な物質、例えば、各種の無機化合物の微粒子、粘土鉱物の微粒子等が挙げられる。該無機粉体は、水に対して適度な親和性を有し、かつ、水に不溶もしくは難溶であるものが好ましい。具体的には、例えば、二酸化珪素や酸化チタン等の金属酸化物、天然ゼオライトや合製ゼオライト等の珪酸（塩）、カオリン、タルク、クレー、ベントナイト等が挙げられる。このうち、二酸化珪素および珪酸（塩）がより好ましく、コールターカウンター法により測定された平均粒子径が２００μｍ以下の二酸化珪素および珪酸（塩）がさらに好ましい。 Examples of the inorganic powder used herein include substances that are inert to aqueous liquids, such as fine particles of various inorganic compounds, fine particles of clay minerals, and the like. The inorganic powder preferably has an appropriate affinity for water and is insoluble or hardly soluble in water. Specific examples include metal oxides such as silicon dioxide and titanium oxide, silicic acid (salts) such as natural zeolite and synthetic zeolite, kaolin, talc, clay, bentonite and the like. Among these, silicon dioxide and silicic acid (salt) are more preferable, and silicon dioxide and silicic acid (salt) having an average particle diameter measured by a Coulter counter method of 200 μm or less are more preferable.
ここでの無機粉末の使用量は、フィルム状吸水材および無機粉体の組み合わせ等にもよるが、セルロース誘導体もしくはその塩１００質量部に対し０．００１〜１０質量部の範囲内、より好ましくは０．０１〜５質量部の範囲内とすればよい。フィルム状吸水材と無機粉体との混合方法は、特に限定されるものではなく、例えばドライブレンド法、湿式混合法等を採用できるが、ドライブレンド法を採用するのが好ましい。 The amount of the inorganic powder used here depends on the combination of the film-like water-absorbing material and the inorganic powder, but is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative or its salt, more preferably What is necessary is just to set it as the range of 0.01-5 mass parts. The mixing method of the film-like water-absorbing material and the inorganic powder is not particularly limited, and for example, a dry blend method, a wet mixing method, or the like can be employed, but it is preferable to employ the dry blend method.
本発明のフィルム状吸水材は、上述した本発明の製造方法により得ることができるものであり、０．９％−生理食塩水に対する吸水量が自重の１０倍以上であり、さらに該水溶液を自重の２０倍吸水した状態におけるゲル強度が３０００×１０-7N／ｍｍ2以上である。 The film-like water-absorbing material of the present invention can be obtained by the above-described production method of the present invention. The water absorption amount with respect to 0.9% -physiological saline is not less than 10 times its own weight. The gel strength in the state of 20 times water absorption is 3000 × 10 −7 N / mm 2 or more.
本発明のフィルム状吸収材は単独でも、他の素材と組み合わせて吸水性物品としても構わない。吸水性物品の構造は特に限定されないが、例えば、パルプ、不織布等にはさみ、サンドイッチ構造にする方法、他の材質の樹脂シート、フィルムを支持体として多層構造とする方法、樹脂シートにキャストし、二層構造とする方法等がある。 The film-like absorbent material of the present invention may be used alone or in combination with other materials as a water absorbent article. The structure of the water-absorbent article is not particularly limited, for example, sandwiched between pulp, nonwoven fabric, etc., a method of making a sandwich structure, a resin sheet of another material, a method of forming a multilayer structure using a film as a support, casting to a resin sheet, There are methods such as a two-layer structure.
本発明のフィルム状吸水材は、血液や尿、汗、膿、胃液、唾液、鼻分泌粘液などの体液を吸収することを目的とした吸水性物品、例えば、子供用紙オムツ、大人用紙オムツ、生理用ナプキン、タンポン、パンティーライナー、生理用シーツ、失禁用パッド、携帯用トイレ、携帯用汚物処理袋、動物用屎尿処理剤、医療用手当材、創傷被覆材、肉や魚などの鮮度保持材、さらには生分解性を有するため、家畜の飼料添加物等に使用することができる。また体液だけでなく、化粧水、液体肥料、液体殺虫剤などの水溶液、あるいは泥水や海水、河川水などを吸水することを目的とした化粧用パック材などの美容化粧用品、防虫シートなどの生活雑品、建材や土壌保水材、汚泥固化剤、止水材、パッキング材、ゲル水嚢等の土木建築用資材、保冷材等の食品用物品、油水分離材、結露防止材などの各種産業用物品、植物や土壌等の保水材、種子被覆材等の農園芸用物品などに好適に用いることができる。 The film-like water-absorbing material of the present invention is a water-absorbent article intended to absorb body fluid such as blood, urine, sweat, pus, gastric juice, saliva, nasal secretion mucus, such as children's paper diapers, adult paper diapers, Napkins, tampons, panty liners, sanitary sheets, incontinence pads, portable toilets, portable waste disposal bags, animal sewage treatment agents, medical dressings, wound dressings, freshness-keeping materials such as meat and fish, Furthermore, since it has biodegradability, it can be used as a feed additive for livestock. In addition to body fluids, cosmetics such as lotions, liquid fertilizers, and liquid insecticides, or cosmetic cosmetics such as cosmetic packs intended to absorb muddy water, seawater, river water, etc. Miscellaneous industrial products such as miscellaneous goods, building materials and soil water retention materials, sludge solidifying agents, water-stopping materials, packing materials, civil engineering and building materials such as gel water sacs, food items such as cold insulation materials, oil and water separators, and anti-condensation materials It can be suitably used for water-holding materials such as plants and soil, and agricultural and horticultural articles such as seed coating materials.
以下、実施例にて本発明を具体的に説明するが、本発明は本実施例に限定されるものではない。
実施例で得られたフィルム状吸水材の０．９％生理食塩水の吸水量、およびゲル強度は以下のようにして測定した。
［０．９％生理食塩水吸水量］
吸水量の測定は、ティーバッグ法にて０．９質量％塩化ナトリウム水溶液を用いて行った。すなわち、２５５メッシュのナイロン製ティーバッグに吸水材１ｇを入れ、１Ｌの０．９質量％塩化ナトリウム水溶液にティーバッグを６０分間浸し、ティーバッグを引き上げ、１０分間水切りを行った後、その重量を測定した。吸水材の吸水量は、６０分間水に浸した吸水材が入っていないティーバッグの重量をブランクとし、吸水して膨潤した吸水材が入ったティーバッグの重量から、膨潤前の吸水材の重量とブランクの重量を減じた値を、膨潤前の吸水材の重量で除した値を吸水量（ｇ／ｇ吸水材）とした。
［吸水後のゲル状態］
吸水後のゲル状態は、上記０．９％生理食塩水吸水量測定後のゲルを目視および感触で判断し、ゲルのヌメリがほとんどないものを良好とし、ゲルの部分的な溶解に伴うヌメリなどが発生した状態を評価した。
［ゲル強度］
０．９％−生理食塩水を２０倍吸水時でのゲル強度の測定は、フィルム状吸水材に２０
倍量の０．９質量％塩化ナトリウム水溶液を吸水させ、サイエンティフィク社のレオメトリック ＳＲ−５０００を用いて１Ｈｚ、室温にて粘弾性Ｇ＊を測定し、その数値をゲル強度とした。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a present Example.
The water absorption of 0.9% physiological saline and the gel strength of the film-like water-absorbing material obtained in the examples were measured as follows.
[0.9% physiological saline water absorption]
The water absorption was measured by a tea bag method using a 0.9% by mass aqueous sodium chloride solution. That is, 1 g of a water absorbing material is put into a 255 mesh nylon tea bag, the tea bag is immersed in 1 L of 0.9 mass% sodium chloride aqueous solution for 60 minutes, the tea bag is pulled up, drained for 10 minutes, It was measured. The water absorption amount of the water absorbing material is the weight of the tea bag without water absorbing material soaked in water for 60 minutes, and the weight of the water absorbing material before swelling from the weight of the tea bag with water absorbing material swollen after absorbing water And the value obtained by dividing the weight of the blank by the weight of the water-absorbing material before swelling was taken as the amount of water absorption (g / g water-absorbing material).
[Gel state after water absorption]
The gel state after water absorption is determined by visual and touching the gel after measuring the 0.9% physiological saline water absorption amount as described above. The state where the occurrence occurred was evaluated.
[Gel strength]
Measurement of gel strength when 0.9% of physiological saline is 20 times absorbed is 20% for film-like water-absorbing material.
Double 0.9% by mass sodium chloride aqueous solution was absorbed and viscoelasticity G * was measured at 1 Hz and room temperature using a rheometric SR-5000 manufactured by Scientific, and the numerical value was taken as the gel strength.
純水１００ｍｌにＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは６．５であった。次に、この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延し、８０℃で３０分間乾燥し、乾燥フィルムを得た。 CMC powder (Daicel Chemical Industry Co., Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1 mass% aqueous solution) was added to 100 ml of pure water while stirring so that the solid content concentration was 2.5 mass%. The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 6.5. Next, after removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm, and dried at 80 ° C. for 30 minutes to obtain a dry film.
次に上記フィルムをガラス板上に担持させたまま、アルミニウムイオン濃度３ｍｍｏｌ／Ｌに調整した硫酸アルミニウムカリウム水溶液を該フィルムに対して２０ｇ／ｇ量噴霧し、ＣＭＣに対するアルミニウムイオン量が６０ｍｍｏｌ／ｋｇになるよう膨潤させた後、８０℃で３０分間乾燥し、フィルム状吸水材を得た。 Next, an aluminum potassium sulfate aqueous solution adjusted to an aluminum ion concentration of 3 mmol / L is sprayed in an amount of 20 g / g while the film is supported on a glass plate, so that the aluminum ion amount relative to CMC is 60 mmol / kg. After swelling so that it was dried at 80 ° C. for 30 minutes, a film-like water-absorbing material was obtained.
得られたフィルム状吸水材の膜厚は３０μｍ、０．９％−生理食塩水に対する吸水量は３５ｇ／ｇ、ゲル強度は１２，０００×１０-7N／ｍｍ2であった。 The film-like water-absorbing material thus obtained had a film thickness of 30 μm, a water absorption of 0.9% -physiological saline of 35 g / g, and a gel strength of 12,000 × 10 −7 N / mm 2 .
純水１００ｍｌにあらかじめ架橋剤として水溶性カルボジイミド（日清紡社製；カルボジライトＶ−０２−Ｌ２）をＣＭＣ１００質量部に対し１質量部になるように添加した。ｐＨ調整剤として２Ｎ-HCl水溶液を該水溶液に適宜添加し、ｐＨを２．４に調整した。 Water-soluble carbodiimide (manufactured by Nisshinbo Co., Ltd .; Carbodilite V-02-L2) was added in advance to 100 ml of pure water so as to be 1 part by mass with respect to 100 parts by mass of CMC. A 2N-HCl aqueous solution was appropriately added to the aqueous solution as a pH adjusting agent to adjust the pH to 2.4.
上記水溶液にＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは５．２であった。次に、この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延し、８０℃で３０分間乾燥し、乾燥フィルムを得た。 CMC powder (manufactured by Daicel Chemical Industries, Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1% by mass aqueous solution) was added to the above aqueous solution while stirring so that the solid concentration was 2.5% by mass, The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 5.2. Next, after removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm, and dried at 80 ° C. for 30 minutes to obtain a dry film.
次に上記フィルムをガラス板上に担持させたまま、アルミニウムイオン濃度３ｍｍｏｌ／Ｌに調整した硫酸アルミニウムカリウム水溶液を該フィルムに対して２０ｇ／ｇ量噴霧し、ＣＭＣに対するアルミニウムイオン量が６０ｍｍｏｌ／ｋｇになるよう膨潤させた後、８０℃で３０分間乾燥し、フィルム状吸水材を得た。 Next, an aluminum potassium sulfate aqueous solution adjusted to an aluminum ion concentration of 3 mmol / L is sprayed in an amount of 20 g / g while the film is supported on a glass plate, so that the aluminum ion amount relative to CMC is 60 mmol / kg. After swelling so that it was dried at 80 ° C. for 30 minutes, a film-like water-absorbing material was obtained.
得られたフィルム状吸水材の膜厚は３１μｍ、０．９％−生理食塩水に対する吸水量は
３２ｇ／ｇ、ゲル強度は１６，５００×１０-7N／ｍｍ2であった。
The film-like water-absorbing material obtained had a film thickness of 31 μm, a water absorption of 0.9% -saline, 32 g / g, and a gel strength of 16,500 × 10 −7 N / mm 2 .
純水１００ｍｌにあらかじめ可塑剤としてグリセリン（石津製薬社製；特級）をＣＭＣ１００質量部に対し５質量部になるように添加した。 Glycerin (manufactured by Ishizu Pharmaceutical Co., Ltd .; special grade) was previously added to 100 ml of pure water as a plasticizer so as to be 5 parts by mass with respect to 100 parts by mass of CMC.
上記水溶液にＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは５．２であった。次に、この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延し、８０℃で３０分間乾燥し、乾燥フィルムを得た。 CMC powder (manufactured by Daicel Chemical Industries, Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1% by mass aqueous solution) was added to the above aqueous solution while stirring so that the solid concentration was 2.5% by mass, The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 5.2. Next, after removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm, and dried at 80 ° C. for 30 minutes to obtain a dry film.
次に上記フィルムをガラス板上に担持させたまま、アルミニウムイオン濃度３ｍｍｏｌ／Ｌに調整した硫酸アルミニウムカリウム水溶液を該フィルムに対して２０ｇ／ｇ量噴霧し、ＣＭＣに対するアルミニウムイオン量が６０ｍｍｏｌ／ｋｇになるよう膨潤させた後、８０℃で３０分間乾燥し、フィルム状吸水材を得た。 Next, an aluminum potassium sulfate aqueous solution adjusted to an aluminum ion concentration of 3 mmol / L is sprayed in an amount of 20 g / g while the film is supported on a glass plate, so that the aluminum ion amount relative to CMC is 60 mmol / kg. After swelling so that it was dried at 80 ° C. for 30 minutes, a film-like water-absorbing material was obtained.
得られたフィルム状吸水材の膜厚は３０μｍであり、非常に柔軟性に富んでいるものが
得られた。０．９％−生理食塩水に対する吸水量は３４ｇ／ｇ、ゲル強度は１１，４００
×１０-7N／ｍｍ2であった。
The film-like water-absorbing material obtained had a film thickness of 30 μm and was very flexible. 0.9%-The water absorption with respect to physiological saline is 34 g / g, and the gel strength is 11,400.
× 10 -7 N / mm 2
純水１００ｍｌにＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは６．５であった。次に、この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延し、８０℃で３０分間乾燥し、乾燥フィルムを得た。 CMC powder (Daicel Chemical Industry Co., Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1 mass% aqueous solution) was added to 100 ml of pure water while stirring so that the solid content concentration was 2.5 mass%. The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 6.5. Next, after removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm, and dried at 80 ° C. for 30 minutes to obtain a dry film.
得られた乾燥フィルムの膜厚は３１μｍ、０．９％−生理食塩水に対する吸水量は測定時にナイロン製ティーバッグから大量に漏れが生じ、測定不能となった。ゲル強度も同様に測定不能であった。 The film thickness of the obtained dry film was 31 μm, and the amount of water absorbed with respect to 0.9% -physiological saline leaked in large amounts from the nylon tea bag during measurement, making measurement impossible. Similarly, the gel strength was not measurable.
純水１００ｍｌにＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは６．５であった。 CMC powder (Daicel Chemical Industry Co., Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1 mass% aqueous solution) was added to 100 ml of pure water while stirring so that the solid content concentration was 2.5 mass%. The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 6.5.
次に、該水溶液にブレンダーで剪断しながら架橋剤；硫酸アルミニウムカリウムをアルミニウムイオン換算量としてＣＭＣ重量１ｋｇ当たり６０ミリモルになるように攪拌しながら添加したが、ゲル化速度が速く、架橋剤を添加した部分のみ瞬時にゲル化し、ゲルとゾルが入り混じったものが得られた。この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延したが、平滑にならなかった。それをそのまま８０℃で３０分間乾燥し、乾燥フィルムを得た。 Next, a cross-linking agent was added to the aqueous solution while stirring with a blender; potassium aluminum sulfate was added with stirring so that the aluminum ion equivalent amount was 60 mmol per kg of CMC, but the gelation rate was high and the cross-linking agent was added. Only the portion that was gelled instantly became a mixture of gel and sol. After removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm. It was directly dried at 80 ° C. for 30 minutes to obtain a dry film.
得られたフィルム状吸水材の膜厚は８〜４２μｍと測定値のバラツキが大きくむらがあった。０．９％−生理食塩水に対する吸水量は測定時にナイロン製ティーバッグから大量に漏れが生じ、測定不能となった。ゲル強度も同様に測定不能であった。 The film-like water-absorbing material obtained had a film thickness of 8 to 42 μm, with large variations in measured values. 0.9% -Amount of water absorbed with respect to physiological saline was not able to be measured due to a large amount of leakage from the nylon tea bag during measurement. Similarly, the gel strength was not measurable.
純水１００ｍｌにＣＭＣ粉末（ダイセル化学工業社製；ダイセルＣＭＣ１１５０、ＤＳ＝０．６９、1質量%水溶液の粘度２９０ｍＰａ・ｓ）を固形分濃度２．５質量％になるように攪拌しながら添加し、膨潤させ、水溶液を調整した。このときのＣＭＣ水溶液のｐＨは６．５であった。 CMC powder (Daicel Chemical Industry Co., Ltd .; Daicel CMC1150, DS = 0.69, viscosity of 290 mPa · s of 1 mass% aqueous solution) was added to 100 ml of pure water while stirring so that the solid content concentration was 2.5 mass%. The aqueous solution was adjusted by swelling. At this time, the pH of the CMC aqueous solution was 6.5.
次に、この水溶液の気泡を抜いた後、ガラス基板上に厚みが２．０ｍｍになるようバーコーターを用いて流延し、アルミニウムイオン濃度３ｍｍｏｌ／Ｌに調整した架橋浴；硫酸アルミニウムカリウム水溶液に３０秒間浸漬したところ、得られたゲル表面に凹凸が生じた。それをそのまま８０℃で３０分間乾燥し、フィルム状吸水材を得た。 Next, after removing bubbles from the aqueous solution, the solution was cast on a glass substrate using a bar coater so as to have a thickness of 2.0 mm and adjusted to an aluminum ion concentration of 3 mmol / L; When immersed for 30 seconds, the resulting gel surface was uneven. It was directly dried at 80 ° C. for 30 minutes to obtain a film-like water absorbing material.
得られたフィルム状吸水材のアルミニウム含有量をICPにより元素分析したところ、ＣＭＣ重量１ｋｇ当たり５５ミリモル含まれていた。膜厚は７〜３５μｍと測定値のバラツキが大きくむらがあった。０．９％−生理食塩水に対する吸水量は４９ｇ／ｇであったが、基板側は吸水後触れると滑りが生じた。ゲル強度は６，９００×１０-7N／ｍｍ2であった。 When the elemental analysis of the aluminum content of the obtained film-like water-absorbing material was performed by ICP, it was found to be 55 mmol / kg of CMC weight. The film thickness was 7 to 35 μm, and the variation in the measured values was greatly uneven. The amount of water absorbed by 0.9% -physiological saline was 49 g / g, but the substrate side slipped when touched after water absorption. The gel strength was 6,900 × 10 −7 N / mm 2 .
本発明を用いた実施例１〜３は、均一な膜厚のフィルムが得られた。また、表１からも明らかなように、吸水量とゲル強度のバランスが良く、優れた吸水性能を有していることが分かる。 In Examples 1 to 3 using the present invention, a film having a uniform film thickness was obtained. Further, as is clear from Table 1, it can be seen that the water absorption amount and the gel strength are well balanced and have excellent water absorption performance.
比較例１は未架橋のＣＭＣフィルムであり、水中で徐々に崩壊、溶解してしまい吸水材とは呼べない。 Comparative Example 1 is an uncrosslinked CMC film, which gradually collapses and dissolves in water and cannot be called a water absorbing material.
比較例２ではＣＭＣゾルを作製し、それを架橋してゲルを作製し、それをガラス基板に流延し、乾燥するという従来の製造方法で行ったが、ゾルとゲルが混ざり合っているためキャストしても不均一となり、結果として得られたフィルムの膜厚も不均一であった。吸水性能についても、架橋部位と未架橋部位が混在し、吸収量、ゲル強度ともに測定不能となった。 In Comparative Example 2, a CMC sol was prepared, a gel was prepared by crosslinking the sol, and the gel was cast on a glass substrate and dried. However, since the sol and the gel are mixed, Even when cast, the film was non-uniform and the resulting film thickness was non-uniform. Regarding the water absorption performance, both cross-linked sites and non-cross-linked sites were mixed, making it impossible to measure both absorption and gel strength.
比較例３ではＣＭＣゾルを作製し、ガラス基板に流延し、架橋浴に浸漬してゲル化した後に乾燥するという従来の製造方法で行ったが、浸漬した際にゾルが流動し、架橋後ゲル表面に凹凸が生じた。結果として得られたフィルムの膜厚も不均一であった。吸水性能については、吸水量は問題ないものの、フィルムの基板に密着した方の面は吸水後触れると滑りが生じ、ゲル強度の値も比較的低かった。よって、架橋液と接触していた面に比べると基板側の内部までは架橋されにくく、架橋むらが生じてことがわかる。 In Comparative Example 3, a CMC sol was prepared, cast on a glass substrate, immersed in a crosslinking bath, gelled, and then dried, but the sol flowed when immersed, and after crosslinking Unevenness was generated on the gel surface. The film thickness of the resulting film was also nonuniform. As for the water absorption performance, although there is no problem with the amount of water absorption, the surface of the film that was in close contact with the substrate was slipped when touched after water absorption, and the gel strength value was relatively low. Therefore, it can be seen that the inner side of the substrate is not easily cross-linked as compared with the surface in contact with the cross-linking liquid, and cross-linking unevenness occurs.
以上のことから本発明のフィルム状吸水材は吸水量、ゲル強度に優れ、性能のバランスがとれていることが分かる。また、本発明の製造方法を用いることによって、均一な膜厚のフィルム状吸水材が容易に効率よく得られ、生産効率の向上とコスト削減が可能である。 From the above, it can be seen that the film-like water-absorbing material of the present invention is excellent in water absorption and gel strength and has a balanced performance. Further, by using the production method of the present invention, a film-like water-absorbing material having a uniform film thickness can be obtained easily and efficiently, and production efficiency can be improved and costs can be reduced.
Claims (14)
ｂ）得られたフィルムゲルを乾燥する工程、
を含む請求項1〜９いずれか記載のフィルム状吸水材の製造方法。 a) An aqueous solution containing a polyvalent metal ion is brought into contact with a dry film containing a cellulose derivative or a salt thereof, and the cellulose derivative or a salt thereof is simultaneously swelled with a swelling degree with respect to water in the range of 1 to 50 g / g (dry film). Cross-linking the
b) drying the obtained film gel;
The manufacturing method of the film-form water absorbing material in any one of Claims 1-9 containing.
ｃ）水にセルロース誘導体もしくはその塩を、添加後の混合液に対して固形分濃度０．１〜２０質量％となるように添加し、セルロース誘導体もしくはその塩を水で膨潤させる工程、
ｄ）得られたセルロース誘導体もしくはその塩のゾルを基板上に流延する工程、
ｅ）流延したゾルを乾燥する工程、
により得られる乾燥フィルムである請求項１０記載のフィルム状吸水材の製造方法。 The dry film used in step a) is
c) adding a cellulose derivative or a salt thereof to water so that the solid content concentration is 0.1 to 20% by mass with respect to the mixed solution after the addition, and swelling the cellulose derivative or a salt thereof with water;
d) a step of casting the sol of the obtained cellulose derivative or a salt thereof on a substrate;
e) drying the cast sol;
The method for producing a film-like water-absorbing material according to claim 10, wherein the film is a dry film obtained by the method.
A water absorbent article comprising the water absorbent material according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009122989A1 (en) | 2008-03-31 | 2009-10-08 | ユニ・チャーム株式会社 | Absorber forming crossbridge upon absorbing |
| JP2017124529A (en) * | 2016-01-13 | 2017-07-20 | 凸版印刷株式会社 | Antifogging film and antifogging composition |
-
2005
- 2005-01-13 JP JP2005006592A patent/JP2006192368A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009122989A1 (en) | 2008-03-31 | 2009-10-08 | ユニ・チャーム株式会社 | Absorber forming crossbridge upon absorbing |
| JP2017124529A (en) * | 2016-01-13 | 2017-07-20 | 凸版印刷株式会社 | Antifogging film and antifogging composition |
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