JP5700928B2 - Water absorbent resin composition - Google Patents
Water absorbent resin composition Download PDFInfo
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- JP5700928B2 JP5700928B2 JP2009270795A JP2009270795A JP5700928B2 JP 5700928 B2 JP5700928 B2 JP 5700928B2 JP 2009270795 A JP2009270795 A JP 2009270795A JP 2009270795 A JP2009270795 A JP 2009270795A JP 5700928 B2 JP5700928 B2 JP 5700928B2
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- bentonite
- absorbent resin
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- 239000011342 resin composition Substances 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 16
- 239000002250 absorbent Substances 0.000 title description 29
- 230000002745 absorbent Effects 0.000 title description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 41
- 239000000440 bentonite Substances 0.000 claims description 40
- 229910000278 bentonite Inorganic materials 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 10
- -1 hydroxyethyl group Chemical group 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000005206 flow analysis Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910021647 smectite Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001595 flow curve Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000275 saponite Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000009974 thixotropic effect Effects 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004078 waterproofing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- RBRXPPLNXDVMKG-GMFCBQQYSA-M bis(2-hydroxyethyl)-methyl-[(z)-octadec-9-enyl]azanium;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCC[N+](C)(CCO)CCO RBRXPPLNXDVMKG-GMFCBQQYSA-M 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、吸水性樹脂組成物に関する。詳しくは、水溶性有機物、有機化ベントナイト、および吸水性樹脂からなり、吸水性樹脂が安定分散された、チクソトロピー性を有する吸水性樹脂組成物に関する。 The present invention relates to a water absorbent resin composition. Specifically, the present invention relates to a water-absorbing resin composition having thixotropy, which is composed of a water-soluble organic substance, an organic bentonite, and a water-absorbing resin, and the water-absorbing resin is stably dispersed.
吸水性樹脂は各種分野に用いられている。例えば、紙おむつ、生理用品、電力・通信ケーブルなどの止水剤や止水テープ、ペットシート、農園芸用土壌改良剤、蓄冷剤などの保水剤等の用途がある。しかしながら、これらに用いられる吸水性樹脂は通常は粉体であることから飛散による作業環境の悪化、吸水時のままこの形成、吸湿性であるために保管状況によっては品質が劣化しやすいといった問題点があった。 Water-absorbing resins are used in various fields. For example, there are uses such as water proofing agents such as paper diapers, sanitary products, power / communication cables, water proofing tapes, pet sheets, soil conditioners for agriculture and horticulture, and water retention agents such as cold storage agents. However, since the water-absorbing resin used in these is usually a powder, the working environment is deteriorated due to scattering, the formation of the water-absorbing water absorbs water, and the quality is likely to deteriorate depending on the storage conditions because it is hygroscopic. was there.
これらの問題点を解決する為に吸水性樹脂をスラリー状にすることが提案されている。特許文献１ではテトラエチレングリコール等の水溶性有機物と水の混合物を用いた吸水性樹脂スラリー、特許文献２ではポリエチレングリコール等の有機溶媒にソルビタン系非イオン界面活性剤を添加し、その後に吸水性樹脂を混合した吸水性樹脂スラリーを提案している。また、特許文献３にはポリエチレングリコール、グリセリン、なたね油等の不活性有機液体に有機処理粘土、吸水性樹脂を混合してなる逸泥防止剤が提案されている。しかしながらいずれも短期間での樹脂の沈降、ケーキの固化がみられ、実用上不十分であった。
この問題点を解決する方法として特許文献４では石油系炭化水素に界面活性剤、微粉末状吸水性樹脂、微粉末シリカ、有機ベントナイトを用いた油性分散液を提案している。しかし、特許文献４に記載の分散液は樹脂の分散安定性はみられるものの、高粘性であることから、吸水性樹脂組成物を噴射して用いるような用途には、十分に対応できるものでなかった。
In order to solve these problems, it has been proposed to make the water-absorbent resin in a slurry state. In
As a method for solving this problem, Patent Document 4 proposes an oily dispersion using a petroleum hydrocarbon, a surfactant, a fine powder water-absorbing resin, fine powder silica, and organic bentonite. However, although the dispersion described in Patent Document 4 is highly viscous, although the dispersion stability of the resin is observed, it can be sufficiently used for applications in which the water-absorbing resin composition is used by spraying. There wasn't.
本発明は、使用時における分散溶液の粘性が低く、且つ使用前に長期間放置しておいた場合においても、溶媒中における吸水性樹脂が沈降することのない吸水性樹脂組成物を提供することを目的とする。 The present invention provides a water-absorbent resin composition in which the viscosity of the dispersion solution at the time of use is low and the water-absorbent resin in the solvent does not settle even when left for a long time before use. With the goal.
本発明者は、かかる事情に鑑み鋭意検討した結果、特定の有機溶媒に有機化ベントナイト、吸水性樹脂を分散させることで樹脂の分散安定性が良好で、かつチクソトロピー性を持つ吸水性樹脂組成物としうることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of such circumstances, the present inventor has obtained a water-absorbing resin composition having good dispersion stability and thixotropy by dispersing an organic bentonite and a water-absorbing resin in a specific organic solvent. As a result, the present invention has been completed.
即ち、本発明は、
（１）Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、ホルムアミド又はＮ−メチルピロリドン３０〜８０質量％、ベントナイトをベントナイトの陽イオン交換容量の０．５〜１．５倍当量の、ヒドロキシエチル基又はオキシエチレン基を有する第四級アンモニウム塩で処理した有機化ベントナイトをそのベントナイト成分量で表して２〜６質量％、およびアクリル酸塩系吸水性樹脂１０〜６０質量％を含有する、チクソトロピー性を有する吸水性樹脂組成物、
（２）前記アクリル酸塩系吸水性樹脂は、ポリアクリル酸ナトリウムを含有することを特徴とする（１）に記載の吸水性樹脂組成物、
を提供するものである。
That is, the present invention
(1) N-methylformamide, N, N-dimethylformamide, formamide or N-methylpyrrolidone 30-80% by mass, bentonite is 0.5 to 1.5 times equivalent to the cation exchange capacity of bentonite , hydroxyethyl group or containing quaternary ammonium 2-6 wt% expressed treated organic bentonite at its bentonite component amount salt, and 10 to 60 wt% of acrylic acid salt-based water-absorbing resin having an oxyethylene group, thixotropic A water absorbent resin composition having
(2) The water absorbent resin composition according to (1), wherein the acrylate-based water absorbent resin contains sodium polyacrylate.
Is to provide.
本発明の吸水性樹脂組成物は、使用前に長期間放置しておいた場合にも、チクソトロピー性を有するため、溶媒中における吸水性樹脂が沈降することがなく、吸水性樹脂の分散安定性が極めて優れ、且つ使用時にせん断応力を加えることで分散液は流動性を回復し、すなわち粘性が低くなることで取り扱い性に優れている。 The water-absorbent resin composition of the present invention has thixotropic properties even when left for a long time before use, so that the water-absorbent resin in the solvent does not settle, and the dispersion stability of the water-absorbent resin In addition, the dispersion recovers its fluidity by applying a shear stress during use, that is, it is excellent in handleability due to its low viscosity.
（アミド基を有する水溶性有機物）
本発明に用いられるアミド基を有する水溶性有機物とは、溶媒として用いるため、常温・常圧（例えば、２０℃、１０１ｋＰａ）では液状のものである。具体的には、例えば、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、ホルムアミド、Ｎ−メチルピロリドンが挙げられ、Ｎ−メチルホルムアミドが好ましい。
本発明の吸水性樹脂組成物中、アミド基を有する水溶性有機物の含有量は、好ましくは３０〜８０質量％、さらに好ましくは４０〜７０質量％、より好ましくは５０〜６０質量％である。また、本発明の吸水性樹脂組成物は、上記アミド基を有する水溶性有機物との相溶性のある有機溶媒により希釈して用いることも可能である。
(Water-soluble organic substance having an amide group)
Since the water-soluble organic substance having an amide group used in the present invention is used as a solvent, it is liquid at room temperature and normal pressure (for example, 20 ° C. and 101 kPa). Specific examples include N-methylformamide, N, N-dimethylformamide, formamide, and N-methylpyrrolidone, with N-methylformamide being preferred.
In the water-absorbent resin composition of the present invention, the content of the water-soluble organic substance having an amide group is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and more preferably 50 to 60% by mass. Moreover, the water-absorbent resin composition of the present invention can also be used by diluting with an organic solvent compatible with the water-soluble organic substance having the amide group.
（有機化ベントナイト）
本発明に用いられるベントナイトは、シリカとアルミナを主成分とする層状ケイ酸塩鉱物の１種であるスメクタイトを主成分とするもので、スメクタイトからなるものが好ましい。スメクタイトとしては、モンモリロナイト、バイデライト、ノントロナイト、ヘクトライト、ソーコナイト、スチブンサイト、サポナイトが好ましく、サポナイトが特に好ましい。合成サポナイトとしては、例えば、スメクトンＳＡ（クニミネ工業（株）製）として市販されている。本発明に用いられる有機化ベントナイトは、スメクタイトの層間に有機化剤を入れ込んだものである。この有機化ベントナイトは市販のものでもよいが有機化合物（ベントナイトの水分散体など）をベントナイトのスメクタイト層間に導入したのち、この処理ベントナイトを分離して調製することもできる。
(Organized bentonite)
The bentonite used in the present invention is mainly composed of smectite, which is one of layered silicate minerals mainly composed of silica and alumina, and is preferably composed of smectite. As the smectite, montmorillonite, beidellite, nontronite, hectorite, soconite, stevensite, and saponite are preferable, and saponite is particularly preferable. Synthetic saponite is commercially available, for example, as Smecton SA (manufactured by Kunimine Industry Co., Ltd.). The organic bentonite used in the present invention is one in which an organic agent is inserted between smectite layers. This organic bentonite may be a commercially available one, but after introducing an organic compound (such as an aqueous dispersion of bentonite) between the smectite layers of bentonite, this treated bentonite can also be prepared separately.
ベントナイトの有機化処理に使用される有機化剤には、塩化ジアルキルジメチルアンモニウム、塩化アルキルトリメチルアンモニウム、塩化アルキルジメチルベンジルアンモニウム塩等の第四級アンモニウム塩、ホスホニウム塩、スルホニウム塩、イミダゾリウム塩、及びピリジニウム塩があるが、特に第四級アンモニウム塩が好ましい。
また、有機化剤の特性として側鎖に極性を有するもの、例えば、ヒドロキシルエチル基、オキシエチレン基を有するものがさらに好ましく、塩化ポリオキシエチレンアルキルメチルアンモニウム、塩化オレイルビス（２−ヒドロキシエチル）メチルアンモニウムがより好ましい。
Organizing agents used for the organic treatment of bentonite include quaternary ammonium salts such as dialkyldimethylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, phosphonium salts, sulfonium salts, imidazolium salts, and Although there are pyridinium salts, quaternary ammonium salts are particularly preferred.
Further, as the characteristics of the organic agent, those having polarity in the side chain, for example, those having a hydroxylethyl group or an oxyethylene group are more preferred, such as polyoxyethylene alkylmethylammonium chloride, oleylbis (2-hydroxyethyl) methylammonium chloride. Is more preferable.
有機化によって得られる有機化ベントナイトの量は、同じベントナイト量であっても、有機化剤の分子量に依存して変化する。本発明で用いる有機化ベントナイトは、有機化剤の処理量が、ベントナイトの陽イオン交換容量の好ましくは０．５〜１．５倍当量、さらに好ましくは０．８〜１．３倍当量、より好ましくは１．０〜１．２倍当量のものである。処理量が多すぎると未反応有機化剤が多くなりチキソトロピー性が小さくなり、少なすぎると処理量が不足し、分散安定性が低くなる。 The amount of organic bentonite obtained by organic change varies depending on the molecular weight of the organic agent even if the amount of bentonite is the same. In the organic bentonite used in the present invention, the treatment amount of the organic agent is preferably 0.5 to 1.5 times equivalent, more preferably 0.8 to 1.3 times equivalent to the cation exchange capacity of bentonite. Preferably, it is 1.0 to 1.2 times equivalent. If the amount is too large, the amount of the unreacted organic agent is increased and the thixotropic property is decreased. If the amount is too small, the amount is not sufficient and the dispersion stability is lowered.
本発明の吸水性樹脂組成物中の有機化ベントナイトの量は、その有機化ベントナイト中のベントナイト成分（未処理のベントナイトに相当）量で表して、２〜６質量％、より好ましくは２．４〜５質量％である。この有機化ベントナイトの量が多すぎると粘性が高くなり、スラリーとしての取扱いが困難になり、少なすぎると吸水性樹脂組成物中の吸水性樹脂が沈降、分離しやすくなる。 The amount of the organic bentonite in the water-absorbent resin composition of the present invention is expressed in terms of the amount of bentonite component (corresponding to untreated bentonite) in the organic bentonite, more preferably 2.4% by mass. ˜5 mass%. If the amount of the organic bentonite is too large, the viscosity becomes high and handling as a slurry becomes difficult. If the amount is too small, the water absorbent resin in the water absorbent resin composition tends to settle and separate.
（吸水性樹脂）
本発明に用いる吸水性樹脂については、特に限定はされないが、例えば、ポリアクリル酸（塩）架橋体、ポリアクリルアミド、澱粉−アクリロニトリルグラフト共重合物の加水分解物、カルボキシメチルセルロース架橋体、アクリル酸（塩）−ビニルアルコール共重合物、ポリオキシエチレン架橋体等が挙げられ、これらの中から、目的に合った吸水能、ゲル径、ゲル強度の市販品を適宜選定して使用することができる。吸水性樹脂は好ましくは粉末状で用いられる。
(Water absorbent resin)
The water-absorbent resin used in the present invention is not particularly limited. For example, polyacrylic acid (salt) crosslinked product, polyacrylamide, hydrolyzate of starch-acrylonitrile graft copolymer, carboxymethylcellulose crosslinked product, acrylic acid ( Salt) -vinyl alcohol copolymer, cross-linked polyoxyethylene, and the like. Of these, commercially available products having a water absorption capacity, gel diameter, and gel strength suitable for the purpose can be appropriately selected and used. The water absorbent resin is preferably used in powder form.
その中でも、ポリアクリル酸塩系を含有することが好ましく、ポリアクリル酸ナトリウム架橋体が特に好ましい。ポリアクリル酸ナトリウム架橋体は現在、市場に最も多く使用されているタイプの物である。通常その平均粒径は２０〜１０００μｍであり、粒子形状は球形、不定形、造粒体の物がある。この中で特に２０〜５０μｍの粒子のものが溶媒中での吸水性樹脂の沈降防止をより抑制する効果が大であり好適である。市販のものとしては、例えばサンフレッシュＳＴ−５００ＭＰＳＡ（サンダイヤポリマー（株）製）を挙げることができる。 Among these, it is preferable to contain a polyacrylate system, and a sodium polyacrylate crosslinked body is particularly preferable. The cross-linked sodium polyacrylate is the type most frequently used on the market. Usually, the average particle size is 20 to 1000 μm, and the particle shape is spherical, indeterminate or granulated. Of these, particles having a particle size of 20 to 50 μm are particularly preferred because they have a great effect of preventing the water-absorbing resin from settling in the solvent. Examples of commercially available products include Sunfresh ST-500MPSA (manufactured by Sundia Polymer Co., Ltd.).
樹脂組成物中の吸水性樹脂の含有量は、１０〜６０質量％が好ましく、２０〜５０質量％がさらに好ましい。吸水性樹脂の量が多すぎると分散液中における樹脂の分散安定性が悪くなり、樹脂の沈降或いは固いケーキが生成する傾向が大きくなり、一方、樹脂の量が少なすぎると樹脂の分散安定性は良くなるが、吸水性樹脂分散液としての性能が低下し、好ましくない。粉末状吸水性樹脂は、最大粒径が好ましくは１０００μｍ以下、さらに好ましくは２００μｍ以下で、平均粒径が好ましくは５００μｍ以下、さらに好ましくは１００μｍ以下のものを使用するのがよい。 The content of the water absorbent resin in the resin composition is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass. If the amount of the water-absorbing resin is too large, the dispersion stability of the resin in the dispersion is deteriorated and the tendency of the resin to settle or form a hard cake increases. On the other hand, if the amount of the resin is too small, the dispersion stability of the resin is increased. Is improved, but the performance as a water-absorbent resin dispersion is lowered, which is not preferable. The powdery water-absorbent resin preferably has a maximum particle size of preferably 1000 μm or less, more preferably 200 μm or less, and an average particle size of preferably 500 μm or less, more preferably 100 μm or less.
本発明の樹脂組成物は、通常の攪拌機を用いて、アミド基を有する水溶性有機物と、有機化ベントナイトからなる混合物に、吸水性樹脂、好ましくは粉末状の吸水性樹脂を混合・分散し作製することができる。
本発明の吸水性樹脂組成物は、安定分散液であり、チクソトロピー性を有する。チクソトロピー性は、通常の回転粘度計や粘弾性流体測定用のレオメーターを用いて算出することができ、チクソトロピー性を有すると、剪断速度を横軸に、剪断応力を縦軸にプロットし、得られる剪断速度を上昇させたときの流動曲線と、下降させたときの流動曲線が、異なり、一つのループを描く。このヒステリシスループの面積が大きいほどチクソトロピー性が高い。
The resin composition of the present invention is prepared by mixing and dispersing a water-absorbing resin, preferably a powdery water-absorbing resin, in a mixture of a water-soluble organic substance having an amide group and an organic bentonite using a normal stirrer. can do.
The water absorbent resin composition of the present invention is a stable dispersion and has thixotropic properties. The thixotropy can be calculated using a normal rotational viscometer or a rheometer for measuring viscoelastic fluids. When thixotropy is obtained, the shear rate is plotted on the horizontal axis and the shear stress is plotted on the vertical axis. The flow curve when the shear rate is increased is different from the flow curve when the shear rate is decreased, and a single loop is drawn. The greater the area of this hysteresis loop, the higher the thixotropy.
本発明の吸水性樹脂組成物は、使用前に長期間放置しておいた場合にも、チクソトロピー性が高いため、溶媒中における吸水性樹脂が沈降することがなく、吸水性樹脂の分散安定性が極めて優れ、且つ使用時にせん断応力を加えることで分散液は流動性を回復し、すなわち粘性が低くなることで取り扱い性に優れている。また、粘性が低くなるので噴射性が良い。 The water-absorbent resin composition of the present invention has high thixotropy even when left for a long time before use, so that the water-absorbent resin does not settle in the solvent, and the dispersion stability of the water-absorbent resin In addition, the dispersion recovers its fluidity by applying a shear stress during use, that is, it is excellent in handleability due to its low viscosity. Moreover, since the viscosity is low, the jetting property is good.
安定分散液である本発明の吸水性樹脂組成物は、水溶性有機物を溶媒として使っているため吸水性樹脂本来の吸水能力を低下させることはない。さらに液体状にすることによりその取り扱い性、搬送性、噴射性が改良されている。主に土木工事用滑剤、止水剤、及び建築用結露防止塗料等に好適に利用できる。 Since the water-absorbent resin composition of the present invention which is a stable dispersion uses a water-soluble organic substance as a solvent, the water-absorbing resin inherent water-absorbing ability is not lowered. Furthermore, the handling property, conveyance property, and jetting property are improved by making it liquid. It can be suitably used mainly for civil engineering lubricants, waterproofing agents, and anti-condensation paints for construction.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限りこれらの実施例に限定されるものではない。
なお、表１に実施例および比較例に用いられた有機化ベントナイトにおける、スメクタイトと有機化剤を示す。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.
Table 1 shows the smectite and the organic agent in the organic bentonite used in Examples and Comparative Examples.
スメクトンＳＡ：合成サポナイト
エソカードＣ/２５：塩化ポリオキシエチレンアルキルメチルアンモニウム
エソカードＯ/１２：塩化オレイルビス（２−ヒドロキシエチル）メチルアンモニウム
アーカード２ＨＰ：塩化ジアルキルジメチルアンモニウム
Smecton SA: Synthetic saponite Esocard C / 25: Polyoxyethylene alkylmethylammonium chloride Esocard O / 12: Oleylbis (2-hydroxyethyl) methylammonium chloride Arcade 2HP: Dialkyldimethylammonium chloride
実施例１
Ｎ−メチルホルムアミド（関東化学（株）製）、表１の有機化ベントナイトＢｔ−１、サンフレッシュＳＴ−５００ＭＰＳＡを表２の含有比率とし、羽根付攪拌機にて、２５℃、５００ｒｐｍで攪拌し、分散させた組成物を得た。
Example 1
N-methylformamide (manufactured by Kanto Chemical Co., Inc.), organized bentonite Bt-1 in Table 1, and Sunfresh ST-500MPSA as the content ratio in Table 2, and stirred with a bladed stirrer at 25 ° C. and 500 rpm, A dispersed composition was obtained.
実施例２
実施例１と同じ原料を用い、有機化ベントナイトＢｔ−１の含有比を表２にあるようにする以外は実施例１と同様の操作を行い、組成物を得た。
Example 2
The same raw material as in Example 1 was used, and the same operation as in Example 1 was performed except that the content ratio of organic bentonite Bt-1 was as shown in Table 2, to obtain a composition.
実施例３
実施例１の有機化ベントナイトＢｔ−１の替わりに有機化ベントナイトＢｔ−２を使用し、含有比を表２にあるようにする以外は実施例１と同様の操作を行い、組成物を得た。
Example 3
An organic bentonite Bt-2 was used in place of the organic bentonite Bt-1 in Example 1, and the same operation as in Example 1 was carried out except that the content ratio was in Table 2. Thus, a composition was obtained. .
比較例１
実施例１の有機化ベントナイトＢｔ−１の替わりに有機化していないＢｔ−ａを表２の含有比において使用する以外は実施例１と同様の操作を行い、組成物を得た。
Comparative Example 1
A composition was obtained in the same manner as in Example 1 except that Bt-a that was not organically used was used in the content ratio shown in Table 2 in place of the organic bentonite Bt-1 of Example 1.
比較例２
実施例１と同じ原料を用い、有機化ベントナイトＢｔ−１の含有比を表２にあるようにする以外は実施例１と同様の操作を行い、組成物を得た。
Comparative Example 2
The same raw material as in Example 1 was used, and the same operation as in Example 1 was performed except that the content ratio of organic bentonite Bt-1 was as shown in Table 2, to obtain a composition.
比較例３
実施例１の有機化ベントナイトＢｔ−１の替わりに有機化ベントナイトＢｔ−３を使用し、含有比を表２にあるようにする以外は実施例１と同様の操作を行い、組成物を得た。
Comparative Example 3
An organic bentonite Bt-3 was used in place of the organic bentonite Bt-1 in Example 1, and the same operation as in Example 1 was performed except that the content ratio was as shown in Table 2 to obtain a composition. .
比較例４
流動パラフィン（関東化学（株）製）とサンフレッシュＳＴ−５００ＭＰＳＡを表２の含有比率（６０：４０）とし、羽根付攪拌機にて攪拌し、分散させた組成物を得た。
Comparative Example 4
Liquid paraffin (manufactured by Kanto Chemical Co., Inc.) and Sunfresh ST-500MPSA were made to have the content ratios shown in Table 2 (60:40), and the mixture was stirred and dispersed using a bladed stirrer.
比較例５
油系増粘剤としてＬＩＲ−５０（クラレ社製）を１２質量％使用し、表２にある含有比で作製した以外は比較例４と同様の操作を行い、組成物を得た。
Comparative Example 5
12% by mass of LIR-50 (manufactured by Kuraray Co., Ltd.) was used as an oil-based thickener, and the same operation as in Comparative Example 4 was carried out except that it was produced at a content ratio shown in Table 2, to obtain a composition.
比較例６
比較例５のＬＩＲ−５０に代えて、ＰＩＯＮＩＥＲ ＧＥＬ １２ＰＡＯ（マツモト公商社製）を表２で示す含有比で使用した以外は比較例６と同様の操作を行い、組成物を得た。
Comparative Example 6
It replaced with LIR-50 of the comparative example 5, and performed operation similar to the comparative example 6 except having used PIONIER GEL 12PAO (made by Matsumoto public trading company) by the content ratio shown in Table 2, and obtained the composition.
なお、各吸水性樹脂組成物１００質量部あたりの正味のベントナイト量（未処理のベントナイト量：質量部）を表３に示す。 In addition, Table 3 shows the net amount of bentonite per 100 parts by mass of each water-absorbent resin composition (amount of untreated bentonite: parts by mass).
試験例１
上記実施例１〜３及び比較例１〜６までの組成物各５０ｇをスクリュー管瓶に移し、室温にて静置させた。３日後、３ヶ月後の試料を肉眼にて観察し、分離の有無より安定性の判断を実施し、その結果を表４に示した。
Test example 1
50 g of each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were transferred to a screw tube and allowed to stand at room temperature. Three days later, three months later, the sample was observed with the naked eye, and the stability was judged from the presence or absence of separation. The results are shown in Table 4.
試験例２
実施例１〜３及び比較例１〜６までの試料について、粘弾性測定装置（Ｒｈｅｏｍｅｔｒｉｃｓ社製、ＲＤＡ−II）にてコーンプレート（直径：２５ｍｍ、コーン角：０．１ｒａｄ）を使用し、レオロジー特性を測定した。なお、作製後、一夜後の試料を用いた。試料履歴を揃えるために、せん断速度１００ｓ−１にて５分間のせん断処理を実施し、その後５分間静置した。測定は３０秒間で０ｓ−１から１００ｓ−１までせん断速度を上昇させ、その後３０秒間で１００ｓ−１から０ｓ−１までせん断速度を下降させ、実施した。得られたせん断応力とせん断速度との関係から上昇・下降曲線を求めた。測定結果は図１〜９に示した。なお、図１から順に、実施例１〜３、比較例１〜６の試料の測定結果を表す。図１〜９中、横軸はせん断速度（単位：ｓ−１）、縦軸はせん断応力（単位：Ｐａ）である。また、図中、●は上昇過程、○は下降過程を表わす。図１〜６では、上昇過程のプロットの方向を矢印１で示し、下降過程のプロットの方向を矢印２で示した。それぞれの一連のプロットにより、流動曲線のグラフが形成されたものとみなされる。
Test example 2
For the samples of Examples 1 to 3 and Comparative Examples 1 to 6, using a cone plate (diameter: 25 mm, cone angle: 0.1 rad) with a viscoelasticity measuring apparatus (RDA-II, manufactured by Rheometrics), rheology Characteristics were measured. In addition, the sample of one night after preparation was used. In order to align the sample history, a shearing treatment was performed at a shear rate of 100
さらに、グラフ形状の観察し、ヒステリシスループが全領域にわたり観察されるものを○、一部領域のみで観察されるものを△、観察されないものを×と評価した。
また、流動曲線により形成されたループ面積の算出、ｃａｓｓｏｎプロットにより各試料の降伏値を求めた。また、粘性が大きく異なる各試料においてヒステリシスループのグラフ形状と面積とを比較できるようにループ面積［Ｐａ×ｓ−１］を１００ｓ−１でのせん断応力［Ｐａ］にて割ることにより各試料においてループ面積を標準化した。
標準化ループ面積＝ループ面積／せん断応力（１００ｓ−１）
以上の結果を表４に示した。
Furthermore, the shape of the graph was observed, and a case where the hysteresis loop was observed over the entire region was evaluated as ◯, a portion observed only in a partial region was evaluated as Δ, and a case where the hysteresis loop was not observed was evaluated as ×.
Moreover, the yield value of each sample was calculated | required by calculation of the loop area formed by the flow curve, and a Casson plot. Further, in each sample by dividing the loop area [Pa × s -1] so that it can compare the graph shape and area of the hysteresis loop in each sample viscosity differs greatly at a shear stress at 100s -1 [Pa] The loop area was standardized.
Standardized loop area = loop area / shear stress (100 s −1 )
The above results are shown in Table 4.
表４からわかるように、ヒステリシスループが観察された試料において分散液の安定性が大きいことがわかる。特に標準化ループ面積が１１以上において安定性が確認された。また、有機化ベントナイトの種類も実施例１、２、３、比較例３を比較して明らかなように極性を有する有機化剤において安定性、チクソトロピー性が大きいことがわかる。図４より、有機化していないベントナイトの比較例１ではチクソトロピー性が観察されなかったことがわかる。図７、８、９のように原点を通る直線的なグラフ形状の試料に関してはニュートン流体として観察され、比較例５のような短期間の分散安定性は油系増粘剤による粘性の高さのみに起因していることがわかる。
As can be seen from Table 4, it can be seen that the stability of the dispersion is large in the sample in which the hysteresis loop was observed. In particular, stability was confirmed when the standardized loop area was 11 or more. In addition, it can be seen that the organic bentonite is large in stability and thixotropy in the organic agent having polarity as is apparent from the comparison of Examples 1, 2, 3 and Comparative Example 3. FIG. 4 shows that thixotropy was not observed in Comparative Example 1 of bentonite that was not organicized. 7, 8, and 9, samples having a linear graph shape passing through the origin are observed as Newtonian fluids, and short-term dispersion stability as in Comparative Example 5 is high in viscosity due to the oil-based thickener. It turns out that it originates only in.
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