JP5473680B2 - Absorbent resin particles and method for producing the same - Google Patents
Absorbent resin particles and method for producing the same Download PDFInfo
- Publication number
- JP5473680B2 JP5473680B2 JP2010047314A JP2010047314A JP5473680B2 JP 5473680 B2 JP5473680 B2 JP 5473680B2 JP 2010047314 A JP2010047314 A JP 2010047314A JP 2010047314 A JP2010047314 A JP 2010047314A JP 5473680 B2 JP5473680 B2 JP 5473680B2
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- Prior art keywords
- carbon atoms
- absorbent resin
- resin particles
- group
- long
- Prior art date
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- 239000002250 absorbent Substances 0.000 title claims description 76
- 230000002745 absorbent Effects 0.000 title claims description 74
- 239000002245 particle Substances 0.000 title claims description 70
- 239000011347 resin Substances 0.000 title claims description 51
- 229920005989 resin Polymers 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 229920006037 cross link polymer Polymers 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 39
- 230000002209 hydrophobic effect Effects 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 30
- -1 long-chain fatty acid salts Chemical class 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 25
- 239000010419 fine particle Substances 0.000 claims description 23
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002646 long chain fatty acid esters Chemical class 0.000 claims description 6
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 2
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- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 125000001165 hydrophobic group Chemical group 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 44
- 238000010521 absorption reaction Methods 0.000 description 28
- 239000000499 gel Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 16
- 235000021355 Stearic acid Nutrition 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 15
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 14
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
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- 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 7
- 239000006096 absorbing agent Substances 0.000 description 7
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 6
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- SZYSLWCAWVWFLT-UTGHZIEOSA-N [(2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)-2-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxolan-2-yl]methyl octadecanoate Chemical compound O([C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@]1(COC(=O)CCCCCCCCCCCCCCCCC)O[C@H](CO)[C@@H](O)[C@@H]1O SZYSLWCAWVWFLT-UTGHZIEOSA-N 0.000 description 5
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- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011246 composite particle Substances 0.000 description 4
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000011802 pulverized particle Substances 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- FABAOYOFJNAVHB-KVVVOXFISA-N (z)-octadec-9-enoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O FABAOYOFJNAVHB-KVVVOXFISA-N 0.000 description 2
- 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 2
- ARWLNYJOVMFZNY-KVVVOXFISA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;(z)-octadec-9-enoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O ARWLNYJOVMFZNY-KVVVOXFISA-N 0.000 description 2
- IUCCYXZWZMFVPE-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dodecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCC(O)=O IUCCYXZWZMFVPE-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 235000012055 fruits and vegetables Nutrition 0.000 description 1
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- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Description
本発明は、吸収性樹脂粒子、これを含有してなる吸収体及びこれを配してなる吸収性物品に関する。また、本発明は吸収性樹脂粒子の製造方法に関する。 The present invention relates to absorbent resin particles, an absorber containing the same, and an absorbent article including the same. The present invention also relates to a method for producing absorbent resin particles.
尿や水を吸液後の吸収性樹脂粒子のゲルブロッキング（ままこ現象）を防止する目的で、吸水性ポリマーの表面を、非揮発性炭化水素、ステアリン酸カルシウム粉末、フッ素活性剤等の疎水性物質により疎水化処理する方法が知られている（特許文献１、特許文献２）。
Hydrophobic surface such as non-volatile hydrocarbons, calcium stearate powder, fluorine activator, etc., for the purpose of preventing gel blocking of absorbent resin particles after absorbing urine and water A method of hydrophobizing with a substance is known (
しかし、吸収性樹脂粒子の表面を疎水化するとゲルブロッキングを生じにくくなるものの、尿や水に対する吸収速度が低下するという問題がある。そして、この吸収性樹脂粒子を吸収性物品に適用した場合、吸収性物品から尿や水が漏れるという問題がある。
すなわち本発明の目的は、ゲルブロッキングが防止でき、かつ尿や水に対する吸収速度が低下しない吸収性樹脂粒子を提供すること、そして、漏れの生じにくい吸収性物品を提供することである。
However, if the surface of the absorbent resin particles is hydrophobized, gel blocking is difficult to occur, but there is a problem that the absorption rate for urine and water is reduced. And when this absorbent resin particle is applied to an absorbent article, there exists a problem that urine and water leak from an absorbent article.
That is, an object of the present invention is to provide an absorbent resin particle that can prevent gel blocking and that does not decrease the absorption rate for urine and water, and to provide an absorbent article that hardly leaks.
本発明者は、上記の目的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、本発明の吸収性樹脂粒子は、（メタ）アクリル酸（塩）及び内部架橋剤（ｂ）を必須構成単位とする架橋重合体（Ａ）と、水素結合性官能基及び／又は共有結合性官能基を有する、シリコーン、変性シリコーン、炭素数８以上の長鎖脂肪酸、炭素数８以上の長鎖脂肪酸塩、炭素数８以上の長鎖脂肪酸エステル及び炭素数８以上の長鎖脂肪族アルコールからなる群より選ばれる少なくとも１種の疎水性物質（ｂ１）と、体積平均粒子径（μｍ）が１〜５００の無機多孔質微粒子（ｃ１）とを含んでなる吸収性樹脂粒子であって、（Ａ）の表面の少なくとも一部を（ｂ１）で被覆したものと（ｃ１）とを混合して得られる点を要旨とする。
The inventor of the present invention has arrived at the present invention as a result of intensive studies to achieve the above object.
That is, the absorbent resin particle of the present invention comprises a crosslinked polymer (A) having (meth) acrylic acid (salt) and an internal crosslinking agent (b) as essential constituent units, a hydrogen-bonding functional group and / or a covalent bond. Silicone, modified silicone, long chain fatty acid having 8 or more carbon atoms, long chain fatty acid salt having 8 or more carbon atoms, long chain fatty acid ester having 8 or more carbon atoms and long chain aliphatic alcohol having 8 or more carbon atoms Absorbent resin particles comprising at least one hydrophobic substance (b1) selected from the group consisting of and inorganic porous fine particles (c1) having a volume average particle diameter (μm) of 1 to 500, The gist is obtained by mixing at least part of the surface of (A) with (b1) and (c1).
本発明の吸収性樹脂粒子の製造方法は、水の存在下で（メタ）アクリル酸（塩）及び内部架橋剤（ｂ）を重合して得られた架橋重合体（Ａ）の表面の少なくとも一部を水素結合性官能基及び／又は共有結合性官能基を有する疎水性物質（ｂ１）で被覆したものと、無機多孔質微粒子（ｃ１）とを混合する工程を含んでなる点を要旨とする。 The method for producing absorbent resin particles according to the present invention comprises at least one surface of a crosslinked polymer (A) obtained by polymerizing (meth) acrylic acid (salt) and an internal crosslinking agent (b) in the presence of water. The main point is that it comprises a step of mixing the inorganic porous fine particles (c1) with a part of which is coated with a hydrophobic substance (b1) having a hydrogen bonding functional group and / or a covalent bonding functional group. .
本発明の吸収性樹脂粒子は、尿や水を吸液後にゲルブロッキングを生じにくく、かつ尿や水に対する吸収速度が低下しない。そして、本発明の吸収性樹脂粒子を用いた吸収性物品（紙おむつ等）は、使用者が装着した状態で座ったり横になったような場合でも、漏れが生じにくい。
また、本発明の吸収性樹脂粒子の製造方法は、尿や水を吸液後にゲルブロッキングを生じにくく、かつ尿や水に対する吸収速度が低下しない吸収性樹脂粒子を製造することができる。
The absorbent resin particles of the present invention hardly cause gel blocking after absorbing urine and water, and the absorption rate for urine and water does not decrease. And the absorbent article (paper diaper etc.) using the absorbent resin particles of the present invention is less likely to leak even when the user is sitting or lying down while wearing it.
Moreover, the manufacturing method of the absorptive resin particle of this invention can manufacture the absorptive resin particle which is hard to produce gel blocking after liquid-absorbing urine and water, and the absorption rate with respect to urine and water does not fall.
本発明の吸水性樹脂粒子は、（メタ）アクリル酸（塩）及び内部架橋剤（ｂ）を必須構成単位とする架橋重合体（Ａ）と、水素結合性官能基及び／又は共有結合性官能基を有する疎水性物質（ｂ１）と、無機多孔質微粒子（ｃ１）とを含有するが、吸水性樹脂粒子中に適宜、４０重量％を超えない量の他の物質を含有させてもよい。 The water-absorbent resin particles of the present invention comprise a crosslinked polymer (A) having (meth) acrylic acid (salt) and an internal crosslinking agent (b) as essential structural units, a hydrogen-bonding functional group and / or a covalent bond functionality. The hydrophobic substance (b1) having a group and the inorganic porous fine particles (c1) are contained, but another substance in an amount not exceeding 40% by weight may be appropriately contained in the water absorbent resin particles.
本発明において、「・・・酸（塩）」は、「・・・酸」及び「・・・酸塩」を意味し、「（メタ）アクリル酸」は、「メタクリル酸」及び「アクリル酸」を意味する。 In the present invention, "... acid (salt)" means "... acid" and "... acid salt", and "(meth) acrylic acid" means "methacrylic acid" and "acrylic acid". "Means.
塩としては、アルカリ金属塩（ナトリウム塩及びカリウム塩等）、アルカリ土類金属塩（カルシウム塩及びマグネシウム塩等）、アンモニウム塩｛アンモニウム塩、テトラアルキル（アルキル基の炭素数１〜８）アンモニウム塩（テトラメチルアンモニウム等）等｝及び有機アミン塩等が挙げられる。なお、有機アミン塩を構成する有機アミンとしては、炭素数１〜８のアルキルアミン、炭素数２〜８のアルカノールアミン、ポリアルキレン（アルキレンの炭素数１〜８）ポリアミン（アミノ基数２〜１０）若しくはポリアルキレンポリアミンの誘導体｛炭素数１〜８のアルキル基でアルキル化された化合物、あるいは炭素数２〜１２のアルキレンオキサイドが付加された化合物（アミノ基１個あたりの平均付加モル数１〜３０モル）｝等が挙げられる。
Examples of the salt include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), ammonium salts {ammonium salts, tetraalkyl (alkyl group having 1 to 8 carbon atoms) ammonium salts. (Tetramethylammonium etc.) etc.} and organic amine salt etc. are mentioned. The organic amine constituting the organic amine salt includes alkylamines having 1 to 8 carbon atoms, alkanolamines having 2 to 8 carbon atoms, polyalkylene (alkylene having 1 to 8 carbon atoms) polyamine (2 to 10 amino groups). Or a derivative of a polyalkylene polyamine {a compound alkylated with an alkyl group having 1 to 8 carbon atoms, or a compound to which an alkylene oxide having 2 to 12 carbon atoms is added (average number of moles added per
内部架橋剤（ｂ）としては特に限定はなく、たとえば、特開２００１−２２０４１５公報に記載の内部架橋剤が使用できる。
内部架橋剤（ｂ）のうち、吸収性能の観点等から、エチレン性不飽和基を２個以上有する内部架橋剤が好ましく、さらに好ましくはトリアリルシアヌレート、トリアリルイソシアヌレート及び炭素数２〜１０のポリオールのポリ（メタ）アリルエーテル、特に好ましくはトリアリルシアヌレート、トリアリルイソシアヌレート、テトラアリロキシエタン及びペンタエリスリトールトリアリルエーテル、最も好ましくはペンタエリスリトールトリアリルエーテルである。
The internal cross-linking agent (b) is not particularly limited, and for example, an internal cross-linking agent described in JP-A-2001-220415 can be used.
Among the internal cross-linking agents (b), an internal cross-linking agent having two or more ethylenically unsaturated groups is preferable from the viewpoint of absorption performance and the like, more preferably triallyl cyanurate, triallyl isocyanurate, and 2 to 10 carbon atoms. Poly (meth) allyl ethers of these polyols, particularly preferably triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane and pentaerythritol triallyl ether, most preferably pentaerythritol triallyl ether.
内部架橋剤（ｂ）単位の含有量（重量％）は、（メタ）アクリル酸（塩）の合計重量に基づいて、０．００１〜５が好ましく、さらに好ましくは０．００２〜２、特に好ましくは０．００３〜１．６である。 The content (% by weight) of the internal crosslinking agent (b) unit is preferably 0.001 to 5, more preferably 0.002 to 2, particularly preferably based on the total weight of (meth) acrylic acid (salt). Is 0.003-1.6.
（メタ）アクリル酸（塩）及び内部架橋剤（ｂ）の他に、これらと共重合可能なその他のビニルモノマー（ａ）を含むことができる In addition to (meth) acrylic acid (salt) and internal cross-linking agent (b), other vinyl monomers (a) copolymerizable therewith can be included.
共重合可能なその他のビニルモノマー（ａ）としては特に限定はなく公知｛たとえば、特許第３６４８５５３号、特開２００３−１６５８８３号、特開２００５−７５９８２号、特開２００５−９５７５９号｝の疎水性ビニルモノマー等が使用できる。 Other vinyl monomers (a) that can be copolymerized are not particularly limited, and are known {for example, hydrophobicity of Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883, Japanese Patent Laid-Open No. 2005-75982, Japanese Patent Laid-Open No. 2005-95759}. Vinyl monomers can be used.
その他のビニルモノマー（ａ）を含む場合、その他のビニルモノマー（ａ）の使用量（モル％）は、（メタ）アクリル酸（塩）のモル数に基づいて、０．０１〜５が好ましく、さらに好ましくは０．０５〜３、次に好ましくは０．０８〜２、特に好ましくは０．１〜１．５である。なお、吸収性能等の観点から、その他のビニルモノマー（ａ）を使用しないことが最も好ましい。 When the other vinyl monomer (a) is included, the amount (mol%) of the other vinyl monomer (a) used is preferably 0.01 to 5 based on the number of moles of (meth) acrylic acid (salt). More preferably, it is 0.05-3, then preferably 0.08-2, particularly preferably 0.1-1.5. In view of absorption performance and the like, it is most preferable not to use other vinyl monomers (a).
（メタ）アクリル酸（塩）及び架橋剤（ｂ）を必須構成単位とする架橋重合体（Ａ）を得る方法としては、（メタ）アクリル酸（塩）及び架橋剤（ｂ）を必須構成単量体として、公知の水溶液重合｛断熱重合、薄膜重合及び噴霧重合法等；特開昭５５−１３３４１３号等｝や、公知の逆相懸濁重合｛特公昭５４−３０７１０号、特開昭５６−２６９０９号及び特開平１−５８０８号等｝と同様にしてできる。 As a method for obtaining a crosslinked polymer (A) having (meth) acrylic acid (salt) and a crosslinking agent (b) as essential constituent units, (meth) acrylic acid (salt) and a crosslinking agent (b) are essential constituent units. As the polymer, known aqueous solution polymerization {adiabatic polymerization, thin film polymerization, spray polymerization method, etc .; JP-A-55-133413, etc.}, known reverse-phase suspension polymerization {JP-B-54-30710, JP-A-56 -26909 and JP-A-1-5808 etc.}.
水素結合性官能基及び／又は共有結合性官能基を有する疎水性物質（ｂ１）において、水素結合性官能基とは、（メタ）アクリル酸（塩）と水素結合を形成し得る官能基を指す。すなわちカルボキシル基、エーテル基及びエステル基等である。 In the hydrophobic substance (b1) having a hydrogen bonding functional group and / or a covalent bonding functional group, the hydrogen bonding functional group refers to a functional group capable of forming a hydrogen bond with (meth) acrylic acid (salt). . That is, a carboxyl group, an ether group, an ester group, and the like.
（ｂ１）において、共有結合性官能基とは、（メタ）アクリル酸（塩）と反応し共有結合を形成し得る官能基を指す。すなわちアミノ基、ヒドロキシル基及びエポキシ基等である。 In (b1), the covalent bond functional group refers to a functional group that can react with (meth) acrylic acid (salt) to form a covalent bond. That is, amino group, hydroxyl group, epoxy group and the like.
（ｂ１）において疎水性物質とは、シリコーン、変性シリコーン、長鎖脂肪酸、長鎖脂肪酸塩、長鎖脂肪酸エステル及び長鎖脂肪族アルコールからなる群より選ばれる少なくとも１種の化合物を指す。 In (b1), the hydrophobic substance refers to at least one compound selected from the group consisting of silicone, modified silicone, long chain fatty acid, long chain fatty acid salt, long chain fatty acid ester, and long chain fatty alcohol.
（ｂ１）のうち、水素結合性官能基を有する疎水性物質としては、ポリエーテル変性シリコーン、カルボキシ変性シリコーン、長鎖脂肪酸及びその塩並びに長鎖脂肪酸エステル等が挙げられる。 Among the (b1), examples of the hydrophobic substance having a hydrogen bonding functional group include polyether-modified silicone, carboxy-modified silicone, long-chain fatty acids and salts thereof, and long-chain fatty acid esters.
ポリエーテル変性シリコーンの有機基（変性基）としては、ポリオキシエチレン基又はポリ（オキシエチレン・オキシプロピレン）基を含有する基等が含まれる。ポリエーテル変性シリコーンに含まれるオキシエチレン基及び／又はオキシプロピレン基の含有量（個）は、ポリエーテル変性シリコーン１分子あたり、２〜４０が好ましく、さらに好ましくは５〜３０、特に好ましくは７〜２０、最も好ましくは１０〜１５である。この範囲であると、吸収速度が良好となる。また、オキシエチレン基及びオキシプロピレン基を含む場合、オキシエチレン基の含有量（重量％）は、シリコーンの重量に基づいて、１〜３０が好ましく、さらに好ましくは３〜２５、特に好ましくは５〜２０である。この範囲であると、吸収速度がさらに良好となる。 Examples of the organic group (modified group) of the polyether-modified silicone include a group containing a polyoxyethylene group or a poly (oxyethylene / oxypropylene) group. The content (pieces) of the oxyethylene group and / or oxypropylene group contained in the polyether-modified silicone is preferably 2 to 40, more preferably 5 to 30, particularly preferably 7 to per molecule of the polyether-modified silicone. 20, most preferably 10-15. Within this range, the absorption rate is good. Moreover, when it contains an oxyethylene group and an oxypropylene group, the content (% by weight) of the oxyethylene group is preferably 1 to 30, more preferably 3 to 25, and particularly preferably 5 to 5, based on the weight of the silicone. 20. Within this range, the absorption rate is further improved.
カルボキシ変性シリコーンの有機基（変性基）としてはカルボキシ基を含有する基等が含まれ、エポキシ変性シリコーンの有機基（変性基）としてはエポキシ基を含有する基等が含まれ、アミノ変性シリコーンの有機基（変性基）としてはアミノ基（１、２、３級アミノ基）を含有する基等が含まれる。これらの変性シリコーンの有機基（変性基）の含有量（ｇ／ｍｏｌ）は、カルボキシ当量、エポキシ当量又はアミノ当量として、２００〜１１０００が好ましく、さらに好ましくは６００〜８０００、特に好ましくは１０００〜４０００である。この範囲であると、吸収特性がさらに良好となる。なお、カルボキシ当量は、ＪＩＳ Ｃ２１０１：１９９９の「１６．全酸価試験」に準拠して測定される。また、エポキシ当量は、ＪＩＳ Ｋ７２３６：２００１に準拠して求められる。また、アミノ当量は、ＪＩＳ Ｋ２５０１：２００３の「８．電位差滴定法（塩基価・塩酸法）」に準拠して測定される。 The organic group (modified group) of the carboxy-modified silicone includes a group containing a carboxy group, and the organic group (modified group) of the epoxy-modified silicone includes a group containing an epoxy group. Examples of the organic group (modifying group) include a group containing an amino group (1, 2, or tertiary amino group). The organic group (modified group) content (g / mol) of these modified silicones is preferably 200 to 11000, more preferably 600 to 8000, and particularly preferably 1000 to 4000 as carboxy equivalent, epoxy equivalent or amino equivalent. It is. Within this range, the absorption characteristics are further improved. The carboxy equivalent is measured according to “16. Total acid value test” of JIS C2101: 1999. Moreover, an epoxy equivalent is calculated | required based on JISK7236: 2001. The amino equivalent is measured according to “8. Potentiometric titration method (base number / hydrochloric acid method)” of JIS K2501: 2003.
長鎖脂肪酸及び長鎖脂肪酸塩としては、炭素数８〜３０の脂肪酸｛たとえば、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸、ダイマー酸及びベヘニン酸等｝が挙げられ、その塩としては亜鉛、カルシウム、マグネシウム又はアルミニウム（以下、Ｚｎ、Ｃａ、Ｍｇ、Ａｌと略す）との塩｛たとえば、パルミチン酸Ｃａ、パルミチン酸Ａｌ、ステアリン酸Ｃａ、ステアリン酸Ｍｇ、ステアリン酸Ａｌ等｝が挙げられる。吸収性物品の耐漏れ性の観点等から、ステアリン酸Ｚｎ、ステアリン酸Ｃａ、ステアリン酸Ｍｇ、ステアリン酸Ａｌが好ましく、さらに好ましくはステアリン酸Ｍｇである。 Examples of the long-chain fatty acid and the long-chain fatty acid salt include fatty acids having 8 to 30 carbon atoms (for example, lauric acid, palmitic acid, stearic acid, oleic acid, dimer acid, and behenic acid). Examples thereof include salts with calcium, magnesium, or aluminum (hereinafter abbreviated as Zn, Ca, Mg, Al) (for example, palmitic acid Ca, palmitic acid Al, stearic acid Ca, stearic acid Mg, stearic acid Al, etc.). From the viewpoint of the leakage resistance of the absorbent article, Zn stearate, Ca stearate, Mg stearate, and Al stearate are preferred, and Mg stearate is more preferred.
長鎖脂肪酸エステルとしては、炭素数８〜３０の脂肪酸と炭素数１〜１２のアルコールとのエステル｛たとえば、ラウリン酸メチル、ラウリン酸エチル、ステアリン酸メチル、ステアリン酸エチル、オレイン酸メチル、オレイン酸エチル、グリセリンラウリン酸モノエステル、グリセリンステアリン酸モノエステル、グリセリンオレイン酸モノエステル、ペンタエリスリットラウリン酸モノエステル、ペンタエリスリットステアリン酸モノエステル、ペンタエリスリットオレイン酸モノエステル、ソルビットラウリン酸モノエステル、ソルビットステアリン酸モノエステル、ソルビットオレイン酸モノエステル、ショ糖パルミチン酸モノエステル、ショ糖パルミチン酸ジエステル、ショ糖パルミチン酸トリエステル、ショ糖ステアリン酸モノエステル、ショ糖ステアリン酸ジエステル、ショ糖ステアリン酸トリエステル及び牛脂等｝が挙げられる。これらのうち、吸収性物品の耐漏れ性の観点等から、ショ糖ステアリン酸モノエステル、ショ糖ステアリン酸ジエステル、ショ糖ステアリン酸トリエステルが好ましく、さらに好ましくはショ糖ステアリン酸モノエステル及びショ糖ステアリン酸ジエステルである。 As long-chain fatty acid esters, esters of fatty acids having 8 to 30 carbon atoms and alcohols having 1 to 12 carbon atoms {for example, methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl oleate, oleic acid Ethyl, glycerin lauric acid monoester, glycerin stearic acid monoester, glycerin oleic acid monoester, pentaerythritol lauric acid monoester, pentaerythritol stearate monoester, pentaerythritol oleic acid monoester, sorbit lauric acid monoester, Sorbit stearic acid monoester, sorbit oleic acid monoester, sucrose palmitic acid monoester, sucrose palmitic acid diester, sucrose palmitic acid triester, sucrose stearic acid monoester Ester, sucrose stearic acid diester, sucrose stearic acid triester, and beef tallow} and the like. Of these, sucrose stearate monoester, sucrose stearate diester, and sucrose stearate triester are preferable from the viewpoint of leakage resistance of the absorbent article, and more preferably sucrose stearate monoester and sucrose. Stearic acid diester.
（ｂ１）のうち、共有結合性官能基を有する疎水性物質としては、エポキシ変性シリコーン及びアミノ変性シリコーン並びに長鎖脂肪族アルコール等が挙げられる。 Among (b1), examples of the hydrophobic substance having a covalent functional group include epoxy-modified silicone, amino-modified silicone, and long-chain aliphatic alcohol.
長鎖脂肪族アルコールとしては、炭素数８〜３０の脂肪族アルコール｛ラウリルアルコール、パルミチルアルコール、ステアリルアルコール及びオレイルアルコール等｝が挙げられる。吸収性物品の耐漏れ性の観点から、パルミチルアルコール、ステアリルアルコール及びオレイルアルコールが好ましく、さらに好ましくはステアリルアルコールである。 Examples of the long-chain aliphatic alcohol include aliphatic alcohols having 8 to 30 carbon atoms (such as lauryl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol). From the viewpoint of leakage resistance of the absorbent article, palmityl alcohol, stearyl alcohol and oleyl alcohol are preferable, and stearyl alcohol is more preferable.
水素結合性及び共有結合性の両方の官能基を有する疎水性物質（ｂ１）としては、炭素数８〜３０の脂肪酸と炭素数１〜１２でヒドロキシル基を２つ以上持つアルコールとのエステル（ｂ１２）｛グリセリンラウリン酸モノエステル、グリセリンステアリン酸モノエステル、グリセリンオレイン酸モノエステル、ペンタエリスリットラウリン酸モノエステル、ペンタエリスリットステアリン酸モノエステル、ペンタエリスリットオレイン酸モノエステル、ソルビットラウリン酸モノエステル、ソルビットステアリン酸モノエステル、ソルビットオレイン酸モノエステル、ショ糖パルミチン酸モノエステル、ショ糖パルミチン酸ジエステル、ショ糖パルミチン酸トリエステル、ショ糖ステアリン酸モノエステル、ショ糖ステアリン酸ジエステル、ショ糖ステアリン酸トリエステル及び牛脂等｝、炭素数８〜３０の脂肪族アルコールと炭素数１〜１２でカルボキシル基を２つ以上持つカルボン酸とのエステル（ｂ１４）｛アジピン酸ステアリルモノエステル、マロン酸ステアリルモノエステル、コハク酸ステアリルモノエステル等｝等が挙げられる。これらのうち、吸収性物品の耐漏れ性の観点等から、ショ糖ステアリン酸モノエステル、ショ糖ステアリン酸ジエステル、ショ糖ステアリン酸トリエステルが好ましく、さらに好ましくはショ糖ステアリン酸モノエステル及びショ糖ステアリン酸ジエステルである。 Examples of the hydrophobic substance (b1) having both hydrogen bonding and covalent bonding functional groups include esters of fatty acids having 8 to 30 carbon atoms and alcohols having 1 to 12 carbon atoms and two or more hydroxyl groups (b12). ) {Glycerin lauric acid monoester, glycerin stearic acid monoester, glycerin oleic acid monoester, pentaerythritol lauric acid monoester, pentaerythritol stearate monoester, pentaerythritol oleic acid monoester, sorbit lauric acid monoester, Sorbit stearic acid monoester, sorbit oleic acid monoester, sucrose palmitic acid monoester, sucrose palmitic acid diester, sucrose palmitic acid triester, sucrose stearic acid monoester, sucrose stearic acid diester Sucrose stearate triester and beef tallow}, ester of aliphatic alcohol having 8 to 30 carbon atoms and carboxylic acid having 1 to 12 carbon atoms and two or more carboxyl groups (b14) {stearyl monoester adipate, malon Acid stearyl monoester, succinic acid stearyl monoester, etc.}. Of these, sucrose stearate monoester, sucrose stearate diester, and sucrose stearate triester are preferable from the viewpoint of leakage resistance of the absorbent article, and more preferably sucrose stearate monoester and sucrose. Stearic acid diester.
本発明の吸収性樹脂粒子中の疎水性物質（ｂ１）の含有量（重量％）は、架橋重合体（Ａ）の重量に基づいて、０．００１〜１０が好ましく、さらに好ましくは０．００２〜５、特に好ましくは０.００５〜１である。この範囲であると、吸収速度の観点から好ましい。 The content (% by weight) of the hydrophobic substance (b1) in the absorbent resin particles of the present invention is preferably 0.001 to 10, more preferably 0.002 based on the weight of the crosslinked polymer (A). To 5, particularly preferably 0.005 to 1. This range is preferable from the viewpoint of absorption rate.
本発明の吸収性樹脂粒子は、架橋重合体（Ａ）の表面の少なくとも一部が疎水性物質（ｂ１）で被覆される。被覆とは、架橋重合体（Ａ）の表面のカルボキシル基又はカルボキシレート基と疎水性物質（ｂ１）とが水素結合を形成、又は共有結合を形成して結合して存在することである。吸収性樹脂粒子のゲル状態のブロッキング性の観点から、架橋重合体（Ａ）の表面のカルボキシル基又はカルボキシレート基の全てが疎水性物質（ｂ１）で被覆されていることが好ましい。 In the absorbent resin particles of the present invention, at least a part of the surface of the crosslinked polymer (A) is coated with the hydrophobic substance (b1). The coating means that the carboxyl group or carboxylate group on the surface of the crosslinked polymer (A) and the hydrophobic substance (b1) are present by forming a hydrogen bond or a covalent bond. From the viewpoint of the gel-state blocking property of the absorbent resin particles, it is preferable that all of the carboxyl groups or carboxylate groups on the surface of the crosslinked polymer (A) are coated with the hydrophobic substance (b1).
架橋重合体（Ａ）に対する疎水性物質（ｂ１）は、架橋重合体（Ａ）表面の少なくとも一部に疎水性物質（ｂ１）が存在するように被覆されれば制限がない。被覆方法としては、粒子状の架橋重合体と固体状の疎水性物質を混合する、粒子状の架橋重合体と液状の疎水性物質を混合する、架橋重合体（Ａ）の含水ゲルと固体状の疎水性物質を混合する、架橋重合体（Ａ）の含水ゲルと液状の疎水性物質を混合する等が挙げられる。 The hydrophobic substance (b1) for the crosslinked polymer (A) is not limited as long as the hydrophobic substance (b1) is coated on at least a part of the surface of the crosslinked polymer (A). As a coating method, a particulate crosslinked polymer and a solid hydrophobic substance are mixed, a particulate crosslinked polymer and a liquid hydrophobic substance are mixed, a water-containing gel of the crosslinked polymer (A) and a solid state For example, mixing the hydrogel of the crosslinked polymer (A) with a liquid hydrophobic substance, and the like.
無機多孔質微粒子（ｃ１）としては、酸化物｛酸化ケイ素、酸化アルミニウム、酸化鉄、酸化チタン、酸化マグネシウム及び酸化ジルコニウム等｝、炭化物｛炭化珪素及び炭化アルミニウム等｝、窒化物｛窒化チタン等｝及びこれらが複合体｛ゼオライト及びタルク等｝等が挙げられる。これらのうち、酸化物が好ましく、さらに好ましくは酸化ケイ素である。
無機多孔質微粒子（ｃ１）の体積平均粒子径（μｍ）は、１〜５００が好ましく、さらに好ましくは３〜１００、特に好ましくは５〜７５、最も好ましくは９〜５０である。この範囲であると、吸収性能がさらに良好となる。
なお、体積平均粒子経は、動的光散乱法により、溶媒中で測定される｛たとえば、装置：ナノトラック粒度分布測定装置ＵＰＡ−ＥＸ１５０（日機装株式会社）、光源：Ｈｅ-Ｎｅレーザー、測定温度：２５℃、溶媒：シクロヘキサン｝。
Examples of the inorganic porous fine particles (c1) include oxides {silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, zirconium oxide, etc.}, carbides {silicon carbide, aluminum carbide, etc.}, nitrides {titanium nitride, etc.} And these are composites {zeolite, talc, etc.} and the like. Of these, oxides are preferable, and silicon oxide is more preferable.
The volume average particle diameter (μm) of the inorganic porous fine particles (c1) is preferably 1 to 500, more preferably 3 to 100, particularly preferably 5 to 75, and most preferably 9 to 50. Within this range, the absorption performance is further improved.
The volume average particle diameter is measured in a solvent by a dynamic light scattering method {for example, apparatus: Nanotrack particle size distribution measuring apparatus UPA-EX150 (Nikkiso Co., Ltd.), light source: He—Ne laser, measurement temperature. : 25 ° C., solvent: cyclohexane}.
無機多孔質微粒子（ｃ１）の比表面積（ｍ２／ｇ）は、２０〜４００が好ましく、さらに好ましくは３０〜３５０、特に好ましくは４０〜３００である。この範囲内であると、吸収性能がさらに良好となる。
なお、比表面積は、ＪＩＳ Ｚ８８３０：２００１（窒素、容量法、多点法）に準拠して測定される。
The specific surface area (m 2 / g) of the inorganic porous fine particles (c1) is preferably 20 to 400, more preferably 30 to 350, and particularly preferably 40 to 300. Within this range, the absorption performance is further improved.
The specific surface area is measured according to JIS Z8830: 2001 (nitrogen, volume method, multipoint method).
無機多孔質微粒子（ｃ１）は、市場から容易に入手でき、たとえば｛以下、商品名（化学組成、体積平均粒子径μｍ、比表面積ｍ２／ｇ）｝、アエロジル１３０（二酸化ケイ素、１６、１３０）、アエロジル２００（二酸化ケイ素、１２、２００）、アエロジル３００（二酸化ケイ素、７、３００）、アエロジルＭＯＸ８０（二酸化ケイ素、３０、８０）、アエロジルＣＯＫ８４（二酸化ケイ素、１２、１７０）、アエロジルＯＸ５０Ｔ（二酸化ケイ素、７、４０）、酸化チタンＰ２５（酸化チタン、２０、３０）及びアルミニウムオキサイドＣ（酸化アルミニウム、１３、１００）｛日本アエロジル株式会社｝；デンカ溶融シリカＦ−３００（二酸化ケイ素、１１、１６０）｛電気化学工業株式会社｝；マイクロイド８５０（二酸化ケイ素、１３、１５０）｛株式会社東海化学工業｝；非晶質シリカＳＰ−１（二酸化ケイ素、１４、４５）｛株式会社ノザワ｝；サイロイド６２２（二酸化ケイ素、１７、３５０）；サイロイドＥＤ５０（二酸化ケイ素、８、４００）｛グレースジャパン株式会社｝；アドマフィンＳＯ−Ｃ１（複合酸化物、０．１、２０）｛アドマッテクス株式会社｝；アエロジル２００（二酸化ケイ素、１００、１２）｛デグサＡＧ：ドイツ｝；トクシール（二酸化ケイ素、２．５、１２０）及びレオロシール（二酸化ケイ素、２．５、１１０）｛株式会社トクヤマ ｝；ニップシールＥ２２０Ａ（二酸化ケイ素、２．５、１３０）｛日本シリカ工業株式会社｝；及びクレボゾール３０ＣＡＬ２５（酸化ケイ素、１２、２００）｛クラリアントジャパン株式会社｝等が好ましく例示できる。 The inorganic porous fine particles (c1) can be easily obtained from the market. For example, {hereinafter, trade name (chemical composition, volume average particle diameter μm, specific surface area m 2 / g)}, Aerosil 130 (silicon dioxide, 16, 130). ), Aerosil 200 (silicon dioxide, 12, 200), Aerosil 300 (silicon dioxide, 7, 300), Aerosil MOX80 (silicon dioxide, 30, 80), Aerosil COK84 (silicon dioxide, 12, 170), Aerosil OX50T (Dioxide) Silicon, 7, 40), titanium oxide P25 (titanium oxide, 20, 30) and aluminum oxide C (aluminum oxide, 13, 100) {Nippon Aerosil Co., Ltd.}; Denka fused silica F-300 (silicon dioxide, 11, 160) ) {Electrochemical Co., Ltd.}; Microid 850 (silicon dioxide) , 13, 150) {Tokai Chemical Industry Co., Ltd.}; amorphous silica SP-1 (silicon dioxide, 14, 45) {Nozawa Corporation}; syloid 622 (silicon dioxide, 17, 350); syloid ED50 (silicon dioxide) , 8, 400) {Grace Japan Co., Ltd.}; Admuffin SO-C1 (Composite oxide, 0.1, 20) {Admatex Corp.}; Aerosil 200 (Silicon dioxide, 100, 12) {Degussa AG: Germany} Toxeal (silicon dioxide, 2.5, 120) and Leoroseal (silicon dioxide, 2.5, 110) {Tokuyama Co., Ltd.}; Nip seal E220A (silicon dioxide, 2.5, 130) {Nippon Silica Industry Co., Ltd.}; And clebosol 30CAL25 (silicon oxide, 12, 200) {Clariant Japan Ltd.} Etc. can be preferably exemplified.
無機多孔質微粒子（ｃ１）の含有量（重量％）は、架橋重合体粒子（Ａ）の重量に基づいて、０．０１〜２．５が好ましく、さらに好ましくは０．０５〜２、特に好ましくは０．１〜１である。この範囲内であると、吸収速度がさらに良好となる。 The content (% by weight) of the inorganic porous fine particles (c1) is preferably 0.01 to 2.5, more preferably 0.05 to 2, particularly preferably based on the weight of the crosslinked polymer particles (A). Is 0.1-1. Within this range, the absorption rate is further improved.
本発明の吸収性樹脂粒子には、他の添加剤｛たとえば、公知（特開２００３−２２５５６５号、特開２００６−１３１７６７号等）の防腐剤、防かび剤、抗菌剤、酸化防止剤、紫外線吸収剤、着色剤、芳香剤、消臭剤及び有機質繊維状物等｝を含むこともできる。これらの添加剤を含有させる場合、添加剤の含有量（重量％）は、架橋重合体（Ａ）の重量に基づいて、０．００１〜１０が好ましく、さらに好ましくは０．０１〜５、特に好ましくは０．０５〜１、最も好ましくは０．１〜０．５である。 The absorbent resin particles of the present invention may contain other additives (for example, known preservatives, fungicides, antibacterial agents, antioxidants, ultraviolet rays (for example, JP 2003-225565 A, JP 2006-131767 A). An absorbent, a colorant, a fragrance, a deodorant, an organic fibrous material, etc.}. When these additives are contained, the content (% by weight) of the additive is preferably 0.001 to 10, more preferably 0.01 to 5, particularly preferably based on the weight of the crosslinked polymer (A). Preferably it is 0.05 to 1, most preferably 0.1 to 0.5.
本発明の吸収性樹脂粒子は、前述の方法で得た架橋重合体（Ａ）を以下に述べる方法で、（ｂ１）で被覆し、（ｃ１）と混合することで得られる。 The absorbent resin particles of the present invention can be obtained by coating the crosslinked polymer (A) obtained by the above-described method with (b1) and mixing with (c1) by the method described below.
重合工程で得られる含水ゲル｛架橋重合体（Ａ）と水とを含む｝は、必要に応じて例えば含水率１０％以上７０％未満の含水重合物の状態で細断して細断ゲルとし、さらに乾燥される。含水ゲルや細断ゲルを乾燥する条件は特に限定されるものではないが、通常１５０℃〜２５０℃の温度範囲で行われる。
なお、乾燥温度はオイルや蒸気を熱媒として用いる場合は熱媒の温度、電子線を照射するなど熱媒を使用せずに乾燥する場合は、材料（乾燥するもの）の温度で規定される。また、乾燥温度を段階的に変化させてもよい。乾燥時間は含水ゲル又は細断ゲルの表面積、含水率や乾燥機の種類等に依存し、目的とする含水率になるよう選択すればよいが、例えば、１０〜１８０分間、より好ましくは、３０〜１２０分間である。
The water-containing gel {including the cross-linked polymer (A) and water} obtained in the polymerization step is chopped into a chopped gel as necessary, for example, in the state of a water-containing polymer having a water content of 10% or more and less than 70%. Further dried. The conditions for drying the hydrated gel or chopped gel are not particularly limited, but are usually performed in a temperature range of 150 ° C to 250 ° C.
The drying temperature is defined by the temperature of the heating medium when oil or steam is used as the heating medium, and the temperature of the material (the one to be dried) when drying without using a heating medium such as irradiation with an electron beam. . Further, the drying temperature may be changed stepwise. The drying time depends on the surface area of the hydrated gel or shredded gel, the moisture content, the type of dryer, etc., and may be selected to achieve the desired moisture content, for example, 10 to 180 minutes, more preferably 30 ~ 120 minutes.
用いられる乾燥方法としては、加熱乾燥、熱風乾燥、減圧乾燥、赤外線乾燥、マイクロ波乾燥、疎水性有機溶媒との共沸による脱水、高温の水蒸気を用いた高湿乾燥等目的の含水率となるように種々の方法を採用することができ、特に限定されるものではない。 The drying method used includes heat drying, hot air drying, vacuum drying, infrared drying, microwave drying, dehydration by azeotropy with a hydrophobic organic solvent, and high moisture content using high-temperature steam. As described above, various methods can be employed, and the method is not particularly limited.
架橋重合体（Ａ）の重合に溶媒（水を含む）を使用する場合、重合後に溶媒を留去することができる。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、１０〜０．０１が好ましく、さらに好ましくは５〜０．０５、特に好ましくは３〜０．１、最も好ましくは１〜０．５である。この範囲であると、吸収性樹脂粒子の吸収性能（特に保水量）がさらに良好となる。 When using a solvent (including water) for the polymerization of the crosslinked polymer (A), the solvent can be distilled off after the polymerization. When the solvent contains an organic solvent, the content (% by weight) of the organic solvent after the distillation is preferably 10 to 0.01, more preferably 5 to 0.00, based on the weight of the crosslinked polymer (A). 05, particularly preferably 3 to 0.1, most preferably 1 to 0.5. Within this range, the absorption performance (particularly the water retention amount) of the absorbent resin particles is further improved.
また、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、さらに好ましくは０〜１０、特に好ましくは０〜５、最も好ましくは０〜２である。この範囲であると、吸収性能（特に保水量）及び乾燥後のハンドリング性（架橋重合体粒子の粉体流動性等）がさらに良好となる。 Moreover, when water is included in the solvent, the water content (% by weight) after the distillation is preferably 0 to 20, more preferably 0 to 10, particularly preferably 0 to 0, based on the weight of the crosslinked polymer (A). 5, most preferably 0-2. Within this range, the absorption performance (particularly the water retention amount) and the handling properties after drying (such as the powder flowability of the crosslinked polymer particles) are further improved.
架橋重合体（Ａ）に対する疎水性物質（ｂ１）の被覆は、架橋重合体（Ａ）表面の少なくとも一部が疎水性物質（ｂ１）で被覆されれば制限がない。被覆方法としては、粒子状の架橋重合体と固体状の疎水性物質を混合する、粒子状の架橋重合体と液状の疎水性物質を混合する、架橋重合体（Ａ）の含水ゲルと固体状の疎水性物質を混合する、架橋重合体（Ａ）の含水ゲルと液状の疎水性物質を混合する等が挙げられる。
架橋重合体（Ａ）と疎水性物質（ｂ１）との混合において、温度（℃）は特に限定ないが、１０〜１３０が好ましく、さらに好ましくは１５〜１２５、特に好ましくは２０〜１２０である。
The coating of the hydrophobic substance (b1) on the crosslinked polymer (A) is not limited as long as at least a part of the surface of the crosslinked polymer (A) is coated with the hydrophobic substance (b1). As a coating method, a particulate crosslinked polymer and a solid hydrophobic substance are mixed, a particulate crosslinked polymer and a liquid hydrophobic substance are mixed, a water-containing gel of the crosslinked polymer (A) and a solid state For example, mixing the hydrogel of the crosslinked polymer (A) with a liquid hydrophobic substance, and the like.
In mixing the crosslinked polymer (A) and the hydrophobic substance (b1), the temperature (° C.) is not particularly limited, but is preferably 10 to 130, more preferably 15 to 125, and particularly preferably 20 to 120.
固体状の疎水性物質（ｂ１）を混合する場合、混合装置としては通常の混合機でよく、例えば、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、双腕型ニーダー、流動式混合機、Ｖ型混合機、リボン型混合機、流動式混合機、気流型混合機、回転円盤型混合機、コニカルブレンダー及びロールミキサー等が挙げられる。 When mixing the solid hydrophobic substance (b1), the mixing apparatus may be an ordinary mixer, for example, a cylindrical mixer, a screw type mixer, a screw type extruder, a turbulizer, a nauter type mixer. , Double-arm kneaders, fluid mixers, V mixers, ribbon mixers, fluid mixers, air flow mixers, rotating disk mixers, conical blenders, roll mixers, and the like.
液状の疎水性物質（ｂ１）を混合する場合には、疎水性物質（ｂ１）が液状である場合だけでなく、疎水性物質（ｂ１）を溶媒に溶解又は乳化・分散させる、又は疎水性物質（ｂ１）の融点以上に加熱して溶融して、液体として用いることも含まれる。 When the liquid hydrophobic substance (b1) is mixed, not only when the hydrophobic substance (b1) is liquid, but also the hydrophobic substance (b1) is dissolved or emulsified / dispersed in a solvent, or the hydrophobic substance It includes heating and melting above the melting point of (b1) and using it as a liquid.
ここで用いる溶媒としては、水及び揮発性有機溶媒が含まれる。揮発性有機溶媒としては、除去しやすさの観点等から、２０℃での蒸気圧（Ｐａ）が０．１３〜５．３のものが好ましく、さらに好ましくは０．１５〜４．５、特に好ましくは０．２３〜３．８のものである。揮発性有機溶媒としては、炭素数１〜３のアルコール（メタノール、エタノール及びイソプロピルアルコール等）、炭素数５〜８の炭化水素（ペンタン、ヘキサン、シクロヘキサン及びトルエン等）、炭素数２〜４のエーテル（ジメチルエーテル、ジエチルエーテル及びテトラヒドロフラン等）、炭素数３〜４のケトン（アセトン及びメチルエチルケトン等）、及び炭素数３〜５のエステル（蟻酸エチル、酢酸エチル、酢酸イソプロピル及び炭酸ジエチル等）等が挙げられる。水及び／又は揮発性有機溶媒を使用する場合、これらの含有量（重量％）は、疎水性物質（ｂ１）の重量に基づいて、１〜９００が好ましく、さらに好ましくは５〜７００、特に好ましくは１０〜４００である。水及び揮発性有機溶媒を使用する場合、水の使用量（重量％）は、水及び揮発性有機溶媒の重量に基づいて、５０〜９８が好ましく、さらに好ましくは６０〜９５、特に好ましくは７０〜９０である。 The solvent used here includes water and volatile organic solvents. The volatile organic solvent preferably has a vapor pressure (Pa) at 20 ° C. of 0.13 to 5.3, more preferably 0.15 to 4.5, particularly from the viewpoint of easy removal. It is preferably 0.23 to 3.8. Examples of volatile organic solvents include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropyl alcohol), hydrocarbons having 5 to 8 carbon atoms (such as pentane, hexane, cyclohexane and toluene), and ethers having 2 to 4 carbon atoms. (Dimethyl ether, diethyl ether, tetrahydrofuran, etc.), C3-C4 ketones (acetone, methyl ethyl ketone, etc.), C3-C5 esters (ethyl formate, ethyl acetate, isopropyl acetate, diethyl carbonate, etc.) and the like. . When water and / or a volatile organic solvent is used, the content (% by weight) thereof is preferably 1 to 900, more preferably 5 to 700, particularly preferably based on the weight of the hydrophobic substance (b1). Is 10-400. When water and a volatile organic solvent are used, the amount of water used (% by weight) is preferably 50 to 98, more preferably 60 to 95, particularly preferably 70, based on the weight of water and the volatile organic solvent. ~ 90.
液状の疎水性物質（ｂ１）を混合する場合、架橋重合体（Ａ）に液状の疎水性物質を噴霧するか、液状の疎水性物質に架橋重合体（Ａ）を浸漬することにより達成できる。なお、架橋重合体（Ａ）粒子に固体状の疎水性物質（ｂ１）を接触させた後、（ｂ１）の融点以上に加熱して混合することもできる。
噴霧、浸漬又は接触に適用できる混合装置としては、ナウターミキサー及びタービュライザ等が挙げられる。
When the liquid hydrophobic substance (b1) is mixed, it can be achieved by spraying the liquid hydrophobic substance on the crosslinked polymer (A) or immersing the crosslinked polymer (A) in the liquid hydrophobic substance. In addition, after making solid hydrophobic substance (b1) contact a crosslinked polymer (A) particle | grain, it can also heat and mix beyond melting | fusing point of (b1).
Examples of a mixing device that can be applied to spraying, dipping, or contact include a nauter mixer and a turbulizer.
本発明の吸収性樹脂粒子は、架橋重合体（Ａ）の表面の少なくとも一部を疎水性物質（ｂ１）で被覆したものと無機多孔質微粒子（ｃ１）とを混合して得られる。架橋重合体（Ａ）の（ｂ１）で被覆したものと無機多孔質微粒子（ｃ１）との混合において、温度（℃）は特に限定ないが、１０〜１３０が好ましく、さらに好ましくは１５〜１２５、特に好ましくは２０〜１２０である。 The absorbent resin particles of the present invention are obtained by mixing at least part of the surface of the crosslinked polymer (A) with a hydrophobic substance (b1) and inorganic porous fine particles (c1). In the mixing of the crosslinked polymer (A) coated with (b1) and the inorganic porous fine particles (c1), the temperature (° C.) is not particularly limited, but is preferably 10 to 130, more preferably 15 to 125, Especially preferably, it is 20-120.
無機多孔質微粒子（ｃ１）を固体として混合する場合、混合装置としては通常の混合機でよく、例えば、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、双腕型ニーダー、流動式混合機、Ｖ型混合機、リボン型混合機、流動式混合機、気流型混合機、回転円盤型混合機、コニカルブレンダー及びロールミキサー等が挙げられる。
無機多孔質微粒子（ｃ１）を液体として混合する場合には、無機多孔質微粒子（ｃ１）が液状である場合だけでなく、無機多孔質微粒子（ｃ１）を溶媒に溶解又は乳化・分散させる、又は無機多孔質微粒子（ｃ１）の融点以上に加熱して溶融して、液体として用いることも含まれる。
When the inorganic porous fine particles (c1) are mixed as a solid, the mixing apparatus may be an ordinary mixer, for example, a cylindrical mixer, a screw mixer, a screw extruder, a turbulator, a nauter mixer. , Double-arm kneaders, fluid mixers, V mixers, ribbon mixers, fluid mixers, air flow mixers, rotating disk mixers, conical blenders, roll mixers, and the like.
When mixing the inorganic porous fine particles (c1) as a liquid, not only when the inorganic porous fine particles (c1) are in a liquid state, but the inorganic porous fine particles (c1) are dissolved or emulsified / dispersed in a solvent, or It includes heating and melting above the melting point of the inorganic porous fine particles (c1) to use as a liquid.
ここで用いる溶媒としては、水及び揮発性有機溶媒が含まれる。揮発性有機溶媒としては、除去しやすさの観点等から、２０℃での蒸気圧（Ｐａ）が０．１３〜５．３のものが好ましく、さらに好ましくは０．１５〜４．５、特に好ましくは０．２３〜３．８のものである。揮発性有機溶媒としては、炭素数１〜３のアルコール（メタノール、エタノール及びイソプロピルアルコール等）、炭素数５〜８の炭化水素（ペンタン、ヘキサン、シクロヘキサン及びトルエン等）、炭素数２〜４のエーテル（ジメチルエーテル、ジエチルエーテル及びテトラヒドロフラン等）、炭素数３〜４のケトン（アセトン及びメチルエチルケトン等）、及び炭素数３〜５のエステル（蟻酸エチル、酢酸エチル、酢酸イソプロピル及び炭酸ジエチル等）等が挙げられる。水及び／又は揮発性有機溶媒を使用する場合、これらの含有量（重量％）は、無機多孔質微粒子（ｃ１）の重量に基づいて、１〜９００が好ましく、さらに好ましくは５〜７００、特に好ましくは１０〜４００である。水及び揮発性有機溶媒を使用する場合、水の使用量（重量％）は、水及び揮発性有機溶媒の重量に基づいて、５０〜９８が好ましく、さらに好ましくは６０〜９５、特に好ましくは７０〜９０である。 The solvent used here includes water and volatile organic solvents. The volatile organic solvent preferably has a vapor pressure (Pa) at 20 ° C. of 0.13 to 5.3, more preferably 0.15 to 4.5, particularly from the viewpoint of easy removal. It is preferably 0.23 to 3.8. Examples of volatile organic solvents include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropyl alcohol), hydrocarbons having 5 to 8 carbon atoms (such as pentane, hexane, cyclohexane and toluene), and ethers having 2 to 4 carbon atoms. (Dimethyl ether, diethyl ether, tetrahydrofuran, etc.), C3-C4 ketones (acetone, methyl ethyl ketone, etc.), C3-C5 esters (ethyl formate, ethyl acetate, isopropyl acetate, diethyl carbonate, etc.) and the like. . When water and / or a volatile organic solvent is used, the content (% by weight) thereof is preferably 1 to 900, more preferably 5 to 700, particularly based on the weight of the inorganic porous fine particles (c1). Preferably it is 10-400. When water and a volatile organic solvent are used, the amount of water used (% by weight) is preferably 50 to 98, more preferably 60 to 95, particularly preferably 70, based on the weight of water and the volatile organic solvent. ~ 90.
無機多孔質微粒子（ｃ１）を液体として混合する場合、（ｂ１）で被覆された架橋重合体（Ａ）に上記液体を噴霧するか、上記液体に（ｂ１）で被覆された架橋重合体（Ａ）を浸漬することにより達成できる。なお、架橋重合体（Ａ）粒子に固体状の無機多孔質微粒子（ｃ１）を接触させた後、（ｃ１）の融点以上に加熱して混合することもできる。
噴霧、ディッピング又は接触に適用できる混合装置としては、ナウターミキサー及びタービュライザ等が挙げられる。
When mixing the inorganic porous fine particles (c1) as a liquid, the liquid is sprayed on the cross-linked polymer (A) coated with (b1) or the cross-linked polymer (A) coated with (b1) on the liquid. ) Can be achieved. In addition, after making solid inorganic fine particle (c1) contact a crosslinked polymer (A) particle | grain, it can also heat and mix more than melting | fusing point of (c1).
Examples of the mixing device applicable to spraying, dipping, or contact include a nauter mixer and a turbulizer.
＜粉砕＞
粉砕は溶媒を留去した後に行うことが好ましい。
粉砕方法は特に限定がなく、公知の粉砕装置｛たとえば、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｝等により粉砕できる。
<Crushing>
The pulverization is preferably performed after the solvent is distilled off.
The pulverization method is not particularly limited, and can be pulverized by a known pulverizer (for example, a hammer-type pulverizer, an impact-type pulverizer, a roll-type pulverizer, and a shet airflow-type pulverizer).
＜粒度調節＞
粉砕された粒子は、必要によりふるい分け等により粒度調節される。
本発明の吸収性樹脂粒子の重量平均粒径（μｍ）は、３５５〜３９５が好ましく、さらに好ましくは３６０〜３９０、特に好ましくは３６５〜３８５、最も好ましくは３７０〜３８０である。この範囲であると、吸収性能がさらに良好となる。なお、重量平均粒径は上記と同様にして求められる。
吸収性樹脂の形状は粒子状であれば制限はないが、不定形（破砕状）、真球状、板状及び棒状が好ましく、さらに好ましくは不定形（破砕状）、真球状又は板状、特に好ましくは不定形（破砕状）又は板状である。
<Granularity control>
The size of the pulverized particles is adjusted by sieving or the like as necessary.
The weight average particle diameter (μm) of the absorbent resin particles of the present invention is preferably 355 to 395, more preferably 360 to 390, particularly preferably 365 to 385, and most preferably 370 to 380. Within this range, the absorption performance is further improved. The weight average particle diameter is obtained in the same manner as described above.
The shape of the absorbent resin is not limited as long as it is in the form of particles, but is preferably indefinite (crushed), true spherical, plate-like and rod-like, more preferably indeterminate (crushed), true spherical or plate-like, particularly Preferably, it is indefinite shape (crushed shape) or plate shape.
＜表面架橋＞
裁断された細断ゲル又は粉砕された粒子は、必要に応じて、表面架橋剤により表面架橋処理を行うことができる。
表面架橋剤としては、公知｛たとえば、特開昭５９−１８９１０３号、特開昭５８−１８０２３３号、特開昭６１−１６９０３号、特開昭６１−２１１３０５号、特開昭６１−２５２２１２号、特開昭５１−１３６５８８号及び特開昭６１−２５７２３５号等｝の表面架橋剤｛多価グリシジル、多価アルコール、多価アミン、多価アジリジン、多価イソシアネート、シランカップリング剤及び多価金属等｝等が使用できる。これらの表面架橋剤のうち、経済性及び吸収性能の観点から、多価グリシジル、多価アルコール及び多価アミンが好ましく、さらに好ましくは多価グリシジル及び多価アルコール、特に好ましくは多価グリシジル、最も好ましくはエチレングリコールジグリシジルエーテルである。
<Surface cross-linking>
The cut chopped gel or the pulverized particles can be subjected to surface cross-linking treatment with a surface cross-linking agent, if necessary.
As the surface crosslinking agent, known {for example, JP 59-189103, JP 58-180233, JP 61-16903, JP 61-2111305, JP 61-252212, Surface cross-linking agents {polyvalent glycidyl, polyhydric alcohol, polyvalent amine, polyvalent aziridine, polyvalent isocyanate, silane coupling agent and polyvalent metal of JP-A-51-136588 and JP-A-61-257235} Etc.} can be used. Of these surface cross-linking agents, from the viewpoint of economy and absorption performance, polyvalent glycidyl, polyhydric alcohol and polyvalent amine are preferable, more preferably polyvalent glycidyl and polyhydric alcohol, particularly preferably polyvalent glycidyl, Preferred is ethylene glycol diglycidyl ether.
表面架橋をする場合、表面架橋剤の使用量（重量％）は、表面架橋剤の種類、架橋の条件、目標とする性能等により種々変化させることができるため特に限定はないが、吸収性能の観点等から、必須構成単量体（ａ）の重量に基づいて、０．００１〜３が好ましく、さらに好ましくは０．００５〜２、特に好ましくは０．０１〜１である。 In the case of surface cross-linking, the amount (% by weight) of the surface cross-linking agent is not particularly limited because it can be changed variously depending on the type of surface cross-linking agent, cross-linking conditions, target performance, etc. From a viewpoint etc., based on the weight of an essential constituent monomer (a), 0.001-3 are preferable, More preferably, it is 0.005-2, Most preferably, it is 0.01-1.
表面架橋をする場合、表面架橋方法は、公知｛たとえば、特許第３６４８５５３号、特開２００３−１６５８８３号、特開２００５−７５９８２号、特開２００５−９５７５９号｝の方法が適用できる。 In the case of surface crosslinking, a known method {for example, Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883, Japanese Patent Laid-Open No. 2005-75982, Japanese Patent Laid-Open No. 2005-95759} can be applied.
＜添加剤の混合＞
細断ゲル、乾燥粒子、粉砕粒子又は表面架橋粒子等には、前述の他の添加剤を混合することができる。
他の添加剤を混合する場合、均一混合できれば混合方法に制限はなく、公知の混合方法が適用できる。
<Mixing of additives>
The above-mentioned other additives can be mixed with the chopped gel, dry particles, pulverized particles, surface cross-linked particles, and the like.
When other additives are mixed, the mixing method is not limited as long as uniform mixing is possible, and a known mixing method can be applied.
本発明の吸収性樹脂粒子は、繊維と共に吸収体とすることができる。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。また、この吸収体は吸収性物品｛紙おむつや生理用ナプキン等｝を構成することが好ましい。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｝と同様である。 The absorbent resin particles of the present invention can be used as an absorbent body together with the fibers. The structure and manufacturing method of the absorber are the same as those known in the art (Japanese Patent Laid-Open Nos. 2003-225565, 2006-131767, and 2005-097569, etc.). Moreover, it is preferable that this absorber comprises absorbent articles {paper diapers, sanitary napkins, etc.}. The manufacturing method and the like of the absorbent article are the same as known ones (Japanese Unexamined Patent Publication Nos. 2003-225565, 2006-131767, and 2005-097569, etc.).
吸収体に対する本発明の吸収性樹脂粒子の添加量（重量％）は、吸収体の種類やサイズ、目標とする吸収性能に応じて種々変化させることができるが、吸収性樹脂粒子と繊維状物の合計重量に基づいて、３０〜９５が好ましく、さらに好ましくは４０〜９４、特に好ましくは５０〜９３である。この範囲であると、得られる吸収体の吸収能がさらに良好となる。 The amount (% by weight) of the absorbent resin particles of the present invention to the absorber can be variously changed according to the type and size of the absorber and the target absorption performance, but the absorbent resin particles and the fibrous material 30-95 are preferable based on the total weight of, more preferably 40-94, particularly preferably 50-93. Within this range, the absorbent capacity of the resulting absorber is further improved.
本発明の吸収性樹脂粒子を用いた吸収体は、被吸収液（汗、尿及び血液等の体液並びに海水、地下水及び泥水等の水等）を吸収した場合であってもさらっとした感触を示すため、紙おむつ及び生理用ナプキン等の衛生用品に適用した場合、優れた吸収性能のみならず、漏れの少ない優れた特徴を発揮する。
従って、本発明の吸収性樹脂粒子を用いることにより、どのような状態においても高い吸収性能を発揮する吸収性物品を容易に製造することができる。すなわち、繰り返し吸水する必要がある状況であっても吸収量及び吸収速度が低下せず、その結果漏れ等の問題が極めて発生しにくい。
The absorbent body using the absorbent resin particles of the present invention has a light touch even when it absorbs liquids to be absorbed (body fluids such as sweat, urine and blood, and water such as seawater, groundwater and muddy water). Therefore, when applied to sanitary products such as disposable diapers and sanitary napkins, it exhibits not only excellent absorption performance but also excellent characteristics with little leakage.
Therefore, by using the absorbent resin particles of the present invention, it is possible to easily manufacture an absorbent article that exhibits high absorption performance in any state. That is, even in a situation where it is necessary to repeatedly absorb water, the amount of absorption and the absorption rate do not decrease, and as a result, problems such as leakage are extremely unlikely to occur.
吸収性物品のうち、吸収体、液体透過性シート、通気性バックシートを備える吸収性物品が好ましく、さらに好ましくは衛生用品としての吸収性物品である。
衛生用品としては、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）等が挙げられる。これらの衛生物品のうち、紙おむつにより適している。
Among the absorbent articles, an absorbent article including an absorbent body, a liquid permeable sheet, and a breathable back sheet is preferable, and an absorbent article as a sanitary article is more preferable.
Hygiene products include paper diapers (children's disposable diapers and adult disposable diapers, etc.), napkins (such as sanitary napkins), paper towels, pads (such as incontinence pads and surgical underpads), and pet sheets (pet urine absorbing sheets). Etc. Of these hygiene articles, they are more suitable for disposable diapers.
＜吸収速度の測定法｛ＤＷ（Demand Wettability）法；ＪＩＳ Ｋ７２２４−１９９６の解説３〜４頁｝＞
２５℃、湿度５０％の室内で、図１に示す装置｛ビューレット（１）の容量２５ｍｌ、長さ５５ｃｍ、小穴（２）の直径２ｍｍ｝を用い、空気流入細管（３）の最下端部と支持板（４）の最上端部とを同一水平面になるように調整した後、バルブ（５）及び（６）を閉じた状態で、約２５ｍｌの生理食塩水をビューレット（１）に入れ、ゴム栓（７）を装着した後、バルブ（５）及び（６）を開けることにより配管（８）を生理食塩水で充填すると共に、支持板（４）の中央に設けられた小穴（２）から生理食塩水を溢れ出させ、バルブ（５）を閉じてから、溢れ出た生理食塩水を拭き取り、ビューレット（１）の液面（ｈ１）を読み取る。引き続き、支持板（４）上に、平織りナイロンメッシュ（９）（目開き６３μｍ、５ｃｍ×５ｃｍ）をのせ、さらにこの平織りナイロンメッシュ（９）の上に、１．０ｇの測定試料（１０）を散布し、３０秒後に、ビューレットの液面（ｈ２）を読み取り、液面の差｛（ｈ１）−（ｈ２）｝を吸収量（Ｚ）とする。
<Measurement Method of Absorption Rate {DW (Demand Wettability) Method; JIS K7224-1996, pages 3-4}>
In the room of 25 ° C. and 50% humidity, the lower end of the air inflow tubule (3) using the apparatus shown in FIG. 1 (volume of the burette (1) is 25 ml, length is 55 cm, diameter of the small hole (2) is 2 mm). And the uppermost end of the support plate (4) are adjusted to the same horizontal plane, and about 25 ml of physiological saline is put into the burette (1) with the valves (5) and (6) closed. After installing the rubber plug (7), the pipe (8) is filled with physiological saline by opening the valves (5) and (6), and a small hole (2 provided in the center of the support plate (4) is provided. ) Overflows the physiological saline, closes the valve (5), wipes off the overflowing physiological saline, and reads the liquid level (h1) of the burette (1). Subsequently, a plain weave nylon mesh (9) (aperture 63 μm, 5 cm × 5 cm) is placed on the support plate (4), and 1.0 g of the measurement sample (10) is placed on the plain weave nylon mesh (9). After 30 seconds, the burette liquid level (h2) is read, and the liquid level difference {(h1)-(h2)} is defined as the absorption amount (Z).
＜ゲルブロッキング率（％）＞
吸水性樹脂のうち、目開き８５０μｍの金属ふるいを５回タッピングしてパスする粒子を測定試料とした。この測定試料１０ｇを、直径５ｃｍのアルミニウム製円柱皿内に均一になるように入れて、円柱皿を３０±１℃、８０±５％ＲＨの恒温恒湿槽内で３時間静置した。３時間後、測定試料の重量（ＴＷ）を計測してから、８５０μｍの金属ふるいで５回タッピングして、金属フルイに残った測定試料の重量（ＯＷ）を計測し、次式からブロッキング率（％）を算出した。
（ゲルブロッキング率（％））＝（ＯＷ）×１００／（ＴＷ）
<Gel blocking rate (%)>
Among the water-absorbent resins, particles passed by tapping a metal sieve having an aperture of 850 μm five times were used as measurement samples. 10 g of this measurement sample was placed uniformly in an aluminum cylindrical dish having a diameter of 5 cm, and the cylindrical dish was allowed to stand in a constant temperature and humidity chamber of 30 ± 1 ° C. and 80 ± 5% RH for 3 hours. After 3 hours, after measuring the weight (TW) of the measurement sample, tapping it 5 times with a 850 μm metal sieve, measuring the weight (OW) of the measurement sample remaining on the metal sieve, the blocking rate ( %) Was calculated.
(Gel blocking rate (%)) = (OW) × 100 / (TW)
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。以下、特記しない限り、部は重量部、％は重量％を示す。 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.
＜実施例１＞
アクリル酸８１．８部（１．１４モル部）、内部架橋剤（ｂ）｛Ｎ，Ｎ’−メチレンビスアクリルアミド｝０．３部（０．００２モル部）及び脱イオン水２４１部を攪拌・混合しながら、温度を１〜２℃に保ち、この混合液中に窒素を流入して、混合液中の溶存酸素量を０．０２ｐｐｍ以下とした。引き続き、この混合液に、１％過酸化水素水溶液１部、０．２％アスコルビン酸水溶液１．２部及び２％の２，２’−アゾビスアミジノプロパンジハイドロクロライド水溶液２．８部を添加・混合して重合を開始させ、反応温度が７０℃に達した後、重合温度７５±５℃で約８時間重合することにより含水重合体（ゲル）を得た。
<Example 1>
Stir and stir 81.8 parts (1.14 mole part) of acrylic acid, 0.3 part (0.002 mole part) of internal crosslinking agent (b) {N, N′-methylenebisacrylamide} and 241 parts of deionized water. While mixing, the temperature was maintained at 1 to 2 ° C., and nitrogen was allowed to flow into the mixed solution, so that the amount of dissolved oxygen in the mixed solution was 0.02 ppm or less. Subsequently, 1 part of a 1% aqueous hydrogen peroxide solution, 1.2 parts of a 0.2% ascorbic acid aqueous solution and 2.8 parts of a 2% 2,2′-azobisamidinopropane dihydrochloride aqueous solution are added to the mixture. Polymerization was started by mixing, and after the reaction temperature reached 70 ° C., polymerization was carried out at a polymerization temperature of 75 ± 5 ° C. for about 8 hours to obtain a water-containing polymer (gel).
この含水重合体（ゲル）をインターナルミキサーで３〜７ｍｍの大きさに細断して細断ゲルを得た後、この細断ゲル３２５部に４８％の水酸化ナトリウム水溶液６７．５部を添加してカルボキシル基の７２当量％を中和（インターナルミキサーで混合した。）して、中和細断ゲルを得た。なお、ＪＩＳ Ｋ０１１３−１９９７に準拠（０．１規定水酸化カリウム水溶液を滴定液として使用、電位差滴定法、変曲点法）して測定した酸価から算出した中和細断ゲルの中和度は７０．１当量％であった。 The water-containing polymer (gel) was chopped to a size of 3 to 7 mm with an internal mixer to obtain a chopped gel, and then 67.5 parts of a 48% aqueous sodium hydroxide solution was added to 325 parts of the chopped gel. It was added to neutralize 72 equivalent% of the carboxyl groups (mixed with an internal mixer) to obtain a neutralized chopped gel. In addition, the neutralization degree of the neutralized chopped gel calculated from the acid value measured according to JIS K0113-1997 (using 0.1 N potassium hydroxide aqueous solution as a titrant, potentiometric titration method, inflection point method) Was 70.1 equivalent%.
次いで、縦２０ｃｍ×横２０ｃｍ×高さ１０ｃｍで、天板を有さず、底板に目開き４ｍｍの金網を装着したステンレス製のトレイに、この混合ゲルを約５ｃｍの厚さに積層し、１５０℃、風速２．０ｍ／ｓの条件で、通気型バンド乾燥機（井上金属製）で乾燥して、乾燥重合体（Ｄ１）を得た。
この乾燥重合体（Ｄ１）をジューサーミキサー（Ｎａｔｉｏｎａｌ ＭＸ−Ｘ５３、松下電器株式会社製）で粉砕し、目開き１５０及び７１０μｍのふるいを用いて１５０〜７１０μｍの粒子径範囲に調整した後、この１００部を高速攪拌（細川ミクロン製 高速攪拌タービュライザーミキサー：回転数２０００ｒｐｍ）しながら、カルボキシ変性シリコーン（信越化学工業社製：Ｘ−２２−１６２Ｃ）／エチレングリコールジグリシジルエーテル／水／メタノール＝０．００５／１／６０／４０（重量比）１部をスプレー噴霧しながら添加・混合し、１００℃で３０分間静置し加熱架橋（表面架橋）することにより複合粒子を得た。
Next, this mixed gel is laminated to a thickness of about 5 cm on a stainless steel tray having a length of 20 cm × width of 20 cm × height of 10 cm, having no top plate, and having a 4 mm mesh wire mesh on the bottom plate. It dried with the ventilation | gas_flowing type band dryer (made by Inoue Metal) on the conditions of (degreeC) and the wind speed of 2.0 m / s, and obtained the dry polymer (D1).
This dried polymer (D1) was pulverized with a juicer mixer (National MX-X53, manufactured by Matsushita Electric Industrial Co., Ltd.) and adjusted to a particle size range of 150 to 710 μm using a sieve with 150 and 710 μm openings, and then 100 Carboxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-162C) / ethylene glycol diglycidyl ether / water / methanol = 0. 0.005 / 1/60/40 (weight ratio) 1 part was added and mixed while spraying, and left at 100 ° C. for 30 minutes, followed by heat crosslinking (surface crosslinking) to obtain composite particles.
複合粒子１００部と無機多孔質微粒子（ｃ１）｛株式会社トクヤマ製二酸化ケイ素、トクシール、体積平均粒子経２．５μｍ、比表面積１２０ｍ２／ｇ｝０．０１部とをコニカルブレンダー｛ホソカワミクロン株式会社製｝で均一混合して、本発明の吸収性樹脂粒子（１）を得た。
吸水剤の生理食塩水に対する１分後の吸収量（Ｚ）（ｇ／ｇ）は、下記方法にて測定される。
Conical blender {manufactured by Hosokawa Micron Co., Ltd.) with 100 parts of composite particles and inorganic porous fine particles (c1) {0.01 parts by silicon dioxide manufactured by Tokuyama Corporation, Tokuseal, volume average particle diameter 2.5 μm, specific surface area 120 m 2 / g} } To obtain the absorbent resin particles (1) of the present invention.
The amount of absorption (Z) (g / g) after 1 minute of the water-absorbing agent with respect to physiological saline is measured by the following method.
＜実施例２＞
実施例１と同様に得られた中和細断ゲル４００部に、ステアリルアルコール０．１部を加え、ミンチ機（目皿の穴径：６ｍｍ、飯塚工業社製 １２ＶＲ−４００Ｋ）にて２５℃で５分間混練した後、インターナルミキサーにて２５℃で５分間混練し、次いで、縦２０ｃｍ×横２０ｃｍ×高さ１０ｃｍで、天板を有さず、底板に目開き４ｍｍの金網を装着したステンレス製のトレイに、この混合ゲルを約５ｃｍの厚さに積層し、１５０℃、風速２．０ｍ／ｓの条件で、通気型バンド乾燥機（井上金属製）で乾燥して、乾燥重合体（Ｄ２）を得た。
この乾燥重合体（Ｄ２）をジューサーミキサー（Ｎａｔｉｏｎａｌ ＭＸ−Ｘ５３、松下電器株式会社製）で粉砕し、目開き１５０及び７１０μｍのふるいを用いて１５０〜７１０μｍの粒子径範囲に調整した後、この１００部を高速攪拌（細川ミクロン製 高速攪拌タービュライザーミキサー：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／水／メタノール＝１／６０／４０（重量比）２部をスプレー噴霧しながら添加・混合し、９０℃で１５分間静置し加熱架橋（表面架橋）することにより複合粒子を得た。
<Example 2>
0.1 part of stearyl alcohol was added to 400 parts of the neutralized chopped gel obtained in the same manner as in Example 1, and 25 ° C. with a mincing machine (diameter hole diameter: 6 mm, 12VR-400K manufactured by Iizuka Kogyo Co., Ltd.). Kneaded for 5 minutes at 25 ° C. with an internal mixer, then 20 cm long × 20 cm wide × 10 cm high, without a top plate, and with a 4 mm mesh wire mesh on the bottom plate This mixed gel is laminated on a stainless steel tray to a thickness of about 5 cm, and dried with a ventilated band dryer (manufactured by Inoue Metal) at 150 ° C. and a wind speed of 2.0 m / s to obtain a dry polymer. (D2) was obtained.
This dry polymer (D2) was pulverized with a juicer mixer (National MX-X53, manufactured by Matsushita Electric Industrial Co., Ltd.), adjusted to a particle size range of 150 to 710 μm using a sieve with 150 and 710 μm openings, and then 100
複合粒子１００部と無機多孔質微粒子（ｃ１）０．０１部とをコニカルブレンダー｛ホソカワミクロン株式会社製｝で均一混合して、本発明の吸収性樹脂粒子（２）を得た。 100 parts of the composite particles and 0.01 part of the inorganic porous fine particles (c1) were uniformly mixed with a conical blender {manufactured by Hosokawa Micron Corporation} to obtain the absorbent resin particles (2) of the present invention.
＜実施例３＞
カルボキシ変性シリコーン（信越化学工業社製：Ｘ−２２−１６２Ｃ）をアミノ変性シリコーン（信越シリコーン社製：ＫＦ−８６４）に変更した以外は実施例１と同様にして、本発明の吸収性樹脂粒子（３）を得た。
<Example 3>
Absorbent resin particles of the present invention in the same manner as in Example 1 except that carboxy-modified silicone (Shin-Etsu Chemical Co., Ltd .: X-22-162C) was changed to amino-modified silicone (Shin-Etsu Silicone Co., Ltd .: KF-864). (3) was obtained.
＜実施例４＞
カルボキシ変性シリコーン（信越化学工業社製：Ｘ−２２−１６２Ｃ）をエポキシ変性シリコーン（信越シリコーン社製：ＫＦ−１００１）に変更した以外は実施例１と同様にして、本発明の吸収性樹脂粒子（４）を得た。
<Example 4>
Absorbent resin particles of the present invention in the same manner as in Example 1 except that carboxy-modified silicone (Shin-Etsu Chemical Co., Ltd .: X-22-162C) was changed to epoxy-modified silicone (Shin-Etsu Silicone Co., Ltd .: KF-1001). (4) was obtained.
＜実施例５＞
ステアリルアルコール０．１部をジメチルシリコーン（信越シリコーン社製：ＫＦ−９６Ａー６ｃｓ）０．００５部に変更した以外は実施例２と同様にして、本発明の吸収性樹脂粒子（５）を得た。
<Example 5>
Absorbent resin particles (5) of the present invention are obtained in the same manner as in Example 2 except that 0.1 part of stearyl alcohol is changed to 0.005 part of dimethyl silicone (manufactured by Shin-Etsu Silicone Co., Ltd .: KF-96A-6cs). It was.
＜実施例６＞
ステアリルアルコール０．１部をステアリン酸０．０２部に変更した以外は実施例２と同様にして、本発明の吸収性樹脂粒子（６）を得た。
<Example 6>
Absorbent resin particles (6) of the present invention were obtained in the same manner as in Example 2 except that 0.1 part of stearyl alcohol was changed to 0.02 part of stearic acid.
＜実施例７＞
｛カルボキシ変性シリコーン（信越化学工業社製：Ｘ−２２−１６２Ｃ）／エチレングリコールジグリシジルエーテル／水／メタノール＝０．００５／１／６０／４０（重量比）２部をスプレー噴霧しながら添加・混合｝を｛エチレングリコールジグリシジルエーテル／水／メタノール＝１／６０／４０（重量比）２部をスプレー噴霧しながら添加・混合し、さらにステアリン酸０．１部を添加・混合｝に変更した以外は実施例１と同様にして、本発明の吸収性樹脂粒子（７）を得た。
<Example 7>
{Carboxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-162C) / ethylene glycol diglycidyl ether / water / methanol = 0.005 / 1/60/40 (weight ratio) added while spraying. Was added and mixed while spraying 2 parts of ethylene glycol diglycidyl ether / water / methanol = 1/60/40 (weight ratio), and 0.1 part of stearic acid was added and mixed. Except that, the absorbent resin particles (7) of the present invention were obtained in the same manner as in Example 1.
＜実施例８＞
ステアリルアルコール０．１部をショ糖ステアリン酸モノエステル０．１部に変更した以外は実施例２と同様にして、本発明の吸収性樹脂粒子（８）を得た。
<Example 8>
Absorbent resin particles (8) of the present invention were obtained in the same manner as in Example 2 except that 0.1 part of stearyl alcohol was changed to 0.1 part of sucrose stearate monoester.
＜比較例１＞
｛カルボキシ変性シリコーン（信越化学工業社製：Ｘ−２２−１６２Ｃ）／エチレングリコールジグリシジルエーテル／水／メタノール＝０．００５／１／６０／４０（重量比）２部をスプレー噴霧しながら添加・混合｝を｛エチレングリコールジグリシジルエーテル／水／メタノール＝１／６０／４０（重量比）２部をスプレー噴霧しながら添加・混合し｝に変更した以外は実施例１と同様にして、吸収性樹脂粒子（９）を得た。
<Comparative Example 1>
{Carboxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-162C) / ethylene glycol diglycidyl ether / water / methanol = 0.005 / 1/60/40 (weight ratio) added while spraying. Absorbability in the same manner as in Example 1 except that {mixing} was changed to {addition and mixing while spraying 2 parts of ethylene glycol diglycidyl ether / water / methanol = 1/60/40 (weight ratio)}. Resin particles (9) were obtained.
＜比較例２＞
無機多孔質微粒子を使用しなかったこと以外は実施例２と同様にして、吸収性樹脂粒子（１０）を得た。
<Comparative example 2>
Absorbent resin particles (10) were obtained in the same manner as in Example 2 except that the inorganic porous fine particles were not used.
＜比較例３＞
ステアリルアルコール０．１部をイコサン０．１部に変更した以外は実施例２と同様にして、本発明の吸収性樹脂粒子（１１）を得た。
<Comparative Example 3>
Absorbent resin particles (11) of the present invention were obtained in the same manner as in Example 2 except that 0.1 part of stearyl alcohol was changed to 0.1 part of icosane.
実施例１〜８及び比較例１〜３で得た吸収性樹脂粒子について、ゲルブロッキング率及び吸収量を表１に示した。 Table 1 shows the gel blocking rate and the absorption amount of the absorbent resin particles obtained in Examples 1 to 8 and Comparative Examples 1 to 3.
表１から判るように、本発明の吸収性樹脂粒子は、比較の吸収性樹脂粒子に比べ、ゲルブロッキング率が少なく、吸収量が大きい。 As can be seen from Table 1, the absorbent resin particles of the present invention have a lower gel blocking rate and a higher absorption amount than the comparative absorbent resin particles.
本発明の吸収性樹脂粒子は、吸収性樹脂粒子と繊維状物とを含有してなる吸収体に適用でき、この吸収体を備えてなる吸収性物品｛紙おむつ、生理用ナプキン及び医療用保血剤等｝に有用である。また、ペット尿吸収剤、携帯トイレ用尿ゲル化剤、青果物用鮮度保持剤、肉類・魚介類用ドリップ吸収剤、保冷剤、使い捨てカイロ、電池用ゲル化剤、植物・土壌用保水剤、結露防止剤、止水剤、パッキング剤及び人工雪等の種々の用途にも使用できる。 The absorbent resin particles of the present invention can be applied to an absorbent body containing absorbent resin particles and a fibrous material, and absorbent articles {paper diapers, sanitary napkins, and medical blood retaining bodies comprising the absorbent body. It is useful for the agent}. In addition, pet urine absorbent, urine gelling agent for portable toilets, freshness preservation agent for fruits and vegetables, drip absorbent for meat and seafood, cooler, disposable warmer, battery gelling agent, water retention agent for plants and soil, dew condensation It can also be used in various applications such as inhibitors, water-stopping agents, packing agents and artificial snow.
１ ビューレット
２ 小穴
３ 空気流入細管
４ 支持板
５ バルブ
６ バルブ
７ ゴム栓
８ 配管
９ 平織りナイロンメッシュ
１０ 測定試料
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| JP5685007B2 (en) * | 2010-06-02 | 2015-03-18 | Ｓｄｐグローバル株式会社 | Absorbent resin particles, absorber containing the same, and absorbent article |
| US20140142269A1 (en) * | 2011-07-08 | 2014-05-22 | Sumitomo Seika Chemicals Co.,,Ltd. | Carboxyl group-containing polymer composition |
| JP2013133399A (en) * | 2011-12-26 | 2013-07-08 | Kao Corp | Water-absorbing polymer particle |
| JP6013730B2 (en) | 2011-12-27 | 2016-10-25 | 株式会社リブドゥコーポレーション | Absorbent articles |
| JP6013729B2 (en) * | 2011-12-27 | 2016-10-25 | 株式会社リブドゥコーポレーション | Water-absorbent resin powder and absorbent body and absorbent article using the same |
| JP2013203842A (en) * | 2012-03-28 | 2013-10-07 | San-Dia Polymer Ltd | Absorptive resin particle and absorber and absorptive article containing the same |
| JP6128791B2 (en) | 2012-10-15 | 2017-05-17 | 株式会社リブドゥコーポレーション | Absorbent articles |
| JP6128790B2 (en) | 2012-10-15 | 2017-05-17 | 株式会社リブドゥコーポレーション | Absorbent articles |
| KR101967807B1 (en) * | 2014-12-23 | 2019-04-10 | 주식회사 엘지화학 | Attrition Resistant Superabsorbent Polymers And Method Of Preparing The Same |
| KR101949458B1 (en) * | 2016-03-11 | 2019-02-18 | 주식회사 엘지화학 | Preparation method of super absorbent polymer, and super absorbent polymer |
| JP6806490B2 (en) * | 2016-08-10 | 2021-01-06 | 双葉電子工業株式会社 | Water catching agent and its manufacturing method, desiccant composition, sealing structure, and organic EL element |
| KR102193459B1 (en) * | 2016-12-20 | 2020-12-21 | 주식회사 엘지화학 | Super absorbent polymer and preparation method for the same |
| TW202005994A (en) * | 2018-06-27 | 2020-02-01 | 日商住友化學股份有限公司 | Gel containing reactive silicon compound condensate |
| KR102562511B1 (en) * | 2018-09-21 | 2023-08-03 | 가부시키가이샤 닛폰 쇼쿠바이 | Manufacturing method of absorbent polymer containing chelating agent |
| JPWO2021117785A1 (en) * | 2019-12-13 | 2021-06-17 | ||
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