WO2019053782A1 - Dispersion-maintaining agent for hydraulic composition - Google Patents

Dispersion-maintaining agent for hydraulic composition Download PDF

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Publication number
WO2019053782A1
WO2019053782A1 PCT/JP2017/032877 JP2017032877W WO2019053782A1 WO 2019053782 A1 WO2019053782 A1 WO 2019053782A1 JP 2017032877 W JP2017032877 W JP 2017032877W WO 2019053782 A1 WO2019053782 A1 WO 2019053782A1
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WIPO (PCT)
Prior art keywords
group
chemical formula
monomer
hydraulic composition
vinyl copolymer
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PCT/JP2017/032877
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French (fr)
Japanese (ja)
Inventor
章宏 古田
静佳 有賀
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竹本油脂株式会社
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Application filed by 竹本油脂株式会社 filed Critical 竹本油脂株式会社
Priority to PCT/JP2017/032877 priority Critical patent/WO2019053782A1/en
Priority to CN201780094648.1A priority patent/CN111051265B/en
Priority to MYPI2020000848A priority patent/MY177858A/en
Priority to KR1020207006559A priority patent/KR102192163B1/en
Publication of WO2019053782A1 publication Critical patent/WO2019053782A1/en
Priority to PH12020500481A priority patent/PH12020500481A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • the present invention relates to a dispersion holding agent for hydraulic compositions.
  • Various dispersants are widely used in the preparation of hydraulic compositions such as mortar and concrete.
  • slump loss decrease in flowability with time
  • the present invention relates to a dispersion holding agent for a hydraulic composition which can sufficiently prevent slump loss.
  • dispersants for hydraulic compositions comprising a water-soluble vinyl copolymer have been proposed as having slump loss prevention performance per se (see, for example, Patent Documents 1 to 4).
  • these conventional proposals have a problem that the slump loss of the prepared hydraulic composition can not be sufficiently prevented.
  • what combined the slump loss prevention agent with the dispersing agent for hydraulic composition is also proposed (for example, refer patent document 5).
  • this conventional proposal there is still a problem that the slump loss of the prepared hydraulic composition can not be sufficiently prevented.
  • the problem to be solved by the present invention is to provide a dispersion holding agent for a hydraulic composition, which can maintain the fluidity of the hydraulic composition even after a long time since kneading, and which is less delayed in curing. is there.
  • the present inventors found that a specific monomer having a carboxyl group in the molecule and a specific monomer having a polyalkylene glycol residue in the molecule. Furthermore, it has been found that vinyl copolymers obtained by copolymerizing these monomers with other monomers copolymerizable with these monomers are properly suitable as dispersion holding agents for hydraulic compositions, if necessary.
  • the present invention comprises a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1 and a monomer B represented by the following chemical formula 2, for a hydraulic composition It relates to the dispersion holding agent. Further, the present invention is obtained from a monomer A represented by the following chemical formula 1, a monomer B represented by the following chemical formula 2, and another monomer C copolymerizable with these monomers.
  • the present invention relates to a dispersion-retaining agent for a hydraulic composition, characterized by containing a vinyl copolymer as described above.
  • R 1 , R 2 a hydrogen atom, a methyl group or an organic group p: 0 or 1 represented by the following chemical formula 3
  • X organic group represented by the following chemical formula 4
  • Y organic group represented by the following chemical formula 5
  • M 1 hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent alkaline earth metal
  • r 0 or 1 M 2 : hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent of alkaline earth metal
  • AO an oxyalkylene group having 2 to 4 carbon atoms
  • m an integer of 1 to 10
  • R 3 an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group
  • s integer from 0 to 4 t: 0 or 1 AO: an oxyalkylene group having a carbon number of 2 to 4 n: an integer of 0 to 300
  • R 4 a hydrogen atom, an alkyl group having a carbon number of 1 to 22 or an aliphatic acyl group having a carbon number of 1 to 22
  • R 4 is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms
  • the dispersion holding agent for a hydraulic composition according to the present invention includes a monomer A shown in the above-mentioned chemical formula 1 and a monomer B shown in the above-mentioned chemical formula 2 And a monomer containing vinyl copolymer (hereinafter referred to as vinyl copolymer P), such monomer A, such monomer B, and other monomers C copolymerizable therewith. And those containing a vinyl copolymer (hereinafter referred to as vinyl copolymer Q) obtained from a monomer A shown in the above-mentioned chemical formula 1 and a monomer B shown in the above-mentioned chemical formula 2 And a monomer containing vinyl copolymer (hereinafter referred to as vinyl copolymer P), such monomer A, such monomer B, and other monomers C copolymerizable therewith. And those containing a vinyl copolymer (hereinafter referred to as vinyl copolymer Q) obtained from
  • the vinyl copolymer P is a vinyl copolymer obtained from the monomer A and the monomer B, and the ratio of the both is not particularly limited.
  • Preferred are vinyl copolymers having a weight average molecular weight of 8,000 to 200,000, having a ratio of 1 to 99 mol% of structural units and 1 to 99 mol% (total of 100 mol%) of structural units derived from monomer B.
  • R 1 is a hydrogen atom, a methyl group or an organic group shown by Chemical Formula 3 above, p is 0 or 1 and X is an organic group shown by Chemical Formula 4 above, M 1 is a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent of an alkaline earth metal.
  • r is 0 or 1
  • M 2 is a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent alkaline earth metal, but the organic group shown in the formula 3 is Is a carboxyl group or a methylene carboxyl group.
  • AO is an oxyalkylene group having 2 to 4 carbon atoms
  • m is an integer of 1 to 10
  • R 3 is an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon.
  • an oxyethylene group, an oxypropylene group and an oxybutylene group may be mentioned, but an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. These may be one kind or two or more kinds.
  • m is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1 or 2.
  • R 3 is an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group, and the number of carbon atoms thereof is not particularly limited.
  • alkylene group which may have a hetero atom examples include methylene group, ethylene group, propylene group, butylene group, cyclohexyl group, oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group and the like.
  • aromatic ring group which may have a hetero atom phenylene group, tolylene group, naphthylene group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiazole, thiazole, etc. Can be mentioned.
  • examples of the unsaturated hydrocarbon group which may have a hetero atom include ethynyl group, propynyl group, butynyl group, and groups having a carbonyl group or an imino group before or after these groups, and organic compounds represented by the following chemical formula 6 Groups are preferred.
  • R 5 is an alkylene group having 1 to 22 carbon atoms which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group, u is an integer of 0 to 2, M 3 is a hydrogen atom, an organic ammonium group , An organic group, an alkali metal or a half equivalent of an alkaline earth metal.
  • R 5 is an alkylene group having 1 to 22 carbon atoms which may have a hetero atom, an aromatic group or an unsaturated hydrocarbon group, and an alkylene group which may have a hetero atom, an aromatic ring group or non-
  • the saturated hydrocarbon group is as described above for R 3 in Chemical formula 4, but among these, R 5 is one having 1 to 22 carbon atoms, preferably one having 1 to 6 carbon atoms.
  • M 1 , M 2 and M 3 are a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent alkaline earth metal. These may be one kind or two or more kinds.
  • the ammonium group include ammonium group, tetramethyl ammonium group, tetrabutyl ammonium group and the like.
  • the organic amine group alkylamine groups such as methylamine group, dimethylamine group, trimethylamine group and triethylamine group, alkanolamine groups such as diethanolamine group and triethanolamine group, and aromatic amine groups such as pyridinium group and rutidinium group Can be mentioned.
  • alkali metal lithium, sodium, potassium, cesium and the like can be mentioned.
  • alkaline earth metal calcium, magnesium, barium and the like can be mentioned. However, in the case of an alkaline earth metal, it is 1/2 equivalent.
  • the monomer A described above examples include 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid And the like, and also a condensation product of an unsaturated carboxylic acid ester having a hydroxyl group at an end such as hydroxyethyl (meth) acrylate, polyoxyethylene mono (meth) acrylic acid ester, and a 2- to 4-basic carboxylic acid anhydride Can be mentioned.
  • Such a condensate is obtained by the condensation of an unsaturated carboxylic acid ester having a hydroxyl group at an end with a 2 to 4 basic carboxylic acid anhydride.
  • unsaturated carboxylic acid esters that can be used for condensation include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyoxyalkylene mono (meth) acrylate, etc. It can be mentioned.
  • a 2- to 4-basic carboxylic acid anhydride which can be used for condensation
  • succinic acid anhydride maleic acid anhydride, trimellitic acid anhydride, cyclohexyl 1, 2 dicarboxylic acid anhydride, pyromellitic acid anhydride, etc.
  • the monomer A one or more of such condensates can be used, but a condensate of hydroxyethyl (meth) acrylate and a 2- to 4-basic carboxylic acid anhydride is preferred.
  • the above condensates can be obtained by known methods. For example, a method of heating and stirring an unsaturated carboxylic acid ester having a hydroxyl group at the end and a 2 to 4 basic carboxylic acid anhydride in the absence of a solvent, an unsaturated carboxylic acid having a hydroxyl group at the end in the presence of a solvent and a condensing agent There is a method of condensing an acid ester and a 2 to 4 basic carboxylic acid anhydride.
  • R 2 is a hydrogen atom, a methyl group or an organic group shown by chemical formula 3 above
  • Y is an organic group shown by chemical formula 5 above.
  • s is an integer of 0 to 4
  • t is 0 or 1
  • AO is an oxyalkylene group having 2 to 4 carbon atoms
  • n is an integer of 0 to 300
  • R 4 is a hydrogen atom, 1 to 22 carbon atoms It is an alkyl group or an aliphatic acyl group having 1 to 22 carbon atoms.
  • R 4 is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
  • R 4 in Chemical Formula 5 1) hydrogen atom, 2) methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, helicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, 2-methyl-pentyl group, 2- Ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2-pentyl-non
  • AO in Chemical Formula 5 is as described above for AO in Chemical formula 4, and n is an integer of 0 to 300, and as (AO) n, 0 to 160 oxyethylene units and / or oxypropylene A (poly) oxyalkylene group composed of units is preferred.
  • the monomer B described above include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, methacrylate Butyl, ⁇ -allyl- ⁇ -acetyl- (poly) oxyethylene, ⁇ -allyl- ⁇ -acetyl- (poly) oxyethylene (poly) oxypropylene, ⁇ -allyl- ⁇ -hydroxy- (poly) oxyethylene, ⁇ -Allyl- ⁇ -hydroxy- (poly) oxyethylene (poly) oxypropylene, ⁇ -methallyl- ⁇ -hydroxy- (poly) oxyethylene, ⁇ -methallyl- ⁇ -methoxy- (poly) oxyethylene, ⁇ -methallyl- ⁇ -hydroxy- (po I) Oxyethylene (poly)
  • the monomer B shown in Chemical formula 2 one or two or more kinds can be used, but it is preferable to use two or more, and in particular, when n in the chemical formula 5 is 0 to 8, a single amount Those containing two types of monomer B when n in the compound B and compound 9 is 9 to 160 are preferable, and more specifically, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Preferably contain one or more monomer B selected from methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate and another monomer B .
  • the vinyl copolymer Q is obtained by copolymerizing another monomer C copolymerizable therewith, in addition to the monomer A and the monomer B described above.
  • monomer C 1, allyl sulfonic acid, methallyl sulfonic acid, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, amine salts etc.
  • acrylic acid monomers such as maleic acid, fumaric acid, itaconic acid and citraconic acid, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters, anhydrides, etc.
  • the proportion of the monomer A in the total monomers used is preferably 1 to 99 mol%, more preferably 50 to 90 mol%.
  • the proportion of the monomer B is preferably 1 to 99% by mole, and more preferably 1 to 55% by mole.
  • the proportion of the other monomer C is preferably 50 mol% or less, more preferably 25 mol% or less, and particularly preferably 10 mol% or less.
  • the mass average molecular weight of the vinyl copolymers P and Q is preferably 8,000 to 200,000, more preferably 9,000 to 150,000, and particularly preferably 10,000 to 100,000.
  • the mass average molecular weight is a value in terms of polyethylene glycol calculated by gel permeation chromatography (hereinafter referred to as GPC).
  • the vinyl copolymers P and Q to be provided for the dispersion holding agent of the present invention can be obtained by known methods.
  • examples thereof include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, radical polymerization using no solvent, and the like.
  • radical polymerization initiators for use in such radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, and azo compounds such as azobisisobutyronitrile at a polymerization reaction temperature. Those which decompose and generate radicals, and optionally include redox initiators which use reducing agents together.
  • a chain transfer agent can also be used to bring the mass average molecular weight of the resulting vinyl copolymer into the desired range.
  • the chain transfer agent is not particularly limited as long as it can adjust the molecular weight of the vinyl copolymer, and known chain transfer agents can be used.
  • the vinyl copolymers P and Q can also be obtained by anionic polymerization or cationic polymerization in addition to the radical polymerization described above, and as an initiator used for these polymerizations, alkali metals, butyl lithium, Grignard reagents, metals Examples thereof include alkoxides, Lewis acids such as boron trifluoride, and Bronsted acids such as sulfuric acid, but a method obtained by radical polymerization in a solvent-free or aqueous solvent is preferable.
  • the dispersion holding agent of the present invention is used as an admixture during preparation of a hydraulic composition such as mortar and concrete, and the slump loss of the mortar and concrete prepared using this is sufficiently prevented.
  • a hydraulic composition such as mortar and concrete
  • materials used for preparation of mortar and concrete there is no particular limitation on the materials used for preparation of mortar and concrete.
  • a binder 1) various portland cements such as ordinary portland cement, early strength portland cement, moderate heat portland cement, low heat portland cement, 2) blast furnace cement, Various mixed cements such as fly ash cement and silica fume cement, 3) alumina cement and the like can be mentioned.
  • the water / binder ratio is also not particularly limited, but the water / binder ratio is preferably 20 to 70%, more preferably 35 to 65%.
  • the type of other dispersants used for preparation of mortar and concrete is not particularly limited, but the dispersant to be used in combination is selected from oxycarboxylic acids and salts thereof, polycarboxylic acids and aromatic sulfonic acids. One or two or more are preferable.
  • additives such as an AE agent, an antifoaming agent, a setting retarder, a hardening accelerator, a shrinkage reducing agent, and a thickener can also be used.
  • the amount of the dispersion holding agent used in the present invention is not particularly limited, but it is usually 0.005 to 1.0 parts by mass, preferably 0.005 to 1.0 parts by mass in terms of solid content per 100 parts by mass of the binder. The amount is 0.5 parts by mass, more preferably 0.01 to 0.5 parts by mass.
  • dispersion holding agent of the present invention According to the dispersion holding agent of the present invention, slump loss of the hydraulic composition can be sufficiently prevented.
  • the dispersion holding agent of the present invention is used in combination with a water-soluble vinyl copolymer as described above, which has been conventionally proposed as a dispersant for hydraulic compositions, both effects combine, and temporally in hydraulic compositions as well. It can provide excellent liquidity.
  • Test Category 1 Synthesis of Monomer A
  • monomer (A-5) 127.7 g of hydroxyethyl acrylate, 192.1 g of trimellitic anhydride, 0.64 g of 4-methoxyphenol, and 300 mL of pyridine were equipped with a thermometer, a stirrer, and an air introduction tube
  • the reaction vessel was charged and dissolved uniformly with stirring, and then heated while raising dry air at a flow rate of 5 mL / min, and reacted at a temperature of 80 ° C. for 8 hours.
  • pyridine was distilled off with an evaporator to obtain a monoester (A-5) of hydroxyethyl acrylate and trimellitic acid.
  • Test Category 2 (Synthesis of Vinyl Copolymer)
  • EX-1 vinyl copolymer
  • a reaction vessel similar to that of Example 1 2.3 g of acid was charged, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was adjusted to 70 ° C. with a hot water bath. The reaction was initiated by adding an aqueous solution of 28.0 g of 3.0% sodium persulfate.
  • each of the vinyl copolymers synthesized as described above is summarized in Table 1.
  • a solution is adjusted so that it may become 5% with heavy water, it measures by NMR of 300 MHz, and each monomer polymerizes. I confirmed that it was.
  • the mass mean molecular weight was shown by polyethylene glycol conversion by GPC.
  • A-1 2-acryloyloxyethylsuccinic acid
  • A-2 2-methacryloyloxyethylsuccinic acid
  • A-3 2-acryloyloxyethylhexahydrophthalic acid
  • A-4 2-acryloyloxyethyl phthalic acid
  • A-5 Monoester of hydroxyethyl acrylate and trimellitic acid
  • A-6 Monoester of hydroxypropyl acrylate and succinic acid
  • Oxyethylene M-2: ⁇ -methacryloyl- ⁇ -methoxy-poly (n 23)
  • M-5 ⁇ -methacrylo
  • Test category 3 Evaluation as dispersant for hydraulic composition
  • Vinyl copolymer (EX-1) synthesized by Takemoto Yushi Co., Ltd.
  • HP-11 Under the trade name Chupol HP-11 (hereinafter referred to as HP-11) 0.6 to 0.8% of ordinary portland cement, in the test category 2 0.1% to 0.3% of a 20% aqueous solution of (EX-9), (CE-1) and (CE-2) to ordinary Portland cement, and an AE agent (trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.)
  • HP-11 0.6 to 0.8% of ordinary portland cement
  • HP-11 0.6 to 0.8% of ordinary portland cement
  • EX-9 a 20% aqueous solution of (EX-9), (CE-1) and (CE-2) to ordinary Portland cement
  • AE agent trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.
  • Table 2 summarizes the unit amounts and the
  • Slump flow Measured according to JIS-A1150 immediately after mixing and at intervals of 30 minutes for each concrete that was allowed to stand. Air content: Immediately after mixing and at intervals of 30 minutes, the concrete which was allowed to stand was measured according to JIS-A1128. Compressive strength: In accordance with JIS-A1108, the sample size was 100 mm in diameter ⁇ 200 mm in height, and was measured at a material age of 24 hours. Bleeding rate: Measured in accordance with JIS-A1123.
  • the fluidity of the hydraulic composition can be held for a long time without causing curing delay.

Abstract

Provided is a dispersion-maintaining agent for a hydraulic composition capable of maintaining the fluidity of the hydraulic composition even when a long time has elapsed since kneading and with little curing delay. A vinyl copolymer obtained by copolymerizing a specific monomer having a carboxyl group in the molecule, a specific monomer having a polyalkylene glycol residue in the molecule, and, when necessary, another monomer copolymerizable with these monomers is used as the dispersion-maintaining agent for a hydraulic composition.

Description

水硬性組成物用分散保持剤Dispersion holding agent for hydraulic composition
　本発明は水硬性組成物用分散保持剤に関する。モルタルやコンクリート等の水硬性組成物の調製に各種の分散剤が広く用いられている。しかし、一般に分散剤を用いて水硬性組成物を調製すると、スランプロス（流動性の経時的低下）が大きく、作業性及び施工性が低下する。本発明はスランプロスを充分に防止できる水硬性組成物用分散保持剤に関する。 The present invention relates to a dispersion holding agent for hydraulic compositions. Various dispersants are widely used in the preparation of hydraulic compositions such as mortar and concrete. However, in general, when a hydraulic composition is prepared using a dispersant, slump loss (decrease in flowability with time) is large and workability and workability are reduced. The present invention relates to a dispersion holding agent for a hydraulic composition which can sufficiently prevent slump loss.
　従来、それ自体がスランプロス防止性能を有するものとして、水溶性ビニル共重合体から成る水硬性組成物用分散剤が提案されている（例えば特許文献１～４参照）。ところが、これら従来の提案では、調製した水硬性組成物のスランプロスを充分に防止できないという問題がある。そこで、水硬性組成物用分散剤にスランプロス防止剤を併用したものも提案されている（例えば特許文献５参照）。しかし、この従来提案でも、依然として調製した水硬性組成物のスランプロスを充分に防止できないという問題がある。 Heretofore, dispersants for hydraulic compositions comprising a water-soluble vinyl copolymer have been proposed as having slump loss prevention performance per se (see, for example, Patent Documents 1 to 4). However, these conventional proposals have a problem that the slump loss of the prepared hydraulic composition can not be sufficiently prevented. Then, what combined the slump loss prevention agent with the dispersing agent for hydraulic composition is also proposed (for example, refer patent document 5). However, even with this conventional proposal, there is still a problem that the slump loss of the prepared hydraulic composition can not be sufficiently prevented.
特開昭６３－２８５１４０号公報Japanese Patent Application Laid-Open No. 63-285140 特開平１－２２６７５７号公報Japanese Patent Application Laid-Open No. 1-226757 特開平１０－６７５４９号公報Japanese Patent Application Laid-Open No. 10-67549 特開２００３－３３５５６２号公報JP 2003-335562 特開２００３－３４５６５号公報Japanese Patent Application Publication No. 2003-34565
　本発明が解決しようとする課題は、混練から長時間経過した後でも、水硬性組成物の流動性を保つことができ、しかも硬化遅延の少ない水硬性組成物用分散保持剤を提供することにある。 The problem to be solved by the present invention is to provide a dispersion holding agent for a hydraulic composition, which can maintain the fluidity of the hydraulic composition even after a long time since kneading, and which is less delayed in curing. is there.
　しかして本発明者らは、前記の課題を解決するべく研究した結果、分子中にカルボキシル基を有する特定の単量体と、分子中にポリアルキレングリコール残基を有する特定の単量体と、更に必要な場合にはこれらの単量体と共重合可能な他の単量体とを共重合して得られるビニル共重合体が水硬性組成物用分散保持剤として正しく好適であることを見出した。 Therefore, as a result of researches to solve the above-mentioned problems, the present inventors found that a specific monomer having a carboxyl group in the molecule and a specific monomer having a polyalkylene glycol residue in the molecule. Furthermore, it has been found that vinyl copolymers obtained by copolymerizing these monomers with other monomers copolymerizable with these monomers are properly suitable as dispersion holding agents for hydraulic compositions, if necessary. The
　すなわち本発明は、下記の化１で示される単量体Ａと、下記の化２で示される単量体Ｂとから得られるビニル共重合体を含有することを特徴とする水硬性組成物用分散保持剤に係る。また本発明は、下記の化１で示される単量体Ａと、下記の化２で示される単量体Ｂと、これらの単量体と共重合可能な他の単量体Ｃとから得られるビニル共重合体を含有することを特徴とする水硬性組成物用分散保持剤に係る。 That is, the present invention comprises a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1 and a monomer B represented by the following chemical formula 2, for a hydraulic composition It relates to the dispersion holding agent. Further, the present invention is obtained from a monomer A represented by the following chemical formula 1, a monomer B represented by the following chemical formula 2, and another monomer C copolymerizable with these monomers. The present invention relates to a dispersion-retaining agent for a hydraulic composition, characterized by containing a vinyl copolymer as described above.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　化１及び化２において、
　Ｒ１，Ｒ２：水素原子、メチル基又は下記の化３で示される有機基
　ｐ：０又は１
　Ｘ：下記の化４で示される有機基
　Ｙ：下記の化５で示される有機基
　Ｍ１：水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属 In chemical formulas 1 and 2,
R 1 , R 2 : a hydrogen atom, a methyl group or an organic group p: 0 or 1 represented by the following chemical formula 3
X: organic group represented by the following chemical formula 4 Y: organic group represented by the following chemical formula 5 M 1 : hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent alkaline earth metal
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　化３において、ｒ：０又は１
　Ｍ２：水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属 In chemical formula 3, r: 0 or 1
M 2 : hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent of alkaline earth metal
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　化４において、
　ＡＯ：炭素数２～４のオキシアルキレン基
　ｍ：１～１０の整数
　Ｒ３：ヘテロ原子を有する場合のあるアルキレン基、芳香環基又は不飽和炭化水素基 In Formula 4,
AO: an oxyalkylene group having 2 to 4 carbon atoms m: an integer of 1 to 10 R 3 : an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　化５において、
　ｓ：０～４の整数
　ｔ：０または１
　ＡＯ：炭素数２～４のオキシアルキレン基
　ｎ：０～３００の整数
　Ｒ４：水素原子、炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基（但し、ｎ＝０のときはＲ４は炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基） In Formula 5,
s: integer from 0 to 4 t: 0 or 1
AO: an oxyalkylene group having a carbon number of 2 to 4 n: an integer of 0 to 300 R 4 : a hydrogen atom, an alkyl group having a carbon number of 1 to 22 or an aliphatic acyl group having a carbon number of 1 to 22 When R 4 is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms)
　本発明に係る水硬性組成物用分散保持剤（以下、本発明の分散保持剤という）には、前記の化１で示される単量体Ａと、前記の化２で示される単量体Ｂとから得られるビニル共重合体（以下、ビニル共重合体Ｐという）を含有するものと、かかる単量体Ａと、かかる単量体Ｂと、これらと共重合可能な他の単量体Ｃとから得られるビニル共重合体（以下、ビニル共重合体Ｑという）を含有するものとが含まれる。 The dispersion holding agent for a hydraulic composition according to the present invention (hereinafter referred to as the dispersion holding agent of the present invention) includes a monomer A shown in the above-mentioned chemical formula 1 and a monomer B shown in the above-mentioned chemical formula 2 And a monomer containing vinyl copolymer (hereinafter referred to as vinyl copolymer P), such monomer A, such monomer B, and other monomers C copolymerizable therewith. And those containing a vinyl copolymer (hereinafter referred to as vinyl copolymer Q) obtained from
　先ず、ビニル共重合体Ｐについて説明する。ビニル共重合体Ｐは、単量体Ａと、単量体Ｂとから得られるビニル共重合体であり、双方の割合等は特に制限されないが、全構成単位中に、単量体Ａ由来の構成単位を１～９９モル％及び単量体Ｂ由来の構成単位を１～９９モル％（合計１００モル％）の割合で有する質量平均分子量が８０００～２０００００のビニル共重合体が好ましい。 First, the vinyl copolymer P will be described. The vinyl copolymer P is a vinyl copolymer obtained from the monomer A and the monomer B, and the ratio of the both is not particularly limited. Preferred are vinyl copolymers having a weight average molecular weight of 8,000 to 200,000, having a ratio of 1 to 99 mol% of structural units and 1 to 99 mol% (total of 100 mol%) of structural units derived from monomer B.
　単量体Ａを示す前記の化１において、Ｒ１は水素原子、メチル基又は前記の化３で示される有機基、ｐは０または１、Ｘは前記の化４で示される有機基、Ｍ１は水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属である。化３において、ｒは０又は１、Ｍ２は水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属であるが、化３で示される有機基は、具体的にはカルボキシル基又はメチレンカルボキシル基である。 In the above Chemical Formula 1 showing monomer A, R 1 is a hydrogen atom, a methyl group or an organic group shown by Chemical Formula 3 above, p is 0 or 1 and X is an organic group shown by Chemical Formula 4 above, M 1 is a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent of an alkaline earth metal. In the formula 3, r is 0 or 1, and M 2 is a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent alkaline earth metal, but the organic group shown in the formula 3 is Is a carboxyl group or a methylene carboxyl group.
　また化４において、ＡＯは炭素数２～４のオキシアルキレン基、ｍは１～１０の整数、Ｒ３はヘテロ原子を有する場合のあるアルキレン基、芳香環基又は不飽和炭化水素である。 Further, in the chemical formula 4, AO is an oxyalkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 10, and R 3 is an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon.
　化４において、ＡＯのオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキシブチレン基が挙げられるが、オキシエチレン基、オキシプロピレン基が好ましく、オキシエチレン基がより好ましい。これらは、１種であっても、２種以上であってもよい。ｍは１～１０の整数であるが、１～５の整数が好ましく、１又は２がより好ましい。Ｒ３はヘテロ原子を有する場合のあるアルキレン基、芳香環基又は不飽和炭化水素基であり、これらの炭素数に特に制限はない。ヘテロ原子を有する場合のあるアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、シクロヘキシル基、オキシメチレン基、オキシエチレン基、オキシプロピレン基、オキシブチレン基等が挙げられる。またヘテロ原子を有する場合のある芳香環基としては、フェニレン基、トリレン基、ナフチレン基、チオフェン、フラン、ピロール、ベンゾチオフェン、ベンゾフラン、ベンゾピロール、トリアジン、イミダゾール、ベンゾイミダゾール、トリアゾール、チアジアゾール、チアゾール等が挙げられる。更にヘテロ原子を有する場合のある不飽和炭化水素基としては、エチニル基、プロピニル基、ブチニル基、これらの前後にカルボニル基やイミノ基を有する基が挙げられるが、下記の化６で示される有機基が好ましい。 In Chemical formula 4, as the oxyalkylene group of AO, an oxyethylene group, an oxypropylene group and an oxybutylene group may be mentioned, but an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. These may be one kind or two or more kinds. m is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1 or 2. R 3 is an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group, and the number of carbon atoms thereof is not particularly limited. Examples of the alkylene group which may have a hetero atom include methylene group, ethylene group, propylene group, butylene group, cyclohexyl group, oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group and the like. Moreover, as an aromatic ring group which may have a hetero atom, phenylene group, tolylene group, naphthylene group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiazole, thiazole, etc. Can be mentioned. Furthermore, examples of the unsaturated hydrocarbon group which may have a hetero atom include ethynyl group, propynyl group, butynyl group, and groups having a carbonyl group or an imino group before or after these groups, and organic compounds represented by the following chemical formula 6 Groups are preferred.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　化６において、Ｒ５はヘテロ原子を有する場合のある炭素数１～２２のアルキレン基、芳香環基又は不飽和炭化水素基、ｕは０～２の整数、Ｍ３は水素原子、有機アンモニウム基、有機基、アルカリ金属又は１／２当量のアルカリ土類金属である。 In Formula 6, R 5 is an alkylene group having 1 to 22 carbon atoms which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group, u is an integer of 0 to 2, M 3 is a hydrogen atom, an organic ammonium group , An organic group, an alkali metal or a half equivalent of an alkaline earth metal.
　化６において、Ｒ５はヘテロ原子を有する場合のある炭素数１～２２のアルキレン基、芳香族基又は不飽和炭化水素基であり、ヘテロ原子を有する場合のあるアルキレン基、芳香環基又は不飽和炭化水素基については化４のＲ３について前記した通りであるが、Ｒ５は、これらのうちで炭素数１～２２のものであり、好ましくは炭素数１～６のものである。 In Formula 6, R 5 is an alkylene group having 1 to 22 carbon atoms which may have a hetero atom, an aromatic group or an unsaturated hydrocarbon group, and an alkylene group which may have a hetero atom, an aromatic ring group or non- The saturated hydrocarbon group is as described above for R 3 in Chemical formula 4, but among these, R 5 is one having 1 to 22 carbon atoms, preferably one having 1 to 6 carbon atoms.
　化１、化３、化６において、Ｍ１、Ｍ２、Ｍ３は水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属である。これらは１種であっても、２種以上であってもよい。アンモニウム基としては、アンモニウム基、テトラメチルアンモニウム基、テトラブチルアンモニウム基等が挙げられる。また有機アミン基としては、メチルアミン基、ジメチルアミン基、トリメチルアミン基、トリエチルアミン基等のアルキルアミン基、ジエタノールアミン基、トリエタノールアミン基等のアルカノールアミン基、ピリジニウム基、ルチジニウム基等の芳香族アミン基が挙げられる。更にアルカリ金属としては、リチウム、ナトリウム、カリウム、セシウム等が挙げられる。そしてアルカリ土類金属としては、カルシウム、マグネシウム、バリウム等が挙げられる。但し、アルカリ土類金属の場合は１／２当量である。 In the formulas (1), (2) and (3), M 1 , M 2 and M 3 are a hydrogen atom, an ammonium group, an organic amine group, an alkali metal or a half equivalent alkaline earth metal. These may be one kind or two or more kinds. Examples of the ammonium group include ammonium group, tetramethyl ammonium group, tetrabutyl ammonium group and the like. As the organic amine group, alkylamine groups such as methylamine group, dimethylamine group, trimethylamine group and triethylamine group, alkanolamine groups such as diethanolamine group and triethanolamine group, and aromatic amine groups such as pyridinium group and rutidinium group Can be mentioned. Further, as the alkali metal, lithium, sodium, potassium, cesium and the like can be mentioned. And, as the alkaline earth metal, calcium, magnesium, barium and the like can be mentioned. However, in the case of an alkaline earth metal, it is 1/2 equivalent.
　以上説明した単量体Ａの具体例としては、２－アクリロイロキシエチルコハク酸、２－メタクリロイロキシエチルコハク酸、２－アクリロイロキシエチルヘキサヒドロフタル酸、２－アクリロイロキシエチルフタル酸等が挙げられ、またヒドロキシエチル（メタ）アクリレート、ポリオキシエチレンモノ（メタ）アクリル酸エステル等の末端に水酸基を有する不飽和カルボン酸エステルと、２～４塩基性カルボン酸無水物との縮合物が挙げられる。かかる縮合物は、末端に水酸基を有する不飽和カルボン酸エステルと２～４塩基性カルボン酸無水物との縮合により得られる。縮合に用いることができる不飽和カルボン酸エステルとしては、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、ポリオキシアルキレンモノ（メタ）アクリル酸エステル等が挙げられる。また縮合に用いることができる２～４塩基性カルボン酸無水物としては、コハク酸無水物、マレイン酸無水物、トリメリット酸無水物、シクロヘキシル１，２ジカルボン酸無水物、ピロメリット酸無水物等が挙げられる。単量体Ａとしては、かかる縮合物の１種又は２種以上を用いることができるが、ヒドロキシエチル（メタ）アクリレートと２～４塩基性カルボン酸無水物との縮合物が好ましい。 Specific examples of the monomer A described above include 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid And the like, and also a condensation product of an unsaturated carboxylic acid ester having a hydroxyl group at an end such as hydroxyethyl (meth) acrylate, polyoxyethylene mono (meth) acrylic acid ester, and a 2- to 4-basic carboxylic acid anhydride Can be mentioned. Such a condensate is obtained by the condensation of an unsaturated carboxylic acid ester having a hydroxyl group at an end with a 2 to 4 basic carboxylic acid anhydride. Examples of unsaturated carboxylic acid esters that can be used for condensation include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyoxyalkylene mono (meth) acrylate, etc. It can be mentioned. Moreover, as a 2- to 4-basic carboxylic acid anhydride which can be used for condensation, succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, cyclohexyl 1, 2 dicarboxylic acid anhydride, pyromellitic acid anhydride, etc. Can be mentioned. As the monomer A, one or more of such condensates can be used, but a condensate of hydroxyethyl (meth) acrylate and a 2- to 4-basic carboxylic acid anhydride is preferred.
　前記の縮合物は公知の方法で得ることができる。これには例えば、無溶媒下で末端に水酸基を有する不飽和カルボン酸エステルと２～４塩基性カルボン酸無水物を加熱撹拌する方法、溶媒及び縮合剤存在下で末端に水酸基を有する不飽和カルボン酸エステルと２～４塩基性カルボン酸無水物を縮合させる方法等がある。 The above condensates can be obtained by known methods. For example, a method of heating and stirring an unsaturated carboxylic acid ester having a hydroxyl group at the end and a 2 to 4 basic carboxylic acid anhydride in the absence of a solvent, an unsaturated carboxylic acid having a hydroxyl group at the end in the presence of a solvent and a condensing agent There is a method of condensing an acid ester and a 2 to 4 basic carboxylic acid anhydride.
　単量体Ｂを示す前記の化２において、Ｒ２は水素原子、メチル基又は前記の化３で示される有機基、Ｙは前記の化５で示される有機基である。化５において、ｓは０～４の整数、ｔは０または１、ＡＯは炭素数２～４のオキシアルキレン基、ｎは０～３００の整数、Ｒ４は水素原子、炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基である。但し、ｎ＝０のときはＲ４は炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基である。 In the above-mentioned chemical formula 2 showing monomer B, R 2 is a hydrogen atom, a methyl group or an organic group shown by chemical formula 3 above, and Y is an organic group shown by chemical formula 5 above. In the chemical formula 5, s is an integer of 0 to 4, t is 0 or 1, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 300, R 4 is a hydrogen atom, 1 to 22 carbon atoms It is an alkyl group or an aliphatic acyl group having 1 to 22 carbon atoms. However, when n = 0, R 4 is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
　化５中のＲ４としては、１）水素原子、２）メチル基、エチル基、ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基、ヘンエイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、２－メチル－ペンチル基、２－エチル－ヘキシル基、２－プロピル－ヘプチル基、２－ブチル－オクチル基、２－ペンチル－ノニル基、２－ヘキシル－デシル基、２－ヘプチル－ウンデシル基、２－オクチル－ドデシル基、２－ノニル－トリデシル基、２－デシル－テトラデシル基、２－ウンデシル－ペンタデシル基、２－ドデシル－ヘキサデシル基等の炭素数１～２２のアルキル基、３）ホルミル基、アセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、エイコセノイル基、オクタデセノイル基等の炭素数１～２２の脂肪族アシル基が挙げられる。なかでもＲ４としては、水素原子、炭素数１～４のアルキル基、炭素数１～４の脂肪族アシル基が好ましい。 As R 4 in Chemical Formula 5, 1) hydrogen atom, 2) methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, helicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, 2-methyl-pentyl group, 2- Ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2-pentyl-nonyl group, 2-hexyl-decyl group, 2-heptyl-undecyl group, 2-octyl-dodecyl group, 2-nonyl group -Tridecyl, 2-decyl-tetradecyl, 2-undecyl-pentadecyl Group, alkyl group having 1 to 22 carbon atoms such as 2-dodecyl-hexadecyl group, 3) formyl group, acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadeca Examples thereof include aliphatic acyl groups having 1 to 22 carbon atoms such as noyl group, octadecanoyl group, hexadecenoyl group, eicosenoyl group and octadecenoyl group. Among them, as R 4 , a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aliphatic acyl group having 1 to 4 carbon atoms are preferable.
　化５中のＡＯについては化４中のＡＯについて前記した通りであり、ｎは０～３００の整数であるが、（ＡＯ）ｎとしては、０～１６０個のオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基が好ましい。 AO in Chemical Formula 5 is as described above for AO in Chemical formula 4, and n is an integer of 0 to 300, and as (AO) n, 0 to 160 oxyethylene units and / or oxypropylene A (poly) oxyalkylene group composed of units is preferred.
　以上説明した単量体Ｂの具体例としては、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、アクリル酸メチルメタクリル酸メチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ブチル、メタクリル酸ブチル、α－アリル－ω－アセチル－（ポリ）オキシエチレン、α－アリル－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタリル－ω－メトキシ－（ポリ）オキシエチレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、－メタリル－ω－アセチル－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ブトキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－（３－メチル－３－ブテニル）－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン等が挙げられる。 Specific examples of the monomer B described above include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, methacrylate Butyl, α-allyl-ω-acetyl- (poly) oxyethylene, α-allyl-ω-acetyl- (poly) oxyethylene (poly) oxypropylene, α-allyl-ω-hydroxy- (poly) oxyethylene, α -Allyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methallyl-ω-hydroxy- (poly) oxyethylene, α-methallyl-ω-methoxy- (poly) oxyethylene, α-methallyl- ω-hydroxy- (po I) Oxyethylene (poly) oxypropylene, -methallyl-ω-acetyl- (poly) oxyethylene, α- (3-methyl-3-butenyl) -ω-hydroxy- (poly) oxyethylene, α- (3-) Methyl-3-butenyl) -ω-butoxy- (poly) oxyethylene, α- (3-methyl-3-butenyl) -ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α- (3-methyl -3-butenyl) -ω-acetyl- (poly) oxyethylene (poly) oxypropylene, α-acryloyl-ω-hydroxy- (poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene, α -Acryloyl-ω-butoxy- (poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) oxypropyle Ren, α-methacryloyl-ω-hydroxy- (poly) oxyethylene, α-methacryloyl-ω-methoxy- (poly) oxyethylene, α-methacryloyl-ω-butoxy- (poly) oxyethylene, α-acryloyl-ω- Methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-acetyl- (poly) oxyethylene (poly) oxypropylene Etc.
　化２で示される単量体Ｂとしては、１種又は２種以上を用いることができるが、２種以上を用いるのが好ましく、なかでも化５中のｎが０～８の場合の単量体Ｂと化５中のｎが９～１６０の場合の単量体Ｂとの２種を含むものが好ましく、より具体的には、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、アクリル酸メチル、メタクリル酸メチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ブチル、メタクリル酸ブチルから選ばれる１種又は２種以上の単量体Ｂと他の単量体Ｂを含むものが好ましい。 As the monomer B shown in Chemical formula 2, one or two or more kinds can be used, but it is preferable to use two or more, and in particular, when n in the chemical formula 5 is 0 to 8, a single amount Those containing two types of monomer B when n in the compound B and compound 9 is 9 to 160 are preferable, and more specifically, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Preferably contain one or more monomer B selected from methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate and another monomer B .
　次に、ビニル共重合体Ｑについて説明する。ビニル共重合体Ｑは、前記した単量体Ａ及び単量体Ｂの他に、これらと共重合可能な他の単量体Ｃを共重合させたものである。かかる他の単量体Ｃとしては、１）アリルスルホン酸、メタリルスルホン酸、これらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩等、２）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、シトラコン酸等のアクリル酸系単量体、これらのアルカリ金属塩、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、無水物等、３）（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等が挙げられる。なかでも、他の単量体Ｃとしては、アクリル酸系単量体が好ましい。 Next, the vinyl copolymer Q will be described. The vinyl copolymer Q is obtained by copolymerizing another monomer C copolymerizable therewith, in addition to the monomer A and the monomer B described above. As such other monomer C, 1) allyl sulfonic acid, methallyl sulfonic acid, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, amine salts etc., 2) acrylic acid, methacrylic acid, crotonic acid And acrylic acid monomers such as maleic acid, fumaric acid, itaconic acid and citraconic acid, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters, anhydrides, etc. 3 ) (Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamido-2-metasulfonic acid, 2- (meth) acrylamido-2-ethanesulfonic acid, 2 And (meth) acrylamido-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. Among them, as another monomer C, an acrylic acid type monomer is preferable.
　ビニル共重合体Ｐ及びＱにおいて、用いる全単量体中、単量体Ａの割合は１～９９モル％とするのが好ましく、５０～９０モル％とするのがより好ましい。また単量体Ｂの割合は１～９９モル％とするのが好ましく、１～５５モル％とするのがより好ましい。更に他の単量体Ｃの割合は、５０モル％以下とするのが好ましく、２５モル％以下とするのがより好ましく、１０モル％以下とするのが特に好ましい。 In the vinyl copolymers P and Q, the proportion of the monomer A in the total monomers used is preferably 1 to 99 mol%, more preferably 50 to 90 mol%. The proportion of the monomer B is preferably 1 to 99% by mole, and more preferably 1 to 55% by mole. Furthermore, the proportion of the other monomer C is preferably 50 mol% or less, more preferably 25 mol% or less, and particularly preferably 10 mol% or less.
　ビニル共重合体Ｐ及びＱの質量平均分子量は、８０００～２０００００のものが好ましく、９０００～１５００００のものがより好ましく、１００００～１０００００のものが特に好ましい。尚、本発明において質量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下ＧＰＣという）によるポリエチレングリコール換算の値である。 The mass average molecular weight of the vinyl copolymers P and Q is preferably 8,000 to 200,000, more preferably 9,000 to 150,000, and particularly preferably 10,000 to 100,000. In the present invention, the mass average molecular weight is a value in terms of polyethylene glycol calculated by gel permeation chromatography (hereinafter referred to as GPC).
　本発明の分散保持剤に供するビニル共重合体Ｐ及びＱは、公知の方法で得ることができる。これには例えば、溶媒として水を用いたラジカル重合、溶媒として有機溶媒を用いたラジカル重合、溶媒を用いないラジカル重合等が挙げられる。かかるラジカル重合に用いるラジカル重合開始剤としては、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過酸化物、アゾビスイソブチロニトリル等のアゾ化合物のように、重合反応温度下において分解し、ラジカル発生するものが挙げられ、また適宜還元剤を一緒に用いたレドックス開始剤が挙げられる。得られるビニル共重合体の質量平均分子量を所望の範囲のものとするため、連鎖移動剤を用いることもできる。かかる連鎖移動剤としては、ビニル共重合体の分子量の調整ができるものであれば特に制限されず、公知の連鎖移動剤が使用できる。具体的には、１）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、メルカプトプロピオン酸、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、２－メルカプトエタンスルホン酸、ｎ－ドデシルメルカプタン、オクチルメルカプタン、ブチルチオグリコレート等のチオール系連鎖移動剤、２）四塩化炭素、四臭化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等のハロゲン化物、３）α－メチルスチレンダイマー、α－テルピネン、γ－テルピネン、ジペンテン、ターピノーレン等の不飽和炭化水素化合物、４）２－アミノプロパン－１－オール等の１級アルコールやイソプロパノール等の第２級アルコール、５）亜リン酸、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム等や、亜硫酸、亜硫酸水素、亜二チオン酸、メタ重亜硫酸、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、亜二チオン酸ナトリウム、亜二チオン酸カリウム、メタ重亜硫酸ナトリウム、メタ重亜硫酸カリウム等の低級酸化物やその塩等が挙げられる。ビニル共重合体Ｐ及びＱは、以上説明したラジカル重合の他に、アニオン重合やカチオン重合によっても得ることができ、これらの重合に用いる開始剤としては、アルカリ金属、ブチルリチウム、グリニャール試薬、金属アルコキシド、三フッ化ホウ素等のルイス酸、硫酸等のブレンステッド酸等が挙げられるが、無溶媒又は水溶媒中でのラジカル重合により得る方法が好ましい。 The vinyl copolymers P and Q to be provided for the dispersion holding agent of the present invention can be obtained by known methods. Examples thereof include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, radical polymerization using no solvent, and the like. Such radical polymerization initiators for use in such radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, and azo compounds such as azobisisobutyronitrile at a polymerization reaction temperature. Those which decompose and generate radicals, and optionally include redox initiators which use reducing agents together. A chain transfer agent can also be used to bring the mass average molecular weight of the resulting vinyl copolymer into the desired range. The chain transfer agent is not particularly limited as long as it can adjust the molecular weight of the vinyl copolymer, and known chain transfer agents can be used. Specifically, 1) mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycollate, octyl 3-mercaptopropionate, 2- Thiol-based chain transfer agents such as mercaptoethane sulfonic acid, n-dodecyl mercaptan, octyl mercaptan and butyl thioglycolate 2) Carbon tetrachloride, carbon tetrabromide, halides such as methylene chloride, bromoform and bromotrichloroethane 3) unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, γ-terpinene, dipentene and terpinorene 4) primary alcohols such as 2-aminopropan-1-ol secondary alcohols such as isopropanol 5 ) Acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, etc., sulfite, hydrogen sulfite, dithionite, metabisulfite, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, Examples thereof include lower oxides such as sodium dithionite, potassium dithionite, sodium metabisulfite and potassium metabisulfite and salts thereof. The vinyl copolymers P and Q can also be obtained by anionic polymerization or cationic polymerization in addition to the radical polymerization described above, and as an initiator used for these polymerizations, alkali metals, butyl lithium, Grignard reagents, metals Examples thereof include alkoxides, Lewis acids such as boron trifluoride, and Bronsted acids such as sulfuric acid, but a method obtained by radical polymerization in a solvent-free or aqueous solvent is preferable.
　本発明の分散保持剤は、水硬性組成物、例えばモルタルやコンクリートの調製時に混和剤として使用するものであり、これを用いて調製したモルタルやコンクリートのスランプロスを充分に防止する。モルタルやコンクリートの調製に用いる材料に特に制限はなく、例えば結合材としては、１）普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント等の各種ポルトランドセメント、２）高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメント、３）アルミナセメント等が挙げられる。また水／結合材比も特に制限はないが、水／結合材比は２０～７０％のものが好ましく、３５～６５％のものがより好ましい。更にモルタルやコンクリートの調製に用いる他の分散剤の種類にも特に制限はないが、併用する分散剤としてはオキシカルボン酸やその塩、ポリカルボン酸系や芳香族スルホン酸系のものから選ばれる一つ又は二つ以上が好ましい。モルタルやコンクリートの調整にはＡＥ剤、消泡剤、凝結遅延剤、硬化促進剤、収縮低減剤、増粘剤等の添加剤を用いることもできる。本発明の分散保持剤の使用量は、これも特に制限はないが、結合材１００質量部に対し、固形分換算で、通常は０．００５～１．０質量部、好ましくは０．００５～０．５質量部、より好ましくは０．０１～０．５質量部とする。 The dispersion holding agent of the present invention is used as an admixture during preparation of a hydraulic composition such as mortar and concrete, and the slump loss of the mortar and concrete prepared using this is sufficiently prevented. There is no particular limitation on the materials used for preparation of mortar and concrete. For example, as a binder, 1) various portland cements such as ordinary portland cement, early strength portland cement, moderate heat portland cement, low heat portland cement, 2) blast furnace cement, Various mixed cements such as fly ash cement and silica fume cement, 3) alumina cement and the like can be mentioned. The water / binder ratio is also not particularly limited, but the water / binder ratio is preferably 20 to 70%, more preferably 35 to 65%. Further, the type of other dispersants used for preparation of mortar and concrete is not particularly limited, but the dispersant to be used in combination is selected from oxycarboxylic acids and salts thereof, polycarboxylic acids and aromatic sulfonic acids. One or two or more are preferable. In the preparation of mortar and concrete, additives such as an AE agent, an antifoaming agent, a setting retarder, a hardening accelerator, a shrinkage reducing agent, and a thickener can also be used. The amount of the dispersion holding agent used in the present invention is not particularly limited, but it is usually 0.005 to 1.0 parts by mass, preferably 0.005 to 1.0 parts by mass in terms of solid content per 100 parts by mass of the binder. The amount is 0.5 parts by mass, more preferably 0.01 to 0.5 parts by mass.
　本発明の分散保持剤によると、水硬性組成物のスランプロスを充分に防止できる。本発明の分散保持剤を、水硬性組成物用分散剤として従来提案されている前記したような水溶性ビニル共重合体と併用すると、双方の効果が相まって、水硬性組成物に経時的にも優れた流動性を付与できる。 According to the dispersion holding agent of the present invention, slump loss of the hydraulic composition can be sufficiently prevented. When the dispersion holding agent of the present invention is used in combination with a water-soluble vinyl copolymer as described above, which has been conventionally proposed as a dispersant for hydraulic compositions, both effects combine, and temporally in hydraulic compositions as well. It can provide excellent liquidity.
　以下、本発明の構成をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。なお、以下の実施例等において、別に記載しない限り、％は質量％を、また部は質量部を意味する。 Hereinafter, examples and the like will be described in order to make the configuration of the present invention more specifically, but the present invention is not limited to the examples. In the following Examples etc., unless otherwise indicated,% means mass%, and a part means mass part.
　試験区分１（単量体Ａの合成）
　・単量体（Ａ－５）の合成
　ヒドロキシエチルアクリレート１２７．７ｇ、トリメリット酸無水物１９２．１ｇ、４－メトキシフェノール０．６４ｇ、ピリジン３００ｍＬを温度計、撹拌機、空気導入管を備えた反応容器に仕込み、撹拌しながら均一に溶解した後、乾燥した空気を５ｍＬ／分の流量で吹き込みながら、昇温し、８０℃の温度で、８時間反応させた。反応終了後、エバポレーターにてピリジンを留去し、ヒドロキシエチルアクリレートとトリメリット酸のモノエステル体（Ａ－５）を得た。 Test Category 1 (Synthesis of Monomer A)
Synthesis of monomer (A-5) 127.7 g of hydroxyethyl acrylate, 192.1 g of trimellitic anhydride, 0.64 g of 4-methoxyphenol, and 300 mL of pyridine were equipped with a thermometer, a stirrer, and an air introduction tube The reaction vessel was charged and dissolved uniformly with stirring, and then heated while raising dry air at a flow rate of 5 mL / min, and reacted at a temperature of 80 ° C. for 8 hours. After completion of the reaction, pyridine was distilled off with an evaporator to obtain a monoester (A-5) of hydroxyethyl acrylate and trimellitic acid.
　・単量体（Ａ－６）の合成
　ヒドロキシプロピルアクリレート１３０．１ｇ、コハク酸無水物１１０．１ｇ、フェノチアジン０．１３ｇを温度計、撹拌機、空気導入管を備えた反応容器に仕込み、乾燥した空気を３ｍＬ／分の流量で吹き込みながら昇温し、１００℃で１０時間反応させた。反応終了後、冷却し、ヒドロキシプロピルアクリレートとコハク酸のモノエステル体（Ａ－６）を得た。 Synthesis of Monomer (A-6) 130.1 g of hydroxypropyl acrylate, 110.1 g of succinic anhydride and 0.13 g of phenothiazine were charged in a reaction vessel equipped with a thermometer, a stirrer and an air introduction tube and dried The temperature was raised while blowing air at a flow rate of 3 mL / min, and the reaction was allowed to proceed at 100 ° C. for 10 hours. After completion of the reaction, the reaction solution was cooled to obtain a monoester form (A-6) of hydroxypropyl acrylate and succinic acid.
　試験区分２（ビニル共重合体の合成）
　・実施例１｛ビニル共重合体（ＥＸ－１）の合成等｝
　イオン交換水２９．２ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５３）オキシエチレン１７４．２ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。次に３．５％過酸化水素水１０．８ｇを３時間かけて滴下すると共に、イオン交換水１７４．２ｇに２－アクリロイロキシエチルコハク酸１５．２ｇとヒドロキシエチルアクリレート２８．３ｇを懸濁させた水溶液を３時間かけて滴下し、またイオン交換７．３ｇにＬ－アスコルビン酸１．０ｇとメルカプトエタノール０．８ｇを溶解させた水溶液を４時間かけて滴下した。その後、２時間６５℃を維持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整すると共に、イオン交換水にて濃度を４０％に調整して反応物の水性液を得た。この反応物をビニル共重合体（ＥＸ－１）とした。 Test Category 2 (Synthesis of Vinyl Copolymer)
Example 1 {Synthesis of vinyl copolymer (EX-1), etc.}
29.2 g of ion-exchanged water, 174.2 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene were equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube After charging into a reaction vessel and dissolving uniformly while stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was brought to 65 ° C. with a warm water bath. Next, 10.8 g of 3.5% hydrogen peroxide water is dropped over 3 hours, and 15.2 g of 2-acryloyloxyethyl succinic acid and 28.3 g of hydroxyethyl acrylate are suspended in 174.2 g of ion-exchanged water. The resulting aqueous solution was dropped over 3 hours, and an aqueous solution in which 1.0 g of L-ascorbic acid and 0.8 g of mercaptoethanol were dissolved in 7.3 g of ion exchange was dropped over 4 hours. Thereafter, the temperature was maintained at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain an aqueous liquid of a reaction product. This reaction product was designated as vinyl copolymer (EX-1).
　・実施例２｛ビニル共重合体（ＥＸ－２）の合成｝
　イオン交換水２０６．５ｇ、α－メタクリロイル－ω－メトキシ－ポリ（ｎ＝２３）オキシエチレン　１５１．７ｇ、２－メタクリロイロキシエチルコハク酸２３．３ｇとヒドロキシエチルアクリレート１９．４ｇ、３－メルカプトプロピオン酸２．３ｇを実施例１と同様の反応容器に仕込み、攪拌しながら雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃とした。３．０％過硫酸ナトリウム２８．０ｇ水溶液を加え反応を開始した。反応を開始してから３時間後、３．０％過硫酸ナトリウム６．８ｇ水溶液を加え、３時間７０℃を保持し、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整すると共に、イオン交換水にて濃度を４０％に調整して反応物の水性液を得た。この反応物をビニル共重合体（ＥＸ－２）とした。 Example 2 {Synthesis of Vinyl Copolymer (EX-2)}
206.5 g of ion-exchanged water, 151.7 g of α-methacryloyl-ω-methoxy-poly (n = 23) oxyethylene, 23.3 g of 2-methacryloyloxyethyl succinic acid and 19.4 g of hydroxyethyl acrylate, 3-mercaptopropion In a reaction vessel similar to that of Example 1, 2.3 g of acid was charged, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was adjusted to 70 ° C. with a hot water bath. The reaction was initiated by adding an aqueous solution of 28.0 g of 3.0% sodium persulfate. Three hours after initiation of the reaction, an aqueous solution of 6.8 g of 3.0% sodium persulfate was added, and the temperature was maintained at 70 ° C. for 3 hours to complete the polymerization reaction. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain an aqueous solution of a reaction product. The reaction product was used as a vinyl copolymer (EX-2).
　・実施例３｛ビニル共重合体（ＥＸ－３）の合成｝
　イオン交換水２７．９ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５３）オキシエチレン１７３．０ｇを実施例１と同様の反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。次に３．５％過酸化水素水１０．８ｇを３時間かけて滴下すると共に、イオン交換水１７３．０ｇに２－アクリロイロキシエチルコハク酸４３．２ｇを懸濁させた水溶液を３時間かけて滴下し、またイオン交換６．１ｇにＬ－アスコルビン酸０．９ｇと３―メルカプトプロピオン酸０．７ｇを溶解させた水溶液を４時間かけて滴下した。その後、２時間６５℃を維持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整すると共に、イオン交換水にて濃度を４０％に調整して反応物の水性液を得た。この反応物をビニル共重合体（ＥＸ－３）とした。 Example 3 {Synthesis of Vinyl Copolymer (EX-3)}
27.9 g of ion-exchanged water and 173.0 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene were charged in the same reaction vessel as in Example 1 and homogenized while stirring. The atmosphere was replaced with nitrogen, and the temperature of the reaction system was brought to 65.degree. C. with a warm water bath. Next, while adding 10.8 g of 3.5% hydrogen peroxide water dropwise over 3 hours, an aqueous solution in which 43.2 g of 2-acryloyloxyethyl succinic acid is suspended in 173.0 g of ion-exchanged water is taken over 3 hours An aqueous solution prepared by dissolving 0.9 g of L-ascorbic acid and 0.7 g of 3-mercaptopropionic acid in 6.1 g of ion exchange was dropped over 4 hours. Thereafter, the temperature was maintained at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain an aqueous liquid of a reaction product. The reaction product was used as a vinyl copolymer (EX-3).
　・実施例４｛ビニル共重合体（ＥＸ－４）の合成｝
　イオン交換水３６．４ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５３）オキシエチレン１７３．５ｇを実施例１と同様の反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。次に４．０％過酸化水素水９．８ｇを３時間かけて滴下すると共にイオン交換水１６４．８ｇに２－アクリロイロキシエチルコハク酸１５．２ｇとヒドロキシエチルアクリレート２６．０ｇとアクリル酸２．２ｇを溶解させた水溶液を３時間かけて滴下し、またイオン交換７．８ｇにＬ－アスコルビン酸０．９ｇと３－メルカプトプロピオン酸１．１ｇを溶解させた水溶液を４時間かけて滴下した。その後、２時間６５℃を維持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整すると共に、イオン交換水にて濃度を４０％に調整して反応物の水性液を得た。この反応物をビニル共重合体（ＥＸ－４）とした。 Example 4 {Synthesis of Vinyl Copolymer (EX-4)}
36.4 g of ion-exchanged water and 173.5 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene were charged in the same reaction vessel as in Example 1 and homogenized while stirring. The atmosphere was replaced with nitrogen, and the temperature of the reaction system was brought to 65.degree. C. with a warm water bath. Next, 9.8 g of 4.0% hydrogen peroxide water is added dropwise over 3 hours, and 15.2 g of 2-acryloyloxyethyl succinic acid, 26.0 g of hydroxyethyl acrylate, and acrylic acid 2 in 164.8 g of ion-exchanged water An aqueous solution in which 2 g was dissolved was dropped over 3 hours, and an aqueous solution in which 0.9 g of L-ascorbic acid and 1.1 g of 3-mercaptopropionic acid were dissolved in 7.8 g of ion exchange was dropped over 4 hours . Thereafter, the temperature was maintained at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain an aqueous liquid of a reaction product. The reaction product was used as a vinyl copolymer (EX-4).
　・実施例５～９｛ビニル共重合体（ＥＸ－５）～（ＥＸ－９）の合成｝
　実施例１～４の場合と同様にして、但し用いた単量体の種類や量等を表１記載のように変えて、ビニル共重合体（ＥＸ－５）～（ＥＸ－９）を合成した。 Examples 5 to 9 {Synthesis of Vinyl Copolymer (EX-5) to (EX-9)}
Vinyl copolymers (EX-5) to (EX-9) were synthesized in the same manner as in Examples 1 to 4 except that the kind, amount, etc. of the used monomers were changed as described in Table 1. did.
　・比較例１｛ビニル共重合体（ＣＥ－１）の合成｝
　イオン交換水２４２．８ｇ 、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５３）オキシエチレン３７０．０ｇ 、アクリル酸０．７ｇを実施例１と同様の反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６０℃とした。次に４．３％過硫酸ナトリウム水溶液４８．８ｇを３．５時間かけて滴下すると共に、イオン交換水２１．６ｇにアクリル酸１８．７ｇを溶解させた水溶液を３時間かけて滴下し、またイオン交換４６．７ｇにメルカプトエタノール０．７ｇを溶解させた水溶液を３．５時間かけて滴下した。その後、２時間６０℃を維持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整すると共に、イオン交換水にて濃度を４０％に調整して反応物の水性液を得た。この反応物をビニル共重合体（ＣＥ－１）とした。 Comparative Example 1 {Synthesis of Vinyl Copolymer (CE-1)}
242.8 g of ion-exchanged water, 370.0 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene, 0.7 g of acrylic acid were placed in the same reaction vessel as in Example 1. After being charged and dissolved uniformly while stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60 ° C. with a warm water bath. Next, 48.8 g of a 4.3% aqueous solution of sodium persulfate is dropped over 3.5 hours, and an aqueous solution in which 18.7 g of acrylic acid is dissolved in 21.6 g of ion-exchanged water is dropped over 3 hours, An aqueous solution prepared by dissolving 0.7 g of mercaptoethanol in 46.7 g of ion exchange was dropped over 3.5 hours. Thereafter, the temperature was maintained at 60 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain an aqueous liquid of a reaction product. This reaction product was designated as vinyl copolymer (CE-1).
　・比較例２｛ＣＥ－２の調整｝
　グルコン酸ナトリウムをイオン交換水にて濃度４０％に調整した。 ・ Comparative example 2 {adjustment of CE-2}
Sodium gluconate was adjusted to a concentration of 40% with ion exchange water.
　以上で合成した各ビニル共重合体について、その組成及び質量平均分子量を表１にまとめて示した。尚、各ビニル共重合体については、その水性液から水を除去した後に、重水にて５％となるように溶液を調整し、３００ＭＨｚのＮＭＲにて測定を行って、各単量体が重合されていることを確認した。また質量平均分子量はＧＰＣによりポリエチレングリコール換算で示した。 The composition and mass average molecular weight of each of the vinyl copolymers synthesized as described above are summarized in Table 1. In addition, about each vinyl copolymer, after removing water from the aqueous solution, a solution is adjusted so that it may become 5% with heavy water, it measures by NMR of 300 MHz, and each monomer polymerizes. I confirmed that it was. Moreover, the mass mean molecular weight was shown by polyethylene glycol conversion by GPC.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表１において、
　Ａ－１：２－アクリロイロキシエチルコハク酸
　Ａ－２：２－メタクリロイロキシエチルコハク酸
　Ａ－３：２－アクリロイロキシエチルヘキサヒドロフタル酸
　Ａ－４：２－アクリロイロキシエチルフタル酸
　Ａ－５：ヒドロキシエチルアクリレートとトリメリット酸のモノエステル
　Ａ－６：ヒドロキシプロピルアクリレートとコハク酸のモノエステル
　Ｍ－１：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５３）オキシエチレン
　Ｍ－２：α－メタクリロイル－ω－メトキシ－ポリ（ｎ＝２３）オキシエチレン
　Ｍ－３：α－メタクリロイル－ω－メトキシ－ポリ（ｎ＝４５）オキシエチレン
　Ｍ－４：α－メタリル－ω－ヒドロキシ－ポリ（ｎ＝１１３）オキシエチレン
　Ｍ－５：α－メタクリロイル－ω－メトキシ－ポリ（ｎ＝９）オキシエチレン
　Ｍ－６：ヒドロキシエチルアクリレート
　Ｍ－７：アクリル酸メチル
　Ｍ－８：ヒドロキシプロピルアクリレート
　Ｃ－１：アクリル酸
　Ｃ－２：メタクリル酸 In Table 1,
A-1: 2-acryloyloxyethylsuccinic acid A-2: 2-methacryloyloxyethylsuccinic acid A-3: 2-acryloyloxyethylhexahydrophthalic acid A-4: 2-acryloyloxyethyl phthalic acid A-5: Monoester of hydroxyethyl acrylate and trimellitic acid A-6: Monoester of hydroxypropyl acrylate and succinic acid M-1: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) Oxyethylene M-2: α-methacryloyl-ω-methoxy-poly (n = 23) oxyethylene M-3: α-methacryloyl-ω-methoxy-poly (n = 45) oxyethylene M-4: α -Methallyl-ω-hydroxy-poly (n = 113) oxyethylene M-5: α-methacryloyl-ω-methoxy-poly (n = 9 Polyoxyethylene M-6: hydroxyethyl acrylate M-7: Methyl acrylate M-8: hydroxypropyl acrylate C-1: acrylic acid C-2: methacrylic acid
　試験区分３（水硬性組成物用分散剤としての評価）
　・コンクリートの調製
　５５Ｌの強制二軸ミキサーに普通ポルトランドセメント（太平洋セメント社製、比重＝３．１６）、細骨材（大井川水系砂、比重＝２．５８）及び粗骨材（岡崎産砕石、比重＝２．６８）を順次投入して５秒間空練りした後、目標スランプが２１±１．５ｃｍ及び空気量が４．５±０．５％の範囲となるよう、高性能ＡＥ減水剤（竹本油脂社製の商品名チューポールＨＰ－１１、以下ＨＰ－１１という）を普通ポルトランドセメントに対し０．６～０．８％、試験区分２で合成したビニル共重合体（ＥＸ－１）～（ＥＸ－９）及び（ＣＥ－１）、（ＣＥ－２）の２０％水溶液を普通ポルトランドセメントに対し０．１～０．３％、ＡＥ剤（竹本油脂社製の商品名ＡＥ－３００）を普通ポルトランドセメントに対し０．００５％、消泡剤（竹本油脂社製の商品名ＡＦＫ－２）を普通ポルトランドセメントに対し０．００１％となるよう、練混ぜ水と共に投入し、９０秒練混ぜた。かくして調製したコンクリートの単位量等を表２にまとめて示した。 Test category 3 (Evaluation as dispersant for hydraulic composition)
Preparation of concrete 55L forced biaxial mixer with ordinary portland cement (Pacific Cement Co., Ltd., specific gravity = 3.16), fine aggregate (Oikawa water sand, specific gravity = 2.58) and coarse aggregate (Okazaki crushed stone, High performance AE water reducing agent so that target slump becomes 21 ± 1.5 cm and air amount becomes 4.5 ± 0.5% after air mixing for 5 seconds by sequentially injecting specific gravity = 2.68) Vinyl copolymer (EX-1) synthesized by Takemoto Yushi Co., Ltd. under the trade name Chupol HP-11 (hereinafter referred to as HP-11) 0.6 to 0.8% of ordinary portland cement, in the test category 2 0.1% to 0.3% of a 20% aqueous solution of (EX-9), (CE-1) and (CE-2) to ordinary Portland cement, and an AE agent (trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.) To ordinary portland cement 0.0 5%, so as to be 0.001% antifoam agent (Takemoto Yushi Co., Ltd. trade name AFK-2) with respect to ordinary portland cement, was charged with Mixing water, mixed for 90 seconds mixing. Table 2 summarizes the unit amounts and the like of the thus prepared concrete.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　・評価
　練り混ぜ直後から３０分間隔で、静置した各コンクリートのスランプフロー、空気量、２４時間後の圧縮強度及びブリーディング率を次のように測定し、結果を表３にまとめて示した。 Evaluation The slump flow, the air content, the compressive strength after 24 hours, and the bleeding rate of each concrete which had been allowed to stand were measured as follows, at intervals of 30 minutes immediately after mixing, and the results are summarized in Table 3.
　・スランプフロー：練り混ぜ直後及び３０分間隔で、静置した各コンクリートについて、ＪＩＳ－Ａ１１５０に準拠して測定した。
　・空気量：練り混ぜ直後及び３０分間隔で、静置した各コンクリートについて、ＪＩＳ－Ａ１１２８に準拠して測定した。
　・圧縮強度：ＪＩＳ－Ａ１１０８に準拠し、供試体寸法を直径１００ｍｍ×高さ２００ｍｍとし、材齢２４時間で測定した。
　・ブリーディング率：ＪＩＳ－Ａ１１２３に準拠して測定した。 Slump flow: Measured according to JIS-A1150 immediately after mixing and at intervals of 30 minutes for each concrete that was allowed to stand.
Air content: Immediately after mixing and at intervals of 30 minutes, the concrete which was allowed to stand was measured according to JIS-A1128.
Compressive strength: In accordance with JIS-A1108, the sample size was 100 mm in diameter × 200 mm in height, and was measured at a material age of 24 hours.
Bleeding rate: Measured in accordance with JIS-A1123.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表３において、
　ＨＰ－１１の添加割合（％）：ＨＰ－１１の有り姿での普通ポルトランドセメントに対する質量％
　ビニル共重合体の添加割合（％）：試験区分２で合成したビニル共重合体等の２０％水性液の普通ポルトランドセメントに対する質量％ In Table 3,
Addition ratio of HP-11 (%):% by mass of ordinary Portland cement in the presence of HP-11
Addition ratio (%) of vinyl copolymer:% by mass relative to ordinary portland cement of 20% aqueous liquid such as vinyl copolymer synthesized in test division 2
　表１や２に対応する表３の結果からも、本発明の分散保持剤によると、硬化遅延を起こすことなく、水硬性組成物の流動性を長時間に亘って保持することができる。 Also from the results of Table 3 corresponding to Tables 1 and 2, according to the dispersion holding agent of the present invention, the fluidity of the hydraulic composition can be held for a long time without causing curing delay.

Claims (7)

  1. 　下記の化１で示される単量体Ａと、下記の化２で示される単量体Ｂとから得られるビニル共重合体を含有することを特徴とする水硬性組成物用分散保持剤。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
     　（化１及び化２において、
    　Ｒ１，Ｒ２：水素原子、メチル基又は化３で示される有機基
    　ｐ：０又は１
    　Ｘ：下記の化４で示される有機基
    　Ｙ：下記の化５で示される有機基
    　Ｍ１：水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属）
    Figure JPOXMLDOC01-appb-C000003
     　（化３において、
    　ｒ：０又は１
    　Ｍ２：水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属）
    Figure JPOXMLDOC01-appb-C000004
     　（化４において、
    　ＡＯ：炭素数２～４のオキシアルキレン基
    　ｍ：１～１０の整数
    　Ｒ３：ヘテロ原子を有する場合のあるアルキレン基、芳香環基又は不飽和炭化水素基）
    Figure JPOXMLDOC01-appb-C000005
     　（化５において、
    　ｓ：０～４の整数
    　ｔ：０または１
    　ＡＯ：炭素数２～４のオキシアルキレン基
    　ｎ：０～３００の整数
    　Ｒ４：水素原子、炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基（但し、ｎ＝０のときはＲ４は炭素数１～２２のアルキル基又は炭素数１～２２の脂肪族アシル基））     A dispersion holding agent for a hydraulic composition comprising a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1 and a monomer B represented by the following chemical formula 2.
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
     (In chemical formula 1 and chemical formula 2,
    R 1 , R 2 : a hydrogen atom, a methyl group or an organic group represented by Chemical Formula p: 0 or 1
    X: organic group represented by the following chemical formula 4 Y: organic group represented by the following chemical formula 5 M 1 : hydrogen atom, ammonium group, organic amine group, alkali metal or half equivalent alkaline earth metal)
    Figure JPOXMLDOC01-appb-C000003
     (In chemical formula 3,
    r: 0 or 1
    M 2 : hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent of alkaline earth metal)
    Figure JPOXMLDOC01-appb-C000004
     (In chemical formula 4,
    AO: an oxyalkylene group having 2 to 4 carbon atoms m: an integer of 1 to 10 R 3 : an alkylene group which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group)
    Figure JPOXMLDOC01-appb-C000005
     (In chemical formula 5,
    s: integer from 0 to 4 t: 0 or 1
    AO: an oxyalkylene group having a carbon number of 2 to 4 n: an integer of 0 to 300 R 4 : a hydrogen atom, an alkyl group having a carbon number of 1 to 22 or an aliphatic acyl group having a carbon number of 1 to 22 When R 4 is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms))
  2. 　請求項１記載の単量体Ａと、請求項１記載の単量体Ｂと、これらの単量体と共重合可能な他の単量体Ｃとから得られるビニル共重合体を含有することを特徴とする水硬性組成物用分散保持剤。 Containing a vinyl copolymer obtained from the monomer A according to claim 1, the monomer B according to claim 1, and another monomer C copolymerizable with these monomers Dispersion retention agent for hydraulic composition characterized by the above.
  3. 　化４中のＲ３が、下記の化６で示される有機基である請求項１又は２記載の水硬性組成物用分散保持剤。
    Figure JPOXMLDOC01-appb-C000006
     　（化６において、
    　Ｒ５：ヘテロ原子を有する場合のある炭素数１～２２のアルキレン基、芳香環基又は不飽和炭化水素基
    　ｕ：０～２の整数
    　Ｍ３：水素原子、アンモニウム基、有機アミン基、アルカリ金属又は１／２当量のアルカリ土類金属）     The dispersion holding agent for a hydraulic composition according to claim 1 or 2, wherein R 3 in the chemical formula 4 is an organic group represented by the following chemical formula 6.
    Figure JPOXMLDOC01-appb-C000006
     (In chemical formula 6,
    R 5 : an alkylene group having 1 to 22 carbon atoms which may have a hetero atom, an aromatic ring group or an unsaturated hydrocarbon group u: an integer of 0 to 2 M 3 : hydrogen atom, ammonium group, organic amine group, alkali metal Or 1/2 equivalent of alkaline earth metal)
  4. 　化６中のＲ５が、炭素数１～６のアルキレン基、芳香環基又は不飽和炭化水素基である請求項１～３のいずれか一つの項記載の水硬性組成物用分散保持剤。 4. The dispersion holding agent for a hydraulic composition according to any one of claims 1 to 3, wherein R 5 in the chemical formula 6 is an alkylene group having 1 to 6 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group.
  5. 　単量体Ａが、ヒドロキシエチル（メタ）アクリレートと２～４塩基性カルボン酸無水物との縮合物である請求項１～４のいずれか一つの項記載の水硬性組成物用分散保持剤。 5. The dispersion holding agent for a hydraulic composition according to any one of claims 1 to 4, wherein the monomer A is a condensate of hydroxyethyl (meth) acrylate and a 2 to 4 basic carboxylic acid anhydride.
  6. 　ビニル共重合体が、質量平均分子量８０００～２０００００のものである請求項１～５のいずれか一つ記載の水硬性組成物用分散保持剤。 The dispersion holding agent for a hydraulic composition according to any one of claims 1 to 5, wherein the vinyl copolymer has a weight average molecular weight of 8,000 to 200,000.
  7. 　ビニル共重合体が、全構成単位中に単量体Ａ由来の構成単位を１～９９モル％及び単量体Ｂ由来の構成単位を１～９９モル％（合計１００モル％）割合で有するものである請求項１～６のいずれか一つの項記載の水硬性組成物用分散保持剤。 A vinyl copolymer having 1 to 99% by mole of a constitutional unit derived from monomer A and 1 to 99% by mole (totally 100 mole%) of constitutional units derived from monomer B in all constitutional units The dispersion holding agent for a hydraulic composition according to any one of claims 1 to 6, which is
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