JP2018111806A - Method for producing water-absorbable resin particle - Google Patents
Method for producing water-absorbable resin particle Download PDFInfo
- Publication number
- JP2018111806A JP2018111806A JP2017238456A JP2017238456A JP2018111806A JP 2018111806 A JP2018111806 A JP 2018111806A JP 2017238456 A JP2017238456 A JP 2017238456A JP 2017238456 A JP2017238456 A JP 2017238456A JP 2018111806 A JP2018111806 A JP 2018111806A
- Authority
- JP
- Japan
- Prior art keywords
- water
- group
- vinyl monomer
- weight
- absorbent resin
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 239000002245 particle Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 77
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- 150000005527 organic iodine compounds Chemical class 0.000 claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims abstract description 3
- 239000002250 absorbent Substances 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- -1 iodide ions Chemical class 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 21
- 150000004694 iodide salts Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- DBESYUOJKJZGLV-UHFFFAOYSA-N 2-iodo-2-methylpropanenitrile Chemical compound CC(C)(I)C#N DBESYUOJKJZGLV-UHFFFAOYSA-N 0.000 abstract description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 abstract description 11
- 229940006461 iodide ion Drugs 0.000 abstract description 8
- AYVTVRNTNCEPSH-UHFFFAOYSA-N ethyl 2-iodo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)I AYVTVRNTNCEPSH-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 description 35
- 238000010521 absorption reaction Methods 0.000 description 35
- 229910052799 carbon Inorganic materials 0.000 description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 239000000835 fiber Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 28
- 238000004132 cross linking Methods 0.000 description 25
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 150000002430 hydrocarbons Chemical group 0.000 description 21
- 239000000499 gel Substances 0.000 description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 14
- 229920006037 cross link polymer Polymers 0.000 description 13
- 239000002504 physiological saline solution Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000002657 fibrous material Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 235000009518 sodium iodide Nutrition 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 244000269722 Thea sinensis Species 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910001511 metal iodide Inorganic materials 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ABFPKTQEQNICFT-UHFFFAOYSA-M 2-chloro-1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1Cl ABFPKTQEQNICFT-UHFFFAOYSA-M 0.000 description 2
- XIWYAAPVEZZWFT-UHFFFAOYSA-N 2-iodo-2-methylpropanoic acid Chemical compound CC(C)(I)C(O)=O XIWYAAPVEZZWFT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
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- 238000004821 distillation Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
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- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- ARSMIBSHEYKMJT-UHFFFAOYSA-M 1,3-dimethylimidazolium iodide Chemical compound [I-].CN1C=C[N+](C)=C1 ARSMIBSHEYKMJT-UHFFFAOYSA-M 0.000 description 1
- QBOZQSOSSUOMJV-UHFFFAOYSA-N 1,4-bis(1-iodoethyl)benzene Chemical compound CC(I)C1=CC=C(C(C)I)C=C1 QBOZQSOSSUOMJV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polymerization Catalysts (AREA)
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Abstract
Description
本発明は吸水性樹脂粒子の製造方法に関するものである。 The present invention relates to a method for producing water absorbent resin particles.
従来、水性液体に対して吸収能を有する粉粒状吸収剤として、吸水性樹脂と呼ばれる親水性架橋ポリマーが使用され、紙オムツ、生理用品等の衛生用品や、結露防止剤、農業・園芸用保水剤等の各種産業分野用途にその応用範囲は拡大している。これらの用途に使用される吸水性樹脂は保水量が高く、膨潤時にべとつき感がないことが要望されている。 Conventionally, hydrophilic cross-linked polymers called water-absorbing resins have been used as powdered and granular absorbents that have the ability to absorb aqueous liquids. Hygiene products such as paper diapers and sanitary products, anti-condensation agents, and water retention for agriculture and horticulture. The range of application is expanding to various industrial fields such as agents. The water-absorbent resin used in these applications is required to have a high water retention amount and not feel sticky when swollen.
吸水性樹脂の常圧下での吸水能力（保水量）は、「（イオン浸透圧＋高分子鎖の水への親和力）／高分子の架橋密度」に比例し、架橋密度が吸水性樹脂の性能に関与することが知られている。そのため保水量を高める方法として、架橋剤の使用量を少なくすることが、通常、実施されているが、吸水性樹脂粒子の性能を更に向上させる方法として、ラジカル重合性モノマーと架橋剤とを含有するモノマー組成物を連鎖移動剤の共存下に水溶液重合する方法が知られている（例えば特許文献１参照）。 The water absorption capacity (water retention amount) of the water absorbent resin under normal pressure is proportional to “(ion osmotic pressure + affinity of polymer chains to water) / polymer crosslink density”, and the crosslink density is the performance of the water absorbent resin. Known to be involved in. Therefore, reducing the amount of crosslinking agent used as a method for increasing the water retention amount is usually practiced, but as a method for further improving the performance of the water-absorbent resin particles, it contains a radical polymerizable monomer and a crosslinking agent. There is known a method in which a monomer composition to be polymerized in an aqueous solution in the presence of a chain transfer agent (see, for example, Patent Document 1).
しかしながら、特許文献１に記載の連鎖移動剤を使用する方法は、保水量の向上に関してはある程度の効果が認められるものの、架橋反応に組み込まれずに膨潤時に水に溶出する成分（以下、可溶分とする）が増えるため、膨潤ゲルのべとつき感が増し、使用時の不快感が大きくなる課題があった。 However, although the method using the chain transfer agent described in Patent Document 1 has a certain effect on the improvement of the water retention amount, it is not incorporated into the crosslinking reaction and is eluted in water during swelling (hereinafter referred to as soluble component). Therefore, there is a problem that the feeling of stickiness of the swollen gel increases and the discomfort during use increases.
本発明者は、上記課題を達成すべく鋭意検討した結果、本発明に到達した。
すなわち、本発明は、水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）並びに架橋剤（ｂ）を含む単量体組成物を、炭素−ヨウ素結合を有する有機ヨウ素化合物（ｃ）及びヨウ化物イオンを含む塩（ｄ）の存在下に重合する工程を有する、吸水性樹脂粒子の製造方法（以下、単に本発明の製造方法ともいう）である。
As a result of intensive studies to achieve the above-mentioned problems, the present inventor has reached the present invention.
That is, the present invention provides a monomer composition containing a water-soluble vinyl monomer (a1) and / or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis and a crosslinking agent (b). A method for producing water-absorbent resin particles (hereinafter, also simply referred to as the production method of the present invention), which comprises a step of polymerizing in the presence of an organic iodine compound (c) having an iodine bond and a salt (d) containing iodide ions. is there.
本発明の製造方法により得られる吸水性樹脂粒子は、保水量と荷重下吸収量に優れ、かつ、可溶分が少ない。そのため、本発明の製造方法により得られる吸水性樹脂粒子はさまざまの使用状況においても安定して優れた吸収性能（例えば液拡散性、吸収速度及び吸収量）を発揮し、かつ膨潤ゲルのべとつき感が小さいため、これらを用いた衛生用品等は不快感が少なくカブレが生じにくい。 The water-absorbent resin particles obtained by the production method of the present invention are excellent in water retention and absorption under load, and have a low soluble content. Therefore, the water-absorbent resin particles obtained by the production method of the present invention stably exhibit excellent absorption performance (for example, liquid diffusibility, absorption rate and absorption amount) even in various usage situations, and the sticky feeling of the swollen gel. Therefore, sanitary goods using these are less uncomfortable and less likely to cause fog.
本発明の製造方法は、水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）並びに架橋剤（ｂ）を含む単量体組成物を、炭素−ヨウ素結合を有する有機ヨウ素化合物（ｃ）及びヨウ化物イオンを含む塩（ｄ）の存在下に重合する工程を有する。 In the production method of the present invention, a monomer composition containing a water-soluble vinyl monomer (a1) and / or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis and a crosslinking agent (b) -It has the process of superposing | polymerizing in the presence of the organic iodine compound (c) which has an iodine bond, and the salt (d) containing an iodide ion.
本発明の製造方法において、有機ヨウ素化合物（ｃ）の正確な作用、効果は不明であるが、有機ヨウ素化合物（ｃ）存在下でビニルモノマーをラジカル重合することにより、有機ヨウ素化合物（ｃ）のヨウ素末端がラジカル重合のドーマント種として働き重合体分子量を制御することで、ゲル網目の均一性が向上し、その結果、吸水性樹脂粒子の保水量及びゲル強度が向上するものと推定される。またヨウ化物イオンを含む塩（ｄ）の正確な作用、効果は不明であるが、有機ヨウ素化合物（ｃ）との共存下でビニルモノマーをラジカル重合することにより、有機ヨウ素化合物（ｃ）のヨウ素末端のドーマント作用を促進し、重合体の分子量制御及びゲル網目の均一化効果を高めているものと推定される。 In the production method of the present invention, the exact action and effect of the organic iodine compound (c) is unknown, but by radical polymerization of the vinyl monomer in the presence of the organic iodine compound (c), the organic iodine compound (c) It is presumed that the iodine terminal acts as a dormant species for radical polymerization and controls the molecular weight of the polymer, thereby improving the uniformity of the gel network and, as a result, improving the water retention amount and gel strength of the water-absorbent resin particles. Although the exact action and effect of the salt (d) containing iodide ion is unclear, the iodine of the organic iodine compound (c) is obtained by radical polymerization of a vinyl monomer in the presence of the organic iodine compound (c). It is presumed that the terminal dormant action is promoted, and the molecular weight control of the polymer and the effect of homogenizing the gel network are enhanced.
本発明の製造方法における水溶性ビニルモノマー（ａ１）としては特に限定はなく、公知のモノマー、例えば、特許第３６４８５５３号公報の０００７〜００２３段落に開示されている少なくとも１個の水溶性置換基とエチレン性不飽和基とを有するビニルモノマー（例えばアニオン性ビニルモノマー、非イオン性ビニルモノマー及びカチオン性ビニルモノマー）、特開２００３−１６５８８３号公報の０００９〜００２４段落に開示されているアニオン性ビニルモノマー、非イオン性ビニルモノマー及びカチオン性ビニルモノマー並びに特開２００５−７５９８２号公報の００４１〜００５１段落に開示されているカルボキシ基、スルホ基、ホスホノ基、水酸基、カルバモイル基、アミノ基及びアンモニオ基からなる群から選ばれる少なくとも１種を有するビニルモノマーが使用できる。 The water-soluble vinyl monomer (a1) in the production method of the present invention is not particularly limited, and may be a known monomer, for example, at least one water-soluble substituent disclosed in paragraphs 0007 to 0023 of Japanese Patent No. 3648553. Vinyl monomers having an ethylenically unsaturated group (for example, anionic vinyl monomers, nonionic vinyl monomers and cationic vinyl monomers), anionic vinyl monomers disclosed in paragraphs 0009 to 0024 of JP-A No. 2003-165883 A nonionic vinyl monomer and a cationic vinyl monomer, and a carboxy group, a sulfo group, a phosphono group, a hydroxyl group, a carbamoyl group, an amino group, and an ammonio group disclosed in paragraphs 0041 to 0051 of JP-A-2005-75982. Less selected from the group Vinyl monomers can be used also with one or.
加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）［以下、加水分解性ビニルモノマー（ａ２）ともいう。］は特に限定はなく、公知｛例えば、特許第３６４８５５３号公報の００２４〜００２５段落に開示されている加水分解により水溶性置換基となる加水分解性置換基を少なくとも１個有するビニルモノマー、特開２００５−７５９８２号公報の００５２〜００５５段落に開示されている少なくとも１個の加水分解性置換基［１，３−オキソ−２−オキサプロピレン（−ＣＯ−Ｏ−ＣＯ−）基、アシル基及びシアノ基等］を有するビニルモノマー｝のビニルモノマー等が使用できる。なお、水溶性ビニルモノマーにおける水溶性とは、当業者に周知の概念であるが、数量を用いて表すなら、例えば、溶質が２５℃の水１００ｇに少なくとも１００ｇ溶解することを意味する。また、加水分解は、当業者に周知の概念であるが、より具体的に表すなら、例えば、水及び必要により触媒（酸又は塩基等）の作用により、加水分解されることを意味する。加水分解性ビニルモノマー（ａ２）の加水分解は、重合中、重合後及びこれらの両方のいずれで行っても良いが、得られる吸水性樹脂粒子の吸収性能の観点から、重合後が好ましい。 Vinyl monomer (a2) which becomes water-soluble vinyl monomer (a1) by hydrolysis [hereinafter also referred to as hydrolyzable vinyl monomer (a2). ] Is not particularly limited, and known {for example, vinyl monomers having at least one hydrolyzable substituent which becomes a water-soluble substituent by hydrolysis disclosed in paragraphs 0024 to 0025 of Japanese Patent No. 3648553, At least one hydrolyzable substituent [1,3-oxo-2-oxapropylene (—CO—O—CO—) group, acyl group and cyano disclosed in paragraphs 0052 to 0055 of JP-A-2005-75982 Vinyl monomer having a group etc.] can be used. In addition, although water solubility in a water-soluble vinyl monomer is a concept well-known to those skilled in the art, when expressed using a quantity, for example, it means that at least 100 g of solute is dissolved in 100 g of water at 25 ° C. Hydrolysis is a concept well-known to those skilled in the art. More specifically, hydrolysis means hydrolysis by the action of water and, if necessary, a catalyst (acid or base). Hydrolysis of the hydrolyzable vinyl monomer (a2) may be performed either during polymerization, after polymerization, or both of them, but from the viewpoint of the absorption performance of the resulting water-absorbent resin particles, it is preferably after polymerization.
これらの内、吸収性能等の観点から、水溶性ビニルモノマー（ａ１）が好ましい。水溶性ビニルモノマー（ａ１）としては、好ましいのは上述のアニオン性ビニルモノマー；カルボキシ（塩）基、スルホ（塩）基、アミノ基、カルバモイル基、アンモニオ基又はモノ−、ジ−若しくはトリ−アルキルアンモニオ基を有するビニルモノマー；更に好ましいのはカルボキシ（塩）基又はカルバモイル基を有するビニルモノマー；特に好ましいのは（メタ）アクリル酸（塩）及び（メタ）アクリルアミド；とりわけ好ましいのは（メタ）アクリル酸（塩）；最も好ましいのはアクリル酸（塩）である。 Among these, the water-soluble vinyl monomer (a1) is preferable from the viewpoint of absorption performance and the like. As the water-soluble vinyl monomer (a1), the above-mentioned anionic vinyl monomers; carboxy (salt) group, sulfo (salt) group, amino group, carbamoyl group, ammonio group or mono-, di- or tri-alkyl are preferable. Vinyl monomers having an ammonio group; more preferred are vinyl monomers having a carboxy (salt) group or a carbamoyl group; particularly preferred are (meth) acrylic acid (salt) and (meth) acrylamide; particularly preferred is (meth) Acrylic acid (salt); most preferred is acrylic acid (salt).
なお、「カルボキシ（塩）基」は「カルボキシ基」又は「カルボキシレート基」を意味し、「スルホ（塩）基」は「スルホ基」又は「スルホネート基」を意味する。また、（メタ）アクリル酸（塩）はアクリル酸、アクリル酸塩、メタクリル酸又はメタクリル酸塩を意味し、（メタ）アクリルアミドはアクリルアミド又はメタクリルアミドを意味する。また、塩としては、アルカリ金属（リチウム、ナトリウム及びカリウム等）塩、アルカリ土類金属（マグネシウム及びカルシウム等）塩及びアンモニウム（ＮＨ４）塩等が挙げられる。これらの塩の内、吸収性能等の観点から、アルカリ金属塩及びアンモニウム塩が好ましく、更に好ましいのはアルカリ金属塩、特に好ましいのはナトリウム塩である。 The “carboxy (salt) group” means “carboxy group” or “carboxylate group”, and the “sulfo (salt) group” means “sulfo group” or “sulfonate group”. Moreover, (meth) acrylic acid (salt) means acrylic acid, acrylate, methacrylic acid or methacrylate, and (meth) acrylamide means acrylamide or methacrylamide. Examples of the salt include alkali metal (such as lithium, sodium and potassium) salts, alkaline earth metal (such as magnesium and calcium) salts and ammonium (NH 4 ) salt. Among these salts, alkali metal salts and ammonium salts are preferable from the viewpoint of absorption performance and the like, more preferable are alkali metal salts, and particularly preferable are sodium salts.
水溶性ビニルモノマー（ａ１）又は加水分解性ビニルモノマー（ａ２）のいずれかを構成単位とする場合、それぞれ１種を単独で構成単位としてもよく、また、必要により２種以上を構成単位としても良い。また、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）を構成単位とする場合も同様である。また、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）を構成単位とする場合、これらの含有モル比［（ａ１）／（ａ２）］は、７５／２５〜９９／１が好ましく、更に好ましくは８５／１５〜９５／５、特に好ましくは９０／１０〜９３／７、最も好ましくは９１／９〜９２／８である。この範囲内であると、吸収性能が更に良好となる。 When either the water-soluble vinyl monomer (a1) or the hydrolyzable vinyl monomer (a2) is used as a structural unit, one kind of each may be used alone as a structural unit, and if necessary, two or more kinds may be used as a structural unit. good. The same applies when the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as constituent units. Further, when the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units, the molar ratio [(a1) / (a2)] is preferably 75/25 to 99/1. The ratio is more preferably 85/15 to 95/5, particularly preferably 90/10 to 93/7, and most preferably 91/9 to 92/8. Within this range, the absorption performance is further improved.
水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）の他に、これらと共重合可能なその他のビニルモノマー（ａ３）を構成単位とすることができる。その他のビニルモノマー（ａ３）は１種を単独で用いても、２種以上を併用してもよい。 In addition to the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), other vinyl monomers (a3) copolymerizable therewith can be used as structural units. Other vinyl monomers (a3) may be used alone or in combination of two or more.
共重合可能なその他のビニルモノマー（ａ３）としては特に限定はなく、公知（例えば、特許第３６４８５５３号公報の００２８〜００２９段落に開示されている疎水性ビニルモノマー、特開２００３−１６５８８３号公報の００２５段落及び特開２００５−７５９８２号公報の００５８段落に開示されているビニルモノマー等）の疎水性ビニルモノマー等が使用でき、具体的には例えば下記の（ｉ）〜（ｉｉｉ）のビニルモノマー等が使用できる。
（ｉ）炭素数８〜３０の芳香族エチレン性モノマー
スチレン、α−メチルスチレン、ビニルトルエン及びヒドロキシスチレン等のスチレン、並びにビニルナフタレン及びジクロルスチレン等のスチレンのハロゲン置換体等。
（ｉｉ）炭素数２〜２０の脂肪族エチレン性モノマー
アルケン（エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン及びオクタデセン等）；並びにアルカジエン（ブタジエン及びイソプレン等）等。
（ｉｉｉ）炭素数５〜１５の脂環式エチレン性モノマー
モノエチレン性不飽和モノマー（ピネン、リモネン及びインデン等）；並びにポリエチレン性ビニルモノマー［シクロペンタジエン、ビシクロペンタジエン及びエチリデンノルボルネン等］等。
Other vinyl monomers (a3) that can be copolymerized are not particularly limited, and are known (for example, hydrophobic vinyl monomers disclosed in paragraphs 0028 to 0029 of Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883). 0025 paragraph and vinyl monomer disclosed in JP-A-2005-75982, paragraph 0058) can be used. Specifically, for example, the following vinyl monomers (i) to (iii) Can be used.
(I) C8-C30 aromatic ethylenic monomer Styrene such as styrene, α-methylstyrene, vinyltoluene and hydroxystyrene, and halogen substituted products of styrene such as vinylnaphthalene and dichlorostyrene.
(Ii) C2-C20 aliphatic ethylenic monomer Alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); and alkadienes (butadiene, isoprene, etc.).
(Iii) C5-C15 alicyclic ethylenic monomer Monoethylenically unsaturated monomer (such as pinene, limonene and indene); and polyethylene vinyl monomer [such as cyclopentadiene, bicyclopentadiene and ethylidene norbornene].
その他のビニルモノマー（ａ３）単位の含有量（モル％）は、吸収性能等の観点から、水溶性ビニルモノマー（ａ１）単位及び加水分解性ビニルモノマー（ａ２）単位の合計モル数に基づいて、０〜５が好ましく、更に好ましくは０〜３、特に好ましくは０〜２、とりわけ好ましくは０〜１．５であり、吸収性能等の観点から、その他のビニルモノマー（ａ３）単位の含有量が０モル％であることが最も好ましい。 The content (mol%) of the other vinyl monomer (a3) unit is based on the total number of moles of the water-soluble vinyl monomer (a1) unit and hydrolyzable vinyl monomer (a2) unit from the viewpoint of absorption performance and the like. 0 to 5 is preferable, more preferably 0 to 3, particularly preferably 0 to 2, particularly preferably 0 to 1.5. From the viewpoint of absorption performance and the like, the content of other vinyl monomer (a3) units is Most preferably, it is 0 mol%.
架橋剤（ｂ）としては特に限定はなく公知（例えば、特許第３６４８５５３号公報の００３１〜００３４段落に開示されているエチレン性不飽和基を２個以上有する架橋剤、水溶性置換基と反応し得る官能基を少なくとも１個有してかつ少なくとも１個のエチレン性不飽和基を有する架橋剤及び水溶性置換基と反応し得る官能基を少なくとも２個有する架橋剤、特開２００３−１６５８８３号公報の００２８〜００３１段落に開示されているエチレン性不飽和基を２個以上有する架橋剤、エチレン性不飽和基と反応性官能基とを有する架橋剤及び反応性置換基を２個以上有する架橋剤、特開２００５−７５９８２号公報の００５９段落に開示されている架橋性ビニルモノマー並びに特開２００５−９５７５９号公報の００１５〜００１６段落に開示されている架橋性ビニルモノマー）の架橋剤等が使用できる。これらの内、吸収性能等の観点から、エチレン性不飽和基を２個以上有する架橋剤が好ましく、更に好ましいのは、Ｎ，Ｎ’−メチレンビスアクリルアミド等のビス（メタ）アクリルアミド類；（ポリ）アルキレングリコール、トリメチロールプロパン、グリセリン、ペンタエリスリトール及びソルビトール等の多価アルコールのポリ（メタ）アクリレート；（ポリ）アルキレングリコール、トリメチロールプロパン、グリセリン、ペンタエリスリトール及びソルビトール等の多価アルコールのポリ（メタ）アリルエーテル、テトラアリロキシエタン並びにトリアリルイソシアヌレート等の多価（メタ）アリル化合物であり、最も好ましいのは多価（メタ）アリル化合物である。架橋剤（ｂ）は１種を単独で用いても、２種以上を併用してもよい。 The cross-linking agent (b) is not particularly limited and is known (for example, it reacts with a cross-linking agent having two or more ethylenically unsaturated groups and water-soluble substituents disclosed in paragraphs 0031 to 0034 of Japanese Patent No. 3648553. Crosslinking agent having at least one functional group and at least one ethylenically unsaturated group, and crosslinking agent having at least two functional groups capable of reacting with a water-soluble substituent, Japanese Patent Application Laid-Open No. 2003-165883 The crosslinking agent having two or more ethylenically unsaturated groups, the crosslinking agent having an ethylenically unsaturated group and a reactive functional group, and the crosslinking agent having two or more reactive substituents disclosed in paragraphs 0028 to 0031 of , A crosslinkable vinyl monomer disclosed in paragraph 0059 of JP-A-2005-75982, and paragraphs 0015 to 0016 of JP-A-2005-95759. Crosslinking agents such as disclosed crosslinkable vinyl monomer) can be used. Among these, from the viewpoint of absorption performance and the like, a crosslinking agent having two or more ethylenically unsaturated groups is preferable, and more preferable are bis (meth) acrylamides such as N, N′-methylenebisacrylamide; ) Poly (meth) acrylates of polyhydric alcohols such as alkylene glycol, trimethylol propane, glycerin, pentaerythritol and sorbitol; (poly) poly (alcohols of polyhydric alcohols such as alkylene glycol, trimethylol propane, glycerin, pentaerythritol and sorbitol ( Multivalent (meth) allyl compounds such as (meth) allyl ether, tetraallyloxyethane and triallyl isocyanurate, and most preferred are polyvalent (meth) allyl compounds. A crosslinking agent (b) may be used individually by 1 type, or may use 2 or more types together.
架橋剤（ｂ）単位の含有量（モル％）は、水溶性ビニルモノマー（ａ１）単位及び加水分解性ビニルモノマー（ａ２）単位、その他のビニルモノマー（ａ３）単位も用いる場合は（ａ１）〜（ａ３）単位の、合計モル数に基づいて、０．００１〜５が好ましく、更に好ましくは０．００５〜３、特に好ましくは０．０１〜１である。この範囲であると、吸収性能が更に良好となる。 The content (mol%) of the crosslinking agent (b) unit is (a1) to when the water-soluble vinyl monomer (a1) unit, hydrolyzable vinyl monomer (a2) unit, and other vinyl monomer (a3) units are used. Based on the total number of moles of the unit (a3), 0.001 to 5 is preferable, 0.005 to 3 is more preferable, and 0.01 to 1 is particularly preferable. Within this range, the absorption performance is further improved.
本発明の製造方法において、炭素−ヨウ素結合を有する有機ヨウ素化合物（ｃ）は、ラジカル重合のドーマント種になり得るものであれば制限はなく、例えばＷＯ２０１１／０１６１６６にドーマント種として記載の有機ヨウ素化合物等を用いることができる。なかでも反応性の観点から、下記一般式（１）で表される有機ヨウ素化合物が好ましい。
これらの有機ヨウ素化合物（ｃ）は単独で使用してもよく、２種以上を併用してもよい。
In the production method of the present invention, the organic iodine compound (c) having a carbon-iodine bond is not limited as long as it can be a dormant species for radical polymerization. For example, an organic iodine compound described as a dormant species in WO2011 / 016166 Etc. can be used. Among these, from the viewpoint of reactivity, an organic iodine compound represented by the following general formula (1) is preferable.
These organic iodine compounds (c) may be used alone or in combination of two or more.
一般式（１）中、Ｒ１及びＲ２はそれぞれ独立に水素原子、炭素数１〜７の飽和炭化水素基又は少なくとも１つの非付加重合性二重結合若しくは少なくとも１つの非付加重合性三重結合を有する炭素数１〜７である１価の基であり、Ｒ３は炭素数１〜７のｎ価の飽和炭化水素基又は少なくとも１つの非付加重合性二重結合若しくは少なくとも１つの非付加重合性三重結合を有する炭素数２〜１２であるｎ価の基であり、ただし、１分子中、Ｒ１〜Ｒ３のうち少なくとも一つは、前記の、対応する、非付加重合性二重結合又は少なくとも１つの非付加重合性三重結合を有する基であり、ｎは１〜３の整数であり、ｎが１である場合にＲ１及びＲ２は互いに結合していてもよい。
本明細書中、非付加重合性二重結合（以下、単に非重合性二重結合ともいう）及び非付加重合性三重結合（以下、単に非重合性三重結合ともいう）とは、不飽和結合のうち、付加重合性不飽和結合（それぞれ、付加重合性炭素−炭素二重結合及び付加重合性炭素−炭素三重結合）を除いた結合であり、非付加重合性二重結合及び非付加重合性三重結合としては、カルボニル基に含まれる炭素−酸素二重結合、ニトリル基に含まれる炭素−窒素三重結合、芳香族炭化水素を構成する炭素−炭素二重結合及び複素芳香族化合物を構成する酸素−窒素二重結合並びに炭素−窒素二重結合等が挙げられ、なかでもカルボニル基に含まれる炭素−酸素二重結合、ニトリル基に含まれる炭素−窒素三重結合及び芳香族炭化水素を構成する炭素−炭素二重結合が好ましい。
In general formula (1), R 1 and R 2 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 7 carbon atoms, at least one non-addition polymerizable double bond, or at least one non-addition polymerizable triple bond. And R 3 is an n-valent saturated hydrocarbon group having 1 to 7 carbon atoms or at least one non-addition polymerizable double bond or at least one non-addition polymerization. N-valent group having 2 to 12 carbon atoms having an ionic triple bond, provided that at least one of R 1 to R 3 in the molecule is a corresponding non-addition polymerizable double bond. Or it is a group having at least one non-addition polymerizable triple bond, n is an integer of 1 to 3, and when n is 1, R 1 and R 2 may be bonded to each other.
In this specification, a non-addition polymerizable double bond (hereinafter also simply referred to as a non-polymerizable double bond) and a non-addition polymerizable triple bond (hereinafter also simply referred to as a non-polymerizable triple bond) are an unsaturated bond. Of these, bonds other than addition-polymerizable unsaturated bonds (addition-polymerizable carbon-carbon double bond and addition-polymerizable carbon-carbon triple bond, respectively), non-addition-polymerizable double bond and non-addition-polymerizable Triple bonds include carbon-oxygen double bonds contained in carbonyl groups, carbon-nitrogen triple bonds contained in nitrile groups, carbon-carbon double bonds constituting aromatic hydrocarbons, and oxygen constituting heteroaromatic compounds. -Nitrogen double bonds and carbon-nitrogen double bonds, among others, carbon-oxygen double bonds contained in carbonyl groups, carbon-nitrogen triple bonds contained in nitrile groups, and carbons constituting aromatic hydrocarbons -Carbon double bond It is preferred.
Ｒ１及びＲ２が炭素数１〜７の飽和炭化水素基である場合、炭素数１〜７の飽和炭化水素基としては、炭素数１〜７の直鎖飽和炭化水素基（メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基及びｎ−ヘキシル基等）及び炭素数１〜７の分岐飽和炭化水素基（ｉ−プロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、１−メチルブチル基、イソヘキシル基、ｓ−ヘキシル基、ｔ−ヘキシル基、ネオヘキシル基、ヘプチル基等）が挙げられる。なかでも溶解性と重合性の観点等から好ましくは炭素数１〜５の直鎖飽和炭化水素基であり、更に好ましくは炭素数１〜３の直鎖飽和炭化水素基である。 When R 1 and R 2 are saturated hydrocarbon groups having 1 to 7 carbon atoms, the saturated hydrocarbon group having 1 to 7 carbon atoms is a straight-chain saturated hydrocarbon group having 1 to 7 carbon atoms (methyl group, ethyl Group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group) and branched saturated hydrocarbon group having 1 to 7 carbon atoms (i-propyl group, isobutyl group, s-butyl group, t -Butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, heptyl group and the like. Among these, from the viewpoint of solubility and polymerizability, a linear saturated hydrocarbon group having 1 to 5 carbon atoms is preferable, and a linear saturated hydrocarbon group having 1 to 3 carbon atoms is more preferable.
Ｒ１及びＲ２が少なくとも１つの非重合性二重結合又は少なくとも１つの非重合性三重結合を有する炭素数１〜７である１価の基である場合、好ましい基としてはカルボキシル基（炭素数１、炭素−酸素二重結合）、フェニル基（炭素数６、非重合性炭素−炭素二重結合）、シアノ基（炭素数１、炭素−窒素三重結合）、シアノメチル基（炭素数２、炭素−窒素三重結合）、シアノエチル基（炭素数３、炭素−窒素三重結合）、シアノプロピル基（炭素数４、炭素−窒素三重結合）、シアノブチル基（炭素数５、炭素−窒素三重結合）、シアノペンチル基（炭素数６、炭素−窒素三重結合）、シアノヘキシル基（炭素数７、炭素−窒素三重結合）、カルボキシメチル基（炭素数２、炭素−酸素二重結合）、カルボキシエチル基（炭素数３、炭素−酸素二重結合）、カルボキシプロピル基（炭素数４、炭素−酸素二重結合）、カルボキシブチル基（炭素数５、炭素―酸素二重結合）、カルボキシペンチル基（炭素数６、炭素―酸素二重結合）、カルボキシヘキシル基（炭素数７、炭素―酸素二重結合）、ベンジル基（炭素数７、非重合性炭素−炭素二重結合）、メトキシカルボニル基（炭素数２、炭素−酸素二重結合）、エトキシカルボニル基（炭素数３、炭素−酸素二重結合）、プロピルオキシカルボニル基（炭素数４、炭素−酸素二重結合）、ブチルオキシカルボニル基（炭素数５、炭素−酸素二重結合）、ペンチルオキシカルボニル基（炭素数６、炭素−酸素二重結合）、ヘキシルオキシカルボニル基（炭素数７、炭素−酸素二重結合）、ヒドロキシエトキシカルボニル基（炭素数３、炭素−酸素二重結合）、ヒドロキシプロピルオキシカルボニル基（炭素数４、炭素−酸素二重結合）、ヒドロキシブチルオキシカルボニル基（炭素数５、炭素−酸素二重結合）、ヒドロキシペンチルオキシカルボニル基（炭素数６、炭素−酸素二重結合）及びヒドロキシヘキシルオキシカルボニル基（炭素数７、炭素−酸素二重結合）等が挙げられる。 When R 1 and R 2 are monovalent groups having 1 to 7 carbon atoms having at least one non-polymerizable double bond or at least one non-polymerizable triple bond, a preferred group is a carboxyl group (carbon number 1, carbon-oxygen double bond), phenyl group (carbon number 6, non-polymerizable carbon-carbon double bond), cyano group (carbon number 1, carbon-nitrogen triple bond), cyanomethyl group (carbon number 2, carbon) -Nitrogen triple bond), cyanoethyl group (carbon number 3, carbon-nitrogen triple bond), cyanopropyl group (carbon number 4, carbon-nitrogen triple bond), cyanobutyl group (carbon number 5, carbon-nitrogen triple bond), cyano Pentyl group (carbon number 6, carbon-nitrogen triple bond), cyanohexyl group (carbon number 7, carbon-nitrogen triple bond), carboxymethyl group (carbon number 2, carbon-oxygen double bond), carboxyethyl group (carbon Number 3, Element-oxygen double bond), carboxypropyl group (carbon number 4, carbon-oxygen double bond), carboxybutyl group (carbon number 5, carbon-oxygen double bond), carboxypentyl group (carbon number 6, carbon- Oxygen double bond), carboxyhexyl group (carbon number 7, carbon-oxygen double bond), benzyl group (carbon number 7, non-polymerizable carbon-carbon double bond), methoxycarbonyl group (carbon number 2, carbon- Oxygen double bond), ethoxycarbonyl group (carbon number 3, carbon-oxygen double bond), propyloxycarbonyl group (carbon number 4, carbon-oxygen double bond), butyloxycarbonyl group (carbon number 5, carbon- Oxygen double bond), pentyloxycarbonyl group (carbon number 6, carbon-oxygen double bond), hexyloxycarbonyl group (carbon number 7, carbon-oxygen double bond), hydroxyethoxycarbonyl group (carbon Prime number 3, carbon-oxygen double bond), hydroxypropyloxycarbonyl group (carbon number 4, carbon-oxygen double bond), hydroxybutyloxycarbonyl group (carbon number 5, carbon-oxygen double bond), hydroxypentyloxy Examples thereof include a carbonyl group (carbon number 6, carbon-oxygen double bond) and a hydroxyhexyloxycarbonyl group (carbon number 7, carbon-oxygen double bond).
Ｒ３は炭素数１〜７のｎ価の飽和炭化水素基又は少なくとも１つの非重合性二重結合若しくは少なくとも１つの非重合性三重結合を有する炭素数２〜１２であるｎ価の基であり、ｎは１〜３の整数である。 R 3 is an n-valent saturated hydrocarbon group having 1 to 7 carbon atoms or an n-valent group having 2 to 12 carbon atoms having at least one non-polymerizable double bond or at least one non-polymerizable triple bond. , N is an integer of 1 to 3.
Ｒ３で表される炭素数１〜７のｎ価の飽和炭化水素基のうち、炭素数１〜７の１価の飽和炭化水素基としては、炭素数１〜７の直鎖飽和炭化水素基（メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ヘプチル基等）及び炭素数１〜７の分岐飽和炭化水素基（ｉ−プロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、１−メチルブチル基、イソヘキシル基、ｓ−ヘキシル基、ｔ−ヘキシル基、ネオヘキシル基、イソヘプチル基等）が挙げられる。
Ｒ３で表される炭素数１〜７のｎ価の飽和炭化水素基のうち、炭素数１〜７の２価の飽和炭化水素基としては、炭素数１〜７の２価の直鎖飽和炭化水素基（メチレン基、エチレン基、プロピレン基、ブチレン基、ペンテン基、ヘキセン基、ヘプテン基等）及び炭素数１〜７の２価の分岐飽和炭化水素基（イソプロピレン基、イソブチレン基、ｓ−ブチレン基、ｔ−ブチレン基、イソペンチレン基、ネオペンチレン基、ｔ−ペンチレン基、１−メチルブチレン基、イソヘキシレン基、ｓ−ヘキシレン基、ｔ−ヘキシレン基、ネオヘキシレン基、イソヘプチレン基等）が挙げられる。
Ｒ３で表される炭素数１〜７のｎ価の飽和炭化水素基のうち、炭素数１〜７の３価の飽和炭化水素基としては、メチン基等が挙げられる。
Ｒ３で表される炭素数１〜７のｎ価の飽和炭化水素基のうち、メチル基、メチレン基、メチン基が好ましく、更に好ましくはメチル基、メチレン基である。
Among the n-valent saturated hydrocarbon groups having 1 to 7 carbon atoms represented by R 3 , the monovalent saturated hydrocarbon group having 1 to 7 carbon atoms is a linear saturated hydrocarbon group having 1 to 7 carbon atoms. (Methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, heptyl group, etc.) and C1-C7 branched saturated hydrocarbon group (i-propyl group, isobutyl) Group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, isoheptyl group, etc.) It is done.
Among the n-valent saturated hydrocarbon groups having 1 to 7 carbon atoms represented by R 3 , the divalent saturated hydrocarbon group having 1 to 7 carbon atoms is a divalent linear saturated group having 1 to 7 carbon atoms. Hydrocarbon group (methylene group, ethylene group, propylene group, butylene group, pentene group, hexene group, heptene group, etc.) and divalent branched saturated hydrocarbon group having 1 to 7 carbon atoms (isopropylene group, isobutylene group, s -Butylene group, t-butylene group, isopentylene group, neopentylene group, t-pentylene group, 1-methylbutylene group, isohexylene group, s-hexylene group, t-hexylene group, neohexylene group, isoheptylene group, etc.).
Among n-valent saturated hydrocarbon groups having 1 to 7 carbon atoms represented by R 3 , examples of the trivalent saturated hydrocarbon group having 1 to 7 carbon atoms include a methine group.
Of the n-valent saturated hydrocarbon groups having 1 to 7 carbon atoms represented by R 3 , a methyl group, a methylene group, and a methine group are preferable, and a methyl group and a methylene group are more preferable.
Ｒ３が少なくとも１つの非重合性二重結合又は少なくとも１つの非重合性三重結合を有する炭素数２〜１２であるｎ価の基のうち、１価の基としては、Ｒ１及びＲ２で例示した基と同じ基が挙げられ、好ましいものも同じである。
Ｒ３が少なくとも１つの非重合性二重結合又は少なくとも１つの非重合性三重結合を有する炭素数２〜１２である２価の基である場合、好ましい基としては、ベンゼンジイル基（炭素数６、非重合性炭素−炭素二重結合）、１−メトキシカルボニル−カルボニルオキシエチレンオキシカルボニル基（炭素数６、酸素−酸素二重結合）及びカルボニルオキシエチレンカルボニル基（炭素数４、酸素−酸素二重結合）等が挙げられる。
Ｒ３が少なくとも１つの非重合性二重結合又は少なくとも１つの非重合性三重結合を有する炭素数２〜１２である３価の基である場合、好ましいものとしては、ベンゼントリイル基（炭素数６、非重合性炭素−炭素二重結合）及び２−カルボニルオキシ−カルボニルオキシプロピレンカルボニル基（炭素数５、酸素−酸素二重結合）等が挙げられる。
Among the n-valent groups having 2 to 12 carbon atoms, in which R 3 has at least one non-polymerizable double bond or at least one non-polymerizable triple bond, the monovalent group includes R 1 and R 2 The same group as the illustrated group is mentioned, and preferable ones are also the same.
When R 3 is a divalent group having 2 to 12 carbon atoms having at least one non-polymerizable double bond or at least one non-polymerizable triple bond, a preferred group is a benzenediyl group (carbon number 6 , Non-polymerizable carbon-carbon double bond), 1-methoxycarbonyl-carbonyloxyethyleneoxycarbonyl group (carbon number 6, oxygen-oxygen double bond) and carbonyloxyethylenecarbonyl group (carbon number 4, oxygen-oxygen two bond). Double bond) and the like.
When R 3 is a trivalent group having 2 to 12 carbon atoms having at least one non-polymerizable double bond or at least one non-polymerizable triple bond, a benzenetriyl group (carbon number) is preferable. 6, non-polymerizable carbon-carbon double bond) and 2-carbonyloxy-carbonyloxypropylenecarbonyl group (5 carbon atoms, oxygen-oxygen double bond).
ｎが１である場合にＲ１及びＲ２は互いに結合していてもよく、Ｒ１及びＲ２が互いに結合して形成される環構造を有する基としてこのましいものとしては、γ−ブチロラクトニル基及びフルオレニル基等が挙げられる。なお、Ｒ１及びＲ２が互いに結合して環構造を形成する基は、Ｒ１及びＲ２が結合した炭素原子を環構造中に含む。 In the case where n is 1, R 1 and R 2 may be bonded to each other, and as a group having a ring structure formed by bonding R 1 and R 2 to each other, γ-butyrolactonyl is preferable. Group and fluorenyl group. In addition, the group in which R 1 and R 2 are bonded to each other to form a ring structure includes a carbon atom to which R 1 and R 2 are bonded in the ring structure.
一般式（１）で表される有機ヨウ素化合物（ｃ）としては、２−ヨードプロピオニトリル、２−メチル−２−ヨードプロピオニトリル、α−ヨードベンジルシアニド、２−ヨードプロピオン酸アミド、２−ヨード−２−メチルプロピオン酸エチル、２−メチル−ヨードプロピオン酸メチル、２−メチル−ヨードプロピオン酸プロピル、２−メチル−ヨードプロピオン酸ブチル、２−メチル−ヨードプロピオン酸ペンチル、２−メチル−ヨードプロピオン酸ヒドロキシエチル、２−メチル−２−ヨード−プロピオン酸、２−ヨードプロピオン酸、２−ヨード酢酸、２−ヨード酢酸メチル、２−ヨード酢酸エチル、２−ヨードペンタン酸エチル、２−ヨードペンタン酸メチル、２−ヨードペンタン酸、２−ヨードヘキサン酸、２−ヨードヘプタン酸、２，５−ジヨードアジピン酸ジエチル、２，５−ジヨードアジピン酸、２，６−ジヨード−ヘプタン二酸ジメチル、２，６−ジヨード−ヘプタン二酸、α−ヨード−γ−ブチロラクトン、２−ヨードアセトフェノン、ベンジルヨージド、２−ヨード−２−フェニル酢酸、２−ヨード−２−フェニル酢酸メチル、２−ヨード−２−フェニル酢酸エチル、２−ヨード−２−（４’−メチルフェニル）酢酸エチル、２−ヨード−２−フェニル酢酸−ヒドロキシエチル、２−ヨード−２−（４’−ニトロフェニル）酢酸エチル、４−ニトロベンジルヨージド、（１−ヨードエチル）ベンゼン、ヨードジフェニルメタン、９−ヨード−９Ｈ−フルオレン、ｐ−キシリレンジヨージド、１，４−ビス（１’−ヨードエチル）ベンゼン、エチレングリコールビス（２−メチル―２−ヨード―プロピネート）、トリス（２−メチル−ヨードプロピオン酸）グリセロール、１，３，５−トリス（１’−ヨードエチルベンゼン）、エチレングリコールビス（２−ヨード―２フェニルアセテート）等が挙げられ、なかでも吸収性能及びかぶれ抑制の観点から好ましいものとしては、２−メチル−２−ヨードプロピオニトリル、２−ヨード−２−メチルプロピオン酸エチル、２−メチル−２−ヨード−プロピオン酸、２−ヨード酢酸、２−ヨード酢酸メチル、２，５−ジヨードアジピン酸ジエチル、２，５−ジヨードアジピン酸、エチレングリコールビス（２−メチル―２−ヨード―プロピネート）、エチレングリコールビス（２−ヨード―２フェニルアセテート）が挙げられる。更に好ましくは、２−メチル−２−ヨードプロピオニトリル、２−ヨード−２−メチルプロピオン酸エチルである。特に好ましくは、２−メチル−２−ヨードプロピオニトリルである。
これらの有機ヨウ素化合物（ｃ）は単独で使用してもよく、２種以上を併用してもよい。
Examples of the organic iodine compound (c) represented by the general formula (1) include 2-iodopropionitrile, 2-methyl-2-iodopropionitrile, α-iodobenzylcyanide, 2-iodopropionic acid amide, 2-ethyl iodo-2-methylpropionate, methyl 2-methyl-iodopropionate, propyl 2-methyl-iodopropionate, butyl 2-methyl-iodopropionate, pentyl 2-methyl-iodopropionate, 2-methyl -Hydroxyethyl iodopropionate, 2-methyl-2-iodo-propionic acid, 2-iodopropionic acid, 2-iodoacetic acid, methyl 2-iodoacetate, ethyl 2-iodoacetate, ethyl 2-iodopentanoate, 2- Methyl iodopentanoate, 2-iodopentanoic acid, 2-iodohexanoic acid, 2-iodoheptane 2,2-diiododipic acid diethyl, 2,5-diiododipic acid, 2,6-diiodo-heptanedioic acid dimethyl, 2,6-diiodo-heptanedioic acid, α-iodo-γ-butyrolactone, 2 -Iodoacetophenone, benzyl iodide, 2-iodo-2-phenylacetic acid, methyl 2-iodo-2-phenylacetate, ethyl 2-iodo-2-phenylacetate, 2-iodo-2- (4'-methylphenyl) Ethyl acetate, 2-iodo-2-phenylacetic acid-hydroxyethyl, 2-iodo-2- (4′-nitrophenyl) ethyl acetate, 4-nitrobenzyl iodide, (1-iodoethyl) benzene, iododiphenylmethane, 9- Iodo-9H-fluorene, p-xylylene diiodide, 1,4-bis (1′-iodoethyl) benzene, ethylene glycol vinyl (2-methyl-2-iodo-propionate), tris (2-methyl-iodopropionic acid) glycerol, 1,3,5-tris (1′-iodoethylbenzene), ethylene glycol bis (2-iodo-2-phenylacetate) Among them, preferred from the viewpoint of absorption performance and rash suppression are 2-methyl-2-iodopropionitrile, ethyl 2-iodo-2-methylpropionate, 2-methyl-2-iodo -Propionic acid, 2-iodoacetic acid, methyl 2-iodoacetate, diethyl 2,5-diiododipinate, 2,5-diiododipic acid, ethylene glycol bis (2-methyl-2-iodo-propinate), ethylene And glycol bis (2-iodo-2-phenylacetate). More preferred are 2-methyl-2-iodopropionitrile and ethyl 2-iodo-2-methylpropionate. Particularly preferred is 2-methyl-2-iodopropionitrile.
These organic iodine compounds (c) may be used alone or in combination of two or more.
有機ヨウ素化合物（ｃ）の使用量は、上記モノマー（ａ１）及び（ａ２）の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）〜（ａ３）の、重量に基づいて、好ましくは０．０００５〜０．１重量％、更に好ましくは０．００５〜０．０５重量％である。有機ヨウ素化合物（ｃ）の量が０．０００５重量％未満では、重合を十分に制御できずに保水及びゲル強度向上の効果が得られない場合がある。一方、０．１重量％を越えると分子鎖が短くなりすぎるため可溶成分が増える場合があり、また経済性が悪い。 The amount of the organic iodine compound (c) used is preferably 0 based on the weight of the above monomers (a1) and (a2) when the other vinyl monomer (a3) is used (a1) to (a3). .0005 to 0.1% by weight, more preferably 0.005 to 0.05% by weight. If the amount of the organic iodine compound (c) is less than 0.0005% by weight, the polymerization may not be sufficiently controlled, and the effects of water retention and gel strength improvement may not be obtained. On the other hand, if it exceeds 0.1% by weight, the molecular chain becomes too short, so that soluble components may increase and the economy is poor.
本発明の製造方法において、ヨウ化物イオンを含む塩（ｄ）は、例えばＷＯ２０１３／０２７４１９に触媒化合物として記載の非金属塩及び、金属ヨウ化物塩等を用いることができる。 In the production method of the present invention, as the salt (d) containing iodide ion, for example, a nonmetallic salt described in WO2013 / 027419 as a catalyst compound, a metal iodide salt, or the like can be used.
ヨウ化物イオンを含む塩（ｄ）の好ましい具体例としては、例えば、非金属原子として窒素を有するものとして、各種イミダゾール塩化合物（例えば、１−メチル−３−メチル−イミダゾリウムヨーダイド（ＥＭＩＺＩ）、１−エチル−３−メチルイミダゾリウムブロマイド（ＥＭＩＺＢｒ））、各種ピリジン塩化合物（例えば、２−クロロ−１−メチルピリジニウムヨーダイド（ＣＭＰＩ））、各種４級アミン塩化合物（例えば、テトラブチルアンモニウムヨーダイド（ＢＮＩ）、テトラブチルアンモニウムトリヨーダイド（ＢＮＩ３）、テトラブチルアンモニウムブロモジヨーダイド（ＢＮＢｒＩ２））、２種類の非金属元素を含む化合物（例えば、ヘキサフェニルジホスファゼニウムクロリド（ＰＰＮＣｌ））およびこれらの誘導体が使用可能である。
非金属元素としてリンを有するものとして、各種ホスホニウム塩化合物（例えば、メチルトリブチルホスホニウムヨーダイド（ＢＭＰＩ）、テトラフェニルホスホニウムヨーダイド（ＰＰＩ））、およびこれらの誘導体などが挙げられる。
非金属元素として硫黄を有するものとして、トリブチルスルホニウムヨーダイド（ＢＳＩ）、およびこれらの誘導体などが挙げられる。
非金属元素としてヨウ素を有するものとして、ジフェニルヨードニウムヨーダイド（ＰＩＩ）などが挙げられる。
金属ヨウ化物塩として、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等のアルカリ金属類；ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等のアルカリ土類金属類；アルミニウム等の典型金属類；鉄や銅、亜鉛等の遷移金属類、のヨウ化物塩が挙げられる。
Preferable specific examples of the salt (d) containing iodide ion include, for example, various imidazole salt compounds (for example, 1-methyl-3-methyl-imidazolium iodide (EMIZI)) having nitrogen as a nonmetallic atom. 1-ethyl-3-methylimidazolium bromide (EMIZBr)), various pyridine salt compounds (for example, 2-chloro-1-methylpyridinium iodide (CMPI)), various quaternary amine salt compounds (for example, tetrabutylammonium) Iodide (BNI), tetrabutylammonium triiodide (BNI3), tetrabutylammonium bromodiiodide (BNBrI 2 )), a compound containing two kinds of non-metallic elements (for example, hexaphenyldiphosphazenium chloride (PPNCl) )) And their derivatives It is possible to use.
Examples of compounds having phosphorus as a nonmetallic element include various phosphonium salt compounds (for example, methyltributylphosphonium iodide (BMPI), tetraphenylphosphonium iodide (PPI)), and derivatives thereof.
Examples of those having sulfur as a nonmetallic element include tributylsulfonium iodide (BSI) and derivatives thereof.
As what has an iodine as a nonmetallic element, diphenyl iodonium iodide (PII) etc. are mentioned.
Examples of metal iodide salts include alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; typical metals such as aluminum; iron and copper And iodide salts of transition metals such as zinc.
これらの内、反応性の観点から金属ヨウ化物塩が好ましく、更に好ましくはアルカリ金属ヨウ化物塩及びアルカリ土類金属ヨウ化物塩、最も好ましくはヨウ化ナトリウム又はヨウ化カリウムである。
これらのヨウ化物イオンを含む塩（ｄ）は単独で使用してもよく、２種以上を併用してもよい。
Of these, metal iodide salts are preferred from the viewpoint of reactivity, more preferably alkali metal iodide salts and alkaline earth metal iodide salts, most preferably sodium iodide or potassium iodide.
These salts (d) containing iodide ions may be used alone or in combination of two or more.
ヨウ化物イオンを含む塩（ｄ）の使用量は、上記モノマー（ａ１）及び（ａ２）の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）〜（ａ３）の、重量に基づいて、好ましくは０．０００５〜０．１重量％、更に好ましくは０．００５〜０．０５重量％である。ヨウ化物イオンを含む塩（ｄ）の量が０．０００５重量％未満では、重合を十分に制御できずに保水及びゲル強度向上の効果が得られない場合がある。一方、０．１重量％を越えると分子鎖が短くなりすぎるため可溶成分が増える場合があり、また経済性が悪い。 The amount of the salt (d) containing iodide ion is based on the weight of (a1) to (a3) when the other vinyl monomer (a3) of the monomers (a1) and (a2) is used. Preferably it is 0.0005 to 0.1 weight%, More preferably, it is 0.005 to 0.05 weight%. If the amount of the salt (d) containing iodide ion is less than 0.0005% by weight, the polymerization may not be sufficiently controlled, and the effects of water retention and gel strength improvement may not be obtained. On the other hand, if it exceeds 0.1% by weight, the molecular chain becomes too short, so that soluble components may increase and the economy is poor.
本発明の製造方法において、水溶性ビニルモノマー（ａ１）及び／又は加水分解性ビニルモノマー（ａ２）並びに架橋剤（ｂ）を含む単量体組成物を前記の有機ヨウ素化合物（ｃ）及びヨウ化物イオンを含む塩（ｄ）の存在下に重合する工程は、従来知られているいずれの方法でもよく、例えば、水溶液重合（断熱重合、薄膜重合及び噴霧重合法等；特開昭５５−１３３４１３号公報等）及び逆相懸濁重合（特公昭５４−３０７１０号公報、特開昭５６−２６９０９号公報及び特開平１−５８０８号公報等）等］等の公知の重合を前記の有機ヨウ素化合物（ｃ）及びヨウ化物イオンを含む塩（ｄ）の存在下で行うことで実施することが出来る。 In the production method of the present invention, a monomer composition containing a water-soluble vinyl monomer (a1) and / or a hydrolyzable vinyl monomer (a2) and a crosslinking agent (b) is used as the organic iodine compound (c) and iodide. The step of polymerizing in the presence of the ion-containing salt (d) may be any method known in the art, such as aqueous solution polymerization (adiabatic polymerization, thin film polymerization, spray polymerization, etc .; JP-A-55-133413). Etc.) and reverse phase suspension polymerization (JP-B 54-30710, JP-A 56-26909 and JP-A 1-5808, etc.)] c) and in the presence of a salt (d) containing iodide ions.
水溶液重合を行う場合、水と有機溶媒とを含む混合溶媒を使用することができる。有機溶媒としては、メタノール、エタノール、アセトン、メチルエチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド及びこれらの２種以上の混合物を挙げられる。
水溶液重合を行う場合、有機溶媒の使用量（重量％）は、水の重量を基準として４０以下が好ましく、更に好ましくは３０以下である。
When aqueous solution polymerization is performed, a mixed solvent containing water and an organic solvent can be used. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, and a mixture of two or more thereof.
When aqueous solution polymerization is performed, the amount (% by weight) of the organic solvent used is preferably 40 or less, more preferably 30 or less, based on the weight of water.
重合方法が懸濁重合法又は逆相懸濁重合法である場合、必要に応じて、従来公知の分散剤又は界面活性剤の存在下に重合を行っても良い。また、逆相懸濁重合法の場合、従来公知のキシレン、ノルマルヘキサン及びノルマルヘプタン等の炭化水素系溶媒を使用して重合を行うことができる。 When the polymerization method is a suspension polymerization method or a reverse phase suspension polymerization method, the polymerization may be performed in the presence of a conventionally known dispersant or surfactant, if necessary. In the case of the reverse phase suspension polymerization method, polymerization can be carried out using a conventionally known hydrocarbon solvent such as xylene, normal hexane and normal heptane.
重合方法のうち、有機溶媒等を使用する必要がなく生産コスト面で有利なことから、好ましいのは水溶液重合法であり、保水量が大きく、且つ水可溶性成分量の少ない水性液体吸収性樹脂が得られ、重合時の温度コントロールが不要である点から、水溶液断熱重合法が更に好ましい。 Among the polymerization methods, it is not necessary to use an organic solvent or the like, and it is advantageous in terms of production cost. Therefore, an aqueous solution polymerization method is preferable, and an aqueous liquid absorbent resin having a large amount of water retention and a small amount of water-soluble components. The aqueous solution adiabatic polymerization method is more preferable because it is obtained and temperature control during polymerization is unnecessary.
重合時の水溶性ビニルモノマー（ａ１）及び／又は加水分解性ビニルモノマー（ａ２）、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）〜（ａ３）、並びに架橋剤（ｂ）を含む単量体組成物の重量パーセント濃度は重合開始時の重合液の総重量に対して２０〜５５％が好ましい。この範囲より低い場合には生産性が悪くなる場合があり、高い場合には十分なゲル強度を得ることができない場合がある。 In the case of using the water-soluble vinyl monomer (a1) and / or hydrolyzable vinyl monomer (a2) at the time of polymerization, and other vinyl monomers (a3), a monomer containing (a1) to (a3) and a crosslinking agent (b) The weight percent concentration of the monomer composition is preferably 20 to 55% with respect to the total weight of the polymerization solution at the start of polymerization. If it is lower than this range, productivity may be deteriorated, and if it is high, sufficient gel strength may not be obtained.
前記の単量体組成物の重合において、必要に応じて公知のラジカル開始剤を用いることが出来る。
公知のラジカル開始剤としては、アゾ化合物［アゾビスイソブチロニトリル、アゾビスシアノ吉草酸及び２，２’−アゾビス（２−アミジノプロパン）ハイドロクロライド、２，２’−アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド]等］、無機過酸化物（過酸化水素、過硫酸アンモニウム、過硫酸カリウム及び過硫酸ナトリウム等）、有機過酸化物［過酸化ベンゾイル、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイド、コハク酸パーオキサイド及びジ（２−エトキシエチル）パーオキシジカーボネート等］、レドックス触媒（アルカリ金属の亜硫酸塩又は重亜硫酸塩、亜硫酸アンモニウム、重亜硫酸アンモニウム及びアスコルビン酸等の還元剤とアルカリ金属の過硫酸塩、過硫酸アンモニウム、過酸化水素及び有機過酸化物等の酸化剤との組み合わせよりなるもの）、光ラジカル発生剤［２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、１−ヒドロキシシクロヘキシル−フェニルケトン−ヒドロキシアルキルフェノン、α−アミノアルキルフェノン等］等があげられる。これらのラジカル開始剤は、単独で使用してもよく、これらの２種以上を併用しても良い。
In the polymerization of the monomer composition, a known radical initiator can be used as necessary.
Known radical initiators include azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid and 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], etc.], inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.), organic peroxides [benzoyl peroxide, di-t-butyl peroxide] , Cumene hydroperoxide, succinic peroxide and di (2-ethoxyethyl) peroxydicarbonate, etc.], redox catalyst (alkali metal sulfite or bisulfite, ammonium sulfite, ammonium bisulfite, ascorbic acid, etc.) Agent and alkali metal persulfate, ammonium persulfate, peroxide water And a radical generator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxycyclohexyl-phenylketone-hydroxyalkylphenone, α-aminoalkylphenone etc.] and the like. These radical initiators may be used alone or in combination of two or more thereof.
ラジカル開始剤の使用量（重量％）は、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）〜（ａ３）の、合計重量に基づいて、０．０００５〜５が好ましく、更に好ましくは０．００１〜２である。 The amount (% by weight) of the radical initiator used is that of the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), in the case of using other vinyl monomers (a3), (a1) to (a3). Based on the total weight, 0.0005 to 5 is preferable, and 0.001 to 2 is more preferable.
水溶性ビニルモノマー（ａ１）及び／又は加水分解性ビニルモノマー（ａ２）並びに架橋剤（ｂ）を含む単量体組成物を前記の有機ヨウ素化合物（ｃ）及びヨウ化物イオンを含む塩（ｄ）の存在下に重合する際の重合開始温度は、０〜１００℃が好ましい。この範囲より低い場合には水溶液が凍結する可能性があり生産が困難であり、高い場合には重合時の温度が高くなり可溶分が増える可能性がある。 A monomer composition containing a water-soluble vinyl monomer (a1) and / or a hydrolyzable vinyl monomer (a2) and a crosslinking agent (b) is converted into the salt containing the organic iodine compound (c) and iodide ion (d). The polymerization initiation temperature when polymerizing in the presence of is preferably 0 to 100 ° C. If it is lower than this range, the aqueous solution may be frozen and production is difficult, and if it is high, the temperature during polymerization may increase and the soluble content may increase.
前記の重合する工程によって、架橋重合体（以下、架橋重合体（Ａ）ともいう）の重合ゲルが得られ、この重合ゲルは、必要に応じて細断することができる。細断後のゲルの大きさ（最長径）は５０μｍ〜１０ｃｍが好ましく、更に好ましくは１００μｍ〜２ｃｍ、特に好ましくは１ｍｍ〜１ｃｍである。この範囲であると、乾燥工程での乾燥性が更に良好となる。 A polymer gel of a cross-linked polymer (hereinafter also referred to as cross-linked polymer (A)) is obtained by the polymerization step, and the polymer gel can be chopped as necessary. The size (longest diameter) of the gel after chopping is preferably 50 μm to 10 cm, more preferably 100 μm to 2 cm, and particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying process is further improved.
細断は、公知の方法で行うことができ、細断装置（例えば、ベックスミル、ラバーチョッパ、ファーマミル、ミンチ機（ミートチョッパー）、衝撃式粉砕機及びロール式粉砕機）等を使用して細断できる。また、必要に応じて、上記のようにして得られる重合ゲルにアルカリを混合して中和することもできる。
アルカリは、公知｛特許第３２０５１６８号公報等｝のものが使用できる。これらのうち、吸水性能の観点から、水酸化リチウム、水酸化ナトリウム及び水酸化カリウムが好ましく、さらに好ましくは水酸化ナトリウム及び水酸化カリウム、特に好ましくは水酸化ナトリウムである。中和率は、通液性の観点から、２０〜１００モル％が好ましく、更に好ましくは、５０〜８０モル％である。中和度が５０モル％未満の場合、得られる含水ゲル重合体の粘着性が高くなり、製造時及び使用時の作業性が悪化する場合がある。更に得られる吸水性樹脂の保水量が低下する場合がある。一方、中和度が８０％を超える場合、得られた樹脂のｐＨが高くなり人体の皮膚に対する安全性が懸念される場合がある。
Shredding can be performed by a known method, and shredding is performed using a shredding device (for example, bex mill, rubber chopper, pharma mill, mincing machine (meet chopper), impact crusher and roll crusher). I can decline. If necessary, the polymerization gel obtained as described above can be neutralized by mixing with an alkali.
As the alkali, those known in the art {Japanese Patent No. 3205168 etc.} can be used. Among these, from the viewpoint of water absorption performance, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable, sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is particularly preferable. The neutralization rate is preferably 20 to 100 mol%, more preferably 50 to 80 mol%, from the viewpoint of liquid permeability. When the degree of neutralization is less than 50 mol%, the resulting water-containing gel polymer has high tackiness, and the workability during production and use may deteriorate. Furthermore, the water retention amount of the water-absorbing resin obtained may decrease. On the other hand, when the degree of neutralization exceeds 80%, the pH of the obtained resin becomes high, and there is a concern that the safety of human skin may be concerned.
本発明の製造方法は、前記の重合ゲルから水及び／又は有機溶剤を留去する工程を含むことが好ましい。水及び／又は有機溶剤を留去する方法としては、８０〜４００℃の温度の熱風で留去（乾燥）する方法、１００〜２３０℃に加熱されたドラムドライヤー等による薄膜乾燥法、（加熱）減圧乾燥法、凍結乾燥法、赤外線による乾燥法、デカンテーション及び濾過等が適用できる。 The production method of the present invention preferably includes a step of distilling off water and / or an organic solvent from the polymer gel. As a method of distilling off water and / or organic solvent, a method of distilling (drying) with hot air at a temperature of 80 to 400 ° C, a thin film drying method using a drum dryer heated to 100 to 230 ° C, (heating) Vacuum drying, freeze drying, infrared drying, decantation, filtration, and the like can be applied.
重合に溶媒（有機溶媒及び水等）を使用する場合、重合後に溶媒を留去することが好ましい。溶媒に有機溶媒を含む場合、留去後の有機溶媒の含有量（重量％）は、架橋重合体（Ａ）の重量に基づいて、０〜１０が好ましく、更に好ましくは０〜５、特に好ましくは０〜３、最も好ましくは０〜１である。この範囲であると、吸水性樹脂粒子の吸収性能が更に良好となる。 When using a solvent (such as an organic solvent and water) for the polymerization, the solvent is preferably distilled off after the polymerization. When the solvent contains an organic solvent, the content (% by weight) of the organic solvent after distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably based on the weight of the crosslinked polymer (A). Is 0-3, most preferably 0-1. Within this range, the absorption performance of the water-absorbent resin particles is further improved.
溶媒に水を含む場合、留去後の水分（重量％）は、架橋重合体（Ａ）の重量に基づいて、０〜２０が好ましく、更に好ましくは０．５〜１０、特に好ましくは１〜９、最も好ましくは２〜８である。この範囲であると、吸収性能が更に良好となる。 When water is contained in the solvent, the water content (% by weight) after distillation is preferably 0 to 20, more preferably 0.5 to 10, particularly preferably 1 to 1, based on the weight of the crosslinked polymer (A). 9, most preferably 2-8. Within this range, the absorption performance is further improved.
なお、有機溶媒の含有量及び水分は、例えば、赤外水分測定器［（株）ＫＥＴＴ社製ＪＥ４００等：１２０±５℃、３０分、加熱前の雰囲気湿度５０±１０％ＲＨ、ランプ仕様１００Ｖ、４０Ｗ］により加熱したときの測定試料の重量減量から求められるが、この手法及びこの機器に限定されない。 The content and moisture of the organic solvent are, for example, an infrared moisture meter [JE400 manufactured by KETT Co., Ltd .: 120 ± 5 ° C., 30 minutes, atmospheric humidity before heating 50 ± 10% RH, lamp specification 100V , 40 W], but is not limited to this method and this apparatus.
本発明の製造方法は、重合ゲルから水及び／又は有機溶剤を留去した後に粉砕する工程を含むことが好ましく、粉砕により好ましく吸水性樹脂粒子が得られる。粉砕する方法については、特に限定はなく、粉砕装置（例えば、ハンマー式粉砕機、衝撃式粉砕機、ロール式粉砕機及びシェット気流式粉砕機、あるいは、実験室規模ではジューサーミキサーも可能）等が使用できる。粉砕による得られる吸水性樹脂粒子は、必要によりふるい分け等により粒度調整できる。 The production method of the present invention preferably includes a step of pulverizing after distilling off water and / or the organic solvent from the polymer gel, and water-absorbing resin particles are preferably obtained by pulverization. The pulverization method is not particularly limited, and a pulverizer (for example, a hammer-type pulverizer, an impact-type pulverizer, a roll-type pulverizer, a shet airflow-type pulverizer, or a juicer mixer on a laboratory scale is also possible). Can be used. The water-absorbent resin particles obtained by pulverization can be adjusted in particle size by sieving if necessary.
必要によりふるい分けした場合の重量平均粒子径（μｍ）は、１００〜８００が好ましく、更に好ましくは２００〜７００、次に好ましくは２５０〜６００、特に好ましくは３００〜５００、最も好ましくは３５０〜４５０である。この範囲であると、吸収性能が更に良好となる。 The weight average particle diameter (μm) when screened if necessary is preferably 100 to 800, more preferably 200 to 700, next preferably 250 to 600, particularly preferably 300 to 500, and most preferably 350 to 450. is there. Within this range, the absorption performance is further improved.
なお、重量平均粒子径は、ロータップ試験篩振とう機及び標準ふるい（ＪＩＳ Ｚ８８０１−１：２００６）を用いて、ペリーズ・ケミカル・エンジニアーズ・ハンドブック第６版（マックグローヒル・ブック・カンバニー、１９８４、２１頁）に記載の方法で測定される。すなわち、ＪＩＳ標準ふるいを、上から１０００μｍ、８５０μｍ、７１０μｍ、５００μｍ、４２５μｍ、３５５μｍ、２５０μｍ、１５０μｍ、１２５μｍ、７５μｍ及び４５μｍ、並びに受け皿、の順に組み合わせる。最上段のふるいに測定粒子の約５０ｇを入れ、ロータップ試験篩振とう機で５分間振とうさせる。各ふるい及び受け皿上の測定粒子の重量を秤量し、その合計を１００重量％として各ふるい上の粒子の重量分率を求め、この値を対数確率紙［横軸がふるいの目開き（粒子径）、縦軸が重量分率］にプロットした後、各点を結ぶ線を引き、重量分率が５０重量％に対応する粒子径を求め、これを重量平均粒子径とする。 In addition, the weight average particle diameter was measured using a low-tap test sieve shaker and a standard sieve (JIS Z8801-1: 2006), Perry's Chemical Engineers Handbook, 6th edition (McGlow Hill Book Company, 1984). , Page 21). That is, JIS standard sieves are combined in the order of 1000 μm, 850 μm, 710 μm, 500 μm, 425 μm, 355 μm, 250 μm, 150 μm, 125 μm, 75 μm and 45 μm, and a tray from the top. About 50 g of the measured particles are put in the uppermost screen and shaken for 5 minutes with a low-tap test sieve shaker. Weigh the measured particles on each sieve and pan, and calculate the weight fraction of the particles on each sieve with the total as 100% by weight. This value is the logarithmic probability paper [horizontal axis is sieve aperture (particle size ), The vertical axis is plotted in the weight fraction], and then a line connecting the points is drawn to obtain the particle diameter corresponding to the weight fraction of 50% by weight, which is defined as the weight average particle diameter.
また、微粒子の含有量は、少ない方が吸収性能が良好となるため、架橋重合体（Ａ）の合計重量に占める１０６μｍ以下（好ましくは１５０μｍ以下）の微粒子の含有率（重量％）は３以下が好ましく、更に好ましくは１以下である。微粒子の含有量は、上記の重量平均粒子径を求める際に作成するグラフを用いて求めることができる。 In addition, the smaller the content of fine particles, the better the absorption performance. Therefore, the content (% by weight) of fine particles of 106 μm or less (preferably 150 μm or less) in the total weight of the crosslinked polymer (A) is 3 or less. Is more preferable, and 1 or less is more preferable. The content of the fine particles can be determined using a graph created when determining the above-mentioned weight average particle diameter.
前記の粉砕する工程を行った後の形状については特に限定はなく、不定形破砕状、リン片状、パール状及び米粒状等が挙げられる。これらの内、紙おむつ用途等での繊維状物とのからみが良く、繊維状物からの脱落の心配がないという観点から、不定形破砕状が好ましい。 There is no particular limitation on the shape after performing the pulverizing step, and examples thereof include an irregularly crushed shape, a flake shape, a pearl shape, and a rice grain shape. Among these, from the viewpoint of good entanglement with the fibrous material for use as a disposable diaper and no fear of dropping off from the fibrous material, an irregularly crushed shape is preferable.
本発明の製造方法は、架橋重合体（Ａ）又は前記重合ゲルを特開２０１３−２３１１９９等に記載の方法等により必要に応じて疎水性物質で処理してもよい。 In the production method of the present invention, the crosslinked polymer (A) or the polymer gel may be treated with a hydrophobic substance as required by the method described in JP2013-231199A or the like.
本発明の製造方法は、架橋重合体（Ａ）を更に表面架橋する工程を有することが好ましい。表面架橋することにより更にゲル強度を向上させることができ、実使用において望ましい保水量と荷重下における吸収量とを満足させることができる。 The production method of the present invention preferably has a step of further surface-crosslinking the crosslinked polymer (A). By surface crosslinking, the gel strength can be further improved, and the water retention amount and the absorption amount under load that are desirable in actual use can be satisfied.
架橋重合体（Ａ）を表面架橋する方法としては、従来公知の方法、例えば、吸水性樹脂を粒子状とした後、表面架橋剤（ｅ）、水及び溶媒の混合溶液を混合し、加熱反応する方法が挙げられる。混合する方法としては、架橋重合体（Ａ）に上記混合溶液を噴霧するか、上記混合溶液に架橋重合体（Ａ）をディッピングする方法等が挙げられ、好ましくは、架橋重合体（Ａ）に上記混合溶液を噴霧して混合する方法である。 As a method for surface cross-linking the cross-linked polymer (A), a conventionally known method, for example, after forming a water-absorbing resin in a particulate form, a mixed solution of a surface cross-linking agent (e), water and a solvent is mixed, followed by a heating reaction. The method of doing is mentioned. Examples of the mixing method include spraying the mixed solution onto the crosslinked polymer (A) or dipping the crosslinked polymer (A) into the mixed solution. Preferably, the crosslinked polymer (A) is mixed with the crosslinked polymer (A). In this method, the mixed solution is sprayed and mixed.
表面架橋剤（ｅ）としては、例えば、エチレングリコールジグリシジルエーテル、グリセロールジグリシジルエーテル及びポリグリセロールポリグリシジルエーテル等のポリグリシジル化合物、グリセリン及びエチレングリコール等の多価アルコール、エチレンカーボネート、ボリアミン並びに多価金属化合物等が挙げられる。これらの内、比較的低い温度で架橋反応を行うことができる点で好ましいのは、ポリグリシジル化合物である。これらの表面架橋剤は単独で使用してもよく、２種以上を併用してもよい。 Examples of the surface cross-linking agent (e) include polyglycidyl compounds such as ethylene glycol diglycidyl ether, glycerol diglycidyl ether and polyglycerol polyglycidyl ether, polyhydric alcohols such as glycerin and ethylene glycol, ethylene carbonate, polyamine and polyhydric acid. A metal compound etc. are mentioned. Among these, a polyglycidyl compound is preferable in that a crosslinking reaction can be performed at a relatively low temperature. These surface crosslinking agents may be used alone or in combination of two or more.
表面架橋剤（ｅ）の使用量は、架橋前の吸水性樹脂の重量に基づいて、好ましくは０．００１〜５重量％、更に好ましくは０．００５〜２重量％である。表面架橋剤（ｅ）の使用量が０．００１重量％未満の場合は、表面架橋度が不足し、荷重下における吸収量の向上効果が不充分となる場合がある。一方、（ｅ）の使用量が５重量％を超える場合は、表面の架橋度が過度となりすぎて保水量が低下する場合がある。 The amount of the surface crosslinking agent (e) used is preferably 0.001 to 5% by weight, more preferably 0.005 to 2% by weight, based on the weight of the water absorbent resin before crosslinking. When the amount of the surface cross-linking agent (e) used is less than 0.001% by weight, the degree of surface cross-linking is insufficient, and the effect of improving the amount of absorption under load may be insufficient. On the other hand, when the amount of (e) used exceeds 5% by weight, the degree of cross-linking of the surface becomes excessive, and the water retention amount may decrease.
表面架橋時の水の使用量は、架橋前の吸水性樹脂の重量に基づいて、好ましくは０．５〜１０重量％、更に好ましくは１〜７重量％である。水の使用量が０．５重量％未満の場合、表面架橋剤（ｅ）の吸水性樹脂粒子内部への浸透度が不充分となり、荷重下における吸収量の向上効果が乏しくなる場合がある。一方、水の使用量が１０重量％を越えると、表面架橋剤（ｅ）の内部への浸透が過度となり、荷重下における吸収量の向上は認められるものの、保水量が低下する場合がある。 The amount of water used for surface crosslinking is preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, based on the weight of the water-absorbent resin before crosslinking. When the amount of water used is less than 0.5% by weight, the degree of penetration of the surface cross-linking agent (e) into the water-absorbent resin particles may be insufficient, and the effect of improving the amount of absorption under load may be poor. On the other hand, when the amount of water used exceeds 10% by weight, penetration of the surface cross-linking agent (e) into the interior becomes excessive, and although an improvement in the amount of absorption under load is observed, the amount of water retained may decrease.
表面架橋時に水と併用して使用される溶媒としては従来公知のものが使用可能であり、表面架橋剤（ｄ）の吸水性樹脂粒子内部への浸透度合い、表面架橋剤（ｅ）の反応性等を考慮し、適宜選択して使用することができるが、好ましくは、メタノール、ジエチレングリコール、プロピレングリコール等の水に溶解しうる親水性有機溶媒である。溶媒は単独で使用してもよいし、２種以上を併用してもよい。
溶媒の使用量は、溶媒の種類により適宜調整できるが、表面架橋前の吸水性樹脂の重量に基づいて、好ましくは１〜１０重量％である。また、水に対する溶媒の比率についても任意に調整することができるが、好ましくは重量基準で２０〜８０重量％、更に好ましくは３０〜７０重量％である。
As the solvent used in combination with water at the time of surface cross-linking, conventionally known solvents can be used, the degree of penetration of the surface cross-linking agent (d) into the water-absorbent resin particles, and the reactivity of the surface cross-linking agent (e). However, it is preferably a hydrophilic organic solvent that can be dissolved in water such as methanol, diethylene glycol, and propylene glycol. A solvent may be used independently and may use 2 or more types together.
Although the usage-amount of a solvent can be suitably adjusted with the kind of solvent, Preferably it is 1-10 weight% based on the weight of the water absorbing resin before surface cross-linking. Moreover, although the ratio of the solvent with respect to water can also be adjusted arbitrarily, Preferably it is 20 to 80 weight% on a weight basis, More preferably, it is 30 to 70 weight%.
表面架橋を行うには、表面架橋剤（ｅ）と水と溶媒との混合溶液を従来公知の方法で吸水性樹脂粒子と混合し、加熱反応を行う。反応温度は、好ましくは１００〜２３０℃、更に好ましくは１２０〜１８０℃である。反応時間は、反応温度により適宜調整することができるが、好ましくは３〜６０分、更に好ましくは１０〜４５分である。表面架橋して得られる粒子状の吸水性樹脂を、最初に用いた表面架橋剤と同種又は異種の表面架橋剤を用いて、更に表面架橋することも可能である。 In order to perform surface crosslinking, a mixed solution of a surface crosslinking agent (e), water and a solvent is mixed with water-absorbent resin particles by a conventionally known method, and a heating reaction is performed. The reaction temperature is preferably 100 to 230 ° C, more preferably 120 to 180 ° C. Although reaction time can be suitably adjusted with reaction temperature, Preferably it is 3 to 60 minutes, More preferably, it is 10 to 45 minutes. The particulate water-absorbing resin obtained by surface cross-linking can be further subjected to surface cross-linking using the same or different type of surface cross-linking agent as the first used surface cross-linking agent.
表面架橋の後、必要により篩別して粒度調整する工程を行ってもよい。粒度調整後に得られた粒子の重量平均粒経は、好ましくは１００〜６００μｍ、更に好ましくは２００〜５００μｍである。微粒子の含有量は少ない方が好ましく、１００μｍ以下の粒子の含有量は３重量％以下であることが好ましく、１５０μｍ以下の粒子の含有量が３重量％以下であることが更に好ましい。 After the surface crosslinking, a step of sieving and adjusting the particle size may be performed as necessary. The weight average particle size of the particles obtained after adjusting the particle size is preferably 100 to 600 μm, more preferably 200 to 500 μm. The content of fine particles is preferably small, the content of particles of 100 μm or less is preferably 3% by weight or less, and the content of particles of 150 μm or less is more preferably 3% by weight or less.
本発明の製造方法においては、任意の段階で、防腐剤、防かび剤、抗菌剤、酸化防止剤、紫外線吸収剤、酸化防止剤、着色剤、芳香剤、消臭剤、多価金属塩、無機質粉末及び有機質繊維状物等を添加することができ、その量は得られた吸水性樹脂の重量に基づいて、好ましくは５重量％以下である。また、必要により本発明の方法における任意の段階で発泡構造を形成するような処理を行ってもよいし、造粒や成型を行うこともできる。 In the production method of the present invention, at any stage, preservatives, fungicides, antibacterial agents, antioxidants, ultraviolet absorbers, antioxidants, colorants, fragrances, deodorants, polyvalent metal salts, An inorganic powder, an organic fibrous material, or the like can be added, and the amount thereof is preferably 5% by weight or less based on the weight of the obtained water absorbent resin. Further, if necessary, a treatment for forming a foamed structure may be performed at any stage in the method of the present invention, and granulation and molding may be performed.
本発明の製造方法で得られる吸水性樹脂粒子の見掛け密度（ｇ／ｍｌ）は、０．５０〜０．８０が好ましく、更に好ましくは０．５１〜０．７５、特に好ましくは０．５２〜０．７０である。この範囲であると、吸収性物品の耐カブレ性が更に良好となる。なお、見掛け密度は、たとえば、ＪＩＳ Ｋ７３６５：１９９９に準拠して、２５℃で測定することができる。 The apparent density (g / ml) of the water absorbent resin particles obtained by the production method of the present invention is preferably 0.50 to 0.80, more preferably 0.51 to 0.75, and particularly preferably 0.52 to 0.52. 0.70. Within this range, the anti-fogging property of the absorbent article is further improved. In addition, an apparent density can be measured at 25 degreeC based on JISK7365: 1999, for example.
本発明の製造方法により得られる吸水性樹脂粒子の生理食塩水に対する保水量は、表面架橋を行わない場合は、好ましくは５０ｇ／ｇ以上７０ｇ／ｇ以下であり、更に好ましくは５３ｇ／ｇ以上６７ｇ／ｇ以下である。表面架橋を行った場合には、好ましくは３０ｇ／ｇ以上６０ｇ／ｇ以下であり、更に好ましくは３５ｇ／ｇ以上５０ｇ／ｇ以下である。保水量が低いとおむつの吸収量が少なくなり、保水量が高すぎる場合には可溶分が多くなり好ましくない。尚、保水量は後述する方法で測定される。 The water retention amount of the water-absorbent resin particles obtained by the production method of the present invention with respect to physiological saline is preferably 50 g / g or more and 70 g / g or less, more preferably 53 g / g or more and 67 g when surface crosslinking is not performed. / G or less. When surface cross-linking is performed, it is preferably 30 g / g or more and 60 g / g or less, and more preferably 35 g / g or more and 50 g / g or less. If the water retention amount is low, the amount of diaper absorbed is reduced, and if the water retention amount is too high, the soluble content increases, which is not preferable. The water retention amount is measured by the method described later.
本発明の製造方法により得られる吸水性樹脂粒子の生理食塩水に対する可溶分量は、表面架橋を行わない場合は、好ましくは０〜１２％であり、更に好ましくは０〜１０％である。表面架橋を行った場合には、好ましくは０〜１０％であり、更に好ましくは０〜８％である。この範囲であれば、膨潤ゲルのべとつき感が抑えられる。尚、可溶分量は後述する方法で測定される。 The soluble content of the water-absorbent resin particles obtained by the production method of the present invention in physiological saline is preferably 0 to 12%, and more preferably 0 to 10%, when surface crosslinking is not performed. When surface crosslinking is performed, it is preferably 0 to 10%, and more preferably 0 to 8%. If it is this range, the sticky feeling of swelling gel is suppressed. The soluble content is measured by the method described later.
本発明の製造方法で得られる吸水性樹脂粒子は、単独で吸収体として用いても良く、他の材料と共に用いて吸収体としても良い。
他の材料としては繊維状物等が挙げられる。繊維状物と共に用いた場合の吸収体の構造及び製造方法等は、公知のもの（特開２００３−２２５５６５号公報、特開２００６−１３１７６７号公報及び特開２００５−０９７５６９号公報等）と同様である。
The water absorbent resin particles obtained by the production method of the present invention may be used alone as an absorber, or may be used together with other materials as an absorber.
Examples of other materials include fibrous materials. The structure and production method of the absorber when used together with the fibrous material are the same as those known (JP 2003-225565 A, JP 2006-131767 A, JP 2005-097569 A, etc.). is there.
上記繊維状物として好ましいのは、セルロース系繊維、有機系合成繊維及びセルロース系繊維と有機系合成繊維との混合物である。 Preferred as the fibrous material are cellulosic fibers, organic synthetic fibers, and mixtures of cellulosic fibers and organic synthetic fibers.
セルロース系繊維としては、例えばフラッフパルプ等の天然繊維、ビスコースレーヨン、アセテート及びキュプラ等のセルロース系化学繊維が挙げられる。このセルロース系天然繊維の原料（針葉樹及び広葉樹等）、製造方法（ケミカルパルプ、セミケミカルパルプ、メカニカルパルプ及びＣＴＭＰ等）及び漂白方法等は特に限定されない。 Examples of cellulosic fibers include natural fibers such as fluff pulp, and cellulosic chemical fibers such as viscose rayon, acetate, and cupra. There are no particular restrictions on the raw materials (conifers, hardwoods, etc.), production methods (chemical pulp, semi-chemical pulp, mechanical pulp, CTMP, etc.), bleaching methods, etc. of this cellulose-based natural fiber.
有機系合成繊維としては、例えばポリプロピレン系繊維、ポリエチレン系繊維、ポリアミド系繊維、ポリアクリロニトリル系繊維、ポリエステル系繊維、ポリビニルアルコール系繊維、ポリウレタン系繊維及び熱融着性複合繊維（融点の異なる上記繊維の少なくとも２種を鞘芯型、偏芯型、並列型等に複合化された繊維、上記繊維の少なくとも２種をブレンドした繊維及び上記繊維の表層を改質した繊維等）が挙げられる。 Examples of organic synthetic fibers include polypropylene fibers, polyethylene fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, polyvinyl alcohol fibers, polyurethane fibers, and heat-fusible composite fibers (the above fibers having different melting points). And a fiber obtained by compounding at least two of the above into a sheath core type, an eccentric type, a parallel type, and the like, a fiber obtained by blending at least two kinds of the above fibers, and a fiber obtained by modifying the surface layer of the above fibers).
これらの繊維状物の内で好ましいのは、セルロース系天然繊維、ポリプロピレン系繊維、ポリエチレン系繊維、ポリエステル系繊維、熱融着性複合繊維及びこれらの混合繊維であり、更に好ましいのは、得られた吸収体の吸水後の形状保持性に優れるという点で、フラッフパルプ、熱融着性複合繊維及びこれらの混合繊維である。 Among these fibrous materials, preferred are cellulose-based natural fibers, polypropylene-based fibers, polyethylene-based fibers, polyester-based fibers, heat-fusible conjugate fibers, and mixed fibers thereof, and more preferable are obtained. The fluff pulp, the heat-fusible conjugate fiber, and the mixed fiber thereof are preferable in that the shape-retaining property of the absorbent body after water absorption is excellent.
上記繊維状物の長さ、太さについては特に限定されず、長さは１〜２００ｍｍ、太さは０．１〜１００デニールの範囲であれば好適に使用することができる。形状についても繊維状であれば特に限定されず、細い円筒状、スプリットヤーン状、ステープル状、フィラメント状及びウェブ状等が例示される。 The length and thickness of the fibrous material are not particularly limited, and can be suitably used as long as the length is 1 to 200 mm and the thickness is in the range of 0.1 to 100 denier. The shape is not particularly limited as long as it is fibrous, and examples thereof include a thin cylindrical shape, a split yarn shape, a staple shape, a filament shape, and a web shape.
前記の吸水性樹脂粒子を、繊維状物と共に吸収体とする場合、吸水性樹脂粒子と繊維の重量比率（吸水性樹脂粒子の重量／繊維の重量）は４０／６０〜９０／１０が好ましく、更に好ましくは７０／３０〜８０／２０である。 When the water-absorbent resin particles are used as an absorbent together with the fibrous material, the weight ratio of the water-absorbent resin particles to the fibers (weight of the water-absorbent resin particles / weight of the fibers) is preferably 40/60 to 90/10, More preferably, it is 70 / 30-80 / 20.
前記の吸水性樹脂粒子を含む吸収体は、吸収性物品として用いることができる。吸収性物品としては、紙おむつや生理用ナプキン等の衛生用品のみならず、後述する各種水性液体の吸収や保持剤用途、ゲル化剤用途等の各種用途に使用されるものとして適用可能である。吸収性物品の製造方法等は、公知のもの（特開２００３−２２５５６５号公報、特開２００６−１３１７６７号公報及び特開２００５−０９７５６９号公報等に記載のもの）と同様である。 The absorber containing the water absorbent resin particles can be used as an absorbent article. The absorbent article is applicable not only to sanitary articles such as paper diapers and sanitary napkins, but also to various uses such as absorption of various aqueous liquids described below, use as a retention agent, and use as a gelling agent. The manufacturing method etc. of an absorbent article are the same as that of what is well-known (The thing of Unexamined-Japanese-Patent No. 2003-225565, Unexamined-Japanese-Patent No. 2006-131767, Unexamined-Japanese-Patent No. 2005-097569, etc.).
以下、実施例及び比較例により本発明を更に説明するが、本発明はこれらに限定されるものではない。以下、特に定めない限り、部は重量部、％は重量％を示す。なお、吸水性樹脂粒子の生理食塩水に対する保水量、荷重下吸収量及び可溶分量は以下の方法により測定した。 Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, parts indicate parts by weight and% indicates% by weight. In addition, the water retention amount with respect to the physiological saline of the water-absorbent resin particles, the absorption amount under load, and the soluble content were measured by the following methods.
＜保水量の測定方法＞
目開き６３μｍ（ＪＩＳ Ｚ８８０１−１：２００６）のナイロン網で作製したティーバッグ（縦２０ｃｍ、横１０ｃｍ）に測定試料１．００ｇを入れ、生理食塩水（食塩濃度０．９％）１，０００ｍｌ中に無撹拌下、１時間浸漬した後引き上げて、１５分間吊るして水切りした。その後、ティーバッグごと、遠心分離器にいれ、１５０Ｇで９０秒間遠心脱水して余剰の生理食塩水を取り除き、ティーバックを含めた重量（ｈ１）を測定し次式から保水量を求めた。（ｈ２）は、測定試料の無い場合について上記と同様の操作により計測したティーバックの重量である。なお、使用した生理食塩水及び測定雰囲気の温度は２５℃±２℃であった。
保水量（ｇ／ｇ）＝（ｈ１）−（ｈ２）
<Measurement method of water retention amount>
1.00 g of a measurement sample is placed in a tea bag (20 cm long, 10 cm wide) made of a nylon net having a mesh size of 63 μm (JIS Z8801-1: 2006) and in 1,000 ml of physiological saline (saline concentration 0.9%). The sample was immersed for 1 hour without stirring and then pulled up, suspended for 15 minutes and drained. Thereafter, each tea bag was placed in a centrifuge, centrifuged at 150 G for 90 seconds to remove excess physiological saline, and the weight (h1) including the tea bag was measured to obtain the water retention amount from the following formula. (H2) is the weight of the tea bag measured by the same operation as described above when there is no measurement sample. In addition, the temperature of the used physiological saline and measurement atmosphere was 25 degreeC +/- 2 degreeC.
Water retention amount (g / g) = (h1)-(h2)
＜荷重下吸収量の測定方法＞
目開き６３μｍ（ＪＩＳ Ｚ８８０１−１：２００６）のナイロン網を底面に貼った円筒型プラスチックチューブ（内径：２５ｍｍ、高さ：３４ｍｍ）内に、３０メッシュふるいと６０メッシュふるいを用いて２５０〜５００μｍの範囲にふるい分けした測定試料０．１６ｇを秤量し、円筒型プラスチックチューブを垂直にしてナイロン網上に測定試料がほぼ均一厚さになるように整えた後、この測定試料の上に分銅（重量：２１０．６ｇ、外径：２４．５ｍｍ、）を乗せた。この円筒型プラスチックチューブ全体の重量（Ｍ１）を計量した後、生理食塩水（食塩濃度０．９％）６０ｍｌの入ったシャーレ（直径：１２ｃｍ）の中に測定試料及び分銅の入った円筒型プラスチックチューブを垂直に立ててナイロン網側を下面にして浸し、６０分静置した。６０分後に、円筒型プラスチックチューブをシャーレから引き上げ、これを斜めに傾けて底部に付着した水を一箇所に集めて水滴として垂らすことで余分な水を除去した後、測定試料及び分銅の入った円筒型プラスチックチューブ全体の重量（Ｍ２）を計量し、次式から加圧下吸収量を求めた。なお、使用した生理食塩水及び測定雰囲気の温度は２５℃±２℃であった。
荷重下吸収量（ｇ／ｇ）＝｛（Ｍ２）−（Ｍ１）｝／０．１６
<Measurement method of absorption under load>
Using a 30-mesh sieve and a 60-mesh sieve in a cylindrical plastic tube (inner diameter: 25 mm, height: 34 mm) with a 63 μm mesh (JIS Z8801-1: 2006) nylon net attached to the bottom, 250-500 μm Weighing 0.16 g of the measurement sample screened in the range, aligning the cylindrical plastic tube vertically and adjusting the measurement sample to a substantially uniform thickness on a nylon mesh, and then weighing on the measurement sample (weight: 210.6 g, outer diameter: 24.5 mm). After measuring the weight (M1) of the entire cylindrical plastic tube, a cylindrical plastic containing a measurement sample and a weight in a petri dish (diameter: 12 cm) containing 60 ml of physiological saline (salt concentration 0.9%). The tube was set up vertically and immersed with the nylon mesh side as the bottom surface and allowed to stand for 60 minutes. After 60 minutes, the cylindrical plastic tube was pulled up from the petri dish, and the slant was tilted to collect the water adhering to the bottom in one place and dropped as water droplets. The total weight (M2) of the cylindrical plastic tube was weighed, and the amount of absorption under pressure was determined from the following equation. In addition, the temperature of the used physiological saline and measurement atmosphere was 25 degreeC +/- 2 degreeC.
Absorption under load (g / g) = {(M2)-(M1)} / 0.16
＜可溶分量の測定方法＞
３００ｍＬビーカーに生理食塩水（食塩濃度０．９％）２００ｍＬと測定試料１．２０ｇを入れ、マグネティックスターラーで１５０ｒｐｍに攪拌下、３時間攪拌した。その後、ＡＤＶＡＮＴＥＣ社製定性濾紙（Ｎｏ．２）を用いて濾過した。濾液４０ｍｌを生理食塩水（食塩濃度０．９％）１０ｍｌで希釈し、測定溶液とする。この測定溶液を、まず、１／５０ＮのＫＯＨ水溶液でｐＨ１０まで滴定を行い（滴定に用いた液量をＷ１（ｍＬ）とする）、次いで１／１０ＮのＨＣｌ水溶液でｐＨ２．７まで滴定する（滴定に用いた液量をＷ２（ｍＬ）とする）。また空試験として生理食塩水５０ｍＬを１／５０ＮのＫＯＨ水溶液でｐＨ１０まで滴定を行い（滴定に用いた液量をＷ３（ｍＬ）とする）、次いで１／２０ＮのＨＣｌ水溶液でｐＨ２．７まで滴定する（滴定に用いた液量をＷ４（ｍＬ）とする）。なお、使用した生理食塩水及び測定雰囲気の温度は２５℃±２℃であった。可溶分量は、吸水性樹脂に対する生理食塩水抽出成分の重量％であり、抽出成分が全てポリアクリル酸（塩）であると仮定した数値として次式から求めた。
可溶分量（％）＝３．９２×（Ｗ２−Ｗ４）−０．１８３×（Ｗ１−Ｗ３）
<Method for measuring soluble content>
A 300 mL beaker was charged with 200 mL of physiological saline (salt concentration: 0.9%) and 1.20 g of a measurement sample, and stirred for 3 hours while stirring at 150 rpm with a magnetic stirrer. Then, it filtered using the qualitative filter paper (No. 2) by ADVANTEC. 40 ml of the filtrate is diluted with 10 ml of physiological saline (saline concentration 0.9%) to obtain a measurement solution. The measurement solution is first titrated with a 1/50 N KOH aqueous solution to pH 10 (the amount of liquid used for the titration is W1 (mL)), and then titrated with a 1/10 N aqueous HCl solution to pH 2.7 ( The amount of liquid used for the titration is W2 (mL)). Also, as a blank test, 50 mL of physiological saline was titrated with 1/50 N KOH aqueous solution to pH 10 (the amount used for titration was set to W3 (mL)), and then titrated with 1/20 N HCl aqueous solution to pH 2.7. (The amount of liquid used for titration is set to W4 (mL)). In addition, the temperature of the used physiological saline and measurement atmosphere was 25 degreeC +/- 2 degreeC. The amount of soluble component was the weight% of the physiological saline extract component relative to the water-absorbent resin, and was calculated from the following equation as a numerical value assuming that all the extract components were polyacrylic acid (salt).
Soluble content (%) = 3.92 × (W2−W4) −0.183 × (W1−W3)
＜実施例１＞
アクリル酸３００部、架橋剤としてのペンタエリスリトールトリアリルエーテル（ダイソー製）０．８３部（アクリル酸のモル数に対して０．０７８モル％）、２−メチル−２−ヨードプロピオニトリル（ＴＣＩ製）０．０３部及びイオン交換水６９０部を混合してモノマー水溶液を調製し、この混合液を断熱重合可能な重合槽に投入した。溶液中に窒素ガスを導入することにより、溶液中の溶存酸素量を０．２ｐｐｍ以下とし、溶液温度を５℃とした。この重合溶液に、１％過酸化水素水溶液１．２部、２％アスコルビン酸水溶液２．３部、３％ヨウ化ナトリウム水溶液０．７部及び２％の２，２’−アゾビス[２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド]水溶液４．５部を添加・混合した。重合開始を示す温度上昇が確認されてから約１時間後に９０℃でほぼ平衡に達し、更に５時間熟成して含水ゲル状重合体を得た。
この含水ゲル状重合体を、ミートチョッパーを用いて小片に砕断しながら、４９％のＮａＯＨ水溶液２４７部を添加し、重合体中のカルボキシル基の約７２モル％をナトリウム塩とした。この中和された含水ゲルを、通気熱風乾燥機（井上金属製）を用い、供給風温１５０℃、風速１．５ｍ／秒の条件下で含水率が３％となるまで通気乾燥した。乾燥体をジューサーミキサー（Ｏｓｔｅｒ社製ＯＳＴＥＲＩＺＥＲ ＢＬＥＮＤＥＲ）にて粉砕した後、ふるい分けして、目開き７１０〜１５０μｍの粒子径範囲に調整して、吸水性樹脂粒子（Ａ１−１）を得た。
<Example 1>
300 parts of acrylic acid, 0.83 part of pentaerythritol triallyl ether (manufactured by Daiso) as a crosslinking agent (0.078 mol% based on the number of moles of acrylic acid), 2-methyl-2-iodopropionitrile (TCI) (Manufactured) 0.03 part and 690 parts of ion-exchanged water were mixed to prepare an aqueous monomer solution, and this mixed liquid was put into a polymerization tank capable of adiabatic polymerization. By introducing nitrogen gas into the solution, the amount of dissolved oxygen in the solution was 0.2 ppm or less, and the solution temperature was 5 ° C. To this polymerization solution, 1.2 parts of 1% aqueous hydrogen peroxide solution, 2.3 parts of 2% aqueous ascorbic acid solution, 0.7 parts of 3% aqueous sodium iodide solution and 2% 2,2′-azobis [2-methyl 4.5 parts of an —N- (2-hydroxyethyl) propionamide] aqueous solution was added and mixed. About 1 hour after the temperature increase indicating the start of polymerization was confirmed, the liquid reached a substantially equilibrium at 90 ° C., and was further aged for 5 hours to obtain a hydrogel polymer.
While this hydrogel polymer was crushed into small pieces using a meat chopper, 247 parts of a 49% NaOH aqueous solution was added, and about 72 mol% of the carboxyl groups in the polymer were converted to sodium salts. This neutralized water-containing gel was air-dried using a ventilated hot air dryer (manufactured by Inoue Metal) under a supply air temperature of 150 ° C. and a wind speed of 1.5 m / sec until the water content became 3%. The dried product was pulverized with a juicer mixer (OSTERIZER BLENDER manufactured by Oster) and then sieved to adjust the particle size to a particle size range of 710 to 150 μm to obtain water absorbent resin particles (A1-1).
＜実施例２＞
実施例１において、３％ヨウ化ナトリウム水溶液０．７部を３％ヨウ化カリウム水溶液１．２部に変更する以外は、実施例１と同様の操作を行い、吸水性樹脂粒子（Ａ１−２）を得た。
<Example 2>
In Example 1, water-absorbent resin particles (A1-2) were prepared in the same manner as in Example 1 except that 0.7 part of 3% aqueous sodium iodide solution was changed to 1.2 parts of 3% aqueous potassium iodide solution. )
＜実施例３＞
実施例１において、３％ヨウ化ナトリウム水溶液０．７部を３％ヨウ化セシウム水溶液３．０部に変更する以外は、実施例１と同様の操作を行い、吸水性樹脂粒子（Ａ１−３）を得た。
<Example 3>
In Example 1, water-absorbent resin particles (A1-3) were prepared in the same manner as in Example 1 except that 0.7 parts of 3% aqueous sodium iodide solution was changed to 3.0 parts of 3% aqueous cesium iodide solution. )
＜実施例４＞
実施例１において、３％ヨウ化ナトリウム水溶液０．７部を３％ヨウ化カルシウム水溶液４．０部に変更する以外は、実施例１と同様の操作を行い、吸水性樹脂粒子（Ａ１−４）を得た。
<Example 4>
In Example 1, water-absorbent resin particles (A1-4) were prepared in the same manner as in Example 1 except that 0.7 part of 3% sodium iodide aqueous solution was changed to 4.0 parts of 3% calcium iodide aqueous solution. )
＜実施例５＞
実施例１において、２−メチル−２−ヨードプロピオニトリル（ＴＣＩ製）０．０３部を２−ヨード−２−メチルプロピオン酸エチル（ＴＣＩ製）０．０３部に変更する以外は、実施例１と同様の操作を行い、吸水性樹脂粒子（Ａ１−５）を得た。
<Example 5>
Example 1 except that 0.03 part of 2-methyl-2-iodopropionitrile (manufactured by TCI) is changed to 0.03 part of ethyl 2-iodo-2-methylpropionate (manufactured by TCI) in Example 1. The same operation as 1 was performed to obtain water-absorbing resin particles (A1-5).
＜実施例６＞
吸水性樹脂（Ａ１−１）１００部を攪拌（ホソカワミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、エチレングリコールジグリシジルエーテル０．０９部、水３．４部及びプロピレングリコール１．４部からなる溶液を噴霧して添加して混合し、１４０℃で４５分加熱して表面架橋を行い、吸水性樹脂粒子（Ａ２−１）を得た。
<Example 6>
While stirring 100 parts of the water-absorbent resin (A1-1) (Hosokawa Micron high-speed stirring turbulizer: rotation speed 2000 rpm), 0.09 part of ethylene glycol diglycidyl ether, 3.4 parts of water and 1.4 parts of propylene glycol The solution consisting of was sprayed and added, mixed and heated at 140 ° C. for 45 minutes for surface crosslinking to obtain water-absorbing resin particles (A2-1).
＜実施例７＞
吸水性樹脂（Ａ１−２）１００部を攪拌（ホソカワミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、エチレングリコールジグリシジルエーテル０．０２部、水０．５部及びプロピレングリコール０．４部からなる溶液を噴霧して添加して混合し、１４０℃で４５分加熱して表面架橋を行い、吸水性樹脂粒子（Ａ２−２）を得た。
<Example 7>
While stirring 100 parts of the water-absorbent resin (A1-2) (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.02 part of ethylene glycol diglycidyl ether, 0.5 part of water and 0.4 part of propylene glycol The solution consisting of was sprayed and added, mixed and heated at 140 ° C. for 45 minutes for surface crosslinking to obtain water-absorbing resin particles (A2-2).
＜実施例８＞
吸水性樹脂（Ａ１−３）１００部を攪拌（ホソカワミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、エチレングリコールジグリシジルエーテル０．０６部、水１．１部及びプロピレングリコール０．８部からなる溶液を噴霧して添加して混合し、１４０℃で４５分加熱して表面架橋を行い、吸水性樹脂粒子（Ａ２−３）を得た。
<Example 8>
While stirring 100 parts of the water-absorbent resin (A1-3) (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.06 part of ethylene glycol diglycidyl ether, 1.1 part of water and 0.8 part of propylene glycol The solution consisting of was sprayed and added, mixed, and heated at 140 ° C. for 45 minutes to perform surface crosslinking to obtain water-absorbing resin particles (A2-3).
＜実施例９＞
吸水性樹脂（Ａ１−４）１００部を攪拌（ホソカワミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、エチレングリコールジグリシジルエーテル０．０５部、水１．０部及びプロピレングリコール０．８部からなる溶液を噴霧して添加して混合し、１４０℃で４５分加熱して表面架橋を行い、吸水性樹脂粒子（Ａ２−４）を得た。
<Example 9>
While stirring 100 parts of the water-absorbent resin (A1-4) (High-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.05 part of ethylene glycol diglycidyl ether, 1.0 part of water and 0.8 part of propylene glycol The solution consisting of was sprayed and added, mixed and heated at 140 ° C. for 45 minutes for surface crosslinking to obtain water-absorbing resin particles (A2-4).
＜実施例１０＞
吸水性樹脂（Ａ１−５）１００部を攪拌（ホソカワミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、エチレングリコールジグリシジルエーテル０．０９部、水４．６部及びプロピレングリコール１．４部からなる溶液を噴霧して添加して混合し、１４０℃で４５分加熱して表面架橋を行い、吸水性樹脂粒子（Ａ２−５）を得た。
<Example 10>
While stirring 100 parts of the water absorbent resin (A1-5) (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.09 part of ethylene glycol diglycidyl ether, 4.6 parts of water and 1.4 parts of propylene glycol The solution consisting of was sprayed and added, mixed and heated at 140 ° C. for 45 minutes for surface crosslinking to obtain water-absorbing resin particles (A2-5).
＜比較例１＞
実施例１において、２−ヨード−２−メチルプロピオニトリルおよび３％ヨウ化ナトリウム水溶液を用いなかった以外は、実施例１と同様の操作を行い、比較用の吸水性樹脂粒子（Ｒ１−１）を得た。
<Comparative Example 1>
In Example 1, except that 2-iodo-2-methylpropionitrile and 3% aqueous sodium iodide solution were not used, the same operation as in Example 1 was performed, and comparative water absorbent resin particles (R1-1) were used. )
＜比較例２＞
実施例１において、２−ヨード−２−メチルプロピオニトリルおよび３％ヨウ化ナトリウム水溶液を用いず、ペンタエリスリトールトリアリルエーテル０．８３部を０．５８部（アクリル酸のモル数に対して０．０５４モル％）に変更した以外は、実施例１と同様の操作を行い、比較用の吸水性樹脂粒子（Ｒ１−２）を得た。
<Comparative example 2>
In Example 1, without using 2-iodo-2-methylpropionitrile and 3% aqueous sodium iodide solution, 0.83 part of pentaerythritol triallyl ether was added to 0.58 part (0 moles per mole of acrylic acid). Except for the change to 0.054 mol%), the same operation as in Example 1 was performed to obtain comparative water-absorbent resin particles (R1-2).
＜比較例３＞
実施例１において、２−ヨード−２−メチルプロピオニトリルの代わりに次亜リン酸ナトリウム一水和物０．２３部を使用し、３％ヨウ化ナトリウム水溶液を用いた以外は、実施例１と同様の操作を行い、比較用の吸水性樹脂粒子（Ｒ１−３）を得た。
<Comparative Example 3>
Example 1 Example 1 except that 0.23 parts of sodium hypophosphite monohydrate was used in place of 2-iodo-2-methylpropionitrile and a 3% aqueous sodium iodide solution was used. The same operation was performed to obtain comparative water absorbent resin particles (R1-3).
＜比較例４＞
吸水性樹脂（Ａ１−１）に代えて比較用の吸水性樹脂粒子（Ｒ１−１）を使用する以外は実施例５と同様にして、比較用の吸水性樹脂粒子（Ｒ２−１）を得た。
<Comparative example 4>
Comparative water absorbent resin particles (R2-1) were obtained in the same manner as in Example 5 except that comparative water absorbent resin particles (R1-1) were used instead of the water absorbent resin (A1-1). It was.
＜比較例５＞
吸水性樹脂（Ａ１−１）に代えて比較用の吸水性樹脂粒子（Ｒ１−２）を使用する以外は実施例５と同様にして、比較用の吸水性樹脂粒子（Ｒ２−２）を得た。
<Comparative Example 5>
Comparative water absorbent resin particles (R2-2) were obtained in the same manner as in Example 5 except that comparative water absorbent resin particles (R1-2) were used instead of the water absorbent resin (A1-1). It was.
＜比較例６＞
吸水性樹脂（Ａ１−２）に代えて比較用の吸水性樹脂粒子（Ｒ１−２）を使用する以外は実施例６と同様にして、比較用の吸水性樹脂粒子（Ｒ２−３）を得た。
<Comparative Example 6>
Comparative water absorbent resin particles (R2-3) were obtained in the same manner as in Example 6 except that comparative water absorbent resin particles (R1-2) were used instead of the water absorbent resin (A1-2). It was.
得られた吸水性樹脂粒子（Ａ１−１）〜（Ａ１−４）及び比較用の吸水性樹脂粒子（Ｒ１−１）〜（Ｒ１−３）の保水量、可溶分量の評価結果を表１に示した。
また、得られた吸水性樹脂粒子（Ａ２−１）〜（Ａ２−４）及び比較用の吸水性樹脂粒子（Ｒ２−１）〜（Ｒ２−３）の保水量、荷重下吸収量、可溶分量の評価結果を表２に示した。
Table 1 shows the evaluation results of the water retention amount and soluble content of the obtained water absorbent resin particles (A1-1) to (A1-4) and comparative water absorbent resin particles (R1-1) to (R1-3). It was shown to.
The water-absorbing resin particles (A2-1) to (A2-4) and the comparative water-absorbing resin particles (R2-1) to (R2-3) were also retained in water, absorbed under load, and soluble. The evaluation results of the amount are shown in Table 2.
表１及び表２の結果から、本発明の製造方法で得られる吸水性樹脂粒子は、比較例の吸水性樹脂粒子に比べて、保水量が高いにも関わらず可溶分量が少ないことがわかる。例えば、比較例３は、保水量が高いにも関わらず本発明の吸水性樹脂粒子に比べて可溶分量が多いことを示し、比較例１は、可溶分量が少ないものの、保水量が低い。比較例２は、架橋剤の使用量を減らして保水量を高める従来手法に相当するが、０００５段落で言及したとおり可溶分量が増えている。また、表２の結果から、比較例の吸水性樹脂に比べて本発明の吸水性樹脂粒子は、同等以上の保水量を有しながら荷重下吸収量が向上しつつ、可溶分量が減少しており、吸収性能が飛躍的に向上していることが分かる。 From the results of Tables 1 and 2, it is understood that the water-absorbent resin particles obtained by the production method of the present invention have a small amount of soluble matter compared to the water-absorbent resin particles of the comparative example, although the water retention amount is high. . For example, Comparative Example 3 shows that the amount of soluble components is large compared to the water-absorbent resin particles of the present invention even though the amount of water retention is high, and Comparative Example 1 has a low amount of water retained, although the amount of soluble components is small. . Comparative Example 2 corresponds to a conventional method in which the amount of the crosslinking agent used is reduced to increase the water retention amount, but the soluble content is increased as mentioned in paragraph 0005. In addition, from the results of Table 2, the water-absorbent resin particles of the present invention have a water retention amount equal to or higher than that of the comparative water-absorbent resin, while improving the absorption amount under load and reducing the soluble content. It can be seen that the absorption performance is dramatically improved.
本発明の製造方法で得られる吸水性樹脂粒子は、保水量と荷重下吸収量に優れ、かつ、可溶分が少ない。そのため、吸水性樹脂粒子はさまざまの使用状況においても安定して優れた吸収性能（例えば液拡散性、吸収速度及び吸収量）を発揮し、かつ膨潤ゲルのべとつき感が小さいため、これらを用いた衛生用品等は不快感が少なくカブレが生じにくい。また、各種の吸収体に適用することにより、吸収量が多く、逆戻り性や表面ドライ感に優れた吸収性物品、例えば、紙おむつ（子供用紙おむつ及び大人用紙おむつ等）、ナプキン（生理用ナプキン等）、紙タオル、パッド（失禁者用パッド及び手術用アンダーパッド等）及びペットシート（ペット尿吸収シート）等の衛生用品に好適に用いられ、特に紙おむつに最適である。なお、本発明の製造方法で得られる吸水性樹脂粒子は衛生用品のみならず、ペット尿吸収剤、携帯トイレの尿ゲル化剤、青果物等の鮮度保持剤、肉類及び魚介類のドリップ吸収剤、保冷剤、使い捨てカイロ、電池用ゲル化剤、植物及び土壌等の保水剤、結露防止剤、止水材やパッキング材並びに人工雪等、種々の用途にも有用である。 The water-absorbent resin particles obtained by the production method of the present invention are excellent in water retention and absorption under load, and have a low soluble content. For this reason, the water-absorbent resin particles are used because they exhibit stable and excellent absorption performance (for example, liquid diffusibility, absorption speed and absorption amount) even under various usage conditions, and the sticky feeling of the swollen gel is small. Sanitary goods and the like are less uncomfortable and less likely to fog. Also, by applying to various absorbents, absorbent articles that absorb a large amount and are excellent in reversibility and surface dryness, such as paper diapers (children's paper diapers, adult paper diapers, etc.), napkins (sanitary napkins, etc.) ), Paper towels, pads (such as incontinence pads and surgical underpads) and pet sheets (pet urine absorbing sheets), etc., and are particularly suitable for paper diapers. The water-absorbent resin particles obtained by the production method of the present invention are not only sanitary products, but also pet urine absorbents, urine gelling agents for portable toilets, freshness retaining agents such as fruits and vegetables, meat and seafood drip absorbents, It is also useful for various applications such as cold insulation agents, disposable warmers, gelling agents for batteries, water retention agents for plants and soil, anti-condensation agents, water-stopping materials and packing materials, and artificial snow.
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| WO2023276925A1 (en) * | 2021-06-28 | 2023-01-05 | Ｓｄｐグローバル株式会社 | Water-absorbing resin composition, absorber and absorbent article obtained using same, and method for producing water-absorbing resin composition |
| WO2023188633A1 (en) * | 2022-03-30 | 2023-10-05 | Ｓｄｐグローバル株式会社 | Water-absorbable resin composition, absorber and absorbent article each using same, and method for producing water-absorbable resin composition |
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