JPH0742093A - Method for producing water-absorbing paper and water-absorvbing paper obtaioned thereby - Google Patents
Method for producing water-absorbing paper and water-absorvbing paper obtaioned therebyInfo
- Publication number
- JPH0742093A JPH0742093A JP18805793A JP18805793A JPH0742093A JP H0742093 A JPH0742093 A JP H0742093A JP 18805793 A JP18805793 A JP 18805793A JP 18805793 A JP18805793 A JP 18805793A JP H0742093 A JPH0742093 A JP H0742093A
- Authority
- JP
- Japan
- Prior art keywords
- water
- paper
- base material
- compound
- polymer compound
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 37
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 15
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 14
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 39
- -1 dicarboxylic acid compound Chemical class 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims 2
- 239000011358 absorbing material Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 description 38
- 238000010521 absorption reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000000740 bleeding effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920000247 superabsorbent polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RPERXDZSUVYBHZ-UHFFFAOYSA-N 2,2-dimethyldecanedioic acid Chemical compound OC(=O)C(C)(C)CCCCCCCC(O)=O RPERXDZSUVYBHZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical group N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高い吸水性を備えた吸
水紙の製法およびそれにより得られる吸水紙に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing water-absorbent paper having high water absorption and a water-absorbent paper obtained thereby.
【０００２】[0002]
【従来の技術】従来の、高吸水性樹脂を用いた吸水紙の
製法としては、例えば、微粉末状の高吸水性樹脂を２層
の紙の間に挟み、エンボス加工を施すことにより吸水紙
を作製する方法があげられる。また、抄紙工程時に、乾
燥前に微粉末状の高吸水性樹脂を散布する方法があげら
れる。2. Description of the Related Art As a conventional method for producing a water-absorbent paper using a super-water-absorbent resin, for example, a super-water-absorbent resin in the form of fine powder is sandwiched between two layers of paper and embossed to form a water-absorbent paper. There is a method for producing. Further, in the papermaking process, a method of spraying a fine powdery super absorbent polymer before drying can be mentioned.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うな従来の高吸水性樹脂を用いて得られた吸水紙の製法
は、高吸水性樹脂そのものを紙に直接添加する方法を採
っているため、紙への添加時に紙面全体に高吸水性樹脂
粉末を均一に添加することが極めて困難となる。したが
って、紙面の部分によって吸水性能に優劣が発生しやす
いという問題を有している。また、添加時に高吸水性樹
脂粉末が吸水してしまい粒子が膨脹し大きくなるため、
一定以上の厚みが必要となり、厚みの薄い吸水紙を作製
することは困難であるという問題をも有している。However, the method for producing water-absorbent paper obtained by using such a conventional super-water-absorbent resin employs a method in which the super-water-absorbent resin itself is directly added to the paper. It becomes extremely difficult to uniformly add the highly water-absorbent resin powder to the entire paper surface when it is added to the paper. Therefore, there is a problem that superiority or inferiority in water absorption performance is likely to occur depending on the paper surface. Also, since the super absorbent polymer powder absorbs water when added and the particles expand and become large,
There is also a problem that it is difficult to produce a water-absorbent paper having a small thickness because a thickness of a certain thickness or more is required.
【０００４】本発明は、このような事情に鑑みなされた
もので、均一な吸水性を有し、しかも任意の厚みに設定
可能な吸水紙の製法およびそれにより得られる吸水紙の
提供をその目的とする。The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a water-absorbent paper which has uniform water absorption and can be set to an arbitrary thickness, and a water-absorbent paper obtained thereby. And
【０００５】[0005]
【課題を解決するための手段】上記の目的を達成するた
め、本発明は、紙製基材に、分子量５万〜３０万のポリ
エチレンオキシドを含浸させ、この含浸紙製基材に、電
離性放射線および活性光線の少なくとも一方を照射する
吸水紙の製法を第１の要旨とし、紙製基材に、下記の一
般式（１）で表される繰り返し単位から構成される水溶
性高分子化合物を含浸させ、この含浸紙製基材に、電離
性放射線および活性光線の少なくとも一方を照射する吸
水紙の製法を第２の要旨とする。In order to achieve the above object, the present invention is to impregnate a paper base material with polyethylene oxide having a molecular weight of 50,000 to 300,000, and to impregnate the impregnated paper base material with an ionizing property. The first gist is the method for producing a water-absorbent paper that is irradiated with at least one of radiation and actinic rays, and a water-soluble polymer compound composed of a repeating unit represented by the following general formula (1) is added to a paper base material. A second gist is a method for producing a water-absorbent paper which is impregnated and the impregnated paper base material is irradiated with at least one of ionizing radiation and actinic rays.
【化３】 [Chemical 3]
【０００６】さらに、紙製基材の繊維組織内に、水不溶
性化されたポリエチレンオキシドが含有されている吸水
紙を第３の要旨とし、紙製基材の繊維組織内に、水不溶
性化された上記の一般式（１）で表される繰り返し単位
から構成される水溶性高分子化合物が含有されている吸
水紙を第４の要旨とする。Further, a water absorbing paper containing water-insolubilized polyethylene oxide in the fiber structure of the paper base material is defined as a third gist, and the water absorption paper is made water-insoluble in the fiber structure of the paper base material. A fourth aspect is a water-absorbent paper containing a water-soluble polymer compound composed of the repeating unit represented by the general formula (1).
【０００７】[0007]
【作用】すなわち、本発明者らは、ばらつきのない均一
な吸水性能を備え、厚みの薄い吸水紙を得るための一連
の研究を重ねた。その結果、紙製基材に、特定のポリエ
チレンオキシドまたは特殊な高分子化合物を含浸させ
て、この含浸させた紙製基材に電離性放射線および活性
光線の少なくとも一方を照射すると、含浸させた上記高
分子化合物が架橋して水不溶性となり、高吸水性樹脂を
形成することを見いだし本発明に到達した。特に、上記
高分子化合物を水に溶解させ水溶液として紙製基材に含
浸させると、水媒体により高分子化合物が均一に含浸さ
れ、かつその均一状態で架橋されることになり内部で均
一な高吸水性樹脂が形成される。したがって、紙製基材
の各部分による吸水性のばらつきが生起せず、均一な吸
水性が得られる。さらに、架橋により形成される高吸水
性樹脂は、紙製基材内で連続層を成すため、強度の向上
が図れる。また、高分子化合物の水溶液により含浸させ
るという方法を採ることにより、紙製基材の厚みが制限
されず、任意の厚みの紙製基材でディッピング処理等の
加工が可能となる。That is, the present inventors have carried out a series of researches for obtaining a water absorbent paper having a uniform water absorbing performance without variation and a thin thickness. As a result, a paper base material was impregnated with a specific polyethylene oxide or a special polymer compound, and when the impregnated paper base material was irradiated with at least one of ionizing radiation and actinic rays, The present inventors have found that the polymer compound crosslinks to become water-insoluble and forms a highly water-absorbent resin, and has reached the present invention. In particular, when the above-mentioned polymer compound is dissolved in water and impregnated into a paper base material as an aqueous solution, the polymer compound is uniformly impregnated by the aqueous medium, and the polymer is cross-linked in a uniform state, so that a uniform high internal A water absorbent resin is formed. Therefore, variation in water absorption does not occur among the respective parts of the paper base material, and uniform water absorption can be obtained. Further, the superabsorbent resin formed by cross-linking forms a continuous layer in the paper base material, so that the strength can be improved. Further, by adopting the method of impregnating with the aqueous solution of the polymer compound, the thickness of the paper base material is not limited, and the dipping treatment or the like can be performed on the paper base material having an arbitrary thickness.
【０００８】つぎに、本発明を詳しく説明する。Next, the present invention will be described in detail.
【０００９】本発明の吸水紙は、紙製基材と、この紙製
基材に含浸させる特定のポリエチレンオキシドあるいは
特殊な高分子化合物を用いて得られる。The water absorbent paper of the present invention is obtained by using a paper base material and a specific polyethylene oxide or a special polymer compound impregnated in the paper base material.
【００１０】上記紙製基材としては、特に限定するもの
ではなく従来公知のものがあげられ、用途に応じて適宜
に選択され用いられる。The above-mentioned paper base material is not particularly limited and may be any conventionally known one, which is appropriately selected and used according to the application.
【００１１】上記特定のポリエチレンオキシドは、分子
量５万〜３０万のものが用いられる。すなわち、上記範
囲の分子量を有するポリエチレンオキシドを用いること
により、この線状ポリエーテルを架橋せしめた際、水不
溶性となり高吸水性樹脂に形成され優れた吸水性が得ら
れるようになる。The specific polyethylene oxide used has a molecular weight of 50,000 to 300,000. That is, by using polyethylene oxide having a molecular weight in the above range, when this linear polyether is crosslinked, it becomes insoluble in water and is formed into a highly water-absorbent resin, whereby excellent water absorption can be obtained.
【００１２】上記特殊な高分子化合物は、下記の一般式
（１）で表される繰り返し単位から構成されるものであ
る。The special polymer compound is composed of repeating units represented by the following general formula (1).
【００１３】[0013]
【化４】 [Chemical 4]
【００１４】上記式（１）中、Ｒ1 において、特にメチ
ル基，エチル基，フェニル基が好ましい。また、上記水
溶性高分子化合物の重量平均分子量は５万以上が好まし
い。より好ましくは重量平均分子量５〜３０万であり、
特に好ましくは１０万〜２０万である。このような特定
の水溶性高分子化合物は、例えば下記に示す二成分、
（Ａ）および（Ｂ）を用いて得られる。 （Ａ）活性水素基を２個有する有機化合物に、エチレン
オキシドを主体とするアルキレンオキシドを付加重合さ
せてなる重量平均分子量１０００以上のポリオキシアル
キレンポリオール。 （Ｂ）ジカルボン酸類化合物およびジイソシアネート化
合物の少なくとも一方。In the above formula (1), R 1 is particularly preferably a methyl group, an ethyl group or a phenyl group. The weight average molecular weight of the water-soluble polymer compound is preferably 50,000 or more. More preferably, the weight average molecular weight is 5 to 300,000,
Particularly preferably, it is 100,000 to 200,000. Such a specific water-soluble polymer compound, for example, two components shown below,
Obtained using (A) and (B). (A) A polyoxyalkylene polyol having a weight average molecular weight of 1000 or more obtained by addition-polymerizing an alkylene oxide mainly composed of ethylene oxide to an organic compound having two active hydrogen groups. (B) At least one of a dicarboxylic acid compound and a diisocyanate compound.
【００１５】上記（Ａ）の活性水素基を２個有する有機
化合物としては、主として、エチレングリコール、ジエ
チレングリコール、プロピレングリコール、ジプロピレ
ングリコール、１，４−ブタンジオール、１，６−ヘキ
サンジオール、ネオペンチルグリコール、ビスフェノー
ルＡ、ポリテトラメチレングリコール、シクロヘキサン
−１，４−ジメタノール等の脂環式ジオール、ブチルア
ミン、オクチルアミン、ラウリルアミン、シクロヘキシ
ルアミン、アニリン等のアミン類があげられる。これら
は単独でもしくは併せて用いられる。The organic compound having two active hydrogen groups (A) is mainly ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl. Examples thereof include glycols, bisphenol A, polytetramethylene glycol, alicyclic diols such as cyclohexane-1,4-dimethanol, and amines such as butylamine, octylamine, laurylamine, cyclohexylamine, and aniline. These may be used alone or in combination.
【００１６】また、上記活性水素基を２個有する有機化
合物に付加重合させるエチレンオキシドを含有するアル
キレンオキシドとしては、エチレンオキシド単独、エチ
レンオキシドを主体とするプロピレンオキシド，ブチレ
ンオキシド，スチレンオキシド等のアルキレンオキシド
混合物があげられる。そして、上記エチレンオキシドの
含有量は、アルキレンオキシド全体の７０重量％（以下
「％」と略す）以上に設定することが好ましい。すなわ
ち、エチレンオキシドの含有量が７０％未満では、得ら
れる高分子化合物が水難溶性となり本発明の製法におい
て紙に含浸させるのに不都合となるからである。Further, as the alkylene oxide containing ethylene oxide to be addition-polymerized to the organic compound having two active hydrogen groups, ethylene oxide alone or a mixture of alkylene oxide mainly containing ethylene oxide such as propylene oxide, butylene oxide and styrene oxide is used. can give. The content of the ethylene oxide is preferably set to 70% by weight (hereinafter abbreviated as "%") of the entire alkylene oxide. That is, when the content of ethylene oxide is less than 70%, the polymer compound obtained becomes poorly soluble in water, which is inconvenient for impregnating paper in the production method of the present invention.
【００１７】そして、上記（Ａ）は、上記各成分を用い
て、例えば、水酸化ナトリウム，水酸化カリウム等の苛
性アルカリを触媒として、約９０〜２００℃の温度で２
〜３０時間反応させて、活性水素基を２個有する有機化
合物にエチレンオキシドを含有するアルキレンオキシド
をブロックまたはランダムで付加重合させることにより
得られる。In the above (A), the above components are used at a temperature of about 90 to 200 ° C. with caustic alkali such as sodium hydroxide or potassium hydroxide as a catalyst.
It is obtained by reacting for 30 hours to add-polymerize an alkylene oxide containing ethylene oxide to an organic compound having two active hydrogen groups in a block or random manner.
【００１８】上記各成分を用いて得られる（Ａ）のポリ
オキシアルキレンポリオールは、重量平均分子量が１０
００以上が好ましく、特に好ましくは５０００〜３００
００である。すなわち、重量平均分子量が１０００未満
では、対応する上記（Ｂ）のジカルボン酸類化合物，ジ
イソシアネート化合物の連結剤の添加割合が多くなるた
め水に対する溶解性が低下する傾向がみられるからであ
る。The polyoxyalkylene polyol (A) obtained by using each of the above components has a weight average molecular weight of 10
00 or more, particularly preferably 5000 to 300
00. That is, if the weight average molecular weight is less than 1000, the proportion of the corresponding coupling agent of the dicarboxylic acid compound or diisocyanate compound of (B) added increases, and the solubility in water tends to decrease.
【００１９】上記（Ａ）と反応させる（Ｂ）のなかのジ
カルボン酸類化合物としては、ジカルボン酸，ジカルボ
ン酸無水物，ジカルボン酸の低級アルキルエステルがあ
げられる。上記ジカルボン酸としては、フタル酸，イソ
フタル酸，テレフタル酸，マロン酸，コハク酸，セバシ
ン酸，マレイン酸，フマル酸，アジピン酸，イタコン酸
等があげられ、上記ジカルボン酸無水物としては、上記
各種ジカルボン酸の無水物があげられる。また、上記ジ
カルボン酸の低級アルキルエステルとしては、上記各種
ジカルボン酸のメチルエステル，ジメチルエステル，エ
チルエステル，ジエチルエステル，プロピルエステル，
ジプロピルエステル等があげられる。これらは単独でも
しくは併せて用いられる。Examples of the dicarboxylic acid compound in (B) to be reacted with the above (A) include dicarboxylic acid, dicarboxylic anhydride, and lower alkyl ester of dicarboxylic acid. Examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, malonic acid, succinic acid, sebacic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, and the like. An anhydride of dicarboxylic acid can be used. Examples of the lower alkyl ester of the above dicarboxylic acid include methyl ester, dimethyl ester, ethyl ester, diethyl ester, propyl ester of the above various dicarboxylic acids,
Examples include dipropyl ester and the like. These may be used alone or in combination.
【００２０】上記（Ｂ）のなかのジイソシアネート化合
物としては、具体的には、トリレンジイソシアネート、
ジフェニルメタンジイソシアネート、ヘキサメチレンジ
イソシアネート、イソホロンジイソシアネート、キシレ
ンジイソシアネート、４，４−メチレン−ビス（シクロ
ヘキシールイソシアネート）等があげられる。Specific examples of the diisocyanate compound in the above (B) include tolylene diisocyanate,
Examples thereof include diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, 4,4-methylene-bis (cyclohexyl isocyanate) and the like.
【００２１】この発明における水溶性高分子化合物は、
上記（Ａ）と（Ｂ）とを用い、つぎのように反応させて
得られる。まず、（Ｂ）がジカルボン酸類化合物の場合
について述べる。すなわち、上記（Ａ）を準備し、これ
に上記（Ｂ）を添加した後、昇温させ、８０〜２５０℃
の加熱下において０．００１〜２０ｍｍＨｇの減圧にし
て脱水または脱アルコールを行うことにより得られる。
この間の反応時間としては、通常、３０分〜１０時間で
ある。The water-soluble polymer compound according to the present invention is
It is obtained by using the above (A) and (B) and reacting as follows. First, the case where (B) is a dicarboxylic acid compound will be described. That is, after preparing the above (A) and adding the above (B) thereto, the temperature is raised to 80 to 250 ° C.
It is obtained by dehydration or dealcoholation under reduced pressure of 0.001 to 20 mmHg under heating.
The reaction time during this period is usually 30 minutes to 10 hours.
【００２２】そして、上記（Ａ）と（Ｂ）とを反応させ
る際の両者の配合割合（Ａ／Ｂ）は、具体的には、当量
比で、Ａ／Ｂ＝１／１．０５〜１／３．５０の範囲に設
定することが好ましい。When the above (A) and (B) are reacted with each other, the mixing ratio (A / B) of both is, specifically, an equivalent ratio of A / B = 1 / 1.05-1. It is preferable to set in the range of /3.50.
【００２３】つぎに、上記（Ｂ）がジイソシアネート化
合物の場合を述べる。すなわち、ジイソシアネート化合
物の場合におけるウレタン化反応は、例えばポリオキシ
アルキレンポリオールとジイソシアネート化合物との配
合割合を、ＮＣＯ／ＯＨ当量比０．５〜１．５の範囲内
で混合させて、８０〜１５０℃，１〜５時間反応させる
ことにより行われる。なお、上記ウレタン化反応におい
ては、ジブチルチンジラウレート等の公知の触媒を使用
してもよい。Next, the case where the above (B) is a diisocyanate compound will be described. That is, the urethanization reaction in the case of a diisocyanate compound is carried out by mixing the compounding ratio of the polyoxyalkylene polyol and the diisocyanate compound within the NCO / OH equivalent ratio range of 0.5 to 1.5, and then at 80 to 150 ° C. , 1 to 5 hours. A known catalyst such as dibutyltin dilaurate may be used in the urethanization reaction.
【００２４】このようにして得られる水溶性高分子化合
物の重量平均分子量は、前述のように、５万以上に設定
することが好ましく、より好ましくは５万〜３０万であ
り、特に好ましくは１０万〜２０万である。すなわち、
重量平均分子量が５万未満では水に対する溶解速度は大
きいが、吸水倍率が小さく所望の条件に満たすことが困
難となる。また、重量平均分子量が３０万を超えると、
水溶液粘度が上昇し、紙に対する含浸が容易ではなくな
る傾向がみられるからである。しかも、この水溶性高分
子化合物中には、エチレンオキシド鎖が７０％以上含有
されている。このようにエチレンオキシド鎖が７０％以
上含有されているため、水溶性を有するものとなる。The weight average molecular weight of the water-soluble polymer compound thus obtained is preferably set to 50,000 or more, more preferably 50,000 to 300,000, and particularly preferably 10 as described above. It is 10,000 to 200,000. That is,
When the weight average molecular weight is less than 50,000, the dissolution rate in water is high, but the water absorption capacity is small and it becomes difficult to satisfy the desired conditions. When the weight average molecular weight exceeds 300,000,
This is because it tends to increase the viscosity of the aqueous solution and make it difficult to impregnate the paper. Moreover, 70% or more of ethylene oxide chains are contained in this water-soluble polymer compound. As described above, since the ethylene oxide chain is contained at 70% or more, it has water solubility.
【００２５】本発明の吸水紙は、上記特殊な水溶性高分
子化合物（特定のポリエチレンオキシドを含む）を用い
ての紙製基材への含浸方法は特に限定するものではない
が、例えばつぎのような三種類の方法により製造するこ
とができる。第一の方法は、上記特殊な水溶性高分子化
合物を１〜２０％の水溶液とし、抄紙時の乾燥工程にお
いて、上記水溶液を散布する方法である。ついで、特殊
な水溶性高分子化合物含浸紙製基材に電離性放射線およ
び活性光線の少なくとも一方を照射することにより上記
特殊な水溶性高分子化合物を架橋させる。このようにし
て吸水紙を製造することができる。また、第二の方法
は、上記特殊な水溶性高分子化合物水溶液に、抄紙後の
紙をディッピングし、乾燥させる方法である。ついで、
上記と同様に電離性放射線および活性光線の少なくとも
一方を照射することにより上記特殊な水溶性高分子化合
物を架橋させる。このようにして吸水紙を製造すること
ができる。さらに、第三の方法は、抄紙乾燥前の工程
で、抄紙に上記特殊な水溶性高分子化合物の粉末を散布
添加し、乾燥工程時に水溶性高分子化合物を溶融し均一
化する方法である。ついで、上記と同様に電離性放射線
および活性光線の少なくとも一方を照射することにより
上記特殊な水溶性高分子化合物を架橋させる。このよう
にして吸水紙を製造することができる。In the water-absorbent paper of the present invention, the method of impregnating the paper base material with the above-mentioned special water-soluble polymer compound (including specific polyethylene oxide) is not particularly limited. It can be manufactured by the following three kinds of methods. The first method is a method in which the above-mentioned special water-soluble polymer compound is used as a 1 to 20% aqueous solution, and the aqueous solution is sprayed in a drying step during papermaking. Then, the special water-soluble polymer compound is crosslinked by irradiating the paper base material impregnated with the special water-soluble polymer compound with at least one of ionizing radiation and actinic rays. In this way, the water absorbent paper can be manufactured. The second method is a method in which the paper after papermaking is dipped in the special aqueous solution of the water-soluble polymer compound and dried. Then,
The special water-soluble polymer compound is crosslinked by irradiating at least one of the ionizing radiation and the actinic ray in the same manner as above. In this way, the water absorbent paper can be manufactured. Furthermore, the third method is a method in which before the paper-making drying, the above-mentioned special water-soluble polymer compound powder is sprinkled and added to the paper, and the water-soluble polymer compound is melted and made uniform during the drying step. Then, the special water-soluble polymer compound is cross-linked by irradiating at least one of the ionizing radiation and the actinic ray in the same manner as above. In this way, the water absorbent paper can be manufactured.
【００２６】上記特殊な高分子化合物を含浸させた紙製
基材に照射する電離性放射線としては、例えばγ線，電
子線，Ｘ線等があげられる。また、上記活性光線として
は、紫外線等があげられる。上記電離性放射線および活
性光線の照射目的は、含浸させた水溶性高分子化合物を
架橋させ水不溶性化し高吸水性樹脂化するためである。
したがって、湿潤状態の紙に、電離性放射線および活性
光線を照射して高分子化合物を架橋せしめ高吸水性樹脂
化する方法は、吸水性に変性した樹脂が吸水し水分の乾
燥効率が低下するため好ましい方法ではない。高分子化
合物を紙に含浸させた後、乾燥させて、その後、照射を
行い架橋せしめることが好ましい。上記電離性放射線で
あるγ線および電子線の照射条件としては、線量として
１〜２０Ｍｒａｄが好ましい。すなわち、１Ｍｒａｄ未
満では、高分子化合物の架橋が不充分となり、２０Ｍｒ
ａｄを超えると、架橋密度が高くなり目的とする吸水性
能が得られないうえ高分子化合物および紙の主成分であ
るセルロースの分子切断が発生し強度が低下する傾向が
みられるからである。一方、上記活性光線の照射条件と
しては、波長は２５４ｎｍ以下に設定することが好まし
く、電離性放射線も含めて水溶性高分子化合物が架橋し
て高吸水性樹脂に形成されればよく特に限定するもので
はない。Examples of the ionizing radiation for irradiating the paper base material impregnated with the above-mentioned special polymer compound include γ rays, electron beams, X rays and the like. Examples of the actinic rays include ultraviolet rays. The purpose of irradiation with the ionizing radiation and actinic rays is to cross-link the impregnated water-soluble polymer compound to make it water-insoluble and to become a highly water-absorbent resin.
Therefore, the wet paper is irradiated with ionizing radiation and actinic rays to crosslink the polymer compound to make it a highly water-absorbent resin, because the resin modified to absorb water absorbs water and the drying efficiency of water decreases. Not the preferred method. It is preferable that paper is impregnated with the polymer compound, dried, and then irradiated to be crosslinked. As the irradiation conditions of the above-mentioned ionizing radiation, γ-rays and electron beams, the dose is preferably 1 to 20 Mrad. That is, if it is less than 1 Mrad, the crosslinking of the polymer compound becomes insufficient, and
This is because if it exceeds ad, the cross-linking density becomes high, the desired water absorption performance cannot be obtained, and molecular breakage of the polymer compound and cellulose, which is the main component of the paper, occurs and the strength tends to decrease. On the other hand, as the irradiation condition of the above-mentioned actinic rays, it is preferable to set the wavelength to 254 nm or less, as long as the water-soluble polymer compound including the ionizing radiation is cross-linked to form the super absorbent polymer, and it is not particularly limited. Not a thing.
【００２７】このようにして得られる本発明の吸水紙
は、紙製基材の繊維組織内部に前記特殊な水溶性高分子
化合物が水不溶化された、すなわち架橋構造をとるもの
が基材全体に均一に含有されており、ばらつきのない均
一な吸水性能を備えている。The water-absorbent paper of the present invention thus obtained has a water-insoluble special water-soluble polymer compound inside the fibrous structure of a paper base material, that is, a material having a crosslinked structure is formed on the entire base material. It is contained uniformly and has uniform water absorption performance without variation.
【００２８】[0028]
【発明の効果】以上のように、本発明は、紙製基材に、
特定のポリエチレンオキシドまたは特殊な水溶性高分子
化合物を含浸させて、この含浸紙製基材に電離性放射線
および活性光線の少なくとも一方を照射し、含浸させた
上記水溶性高分子化合物を水不溶化させて吸水紙を製造
するものである。すなわち、紙製基材の繊維組織内の水
溶性高分子化合物を架橋させることにより高吸水性樹脂
が形成される。このため、基材全面にばらつきのない均
一な吸水性を備えた吸水紙が得られる。特に、上記水溶
性高分子化合物を水に溶解させ水溶液として紙製基材に
含浸させると、水溶性高分子化合物が紙製基材の繊維組
織内に均一に含浸され、かつその均一状態で架橋される
ことになり均一な高吸水性樹脂が形成される。したがっ
て、従来のように紙製基材の各部分による吸水性のばら
つきが生起せず、均一な吸水性が得られる。さらに、架
橋により形成される高吸水性樹脂は、紙製基材内部で連
続層を成すため、強度の向上が図れる。また、水溶性高
分子化合物の水溶液を用いて紙製基材に含浸させるとい
う方法を採ることにより、紙製基材の厚みが制限され
ず、所望の厚み、例えば厚みの薄い紙製基材でのディッ
ピング処理等の加工が可能となる。したがって、近年、
その使用が急増しているインクジェット用印刷紙等への
応用が期待できる。As described above, the present invention provides a paper base material,
A specific polyethylene oxide or a special water-soluble polymer compound is impregnated, and the impregnated paper base material is irradiated with at least one of ionizing radiation and actinic rays to make the impregnated water-soluble polymer compound insoluble in water. To produce absorbent paper. That is, a highly water-absorbent resin is formed by crosslinking the water-soluble polymer compound in the fiber structure of the paper base material. Therefore, it is possible to obtain water-absorbent paper having uniform water-absorption on the entire surface of the base material. In particular, when the above water-soluble polymer compound is dissolved in water and impregnated into a paper base material as an aqueous solution, the water-soluble polymer compound is uniformly impregnated into the fiber structure of the paper base material and crosslinked in the uniform state. As a result, a uniform super absorbent polymer is formed. Therefore, unlike the conventional case, variations in water absorption due to the respective parts of the paper base material do not occur, and uniform water absorption can be obtained. Further, the superabsorbent resin formed by cross-linking forms a continuous layer inside the paper base material, so that the strength can be improved. Further, by adopting a method of impregnating a paper base material with an aqueous solution of a water-soluble polymer compound, the thickness of the paper base material is not limited, and a desired thickness, for example, a thin paper base material is used. It is possible to process such as dipping treatment. Therefore, in recent years
It can be expected to be applied to inkjet printing papers, etc., whose use is rapidly increasing.
【００２９】つぎに、実施例について比較例と併せて説
明する。Next, examples will be described together with comparative examples.
【００３０】[0030]
【実施例１】ポリエチレンオキシド（分子量１２０００
０）の５％水溶液を作製し、これに、密度０．４６の基
紙を５分間浸漬し、金網上で３分間放置した後、６０℃
のオーブンで６０分間乾燥させた。その後、低圧水銀ラ
ンプ（２５４ｎｍ）で２０分間照射することにより目的
とする吸水紙を得た。Example 1 Polyethylene oxide (molecular weight 12000
0) 5% aqueous solution was prepared, and a base paper having a density of 0.46 was immersed in this for 5 minutes and left on a wire mesh for 3 minutes, and then at 60 ° C.
Oven for 60 minutes. Then, irradiation with a low-pressure mercury lamp (254 nm) for 20 minutes was performed to obtain the desired water-absorbent paper.
【００３１】[0031]
【実施例２】分子量５万のポリエチレンオキシドを用い
た。それ以外は実施例１と同様にして目的とする吸水紙
を得た。Example 2 Polyethylene oxide having a molecular weight of 50,000 was used. A target water-absorbent paper was obtained in the same manner as in Example 1 except for the above.
【００３２】[0032]
【実施例３】分子量３０万のポリエチレンオキシドを用
いた。それ以外は実施例１と同様にして目的とする吸水
紙を得た。Example 3 Polyethylene oxide having a molecular weight of 300,000 was used. A target water-absorbent paper was obtained in the same manner as in Example 1 except for the above.
【００３３】[0033]
【実施例４】エチレングリコールにエチレンオキシドを
単独で付加重合させてポリエチレングリコール（分子量
１２０００）を作製した。ついで、このポリエチレング
リコール１００重量部（以下「部」と略す）に、ジメチ
ルフタレートを１．８６部加えエステル交換反応を行い
分子量１３００００の水溶性高分子化合物を得た（前記
一般式（１）で表される繰り返し単位において、Ａ，
Ｘ，Ｒ2 は下記のとおりである）。この水溶性高分子化
合物を水で５％水溶液として実施例１と同様にして基紙
に含浸させた。そして、電子線で線量５Ｍｒａｄの照射
を行うことにより目的とする吸水紙を得た。Example 4 Polyethylene glycol (molecular weight 12000) was prepared by adding and polymerizing ethylene oxide alone to ethylene glycol. Then, 1.86 parts of dimethyl phthalate was added to 100 parts by weight of this polyethylene glycol (hereinafter abbreviated as "part") to perform a transesterification reaction to obtain a water-soluble polymer compound having a molecular weight of 130000 (in the above general formula (1)). In the repeating unit represented, A,
X and R 2 are as follows). A base paper was impregnated with this water-soluble polymer compound as a 5% aqueous solution with water in the same manner as in Example 1. Then, the intended water-absorbent paper was obtained by irradiating the electron beam with a dose of 5 Mrad.
【００３４】[0034]
【化５】 [Chemical 5]
【００３５】[0035]
【実施例５】エチレングリコールにプロピレンオキシド
およびエチレンオキシドを付加重合させてポリエチレン
ポリプロピレングリコール（エチレンオキシド８５％，
プロピレンオキシド１５％，分子量２００００）を作製
した。このポリエチレンポリプロピレングリコール１０
０部に、ジフェニルメタンジイソシアネートを１．０９
部加え、８５℃で９０分間反応させて分子量１１０００
０の水溶性高分子化合物を得た（前記一般式（１）で表
される繰り返し単位において、Ａ，Ｘ，Ｒ2 は下記のと
おりである）。この水溶性高分子化合物を水で５％水溶
液として実施例１と同様にして基紙に含浸させた。そし
て、γ線で線量８Ｍｒａｄの照射を行うことにより目的
とする吸水紙を得た。Example 5 Polyethylene polypropylene glycol (ethylene oxide 85%, ethylene oxide 85%,
Propylene oxide 15%, molecular weight 20000) was prepared. This polyethylene polypropylene glycol 10
To 0 parts, 1.09 of diphenylmethane diisocyanate
Part, and reacted at 85 ° C for 90 minutes to give a molecular weight of 11,000.
A water-soluble polymer compound of 0 was obtained (in the repeating unit represented by the general formula (1), A, X and R 2 are as follows). A base paper was impregnated with this water-soluble polymer compound as a 5% aqueous solution with water in the same manner as in Example 1. Then, the target water-absorbent paper was obtained by irradiating with γ-rays at a dose of 8 Mrad.
【００３６】[0036]
【化６】 [Chemical 6]
【００３７】[0037]
【実施例６】実施例４で得られた水溶性高分子化合物
（分子量１３００００）を用い水で３％水溶液とし、実
施例１と同様にして基紙に含浸させた。その後、低圧水
銀ランプ（２５４ｎｍ）で２０分間照射することにより
目的とする吸水紙を得た。Example 6 Using the water-soluble polymer compound (molecular weight 130000) obtained in Example 4, a 3% aqueous solution was prepared with water, and the base paper was impregnated in the same manner as in Example 1. Then, irradiation with a low-pressure mercury lamp (254 nm) for 20 minutes was performed to obtain the desired water-absorbent paper.
【００３８】[0038]
【実施例７】実施例５で得られたポリエチレンポリプロ
ピレングリコール（エチレンオキシド８５％，プロピレ
ンオキシド１５％，分子量２００００）１００部に、ジ
メチルセバシン酸１．３３部を加え、エステル交換反応
を行い分子量１５００００の水溶性高分子化合物を得た
（前記一般式（１）で表される繰り返し単位において、
Ａ，Ｘ，Ｒ2 は下記のとおりである）。この水溶性高分
子化合物を水で３％水溶液として実施例１と同様にして
基紙に含浸させた。そして、γ線で線量１０Ｍｒａｄの
照射を行うことにより目的とする吸水紙を得た。Example 7 To 100 parts of polyethylene polypropylene glycol (ethylene oxide 85%, propylene oxide 15%, molecular weight 20,000) obtained in Example 5, 1.33 parts of dimethyl sebacic acid was added, and transesterification reaction was carried out to obtain a molecular weight of 150,000. A water-soluble polymer compound was obtained (in the repeating unit represented by the general formula (1),
A, X, R 2 are as follows). A base paper was impregnated with this water-soluble polymer compound as a 3% aqueous solution with water in the same manner as in Example 1. Then, the target water-absorbent paper was obtained by irradiating with γ-rays at a dose of 10 Mrad.
【００３９】[0039]
【化７】 [Chemical 7]
【００４０】[0040]
【比較例】実施例１で用いた基紙を水に５分間浸漬し、
金網上で３分間放置した。その後、これを６０℃のオー
ブンで６０分間乾燥した。Comparative Example The base paper used in Example 1 was immersed in water for 5 minutes,
It was left on the wire mesh for 3 minutes. Then, this was dried in an oven at 60 ° C. for 60 minutes.
【００４１】このようにして得られた実施例品および比
較例品の、吸水度，インク吸収性，インク滲み性，水滲
み性，引張強度，密度を測定し評価した。その結果を下
記の表１に示す。なお、上記各特性は、下記の方法に従
って測定した。The water absorption, the ink absorption, the ink bleeding property, the water bleeding property, the tensile strength, and the density of the example product and the comparative example product thus obtained were measured and evaluated. The results are shown in Table 1 below. The above characteristics were measured according to the following methods.
【００４２】〔吸水度〕クレム法による吸水度試験をＪ
ＩＳ Ｐ８１４１に準じて行った。その試験結果を、吸
水高さ（ｍｍ）で表示した。[Water Absorption] A water absorption test by Klemm method
It carried out according to ISP8141. The test result was expressed by the water absorption height (mm).
【００４３】〔インク吸収性〕市販の万年筆用インク
（パイロットインク：ブルーブラック）０．１ｍｌを紙
面からの高さ１３ｍｍのところから滴下し、完全にイン
クが吸収されるまでの時間（秒）を測定した。[Ink Absorption] 0.1 ml of commercially available fountain pen ink (pilot ink: blue black) was dropped from a height of 13 mm from the paper surface, and the time (seconds) until the ink was completely absorbed was determined. It was measured.
【００４４】〔インク滲み性〕インク吸収性試験を行っ
た後、紙面のインク着色面の面積を測定した。その測定
結果を、インク滲み性として面積（ｃｍ2 ）で表示し
た。[Ink bleeding property] After the ink absorption test, the area of the ink-colored surface of the paper was measured. The measurement result was expressed as an area (cm 2 ) as the ink bleeding property.
【００４５】〔水滲み性〕インク滲み性試験に準じて、
蒸留水を使用して同様の方法により測定した。その測定
結果を、水滲み性として面積（ｃｍ2 ）で表示した。[Water bleeding property] In accordance with the ink bleeding test,
It measured by the same method using distilled water. The measurement result was expressed as an area (cm 2 ) as water bleeding property.
【００４６】〔引張強度〕引張強度をＪＩＳ Ｐ８１１
３に準じて測定した。[Tensile Strength] Tensile strength is measured according to JIS P811.
It measured according to 3.
【００４７】〔密度〕密度の測定は、ＪＩＳ Ｐ８１１
８に準じて行った。[Density] The density is measured according to JIS P811.
It carried out according to 8.
【００４８】[0048]
【表１】 [Table 1]
【００４９】上記表１の結果から、実施例品は全て吸水
性に優れ、しかも高強度のものであることがわかる。特
に、インクおよび水の滲み性の滲み程度が小さく、これ
が素早く吸収されたことは明らかである。From the results shown in Table 1 above, it is understood that all the products of the Examples are excellent in water absorption and have high strength. In particular, the degree of bleeding of ink and water was small, and it was clear that this was absorbed quickly.
Claims (6)
エチレンオキシドを含浸させ、この含浸紙製基材に、電
離性放射線および活性光線の少なくとも一方を照射する
ことを特徴とする吸水紙の製法。1. A water absorbing material characterized in that a paper base material is impregnated with polyethylene oxide having a molecular weight of 50,000 to 300,000, and the impregnated paper base material is irradiated with at least one of ionizing radiation and actinic rays. How to make paper.
れる繰り返し単位から構成される水溶性高分子化合物を
含浸させ、この含浸紙製基材に、電離性放射線および活
性光線の少なくとも一方を照射することを特徴とする吸
水紙の製法。 【化１】 2. A paper base material is impregnated with a water-soluble polymer compound composed of a repeating unit represented by the following general formula (1), and the impregnated paper base material is subjected to ionizing radiation and activation. A method for producing water-absorbent paper, which comprises irradiating at least one of light rays. [Chemical 1]
よび（Ｂ）を反応させてなる重量平均分子量５万以上の
ものである請求項２記載の吸水紙の製法。 （Ａ）活性水素基を２個有する有機化合物にエチレンオ
キシドを主体とするアルキレンオキシドを付加重合させ
てなるポリアルキレンオキシド化合物。 （Ｂ）ジカルボン酸類化合物およびジイソシアネート化
合物の少なくとも一方。3. The method for producing water-absorbent paper according to claim 2, wherein the water-soluble polymer compound has a weight average molecular weight of 50,000 or more obtained by reacting the following (A) and (B). (A) A polyalkylene oxide compound obtained by addition-polymerizing an alkylene oxide mainly containing ethylene oxide to an organic compound having two active hydrogen groups. (B) At least one of a dicarboxylic acid compound and a diisocyanate compound.
れたポリエチレンオキシドが含有されていることを特徴
とする吸水紙。4. A water-absorbent paper, characterized in that a fibrous structure of a paper base material contains water-insoluble polyethylene oxide.
れた下記の一般式（１）で表される繰り返し単位から構
成される水溶性高分子化合物が含有されていることを特
徴とする吸水紙。 【化２】 5. A water-soluble polymer compound comprising a water-insoluble repeating unit represented by the following general formula (1) is contained in the fibrous structure of a paper base material. Water absorbent paper. [Chemical 2]
よび（Ｂ）を反応させてなる重量平均分子量５万以上の
ものである請求項５記載の吸水紙。 （Ａ）活性水素基を２個有する有機化合物にエチレンオ
キシドを主体とするアルキレンオキシドを付加重合させ
てなるポリアルキレンオキシド化合物。 （Ｂ）ジカルボン酸類化合物およびジイソシアネート化
合物の少なくとも一方。6. The water-absorbent paper according to claim 5, wherein the water-soluble polymer compound has a weight average molecular weight of 50,000 or more obtained by reacting the following (A) and (B). (A) A polyalkylene oxide compound obtained by addition-polymerizing an alkylene oxide mainly containing ethylene oxide to an organic compound having two active hydrogen groups. (B) At least one of a dicarboxylic acid compound and a diisocyanate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18805793A JPH0742093A (en) | 1993-07-29 | 1993-07-29 | Method for producing water-absorbing paper and water-absorvbing paper obtaioned thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18805793A JPH0742093A (en) | 1993-07-29 | 1993-07-29 | Method for producing water-absorbing paper and water-absorvbing paper obtaioned thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0742093A true JPH0742093A (en) | 1995-02-10 |
Family
ID=16216941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18805793A Pending JPH0742093A (en) | 1993-07-29 | 1993-07-29 | Method for producing water-absorbing paper and water-absorvbing paper obtaioned thereby |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742093A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222536A (en) * | 2009-03-25 | 2010-10-07 | Mitsubishi Chemicals Corp | Method for producing cellulose and polymer cellulose composite |
-
1993
- 1993-07-29 JP JP18805793A patent/JPH0742093A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222536A (en) * | 2009-03-25 | 2010-10-07 | Mitsubishi Chemicals Corp | Method for producing cellulose and polymer cellulose composite |
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