JPH0474066B2 - - Google Patents
Info
- Publication number
- JPH0474066B2 JPH0474066B2 JP2384788A JP2384788A JPH0474066B2 JP H0474066 B2 JPH0474066 B2 JP H0474066B2 JP 2384788 A JP2384788 A JP 2384788A JP 2384788 A JP2384788 A JP 2384788A JP H0474066 B2 JPH0474066 B2 JP H0474066B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- water
- group
- coating
- absorbing
- 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.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000007942 carboxylates Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000011358 absorbing material Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は吸水性被膜の製造方法に関するもの
で、吸水性不織布などの吸水材料を提供する。自
重の数百倍の吸水能を有する高吸水性樹脂が商品
化され、樹脂粉末を紙、パルプ綿などに散布した
吸水材料が紙おむつ、ナプキン、結露防止壁紙な
どに使用され、産業上の利用分野は広い。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a water-absorbing coating, and provides a water-absorbing material such as a water-absorbing nonwoven fabric. Super absorbent resins with water absorption capacity hundreds of times their own weight have been commercialized, and water-absorbing materials made by sprinkling resin powder on paper, pulp cotton, etc. are used in disposable diapers, napkins, anti-condensation wallpaper, etc., and are being used in industrial applications. is wide.
従来の技術
高吸水性樹脂として種々の製品があり、ポリア
クリル酸架橋（共）重合体、デンプン−アクリロ
ニトリルグラフト重合体加水分解物、デンプン−
アクリル酸グラフト架橋重合体、酢酸ビニル−ア
クリル酸エステル共重合体ケン化物、無水マレイ
ン酸−イソブチレン共重合体などがあげられる。
これら重合体はカルボキシル基が部分的にアルカ
リ金属塩に中和され、水に不溶であるが高度の膨
潤性を有する。Conventional technology There are various products as super absorbent resins, including polyacrylic acid crosslinked (co)polymers, starch-acrylonitrile graft polymer hydrolysates, and starch-acrylonitrile graft polymer hydrolysates.
Examples include acrylic acid graft crosslinked polymers, saponified vinyl acetate-acrylic acid ester copolymers, and maleic anhydride-isobutylene copolymers.
These polymers have carboxyl groups partially neutralized with alkali metal salts, and are insoluble in water but have a high degree of swelling.
高吸水性樹脂の前躯体としてのカルボキシレー
ト基含有重合体の水溶液を基材に塗布し、加熱乾
燥過程で重合体に架橋を導入して吸水性被膜をつ
くることができる。重合体水溶液にカルボキシレ
ート基と反応性の架橋剤を加え、加熱乾燥過程で
架橋を導入する方法が知られる（特開昭62−
30125）。架橋剤として、ポリハロアルカノール、
ポリグリシジルエーテルなどが用いられる。 A water-absorbent coating can be created by applying an aqueous solution of a carboxylate group-containing polymer as a precursor of a super-absorbent resin to a base material, and introducing crosslinking into the polymer during a heat-drying process. A method is known in which a crosslinking agent reactive with carboxylate groups is added to an aqueous polymer solution and crosslinking is introduced during the heat drying process (Japanese Patent Application Laid-Open No. 1986-1999).
30125). As a crosslinking agent, polyhaloalkanol,
Polyglycidyl ether and the like are used.
本発明者は、先にポリアクリル酸系重合体の水
性組成物を過酸化物ラジカル開始剤の存在で加熱
し、ラジカル架橋による高吸水性樹脂の製造法
（特公昭62−40361）およびこの方法による吸水性
被膜の製造法（特開昭62−275146）を発明した。 The present inventor first disclosed a method for producing a superabsorbent resin by radical crosslinking by heating an aqueous composition of a polyacrylic acid polymer in the presence of a peroxide radical initiator (Japanese Patent Publication No. 62-40361) and this method. He invented a method for producing a water-absorbing film (Japanese Patent Application Laid-Open No. 62-275146).
発明が解決しようとする問題点
重合体のカルボキシレート基と反応性の多官能
架橋剤を用いる場合、重合体水溶液の貯蔵安定性
が不充分であつたり、架橋の形成に長時間を要す
るなどの問題がある。また上記先行発明のラジカ
ル架橋法による吸水性被膜の製造について検討を
進めたところ、次ぎの問題点が明らかになつた。
該ポリマー水溶液の架橋反応における過酸化物開
始剤の架橋効率が低いので、多量の開始剤を必要
とし、また架橋効率は反応過程における温度特に
水分量による変動が大で、被膜の架橋度（吸水
能）が不均一になる。また開始剤を多量使用する
と、ポリマー分子の酸化分解による吸水性被膜の
品質低下が生じ、吸水ゲルの感触にべたつきが生
じる。さらに開始剤のかなりの残存が避けられ
ず、そのため人体に対する安全性の危惧が発生す
る。Problems to be Solved by the Invention When using a polyfunctional crosslinking agent that is reactive with the carboxylate group of a polymer, there are problems such as insufficient storage stability of the aqueous polymer solution and the need for a long time to form crosslinks. There's a problem. Further, as a result of further investigation into the production of a water-absorbing film by the radical crosslinking method of the prior invention, the following problem became clear.
Since the crosslinking efficiency of the peroxide initiator in the crosslinking reaction of the aqueous polymer solution is low, a large amount of initiator is required, and the crosslinking efficiency fluctuates greatly depending on the temperature, especially the water content, during the reaction process, and the degree of crosslinking of the film (water absorption performance) becomes uneven. Furthermore, if a large amount of initiator is used, the quality of the water-absorbing film will deteriorate due to oxidative decomposition of the polymer molecules, and the water-absorbing gel will have a sticky feel. Furthermore, a considerable amount of the initiator remains unavoidably, which poses a safety concern for humans.
問題点を解決するための手段
本発明者は、上記の問題点を解決するため研究
し、カルボキシレート基含有重合体系水溶液から
吸水性被膜の製造におけるポリマーの架橋法とし
て、エポキシ基含有重合性不飽和化合物および比
較的少量のラジカル開始剤を用いる本発明の新規
方法を完成した。Means for Solving the Problems The present inventor conducted research to solve the above problems, and developed an epoxy group-containing polymerizable polymer as a polymer crosslinking method for producing a water-absorbing coating from a carboxylate group-containing polymer aqueous solution. The new process of the present invention using saturated compounds and relatively small amounts of radical initiators has been completed.
本発明のカルボキシレート基含有重合体は、架
橋の導入により高吸水性樹脂となる水溶性重合体
である。ポリアクリル酸系重合体として、アクリ
ル酸単独および共重合体、デンプン−アクリロニ
トリルグラフト重合体加水分解物、デンプン−ア
クリル酸グラフト重合体、アクリル酸エステル共
重合体ケン化物などがあげられる。また無水マレ
イン酸−イソブチレン共重合体も含まれる。これ
らの重合体は、通常カルボキシル基の60〜90％が
アルカリ金属塩として中和され、高吸水性樹脂の
前躯体として公知である。 The carboxylate group-containing polymer of the present invention is a water-soluble polymer that becomes a highly water-absorbent resin by introducing crosslinking. Examples of polyacrylic acid-based polymers include acrylic acid alone and copolymers, starch-acrylonitrile graft polymer hydrolysates, starch-acrylic acid graft polymers, and saponified acrylic ester copolymers. Also included are maleic anhydride-isobutylene copolymers. These polymers usually have 60 to 90% of their carboxyl groups neutralized as alkali metal salts, and are known as precursors of superabsorbent resins.
エポキシ基含有重合性不飽和化合物として、グ
リシジルアクリレート、グリシジルメタクリレー
ト、アリルグリシジルエーテルなどがあげられ
る。添加量は重合体に対して通常0.2〜３重量％
である。 Examples of the epoxy group-containing polymerizable unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. The amount added is usually 0.2 to 3% by weight based on the polymer.
It is.
ラジカル開始剤として、過硫酸アンモン、過硫
酸カリ、過酸化水素、あるいはこれらと亜硫酸ソ
ーダ、アスコルビン酸などの還元剤を組合わせた
レドツクス系開始剤、および４，4′−アゾビス
（４−シアノ草酸）などのアゾ系開始剤が用い
られる。添加量は重合体に対して通常0.2〜２重
量％である。また架橋助剤として、Ｎ，N′−メ
チレンビスアクリルアミドなどの多官能不飽和化
合物を加えてもよく、本発明の架橋剤系に含まれ
る。 As a radical initiator, ammonium persulfate, potassium persulfate, hydrogen peroxide, or a redox initiator in which these are combined with a reducing agent such as sodium sulfite or ascorbic acid, and 4,4'-azobis(4-cyanograsic acid) are used. ) and other azo initiators are used. The amount added is usually 0.2 to 2% by weight based on the polymer. Further, a polyfunctional unsaturated compound such as N,N'-methylenebisacrylamide may be added as a crosslinking aid and is included in the crosslinking agent system of the present invention.
重合体水性溶液の粘度は塗工可能な範囲に調節
される。重合体の分子量は、通常濃度５〜10％の
範囲で適当な粘度になるように設計される。溶媒
として、水にメタノール、エタノール、アセトン
などの有機溶剤を混合して粘度を低下させること
ができる。貧溶媒化することにより溶液粘度を下
げることは塗料技術において周知である。これら
の有機溶剤は乾燥初期に揮発除去されるので、架
橋反応に実質的に関与しない。 The viscosity of the aqueous polymer solution is adjusted to a range that allows coating. The molecular weight of the polymer is usually designed to provide an appropriate viscosity at a concentration of 5 to 10%. As a solvent, an organic solvent such as methanol, ethanol, or acetone can be mixed with water to lower the viscosity. It is well known in paint technology to reduce the viscosity of a solution by making it a poor solvent. Since these organic solvents are volatilized and removed in the early stage of drying, they do not substantially participate in the crosslinking reaction.
架橋形成の機構は大略次のように説明される。
基材に塗布された重合体水性溶液は、加熱乾燥の
初期に溶媒が急速に蒸発し、反応は濃度が50％以
上に増大した後に実質的に生ずる。架橋形成に関
与する反応として、エポキシ基含有不飽和化合物
の重合体へのグラフト重合およびエポキシ基とカ
ルボキシレート基とのエステル化反応があげられ
る。これらの反応を通じて重合体分子間に架橋が
形成される。 The mechanism of crosslink formation can be roughly explained as follows.
The aqueous polymer solution applied to the substrate undergoes rapid evaporation of the solvent during the early stages of heat drying, and the reaction substantially occurs after the concentration increases to 50% or more. Reactions involved in crosslinking include graft polymerization of an epoxy group-containing unsaturated compound onto a polymer and esterification reaction between an epoxy group and a carboxylate group. Through these reactions, crosslinks are formed between polymer molecules.
グラフト重合は、ラジカル開始剤の分解によ
り、短時間で生ずるのに対して、エステル化反応
はかなりの時間を要する。たとえば100℃の温度
で加熱しても、反応の完結には通常20分以上要す
る。 Graft polymerization occurs in a short time due to the decomposition of the radical initiator, whereas esterification reactions require a considerable amount of time. For example, even when heated to a temperature of 100°C, it usually takes 20 minutes or more for the reaction to complete.
塗布−加熱乾燥工程において架橋を短時間に終
了させる方法も見出された。重合体水性溶液にエ
ポキシ化合物を加え、この溶液を比較的低温で加
熱し、エポキシ基とカルボキシレート基の反応を
あらかじめ行なう。この場合、モノエポキシ化合
物が選ばれる。この反応は、60〜80℃の温度で１
〜２時間でほぼ終了する。常温で長時間放置して
もよい。反応によつて重合体に重合性不飽和基が
側鎖として導入される。生成重合体は水性溶液と
して得られる。反応により粘度の著しい変化は認
められない。この溶液にラジカル開始剤を加え、
基材に塗布する。塗膜の加熱乾燥過程で、重合体
側鎖不飽和基の重合反応によつて、短時間で架橋
が形成される。 A method for completing crosslinking in a short time during the coating-heat-drying process was also discovered. An epoxy compound is added to an aqueous polymer solution and the solution is heated at a relatively low temperature to pre-react the epoxy groups and carboxylate groups. In this case, monoepoxy compounds are chosen. This reaction takes place at a temperature of 60-80°C.
It will be almost finished in ~2 hours. It may be left at room temperature for a long time. Through the reaction, a polymerizable unsaturated group is introduced into the polymer as a side chain. The resulting polymer is obtained as an aqueous solution. No significant change in viscosity was observed due to the reaction. Add a radical initiator to this solution,
Apply to the base material. During the heat-drying process of the coating film, crosslinks are formed in a short time due to the polymerization reaction of the unsaturated groups in the side chains of the polymer.
重合体水性溶液の塗布は公知の方法で行われ、
特に高粘度用塗工機が用いられる。 Application of the aqueous polymer solution is carried out by a known method,
In particular, a coating machine for high viscosity is used.
本発明に用いられる基材は特に制限されない
が、紙、不織布などの多孔性シートが多用され
る。 The base material used in the present invention is not particularly limited, but porous sheets such as paper and nonwoven fabric are often used.
作 用
本発明の被膜は高吸水性樹脂からなり、水に実
質的に不溶であるが、高度の吸水能を有する。被
膜は基材からはく離してフイルムの形態で取得す
ることも可能であるが、通常多孔性シート基材に
施され、吸水性不織布などの吸水材料を提供す
る。Function The film of the present invention is made of a highly water-absorbing resin and is substantially insoluble in water, but has a high water-absorbing ability. Although the coating can be peeled off from the substrate and obtained in the form of a film, it is usually applied to a porous sheet substrate to provide a water-absorbing material such as a water-absorbing nonwoven fabric.
実施例 １
カルボキシル基の75％がナトリウム塩として中
和されたポリアクリル酸の濃度10％の水溶液（25
℃における粘度28万センチポイズ）100部にグリ
シジルメタクリレート0.1部、過硫酸カリ0.1部を
加えて溶解した。この水溶液をパルプ系不織布
（ペーパータオル）の片面に重合体塗布量が20
ｇ／m2になるようにナイフコーター方式で塗布し
た。Example 1 A 10% aqueous solution of polyacrylic acid in which 75% of the carboxyl groups were neutralized as sodium salt (25
0.1 part of glycidyl methacrylate and 0.1 part of potassium persulfate were added to 100 parts (viscosity at °C of 280,000 centipoise) and dissolved. Apply this aqueous solution to one side of a pulp-based nonwoven fabric (paper towel) so that the polymer coating amount is 20%.
It was coated using a knife coater method to give a coating weight of g/m 2 .
次に塗布物を100℃の乾燥器中で60分加熱して
乾燥した。生成物を10cm×10cmの大きさに切断し
て水中に30分間浸漬した後、水切りして重量を測
定し、一方塗布しない不織布を同様に処理し、重
量の差から樹脂の吸水能を求めた。試料は66ｇの
吸水能を有し、これより樹脂は自重の280倍の水
を吸収することがわかる。 The coated material was then heated and dried in a dryer at 100° C. for 60 minutes. The product was cut to a size of 10 cm x 10 cm and immersed in water for 30 minutes, then drained and weighed. On the other hand, the uncoated nonwoven fabric was treated in the same way, and the water absorption capacity of the resin was determined from the difference in weight. . The sample has a water absorption capacity of 66g, which indicates that the resin absorbs 280 times its own weight in water.
実施例 ２
実施例１のポリアクリル酸水溶液100部にグリ
シジルアクリレート0.1部を加えて溶解し、密閉
容器に入れ、70℃の温度で120分加熱した後室温
に冷却してから、過硫酸アンモン0.1部を加えて
溶解した。この水溶液を重合体塗布量が22ｇ／m2
になるように実施例１と同様に不織布に塗布し
た。Example 2 0.1 part of glycidyl acrylate was added to 100 parts of the polyacrylic acid aqueous solution of Example 1, dissolved, placed in a sealed container, heated at 70°C for 120 minutes, cooled to room temperature, and then added 0.1 part of ammonium persulfate. part was added and dissolved. This aqueous solution has a polymer coating amount of 22g/m 2
It was applied to a nonwoven fabric in the same manner as in Example 1 so that the following results were obtained.
塗布物を120℃の乾燥器中で10分間加熱乾燥し
た。生成物を10cm×10cmの大きさに切断して実施
例１と同様に吸水能を測定した。この試料は82ｇ
の吸水能を有し、これより樹脂の吸水倍率は330
倍と求められた。 The coated material was heated and dried in a dryer at 120°C for 10 minutes. The product was cut into pieces of 10 cm x 10 cm, and the water absorption capacity was measured in the same manner as in Example 1. This sample is 82g
The water absorption capacity of the resin is 330.
I was asked to double it.
実施例 ３
実施例１のポリアクリル酸水溶液100部にグリ
シジルメタクリレート0.1部、過硫酸カリ0.05部
を加えて溶解した。この水溶液を実施例１と同様
に不織布に塗布し、塗布物を100℃にて60分加熱
して乾燥した。生成物を実施例１と同様にして吸
水能を測定した。試料は吸水能は68ｇの吸水能を
有し、これより樹脂の吸水倍率は290倍であつた。Example 3 0.1 part of glycidyl methacrylate and 0.05 part of potassium persulfate were added and dissolved in 100 parts of the aqueous polyacrylic acid solution of Example 1. This aqueous solution was applied to a nonwoven fabric in the same manner as in Example 1, and the applied material was heated at 100° C. for 60 minutes to dry. The water absorption capacity of the product was measured in the same manner as in Example 1. The sample had a water absorption capacity of 68 g, which indicated that the water absorption capacity of the resin was 290 times.
実施例 ４
実施例２のグリシジルアクリレートを付加反応
したポリアクリル酸系水溶液100部に、過硫酸ア
ンモン0.05部を加えて溶解した。この水溶液を実
施例２と同様に不織布に塗布し、120℃にて10分
間加熱して乾燥した。生成物を実施例１と同様に
して吸水能を測定した。試料は80ｇの吸水能を有
し、これより樹脂の吸水倍率は320倍と求められ
た。Example 4 0.05 part of ammonium persulfate was added to 100 parts of an aqueous polyacrylic acid solution in which the glycidyl acrylate of Example 2 was subjected to an addition reaction. This aqueous solution was applied to a nonwoven fabric in the same manner as in Example 2, and dried by heating at 120° C. for 10 minutes. The water absorption capacity of the product was measured in the same manner as in Example 1. The sample had a water absorption capacity of 80g, and from this the water absorption capacity of the resin was determined to be 320 times.
実施例３および４において、開始剤の使用量は
それぞれ相当する実施例１および２に比べて半分
に減少したにも拘らず、樹脂の吸水倍率に実質的
な差が見られない。吸水倍率（架橋度）が不飽和
グリシジル化合物によることがわかる。 In Examples 3 and 4, although the amount of initiator used was reduced by half compared to corresponding Examples 1 and 2, there is no substantial difference in the water absorption capacity of the resins. It can be seen that the water absorption capacity (degree of crosslinking) is due to the unsaturated glycidyl compound.
効 果
実施例にみられる如く、本発明の方法により、
高度の吸水能を有する重合体被膜が得られ、吸水
性不織布などの吸水材料を提供することができ
る。Effects As seen in the examples, the method of the present invention has the following effects:
A polymer coating with a high water absorption capacity is obtained, and it is possible to provide a water absorbing material such as a water absorbent nonwoven fabric.
Claims (1)
含有重合性不飽和化合物および水溶性ラジカル開
始剤を含んでなる水性溶液を基材に塗布し、塗膜
を加熱乾燥して該重合体に架橋を形成させること
を特徴とする吸水性被膜の製造方法。 ２ カルボキシレート基含有重合体を含む水性溶
液にモノエポキシ基含有重合性不飽和化合物を添
加溶解し、エポキシ基をカルボキシレート基と反
応させて該重合体に不飽和基を導入した後、水溶
性ラジカル開始剤を添加溶解してなる溶液を基材
に塗布し、塗膜を加熱乾燥して該重合体に架橋を
形成させることを特徴とする吸水性被膜の製造方
法。[Scope of Claims] 1. An aqueous solution containing a carboxylate group-containing polymer, an epoxy group-containing polymerizable unsaturated compound, and a water-soluble radical initiator is applied to a substrate, and the coating film is heated and dried to remove the polymer. A method for producing a water-absorbing film, characterized by forming a crosslink during coalescence. 2. A monoepoxy group-containing polymerizable unsaturated compound is added and dissolved in an aqueous solution containing a carboxylate group-containing polymer, and the epoxy group is reacted with the carboxylate group to introduce an unsaturated group into the polymer. 1. A method for producing a water-absorbing coating, which comprises applying a solution prepared by adding and dissolving a radical initiator to a substrate, and heating and drying the coating to form a crosslink in the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2384788A JPH01203084A (en) | 1988-02-05 | 1988-02-05 | Formation of water-absorptive coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2384788A JPH01203084A (en) | 1988-02-05 | 1988-02-05 | Formation of water-absorptive coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203084A JPH01203084A (en) | 1989-08-15 |
| JPH0474066B2 true JPH0474066B2 (en) | 1992-11-25 |
Family
ID=12121799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2384788A Granted JPH01203084A (en) | 1988-02-05 | 1988-02-05 | Formation of water-absorptive coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01203084A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7338625B2 (en) | 2002-09-18 | 2008-03-04 | Kimberly-Clark Worldwide, Inc. | Methods of restoring elasticity after stiffening treatments |
| CN108004837A (en) * | 2017-11-27 | 2018-05-08 | 郑艳 | A kind of preparation method of biodegradation type moisturizing vegetables packaging fibrous paper |
-
1988
- 1988-02-05 JP JP2384788A patent/JPH01203084A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203084A (en) | 1989-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4647617A (en) | Water absorbent crosslinked polymer and a method of producing the same containing cellulosis fibers | |
| JP4210432B2 (en) | Postcrosslinking of hydrogels with 2-oxazolidinone | |
| KR940010532B1 (en) | Process for the preparation of water-absorptive material | |
| JP2877255B2 (en) | Manufacturing method of water absorbent resin with excellent durability | |
| US5624967A (en) | Water-absorbing resin and process for producing same | |
| KR950013035B1 (en) | Process for the preparation of a water-absorptive fibrous material | |
| CA1266404A (en) | Process for preparation of water absorptive composite material | |
| EP1732974A1 (en) | Improved method of manufacturing superabsorbent polymers | |
| JPH078883B2 (en) | Method for producing modified water absorbent resin | |
| JPH06397B2 (en) | Super absorbent sheet and its manufacturing method | |
| JPH1045812A (en) | Production of fiber-containing water absorbing resin | |
| EP0207714B1 (en) | Improved process for preparing water-absorbing resins | |
| JPH04120176A (en) | Water absorbing agent and production thereof | |
| JP2954360B2 (en) | Manufacturing method of water-absorbing composite | |
| JPH0474066B2 (en) | ||
| JPH0214925B2 (en) | ||
| JP2002501088A (en) | Hydrogel wrapped in a coating | |
| JPH0192226A (en) | Water-absorbing polymer | |
| JP2002504580A (en) | Postcrosslinking of hydrogels using borate esters | |
| JP2745703B2 (en) | Method for producing water-absorbing polymer | |
| JPS6342641B2 (en) | ||
| JPH0656933A (en) | Water-absorbing resin and its production | |
| JPS62243606A (en) | Production of liquid-absorbing composite | |
| JPH03767A (en) | Manufacture of water-absorptive film | |
| JPH01201312A (en) | Modification of water-absorptive resin |