JP2007297435A - Composition, grouting material and repairing method using the same - Google Patents
Composition, grouting material and repairing method using the same Download PDFInfo
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- JP2007297435A JP2007297435A JP2006124696A JP2006124696A JP2007297435A JP 2007297435 A JP2007297435 A JP 2007297435A JP 2006124696 A JP2006124696 A JP 2006124696A JP 2006124696 A JP2006124696 A JP 2006124696A JP 2007297435 A JP2007297435 A JP 2007297435A
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 28
- 239000002734 clay mineral Substances 0.000 claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 4
- 235000015165 citric acid Nutrition 0.000 claims abstract description 4
- 239000004310 lactic acid Substances 0.000 claims abstract description 4
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 4
- 239000001630 malic acid Substances 0.000 claims abstract description 4
- 235000011090 malic acid Nutrition 0.000 claims abstract description 4
- 239000011975 tartaric acid Substances 0.000 claims abstract description 4
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 239000000499 gel Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Lining And Supports For Tunnels (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
本発明は、主に土木・建築分野において使用される組成物およびそれを用いた注入材ならびに補修工法に関するものである。 The present invention relates to a composition mainly used in the field of civil engineering and construction, an injection material using the composition, and a repair method.
トンネルや下水管などの地下構造物の周囲には、地下水の移動によって空洞が生じる。空洞は構造物内への地下水侵入の経路となるほか、地震や地山の圧力による応力集中の要因となり、構造物が破壊されやすくなるため、対策としてトンネルや下水管などの周囲の空洞に裏込材を注入することが有効である。
従来、セメント系材料や水ガラス系材料が主に使用されており、コンクリートポンプ等でトンネルや下水管背面に充填されている（特許文献１）。また、地下水の移動によって充填した材料が施工中に流されるのを防止するため、急結性を付与した材料の開発が進められている（特許文献２）。さらに、高分子系材料を注入することも検討されている（特許文献３、４、５）。一方、弾力性を有する組成物として水溶性ポリビニルアルコールを用いたゲル組成物に関する検討も行われている（特許文献６、７）。
Conventionally, cement-based materials and water glass-based materials have been mainly used, and the back surface of tunnels and sewage pipes is filled with a concrete pump or the like (Patent Document 1). Moreover, in order to prevent the material filled with the movement of groundwater from being washed away during construction, development of a material imparted with quick setting has been promoted (Patent Document 2). In addition, injection of a polymer material has been studied (Patent Documents 3, 4, and 5). On the other hand, studies on gel compositions using water-soluble polyvinyl alcohol as elastic compositions have also been conducted (Patent Documents 6 and 7).
地下構造物周囲の空洞や空隙を従来の材料で充填する場合、セメント系材料や水ガラス系材料では弾性がないためひび割れが生じやすく、再び地下水が侵入することがある。また、高分子系材料では物理的強度が小さいため、地下における特有の応力に対して充分とは云えない。
そこで、本発明は、構造物の耐久性を向上させる組成物およびそれを用いた注入材ならびに補修工法を提供する。
When filling cavities and voids around underground structures with conventional materials, cement-based materials and water-glass-based materials are not elastic, so cracks are likely to occur, and groundwater may enter again. Moreover, since the physical strength of the polymer material is small, it cannot be said to be sufficient for the specific stress in the underground.
Therefore, the present invention provides a composition that improves the durability of a structure, an injection material using the composition, and a repair method.
すなわち、本発明は、（１）ポリビニルアルコール、水、有機チタン化合物、および層状アルミノケイ酸塩を主成分とする粘土鉱物を含有してなる組成物、（２）有機チタン化合物が水溶性である（１）の組成物、（３）有機チタン化合物の配位子が、トリエタノールアミン、アセチルアセトン、クエン酸、乳酸、リンゴ酸、酒石酸、およびグリコール酸の中から選ばれる少なくとも１種であり、かつ、配位子がチタン１原子あたり２つ以上配位している（１）または（２）の組成物、（４）有機チタン化合物が、チタンラクテート、ジイソプロポキシチタンビス（トリエタノールアミネート）、およびチタンペルオキソクエン酸の中から選ばれる（１）〜（３）のいずれかの組成物、（５）粘土鉱物が、層間にアルカリ金属イオンまたはアルカリ土類金属イオンを担持している（１）〜（４）のいずれかの組成物、（６）ポリビニルアルコール２〜２０質量％、水４０〜９０質量％、有機チタン化合物１〜２０質量％、および粘土鉱物２〜４０質量％を含有してなる（１）〜（５）のいずれかの組成物、（７）混合物のｐＨが１０を超える（１）〜（６）のいずれかの組成物、（８）粘土鉱物が、セピオライト、モンモリロナイトまたはベントナイトである（１）〜（７）のいずれかの組成物、（９）（１）〜（８）のいずれかの組成物を用いた注入材、（１０）（９）の注入材を地下構造物周囲に注入することを特徴とする補修工法、である。 That is, the present invention comprises (1) a composition comprising a clay mineral mainly composed of polyvinyl alcohol, water, an organic titanium compound, and a layered aluminosilicate, and (2) the organic titanium compound is water-soluble ( The composition of 1), (3) the ligand of the organic titanium compound is at least one selected from triethanolamine, acetylacetone, citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and The composition of (1) or (2) in which two or more ligands are coordinated per atom of titanium, (4) the organic titanium compound is titanium lactate, diisopropoxytitanium bis (triethanolaminate), and The composition according to any one of (1) to (3) selected from titanium peroxocitric acid, and (5) a clay mineral having an alkali metal ion or The composition according to any one of (1) to (4) supporting a potash earth metal ion, (6) 2 to 20% by mass of polyvinyl alcohol, 40 to 90% by mass of water, and 1 to 20% by mass of an organic titanium compound And the composition according to any one of (1) to (5), comprising 2 to 40% by mass of clay mineral, (7) the composition according to any one of (1) to (6), wherein the pH of the mixture exceeds 10 (8) The clay mineral is sepiolite, montmorillonite or bentonite, the composition according to any one of (1) to (7), or the injection using the composition according to any one of (9) (1) to (8) A repair method characterized by injecting the material, (10), and the injection material of (9) around the underground structure.
本発明の組成物は、適度なゲル化時間、強度、弾力性、遮水性を有する。そのため、例えば、トンネルおよび下水管などの地下構造物周囲の空洞や空隙に注入することにより、構造物の耐久性を向上させることができる。 The composition of the present invention has an appropriate gel time, strength, elasticity, and water barrier properties. Therefore, the durability of the structure can be improved by, for example, injecting it into cavities and voids around underground structures such as tunnels and sewer pipes.
本発明で使用するポリビニルアルコール（以下、ＰＶＡと略記）は、特に限定されるものではないが、他の成分により変性・共重合されているものでも良く、平均重合度は、５００〜３０００が好ましく、１０００〜２０００がより好ましい。また、ＰＶＡの鹸化度は８０ｍｏｌ％以上のものが好ましく、９０ｍｏｌ％以上がより好ましい。ＰＶＡの重合度や鹸化度が前記範囲外の場合には、硬化前の流動性、硬化後の強度、弾性、遮水性に影響する場合がある。 Polyvinyl alcohol (hereinafter abbreviated as PVA) used in the present invention is not particularly limited, but may be modified or copolymerized with other components, and the average degree of polymerization is preferably 500 to 3000. 1000-2000 is more preferable. The saponification degree of PVA is preferably 80 mol% or more, more preferably 90 mol% or more. When the degree of polymerization or saponification of PVA is outside the above range, it may affect the fluidity before curing, the strength after curing, elasticity, and water shielding.
本発明で使用されるＰＶＡは、あらかじめ水溶液として調製しておくことが好ましい。その固形分濃度は用途によって適宜決定されるものであり、特に限定されるものではないが、通常、３〜２０質量％程度とすることが好ましい。３質量％未満では硬化体の弾性が不足する場合があり、２０質量％を超えると水溶液の粘性が高くなるばかりか、低温条件下では水溶液がゲル化してしまう問題も発生する。 The PVA used in the present invention is preferably prepared in advance as an aqueous solution. The solid content concentration is appropriately determined depending on the application, and is not particularly limited, but is usually preferably about 3 to 20% by mass. If the amount is less than 3% by mass, the cured body may have insufficient elasticity. If the amount exceeds 20% by mass, not only the viscosity of the aqueous solution increases, but also a problem that the aqueous solution gels under low temperature conditions.
本発明で使用する有機チタン化合物は、特に限定されるものではないが、水酸基やカルボキシル基と反応するもの（架橋剤）である。さらに、有機チタン化合物が水溶性であり、水中で解離などによる変性が無く、水溶液中で反応性を失わないものが好ましい。
本発明で使用する有機チタン化合物は、配位子が、トリエタノールアミン、アセチルアセトン、クエン酸、乳酸、リンゴ酸、酒石酸、およびグリコール酸の中から選ばれる少なくとも１種であり、かつ、配位子がチタン１原子あたり２つ以上配位しているものが好ましい。有機チタン化合物の具体例としては、チタンラクテート、ジイソプロポキシチタンビス（トリエタノールアミネート）、およびチタンペルオキソクエン酸の中から選ばれるものが好ましい。
The organic titanium compound used in the present invention is not particularly limited, but is one that reacts with a hydroxyl group or a carboxyl group (crosslinking agent). Further, it is preferable that the organic titanium compound is water-soluble, does not undergo modification due to dissociation in water, and does not lose reactivity in an aqueous solution.
In the organotitanium compound used in the present invention, the ligand is at least one selected from triethanolamine, acetylacetone, citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and the ligand In which two or more atoms are coordinated per one atom of titanium. Specific examples of the organic titanium compound are preferably selected from titanium lactate, diisopropoxy titanium bis (triethanolaminate), and titanium peroxocitric acid.
本発明で使用する粘土鉱物は、層状アルミノケイ酸塩を主成分とするものであり、例えば、セピオライト、モンモリロナイトやベントナイトなどである。この中では大量に生産され安価であるベントナイトが好ましい。粘土鉱物は、天然品、合成品、加工処理品のいずれも使用可能であるが、層間にナトリウム、カリウムなどのアルカリ金属イオンや、カルシウムやマグネシウムなどのアルカリ土類金属イオンを担持していることが好ましい。粘土鉱物は、風化や加工処理などで層間に水素イオンが担持されると、水と混合した際に酸性を示し、ＰＶＡがゲル化しない場合がある。本発明の組成物であるポリビニルアルコール、水、有機チタン化合物、および粘土鉱物を含有した混合物の最終的なｐＨは１０以上であることが好ましく、１１以上がより好ましい。
粘土鉱物は、本発明の組成物の混合物のｐＨを徐々に上昇させ、ゲル強度を高め遮水性を向上させるものである。粘土鉱物の代わりに水酸化ナトリウムなどのアルカリ性物質でｐＨを調整すると、混合物のｐＨが１０以上の強アルカリ性では部分的にゲルが形成され不均一となり、充分な遮水効果が得られない。
The clay mineral used in the present invention has a layered aluminosilicate as a main component, for example, sepiolite, montmorillonite, bentonite and the like. Of these, bentonite is preferable because it is produced in large quantities and is inexpensive. Clay minerals can be natural, synthetic or processed, but carry alkali metal ions such as sodium and potassium and alkaline earth metal ions such as calcium and magnesium between the layers. Is preferred. When the clay mineral is supported with hydrogen ions between layers due to weathering or processing, the clay mineral exhibits acidity when mixed with water, and PVA may not gel. The final pH of the mixture containing polyvinyl alcohol, water, organotitanium compound, and clay mineral, which is the composition of the present invention, is preferably 10 or more, and more preferably 11 or more.
The clay mineral gradually raises the pH of the mixture of the composition of the present invention, thereby increasing the gel strength and improving the water barrier property. When the pH is adjusted with an alkaline substance such as sodium hydroxide in place of the clay mineral, a gel is partially formed and becomes non-uniform when the pH of the mixture is 10 or more, and a sufficient water shielding effect cannot be obtained.
本発明におけるＰＶＡ、水、有機チタン化合物、および粘土鉱物の配合割合は、用途によって異なるため特に限定されるものではないが、ＰＶＡ、水、有機チタン化合物、および粘土鉱物の合計１００質量部中、ＰＶＡは２〜２０質量部が好ましく、５〜１５質量部がより好ましい。水は４０〜９０質量部が好ましく、５０〜８０質量部がより好ましい。有機チタン化合物は、１〜２０質量部が好ましく、３〜１０部がより好ましい。粘土鉱物は、２〜４０質量部が好ましく、１０〜３０質量部がより好ましい。これら範囲外では硬化前の流動性や、硬化後の弾力性、強度、耐水性に影響する場合がある。 The blending ratio of PVA, water, organotitanium compound, and clay mineral in the present invention is not particularly limited because it varies depending on the use, but in a total of 100 parts by mass of PVA, water, organotitanium compound, and clay mineral, 2-20 mass parts is preferable and, as for PVA, 5-15 mass parts is more preferable. 40-90 mass parts is preferable and, as for water, 50-80 mass parts is more preferable. The organic titanium compound is preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts. The clay mineral is preferably 2 to 40 parts by mass, and more preferably 10 to 30 parts by mass. Outside these ranges, the fluidity before curing, the elasticity after curing, the strength, and the water resistance may be affected.
本発明の組成物は、水酸基やカルボキシル基の架橋剤として従来から使用されているものを、本発明の効果を損なわない範囲で併用することができる。ただし、従来の架橋剤には、ＰＶＡ水溶液との混合時にすぐにゲル化したり、酸性雰囲気下でのみゲル化したり、硬化体の強度が低いものがある。従来の架橋剤としては、脂肪族アルデヒド類、芳香族アルデヒド類、トリメチロールメラミンなどのメチロール基を有する化合物、ホウ砂やホウ酸などのホウ素化合物、Ｚｒ、Ａｌなどが有機物質と結合した金属アルコキシド類、イソシアネート基を有する化合物などが挙げられる。 In the composition of the present invention, those conventionally used as a crosslinking agent for a hydroxyl group or a carboxyl group can be used in combination as long as the effects of the present invention are not impaired. However, some conventional cross-linking agents gel immediately upon mixing with an aqueous PVA solution, gel only in an acidic atmosphere, or have a cured body with low strength. Conventional cross-linking agents include aliphatic aldehydes, aromatic aldehydes, compounds having a methylol group such as trimethylol melamine, boron compounds such as borax and boric acid, metal alkoxides in which Zr, Al, etc. are bonded to an organic substance. And compounds having an isocyanate group.
本発明の組成物は、硬化体の強度や弾性率、密度をコントロールする目的でフィラーを併用することができる。フィラーは、特に限定されることはなく、無機系や有機系のものが使用可能である。無機系化合物無機系としては、珪石、石灰石などの骨材、ゼオライトなどのイオン交換体などが挙げられ、有機系材料としては、ビニロン繊維、アクリル繊維、炭素繊維などの繊維状物質、イオン交換樹脂、吸水性ポリマーなどが挙げられ、これらを本発明の目的を阻害しない範囲で使用することができる。 In the composition of the present invention, a filler can be used in combination for the purpose of controlling the strength, elastic modulus and density of the cured product. The filler is not particularly limited, and an inorganic or organic filler can be used. Inorganic compounds Inorganic systems include aggregates such as silica and limestone, ion exchangers such as zeolite, and organic materials include fibrous materials such as vinylon fibers, acrylic fibers, and carbon fibers, and ion exchange resins. And water-absorbing polymers. These can be used as long as the object of the present invention is not impaired.
本発明における弾性組成物の混合装置としては、既存のいかなる装置も使用可能であり、例えば、傾胴ミキサー、オムニミキサー、ヘンシェルミキサー、Ｖ型ミキサー、ナウタ−ミキサーなどが挙げられる。 As the mixing device for the elastic composition in the present invention, any existing device can be used, and examples thereof include a tilting barrel mixer, an omni mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer.
本発明の組成物を用いて地下構造物周囲の空洞に充填し補修する工法は、特に限定されないが、以下の方法などが適用できる。空洞や漏水が見られるコンクリート壁にドリルで穴を開け、注入プラグをセットする。その後、本発明の組成物を注入材として、各種ポンプを用いて注入し、空洞部を充填したりコンクリート背面に遮水層を形成する。また、地上から空洞部や構造物周囲に注入管を挿入して、各種注入ポンプを用いて注入することも可能である。 Although the construction method of filling and repairing the cavity around the underground structure using the composition of the present invention is not particularly limited, the following methods can be applied. Drill a hole in the concrete wall where cavities and water leakage are seen, and set the injection plug. Thereafter, the composition of the present invention is injected as an injection material using various pumps to fill the cavity or form a water shielding layer on the concrete back surface. Moreover, it is also possible to inject using various injection pumps by inserting an injection tube from the ground around the cavity or around the structure.
以下、実施例で詳細に説明する。 Examples will be described in detail below.
「実験例１」
重合度１７００、鹸化度９８．７ｍｏｌ％のＰＶＡ（ａ）と水を用いて、表１に示す割合となるように種々の固形分濃度のＰＶＡ水溶液を調製した。このＰＶＡ水溶液を用いて、表1に示す割合となるように有機チタン化合物(ａ)、粘土鉱物（a）を配合して混合し、ゲル化時間、２８日経過後の弾性係数、遮水性を評価した。なお、実験No.1-2では、水酸化ナトリウムを用いて組成物のｐＨを８．０に調整した。結果を表1に示す。
"Experiment 1"
Using PVA (a) having a polymerization degree of 1700 and a saponification degree of 98.7 mol% and water, PVA aqueous solutions having various solid content concentrations were prepared so as to have the ratios shown in Table 1. Using this PVA aqueous solution, the organic titanium compound (a) and the clay mineral (a) are blended and mixed so as to have the ratio shown in Table 1, and the gelation time, the elastic modulus after 28 days, and the water impermeability are evaluated. did. In Experiment No. 1-2, the pH of the composition was adjusted to 8.0 using sodium hydroxide. The results are shown in Table 1.
「使用材料」
ＰＶＡ（ａ）：電気化学工業社製、商品名「Ｋ−１７Ｅ」、重合度１７００、鹸化度９８．７ｍｏｌ％
有機チタン化合物（ａ）：チタンラクテート、松本製薬工業社製、商品名「ＴＣ−３１０」
粘土鉱物（ａ）：ベントナイト、ホージュン社製、商品名「榛名」
水酸化ナトリウム：試薬、市販品
水：純水
"Materials used"
PVA (a): manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “K-17E”, polymerization degree 1700, saponification degree 98.7 mol%
Organic titanium compound (a): Titanium lactate, manufactured by Matsumoto Pharmaceutical Co., Ltd., trade name “TC-310”
Clay mineral (a): Bentonite, manufactured by Hojun Co., Ltd., trade name “Haruna”
Sodium hydroxide: Reagent, Commercial water: Pure water
「測定方法」
ゲル化時間：混合した組成物を透明なスチロール瓶に流し込み、容器を傾けても液面が変動しなくなるまでの時間を計測した。
組成物のｐＨ：組成物を混合してから１時間後にｐＨ電極を差し込み測定した。
圧縮強度、弾性係数：混合した組成物をφ３ｃｍ、高さ３ｃｍの型枠に流し込み、２８日間２０℃環境下で封緘養生して供試体を作成した。測定は市販の万能試験機（オートグラフ）を用い、供試体に載荷した時の応力とひずみを測定し、圧縮強度は最大応力を基に、弾性係数は５ｍｍ変位させた時の応力と変位からを算出した。
遮水性：模擬試験体に組成物を注入し、注入から４８ｈｒ後の模擬試験体重量を測定して、漏水量を算出することで遮水性を評価した。模擬試験体は、容量３Ｌの直方体状ポリプロピレン製容器の側面の中央に直径２ｍｍの穴を開け、川砂２．７ｋｇを充填し、さらに水道水６００ｍｌを加えて漏水を生じさせた。その直後、容量１０ｍｌのシリンジを用いて、漏水している模擬試験体の穴から組成物を毎秒１ｍｌの速度で合計１０ｍｌ注入を行った。注入孔はテープで塞ぎ、注入から２４ｈｒ後にテープを取り外した。
"Measuring method"
Gelation time: The mixed composition was poured into a transparent polystyrene bottle, and the time until the liquid level did not fluctuate even when the container was tilted was measured.
Composition pH: One hour after mixing the composition, a pH electrode was inserted and measured.
Compressive strength, elastic modulus: The mixed composition was poured into a mold having a diameter of 3 cm and a height of 3 cm, and sealed and cured in an environment of 20 ° C. for 28 days to prepare a specimen. The measurement uses a commercially available universal testing machine (autograph) to measure the stress and strain when loaded on the specimen. The compressive strength is based on the maximum stress and the elastic modulus is calculated from the stress and displacement when displaced by 5 mm. Was calculated.
Water impermeability: The composition was injected into the simulated test specimen, the weight of the simulated specimen 48 hours after injection was measured, and the amount of water leakage was calculated to evaluate the water impermeability. The simulated test specimen was formed by making a hole with a diameter of 2 mm in the center of the side surface of a 3 L rectangular parallelepiped polypropylene container, filling with 2.7 kg of river sand, and adding 600 ml of tap water to cause water leakage. Immediately thereafter, a total of 10 ml of the composition was injected at a rate of 1 ml per second from a hole in the simulated test specimen leaking with a syringe having a capacity of 10 ml. The injection hole was closed with tape, and the tape was removed 24 hours after injection.
表１に示すように、本発明の組成物は、適度なゲル化時間を持ちつつ、強度が高く、弾力性に富み、かつ遮水性を有することが分かる。粘土鉱物の代わりに水酸化ナトリウムを用いて組成物のｐＨを調整した実験No.1-2では、ゲルの強度は低く、遮水性が不充分であった。 As shown in Table 1, it can be seen that the composition of the present invention has an appropriate gelation time, is high in strength, is rich in elasticity, and has water shielding properties. In Experiment No. 1-2 in which the pH of the composition was adjusted using sodium hydroxide instead of the clay mineral, the gel strength was low and the water barrier was insufficient.
「実験例２」
予め水１０．０質量部に有機チタン化合物３．８質量部を混合して、室温にて１時間放置した後に、ＰＶＡ７．６質量部、水５９．２質量部、粘土鉱物１９．４質量部をさらに混合し、１時間経過後のゲルの状態を目視で判断したこと以外は実験例１と同様に行った。結果を表２に示す。
"Experimental example 2"
3.8 parts by mass of an organic titanium compound is mixed in advance with 10.0 parts by mass of water and left at room temperature for 1 hour, and then 7.6 parts by mass of PVA, 59.2 parts by mass of water, and 19.4 parts by mass of clay minerals. Were further mixed and performed in the same manner as in Experimental Example 1 except that the gel state after 1 hour was visually judged. The results are shown in Table 2.
「使用材料」
有機チタン化合物（ｂ）：ジイソプロキシチタンビス（トリエタノールアミネート）、松本製薬工業社製、商品名「ＴＣ−４００」
有機チタン化合物（ｃ）：チタンペルオキソクエン酸アンモニウム、フルウチ化学社製、商品名ＴＡＳ−ｆｉｎｅ、チタン濃度５．０％水溶液
"Materials used"
Organic titanium compound (b): diisoproxy titanium bis (triethanolaminate), manufactured by Matsumoto Pharmaceutical Co., Ltd., trade name “TC-400”
Organotitanium compound (c): Titanium peroxocitrate ammonium, manufactured by Furuuchi Chemical Co., Ltd., trade name TAS-fine, titanium concentration 5.0% aqueous solution
表２に示すように、本発明の組成物は、均一なゲルとなることが分かる。 As shown in Table 2, it can be seen that the composition of the present invention becomes a uniform gel.
「実験例３」
ＰＶＡ、水、有機チタン化合物、および粘土鉱物または無機物質の配合割合を、それぞれ７．６質量部、６９．２質量部、３．８質量部、１９．４質量部に固定し、粘土鉱物の種類を変え、実験例１と同様に、ゲル化時間、組成物のｐＨ、弾性係数、遮水性の測定を行った。また、実験例２と同様にゲルの状態を目視で判断した。結果を表３に示す。
"Experiment 3"
The blending ratio of PVA, water, organotitanium compound, and clay mineral or inorganic substance is fixed at 7.6 parts by mass, 69.2 parts by mass, 3.8 parts by mass, and 19.4 parts by mass, respectively. The type was changed, and the gelation time, the pH of the composition, the elastic modulus, and the water barrier were measured in the same manner as in Experimental Example 1. Moreover, the state of the gel was determined visually as in Experimental Example 2. The results are shown in Table 3.
「使用材料」
粘土鉱物（ｂ）：セピオライト、巴工業社製、商品名「ＭＩＮ−Ｕ−ＧＥＬ２００ｉ」
無機物質(ａ)：消石灰、関東化学社製、試薬一級
"Materials used"
Clay mineral (b): Sepiolite, manufactured by Sakai Kogyo Co., Ltd., trade name “MIN-U-GEL200i”
Inorganic substance (a): Slaked lime, manufactured by Kanto Chemical Co., Inc., reagent grade 1
表３に示すように、本発明の組成物は、適度なゲル化時間を持ちつつ弾力性に富み、ｐＨはアルカリ性を示し遮水性を有する均一なゲルとなることが分かる。また、消石灰でｐＨ調整したものは、混合直後に増粘したもののゲル化しなかった（実験No.3-3）。 As shown in Table 3, it can be seen that the composition of the present invention has an appropriate gelation time and is highly elastic, and has a pH that is alkaline and has a water shielding property. Moreover, what adjusted pH with slaked lime did not gelatinize although it thickened immediately after mixing (experiment No.3-3).
「実験例４」
ＰＶＡ、水、有機チタン化合物、および粘土鉱物の配合割合を、それぞれ７．６質量部、６９．２質量部、３．８質量部、１９．４質量部に固定し、ＰＶＡの重合度とケン化度を変えたこと以外は実験例１と同様に行った。結果を表４に示す。
"Experimental example 4"
The blending ratios of PVA, water, organotitanium compound, and clay mineral were fixed at 7.6 parts by mass, 69.2 parts by mass, 3.8 parts by mass, and 19.4 parts by mass, respectively, The procedure was the same as in Experimental Example 1 except that the degree of conversion was changed. The results are shown in Table 4.
「使用材料」
ＰＶＡ（ｂ）：電気化学工業社製、商品名「Ｂ−１７」、重合度１７００、鹸化度８７．５ｍｏｌ％
ＰＶＡ（ｃ）：電気化学工業社製、商品名「Ｋ−１７Ｃ」、重合度１７００、鹸化度９９．３ｍｏｌ％
ＰＶＡ（ｄ）：電気化学工業社製、商品名「Ｋ−０５」、重合度５００、鹸化度９８．７ｍｏｌ％
ＰＶＡ（ｅ）：電気化学工業社製、商品名「Ｋ−２４Ｅ」、重合度２４００、鹸化度９８．７ｍｏｌ％
"Materials used"
PVA (b): manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “B-17”, polymerization degree 1700, saponification degree 87.5 mol%
PVA (c): manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “K-17C”, polymerization degree 1700, saponification degree 99.3 mol%
PVA (d): manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “K-05”, polymerization degree 500, saponification degree 98.7 mol%
PVA (e): manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “K-24E”, polymerization degree 2400, saponification degree 98.7 mol%
表４に示すように、本発明の組成物は、適度なゲル化時間を持ちつつ弾力性に富み、遮水性を有するゲルとなることが分かる。 As shown in Table 4, it can be seen that the composition of the present invention is a gel having an adequate gelation time and a high elasticity and water shielding properties.
本発明の組成物は、適度なゲル化時間、強度、弾力性、遮水性を有し、例えば、トンネルおよび下水管などの地下構造物周囲の空洞や空隙に注入することにより、構造物の耐久性を向上させることができるため、土木・建築分野などで幅広く適用できる。 The composition of the present invention has an appropriate gelation time, strength, elasticity, and water barrier property. For example, the composition is durable by injecting it into cavities and voids around underground structures such as tunnels and sewer pipes. Therefore, it can be widely applied in civil engineering and construction fields.
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