JP4281060B2 - Absorbent / release paper and method for producing the same - Google Patents
Absorbent / release paper and method for producing the same Download PDFInfo
- Publication number
- JP4281060B2 JP4281060B2 JP2004059189A JP2004059189A JP4281060B2 JP 4281060 B2 JP4281060 B2 JP 4281060B2 JP 2004059189 A JP2004059189 A JP 2004059189A JP 2004059189 A JP2004059189 A JP 2004059189A JP 4281060 B2 JP4281060 B2 JP 4281060B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- moisture
- absorbing
- fibers
- acidic group
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002250 absorbent Substances 0.000 title description 10
- 230000002745 absorbent Effects 0.000 title description 10
- 239000000835 fiber Substances 0.000 claims description 162
- 230000002378 acidificating effect Effects 0.000 claims description 86
- 230000003578 releasing effect Effects 0.000 claims description 69
- 238000010521 absorption reaction Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229910021645 metal ion Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 21
- 239000012784 inorganic fiber Substances 0.000 claims description 21
- -1 alkali metal salts Chemical class 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 17
- 230000008961 swelling Effects 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 239000000123 paper Substances 0.000 description 68
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000003795 desorption Methods 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 125000002560 nitrile group Chemical group 0.000 description 6
- 229910001414 potassium ion Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 229920002978 Vinylon Polymers 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 238000000954 titration curve Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000877 Melamine resin Chemical group 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- DVHXJLRODLTJOD-UHFFFAOYSA-N aminoazanium;bromide Chemical compound Br.NN DVHXJLRODLTJOD-UHFFFAOYSA-N 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000002166 wet spinning Methods 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/18—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylonitriles
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
- D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Description
本発明は高い吸放湿性と高い寸法安定性を両立した吸放湿紙およびその製造方法に関する。 The present invention relates to a moisture-absorbing / releasing paper having both high moisture-absorbing / releasing properties and high dimensional stability and a method for producing the same.
吸放湿紙、すなわち、吸放湿性を有する紙については従来から多くの研究開発がなされており、紙に吸放湿性を有する物質を含有させたものがよく知られている。吸放湿性を有する物質としては、吸放湿性を有する繊維や吸放湿性を有する微粒子が多く利用されている。一般にこのような吸放湿性を有する物質には、有機系のものと無機系のものが存在するが、前者は吸放湿性は高いが膨潤する、後者は膨潤はないが吸湿量が少ないという特徴がある。このため、高い吸放湿性と高い寸法安定性を両立した吸放湿紙を得ることは容易でない。 Much research and development has been conducted on moisture-absorbing / releasing paper, that is, paper having moisture-absorbing / releasing properties, and paper containing moisture-absorbing / releasing material is well known. As a material having moisture absorption / release properties, fibers having moisture absorption / release properties and fine particles having moisture absorption / release properties are often used. In general, there are organic and inorganic substances having such hygroscopic properties, but the former is highly hygroscopic but swells, while the latter is not swollen but has low moisture absorption. There is. For this reason, it is not easy to obtain moisture-absorbing / releasing paper having both high moisture-absorbing / releasing properties and high dimensional stability.
吸放湿性を有する繊維を利用する吸放湿紙としては、アクリル系繊維に架橋結合とカルボキシル基を導入しナトリウムイオンを付加して得られる吸放湿性繊維、ポリエステルバインダー繊維及び針葉樹パルプからなる吸放湿紙などが知られている(特許文献1参照)。上記吸放湿性繊維は、多量のカルボキシル基を含有せしめることができるため、吸放湿性が優れており、また、架橋結合によって通常の吸放湿性繊維よりも繊維の膨潤を抑制しうるものであるため、少量の使用であれば吸放湿紙の寸法安定性を保持できる。しかし、高吸湿率の吸放湿紙とするために使用量を増やした場合には、その膨潤抑制効果は十分とは言えず、寸法安定性の低下は避けられない。このため、該文献に開示されている吸放湿紙においては、バインダー繊維を多量に使用したり、さらに紙とした後に熱プレスを施したりすることで寸法安定性の向上を図っている。しかし、バインダー繊維を多く使用すると、吸放湿性繊維が融着したバインダー繊維で覆われ束縛されてしまうので、吸放湿性繊維の本来の吸放湿性が優れていても、その性能を十分に発揮させることはできず、吸放湿紙としての吸放湿性を高めることは難しい。 Moisture-absorbing / releasing paper using moisture-absorbing / releasing fibers includes moisture-absorbing / absorbing fibers obtained by adding crosslinks and carboxyl groups to acrylic fibers and adding sodium ions, polyester binder fibers, and softwood pulp. A moisture-releasing paper or the like is known (see Patent Document 1). The moisture-absorbing / releasing fibers can contain a large amount of carboxyl groups, so that they have excellent moisture-absorbing / releasing properties, and can suppress the swelling of fibers more than ordinary moisture-absorbing / releasing fibers by crosslinking. Therefore, the dimensional stability of the moisture-absorbing / releasing paper can be maintained with a small amount of use. However, when the amount used is increased in order to obtain a moisture-absorbing / releasing paper having a high moisture absorption rate, the swelling suppression effect cannot be said to be sufficient, and a reduction in dimensional stability is inevitable. For this reason, in the moisture-absorbing / releasing paper disclosed in this document, dimensional stability is improved by using a large amount of binder fibers or by applying a hot press after making the paper. However, if a large amount of binder fiber is used, the moisture absorbing / releasing fiber is covered and bound by the fused binder fiber, so even if the moisture absorbing / releasing property of the moisture absorbing / releasing fiber is excellent, its performance is fully demonstrated. Therefore, it is difficult to improve the moisture absorption / release properties of the moisture absorbent paper.
吸放湿性を有する微粒子を利用する例としては、シリカゲルやゼオライトなどの無機粒子、木材パルプ及び熱融着性繊維からなる吸放湿紙などが知られている(特許文献2参照)。該吸放湿紙は、吸放湿性を担うシリカゲルやゼオライトなどの無機粒子が吸湿しても膨潤しないため、寸法安定性の面では優れている。しかし、上述したように無機粒子は吸湿量が少ないため高吸放湿性の吸放湿紙とすることは難しく、さらに吸湿速度が遅い、放湿に高温を要す、あるいは吸放湿を繰り返すと破砕して性能低下を引き起こすなどの欠点があるため、利用分野が限られてしまうという問題を有している。
上述したように従来の技術においては、高い吸放湿性と高い寸法安定性を両立させた吸放湿紙を得ることは極めて困難なことであった。本発明の目的は、かかる問題点を克服した高い吸放湿性と高い寸法安定性を両立させる吸放湿紙およびその製造方法を提供することである。 As described above, in the prior art, it has been extremely difficult to obtain moisture-absorbing / releasing paper having both high moisture-absorbing / releasing properties and high dimensional stability. An object of the present invention is to provide a moisture-absorbing / releasing paper and a method for producing the same that can achieve both high moisture-absorbing / releasing properties and high dimensional stability that overcomes such problems.
本発明者は上述の目的を達成すべく鋭意検討を進めた結果、寸法安定性に優れた無機繊維を採用することでバインダー繊維の使用量を抑制し、加えて、吸放湿性を有する物質として架橋構造および酸性基を有する繊維を採用し、抄紙方法の工夫により抄紙後も該繊維の吸放湿性を最大限に高めた状態とすることで、高い吸放湿性と高い寸法安定性を両立させた吸放湿紙が得られることを見出し、本発明に到達した。 As a result of diligent investigation to achieve the above-mentioned object, the present inventor suppresses the amount of binder fibers used by adopting inorganic fibers having excellent dimensional stability, and in addition, as a substance having moisture absorption / release properties Adopting a fiber having a cross-linked structure and an acidic group, and making the fiber absorb and release moisture as much as possible even after papermaking by devising the papermaking method, achieving both high moisture absorption and release and high dimensional stability. The present inventors have found that a moisture-absorbing and releasing paper can be obtained, and have reached the present invention.
すなわち、本発明は以下の手段によって達成される。
(1)架橋構造および1〜10mmol/gの酸性基を有し、該酸性基にLi、Na、K、Mg、Caよりなる群から選ばれる少なくとも1種類の金属の金属イオンが1mmol/g以上結合している繊維(以下、架橋構造および酸性基を有する繊維ともいう)、無機繊維、並びにパルプ状繊維からなる吸放湿紙であり、前記酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下の水を用いて、架橋構造および酸性基を有する繊維、無機繊維、並びにパルプ状繊維を含有する水性スラリーを調製し抄紙されたものであり、かつ、架橋構造および酸性基を有する繊維が、アクリロニトリル系繊維にヒドラジン系化合物による架橋導入処理およびアルカリ金属塩による加水分解処理を施してなるアクリル酸系吸放湿性繊維であることを特徴とする吸放湿紙。
(2)架橋構造および酸性基を有する繊維の一部または全てがフィブリル化されたものであることを特徴とする(1)に記載の吸放湿紙。
(3)パルプ状繊維がフィブリル化アクリル繊維であることを特徴とする(1)または(2)に記載の吸放湿紙。
(4)20℃−65%RH雰囲気下における飽和吸湿率が15%以上であることを特徴とする(1)〜(3)のいずれかに記載の吸放湿紙。
(5)熱融着性繊維の含有量が20重量%以下であることを特徴とする(1)〜(4)のいずれかに記載の吸放湿紙。
(6)水膨潤率が50%以下であることを特徴とする(1)〜(5)のいずれかに記載の吸放湿紙。
(7)架橋構造および1〜10mmol/gの酸性基を有し、該酸性基にLi、Na、K、Mg、Caよりなる群から選ばれる少なくとも1種類の金属の金属イオンが1mmol/g以上結合している繊維、無機繊維、並びにパルプ状繊維を含有する水性スラリーの調製、並びに、該水性スラリーを用いての湿式抄紙法による抄紙工程において、前記酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下である水を使用することを特徴とする(1)〜(6)のいずれかに記載の吸放湿紙の製造方法。
That is, the present invention is achieved by the following means.
(1) It has a crosslinked structure and 1 to 10 mmol / g acidic group, and the acidic group contains at least 1 mmol / g or more of metal ions selected from the group consisting of Li, Na, K, Mg, and Ca. A cation excluding metal ions bonded to the acidic group, which is a moisture absorbent paper composed of bonded fibers (hereinafter also referred to as fibers having a crosslinked structure and acidic groups), inorganic fibers, and pulp-like fibers. An aqueous slurry containing a fiber having a crosslinked structure and an acidic group, an inorganic fiber, and a pulp-like fiber was prepared using water having a concentration of 1 ppm or less, and the paper was made and has a crosslinked structure and an acidic group. fibers, are acrylic acid type moisture absorptive and desorptive fiber consisting subjected to hydrolysis treatment with acrylonitrile fiber crosslinking introducing treatment by a hydrazine compound and an alkali metal salt Absorbing and wet paper characterized the door.
( 2 ) The moisture absorbing / releasing paper according to ( 1 ), wherein a part or all of the fiber having a crosslinked structure and an acidic group is fibrillated.
( 3 ) The moisture absorbent paper according to (1) or (2) , wherein the pulp-like fiber is a fibrillated acrylic fiber.
( 4 ) The moisture-absorbing / releasing paper according to any one of (1) to ( 3 ), wherein a saturated moisture absorption rate in a 20 ° C.-65% RH atmosphere is 15% or more.
( 5 ) The moisture-absorbing / releasing paper according to any one of (1) to ( 4 ), wherein the content of the heat-fusible fiber is 20% by weight or less.
( 6 ) The moisture absorbing / releasing paper according to any one of (1) to ( 5 ), wherein the water swelling rate is 50% or less.
( 7 ) having a crosslinked structure and 1 to 10 mmol / g acidic group, and at least 1 mmol / g or more of metal ions of at least one metal selected from the group consisting of Li, Na, K, Mg and Ca in the acidic group In the preparation of an aqueous slurry containing bonded fibers, inorganic fibers, and pulp-like fibers, and in the papermaking process by a wet papermaking method using the aqueous slurry, metal ions bonded to the acidic groups are removed. Water having a cation concentration of 1 ppm or less is used. The method for producing a moisture absorbent paper according to any one of (1) to ( 6 ).
本発明の吸放湿紙は、高い吸放湿性と高い寸法安定性を両立したものであるため、寸法維持のために吸放湿性を抑制せざるを得なかったような用途においても、高い吸放湿性を提供することが可能である。また、吸湿放湿の繰り返しによる寸法の変化が小さいため、吸放湿紙自体の耐久性が高く、除湿空調機用の吸湿素子などにも好適に使用することができる。 The moisture-absorbing / releasing paper of the present invention has both high moisture-absorbing / releasing properties and high dimensional stability. Therefore, even in applications where the moisture-absorbing / releasing properties must be suppressed to maintain the dimensions, It is possible to provide moisture release. Further, since the change in dimensions due to repeated moisture absorption and desorption is small, the moisture absorption and desorption paper itself has high durability and can be suitably used for a moisture absorption element for a dehumidifying air conditioner.
以下、本発明を詳述する。本発明の吸放湿紙は、架橋構造および1〜10mmol/gの酸性基を有し、該酸性基にLi、Na、K、Mg、Caよりなる群から選ばれる少なくとも1種類の金属の金属イオンが1mmol/g以上結合している繊維(以下、架橋構造および酸性基を有する繊維ともいう)、無機繊維、並びにパルプ状繊維からなる吸放湿紙であり、前記酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下の水を用いて、架橋構造および酸性基を有する繊維、無機繊維、並びにパルプ状繊維を含有する水性スラリーを調製し抄紙されたものである。 The present invention is described in detail below. The moisture-absorbing / releasing paper of the present invention has a cross-linked structure and an acidic group of 1 to 10 mmol / g, and the acidic group has at least one metal selected from the group consisting of Li, Na, K, Mg, and Ca. A moisture-absorbing / releasing paper composed of fibers (hereinafter also referred to as fibers having a crosslinked structure and acidic groups) in which ions are bonded at 1 mmol / g or more, inorganic fibers, and pulp-like fibers, and bonded to the acidic groups. An aqueous slurry containing a fiber having a cross-linked structure and an acidic group, an inorganic fiber, and a pulp-like fiber is prepared using water having a cation concentration excluding metal ions of 1 ppm or less, and is made into paper.
本発明にかかる架橋構造および酸性基を有する繊維は、本発明の吸放湿紙において吸放湿性を担う主成分である。該酸性基としては、カルボキシル基、スルホン酸基が代表的なものである。これらの酸性基は繊維を構成する高分子を重合する際にこれらの酸性基を含有した単量体を共重合したり、あるいはカルボキシル基の場合であれば、ニトリル基やカルボン酸エステルを含有する単量体を共重合した後に加水分解したりするなどして導入することができる。 The fiber having a crosslinked structure and an acidic group according to the present invention is a main component responsible for moisture absorption / release in the moisture absorbent paper of the present invention. Typical examples of the acidic group include a carboxyl group and a sulfonic acid group. These acidic groups copolymerize monomers containing these acidic groups when polymerizing the polymer constituting the fiber, or, in the case of carboxyl groups, contain nitrile groups or carboxylic acid esters. The monomer can be introduced by copolymerization and then hydrolysis.
また、架橋構造および酸性基を有する繊維中の酸性基量は、1〜10mmol/gであり、好ましくは3〜10mmol/g、より好ましくは3〜8mmol/gである。酸性基の量が1mmol/g未満の場合には、後述する金属イオンを少量しか結合させることができないので、十分な吸放湿性が得られないことがあり、また10mmol/gを超える場合には、吸湿時の膨潤が激しくなり吸放湿紙の寸法安定性が不十分となる、あるいは実用上満足し得る繊維物性が得られないなどの問題を起こすことがある。 Moreover, the amount of acidic groups in the fiber having a crosslinked structure and acidic groups is 1 to 10 mmol / g, preferably 3 to 10 mmol / g, more preferably 3 to 8 mmol / g. When the amount of acidic groups is less than 1 mmol / g, only a small amount of metal ions described below can be bound, so that sufficient moisture absorption / release properties may not be obtained, and when the amount exceeds 10 mmol / g. In some cases, the swelling during moisture absorption becomes severe and the dimensional stability of the moisture-absorbing / releasing paper becomes insufficient, or the fiber physical properties that are practically satisfactory cannot be obtained.
さらに、架橋構造および酸性基を有する繊維中の酸性基の少なくとも一部には、Li、Na、K、Mg、Caよりなる群から選ばれる少なくとも1種類の金属の金属イオンが結合していることが必要である。これらの金属イオンを採用することで高い吸放湿性を発現することが可能である。特に、ナトリウムイオンを採用した場合には飽和吸湿量の優れたものとすることができ、カリウムイオンを採用した場合には吸放湿速度の優れたものとすることができる。 Furthermore, at least part of the acidic groups in the fiber having a crosslinked structure and acidic groups is bound with metal ions of at least one metal selected from the group consisting of Li, Na, K, Mg, and Ca. is required. By adopting these metal ions, it is possible to exhibit high moisture absorption / release properties. In particular, when sodium ions are employed, the saturated moisture absorption amount can be excellent, and when potassium ions are employed, the moisture absorption / release rate can be excellent.
前記金属イオンの結合量は、吸放湿性を得るためには、総量で1mmol/g以上であることが望ましい。すなわち、ナトリウムイオンおよびカリウムイオンが結合している場合であれば、ナトリウムイオンおよびカリウムイオンの合計量が1mmol/g以上であることが望ましい。なお、結合量の上限については、架橋構造および酸性基を有する繊維中の酸性基に結合できる最大量である。 In order to obtain moisture absorption and desorption, the total amount of the metal ions is desirably 1 mmol / g or more. That is, if sodium ions and potassium ions are bonded, the total amount of sodium ions and potassium ions is preferably 1 mmol / g or more. In addition, about the upper limit of the coupling | bonding amount, it is the maximum amount which can couple | bond with the acidic group in the fiber which has a crosslinked structure and an acidic group.
なお、架橋構造および酸性基を有する繊維中に酸性基が1mmol/gよりも多量にある場合でも、上述したように金属イオンが1mmol/g結合していれば吸放湿性が得られる。しかし、多くの酸性基はその潜在的な吸放湿性を有効に利用されないまま存在するだけで、多量の酸性基を有することの吸放湿性に対する利点が現れない。この利点を顕在させるには酸性基全体の少なくとも50mol%以上、好ましくは70mol%以上に金属イオンが結合していることが望ましい。 In addition, even when the amount of acidic groups is greater than 1 mmol / g in the fiber having a crosslinked structure and acidic groups, moisture absorption and desorption can be obtained if the metal ions are bonded at 1 mmol / g as described above. However, many acidic groups are present without effectively utilizing their potential moisture absorption / release properties, and the advantage of having a large amount of acid groups does not appear on the moisture absorption / release properties. In order to realize this advantage, it is desirable that metal ions are bonded to at least 50 mol% or more, preferably 70 mol% or more of the entire acidic group.
上述してきた架橋構造および酸性基を有する繊維中の酸性基に結合している金属イオンは酸性基とイオン結合をしているので、紙原料を濃度1〜3重量%の水性スラリーとした後、さらに0.1〜1重量%に希釈して抄紙するといったいわゆる抄紙工程のように大量の水を使用する場合などには、該金属イオンが水中に存在する他のカチオンと交換することがある。そのため、本発明の吸放湿紙の作成にあたっては、そのような他のカチオンとの交換が起こらないように配慮する必要がある。 Since the metal ion bonded to the acidic group in the fiber having a crosslinked structure and an acidic group described above has an ionic bond with the acidic group, after making the paper raw material into an aqueous slurry having a concentration of 1 to 3% by weight, Further, when a large amount of water is used as in the so-called paper making process in which the paper is diluted to 0.1 to 1% by weight, the metal ions may exchange with other cations present in the water. For this reason, in making the moisture-absorbing / releasing paper of the present invention, it is necessary to consider such exchange with other cations.
すなわち、湿式抄紙法による場合、水性スラリーの調製およびその後の抄紙工程において、酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下の水を用いることが肝要である。ここで、酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下の水とは、例えば、酸性基にナトリウムイオンが結合している場合であれば、ナトリウムイオンを除くその他のカチオンの濃度の合計が1ppm以下の水を指す。このような水であれば、酸性基に結合している金属イオンと他のカチオンとの交換を最小限に留めることができる。これに対して、工業用水のようなカチオンを50〜100ppm程度と多く含むような水を使用すると、他のカチオンとの交換がある程度起こるので、場合によっては所期の吸放湿性が得られないことがある。 That is, in the case of the wet papermaking method, it is important to use water having a cation concentration of 1 ppm or less excluding metal ions bonded to acidic groups in the preparation of the aqueous slurry and the subsequent papermaking process. Here, water having a cation concentration of 1 ppm or less excluding metal ions bonded to acidic groups is, for example, when other ions than sodium ions are excluded if sodium ions are bonded to acidic groups. It refers to water with a total concentration of 1 ppm or less. With such water, exchange between the metal ion bonded to the acidic group and another cation can be minimized. On the other hand, if water containing a large amount of cations such as industrial water, such as about 50 to 100 ppm, is used, exchange with other cations occurs to some extent, and in some cases, the desired moisture absorption / release properties cannot be obtained. Sometimes.
酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下の水としては、蒸留水やイオン交換水を使用することを推奨する。これらは、吸放湿性に与える影響が小さく、また、工業的にも利用しやすい。なお、本発明においてイオン交換水とは導電率が3μS/cm以下の水を指す。通常、3μS/cmの場合で全カチオン濃度が0.6ppm程度である。また、蒸留水やイオン交換水に限らず、酸性基に結合している金属イオンと同じイオンのみを含む水なども使用することができる。 It is recommended to use distilled water or ion-exchanged water as water having a cation concentration of 1 ppm or less excluding metal ions bonded to acidic groups. These have little influence on moisture absorption and desorption, and are easy to use industrially. In the present invention, ion-exchanged water refers to water having a conductivity of 3 μS / cm or less. Usually, in the case of 3 μS / cm, the total cation concentration is about 0.6 ppm. Moreover, not only distilled water and ion-exchanged water but also water containing only the same ions as the metal ions bonded to the acidic group can be used.
本発明にかかる架橋構造および酸性基を有する繊維は、架橋構造によって繊維を構成する高分子同士が結び付けられているため、吸湿時の膨潤を抑制することが可能となる。 In the fiber having a crosslinked structure and an acidic group according to the present invention, since the polymers constituting the fiber are linked to each other by the crosslinked structure, swelling at the time of moisture absorption can be suppressed.
架橋構造および酸性基を有する繊維としては、アクリロニトリル系繊維にヒドラジン系化合物による架橋導入処理およびアルカリ金属塩による加水分解処理を施してなるアクリル酸系吸放湿性繊維を採用する。該繊維は、架橋構造の量およびカルボキシル基量の調節が比較的容易であり、多量のカルボキシル基を含有せしめることも可能であるため、吸放湿紙に求められる吸放湿性および寸法安定性に柔軟に対応することができる。以下に該アクリル酸系吸放湿性繊維について詳述する。
As the fiber having a cross-linked structure and an acidic group, an acrylic acid-based moisture absorbing / releasing fiber obtained by subjecting an acrylonitrile-based fiber to a cross-linking introduction treatment with a hydrazine compound and a hydrolysis treatment with an alkali metal salt is employed . The fiber is relatively easy to adjust the amount of the cross-linked structure and the amount of carboxyl groups, and can contain a large amount of carboxyl groups, so that the moisture absorption and release properties and dimensional stability required for moisture absorbent paper are improved. It can respond flexibly. The acrylic acid-based moisture absorbing / releasing fiber will be described in detail below.
アクリル酸系吸放湿性繊維の原料繊維となるアクリロニトリル系繊維としては、アクリロニトリル単独重合体またはアクリロニトリルを40重量%以上、好ましくは50重量%以上、より好ましくは80重量%以上含有するアクリロニトリル系共重合体により形成された繊維を採用することができる。なお、アクリロニトリルと共重合させる単量体については、特に制限はなく、適宜選択すればよい。 The acrylonitrile fiber used as the raw fiber of the acrylic acid-based moisture-absorbing / releasing fiber is an acrylonitrile copolymer containing acrylonitrile homopolymer or acrylonitrile in an amount of 40% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more. A fiber formed by coalescence can be employed. The monomer copolymerized with acrylonitrile is not particularly limited and may be appropriately selected.
アクリロニトリル系繊維はヒドラジン系化合物による架橋導入処理を施されるが、該処理においてはアクリロニトリル系繊維の有するニトリル基とヒドラジン系化合物の有するアミノ基が反応することによって架橋構造が形成され、繊維中の窒素含有量が増加する。この窒素含有量の増加は架橋度合の目安となるが、本発明の吸放湿紙に採用する場合、1.0〜10重量%とするのが好ましい。 The acrylonitrile fiber is subjected to a crosslinking introduction treatment with a hydrazine compound. In this treatment, a nitrile group of the acrylonitrile fiber reacts with an amino group of the hydrazine compound to form a crosslinked structure. Nitrogen content increases. This increase in nitrogen content is a measure of the degree of crosslinking, but when employed in the moisture-absorbing and releasing paper of the present invention, it is preferably 1.0 to 10% by weight.
窒素含有量の増加を1.0〜10重量%に調整し得る方法としては、上述のアクリロニトリル系繊維をヒドラジン系化合物の濃度5〜60重量%の水溶液中、温度50〜120℃で5時間以内で処理する方法が工業的に好ましい。 As a method for adjusting the increase in nitrogen content to 1.0 to 10% by weight, the above-mentioned acrylonitrile fiber is used in an aqueous solution having a hydrazine compound concentration of 5 to 60% by weight at a temperature of 50 to 120 ° C. within 5 hours. The method of treating with is industrially preferred.
ここで使用されるヒドラジン系化合物としては、特に限定はなく、水加ヒドラジンや、硫酸ヒドラジン、塩酸ヒドラジン、臭化水素酸ヒドラジン、炭酸ヒドラジンなどのヒドラジン誘導体、エチレンジアミン、硫酸グアニジン、塩酸グアニジン、リン酸グアニジン、メラミン等のアミノ基を複数含有する化合物が例示される。 The hydrazine-based compound used here is not particularly limited, and hydrazine derivatives such as hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrobromide, hydrazine carbonate, ethylenediamine, guanidine sulfate, guanidine hydrochloride, and phosphoric acid. Examples thereof include compounds containing a plurality of amino groups such as guanidine and melamine.
ヒドラジン系化合物による架橋導入処理を施された繊維は、該処理で残留したヒドラジン系化合物を十分に除去した後、酸処理を施しても良い。ここに使用する酸としては、特に限定されず、硝酸、硫酸、塩酸等の鉱酸や、有機酸等が挙げられる。該酸処理の条件としても、特に限定されないが、酸濃度3〜20重量%、好ましくは7〜15重量%の水溶液に、温度50〜120℃で0.5〜10時間被処理繊維を浸漬するといった例が挙げられる。 The fiber subjected to the cross-linking introduction treatment with the hydrazine compound may be subjected to an acid treatment after sufficiently removing the hydrazine compound remaining in the treatment. The acid used here is not particularly limited, and examples thereof include mineral acids such as nitric acid, sulfuric acid, and hydrochloric acid, and organic acids. The conditions for the acid treatment are not particularly limited, but the treated fiber is immersed in an aqueous solution having an acid concentration of 3 to 20% by weight, preferably 7 to 15% by weight, at a temperature of 50 to 120 ° C. for 0.5 to 10 hours. Examples are given.
ヒドラジン系化合物による架橋導入処理を経た繊維、或いはさらに酸処理を経た繊維は、続いてアルカリ性金属塩による加水分解処理を施される。この加水分解処理により、ヒドラジン系化合物による架橋導入処理に関与せずに残留しているニトリル基、又は架橋導入処理後酸処理を施した場合には残留しているニトリル基と一部酸処理で加水分解されて生成しているアミド基がカルボキシル基に変換されるが、該カルボキシル基には使用したアルカリ性金属塩に対応する金属イオンが結合した状態となる。 The fiber that has undergone the cross-linking introduction treatment with the hydrazine-based compound or the fiber that has undergone the acid treatment is subsequently subjected to a hydrolysis treatment with an alkaline metal salt. By this hydrolysis treatment, the nitrile group remaining without being involved in the cross-linking introduction treatment with the hydrazine-based compound, or the residual nitrile group in the case of performing the acid treatment after the cross-linking introduction treatment, is partially acid-treated. The amide group generated by hydrolysis is converted into a carboxyl group, and the carboxyl group is in a state in which a metal ion corresponding to the alkaline metal salt used is bonded.
ここで使用するアルカリ性金属塩としては、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属炭酸塩等が挙げられ、金属種としては、Li,Na,K等のアルカリ金属、Mg,Ca等のアルカリ土類金属を挙げることができる。 Examples of the alkaline metal salt used here include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, etc., and the metal species include alkali metals such as Li, Na, and K, Mg, Mention may be made of alkaline earth metals such as Ca.
加水分解処理によって生成されるカルボキシル基の量は1〜10mmol/g、好ましくは3〜10mmol/g、より好ましくは3〜8mmol/gである。カルボキシル基の量が1mmol/g未満の場合には、充分な吸放湿性が得られないことがあり、また10mmol/gを超える場合には、吸湿時の膨潤が激しくなり吸放湿紙の寸法安定性が不十分となる、あるいは実用上満足し得る繊維物性が得られないなどの問題を起こすことがある。 The amount of the carboxyl group generated by the hydrolysis treatment is 1 to 10 mmol / g, preferably 3 to 10 mmol / g, more preferably 3 to 8 mmol / g. When the amount of the carboxyl group is less than 1 mmol / g, sufficient moisture absorption / release characteristics may not be obtained. When the amount exceeds 10 mmol / g, the swelling during moisture absorption becomes severe and the dimensions of the moisture absorption / release paper. There may be problems such as insufficient stability or failure to obtain fiber properties that are practically satisfactory.
加水分解処理の条件は、必要量のカルボキシル基が生成されるように適宜設定すればよいが、好ましくは0.5〜10重量%、さらに好ましくは1〜5重量%のアルカリ性金属塩水溶液中、温度50〜120℃で1〜10時間処理する方法が工業的、繊維物性的にも好ましい。なお、加水分解処理を経た繊維は、ニトリル基が残留していてもいなくてもよい。ニトリル基が残留していれば、その反応性を利用して、さらなる機能を付与できる可能性がある。 The conditions for the hydrolysis treatment may be appropriately set so that a necessary amount of carboxyl groups is generated, but preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight in an aqueous alkaline metal salt solution, A method of treating at a temperature of 50 to 120 ° C. for 1 to 10 hours is preferable from an industrial and fiber property viewpoint. The fiber that has undergone the hydrolysis treatment may or may not have a nitrile group remaining. If the nitrile group remains, there is a possibility that a further function can be imparted using its reactivity.
加水分解処理を施された繊維は、必要に応じ金属塩を用いてカルボキシル基に結合させる金属イオンを調整する処理を行っても良い。かかる金属イオン調整処理に採用される金属塩の金属種としては、Li、Na、K、Ca、Mgから選ばれるが、Na、K、Caが特に推奨される。また、該処理に用いる塩の種類としては、これらの金属の水溶性塩であれば良く、例えば水酸化物,ハロゲン化物,硝酸塩,硫酸塩,炭酸塩等が挙げられる。具体的には、夫々の金属で代表的なものとして、Na塩としてはNaOH、Na2CO3、K塩としてはKOH、Ca塩としてはCa(OH)2、Ca(NO3)2、CaCl2が好適である。 The fiber subjected to the hydrolysis treatment may be subjected to a treatment for adjusting a metal ion to be bonded to a carboxyl group using a metal salt, if necessary. The metal species of the metal salt employed in the metal ion adjustment treatment is selected from Li, Na, K, Ca, and Mg, and Na, K, and Ca are particularly recommended. The salt used for the treatment may be a water-soluble salt of these metals, and examples thereof include hydroxides, halides, nitrates, sulfates and carbonates. Specifically, as typical metals, NaOH, Na 2 CO 3 as Na salt, KOH as K salt, Ca (OH) 2 , Ca (NO 3 ) 2 , CaCl as Ca salt 2 is preferred.
なお、既述したとおり、アクリル酸系吸放湿性繊維のカルボキシル基に結合させる金属イオンは、飽和吸湿量を高くしたい場合にはナトリウムイオン、吸放湿速度を高くしたい場合にはカリウムイオンとすることが望ましい。 In addition, as described above, the metal ion to be bonded to the carboxyl group of the acrylic acid-based moisture-absorbing / releasing fiber is sodium ion for increasing the saturated moisture absorption amount, and potassium ion for increasing the moisture absorption / release rate. It is desirable.
また、アクリル酸系吸放湿性繊維は上述してきたヒドラジン系化合物による架橋導入処理、酸処理、アルカリ金属塩による加水分解処理、金属イオン調整処理以外に、さらに別の処理を施したものであっても構わないし、架橋導入処理と加水分解処理を同時に施したものであっても構わない。 Further, the acrylic acid-based moisture-absorbing / releasing fiber has been subjected to further treatment in addition to the above-described cross-linking introduction treatment with a hydrazine-based compound, acid treatment, hydrolysis treatment with an alkali metal salt, and metal ion adjustment treatment. Alternatively, the cross-linking introduction treatment and the hydrolysis treatment may be performed at the same time.
さらに、本発明にかかる架橋構造および酸性基を有する繊維はその一部または全てがフィブリル化されたものであることがより望ましい。架橋構造および酸性基を有する繊維の一部または全てがフィブリル化されたものであれば、抄紙した際に繊維同士の絡み合いがより強固となり、得られる吸放湿紙を寸法安定性のより優れたものとすることができる。また、繊維が細分化されることにより表面積が大きくなるので、吸湿速度も向上させることができる。なお、上述したアクリル酸系吸放湿性繊維について、フィブリル化されたものを得る方法としては、上述の方法で得られたアクリル酸系吸放湿性繊維を直接フィブリル化する方法のほかに、原料繊維であるアクリロニトリル系繊維をフィブリル化した後に上述した処理を施す方法を採用することができる。 Furthermore, it is more desirable that a part or all of the fiber having a crosslinked structure and acidic group according to the present invention is fibrillated. If some or all of the fibers having a cross-linked structure and acidic groups are fibrillated, the entanglement between fibers becomes stronger when paper is made, and the resulting moisture-absorbing paper is more excellent in dimensional stability. Can be. Further, since the surface area is increased by subdividing the fibers, the moisture absorption rate can be improved. In addition, as a method for obtaining the fibrillated fiber for the above-described acrylic acid-based moisture-absorbing / releasing fiber, in addition to the method for directly fibrillating the acrylic acid-based moisture-absorbing / releasing fiber obtained by the above method, raw fiber It is possible to employ a method in which the above-described treatment is performed after fibrillation of the acrylonitrile-based fiber.
フィブリル化の方法としては特に制限はなく、通常の叩解方法を採用することができる。代表的な例としては、ビーターやリファイナーなどの叩解機を用いてフィブリル化する方法が挙げられる。 There is no restriction | limiting in particular as the method of fibrillation, A normal beating method can be employ | adopted. A typical example is a fibrillation method using a beater such as a beater or refiner.
以上、架橋構造および酸性基を有する繊維について述べてきたが、上述したような架橋構造および酸性基を有する繊維であっても、吸放湿や加熱などによってある程度の寸法変化が起こる。このため、高い寸法安定性を発現させようとする本発明の吸放湿紙を架橋構造および酸性基を有する繊維のみで構成することは極めて困難である。そこで本発明では、高い寸法安定性を発現させる方策として、無機繊維を併用する。無機繊維は吸放湿や加熱などによる寸法変化が極めて小さく、吸放湿紙の寸法安定性を向上させるうえで極めて有効である。このような無機繊維としては、特に限定はなく、ガラス繊維、炭素繊維、アルミナ繊維、金属繊維などが例示される。 As mentioned above, although the fiber which has a crosslinked structure and an acidic group has been described, even if it is a fiber which has a crosslinked structure and an acidic group as mentioned above, a certain amount of dimensional change occurs by moisture absorption / release or heating. For this reason, it is extremely difficult to construct the moisture-absorbing / releasing paper of the present invention, which is intended to exhibit high dimensional stability, only with fibers having a crosslinked structure and acidic groups. Therefore, in the present invention, inorganic fibers are used in combination as a measure for developing high dimensional stability. Inorganic fibers are extremely effective in improving the dimensional stability of moisture-absorbing / releasing paper, since the dimensional change due to moisture-absorbing / releasing and heating is extremely small. Such inorganic fibers are not particularly limited, and examples thereof include glass fibers, carbon fibers, alumina fibers, and metal fibers.
本発明においては、架橋構造および酸性基を有する繊維と無機繊維に加えてパルプ状繊維を使用する。パルプ状繊維を使用しなければ、繊維同士の絡み合いが不十分となり、各繊維の拘束が緩くなってしまうので、上述した無機繊維の寸法安定の効果が現れにくくなり、場合によっては紙とすることが困難となる。該パルプ状繊維としては、特に限定はなく、針葉樹パルプ、広葉樹パルプなどの木材パルプ、麻パルプ、コットンパルプ、ケナフパルプなどの非木材パルプ、レーヨン、ビニロン、アクリルなどの合成繊維をフィブリル化したものなどを採用することができる。なかでも、アクリルパルプを採用した場合には、セルロース系のパルプに比べて耐水性が増し、含水時の強度が高い紙を得ることができるため、吸湿放湿を繰り返すような耐久性を求められる用途に好適である。 In the present invention, a pulp-like fiber is used in addition to a fiber having a crosslinked structure and an acidic group and an inorganic fiber. If pulp-like fibers are not used, the entanglement between the fibers will be insufficient, and the restraint of each fiber will be loosened. It becomes difficult. The pulp fiber is not particularly limited, and wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as hemp pulp, cotton pulp and kenaf pulp, and fibrillated synthetic fiber such as rayon, vinylon and acrylic. Can be adopted. In particular, when acrylic pulp is used, water resistance increases compared to cellulosic pulp, and a paper having high strength when containing water can be obtained, so durability such as repeated moisture absorption and desorption is required. Suitable for use.
なお、上述したフィブリル化させた架橋構造および酸性基を有する繊維もパルプ状繊維として使用できることは言うまでもない。この場合、実質的に吸放湿紙を構成する架橋構造および酸性基を有する繊維の量が多くなるので、高い吸放湿性を発現させることが可能となる。さらに、架橋構造および酸性基を有する繊維およびパルプ状繊維の両方にフィブリル化させた架橋構造および酸性基を有する繊維を採用すれば、より吸放湿性を高めることができる上、寸法安定性を向上させることも可能となる。 Needless to say, the fibrillated cross-linked structure and the fiber having an acidic group can also be used as the pulp-like fiber. In this case, since the amount of the fiber having a cross-linked structure and an acidic group that substantially constitute the moisture-absorbing / releasing paper is increased, it is possible to exhibit high moisture-absorbing / releasing properties. Furthermore, if the cross-linked structure and the fiber having the acidic group and the fiber having the acidic group are fibrillated in both the fiber having the cross-linked structure and the acidic group, the moisture absorption and release can be further improved and the dimensional stability is improved. It is also possible to make it.
以上、本発明の吸放湿紙の構成成分である、架橋構造および酸性基を有する繊維、無機繊維、並びにパルプ状繊維について述べてきたが、各構成成分の使用割合は、一般的には、架橋構造および酸性基を有する繊維が5〜80重量%、無機繊維が10〜40重量%、パルプ状繊維が10〜55重量%とするのが望ましい。これらの範囲内を外れると、高い吸放湿性と高い寸法安定性を両立できなくなることがある。 As described above, the fiber having a crosslinked structure and an acidic group, the inorganic fiber, and the pulp-like fiber, which are constituents of the moisture-absorbing and releasing paper of the present invention, have been described. It is desirable that the fiber having a crosslinked structure and an acidic group is 5 to 80% by weight, the inorganic fiber is 10 to 40% by weight, and the pulp-like fiber is 10 to 55% by weight. Outside these ranges, it may be impossible to achieve both high moisture absorption and release and high dimensional stability.
また、より高い寸法安定性が望まれる場合には、上述した構成に加えて熱融着性繊維を使用することも可能である。熱融着性繊維としては、特に限定はなく、ポリエステル、ポリエチレン、ポリプロピレン、ポリアミド、ビニロンなどの合成繊維などを採用することができる。ただし、熱融着性繊維は、熱融着させた際に架橋構造および酸性基を有する繊維を覆ったり束縛したりするなどして少なからず吸放湿性を低下させるので、その使用には十分な注意が必要であり、できれば使用しないことが望ましい。止むを得ず使用する場合であっても、その使用量としては20重量%以下、より好ましくは10重量%以下、さらに好ましくは5重量%以下に留めることが望ましい。 Further, in the case where higher dimensional stability is desired, it is possible to use a heat-fusible fiber in addition to the above-described configuration. The heat-fusible fiber is not particularly limited, and synthetic fibers such as polyester, polyethylene, polypropylene, polyamide, and vinylon can be used. However, the heat-fusible fiber is not sufficient for its use because it reduces the moisture absorption / release property by covering or constraining the fiber having a crosslinked structure and an acidic group when heat-sealing. Care should be taken and it is desirable not to use it if possible. Even when it is unavoidably used, it is desirable that the amount used be 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less.
なお、本発明の吸放湿紙には、上述した架橋構造および酸性基を有する繊維、無機繊維、パルプ状繊維および熱融着性繊維のほかに、その他の天然繊維や合成繊維などを併用しても構わないことは言うまでもない。 The moisture-absorbing / releasing paper of the present invention uses other natural fibers or synthetic fibers in addition to the above-mentioned fibers having a crosslinked structure and acidic groups, inorganic fibers, pulp-like fibers, and heat-fusible fibers. It goes without saying that it doesn't matter.
また、本発明の吸放湿紙の飽和吸湿率としては、20℃−65%RH雰囲気下で15%以上、より好ましくは20%以上であることが望ましい。飽和吸湿率が15%以下では、吸放湿紙としてはあまり有用ではなくなる。さらに、本発明の吸放湿紙の水膨潤率としては50%以下、より好ましくは40%以下であることが望ましい。水膨潤率が50%以上の場合、吸湿時と放湿時の寸法の変化が大きくなりすぎるため、使用できない用途が多くなる。なお、本発明にいう飽和吸湿率および水膨潤率は後述する測定方法により求められるものである。 The saturated moisture absorption rate of the moisture-absorbing / releasing paper of the present invention is preferably 15% or more, more preferably 20% or more in a 20 ° C.-65% RH atmosphere. When the saturated moisture absorption is 15% or less, it is not very useful as a moisture absorbent paper. Furthermore, the water swelling rate of the moisture-absorbing / releasing paper of the present invention is preferably 50% or less, more preferably 40% or less. When the water swelling rate is 50% or more, the change in dimensions at the time of moisture absorption and moisture release becomes too large, so that there are many applications that cannot be used. In addition, the saturated moisture absorption rate and water swelling rate said to this invention are calculated | required by the measuring method mentioned later.
次に本発明の吸放湿紙の製造方法について説明する。一般的には以下のような湿式抄紙法を採用することができる。 Next, the manufacturing method of the moisture absorption / release paper of this invention is demonstrated. In general, the following wet papermaking methods can be employed.
まず、架橋構造および1〜10mmol/gの酸性基を有し、該酸性基にLi、Na、K、Mg、Caよりなる群から選ばれる少なくとも1種類の金属の金属イオンが1mmol/g以上結合している繊維、無機繊維、並びにパルプ状繊維を水中に均一に混合分散し、水性スラリーとする。次いで、該水性スラリーを、円網、短網、長網、あるいはこれらの複合マシーンなどの抄紙機を用いて抄紙する。抄紙後、シリンダードライヤー、ヤンキードライヤー、エアードライヤーなどの通常の乾燥機を用いて乾燥することにより本発明の吸放湿紙を得ることができる。ここで、水性スラリーおよび抄紙工程に使用する水としては既述したように酸性基に結合している金属イオンを除いたカチオン濃度が1ppm以下である水を使用するが、なかでもイオン交換水または蒸留水を使用するのが好ましい。 First, it has a crosslinked structure and an acidic group of 1 to 10 mmol / g, and metal ions of at least one metal selected from the group consisting of Li, Na, K, Mg, and Ca are bonded to the acidic group in an amount of 1 mmol / g or more. The fibers, inorganic fibers, and pulp fibers are uniformly mixed and dispersed in water to form an aqueous slurry. Next, the aqueous slurry is subjected to paper making using a paper machine such as a circular net, a short net, a long net, or a composite machine thereof. After paper making, the moisture-absorbing / releasing paper of the present invention can be obtained by drying using a normal dryer such as a cylinder dryer, Yankee dryer or air dryer. Here, as the water used in the aqueous slurry and the papermaking process, as described above, water having a cation concentration of 1 ppm or less excluding metal ions bonded to acidic groups is used. It is preferred to use distilled water.
なお、上述した製造方法においては、水性スラリーに、その他の繊維や通常の湿式抄紙で用いる粘剤、サイズ剤、染料、紙力増強剤などを添加しても構わない。また、必要に応じて、填料の流失を抑制するために定着剤を添加することもできる。この定着剤としては、ポリエチレンイミン変性物、ポリアクリルアミド変性物、アルギン酸ナトリウム、アラビアゴム、陽性デンプン、硫酸アルミニウム、カリミョウバンなどを挙げることができる。
In the above-described production method, other fibers, a sticking agent used in normal wet papermaking, a sizing agent, a dye, a paper strength enhancer, and the like may be added to the aqueous slurry. If necessary, a fixing agent can be added in order to suppress the loss of the filler. Examples of the fixing agent include polyethyleneimine modified products, polyacrylamide modified products, sodium alginate, gum arabic, positive starch, aluminum sulfate, and potassium alum.
以下実施例により本発明を具体的に説明するが、これらはあくまでも例示的なものであり、本発明の要旨はこれらにより限定されるものではない。なお、実施例中の部及び百分率は、断りのない限り重量基準で示す。また、実施例中のイオン交換水はカチオン濃度0.6ppmのものである。以下に実施例中の測定方法、評価方法を示す。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, these are merely illustrative, and the gist of the present invention is not limited thereto. In addition, unless otherwise indicated, the part and percentage in an Example are shown on a weight basis. In addition, the ion-exchanged water in the examples has a cation concentration of 0.6 ppm. The measurement methods and evaluation methods in the examples are shown below.
(1)酸性基量(全カルボキシル基量)
十分乾燥した試料約1gを精秤し(W1[g])、これに200mlの水を加えた後、50℃に加温しながら1mol/l塩酸水溶液を添加してpH2にし、次いで0.1mol/l水酸化ナトリウム水溶液で常法に従って滴定曲線を求めた。該滴定曲線からカルボキシル基に消費された水酸化ナトリウム水溶液消費量(V1[ml])を求め、次式によって全カルボキシル基量(A1[mmol/g])を算出した。
全カルボキシル基量[mmol/g]=0.1×V1/W1
(1) Amount of acidic groups (total amount of carboxyl groups)
About 1 g of a well-dried sample is precisely weighed (W1 [g]), 200 ml of water is added thereto, 1 mol / l hydrochloric acid aqueous solution is added to the mixture while being heated to 50 ° C. to pH 2, and then 0.1 mol A titration curve was determined according to a conventional method with an aqueous / 1 sodium hydroxide solution. From the titration curve, the amount of aqueous sodium hydroxide consumed (V1 [ml]) consumed by carboxyl groups was determined, and the total amount of carboxyl groups (A1 [mmol / g]) was calculated according to the following equation.
Total carboxyl group amount [mmol / g] = 0.1 × V1 / W1
(2)金属イオン結合カルボキシル基量
上述の全カルボキシル基量測定操作中の1mol/l塩酸水溶液添加によるpH2への調整をすることなく同様に滴定曲線を求め、試料中に含まれるH型カルボキシル基(COOH)の量(A2[mmol/g])を求めた。これらの結果から次式により金属イオン結合カルボキシル基量を算出した。
金属イオン結合カルボキシル基量[mmol/g]=A1−A2
(2) Amount of metal ion-bonded carboxyl groups The titration curve was determined in the same manner without adjusting to pH 2 by adding a 1 mol / l aqueous hydrochloric acid solution during the above total carboxyl group content measurement procedure, and H-type carboxyl groups contained in the sample. The amount of (COOH) (A2 [mmol / g]) was determined. From these results, the amount of carboxyl groups bound to metal ions was calculated by the following formula.
Metal ion bond carboxyl group amount [mmol / g] = A1-A2
(3)金属イオン量
十分乾燥した試料を精秤した後、湿式分解し、原子吸光法を用いて金属イオン量を求めた
。
(3) The amount of metal ions was precisely weighed and then wet-decomposed, and the amount of metal ions was determined using an atomic absorption method.
(4)飽和吸湿率
試料約5.0gを絶乾し、重量を測定する(W2[g])。次に該試料を温度20℃で65%RHの恒湿槽に24時間入れておく。このようにして吸湿した試料の重量を測定する(W3[g])。以上の測定結果から、次式によって算出した。
飽和吸湿率[%]=(W3−W2)/W2×100
(4) About 5.0 g of saturated moisture absorption sample is absolutely dried and the weight is measured (W2 [g]). Next, the sample is placed in a constant humidity bath at a temperature of 20 ° C. and 65% RH for 24 hours. The weight of the sample thus absorbed is measured (W3 [g]). From the above measurement results, calculation was performed according to the following equation.
Saturated moisture absorption [%] = (W3-W2) / W2 × 100
(5)水膨潤率
試料を絶乾し、厚みを測定する(T1)。該試料を水に24時間浸漬した後、遠心脱水機(国産遠心機(株)社製TYPE H−770A)で遠心加速度160G(Gは重力加速度を示す)下2分間脱水し、再度厚みを測定する(T2)。これらの測定値から、次式によって算出した。
水膨潤率[%]=(T2−T1)/T1×100
(5) The water swelling rate sample is absolutely dried and the thickness is measured (T1). The sample was immersed in water for 24 hours, then dehydrated with a centrifugal dehydrator (TYPE H-770A manufactured by Kokusan Centrifuge Co., Ltd.) for 2 minutes under a centrifugal acceleration of 160G (G indicates gravitational acceleration), and the thickness was measured again. (T2). From these measured values, it calculated by the following formula.
Water swelling rate [%] = (T2-T1) / T1 × 100
また、実施例中の架橋構造および酸性基を有する繊維およびアクリルパルプの作成方法は以下のとおりである。 Moreover, the preparation method of the fiber and acrylic pulp which have a crosslinked structure and an acidic group in an Example is as follows.
<架橋構造および酸性基を有する繊維A>
アクリロニトリル90重量%、酢酸ビニル10重量%からなるアクリロニトリル系重合体10部を48%のチオシアン酸ナトリウム水溶液90部に溶解した紡糸原液を、常法に従って紡糸、延伸(全延伸倍率:10倍)した後、乾球/湿球=120℃/60℃の雰囲気下で乾燥後、湿熱処理、カットを経て、繊維長7mm、単繊維繊度0.9dtexの原料繊維aを得た。原料繊維aに、ヒドラジンの20重量%水溶液中で、98℃×5Hr架橋導入処理を行い、水洗した。次に、硝酸の3重量%水溶液中、90℃×2Hr酸処理を行った。続いて水酸化ナトリウムの1重量%水溶液中で、90℃×2Hr加水分解処理を行い、イオン交換水で洗浄し、架橋構造および酸性基を有する繊維Aの繊維を得た。該繊維は酸性基量が1.2mmol/g、金属イオン結合カルボキシル基量が1.1mmol/g、ナトリウムイオン量が1.1mmol/gであった。
<Fiber A having cross-linked structure and acidic group>
A spinning stock solution in which 10 parts of an acrylonitrile polymer consisting of 90% by weight of acrylonitrile and 10% by weight of vinyl acetate was dissolved in 90 parts of a 48% aqueous sodium thiocyanate solution was spun and stretched according to a conventional method (total stretching ratio: 10 times). Thereafter, after drying in an atmosphere of dry bulb / wet bulb = 120 ° C./60° C., through wet heat treatment and cutting, a raw fiber a having a fiber length of 7 mm and a single fiber fineness of 0.9 dtex was obtained. The raw fiber a was subjected to 98 ° C. × 5 Hr cross-linking introduction treatment in a 20 wt% aqueous solution of hydrazine and washed with water. Next, 90 ° C. × 2 Hr acid treatment was performed in a 3 wt% aqueous solution of nitric acid. Subsequently, hydrolysis was performed at 90 ° C. × 2 Hr in a 1% by weight aqueous solution of sodium hydroxide and washed with ion-exchanged water to obtain a fiber of fiber A having a crosslinked structure and acidic groups. The fiber had an acid group amount of 1.2 mmol / g, a metal ion-bonded carboxyl group amount of 1.1 mmol / g, and a sodium ion amount of 1.1 mmol / g.
<架橋構造および酸性基を有する繊維B>
原料繊維aの加水分解処理において水酸化カリウムの3重量%水溶液で処理した以外は、架橋構造および酸性基を有する繊維Aと同様の方法により、架橋構造および酸性基を有する繊維Bを得た。該繊維は酸性基量が6.1mmol/g、金属イオン結合カルボキシル基量が5.4mmol/g、カリウムイオン量が5.3mmol/gであった。
<Fiber B having cross-linked structure and acidic group>
A fiber B having a crosslinked structure and an acidic group was obtained in the same manner as the fiber A having a crosslinked structure and an acidic group, except that the raw material fiber a was hydrolyzed with a 3% by weight aqueous solution of potassium hydroxide. The fiber had an acid group amount of 6.1 mmol / g, a metal ion-bonded carboxyl group amount of 5.4 mmol / g, and a potassium ion amount of 5.3 mmol / g.
<架橋構造および酸性基を有する繊維C>
原料繊維aの加水分解処理において水酸化ナトリウムの10重量%水溶液で処理した以外は、架橋構造および酸性基を有する繊維Aと同様の方法により、架橋構造および酸性基を有する繊維Cを得た。該繊維は酸性基量が8.8mmol/g、金属イオン結合カルボキシル基量が7.7mmol/g、ナトリウムイオン量が7.9mmol/gであった。
<Fiber C having crosslinked structure and acidic group>
A fiber C having a crosslinked structure and an acidic group was obtained in the same manner as the fiber A having a crosslinked structure and an acidic group, except that the raw material fiber a was hydrolyzed with a 10% by weight aqueous solution of sodium hydroxide. The fiber had an acid group amount of 8.8 mmol / g, a metal ion-bonded carboxyl group amount of 7.7 mmol / g, and a sodium ion amount of 7.9 mmol / g.
<架橋構造および酸性基を有する繊維D>
アクリロニトリル98重量%、アクリル酸2重量%からなるアクリロニトリル系重合体10部を48%のロダンソーダ水溶液90部に溶解した紡糸原液を、常法に従い湿式紡糸法にて単繊維繊度0.9dtexの原料繊維dを得た。次いで、原料繊維dを5mmにカットした後、熊谷理機工業(株)製ナイヤガラ式ビーター(タイプBE−10)を用い叩解し、カナダ標準濾水度180mlのフィブリル化原料繊維dを作成した。フィブリル化原料繊維dに、ヒドラジンの20重量%水溶液中で、98℃×5Hr架橋導入処理を行い、水洗した。次に、硝酸の3重量%水溶液中、90℃×2Hr酸処理を行った。続いて水酸化カリウムの3重量%水溶液中で、90℃×2Hr加水分解処理を行い、イオン交換水で洗浄し、架橋構造および酸性基を有する繊維Dを得た。該繊維は酸性基量が5.8mmol/g、金属イオン結合カルボキシル基量が5.2mmol/g、カリウムイオン量が5.3mmol/g含有していた。
<Fiber D having cross-linked structure and acidic group>
A raw material fiber having a single fiber fineness of 0.9 dtex is obtained by dissolving a spinning stock solution obtained by dissolving 10 parts of acrylonitrile-based polymer composed of 98% by weight of acrylonitrile and 2% by weight of acrylic acid in 90 parts of a 48% rhodium soda aqueous solution by a wet spinning method according to a conventional method. d was obtained. Next, the raw fiber d was cut into 5 mm, and then beaten using a Niagara-type beater (type BE-10) manufactured by Kumagai Riki Kogyo Co., Ltd. to prepare a fibrillated raw fiber d having a Canadian standard freeness of 180 ml. The fibrillated raw fiber d was subjected to 98 ° C. × 5 Hr cross-linking introduction treatment in a 20 wt% aqueous solution of hydrazine and washed with water. Next, 90 ° C. × 2 Hr acid treatment was performed in a 3 wt% aqueous solution of nitric acid. Subsequently, a hydrolysis treatment was performed at 90 ° C. × 2 Hr in a 3 wt% aqueous solution of potassium hydroxide and washed with ion-exchanged water to obtain a fiber D having a crosslinked structure and an acidic group. The fiber contained an acid group amount of 5.8 mmol / g, a metal ion-bonded carboxyl group amount of 5.2 mmol / g, and a potassium ion amount of 5.3 mmol / g.
[実施例1〜5]
表1に示す割合の架橋構造および酸性基を有する繊維、無機繊維、パルプ状繊維および熱融着性繊維を、イオン交換水中に分散させ、濃度0.5%の水性スラリーを作成した。作成した水性スラリーを熊谷理機工業(株)製角型シートマシンを用いて抄紙した後、濾紙の間に挟み、熊谷理機工業(株)製ロータリードライヤーを用いて、145℃で乾燥させることで吸放湿紙を作成した。得られた吸放湿紙について、寸法安定性の指標として水膨潤率を、吸放湿性の指標として飽和吸湿率を測定した。これらの評価結果を表1に示す。なお、表中の無機繊維、パルプ状繊維および熱融着性繊維の詳細は以下のとおりである。
・ガラス繊維:繊維径6μm、繊維長6mm
・Bi-PUL:日本エクスラン工業(株)製アクリルパルプ、カナダ標準濾水度150ml
・針葉樹クラフトパルプ:カナダ標準濾水度600ml
・VPB-105:(株)クラレ製ビニロンバインダー繊維、繊度1T、繊維長3mm
[Examples 1 to 5]
Fibers having a crosslinked structure and acidic groups in the proportions shown in Table 1, inorganic fibers, pulp-like fibers and heat-fusible fibers were dispersed in ion-exchanged water to prepare an aqueous slurry having a concentration of 0.5%. Papermaking the prepared aqueous slurry using a square sheet machine manufactured by Kumagaya Riki Kogyo Co., Ltd., sandwiching between the filter papers, and drying at 145 ° C. using a rotary dryer manufactured by Kumagaya Riki Kogyo Co., Ltd. A moisture-absorbing / releasing paper was prepared. With respect to the obtained moisture absorbing / releasing paper, the water swelling rate was measured as an index of dimensional stability, and the saturated moisture absorption rate was measured as an index of moisture absorbing / releasing property. These evaluation results are shown in Table 1. In addition, the detail of the inorganic fiber in the table | surface, a pulp-like fiber, and a heat-fusible fiber is as follows.
・ Glass fiber: Fiber diameter 6μm, fiber length 6mm
・ Bi-PUL: Nippon Exlan Industrial Co., Ltd. acrylic pulp, Canadian standard freeness 150ml
・ Conifer kraft pulp: Canadian standard freeness 600ml
・ VPB-105: Kuraray Co., Ltd. vinylon binder fiber, fineness 1T, fiber length 3mm
実施例1〜5の吸放湿紙はいずれも水膨潤率が低く、飽和吸湿率の高いものであった。特に実施例5の吸放湿紙は、架橋構造および酸性基を有する繊維としてフィブリル化されたものを使用しており、繊維同士の絡み合いが強いため、同等の飽和吸湿率を有する実施例2の吸放湿紙に比べて、水膨潤率がより低くなったものと思われる。 All of the moisture absorbent papers of Examples 1 to 5 had a low water swelling rate and a high saturated moisture absorption rate. In particular, the moisture-absorbing / releasing paper of Example 5 uses a fibrillated fiber having a cross-linked structure and an acidic group, and since the entanglement of the fibers is strong, the moisture absorption paper of Example 2 having an equivalent saturated moisture absorption rate. It seems that the water swelling rate is lower than that of moisture-absorbing and releasing paper.
[比較例1〜3]
実施例1〜5と同様にして、表2に示す割合の架橋構造および酸性基を有する繊維、無機繊維、パルプ状繊維および熱融着性繊維から吸放湿紙を作成した。得られた吸放湿紙の評価結果を表2に示す。なお、比較例3については、イオン交換水に代えて工業用水を使用した。
[Comparative Examples 1-3]
In the same manner as in Examples 1 to 5, moisture-absorbing and releasing paper was prepared from fibers having a cross-linked structure and acidic groups, inorganic fibers, pulp-like fibers, and heat-fusible fibers in the proportions shown in Table 2. Table 2 shows the evaluation results of the moisture absorbent paper obtained. In addition, about the comparative example 3, it replaced with ion-exchange water and used industrial water.
比較例1では、パルプ状繊維を増やしたが、無機繊維を使用しなかったため、水膨潤を十分に抑制することができなかったものと思われる。また、比較例2では、熱融着性繊維の使用量を増やしたため、水膨潤率は抑制することができたが、熱融着性繊維による吸湿の阻害が大きくなったため飽和吸湿率が大きく低下したものと思われる。比較例3の吸放湿紙は繊維構成としては実施例1と全く同じであるが、工業用水を使用して作成したため、工業用水中のカチオンと架橋構造および酸性基を有する繊維Aのナトリウムイオンがイオン交換を起こし、飽和吸湿率が低下したものと思われる。 In Comparative Example 1, although pulp-like fibers were increased, it was considered that water swelling could not be sufficiently suppressed because inorganic fibers were not used. In Comparative Example 2, the amount of heat-fusible fiber used was increased, so that the water swelling rate could be suppressed. However, since the inhibition of moisture absorption by the heat-fusible fiber was increased, the saturated moisture absorption rate was greatly reduced. It seems to have done. The moisture-absorbing / releasing paper of Comparative Example 3 has exactly the same fiber configuration as that of Example 1, but was prepared using industrial water. Therefore, the sodium ion of fiber A having a cation, a crosslinked structure, and an acidic group in industrial water. Seems to have caused ion exchange and reduced saturated moisture absorption.
Claims (7)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004059189A JP4281060B2 (en) | 2004-03-03 | 2004-03-03 | Absorbent / release paper and method for producing the same |
PCT/JP2004/017357 WO2005085522A1 (en) | 2004-03-03 | 2004-11-22 | Paper capable of moisture absorption and desorption and process for producing the same |
TW094105336A TWI347991B (en) | 2004-03-03 | 2005-02-23 | Moisture-transfering paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004059189A JP4281060B2 (en) | 2004-03-03 | 2004-03-03 | Absorbent / release paper and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005248361A JP2005248361A (en) | 2005-09-15 |
JP4281060B2 true JP4281060B2 (en) | 2009-06-17 |
Family
ID=34917963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004059189A Expired - Fee Related JP4281060B2 (en) | 2004-03-03 | 2004-03-03 | Absorbent / release paper and method for producing the same |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP4281060B2 (en) |
TW (1) | TWI347991B (en) |
WO (1) | WO2005085522A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008004703A1 (en) * | 2006-07-05 | 2008-01-10 | Mitsubishi Paper Mills Limited | Sheetlike products and works |
JP6656608B1 (en) * | 2018-05-31 | 2020-03-04 | 日本エクスラン工業株式会社 | Carboxyl group-containing beaten acrylonitrile fiber, method for producing the fiber, and structure containing the fiber |
CN114134756A (en) * | 2020-09-04 | 2022-03-04 | 中国制浆造纸研究院有限公司 | Polydopamine type anhydrous humidifying device and preparation method and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5530482A (en) * | 1978-08-28 | 1980-03-04 | Japan Exlan Co Ltd | Production of water wettable sheet like article |
JPS55132754A (en) * | 1979-04-02 | 1980-10-15 | Japan Exlan Co Ltd | High water absorbable sheet like fiber product |
JP2605666B2 (en) * | 1986-05-06 | 1997-04-30 | 日本エクスラン工業株式会社 | Water-swellable fiber |
JPH06207398A (en) * | 1992-11-17 | 1994-07-26 | Mitsubishi Paper Mills Ltd | Moisture absorbing and releasing fiber sheet and its production |
JP3248401B2 (en) * | 1995-06-05 | 2002-01-21 | 日本エクスラン工業株式会社 | Hygroscopic cross-linked acrylic fiber and fiber structure using the fiber |
-
2004
- 2004-03-03 JP JP2004059189A patent/JP4281060B2/en not_active Expired - Fee Related
- 2004-11-22 WO PCT/JP2004/017357 patent/WO2005085522A1/en active Application Filing
-
2005
- 2005-02-23 TW TW094105336A patent/TWI347991B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
TWI347991B (en) | 2011-09-01 |
TW200533810A (en) | 2005-10-16 |
JP2005248361A (en) | 2005-09-15 |
WO2005085522A1 (en) | 2005-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4375397B2 (en) | Absorbent / release paper and method for producing the same | |
KR0159921B1 (en) | A composition comprising cathionic and anionic polymer process thereof | |
CN109518519B (en) | Flame-retardant sheet | |
JP6233157B2 (en) | Water-resistant cellulose fiber and production method thereof, cellulose sheet and production method thereof | |
JPWO2003010384A1 (en) | Bulk pulp, method for producing the same, processed paper or multilayer paper using the bulky pulp | |
JP4281060B2 (en) | Absorbent / release paper and method for producing the same | |
JP2024032705A (en) | Adsorption sheet and method for producing the same | |
JP6558421B2 (en) | Cellulose sheet | |
JP7166263B2 (en) | Multilayer sheet and manufacturing method thereof | |
ES2383762T3 (en) | Paper making process | |
JP6711432B2 (en) | Cellulose sheet | |
EP4058631B1 (en) | Method of producing a sheet comprising chemically modified cellulose fibres | |
JP7490053B2 (en) | Wet-laid webs containing viscose fibers | |
JP2020133063A (en) | Total heat exchange element Paper and total heat exchange element | |
KR101895789B1 (en) | The Method of Preparing a Stencil of Moisture Absoption Pad for Kit to Dianosise Animal Disease | |
JPH06207398A (en) | Moisture absorbing and releasing fiber sheet and its production | |
CN111287017A (en) | Base paper preparation process based on calcium carbonate fiber composite filler | |
CN113424008A (en) | Total heat exchange element paper and total heat exchange element | |
US20230088379A1 (en) | Composite Paper-Based Sorbents For CO2 Capture | |
RU2260086C2 (en) | Method for producing paper protected from falsification | |
WO2018123891A1 (en) | Fibrillated polyvinyl alcohol fiber and production method therefor | |
JP2005060905A (en) | Method for producing humidity controlling paper, and humidity controlling paper | |
JP3796248B2 (en) | Polyvinyl alcohol binder fiber and paper or nonwoven fabric using the same | |
JP2021021173A (en) | Sheet for heat exchange element and manufacturing method thereof | |
JP2021169685A (en) | Particle supporting fiber structure and its manufacturing method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060920 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081216 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090129 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090220 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090305 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4281060 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120327 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120327 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130327 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130327 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130327 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140327 Year of fee payment: 5 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |