JP6688413B1 - Water-curable composition, cured product thereof, and method for preventing white flower phenomenon - Google Patents
Water-curable composition, cured product thereof, and method for preventing white flower phenomenon Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 54
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 36
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 18
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 18
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 16
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 16
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000005871 repellent Substances 0.000 claims abstract description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 14
- 150000003673 urethanes Chemical class 0.000 claims abstract description 14
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 abstract description 7
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 239000004568 cement Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 8
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- 229920005989 resin Polymers 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011414 polymer cement Substances 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- -1 calcium aluminate compound Chemical class 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000287127 Passeridae Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-OUBTZVSYSA-N magnesium-25 atom Chemical group [25Mg] FYYHWMGAXLPEAU-OUBTZVSYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
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- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
【課題】白華現象の発生を回避できる硬化物の形成に適した、マグネシア系結合材を含む水硬化型組成物及びその硬化物を提供する。【解決手段】下記成分を含有する水硬化型組成物。成分（Ａ）：酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含み、酸化マグネシウムの含有量（重量基準）が、硫酸マグネシウムおよび塩化マグネシウムのいずれの含有量より多いマグネシア系結合材成分（Ｂ）：針状メタケイ酸カルシウム成分（Ｃ）：水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョン成分（Ｄ）：水溶性高分子分散助剤【選択図】なしPROBLEM TO BE SOLVED: To provide a water-curable composition containing a magnesia-based binder and a cured product thereof, which is suitable for forming a cured product capable of avoiding the occurrence of the white flower phenomenon. A water-curable composition containing the following components. Component (A): Magnesia-based binder containing magnesium oxide, magnesium sulfate and magnesium chloride and having a magnesium oxide content (weight basis) higher than that of either magnesium sulfate or magnesium chloride Component (B): acicular Calcium metasilicate component (C): Water-based silicone modified urethane resin emulsion and / or water-based silane water-repellent emulsion component (D): Water-soluble polymer dispersion aid [Selection diagram] None
Description
本発明は、白華現象の防止性に優れた硬化物を与えることができる水硬化型組成物及びその硬化物に関する。 TECHNICAL FIELD The present invention relates to a water-curable composition capable of giving a cured product excellent in the prevention of white bloom phenomenon and a cured product thereof.
マグネシア系結合材ベースの水硬化型組成物は、製造に焼成工程を必要とせず、軽量で機械的強度に優れた硬化物を与えることができる。そのため、このような水硬化型組成物は、セメント組成物の代替材料として、様々な用途に応用されている。
例えば、特許文献１にはマグネシア系結合材及び針状メタケイ酸カルシウムを含有する水硬化型組成物に加水して硬化した硬化物は、機械的強度と意匠性に優れるため、壁やタイル等の用途に適用することが記載されている。
また、特許文献２には、所定割合の酸化マグネシウム、硫酸マグネシウム及び塩化マグネシウムを含有するマグネシア系結合材とペーパースラッジ灰とを混合して加水して硬化した硬化物は、圧縮硬度に優れたポルトランドセメント硬化物の代替材料として好適であることが記載されている。
The magnesia-based binder-based water-curable composition does not require a firing step for production and can provide a cured product that is lightweight and has excellent mechanical strength. Therefore, such a water-curable composition is applied to various applications as a substitute material for a cement composition.
For example, in Patent Document 1, a cured product obtained by adding water to a water-curable composition containing a magnesia-based binder and acicular calcium metasilicate and cured is excellent in mechanical strength and designability, and thus is used for walls, tiles, and the like. It is described that it is applicable to the intended use.
In addition, in Patent Document 2, a cured product obtained by mixing a magnesia-based binder containing a predetermined ratio of magnesium oxide, magnesium sulfate and magnesium chloride and paper sludge ash and hydrolyzing the mixture is a Portland semé having excellent compression hardness. It is described that it is suitable as a substitute material for a cured product.
一方、セメント組成物は、その硬化物に含まれる成分が水分との過剰接触によって水に溶解して硬化物表面に移行し空気中の二酸化炭素と化学反応して水不溶性の反応物を形成する、いわゆる「白華現象」による外観不良という問題がある。マグネシア系結合材ベースの水硬化型組成物の硬化物についても白華現象は解決すべき課題となっていた。 On the other hand, in the cement composition, the components contained in the hardened product are dissolved in water due to excessive contact with water to migrate to the surface of the hardened product and chemically react with carbon dioxide in the air to form a water-insoluble reaction product. There is a problem of poor appearance due to the so-called "white flower phenomenon". The white flower phenomenon has also been a problem to be solved in a cured product of a water-curable composition based on a magnesia-based binder.
従来のセメント組成物の白華現象を防止する技術として、セメント原料に無機材料やポリマーを配合する方法が知られている。
無機材料を配合した低白華性のセメント組成物として、例えば、特許文献３には、セメント組成物に焼成粘土鉱物を特定の割合で配合したモルタルの白華抑制剤組成物が報告されている。また、特許文献４には、白華抑制剤として酸化亜鉛を配合した石灰系のセメント組成物が報告されている。また、特許文献５には、アルミナセメントに対し、特定割合のマイクロシリカ及びジルコニアを配合した白華しにくいセメント系固化材が報告されている。
また、ポリマーを配合した低白華性のセメント組成物として、例えば、特許文献６にはエポキシ樹脂及び硬化剤、ポルトランドセメント、カルシウムアルミネート系化合物、石膏並びにリチウム化合物を含有してなるポリマーセメント系複合材が報告されている。また、特許文献７には、ポルトランドセメント等のセメント原料に特定の組成、分子量のフッ素樹脂とアクリル樹脂の混合体を配合したポリマーセメント組成物が報告されている。また、特許文献８には、ポルトランドセメント、ホワイトセメント、早強セメント、アルミナセメント等のセメント原料に、特定のα，β−不飽和カルボン酸エステル単量体の構造単位及び芳香環含有不飽和単量体由来の構造単位を含む疎水性単量体由来の構造単位（Ａ）と、特定の親水性単量体由来の構造単位の共重合体を配合した合成樹脂エマルジョンを配合したポリマーセメント組成物が報告されている。
As a conventional technique for preventing the whitening phenomenon of a cement composition, a method of blending an inorganic material or a polymer with a cement raw material is known.
As a low whitening cement composition containing an inorganic material, for example, Patent Document 3 reports a mortar whitening inhibitor composition in which a cement composition is mixed with a calcined clay mineral at a specific ratio. . In addition, Patent Document 4 reports a lime-based cement composition containing zinc oxide as a whitening inhibitor. In addition, Patent Document 5 reports a cement-based solidifying material which is a mixture of alumina cement with a specific ratio of microsilica and zirconia and is resistant to whitening.
Further, as a low-whitening cement composition containing a polymer, for example, Patent Document 6 discloses a polymer cement system containing an epoxy resin and a curing agent, Portland cement, a calcium aluminate compound, gypsum and a lithium compound. Composites have been reported. Further, Patent Document 7 reports a polymer cement composition in which a cement raw material such as Portland cement is mixed with a mixture of a fluororesin and an acrylic resin having a specific composition and molecular weight. Further, in Patent Document 8, a cement raw material such as Portland cement, white cement, early-strength cement, and alumina cement is used, and a structural unit of a specific α, β-unsaturated carboxylic acid ester monomer and an aromatic ring-containing unsaturated unity are used. Polymer cement composition containing a synthetic resin emulsion containing a structural unit (A) derived from a hydrophobic monomer containing a structural unit derived from a monomer and a copolymer of structural units derived from a specific hydrophilic monomer Has been reported.
上述の特許文献３〜８の通り、セメント組成物の白華現象抑制方法が種々提案されている。しかしながら、これらの方法は、ポルトランドセメント、ホワイトセメント、早強セメント、アルミナセメントのセメント原料が対象であって、マグネシア系セメントを対象としたものではない。そして、マグネシア系セメントは、他のセメント材料と性質が異なるため、他のセメントで有効な白華現象抑制方法が必ずしもマグネシア系セメントに適用できるとは限らないのが実情である。 As described in Patent Documents 3 to 8 above, various methods for suppressing the white bloom phenomenon of cement compositions have been proposed. However, these methods target cement raw materials such as Portland cement, white cement, early-strength cement, and alumina cement, and do not target magnesia-based cement. Since magnesia-based cements have different properties from other cement materials, the fact that the method for suppressing the white flower phenomenon that is effective with other cements is not always applicable to magnesia-based cements.
かかる状況下、本発明の目的は、白華現象の発生を回避できる硬化物の形成に適した、マグネシア系結合材を含む水硬化型組成物及びその硬化物を提供することである。 Under such circumstances, an object of the present invention is to provide a water-curable composition containing a magnesia-based binder and a cured product thereof, which is suitable for forming a cured product that can avoid the occurrence of a white sinter phenomenon.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of earnest studies to solve the above problems, the present inventor has found that the following invention meets the above object, and has reached the present invention.
すなわち、本発明は、以下の発明に係るものである。
＜１＞ 下記成分を含有する水硬化型組成物。
成分（Ａ）：酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含み、酸化マグネシウムの含有量（重量基準）が、硫酸マグネシウムおよび塩化マグネシウムのいずれの含有量より多いマグネシア系結合材
成分（Ｂ）：針状メタケイ酸カルシウム
成分（Ｃ）：水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョン
成分（Ｄ）：水溶性高分子分散助剤
＜２＞ 成分（Ｃ）が、水系シラン撥水性エマルジョンである＜１＞に記載の水硬化型組成物。
＜３＞ 成分（Ｄ）が、カルボキシメチルセルロースである＜１＞または＜２＞に記載の水硬化型組成物。
＜４＞ 成分（Ａ）１００重量部に対する成分（Ｂ）の重量割合が５〜４５重量部であり、
成分（Ａ）及び成分（Ｂ）の合計１００重量部に対する成分（Ｃ）の重量割合が３〜１５重量部、成分（Ｄ）の重量割合が０．３〜５重量部である＜１＞から＜３＞のいずれかに記載の水硬化型組成物。
＜５＞ さらに成分（Ｅ）として、修飾フィラーを含有する＜１＞から＜４＞のいずれかに記載の水硬化型組成物。
＜６＞ ＜１＞から＜５＞のいずれかに記載の水硬化型組成物に加水して硬化させてなる硬化物。
＜７＞ ＜１＞から＜５＞のいずれかに記載の水硬化型組成物を、水と混合して硬化する前に、白華現象が生じる対象に塗工し、硬化させる工程を有する白華現象の防止方法。
That is, the present invention relates to the following inventions.
<1> A water-curable composition containing the following components.
Ingredient (A): Magnesia-based binder containing magnesium oxide, magnesium sulfate and magnesium chloride and having a magnesium oxide content (weight basis) higher than that of either magnesium sulfate or magnesium chloride Component (B): acicular Calcium metasilicate component (C): Water-based silicone-modified urethane resin emulsion and / or water-based silane water-repellent emulsion component (D): Water-soluble polymer dispersion aid <2> Component (C) is a water-based silane water-repellent emulsion The water-curable composition according to <1>.
<3> The water-curable composition according to <1> or <2>, wherein the component (D) is carboxymethyl cellulose.
<4> The weight ratio of the component (B) to 100 parts by weight of the component (A) is 5 to 45 parts by weight,
From <1> in which the weight ratio of the component (C) to the total 100 parts by weight of the component (A) and the component (B) is 3 to 15 parts by weight, and the weight ratio of the component (D) is 0.3 to 5 parts by weight. The water-curable composition according to any one of <3>.
<5> The water-curable composition according to any one of <1> to <4>, which further contains a modified filler as the component (E).
<6> A cured product obtained by adding water to the water-curable composition according to any one of <1> to <5> and curing the composition.
<7> White having a step of applying the water-curable composition according to any one of <1> to <5> to an object on which a white sinter phenomenon occurs and curing the mixture before curing the water-curable composition by mixing with water. How to prevent blooming.
本発明によれば、白華現象が抑制されたマグネシア硬化物を与えることができる水硬化型組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the water curable composition which can give the magnesia hardened | cured material in which the white flower phenomenon was suppressed is provided.
以下、本発明について例示物等を示して詳細に説明するが、本発明は以下の例示物等に限定されるものではなく、本発明の要旨を逸脱しない範囲において任意に変更して実施できる。なお、本明細書において、「〜」とはその前後の数値又は物理量を含む表現として用いるものとする。 Hereinafter, the present invention will be described in detail with reference to examples and the like, but the present invention is not limited to the following examples and the like, and may be arbitrarily modified and implemented without departing from the scope of the present invention. In addition, in this specification, "-" shall be used as an expression including numerical values or physical quantities before and after it.
本発明は、下記成分を含有する水硬化型組成物に関する。
成分（Ａ）：酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含み、酸化マグネシウムの含有量（重量基準）が、硫酸マグネシウムおよび塩化マグネシウムのいずれの含有量より多いマグネシア系結合材
成分（Ｂ）：針状メタケイ酸カルシウム
成分（Ｃ）：水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョン
成分（Ｄ）：水溶性高分子分散助剤
The present invention relates to a water-curable composition containing the following components.
Ingredient (A): Magnesia-based binder containing magnesium oxide, magnesium sulfate and magnesium chloride and having a magnesium oxide content (weight basis) higher than that of either magnesium sulfate or magnesium chloride Component (B): acicular Calcium metasilicate component (C): Water-based silicone modified urethane resin emulsion and / or water-based silane water-repellent emulsion component (D): Water-soluble polymer dispersion aid
本発明の水硬化型組成物は、白華現象が抑制されたマグネシア硬化物を与えることができる。本発明の水硬化型組成物において、上記成分のうち、成分（Ａ）及び成分（Ｂ）はマグネシア系硬化物の主材成分であり、成分（Ａ）はマグネシア系セメントの主成分であり、成分（Ｂ）は硬化物に機械的強度を付与する成分である。そして、硬化物に「白華現象抑制作用」を付与する成分は、成分（Ｃ）及び成分（Ｄ）である。
このように、マグネシア系水硬化型組成物において、主材成分（成分（Ａ）及び成分（Ｂ））に対し、成分（Ｃ）やその分散助剤である成分（Ｄ）を含有させることによって、得られるマグネシア硬化物の白華現象を抑制することについては、これまでに全く報告されていない。
The water-curable composition of the present invention can give a magnesia cured product in which the white bloom phenomenon is suppressed. In the water-curable composition of the present invention, among the above components, the component (A) and the component (B) are main material components of the magnesia-based cured product, and the component (A) is a main component of the magnesia-based cement, The component (B) is a component that imparts mechanical strength to the cured product. The components that impart the "white flower phenomenon suppressing effect" to the cured product are the component (C) and the component (D).
Thus, in the magnesia-based water-curable composition, by incorporating the component (C) and the component (D) which is a dispersion aid thereof into the main material components (component (A) and component (B)) Up to now, it has not been reported at all about suppressing the white bloom phenomenon of the obtained magnesia cured product.
以下、本発明の水硬化型組成物が含有する各成分について詳細に説明する。 Hereinafter, each component contained in the water-curable composition of the present invention will be described in detail.
＜成分（Ａ）＞
成分（Ａ）は、酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含み、酸化マグネシウムの含有量（重量基準）が、硫酸マグネシウムおよび塩化マグネシウムのいずれの含有量より多いマグネシア系結合材である。すなわち、成分（Ａ）は、酸化マグネシウムを主原料とするマグネシア系結合材である。
本発明の水硬化型組成物において、マグネシア系結合材は、加水して混合することによって硬化し、水硬化型組成物を固化させる作用を有する。
<Component (A)>
The component (A) is a magnesia-based binder containing magnesium oxide, magnesium sulfate, and magnesium chloride, and the content of magnesium oxide (by weight) is higher than the content of either magnesium sulfate or magnesium chloride. That is, the component (A) is a magnesia-based binder containing magnesium oxide as a main raw material.
In the water-curable composition of the present invention, the magnesia-based binder has a function of hardening by being mixed with water and solidifying the water-curable composition.
成分（Ａ）は、酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含むことが必須である。マグネシア系結合材の原料として、酸化マグネシウムを使用せず、酸化マグネシウム及び塩化マグネシウムのみを用いた場合、当該原料に水を混合して水硬させてなる硬化物は、吸湿性が高いため反り及び膨張が生じ易いのに加え、耐水性及び耐久性が著しく低い場合がある。一方、マグネシア系結合材の原料として酸化マグネシウム及び硫酸マグネシウムのみを用いた場合、当該原料に水を混合して水硬させてなる固形体に膨張又はひび割れが発生するおそれがある。 It is essential that the component (A) contains magnesium oxide, magnesium sulfate and magnesium chloride. As the raw material of the magnesia-based binder, without using magnesium oxide, when only magnesium oxide and magnesium chloride is used, a cured product obtained by mixing water into the raw material and hydraulically hardening the warp and In addition to swelling, water resistance and durability may be extremely low. On the other hand, when only magnesium oxide and magnesium sulfate are used as the raw material for the magnesia-based binder, there is a possibility that a solid body formed by mixing water into the raw material and hydraulically hardening it may cause expansion or cracking.
これに対して、結合材の原料として酸化マグネシウム、硫酸マグネシウム及び塩化マグネシウムを用いた場合は、３つの原料を所定の割合で混合することによって、固形体に前述した如き反り、膨張及びひび割れが生じることなく、また、「酸化マグネシウム及び塩化マグネシウムのみ」あるいは「酸化マグネシウム及び硫酸マグネシウムのみ」の場合よりも耐水性及び耐久性が著しく改善される。 On the other hand, when magnesium oxide, magnesium sulfate and magnesium chloride are used as the raw material of the binder, the three raw materials are mixed at a predetermined ratio, so that the solid body is warped, expanded and cracked as described above. In addition, the water resistance and durability are significantly improved as compared with the case of "only magnesium oxide and magnesium chloride" or "only magnesium oxide and magnesium sulfate".
酸化マグネシウム、硫酸マグネシウム及び塩化マグネシウムの３原料を混合する好ましい割合を例示すると、酸化マグネシウム含有量が３５〜６５重量％であり、硫酸マグネシウム含有量が２５〜４０重量％であり、塩化マグネシウム含有量が１０〜２５重量％である。 Illustrating a preferable ratio of mixing three raw materials of magnesium oxide, magnesium sulfate and magnesium chloride, the magnesium oxide content is 35 to 65% by weight, the magnesium sulfate content is 25 to 40% by weight, and the magnesium chloride content is Is 10 to 25% by weight.
成分（Ａ）の粒径は、他の成分と均一に混合できる範囲で決定され、通常、５〜６０μｍである。 The particle size of the component (A) is determined within a range in which it can be uniformly mixed with other components, and is usually 5 to 60 μm.
＜成分（Ｂ）＞
成分（Ｂ）である針状メタケイ酸カルシウムは、いわゆる針状無機フィラーであり、本発明の硬化物に優れた機械的強度（曲げ強度、衝撃強度等）を与えることができる。また、針状メタケイ酸カルシウムは、化学的に安定が高いため、本発明の硬化物に耐久性を付与することができる。
<Component (B)>
The acicular calcium metasilicate which is the component (B) is a so-called acicular inorganic filler, and can impart excellent mechanical strength (bending strength, impact strength, etc.) to the cured product of the present invention. Further, since acicular calcium metasilicate is highly chemically stable, durability can be imparted to the cured product of the present invention.
針状メタケイ酸カルシウムは、化学式ＣａＳｉＯ3を主成分とする、白色の針状の結晶形状を有し、アスペクト比（直径に対する長さの比）が１０倍以上である物質である。針状メタケイ酸カルシウムは、数十〜数百μｍ程度の範囲で長さ分布があるが、本発明の水硬化型組成物として適した長さ分布のものを使用すればよい。
なお、本発明で使用される針状メタケイ酸カルシウムには、針状形状に類似する細管状、短冊状の結晶形状も含まれるものとする。強度のバランスに優れた硬化物が供給される点で、アスペクト比（直径に対する長さの比）は、１５以上が好ましい。
The acicular calcium metasilicate is a substance having a chemical formula CaSiO 3 as a main component, having a white acicular crystal shape, and having an aspect ratio (ratio of length to diameter) of 10 times or more. The acicular calcium metasilicate has a length distribution in the range of about several tens to several hundreds of μm, and a length distribution suitable for the water-curable composition of the present invention may be used.
It should be noted that the acicular calcium metasilicate used in the present invention includes a crystal form of a thin tube or a strip that is similar to the acicular shape. The aspect ratio (ratio of length to diameter) is preferably 15 or more from the viewpoint of supplying a cured product having an excellent balance of strength.
針状メタケイ酸カルシウムは、天然物であっても、人工物であってもよい。特に天然物であるワラストナイト（Wollastonite）が好適である。ワラストナイトは、硬度４．５〜５の結晶性鉱物であり、粉砕すると白色の針状粒子となる。当該針状粒子を針状メタケイ酸カルシウムとして本発明の水硬化型組成物に使用すると、曲げ強度が顕著に増大する。 The acicular calcium metasilicate may be a natural product or an artificial product. Wollastonite which is a natural product is particularly preferable. Wollastonite is a crystalline mineral having a hardness of 4.5 to 5, and becomes white needle-shaped particles when pulverized. When the acicular particles are used as acicular calcium metasilicate in the water-curable composition of the present invention, the bending strength is remarkably increased.
針状メタケイ酸カルシウムの長さはレーザー解析散乱式測定、アスペクト比は電子顕微鏡（ＳＥＭ）で観察した任意の粒子１０個の平均値として求めることができる。 The length of the acicular calcium metasilicate can be determined by laser analysis scattering measurement, and the aspect ratio can be determined as an average value of 10 arbitrary particles observed by an electron microscope (SEM).
本発明の水硬化型組成物において、マグネシア系結合材（成分（Ａ））１００重量部に対する成分（Ｂ）の重量割合が、５〜４５重量部であることが好ましく、より好ましくは、２０〜４０重量部である。
この範囲であれば、得られる硬化物は結合性が高く、高硬度で緻密であり、ひび割れなどが生じづらい水硬化型組成物を与えることができる。この範囲において、その使用時の状況に応じてそれぞれの成分含量を適宜設定し使用すればよい。
In the water-curable composition of the present invention, the weight ratio of the component (B) to 100 parts by weight of the magnesia-based binder (component (A)) is preferably 5 to 45 parts by weight, more preferably 20 to 20 parts by weight. 40 parts by weight.
Within this range, the obtained cured product has a high bonding property, high hardness and denseness, and a water-curable composition that is resistant to cracking can be provided. Within this range, the content of each component may be appropriately set and used depending on the situation at the time of use.
＜成分（Ｃ）＞
成分（Ｃ）は、水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョンである。以下、水性シリコーン変性ウレタン樹脂エマルジョンを「成分（Ｃ１）」、水系シラン撥水性エマルジョンを「成分（Ｃ２）」と称す。
<Component (C)>
Component (C) is an aqueous silicone modified urethane resin emulsion and / or an aqueous silane water repellent emulsion. Hereinafter, the aqueous silicone-modified urethane resin emulsion is referred to as “component (C1)” and the water-based silane water-repellent emulsion is referred to as “component (C2)”.
本発明の水硬化型組成物において、成分（Ｃ）である水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョンは、その分散助剤である成分（Ｄ）と共に、主材成分（成分（Ａ）及び成分（Ｂ））に含有させることによって、マグネシア硬化物の白華現象を抑制する作用を有する。なお、成分（Ｃ）の添加により、マグネシア硬化物の白華が抑制される理由については現段階では完全には明らかではないが、無機系樹脂であるシリコーン変性ウレタン樹脂（成分（Ｃ１））、水系シラン（成分（Ｃ２））が無機系のマグネシア成分に対して親和性を有すること、これらの樹脂成分が水分を排除する作用を有していることに一因があると予測される。 In the water-curable composition of the present invention, the water-based silicone-modified urethane resin emulsion and / or the water-based silane water-repellent emulsion, which is the component (C), together with the component (D) which is the dispersion aid thereof, the main material component (component (component (C When it is contained in A) and component (B)), it has the effect of suppressing the white bloom phenomenon of the magnesia cured product. The reason why the addition of component (C) suppresses whitening of the magnesia cured product is not completely clear at this stage, but a silicone-modified urethane resin (component (C1)), which is an inorganic resin, It is expected that this is partly due to the fact that the water-based silane (component (C2)) has an affinity for the inorganic magnesia component and that these resin components have the action of eliminating water.
成分（Ｃ１）「水性シリコーン変性ウレタン樹脂エマルジョン」、成分（Ｃ２）「水系シラン撥水性エマルジョン」のいずれにも白華現象抑制作用が認められるが、特に成分（Ｃ２）「水系シラン撥水性エマルジョン」はより白華の抑制作用に優れる。 Both the component (C1) "water-based silicone modified urethane resin emulsion" and the component (C2) "water-based silane water-repellent emulsion" are observed to have the effect of suppressing the white flower phenomenon. Is more effective in suppressing white sinter.
以下、成分（Ｃ１），成分（Ｃ２）について詳述する。 Hereinafter, the components (C1) and (C2) will be described in detail.
成分（Ｃ１）：シリコーン変性ウレタン樹脂エマルジョン
成分（Ｃ１）は、透明なシリコーン変性ウレタン樹脂エマルジョンであり、樹脂組成中にポリシロキサンを含有する水性シリコーン変性ウレタン樹脂を、溶剤として水、及び水を含む有機溶媒（例えば、メタノール、エタノール、イソプロピルアルコール、ジエチレングリコールモノブチルエーテル等）に分散したものが挙げられる。
Component (C1): Silicone-modified urethane resin emulsion Component (C1) is a transparent silicone-modified urethane resin emulsion, and contains water and water as a solvent, an aqueous silicone-modified urethane resin containing polysiloxane in the resin composition. Examples thereof include those dispersed in an organic solvent (eg, methanol, ethanol, isopropyl alcohol, diethylene glycol monobutyl ether, etc.).
本発明に好適に用いられる水性シリコーン変性樹脂エマルジョンとして、具体的には、ＤＩＣ社製のセラネート（登録商標）ＷＳＡ−１０４、ＷＳＡ−１０６０、ＷＳＡ−１０７０、ＷＨＷ−８２２、ＭＦＧコートＳＤ−１０１等を好ましく例示することができ、また特開平１０−３６５１４号公報、特開平１０−３６５１５号公報、特開平１１−９２５３６号公報等に記載された方法で製造される水性シリコーン変性樹脂を使用したエマルジョンも好ましい。 As the aqueous silicone-modified resin emulsion preferably used in the present invention, specifically, DIC Corporation's Celanate (registered trademark) WSA-104, WSA-1060, WSA-1070, WHW-822, MFG coat SD-101, etc. And an emulsion using an aqueous silicone-modified resin produced by the method described in JP-A-10-36514, JP-A-10-36515, JP-A-11-92536 and the like. Is also preferable.
後述する実施例で使用したＤＩＣ社製のセラネートＷＨＷ−８２２は、特に好ましい水性シリコーン変性樹脂エマルジョンの一例である。 Clanate WHW-822 manufactured by DIC Co., Ltd. used in Examples described later is an example of a particularly preferable aqueous silicone-modified resin emulsion.
成分（Ｃ２）：水系シラン撥水性エマルジョン
成分（Ｃ２）は、水系シラン撥水性エマルジョンであり、樹脂組成中に水系シランを含有する樹脂を溶剤として水、及び水を含む有機溶媒（例えば、メタノール、エタノール、イソプロピルアルコール、ジエチレングリコールモノブチルエーテル等）に分散したものが挙げられる。
Component (C2): Water-based silane water-repellent emulsion The component (C2) is a water-based silane water-repellent emulsion, and uses water containing a resin containing a water-based silane in a resin composition as a solvent, and an organic solvent containing water (for example, methanol, Examples thereof include those dispersed in ethanol, isopropyl alcohol, diethylene glycol monobutyl ether, etc.).
本発明に用いられる水性シリコーン変性樹脂エマルジョンとして、具体的には、ＢＡＳＦポゾリス社製「プロテクトシルＳＣコンセントレイト（商品名）」が好適な一例として挙げられる。当該水性シリコーン変性樹脂エマルジョンは水に対する分散性がよく、任意の量の水に添加して希釈して使用することができる。 A specific example of the water-based silicone-modified resin emulsion used in the present invention is “Protect Sil SC Concentrate (trade name)” manufactured by BASF Pozzolis Co., Ltd. The aqueous silicone-modified resin emulsion has good dispersibility in water, and can be used by adding it to any amount of water and diluting it.
本発明の水硬化型組成物において、成分（Ｃ）の含有量は、白華現象が抑制できる範囲で適宜決定される。好適には主材成分（成分（Ａ）及び成分（Ｂ）の合計）１００重量部に対する成分（Ｃ）の重量割合が、３〜１５重量部であることが好ましく、より好ましくは、５〜１２重量部である。この範囲において、その使用時の状況に応じてそれぞれの成分含量を適宜設定し使用すればよい。 In the water-curable composition of the present invention, the content of the component (C) is appropriately determined within the range where the white bloom phenomenon can be suppressed. Suitably, the weight ratio of the component (C) to 100 parts by weight of the main material components (the total of the components (A) and (B)) is preferably 3 to 15 parts by weight, more preferably 5 to 12 parts. Parts by weight. Within this range, the content of each component may be appropriately set and used depending on the situation at the time of use.
＜成分（Ｄ）＞
成分（Ｄ）である水溶性高分子分散助剤は、主材成分（成分（Ａ）及び成分（Ｂ））に対して、成分（Ｃ）を均一に分散させるために加えられる助剤である。成分（Ｄ）を含ませない場合、硬化の際に成分（Ｃ）が偏在して、組成物中に成分（Ｃ）が均一に分散できず、部分的に白華現象が生じる場合がある。
<Component (D)>
The water-soluble polymer dispersion aid which is the component (D) is an aid added to uniformly disperse the component (C) in the main material components (component (A) and component (B)). . When the component (D) is not contained, the component (C) may be unevenly distributed during curing, the component (C) cannot be uniformly dispersed in the composition, and a white bloom phenomenon may occur partially.
成分（Ｄ）は、成分（Ｃ）の分散性を高める作用を有し、具体的には、カルボキシアルキルセルロース、アルキルセルロース、ヒドロキシアルキルセルロース、ポリビニルアルコール及びアルギン酸ナトリウム等を使用できるが、カルボキシアルキルセルロースが好ましく用いられる。カルボキシアルキルセルロースして具体的には、カルボキシメチルセルロース、ヒドロキシエチルセルロース（ＨＥＣ）、カルボキシエチルセルロース等が挙げられ、特に入手しやすく、化学的な安定性に優れた、カルボキシメチルセルロースが好ましい。 The component (D) has a function of enhancing the dispersibility of the component (C), and specifically, carboxyalkyl cellulose, alkyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, sodium alginate and the like can be used. Is preferably used. Specific examples of the carboxyalkyl cellulose include carboxymethyl cellulose, hydroxyethyl cellulose (HEC), carboxyethyl cellulose, and the like. Particularly preferred is carboxymethyl cellulose, which is easily available and has excellent chemical stability.
本発明の水硬化型組成物において、成分（Ｄ）の含有量は、組成物中に成分（Ｃ）が均一に分散できる範囲で適宜決定される。好適には成分（Ｃ）に対して、通常、５〜２０重量％であり、主材成分（成分（Ａ）及び成分（Ｂ））１００重量部に対して０．３〜５重量部である。 In the water-curable composition of the present invention, the content of the component (D) is appropriately determined within the range in which the component (C) can be uniformly dispersed in the composition. Suitably, it is usually 5 to 20% by weight based on the component (C), and 0.3 to 5 parts by weight based on 100 parts by weight of the main material components (component (A) and component (B)). .
（その他の成分）
本発明の水硬化型組成物は、成分（Ａ）〜（Ｄ）を必須成分として含有するが、本発明の効果を損なわない範囲で他の成分を含んでいてよい。これらの添加物の添加量は任意であり、目的に応じて適時設定される。
本発明の水硬化型組成物に含有させる好ましい成分として、以下に説明する修飾フィラー（成分（Ｅ）と称す）が挙げられる。
(Other ingredients)
The water-curable composition of the present invention contains the components (A) to (D) as essential components, but may contain other components as long as the effects of the present invention are not impaired. The amount of these additives to be added is arbitrary and is appropriately set according to the purpose.
As a preferable component to be contained in the water-curable composition of the present invention, a modified filler (referred to as component (E)) described below can be mentioned.
＜成分（Ｅ）＞
成分（Ｅ）である修飾フィラーは、本発明の水硬化型組成物に様々な機能や意匠性等を付与するために含有させるフィラーである。成分（Ｅ）は１種類でもよく、２種類以上を併せて使用してもよい。
成分（Ｅ）としては、必須成分である成分（Ａ）〜（Ｄ）に基づく作用、機能が損なわれないものであれば任意であるが、以下に説明する自然材料、特には石粒・石粉や木材チップスが好適に使用される。なお、これらの自然素材の産地は特に限定はないが、特には天草阿蘇横断地域の自然素材が好ましく使用される。
<Component (E)>
The modified filler, which is the component (E), is a filler that is added to the water-curable composition of the present invention in order to impart various functions, design properties and the like. As the component (E), one type may be used, or two or more types may be used in combination.
The component (E) is optional as long as the action and function based on the essential components (A) to (D) are not impaired, but natural materials described below, particularly stone grains and stone powder Wood chips are preferably used. In addition, the production areas of these natural materials are not particularly limited, but natural materials in the Amakusa-Aso crossing region are particularly preferably used.
（石粒粉）
石粒粉は、石粒や石粉を総称したものである。粒径は任意であるが、粒径が０．３〜２．４ｍｍの石粒、０．３ｍｍ未満の石粉を、成分（Ａ）〜（Ｄ）に基づく作用、機能が損なわれない範囲で必要に応じて含有させて使用することが好ましい。
（木材チップス）
木質チップスは木繊維あるいは木チップなどの総称であり、得られる硬化物に意匠性と共に超軽量化をもたらす。特に、木繊維の場合にはすずめ模様を、木チップの場合には白みかがったかすかな輪郭模様が浮かび上がる。原料となる木材の限定はないが、杉は好ましい材の一例である。
(Stone powder)
Stone grain powder is a general term for stone grains and stone powder. Although the particle size is arbitrary, stone particles with a particle size of 0.3 to 2.4 mm and stone powder with a particle size of less than 0.3 mm are required within a range in which the functions and functions based on the components (A) to (D) are not impaired. It is preferable to use it by incorporating it according to the above.
(Wood chips)
Wood chips are a general term for wood fibers, wood chips, etc., and bring to the obtained cured product an ultralight weight as well as design. In particular, a sparrow pattern appears in the case of wood fiber, and a whitish faint outline pattern appears in the case of wood chips. There is no limitation on the wood used as a raw material, but cedar is an example of a preferable material.
他の成分して、例えば、天草白土、天草黄土、朝倉黄土、新紅土、竹チップ、竹炭等も挙げられる。 Other components include, for example, Amakusa clay, Amakusa loess, Asakura loess, fresh red clay, bamboo chips, and bamboo charcoal.
本発明の水硬化型組成物は、従来公知の手段によって製造することができる。混合順序も任意であり、水硬化型組成物の構成成分（成分（Ａ）〜（Ｄ）、任意成分（成分（Ｅ）））のうち、何れか２成分又は３成分以上を予め配合し、その後に残りの成分を混合してもよいし、一度に全部を混合してもよい。 The water-curable composition of the present invention can be produced by conventionally known means. The mixing order is also arbitrary, and any two or three or more of the constituent components (components (A) to (D) and optional component (component (E)) of the water-curable composition) are pre-blended, After that, the remaining components may be mixed, or all of them may be mixed at once.
本発明の硬化物は、上述の水硬化型組成物と、加水して水と混合し硬化して製造される。より詳細には本発明の硬化物は、所定の量の水硬化型組成物に、適宜量の水を入れて十分に撹拌混練し、必要に応じて成形用の型に入れたのち混練物の水硬化・養成を行うことで得ることができる。本発明の水硬化型組成物は、加水し水と混合して硬化するまで、ある程度の時間があるため、適用状況に応じて適当な形状の硬化物を得ることができる。 The cured product of the present invention is produced by mixing the above-mentioned water-curable composition with water, mixing with water and curing. More specifically, the cured product of the present invention, a predetermined amount of water-curable composition, put an appropriate amount of water and sufficiently kneaded with stirring, if necessary, put into a mold for molding and then kneaded product It can be obtained by carrying out water curing and training. Since the water-curable composition of the present invention has a certain amount of time until it is mixed with hydrous water and cured, a cured product having an appropriate shape can be obtained depending on the application situation.
水硬化型組成物に加える水の量は、水硬化型組成物の成分割合や、温度、湿度、目標とする硬化時間等の諸条件を考慮して適宜決定すればよい。 The amount of water added to the water-curable composition may be appropriately determined in consideration of the component ratio of the water-curable composition, various conditions such as temperature, humidity and target curing time.
本発明の硬化物は、白華現象が発生することが回避又は抑制できるため、室外、室内を問わず、水分と接触しやすい環境下においても白華現象による外観不良が生じず、長期間使用することができる。また、機械的強度や付着特性にも優れるため、機械的強度と表面装飾性を有する用途に好適である。
本発明の硬化物は、針状メタケイ酸カルシウムに由来する表面光沢性を有する。また、成分（Ｅ）である修飾フィラーを含む場合には、それぞれの修飾フィラーに由来する意匠性を有する。
Since the cured product of the present invention can avoid or suppress the occurrence of the white fluff phenomenon, it does not cause a defective appearance due to the white fluff phenomenon even in an environment where it is likely to come into contact with moisture both outdoors and indoors, and is used for a long period of time. can do. Further, since it has excellent mechanical strength and adhesion properties, it is suitable for applications having mechanical strength and surface decoration.
The cured product of the present invention has surface glossiness derived from acicular calcium metasilicate. In addition, when the modified filler as the component (E) is included, the modified filler has a design property derived from each modified filler.
本発明の硬化物の用途は特に限定がなく、水分が接触しうる環境で使用される任意の用途に使用できる。具体的には、艶のあるパネル、塗り壁、各種プランターおよび花器などがある。 The application of the cured product of the present invention is not particularly limited, and it can be used for any application used in an environment where moisture can come into contact. Specific examples include glossy panels, painted walls, various planters, and vase.
本発明の水硬化型組成物は、既存の白華現象が生じる対象に対しても使用することもできる。すなわち、本発明の白華現象の防止方法は、本発明の水硬化型組成物を、水と混合して硬化する前に、白華現象が生じる対象に塗工し、硬化させる工程を有する方法である。 The water-curable composition of the present invention can also be used for an object in which existing white bloom phenomenon occurs. That is, the method for preventing the white flower phenomenon of the present invention is a method having a step of applying the water-curable composition of the present invention to an object on which the white flower phenomenon occurs and curing the mixture before curing by mixing with water. Is.
このような用途で使用する対象は、加水した本発明の水硬化型組成物を塗工できるものであれば任意である。特に、コンクリートを使用した既存の建設物は好適な対象であり、内外壁や床面にも使用することができる。 The object to be used in such an application is arbitrary as long as it can be coated with the water-curable water-curable composition of the present invention. In particular, existing constructions using concrete are suitable targets, and can also be used for inner and outer walls and floor surfaces.
また、水硬化型組成物は、塗工対象に対する接着力に優れ、かつ、硬化した後には優れた機械的強度と意匠性を有する。また、ベースとなる水硬化型組成物（成分（Ａ）〜（Ｄ））は白色であるため着色材を混合したり、硬化後の表面を着色したりして、任意の色にすることができる。そのため、塗工対象が既に白華現象が生じていた場合でも、外観を改善することが容易である。 In addition, the water-curable composition has excellent adhesion to the object to be coated, and also has excellent mechanical strength and design after being cured. In addition, since the water-curable composition (components (A) to (D)) serving as a base is white, it is possible to mix it with a coloring material or to color the surface after curing to obtain an arbitrary color. it can. Therefore, it is easy to improve the appearance even if the subject to be coated has already had the white bloom phenomenon.
以上、本発明を詳細に説明したが、これらは例示であって制限的なものではない。特に、上記で明示的に開示されていない事項は、当業者が通常実施する範囲を逸脱するものではなく、通常の当業者であれば、容易に想定することが可能な値を採用することができる。 Although the present invention has been described in detail above, these are examples and are not restrictive. In particular, matters that are not explicitly disclosed above do not depart from the scope normally practiced by those skilled in the art, and those skilled in the art can easily adopt values that can be easily assumed. it can.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
（１）原材料
成分（Ａ）〜（Ｄ）として、以下を使用した。
・成分（Ａ）：「マグネシア系結合材」
酸化マグネシウム５０重量部、硫酸マグネシウム２５重量部、塩化マグネシウム２５重 量部を、均一になるまで混合して得られたマグネシア系結合材を使用した。
・成分（Ｂ）：「針状メタケイ酸カルシウム」
ワラストナイト（NYCO Miner ala社、長さ：６００μｍ、アスペクト比：１５）を使用した。
・成分（Ｃ１）：「水性シリコーン変性ウレタン樹脂エマルジョン」
製品名：セラネートＷＨＷ−８２２、メーカー：ＤＩＣ（株）
・成分（Ｃ２）：「水系シラン撥水性エマルジョン」
製品名：プロテクトシルＳＣコンセントレイト、メーカー：ＢＡＳＦジャパン（株）
・成分（Ｄ）：「カルボキシメチルセルロース」
製品名：ＣＭＣＴＤ−１、メーカー：(株)立花マテリアル
(1) Raw materials The following were used as components (A) to (D).
・ Component (A): "Magnesia binder"
A magnesia-based binder obtained by mixing 50 parts by weight of magnesium oxide, 25 parts by weight of magnesium sulfate, and 25 parts by weight of magnesium chloride until they were homogeneous was used.
・ Component (B): "Needle-shaped calcium metasilicate"
Wollastonite (NYCO Miner ala, length: 600 μm, aspect ratio: 15) was used.
・ Component (C1): "Aqueous silicone modified urethane resin emulsion"
Product name: Serrate WHW-822, Manufacturer: DIC Corporation
・ Component (C2): "Water-based silane water-repellent emulsion"
Product name: Protect Sil SC Concentrate, Manufacturer: BASF Japan Ltd.
・ Component (D): "Carboxymethyl cellulose"
Product name: CMCTD-1, Manufacturer: Tachibana Material Co., Ltd.
（２）サンプルの調製
（実験例１）
成分（Ａ）１００重量部と成分（Ｂ）１０重量部とを均一になるまで混合することにより、実験例１の組成物を得た。実験例１の組成物１０００ｇに、水３００ｇを加えて、均一になるまで混合し、シート状に成形したのちに、室温で４８時間養生し、実験例１の硬化物（シート状）を得た。
(2) Preparation of sample (Experimental example 1)
The composition of Experimental Example 1 was obtained by mixing 100 parts by weight of the component (A) and 10 parts by weight of the component (B) until uniform. To 1000 g of the composition of Experimental Example 1, 300 g of water was added, mixed until uniform, molded into a sheet, and then cured at room temperature for 48 hours to obtain a cured product (sheet) of Experimental Example 1. .
（実験例２）
実験例１の組成物１００重量部に対し、成分（Ｄ）１重量部を加え、均一になるまで混合することにより、実験例２の組成物を得た。実験例２の組成物１０００ｇに、水３００ｇを加えて、均一になるまで混合し、シート状に成形したのちに、室温で４８時間養生し、実験例２の硬化物（シート状）を得た。
(Experimental example 2)
To 100 parts by weight of the composition of Experimental Example 1, 1 part by weight of the component (D) was added and mixed until uniform to obtain a composition of Experimental Example 2. To 1000 g of the composition of Experimental Example 2, 300 g of water was added, mixed until uniform, molded into a sheet, and then aged at room temperature for 48 hours to obtain a cured product (sheet) of Experimental Example 2. .
（実験例３）
実験例１の組成物１００重量部に対し、成分（Ｃ１）８重量部、成分（Ｄ）１重量部を加え、均一になるまで混合することにより、実験例３の組成物を得た。実験例３の組成物１０００ｇに、水３００ｇを加えて、均一になるまで混合し、シート状に成形したのちに、室温で４８時間養生し、実験例３の硬化物（シート状）を得た。
(Experimental example 3)
To 100 parts by weight of the composition of Experimental Example 1, 8 parts by weight of the component (C1) and 1 part by weight of the component (D) were added and mixed until uniform to obtain a composition of the experimental example 3. To 1000 g of the composition of Experimental Example 3, 300 g of water was added, mixed until uniform, molded into a sheet, and then aged at room temperature for 48 hours to obtain a cured product (sheet) of Experimental Example 3. .
（実験例４）
実験例１の組成物１００重量部に対し、成分（Ｃ２）４重量部、成分（Ｄ）１重量部を加え、均一になるまで混合することにより、実験例４の組成物を得た。実験例４の組成物１０００ｇに、水３００ｇを加えて、均一になるまで混合し、シート状に成形したのちに、室温で４８時間養生し、実験例４の硬化物（シート状）を得た。
(Experimental example 4)
To 100 parts by weight of the composition of Experimental Example 1, 4 parts by weight of the component (C2) and 1 part by weight of the component (D) were added and mixed until uniform to obtain a composition of the experimental example 4. To 1000 g of the composition of Experimental Example 4, 300 g of water was added, mixed until uniform and molded into a sheet, and then cured at room temperature for 48 hours to obtain a cured product (sheet) of Experimental Example 4. .
（３）評価方法・結果
白華現象の評価は以下の方法で行った。
実験例１〜４の硬化物（シート状、約１０×２０ｃｍ、厚み：約１ｃｍ）の下半分を水につけて、上半分を空気中に晒した状態で、経過日数７日の間に、水面の境界の上（上半分）で、どのような変状が生じるかを観察した。温度は２０〜２５℃であった。
この評価では、空気中に晒された部分（硬化物上半分）には常に水蒸気が接触し、白華現象が起こりやすい条件である。
評価開始から、それぞれの硬化物（空気暴露部分）を目視にて確認したところ、成分（Ａ）「マグネシア系結合材」及び成分（Ｂ）「針状メタケイ酸カルシウム」からなる実験例１の硬化物は、評価開始１日後には全面に白い粉状物が生成する著しい白華現象が確認された（図示せず）。また、成分（Ａ）、（Ｂ）及び成分（Ｄ）「カルボキシメチルセルロース」からなる実験例２の硬化物についても、評価開始１日後には白い粉状物が生成しはじめ、評価開始７日後には多量の粉状物が生成していた（図１（写真１）参照）。
(3) Evaluation method / result The evaluation of the white flower phenomenon was performed by the following method.
In the state where the lower half of the cured product of Experimental Examples 1 to 4 (sheet, about 10 × 20 cm, thickness: about 1 cm) was immersed in water and the upper half was exposed to the air, the surface of the water surface was changed over 7 days. We observed what kind of deformation occurred above the boundary (upper half). The temperature was 20-25 ° C.
In this evaluation, water vapor is always in contact with the part exposed to the air (upper half of the cured product), which is a condition under which the white bloom phenomenon easily occurs.
When each cured product (air-exposed portion) was visually confirmed from the start of the evaluation, curing of Experimental Example 1 composed of component (A) "magnesia-based binder" and component (B) "acicular calcium metasilicate" One day after the start of evaluation, it was confirmed that a white powdery substance was generated on the entire surface of the product (not shown). Also, with regard to the cured product of Experimental Example 2 composed of the components (A), (B) and the component (D) "carboxymethyl cellulose", a white powdery substance started to be formed one day after the start of evaluation, and seven days after the start of evaluation. A large amount of powder was generated (see Fig. 1 (Photo 1)).
一方、成分（Ａ）、（Ｂ）、（Ｄ）及び成分（Ｃ１）「水性シリコーン変性ウレタン樹脂エマルジョン」からなる実験例３の硬化物では、評価開始１日後には白い粉状物が認められず、評価開始７日後においてもわずかな粉状物が認められるのみであった（図２（写真２）参照）。
さらに、成分（Ａ）、（Ｂ）、（Ｄ）及び成分（Ｃ２）「水系シラン撥水性エマルジョン」からなる実験例４の硬化物では、評価開始１日後のみならず、評価開始７日後においても粉状物の生成が認められなかった。（図３（写真３）参照）。
以上の結果から、成分（Ｃ１）、成分（Ｃ２）を含有させることによって、マグネシア系水硬化型組成物の白華現象を抑制できることが確認された。
On the other hand, in the cured product of Experimental Example 3 composed of the components (A), (B), (D) and the component (C1) "aqueous silicone modified urethane resin emulsion", a white powdery substance was observed one day after the start of evaluation. Nonetheless, a slight amount of powdery matter was observed even 7 days after the start of evaluation (see FIG. 2 (Photo 2)).
Furthermore, in the cured product of Experimental Example 4 including the components (A), (B), (D) and the component (C2) "water-based silane water-repellent emulsion", not only 1 day after the start of evaluation but also 7 days after the start of evaluation. No formation of powder was observed. (See FIG. 3 (Photo 3)).
From the above results, it was confirmed that the white bloom phenomenon of the magnesia-based water-curable composition can be suppressed by containing the component (C1) and the component (C2).
本発明の水硬化型組成物は、加水するだけで容易に硬化させることでき、白華現象の生じない硬化物が得られるので、産業上有望である。 INDUSTRIAL APPLICABILITY The water-curable composition of the present invention is industrially promising because it can be easily cured by just adding water to obtain a cured product that does not cause the white bloom phenomenon.
Claims (7)
成分（Ａ）：酸化マグネシウム、硫酸マグネシウムおよび塩化マグネシウムを含み、酸化マグネシウムの含有量（重量基準）が、硫酸マグネシウムおよび塩化マグネシウムのいずれの含有量より多いマグネシア系結合材
成分（Ｂ）：針状メタケイ酸カルシウム
成分（Ｃ）：水性シリコーン変性ウレタン樹脂エマルジョン及び/又は水系シラン撥水性エマルジョン
成分（Ｄ）：カルボキシメチルセルロース、ヒドロキシエチルセルロース又はカルボキシエチルセルロースからなる水溶性高分子分散助剤 A water-curable composition comprising the following components.
Ingredient (A): Magnesia-based binder containing magnesium oxide, magnesium sulfate and magnesium chloride and having a magnesium oxide content (weight basis) higher than that of either magnesium sulfate or magnesium chloride Component (B): acicular Calcium metasilicate component (C): Water-based silicone-modified urethane resin emulsion and / or water-based silane water-repellent emulsion component (D): Water-soluble polymer dispersion aid consisting of carboxymethyl cellulose, hydroxyethyl cellulose or carboxyethyl cellulose
成分（Ａ）及び成分（Ｂ）の合計１００重量部に対する成分（Ｃ）の重量割合が３〜１５重量部、成分（Ｄ）の重量割合が０．３〜５重量部である請求項１から３のいずれかに記載の水硬化型組成物。 The weight ratio of the component (B) to 100 parts by weight of the component (A) is 5 to 45 parts by weight,
The weight ratio of the component (C) to the total of 100 parts by weight of the component (A) and the component (B) is 3 to 15 parts by weight, and the weight ratio of the component (D) is 0.3 to 5 parts by weight. The water-curable composition according to any one of 3 above.
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