JP2007106615A - Dispersant for self-leveling material - Google Patents
Dispersant for self-leveling material Download PDFInfo
- Publication number
- JP2007106615A JP2007106615A JP2005296076A JP2005296076A JP2007106615A JP 2007106615 A JP2007106615 A JP 2007106615A JP 2005296076 A JP2005296076 A JP 2005296076A JP 2005296076 A JP2005296076 A JP 2005296076A JP 2007106615 A JP2007106615 A JP 2007106615A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- acid
- self
- hydrogen atom
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 140
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- -1 phosphate ester Chemical class 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
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- 238000000926 separation method Methods 0.000 abstract description 14
- 150000005690 diesters Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 49
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical class [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 35
- 239000000203 mixture Substances 0.000 description 34
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- 230000032683 aging Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000012986 chain transfer agent Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 10
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 9
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- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 235000021317 phosphate Nutrition 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
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- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000002440 hydroxy compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000865 phosphorylative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZRIMDWRLVGDUBW-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid phosphoric acid Chemical compound P(=O)(O)(O)O.OCCC=C(C(=O)O)C ZRIMDWRLVGDUBW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
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- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 0 C*1=*CCC1 Chemical compound C*1=*CCC1 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 150000003573 thiols Chemical group 0.000 description 3
- 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 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
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- DHUSXRNOMZWNNA-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCS(O)(=O)=O DHUSXRNOMZWNNA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、セメント、石膏等の水硬性化合物を用いたセルフレベリング材用分散剤及びこれを含有するセルフレベリング材に関する。 The present invention relates to a dispersant for a self-leveling material using a hydraulic compound such as cement and gypsum and a self-leveling material containing the same.
セルフレベリング材用分散剤及び不定形耐火物用分散剤として、従来からナフタレンスルホン酸ホルムアルデヒド縮合物、メラミンスルホン酸ホルムアルデヒド縮合物、ポリカルボン酸共重合体等が用いられている。このうちポリカルボン酸共重合体は他の分散剤に比べて、流動性が高いあるいは可使時間が長いという利点を有する。 Conventionally, naphthalene sulfonic acid formaldehyde condensates, melamine sulfonic acid formaldehyde condensates, polycarboxylic acid copolymers, and the like have been used as dispersants for self-leveling materials and dispersants for amorphous refractories. Among these, the polycarboxylic acid copolymer has an advantage that the fluidity is high or the pot life is long compared to other dispersants.
特許文献１には、作業特性と硬化特性に優れたセルフレベリング性セメント組成物を得るために、特定の無機成分に対して、特定のビニル系単量体ａ、ｂを特定モル比で重合させたポリカルボン系共重合体を用いることが開示されている。また、特許文献２には、使用温度による流動性の振れを安定化するために、特定のポリカルボン系共重合体の混合物を用いることが開示されている。特許文献３には、流動性に優れるリン酸基を有するセメント用分散剤が提案されている。
しかしながら、ポリカルボン酸系分散剤をセルフレベリング材に用いた場合、流動性には優れるものの、分離抵抗性は小さく、水溶性高分子化合物等の分離低減剤を多くすると流動性が低下する傾向となる。セルフレベリング材においては、流動性を維持したまま優れた分離抵抗性が得られる技術が望まれる。 However, when a polycarboxylic acid-based dispersant is used for a self-leveling material, although it has excellent fluidity, the separation resistance is small, and if a separation reducing agent such as a water-soluble polymer compound is increased, the fluidity tends to decrease. Become. In the self-leveling material, a technique is desired that provides excellent separation resistance while maintaining fluidity.
本発明の課題は、流動性と分離抵抗性に優れたセルフレベリング材を調製することができる分散剤を提供することである。 The subject of this invention is providing the dispersing agent which can prepare the self-leveling material excellent in fluidity | liquidity and separation resistance.
本発明は、下記一般式（１）で表される単量体１と、下記一般式（２）で表される単量体２及び下記一般式（３）で表される単量体３を含む混合単量体とを共重合して得られるリン酸エステル系重合体（Ａ）〔以下、（Ａ）成分という〕と、非イオン性水溶性高分子化合物（Ｂ）〔以下、（Ｂ）成分という〕とを含有するセルフレベリング材用分散剤に関する。 The present invention comprises a monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3). A phosphoric ester polymer (A) [hereinafter referred to as component (A)] obtained by copolymerization with a mixed monomer, and a nonionic water-soluble polymer compound (B) [hereinafter referred to as (B) And a dispersant for a self-leveling material.
〔式中、Ｒ1、Ｒ2は、それぞれ水素原子又はメチル基、Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4、ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基、pは０又は１の数、ｑは０〜２の数、ｒはＡＯの平均付加モル数であり、３〜３００の数、Ｒ4は水素原子又は炭素数１〜１８のアルキル基を表す。〕 [Wherein R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 is a hydrogen atom or — (CH 2 ) q (CO) pO (AO) rR 4 , and AO is an oxyalkylene having 2 to 4 carbon atoms. Group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R 4 is a hydrogen atom or a carbon number of 1 to 18 Represents an alkyl group. ]
〔式中、Ｒ11は水素原子又はメチル基、Ｒ12は炭素数２〜１２のアルキレン基、ｍ１は１〜３０の数、Ｍ3、Ｍ4はそれぞれ水素原子、アルカリ金属又はアルカリ土類金属を表す。〕 [Wherein R 11 is a hydrogen atom or a methyl group, R 12 is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M 3 and M 4 are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]
〔式中、Ｒ13、Ｒ15は、それぞれ水素原子又はメチル基、Ｒ14、Ｒ16は、それぞれ炭素数２〜１２のアルキレン基、ｍ２、ｍ３は、それぞれ１〜３０の数、Ｍ5は水素原子、アルカリ金属又はアルカリ土類金属を表す。〕 [Wherein R 13 and R 15 are each a hydrogen atom or a methyl group, R 14 and R 16 are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M 5 is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]
また、本発明は、上記本発明のセルフレベリング材用分散剤と水硬性粉体とを含有するセルフレベリング材に関する。 The present invention also relates to a self-leveling material containing the dispersant for self-leveling material of the present invention and a hydraulic powder.
本発明によれば、流動性と分離抵抗性に優れたセルフレベリング材を調製することができる分散剤が提供される。 According to the present invention, there is provided a dispersant capable of preparing a self-leveling material excellent in fluidity and separation resistance.
＜（Ａ）成分＞
（Ａ）成分は、前述の一般式（１）で表される単量体１と、前述の一般式（２）で表される単量体２と、前述の一般式（３）で表される単量体３とを共重合して得られるリン酸エステル系重合体である。
<(A) component>
The component (A) is represented by the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the general formula (3). It is a phosphoric ester polymer obtained by copolymerizing the monomer 3.
［単量体１］
単量体１において、一般式（１）中のＲ1、Ｒ2は、それぞれ水素原子又はメチル基である。Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4であり、水素原子が好ましい。Ｒ4は水素原子又は炭素数１〜１８のアルキル基であり、更に１〜１２、更に１〜４、更に１、２のアルキル基が好ましく、特にメチル基が好ましい。ｐが０の場合はＡＯは(ＣＨ2)qとエーテル結合、ｐが１の場合はエステル結合をする。ｑは０〜２であり、好ましくは０又は１であり、更に好ましくは０である。ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基であり、ＡＯは炭素数２〜４のオキシアルキレン基が好ましく、エチレンオキシ基（以下、ＥＯ基）を含むことがより好ましく、ＥＯ基が７０モル％以上、更に８０モル％以上、更に９０モル％以上、特に全ＡＯがＥＯ基であることが好ましい。ｒはＡＯの平均付加モル数であり、３〜３００の数であり、重合体の水硬性組成物に対する流動性の点で、３〜３００であり、好ましくは４〜１２０であり、より好ましくは４〜８０、さらに好ましくは４〜５０、特に好ましくは４〜３０である。また、平均ｒ個の繰り返し単位中にＡＯが異なるもので、ランダム付加又はブロック付加又はこれらの混在を含むものであっても良い。例えばＡＯは、ＥＯ基以外にもプロピレンオキシ基等を含むこともできる。
[Monomer 1]
In monomer 1, R 1 and R 2 in general formula (1) are each a hydrogen atom or a methyl group. R 3 is a hydrogen atom or — (CH 2 ) q (CO) p O (AO) r R 4 , preferably a hydrogen atom. R 4 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 4, and further preferably 1 or 2, and particularly preferably a methyl group. When p is 0, AO forms an ether bond with (CH 2 ) q, and when p is 1, it forms an ester bond. q is 0 to 2, preferably 0 or 1, and more preferably 0. AO is an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group (hereinafter referred to as EO group), and an EO group. Is 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. r is the average added mole number of AO, is a number of 3 to 300, and is 3 to 300, preferably 4 to 120, more preferably from the viewpoint of the fluidity of the polymer to the hydraulic composition. It is 4 to 80, more preferably 4 to 50, particularly preferably 4 to 30. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. For example, AO can contain a propyleneoxy group etc. besides EO group.
単量体１としては、メトキシポリエチレングリコール、メトキシポリプロピレングリコール、メトキシポリブチレングリコール、メトキシポリスチレングリコール、エトキシポリエチレンポリプロピレングリコール等の片末端アルキル封鎖ポリアルキレングリコールと（メタ）アクリル酸、マレイン酸との（ハーフ）エステル化物や、（メタ）アリルアルコールとのエーテル化物、及び（メタ）アクリル酸、マレイン酸、（メタ）アリルアルコールへの炭素数２〜４のアルキレンオキシド付加物付加物が好ましく用いられる。なお、（メタ）アクリル酸は、アクリル酸及び／又はメタクリル酸の意味であり、（メタ）アリルは、アリル及び／又はメタリルの意味である（以下同様）。 Monomer 1 includes a half-terminated alkyl-capped polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, (meth) acrylic acid, maleic acid (half ) Esterified products, etherified products with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, and (meth) allyl alcohol adducts having 2 to 4 carbon atoms are preferably used. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) allyl means allyl and / or methallyl (the same applies hereinafter).
より好ましくはアルコキシ、特にはメトキシポリエチレングリコールと（メタ）アクリル酸とのエステル化物である。具体的には、ω−メトキシポリオキシアルキレンメタクリル酸エステル、ω−メトキシポリオキシアルキレンアクリル酸エステル等を挙げることができ、ω−メトキシポリオキシアルキレンメタクリル酸エステルがより好ましい。 More preferred is an esterified product of alkoxy, particularly methoxypolyethylene glycol and (meth) acrylic acid. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable.
（Ａ）成分の製造に用いる単量体１は、例えば、アルコキシポリアルキレングリコールと（メタ）アクリル酸とのエステル化によって得ることができる。該エステル化物は、本発明のコンクリート混和剤に用いた場合の必要添加量および粘性低減の観点から、未反応の（メタ）アクリル酸は、酸型換算で単量体１に対して５重量％以下が好ましく、３重量％以下がより好ましく、１．５重量％以下がさらに好ましく、１重量％以下がさらに好ましい。単量体１の製造時に残留する（メタ）アクリル酸の量を低減する方法として、トッピング、スチーミング、溶媒抽出等が挙げられる。 The monomer 1 used for the production of the component (A) can be obtained, for example, by esterification of an alkoxypolyalkylene glycol and (meth) acrylic acid. From the viewpoint of the required addition amount and viscosity reduction when the esterified product is used in the concrete admixture of the present invention, the unreacted (meth) acrylic acid is 5% by weight based on the monomer 1 in terms of acid type. The following is preferable, 3% by weight or less is more preferable, 1.5% by weight or less is further preferable, and 1% by weight or less is more preferable. Examples of a method for reducing the amount of (meth) acrylic acid remaining during the production of the monomer 1 include topping, steaming, and solvent extraction.
［単量体２］
単量体２は、一般式（２）において、Ｒ11は水素原子又はメチル基であり、Ｒ12は炭素数２〜１２のアルキレン基である。ｍ１は１〜３０の数であり、Ｍ3、Ｍ4はそれぞれ水素原子、アルカリ金属又はアルカリ土類金属である。一般式（２）中のｍ１は１〜２０が好ましく、１〜１０が更に好ましく、１〜５が特に好ましい。
[Monomer 2]
In the monomer (2), R 11 is a hydrogen atom or a methyl group, and R 12 is an alkylene group having 2 to 12 carbon atoms. m1 is a number from 1 to 30, and M 3 and M 4 are each a hydrogen atom, an alkali metal, or an alkaline earth metal. 1-20 are preferable, as for m1 in General formula (2), 1-10 are more preferable, and 1-5 are especially preferable.
具体的には、有機ヒドロキシ化合物のリン酸モノエステルが挙げられる。具体的には、ポリアルキレングリコールモノ（メタ）アクリレートアシッドリン酸エステル等が挙げられる。例えば、リン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステル、リン酸モノ−〔（２−ヒドロキシエチル）アクリル酸エステル〕等が挙げられる。中でも、製造の容易さ及び製造物の品質安定性の観点から、リン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルが好ましい。また、これらの化合物のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルキルアンモニウム塩などであっても良い。 Specific examples include phosphoric acid monoesters of organic hydroxy compounds. Specific examples include polyalkylene glycol mono (meth) acrylate acid phosphates. For example, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid mono-[(2-hydroxyethyl) acrylic acid ester] and the like can be mentioned. Among these, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester is preferable from the viewpoint of ease of production and product quality stability. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.
［単量体３］
単量体３は、一般式（３）において、Ｒ13、Ｒ15は、それぞれ水素原子又はメチル基であり、Ｒ14、Ｒ16は、それぞれ炭素数２〜１２のアルキレン基である。ｍ２、ｍ３は、それぞれ１〜３０の数であり、Ｍ5は水素原子、アルカリ金属又はアルカリ土類金属である。一般式（３）中のｍ２、ｍ３は、それぞれ１〜２０が好ましく、１〜１０が更に好ましく、１〜５が特に好ましい。
[Monomer 3]
In the monomer 3, in the general formula (3), R 13 and R 15 are each a hydrogen atom or a methyl group, and R 14 and R 16 are each an alkylene group having 2 to 12 carbon atoms. m2, m3 is a number of each 1 to 30, M 5 represents a hydrogen atom, an alkali metal or alkaline earth metal. M2 and m3 in the general formula (3) are each preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.
具体的には、有機ヒドロキシ化合物のリン酸ジエステルが挙げられる。具体的には、ポリアルキレングリコールジ（メタ）アクリレートアシッドリン酸ジエステル等が挙げられる。例えば、リン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステル、リン酸ジ−〔（２−ヒドロキシエチル）アクリル酸〕エステル等が挙げられる。中でも、製造の容易さ及び製造物の品質安定性の観点から、リン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルが好ましい。また、これらの化合物のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルキルアンモニウム塩などであっても良い。 Specific examples include phosphoric acid diesters of organic hydroxy compounds. Specific examples include polyalkylene glycol di (meth) acrylate acid phosphoric acid diester. Examples include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.
単量体２及び３は、単量体２及び単量体３を含む混合単量体として用いることができる。また、単量体２及び単量体３として、一般式（４）で表される有機ヒドロキシ化合物とリン酸化剤とを反応させて得られるリン酸エステルを用いても良い。 Monomers 2 and 3 can be used as a mixed monomer including monomer 2 and monomer 3. Further, as the monomer 2 and the monomer 3, a phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent may be used.
単量体２及び単量体３を含む混合単量体は、例えば、一般式（４）で表される有機ヒドロキシ化合物とリン酸化剤を所定の仕込み比で反応させることで、反応生成物として製造することもできる。 The mixed monomer including the monomer 2 and the monomer 3 is obtained as a reaction product by reacting, for example, an organic hydroxy compound represented by the general formula (4) and a phosphorylating agent at a predetermined charge ratio. It can also be manufactured.
〔式中、Ｒ20は水素原子又はメチル基、Ｒ21は炭素数２〜１２のアルキレン基、ｍ４は１〜３０の数を表す。〕 [Wherein, R 20 represents a hydrogen atom or a methyl group, R 21 represents an alkylene group having 2 to 12 carbon atoms, and m4 represents a number of 1 to 30. ]
一般式（４）中のｍ４は、１〜２０が好ましく、１〜１０が更に好ましく、１〜５が特に好ましい。 1-20 are preferable, as for m4 in General formula (4), 1-10 are more preferable, and 1-5 are especially preferable.
リン酸化剤としては、オルトリン酸、五酸化リン（無水リン酸）、ポリリン酸、オキシ塩化リン等が挙げられ、オルトリン酸、五酸化リンが好ましい。これらは単独でも２種以上を組み合わせて用いることも出来る。有機ヒドロキシ化合物とリン酸化剤とを反応させる際のリン酸化剤の量は目的とするリン酸エステル組成に応じ適時決めることができる。 Examples of the phosphorylating agent include orthophosphoric acid, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, phosphorus oxychloride and the like, and orthophosphoric acid and phosphorus pentoxide are preferable. These may be used alone or in combination of two or more. The amount of the phosphorylating agent in the reaction of the organic hydroxy compound and the phosphorylating agent can be appropriately determined according to the target phosphate ester composition.
単量体２及び単量体３を含む混合単量体として、例えばリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物を製造する場合、公知の技術（例えば特開昭５７−１８０６１８号）により、合成することができる。 Examples of mixed monomers including monomer 2 and monomer 3 include mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate. When the mixture is produced, it can be synthesized by a known technique (for example, JP-A-57-180618).
単量体２及び単量体３を含む混合単量体としては、モノエステル体とジエステル体とを含む市販品を使用することもでき、例えば、ホスマーＭ、ホスマーＰＥ、ホスマーＰ（ユニケミカル）、ＪＡＭＰ５１４、ＪＡＭＰ５１４Ｐ、ＪＭＰ１００（何れも城北化学）、ライトエステルＰ−１Ｍ、ライトアクリレートＰ−１Ａ（いずれも共栄社化学）、ＭＲ２００（大八化学）、カヤマー（日本化薬）、Ethyleneglycol methacrylate phosphate（アルドリッチ試薬）などとして入手できる。 As the mixed monomer including the monomer 2 and the monomer 3, a commercial product including a monoester and a diester can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical) , JAMP514, JAMP514P, JMP100 (all Johoku Chemical), light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich) Reagent).
上記の市販品や反応生成物にはモノエステル体（単量体２）とジエステル体（単量体３）以外の化合物を含んでいる事が確認されている。それらの他の化合物は、重合性、非重合性のものが混在していると考えられるが、本発明ではこのような混合物（混合単量体）をそのまま使用することができる。 It has been confirmed that the above-mentioned commercial products and reaction products contain compounds other than the monoester (monomer 2) and diester (monomer 3). These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds, but in the present invention, such a mixture (mixed monomer) can be used as it is.
本発明に係る（Ａ）成分は、単量体１と、単量体２と、単量体３とを、共重合させて得られるリン酸エステル系重合体である。単量体２及び単量体３を含有する混合単量体を用いることも好ましい。 The component (A) according to the present invention is a phosphate ester polymer obtained by copolymerizing the monomer 1, the monomer 2, and the monomer 3. It is also preferable to use a mixed monomer containing monomer 2 and monomer 3.
単量体の共重合に際して、単量体１と、単量体２、３とのモル比は、単量体１／（単量体２＋単量体３）＝５／９５〜９５／５、更に、１０／９０〜９０／１０が好ましい。また、単量体１と単量体２と単量体３のモル比は、単量体１／単量体２／単量体３＝５〜９５／３〜９０／１〜８０、更に５〜９６／３〜８０／１〜６０（ただし合計は１００である）が好ましい。なお、単量体２と単量体３については、酸型の化合物に基づきモル比やモル％を算出するものとする（以下、同様）。 In the copolymerization of the monomers, the molar ratio between the monomer 1 and the monomers 2 and 3 is as follows: monomer 1 / (monomer 2 + monomer 3) = 5/95 to 95/5, Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 2 and monomer 3 is as follows: monomer 1 / monomer 2 / monomer 3 = 5 to 95/3 to 90/1 to 80, and further 5 -96 / 3-80 / 1-60 (however, the total is 100) is preferable. In addition, about the monomer 2 and the monomer 3, the molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).
また、（Ａ）成分の製造では、反応に用いる全単量体中、単量体３の比率を１〜６０モル％、更に１〜３０モル％とすることが好ましい。 Moreover, in manufacture of (A) component, it is preferable that the ratio of the monomer 3 shall be 1-60 mol% and also 1-30 mol% in all the monomers used for reaction.
また、単量体２と単量体３のモル比を、単量体２／単量体３＝９９／１〜４／９６、更に９９／１〜５／９５とすることが好ましい。 The molar ratio of monomer 2 to monomer 3 is preferably monomer 2 / monomer 3 = 99/1 to 4/96, more preferably 99/1 to 5/95.
ゲル化を抑制する観点から、単量体２及び／又は単量体３を含む単量体溶液のｐＨを７以下で反応に用いることが好ましい。 From the viewpoint of suppressing gelation, the monomer solution containing monomer 2 and / or monomer 3 is preferably used for the reaction at a pH of 7 or less.
以下、ゲル化抑制、好適分子量の調整及び混和剤の性能設計の観点から、更に好ましい製造条件を説明する。このような観点から、共重合の際に、単量体１、２及び３の合計モル数に対して４モル％以上、更に６モル％以上、特に８モル％以上の連鎖移動剤を使用することが好ましい。また、連鎖移動剤の使用量の上限は、単量体１、２及び３の合計モル数に対して好ましくは１００モル％以下、より好ましくは６０モル％以下、更に好ましくは３０モル％以下、特に好ましくは１５モル％以下とすることができる。更に詳しくは、（１）単量体１のｒが３〜３０の場合で、
（１−１）単量体２と単量体３の単量体１、２及び３の合計のモル比が５０モル％以上の場合は、連鎖移動剤は、単量体１、２及び３の合計に対して６〜１００モル％、特に８〜６０モル％を用いるのが好ましく、
（１−２）単量体２と単量体３の単量体１、２及び３の合計中のモル比が５０モル％未満の場合は、連鎖移動剤は、単量体１、２及び３の合計に対して４〜６０モル％、特に５〜３０モル％を用いるのが好ましい。
（２）（Ａ）成分に用いる単量体１のｒが３０超の場合は、連鎖移動剤は、単量体１〜３に対して６〜５０モル％、特に８〜４０モル％を用いるのが好ましい。
Hereinafter, more preferable production conditions will be described from the viewpoint of gelation suppression, adjustment of a suitable molecular weight, and performance design of an admixture. From such a viewpoint, at the time of copolymerization, 4 mol% or more, further 6 mol% or more, particularly 8 mol% or more of the chain transfer agent is used with respect to the total number of moles of the monomers 1, 2 and 3. It is preferable. The upper limit of the amount of chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, based on the total number of moles of monomers 1, 2 and 3. Most preferably, it can be 15 mol% or less. More specifically, (1) when r of monomer 1 is 3 to 30,
(1-1) When the total molar ratio of the monomers 1, 2 and 3 of the monomer 2 and the monomer 3 is 50 mol% or more, the chain transfer agent is the monomers 1, 2 and 3 It is preferable to use 6 to 100 mol%, particularly 8 to 60 mol%, based on the total of
(1-2) When the molar ratio in the sum of monomers 1, 2 and 3 of monomer 2 and monomer 3 is less than 50 mol%, the chain transfer agent is monomer 1, 2 and It is preferable to use 4 to 60 mol%, particularly 5 to 30 mol%, based on the total of 3.
(2) When r of monomer 1 used for component (A) is more than 30, the chain transfer agent is used in an amount of 6 to 50 mol%, particularly 8 to 40 mol%, based on monomers 1 to 3. Is preferred.
単量体２と３の反応率は６０％以上、更に７０％以上、更に８０％以上、更に９０％以上、特に９５％以上を目標に行うことが好ましく、連鎖移動剤の使用量は、この観点から選定することができる。ここに、単量体２と３の反応率は、下記の式によって算出する。 The reaction rate of the monomers 2 and 3 is preferably 60% or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. It can be selected from the viewpoint. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.
なお、反応開始時と反応終了時の反応系中のリン含有化合物中の単量体２と単量体３のエチレン性不飽和結合の割合（モル％）は、下記の1Ｈ−ＮＭＲの測定結果に基づき算出することができる。
［1Ｈ−ＮＭＲ条件］
水に溶解した（Ａ）成分を減圧乾燥したものを３〜４重量％の濃度で重メタノールに溶解し、1Ｈ−ＮＭＲを測定する。エチレン性不飽和結合の残存率は、５．５〜６．２ｐｐｍの積分値により測定される。なお、1Ｈ−ＮＭＲの測定は、Varian社製「Mercury 400 NMR」を用い、データポイント数４２０５２、測定範囲６４１０．３Ｈｚ、パルス幅４．５μｓ、パルス待ち時間１０Ｓ、測定温度２５．０℃の条件で行う。
In addition, the ratio (mol%) of the ethylenically unsaturated bond of the monomer 2 and the monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction is measured by the following 1 H-NMR. It can be calculated based on the result.
[ 1 H-NMR conditions]
The component (A) dissolved in water and dried under reduced pressure is dissolved in deuterated methanol at a concentration of 3 to 4% by weight, and 1 H-NMR is measured. The residual ratio of ethylenically unsaturated bonds is measured by an integral value of 5.5 to 6.2 ppm. In addition, the measurement of 1 H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 S, and the measurement temperature is 25.0 ° C. Perform under conditions.
（Ａ）成分の製造においては、上記単量体１、２及び３の他に、共重合可能なその他の単量体を用いることもできる。共重合可能な他の単量体としては、アリルスルホン酸、メタリルスルホン酸、これら何れかのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、又はアミン塩を挙げることができる。また、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸などのアクリル酸系単量体を挙げることができ、またこれらの何れか１種以上のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩、メチルエステル、エチルエステルや無水マレイン酸などの無水化合物であっても良い。更に、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、２−（メタ）アクリルアミド−２−メタスルホン酸、２−（メタ）アクリルアミド−２−エタンスルホン酸、２−（メタ）アクリルアミド−２−プロパンスルホン酸、スチレン、スチレンスルホン酸などが挙げられる。全単量体中、単量体１、２及び３の合計の割合は、３０〜１００モル％、更に５０〜１００モル％、特に７５〜１００モル％が好ましく、更に、９５モル％超〜１００モル％、更に９７〜１００モル％が好ましい。 In the production of the component (A), in addition to the monomers 1, 2, and 3, other monomers that can be copolymerized can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. In addition, acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and any one or more of alkali metal salts, alkalis Anhydrous compounds such as earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters and maleic anhydride may also be used. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. The total proportion of monomers 1, 2, and 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 75 to 100 mol%, and more than 95 mol% to 100 Mole%, more preferably 97-100 mol% is preferred.
（Ａ）成分の製造は、好ましくは所定量の連鎖移動剤の存在下で、単量体を共重合させる。また、共重合可能な他の単量体や重合開始剤等を用いても良い。 In the production of component (A), the monomer is preferably copolymerized in the presence of a predetermined amount of chain transfer agent. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.
単量体１、２及び３の反応温度は、４０〜１００℃、更に６０〜９０℃が好ましく、反応圧力はゲージ圧で１０１．３〜１１１．５ｋＰａ（１〜１．１ａｔｍ）、更に１０１．３〜１０６．４ｋＰａ（１〜１．０５ａｔｍ）が好ましい。 The reaction temperature of the monomers 1, 2 and 3 is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and the reaction pressure is 101.3 to 111.5 kPa (1 to 1.1 atm) in gauge pressure. 3-106.4 kPa (1-1.05 atm) is preferred.
なお、反応系のｐＨは、必要に応じて、無機酸（リン酸、塩酸、硝酸、硫酸等）や、ＮａＯＨ、ＫＯＨ、トリエタノールアミンなどを用いて調整できる。 The pH of the reaction system can be adjusted with an inorganic acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.), NaOH, KOH, triethanolamine, or the like, if necessary.
ここで、単量体２及び／又は単量体３を含む単量体溶液は、ｐＨ測定上、含水系（すなわち、溶媒が水を含むこと）である事が好ましいが、非水系の場合には必要量の水を加えて測定しても良い。単量体溶液の均一性、ゲル化防止、性能低下の抑制の観点で、ｐＨは７以下が好ましく、０．１〜６がより好ましく、更に０．２〜４．５が好ましい。また、単量体１もｐＨ７以下の単量体溶液として用いることが好ましい。このｐＨは、２０℃のものである。 Here, the monomer solution containing the monomer 2 and / or the monomer 3 is preferably a water-containing system (that is, the solvent contains water) for pH measurement. May be measured by adding the required amount of water. From the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation, the pH is preferably 7 or less, more preferably 0.1 to 6, and further preferably 0.2 to 4.5. Monomer 1 is also preferably used as a monomer solution having a pH of 7 or less. This pH is at 20 ° C.
本発明では、反応途中（反応開始時〜反応終了時）で採取した反応液の２０℃でのｐＨを、反応中のｐＨとする。反応中のｐＨが７以下となることが明らかな条件（単量体比率、溶媒、その他の成分等）で反応を開始することが好ましい。 In the present invention, the pH at 20 ° C. of the reaction solution collected during the reaction (from the start of the reaction to the end of the reaction) is defined as the pH during the reaction. It is preferable to start the reaction under conditions that clearly show that the pH during the reaction is 7 or less (monomer ratio, solvent, other components, etc.).
なお、反応系が非水系の場合は、ｐＨ測定可能な量の水を反応系に加えて測定することができる。 When the reaction system is non-aqueous, it can be measured by adding an amount of water capable of measuring pH to the reaction system.
（Ａ）成分の製造方法において、単量体１、２及び３は、以下の（１）、（２）に例示した条件で反応を行えば、その他の条件の考慮の下で、通常は、反応中のｐＨも７以下になると考えられる。
（１）単量体１、２及び３を全て含むｐＨ７以下の単量体溶液を、単量体１、２及び３の共重合反応に用いる。
（２）単量体１、２及び３の共重合反応をｐＨ７以下で開始する。すなわち、単量体１、２及び３を含む反応系を、ｐＨ７以下にした後、反応を開始する。
In the method for producing the component (A), the monomers 1, 2 and 3 are reacted under the conditions exemplified in the following (1) and (2), usually under consideration of other conditions, The pH during the reaction is considered to be 7 or less.
(1) A monomer solution having a pH of 7 or less containing all of the monomers 1, 2 and 3 is used for the copolymerization reaction of the monomers 1, 2 and 3.
(2) The copolymerization reaction of the monomers 1, 2 and 3 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1, 2 and 3 is brought to pH 7 or lower.
［連鎖移動剤］
連鎖移動剤は、ラジカル重合における連鎖移動反応（成長しつつある重合体ラジカルが他の分子と反応してラジカル活性点の移動が起こる反応）をもたらす機能を有し、連鎖単体の移動を目的として添加される物質である。
[Chain transfer agent]
The chain transfer agent has a function of causing a chain transfer reaction in radical polymerization (a reaction in which a growing polymer radical reacts with another molecule to move a radical active site). It is a substance to be added.
連鎖移動剤としては、チオール系連鎖移動剤、ハロゲン化炭化水素系連鎖移動剤等が挙げられ、チオール系連鎖移動剤が好ましい。 Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.
チオール系連鎖移動剤としては、−ＳＨ基を有するものが好ましく、特に一般式ＨＳ−Ｒ−Ｅｇ（ただし、式中Ｒは炭素原子数１〜４の炭化水素由来の基を表し、Ｅは−ＯＨ、−ＣＯＯＭ、−ＣＯＯＲ’または−ＳＯ3Ｍ基を表し、Ｍは水素原子、一価金属、二価金属、アンモニウム基または有機アミン基を表し、Ｒ’は炭素原子数１〜１０のアルキル基を表わし、ｇは１〜２の整数を表す。）で表されるものが好ましく、例えば、メルカプトエタノール、チオグリセロール、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸オクチル、３−メルカプトプロピオン酸オクチル等が挙げられ、単量体１〜３を含む共重合反応での連鎖移動効果の観点から、メルカプトプロピオン酸、メルカプトエタノールが好ましく、メルカプトプロピオン酸が更に好ましい。これらの１種または２種以上を用いることができる。 As the thiol chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and E is − OH, —COOM, —COOR ′ or —SO 3 M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. In which g represents an integer of 1 to 2, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.
ハロゲン化炭化水素系連鎖移動剤としては、四塩化炭素、四臭化炭素などが挙げられる。 Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.
その他の連鎖移動剤としては、α−メチルスチレンダイマー、ターピノーレン、α−テルピネン、γ−テルピネン、ジペンテン、２−アミノプロパン−１−オールなどを挙げることができる。連鎖移動剤は、１種又は２種以上を用いることができる。 Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.
［重合開始剤］
（Ａ）成分の製造方法では、重合開始剤を使用することが好ましく、特に、単量体１、２及び３の合計モル数に対して重合開始剤を５モル％以上、更に７〜５０モル％、特に１０〜３０モル％使用することが好ましい。
[Polymerization initiator]
In the method for producing the component (A), it is preferable to use a polymerization initiator. %, Particularly 10 to 30 mol% is preferred.
水系の重合開始剤としては、過硫酸アンモニウム塩又はアルカリ金属塩あるいは過酸化水素、２，２’−アゾビス（２−アミジノプロパン）ジヒドロクロライド、２，２’−アゾビス（２−メチルプロピオンアミド）ジハイドレート等の水溶性アゾ化合物が使用できる。また、重合開始剤と併用して、亜硫酸水素ナトリウム、アミン化合物などの促進剤を使用することもできる。 Examples of aqueous polymerization initiators include ammonium persulfate salt or alkali metal salt, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) dihydrate, etc. These water-soluble azo compounds can be used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.
［溶媒］
（Ａ）成分の製造では、溶液重合法で実施することができ、その際に使用される溶媒としては、水、あるいは、水と、メチルアルコール、エチルアルコール、イソプロピルアルコールアセトン、メチルエチルケトン等とを含有する含水溶媒系の溶媒が挙げられる。取り扱いと反応設備から考慮すると、水が好ましい。特に水系の溶媒を用いる場合、単量体２及び／又は単量体３を含む単量体溶液のｐＨは７以下であることが好ましく、更に０．１〜６、特に０．２〜４で反応に用いて共重合反応を行うことが、モノマー混液の均一性（取り扱い性）、モノマー反応率の観点や、リン酸系化合物のピロ体の加水分解により架橋を抑制する点で好ましい。
[solvent]
In the production of the component (A), it can be carried out by a solution polymerization method, and the solvent used at that time contains water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, methyl ethyl ketone or the like. And hydrous solvent solvents. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solvent is used, the pH of the monomer solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less, more preferably 0.1 to 6, particularly 0.2 to 4. A copolymerization reaction is preferably used for the reaction in terms of uniformity of the monomer mixture (handleability), monomer reaction rate, and suppression of crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.
（Ａ）成分の製造方法の一例を示す。反応容器に所定量の水を仕込み、窒素等の不活性気体で雰囲気を置換し昇温する。予め単量体１、単量体２、単量体３、連鎖移動剤を水に混合溶解したものと、重合開始剤を水に溶解したものとを用意し、０．５〜５時間かけて反応容器に滴下する。その際、各単量体、連鎖移動剤及び重合開始剤を別々に滴下してもよく、また、単量体の混合溶液を予め反応容器に仕込み、重合開始剤のみを滴下することも可能である。すなわち、連鎖移動剤、重合開始剤、その他の添加剤は、単量体溶液とは別に添加剤溶液として添加しても良いし、単量体溶液に配合して添加してもよいが、重合の安定性の観点からは、単量体溶液とは別に添加剤溶液として反応系に供給することが好ましい。何れの場合も、単量体２及び／又は単量体３を含有する溶液はｐＨ７以下が好ましい。また、酸剤等により、好ましくはｐＨを７以下に維持して共重合反応を行い、好ましくは所定時間の熟成を行う。なお、重合開始剤は、全量を単量体と同時に滴下しても良いし、分割して添加しても良いが、分割して添加することが未反応単量体の低減の点では好ましい。例えば、最終的に使用する重合開始剤の全量中、１／２〜２／３の重合開始剤を単量体と同時に添加し、残部を単量体滴下終了後１〜２時間熟成した後、添加することが好ましい。必要に応じ、熟成終了後に更にアルカリ剤（水酸化ナトリウム等）で中和し、本発明に係るリン酸エステル系重合体を得る。この製造例は、本発明に係る（Ａ）成分の製造方法として好適である。 (A) An example of the manufacturing method of a component is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. In any case, the pH of the solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less. Further, the copolymerization reaction is preferably performed with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is performed for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, it is further neutralized with an alkali agent (such as sodium hydroxide) after completion of ripening to obtain the phosphate ester polymer according to the present invention. This production example is suitable as a method for producing the component (A) according to the present invention.
反応系の単量体１、２及び３並びに共重合可能なその他の単量体の総量は、５〜８０重量％が好ましく、１０〜６５重量％がより好ましく、２０〜５０重量％が特に好ましい。 The total amount of monomers 1, 2 and 3 in the reaction system and other copolymerizable monomers is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, and particularly preferably 20 to 50% by weight. .
（Ａ）成分は、重量平均分子量（Ｍｗ）が１０，０００〜１５０，０００であることが好ましい。この（Ａ）成分は、流動性の発現や（Ｂ）成分と併用した場合の分離抑制の観点から、Ｍｗが１０，０００以上であり、好ましくは１２，０００以上、さらに好ましくは１３，０００以上、より好ましくは１４，０００以上、特に好ましくは１５，０００以上で、架橋による高分子量化、ゲル化の抑制や性能面では流動性の発現と分離抑制の観点から、１５０，０００以下であり、好ましくは１３０，０００以下、さらに好ましくは１２０，０００以下、より好ましくは１１０，０００以下、特に好ましくは１００，０００以下であり、前記両者の観点から、好ましくは１２，０００〜１３０，０００、より好ましくは１３，０００〜１２０，０００、さらに好ましくは１４，０００〜１１０，０００、特に好ましくは１５，０００〜１００，０００である。この範囲のＭｗを有し、かつＭｗ／Ｍｎが１．０〜２．６であることが好ましい。ここで、Ｍｎは数平均分子量である。 The component (A) preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. This component (A) has a Mw of 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, from the viewpoint of fluidity expression and separation suppression when used in combination with the component (B). More preferably, it is 14,000 or more, particularly preferably 15,000 or more, and from the viewpoint of high molecular weight by crosslinking, suppression of gelation and performance in terms of expression of fluidity and suppression of separation, 150,000 or less, Preferably it is 130,000 or less, more preferably 120,000 or less, more preferably 110,000 or less, particularly preferably 100,000 or less, and from the viewpoints of both, preferably 12,000 to 130,000, more Preferably 13,000 to 120,000, more preferably 14,000 to 110,000, particularly preferably 15,000 to 100. Is 000. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, Mn is a number average molecular weight.
（Ａ）成分のＭｗ及びＭｎは、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定されたものである。
［ＧＰＣ条件］
カラム：G4000PWXL+G2500PWXL（東ソー）
溶離液：0.2Ｍリン酸バッファー／CH3CN＝9／1
流量：1.0mL/min
カラム温度：４０℃
検出：ＲＩ
サンプルサイズ：0.2ｍg/ｍL
標準物質：ポリエチレングリコール換算
(A) Mw and Mn of a component are measured by the gel permeation chromatography (GPC) method of the following conditions.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (Tosoh)
Eluent: 0.2M phosphate buffer / CH 3 CN = 9/1
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Reference material: Polyethylene glycol equivalent
また、上記条件でのＧＰＣ法で得られる分子量分布を示すチャートのパターンにおいて、分子量１０万以上の面積が当該チャート全体の面積の５％以下であることが、流動性（必要添加量低減）の点でより好ましい。 Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area where the molecular weight is 100,000 or more is 5% or less of the total area of the chart, and the fluidity (required addition amount reduction) More preferable in terms.
＜（Ｂ）成分＞
（Ｂ）成分の非イオン性水溶性高分子化合物としては、ポリビニルアルコール、ポリアルキレングリコール、非イオン性の水溶性セルローズエーテル等が挙げられる。
<(B) component>
Examples of the nonionic water-soluble polymer compound (B) include polyvinyl alcohol, polyalkylene glycol, and nonionic water-soluble cellulose ether.
ポリビニルアルコールとしては、重合度５００〜２０００が挙げられ、重合度１４００超２０００が好ましい。 Examples of the polyvinyl alcohol include a polymerization degree of 500 to 2000, and a polymerization degree of more than 1400 and 2000 is preferable.
ポリアルキレングリコールとしては、ポリエチレングリコール（ポリエチレンオキサイド）が挙げられる。ポリアルキレングリコールは、重量平均分子量が２万超、更に２万超５００万以下のものが好ましい。 Polyalkylene glycol includes polyethylene glycol (polyethylene oxide). The polyalkylene glycol preferably has a weight average molecular weight of more than 20,000, more preferably more than 20,000 and not more than 5,000,000.
非イオン性の水溶性セルローズエーテルとしては、メチルセルローズ、エチルセルローズ、ヒドロキシメチルセルローズ、ヒドロキシエチルセルローズ、カルボキシメチルセルローズ、カルボキシエチルセルローズ等が挙げられるが、メチルセルローズ、ヒドロキシエチルセルローズが特に好ましい。 Examples of the nonionic water-soluble cellulose ether include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and the like, and methyl cellulose and hydroxyethyl cellulose are particularly preferable.
（Ｂ）成分は、増粘剤として使用されるものであり、これを（Ａ）成分と併用することで、少量の添加でも分離抵抗性が向上し、セルフレベリング材としての調製が容易となる。 The component (B) is used as a thickener, and by using this together with the component (A), the separation resistance is improved even when added in a small amount, and the preparation as a self-leveling material becomes easy. .
＜セルフレベリング材用分散剤＞ <Dispersant for self-leveling material>
本発明の分散剤は、（Ｂ）成分との併用において、流動性と分離抵抗性の両性能を満足する観点から、水硬性粉体１００重量部に対して（Ａ）成分を０．０１〜５重量部、特に０．１〜３重量部含有するように材中に添加することが好ましい。 In the combined use with the component (B), the dispersant of the present invention has a component (A) of 0.01 to 100 parts by weight of the hydraulic powder from the viewpoint of satisfying both fluidity and separation resistance. It is preferable to add 5 parts by weight, particularly 0.1 to 3 parts by weight in the material.
本発明の分散剤は、分散性を阻害せず、分離抵抗性を満足させる観点から、水硬性粉体１００重量部に対して（Ｂ）成分を０．０１〜２重量部、更に０．０２〜１重量部含有するように材中に添加することが好ましい。（Ａ）成分と（Ｂ）成分の重量比は１００／５０〜１００／１が好ましく、１００／１０〜１００／２が特に好ましい。 In the dispersant of the present invention, from the viewpoint of satisfying the separation resistance without inhibiting the dispersibility, the component (B) is added in an amount of 0.01 to 2 parts by weight, and further 0.02 in 100 parts by weight of the hydraulic powder. It is preferably added to the material so as to contain ˜1 part by weight. The weight ratio of the component (A) to the component (B) is preferably 100/50 to 100/1, and particularly preferably 100/10 to 100/2.
本発明の分散剤は、上記の添加量に適した配合量で（Ａ）成分及び（Ｂ）成分を含有することができる。水溶液等液体状の場合、製造容易性及び作業性の観点から、（Ａ）成分と（Ｂ）成分の合計で分散剤中で好ましくは５〜４０重量％、さらに好ましくは２０〜３５重量％である。更に必要に応じて配合される任意成分を混合して得ることができる。 The dispersing agent of this invention can contain (A) component and (B) component with the compounding quantity suitable for said addition amount. In the case of a liquid form such as an aqueous solution, from the viewpoint of ease of production and workability, the total of the component (A) and the component (B) is preferably 5 to 40% by weight, more preferably 20 to 35% by weight in the dispersant. is there. Furthermore, it can obtain by mixing the arbitrary components mix | blended as needed.
本発明の分散剤には、消泡性の観点から、消泡剤を添加することが望ましく、消泡剤としては、メタノール、エタノール等の低級アルコール系、ジメチルシリコーンオイル、フルオロシリコーンオイル等のシリコーン系、鉱物油と界面活性剤の配合品等の鉱物油系、リン酸トリブチル等のリン酸エステル、オレイン酸、ソルビタンオレイン酸モノエステル、ソルビタンオレイン酸モノエステル、ポリエチレングリコール脂肪酸エステル、ポリエチレン／ポリプロピレングリコール脂肪酸エステル等の脂肪酸又はそのエステル系、ポリプロピレングリコール（重量平均分子量２００００以下のもの）、ポリエチレン／ポリプロピレングリコールアルキルエーテル等のノニオン系が挙げられる。好ましくは、脂肪酸又はそのエステル系であり、更に好ましくはポリエチレン／ポリプロピレングリコール脂肪酸エステルである。消泡剤の添加量は（Ａ）成分と（Ｂ）成分の合計１００重量部に対して0.01〜10重量部が好ましく、0.05〜５重量部が更に好ましく、0.1〜３重量部が特に好ましい。 From the viewpoint of antifoaming properties, it is desirable to add an antifoaming agent to the dispersant of the present invention. Examples of the antifoaming agent include lower alcohols such as methanol and ethanol, and silicones such as dimethylsilicone oil and fluorosilicone oil. Oils, mineral oils such as blends of mineral oil and surfactant, phosphate esters such as tributyl phosphate, oleic acid, sorbitan oleic acid monoester, sorbitan oleic acid monoester, polyethylene glycol fatty acid ester, polyethylene / polypropylene glycol Nonionics such as fatty acids such as fatty acid esters or esters thereof, polypropylene glycol (having a weight average molecular weight of 20000 or less), and polyethylene / polypropylene glycol alkyl ethers may be mentioned. Preferred are fatty acids or esters thereof, and more preferred are polyethylene / polypropylene glycol fatty acid esters. The addition amount of the antifoaming agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B).
更に本発明の分散剤は、他の公知の添加剤（材）、例えば、AE剤、AE減水剤、高性能減水剤、遅延剤、早強剤、促進剤、起泡剤、発泡剤、（Ｂ）成分以外の増粘剤、防水剤、防泡剤等の各種添加剤（材）を含有しても良い。しかし、本発明の分散剤の固形分中には（Ａ）成分と（Ｂ）成分が合計で50重量％以上、更には70〜100重量％、特に80〜99.95重量％含まれていることが好ましい。 Furthermore, the dispersant of the present invention may be prepared by using other known additives (materials) such as AE agent, AE water reducing agent, high performance water reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent ( Various additives (materials) such as thickeners, waterproofing agents and antifoaming agents other than the component B) may be contained. However, in the solid content of the dispersant of the present invention, the total amount of the component (A) and the component (B) is 50% by weight or more, more preferably 70 to 100% by weight, and particularly 80 to 99.95% by weight. preferable.
なお、本発明において、セルフレベリング材とは、セメント等の水硬性粉体と水を含む水硬性組成物のうち、建築物の床下地や基礎の天端部分を水平に調整するために用いられる材をいう。水硬性粉体としては、水硬性化合物としては、ポルトランドセメント、高炉セメント、シリカセメント、フライアッシュセメント、アルミナセメント、天然石膏、副成石膏等が挙げられる。特に、普通ポルトランドセメントと石膏とを含有することが好ましい。 In the present invention, the self-leveling material is used for horizontally adjusting the floor base of a building and the top end portion of a foundation among hydraulic compositions containing hydraulic powder such as cement and water. Say the material. As the hydraulic powder, examples of the hydraulic compound include Portland cement, blast furnace cement, silica cement, fly ash cement, alumina cement, natural gypsum, by-product gypsum, and the like. In particular, it is preferable to contain ordinary portland cement and gypsum.
本発明のセルフレベリング材の水／水硬性粉体の重量比（Ｗ／Ｐ）は２０〜６０％が好ましく、２５〜５０％がより好ましい。また、本発明のセルフレベリング材としての流動性の拡がりであるフロー値（内径５０ｍｍ、高さ５０ｍｍの円筒コーン）は、１８０〜２５０ｍｍが好ましく、２００〜２４０ｍｍがより好ましい。さらに、セルフレベリング材にフライアッシュ、スラグ、石灰石粉等の増量材公知の増量材や、砂や珪砂等の細骨材を含有することが好ましい。 20-60% is preferable and, as for the weight ratio (W / P) of the water / hydraulic powder of the self-leveling material of this invention, 25-50% is more preferable. Further, the flow value (cylindrical cone having an inner diameter of 50 mm and a height of 50 mm), which is an increase in fluidity as the self-leveling material of the present invention, is preferably 180 to 250 mm, and more preferably 200 to 240 mm. Furthermore, it is preferable that the self-leveling material contains a known bulking material such as fly ash, slag, limestone powder, or fine aggregates such as sand or quartz sand.
製造例Ａ１
撹拌機付きガラス製反応容器（四つ口フラスコ）に水３６６ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数２３）４５０ｇ（有効分６０．８重量％、水分３５重量％）とリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物であるリン酸エステル化物（Ａ）７１．６ｇと３−メルカプトプロピオン酸４．５ｇを混合したものと、過硫酸アンモニウム８．４ｇを水４８ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム１．８ｇを水１０ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に３２％水酸化ナトリウム水溶液４４．４ｇで中和し、重量平均分子量３５０００の重合体ａ−１を得た。（単量体重合pH：１．０、反応率１００％）
Production Example A1
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 450 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 71.6 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 4.5 g of 3-mercaptopropionic acid, and 8.4 g of ammonium persulfate in water Two of those dissolved in 48 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-1 having a weight average molecular weight of 35,000. (Monomer polymerization pH: 1.0, reaction rate 100%)
なお、本製造例で使用したリン酸エステル化物（Ａ）は、反応容器中にメタクリル酸2-ヒドロキシエチル200ｇと85%リン酸（H3PO4）36.0ｇを仕込み、５酸化２リン（無水リン酸）（P2O5）89.1ｇを温度が60℃を超えないように冷却しながら徐々に添加した。終了後、反応温度を80℃に設定し、6時間反応させ、冷却して得られたものである。以下の製造例の一部でも、このリン酸エステル化物（Ａ）を使用した。 The phosphoric acid ester (A) used in this production example was prepared by charging 200 g of 2-hydroxyethyl methacrylate and 36.0 g of 85% phosphoric acid (H 3 PO 4 ) in a reaction vessel. Phosphoric acid) (P 2 O 5 ) 89.1 g was gradually added while cooling so that the temperature did not exceed 60 ° C. After completion, the reaction temperature was set to 80 ° C., reacted for 6 hours, and cooled. This phosphate esterified product (A) was also used in some of the following production examples.
製造例Ａ２
撹拌機付きガラス製反応容器（四つ口フラスコ）に水３７１ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数２３）５００ｇ（有効分６０．８重量％、水分３５重量％）とリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物であるリン酸エステル化物（Ａ）３４．１ｇと３−メルカプトプロピオン酸２．８ｇを混合したものと、過硫酸アンモニウム７．２ｇを水４１ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム１．６ｇを水９ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に３２％水酸化ナトリウム水溶液２１．２ｇで中和し、重量平均分子量３４０００の重合体ａ−２を得た。（単量体重合pH：１．１、反応率１００％）
Production Example A2
371 g of water was charged into a glass reaction vessel with a stirrer (four-necked flask), purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 500 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 34.1 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of the aging, the mixture was neutralized with 21.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-2 having a weight average molecular weight of 34,000. (Monomer polymerization pH: 1.1, reaction rate 100%)
製造例Ａ３
撹拌機付きガラス製反応容器（四つ口フラスコ）に水３８１ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数２３）５２０ｇ（有効分６０．８重量％、水分３５重量％）とリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物であるリン酸エステル化物（Ａ）２８．６ｇと３−メルカプトプロピオン酸２．８ｇを混合したものと、過硫酸アンモニウム７．２ｇを水４１ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム１．６ｇを水９ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に３２％水酸化ナトリウム水溶液１７．７ｇで中和し、重量平均分子量３６０００の重合体ａ−３を得た。（単量体重合pH：１．１、反応率１００％）
Production Example A3
A glass reaction vessel (four-necked flask) with a stirrer was charged with 381 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 520 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and phosphorus A mixture of 28.6 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 17.7 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-3 having a weight average molecular weight of 36000. (Monomer polymerization pH: 1.1, reaction rate 100%)
製造例Ａ４
撹拌機付きガラス製反応容器（四つ口フラスコ）に水４７１ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数９）２９０ｇ（有効分８４．４重量％、水分１０重量％）とリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物であるリン酸エステル化物（Ａ）９３．８ｇと３−メルカプトプロピオン酸１１．３ｇを混合したものと、過硫酸アンモニウム８．２ｇを水４６ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム３．３ｇを水１９ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に３２％水酸化ナトリウム水溶液５８．２ｇで中和し、重量平均分子量２５０００の重合体ａ−４を得た。（単量体重合pH：１．０、反応率９９％）
Production Example A4
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 471 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 93.8 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 11.3 g of 3-mercaptopropionic acid, and 8.2 g of ammonium persulfate in water Two of those dissolved in 46 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.3 g of ammonium persulfate in 19 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the solution was neutralized with 58.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-4 having a weight average molecular weight of 25,000. (Monomer polymerization pH: 1.0, reaction rate 99%)
製造例Ａ５
撹拌機付きガラス製反応容器（四つ口フラスコ）に水４８９ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数９）２９０ｇ（有効分８４．４重量％、水分１０重量％）とリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物であるリン酸エステル化物（Ａ）５３．２ｇと３−メルカプトプロピオン酸９．１ｇを混合したものと、過硫酸アンモニウム７．８ｇを水４４ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム３．１ｇを水１８ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に３２％水酸化ナトリウム水溶液３３．０ｇで中和し、重量平均分子量２１０００の重合体ａ−５を得た。（単量体重合pH：１．１、反応率９８％）
Production Example A5
489 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 53.2 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 9.1 g of 3-mercaptopropionic acid and 7.8 g of ammonium persulfate in water Two of those dissolved in 44 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.1 g of ammonium persulfate in 18 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 33.0 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-5 having a weight average molecular weight of 21,000. (Monomer polymerization pH: 1.1, reaction rate 98%)
製造例Ａ６
撹拌機付きガラス製反応容器（四つ口フラスコ）に水１８９ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの付加モル数９：新中村化学製ＮＫエステルＭ９０Ｇ）４０ｇとリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物（ホスマーＭ：ユニケミカル（株））４３．８ｇと３−メルカプトプロピオン酸１．６ｇとを水４０ｇに溶解したものと、過硫酸アンモニウム５．４ｇを水６２ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム２．７ｇを水３１ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に２０％水酸化ナトリウム水溶液５４．４ｇで中和し、重量平均分子量５１０００の重合体ａ−６を得た。（単量体重合pH：１．１、反応率１００％）
Production Example A6
A glass reaction vessel (four-necked flask) with a stirrer was charged with 189 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 40 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 9: NK ester M90G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 43.8 g and 3-mercaptopropionic acid 1.6 g in water 40 g and ammonium persulfate 5.4 g in water 62 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 2.7 g of ammonium persulfate dissolved in 31 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 54.4 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-6 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.1, reaction rate 100%)
製造例Ａ７
撹拌機付きガラス製反応容器（四つ口フラスコ）に水２１８ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの付加モル数２３：新中村化学製ＮＫエステルＭ２３０Ｇ）５５ｇとリン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルとリン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルの混合物（ホスマーＭ：ユニケミカル（株））３２．３ｇと３−メルカプトプロピオン酸１．１ｇとを水５５ｇに溶解したものと、過硫酸アンモニウム３．８ｇを水４３ｇに溶解したものの２者を、それぞれ１．５時間かけて滴下した。１時間の熟成後、過硫酸アンモニウム１．９ｇを水２２ｇに溶解したものを３０分かけて滴下し、その後１．５時間同温度（８０℃）で熟成した。熟成終了後に２０％水酸化ナトリウム水溶液４０．１ｇで中和し、重量平均分子量５１０００の重合体ａ−７を得た。（単量体重合pH：１．３、反応率１００％）
Production Example A7
A glass reaction vessel (four-necked flask) with a stirrer was charged with 218 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 55 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 32.3 g and 3-mercaptopropionic acid 1.1 g dissolved in water 55 g and ammonium persulfate 3.8 g in water 43 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 1.9 g of ammonium persulfate dissolved in 22 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 40.1 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-7 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.3, reaction rate 100%)
製造例Ｃ１
撹拌機付きガラス製反応容器（四つ口フラスコ）に水281.4g仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で80℃まで昇温した。ω-メトキシポリエチレングリコールメタクリレート（エチレンオキサイドの付加モル数120）336.5ｇとメタクリル酸22.2ｇと2-メルカプトエタノール1.89gを水238.2gに溶解したものと、過硫酸アンモニウム3.68ｇを水45gに溶解したものの二者をそれぞれ1.5時間かけて滴下した。引き続き、過硫酸アンモニウム1.47ｇを水15ｇに溶解したものを30分かけて滴下し、その後1時間同温度（80℃）で熟成した。熟成終了後に48%水酸化ナトリウム18.7ｇで中和し、共重合体ｃ−１を得た。（重量平均分子量79000）
Production Example C1
A glass reaction vessel with a stirrer (four-necked flask) was charged with 281.4 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol methacrylate (added mole number of ethylene oxide 120) 336.5g, methacrylic acid 22.2g and 2-mercaptoethanol 1.89g dissolved in water 238.2g, and ammonium persulfate 3.68g dissolved in water 45g The two were added dropwise over 1.5 hours each. Subsequently, 1.47 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 18.7 g of 48% sodium hydroxide to obtain a copolymer c-1. (Weight average molecular weight 79000)
製造例Ｃ２
撹拌機付きガラス製反応容器（四つ口フラスコ）に水246.4g仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で56℃まで昇温した。ω-メトキシポリエチレングリコールメタクリレート（エチレンオキサイドの付加モル数10）148.8ｇとメタクリル酸39.2ｇと3-メルカプトプロピオン酸2.32gを混合したものと、過硫酸アンモニウム5%水溶液43.3ｇの二者をそれぞれ1.5時間かけて滴下した。その後3時間同温度（56℃）で熟成した。熟成終了後に48%水酸化ナトリウムでpH=6まで中和し、共重合体ｃ−２を得た。（分子量34000）
Production Example C2
A glass reaction vessel with a stirrer (four-necked flask) was charged with 246.4 g of water, purged with nitrogen while stirring, and heated to 56 ° C. in a nitrogen atmosphere. The mixture of 148.8 g of ω-methoxypolyethyleneglycol methacrylate (ethylene oxide addition mole number 10), 39.2 g of methacrylic acid and 2.32 g of 3-mercaptopropionic acid and 43.3 g of 5% aqueous solution of ammonium persulfate for 1.5 hours each It was dripped over. Thereafter, aging was performed at the same temperature (56 ° C.) for 3 hours. After completion of aging, the mixture was neutralized with 48% sodium hydroxide to pH = 6 to obtain a copolymer c-2. (Molecular weight 34000)
実施例１〜１１及び比較例１〜６
上記で得られた共重合体〔便宜的にまとめて（Ａ）成分と表記する〕と下記の（Ｂ）成分を用いて、以下のセルフレベリング材に対する評価を行った。結果を表１に示す。
Examples 1-11 and Comparative Examples 1-6
The following self-leveling materials were evaluated using the copolymer obtained above (for convenience and collectively referred to as component (A)) and the following component (B). The results are shown in Table 1.
（Ｂ）成分
・メチルセルローズ：ハイメトローズ６５Ｈ、信越化学工業（株）製
・ＨＥＣ（ヒドロキシエチルセルローズ）：ユニセルＱＰ−４４００Ｈ、ダイセル化学工業（株）製
(B) Component ・ Methylcellulose: High Metroise 65H, manufactured by Shin-Etsu Chemical Co., Ltd. ・ HEC (Hydroxyethyl Cellulose): Unicel QP-4400H, manufactured by Daicel Chemical Industries, Ltd.
（１）セルフレベリング材の成分及び配合量
・普通ポルトランドセメント（太平洋社製） １０００重量部
・石膏（半水、試薬） １５０重量部
・高炉スラグ（新日鉄社製） ５００重量部
・珪砂５号 １０００重量部
・消泡剤（ＳＮフォーマーEX-301；サンノプコ社製） ０．５重量部
・硫酸カリウム（試薬） ５重量部
・表１の（Ａ）成分 表１の添加量（セメント＋石膏に対する重量％）
・表１の（Ｂ）成分 表１の添加量（セメント＋石膏に対する重量％）
(1) Ingredients and blending amount of self-leveling material: Normal Portland cement (manufactured by Taiheiyo) 1000 parts by weight Gypsum (semi-water, reagent) 150 parts by weight Blast furnace slag (manufactured by Nippon Steel) 500 parts by weight Silica sand No. 5 1000 Part by weight: Antifoaming agent (SN Former EX-301; manufactured by San Nopco) 0.5 part by weight: Potassium sulfate (reagent) 5 parts by weight: Component (A) in Table 1 Addition amount in Table 1 (weight relative to cement + gypsum) %)
-Component (B) in Table 1 Addition amount in Table 1 (weight% relative to cement + gypsum)
（２）セルフレベリング材の調製方法
上記セルフレベリング材の成分に、（Ｂ）成分と、（Ａ）成分を溶解させた水８００重量部とを加えて、４枚羽根つきハンドミキサーで１分間混合して、セルフレベリング材を調製した。（Ｂ）成分は他の成分〔（Ａ）成分を除く〕とプレミックスして用いた。
(2) Preparation method of self-leveling material Add the component (B) and 800 parts by weight of water in which the component (A) is dissolved to the above-mentioned self-leveling material, and mix for one minute using a hand mixer with four blades. Thus, a self-leveling material was prepared. Component (B) was premixed with other components [excluding component (A)].
（３）評価方法
（３−１）流動性
セルフレベリング材を内径５０ｍｍ、高さ５０ｍｍの円筒コーンに詰め、引き上げた後の拡がりであるフロー値（ｍｍ）を測定した。
(3) Evaluation method (3-1) Flowability The self-leveling material was packed in a cylindrical cone having an inner diameter of 50 mm and a height of 50 mm, and the flow value (mm), which is the spread after being pulled up, was measured.
（３−２）分離抵抗性
目盛り付き３００ｍｌメスシリンダーに、セルフレベリング材を３００ｍｌ入れ、水分が蒸発しないように上蓋をして、２０℃、１日放置後の上澄み水を測定した。その測定結果から、下記の基準で評価を行った。
◎：上澄み液なし
〇：上澄み液が５ｍｌ以下
△：上澄み液が５ｍｌ超１０ｍｌ未満
×：上澄み液が１０ｍｌ以上
(3-2) Separation resistance 300 ml of a self-leveling material was placed in a graduated 300 ml graduated cylinder, the upper lid was placed so as not to evaporate the water, and the supernatant water after standing at 20 ° C. for 1 day was measured. From the measurement results, the following criteria were used for evaluation.
◎: No supernatant liquid ○: Supernatant liquid is 5 ml or less Δ: Supernatant liquid is more than 5 ml and less than 10 ml x: Supernatant liquid is 10 ml or more
（注）（Ａ）成分、（Ｂ）成分の添加量は、セメントと石膏の合計に対する有効分換算の重量％である。本発明品は流動性と分離抵抗性を両立しているのに対して、比較品は同等の流動性では分離抵抗性に劣ることがわかる。 (Note) The amount of component (A) and component (B) added is the weight percentage in terms of the effective component based on the total amount of cement and gypsum. It can be seen that the product of the present invention has both fluidity and separation resistance, while the comparative product is inferior in separation resistance at the same fluidity.
Claims (4)
〔式中、Ｒ1、Ｒ2は、それぞれ水素原子又はメチル基、Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4、ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基、pは０又は１の数、ｑは０〜２の数、ｒはＡＯの平均付加モル数であり、３〜３００の数、Ｒ4は水素原子又は炭素数１〜１８のアルキル基を表す。〕
〔式中、Ｒ11は水素原子又はメチル基、Ｒ12は炭素数２〜１２のアルキレン基、ｍ１は１〜３０の数、Ｍ3、Ｍ4はそれぞれ水素原子、アルカリ金属又はアルカリ土類金属を表す。〕
〔式中、Ｒ13、Ｒ15は、それぞれ水素原子又はメチル基、Ｒ14、Ｒ16は、それぞれ炭素数２〜１２のアルキレン基、ｍ２、ｍ３は、それぞれ１〜３０の数、Ｍ5は水素原子、アルカリ金属又はアルカリ土類金属を表す。〕 Monomer 1 containing monomer 1 represented by the following general formula (1), monomer 2 represented by the following general formula (2) and monomer 3 represented by the following general formula (3) A dispersant for a self-leveling material, comprising a phosphate ester polymer (A) obtained by copolymerizing a body and a nonionic water-soluble polymer compound (B).
[Wherein R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 is a hydrogen atom or — (CH 2 ) q (CO) pO (AO) rR 4 , and AO is an oxyalkylene having 2 to 4 carbon atoms. Group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R 4 is a hydrogen atom or a carbon number of 1 to 18 Represents an alkyl group. ]
[Wherein R 11 is a hydrogen atom or a methyl group, R 12 is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M 3 and M 4 are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]
[Wherein R 13 and R 15 are each a hydrogen atom or a methyl group, R 14 and R 16 are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M 5 is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186636A (en) * | 2006-01-16 | 2007-07-26 | Kao Corp | Method for producing phosphate-based polymer |
| JP2015113248A (en) * | 2013-12-11 | 2015-06-22 | 花王株式会社 | Gypsum slurry |
| JP2017075444A (en) * | 2015-10-13 | 2017-04-20 | 株式会社アマケンテック | Weed-proofing and water-proofing reinforcement method using water-based paint for paved road and paved surface of road bridge |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069258A (en) * | 1991-03-07 | 1994-01-18 | Nippon Cement Co Ltd | Superhigh-fluidity concrete |
| JPH1179811A (en) * | 1997-09-03 | 1999-03-23 | Kao Corp | Concrete admixture |
| JP2000327386A (en) * | 1999-05-14 | 2000-11-28 | Taiheiyo Cement Corp | Cement dispersant and hydraulic composition including the same |
| JP2003002716A (en) * | 2001-06-20 | 2003-01-08 | Kao Corp | Dispersing agent for self leveling material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069258A (en) * | 1991-03-07 | 1994-01-18 | Nippon Cement Co Ltd | Superhigh-fluidity concrete |
| JPH1179811A (en) * | 1997-09-03 | 1999-03-23 | Kao Corp | Concrete admixture |
| JP2000327386A (en) * | 1999-05-14 | 2000-11-28 | Taiheiyo Cement Corp | Cement dispersant and hydraulic composition including the same |
| JP2003002716A (en) * | 2001-06-20 | 2003-01-08 | Kao Corp | Dispersing agent for self leveling material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186636A (en) * | 2006-01-16 | 2007-07-26 | Kao Corp | Method for producing phosphate-based polymer |
| JP2015113248A (en) * | 2013-12-11 | 2015-06-22 | 花王株式会社 | Gypsum slurry |
| JP2017075444A (en) * | 2015-10-13 | 2017-04-20 | 株式会社アマケンテック | Weed-proofing and water-proofing reinforcement method using water-based paint for paved road and paved surface of road bridge |
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