JP2018145043A - Viscosity modifier for cement compositions, and cement composition - Google Patents
Viscosity modifier for cement compositions, and cement composition Download PDFInfo
- Publication number
- JP2018145043A JP2018145043A JP2017040265A JP2017040265A JP2018145043A JP 2018145043 A JP2018145043 A JP 2018145043A JP 2017040265 A JP2017040265 A JP 2017040265A JP 2017040265 A JP2017040265 A JP 2017040265A JP 2018145043 A JP2018145043 A JP 2018145043A
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- Japan
- Prior art keywords
- fatty acid
- full ester
- acid full
- cement composition
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
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Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明はセメント組成物粘性調整剤及びこれを含んでなるセメント組成物に関する。 The present invention relates to a cement composition viscosity modifier and a cement composition comprising the same.
保水性、鏝すべり性、鏝切れ性及び再接着性防止に優れる水硬性材料用混和剤として、「水溶性セルロースエーテル（Ａ）及び水不溶性樹脂粒子（Ｂ）を必須とする水硬性材料用混和剤であって、
前記樹脂粒子（Ｂ）の平均粒子径が１〜５０μｍであり、
前記樹脂粒子（Ｂ）の比重が０．５〜１．５であり、
前記セルロースエーテル（Ａ）１００重量部に対する、前記樹脂粒子（Ｂ）の重量割合が５〜２００重量部である、水硬性材料用混和剤」が提案されている（特許文献１）。
As an admixture for hydraulic materials that is excellent in water retention, slipperiness, tearability, and re-adhesion prevention, “admixture for hydraulic materials that requires water-soluble cellulose ether (A) and water-insoluble resin particles (B) as essential. An agent,
The resin particles (B) have an average particle diameter of 1 to 50 μm,
The resin particles (B) have a specific gravity of 0.5 to 1.5,
There has been proposed a hydraulic material admixture in which the weight ratio of the resin particles (B) is 5 to 200 parts by weight with respect to 100 parts by weight of the cellulose ether (A) (Patent Document 1).
従来の水硬性材料用混和剤を用いると、セメント組成物の鏝捌き性（鏝切れ性、鏝伸び性等）が不十分であるという問題に加え、セメント組成物硬化体の耐水性が不十分であるという問題がある。
本発明の目的は、セメント組成物の鏝捌き性（鏝切れ性、鏝伸び性等）に優れ、セメント組成物硬化体の耐水性に優れたセメント組成物粘性調整剤を提供することである。
When conventional admixtures for hydraulic materials are used, in addition to the problem that the cement composition is insufficiently pliable (breakability, wrinkle elongation, etc.), the water resistance of the cured cement composition is insufficient. There is a problem that.
An object of the present invention is to provide a cement composition viscosity modifier that is excellent in the tearability (breakability, tear elongation, etc.) of the cement composition and excellent in water resistance of the hardened cement composition.
本発明のセメント組成物用粘性調整剤は、多価アルコール脂肪酸フルエステル（Ａ）を含んでなる点を要旨とする。 The viscosity adjusting agent for cement composition of the present invention is summarized as comprising a polyhydric alcohol fatty acid full ester (A).
本発明のセメント組成物用粘性調整剤は、セメント組成物に優れた鏝捌き性（鏝切れ性、鏝伸び性等）を付与でき、セメント組成物硬化体に優れた耐水性を付与できる。 The viscosity adjusting agent for a cement composition of the present invention can impart excellent tearability (breakability, tear elongation, etc.) to the cement composition, and can impart excellent water resistance to the cured cement composition.
多価アルコール脂肪酸フルエステル（Ａ）は、多価アルコールと脂肪酸とのフルエステルであれば制限なく使用でき、１種類の多価アルコールと複数種類の脂肪酸とのフルエステルであってもよく、１種類の多価アルコールと１種類の脂肪酸とのフルエステルであってもよく、これらのいずれかの混合物又はこれらの混合物であってもよい。 The polyhydric alcohol fatty acid full ester (A) can be used without limitation as long as it is a full ester of a polyhydric alcohol and a fatty acid, and may be a full ester of one kind of polyhydric alcohol and a plurality of kinds of fatty acids. It may be a full ester of one kind of polyhydric alcohol and one kind of fatty acid, or a mixture of these or a mixture thereof.
多価アルコールとしては、ジオール、トリオール及び４〜１４価のポリオールが含まれる。
ジオールとしては、炭素数２〜６のジオールが含まれ、エチレングリコール、プロピレングリコール、ブチレングリコール、イソブチレングリコール及びシクロヘキサンジオール等が挙げられる。
Examples of the polyhydric alcohol include diols, triols, and 4- to 14-valent polyols.
Examples of the diol include diols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, isobutylene glycol, and cyclohexanediol.
トリオールとしては、炭素数３〜６のトリオールが含まれ、トリメチロールエタン、トリメチロールプロパン、グリセリン、ヘキサントリオール及びシクロヘキサントリオール等が挙げられる。 Triols include triols having 3 to 6 carbon atoms, and examples include trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and cyclohexanetriol.
４〜１４価のポリオールとしては、ポリグリセリン｛ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン、ノナグリセリン、デカグリセリン、ウンデカグリセリン、ドデカグリセリン等｝及び糖類｛ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ソルビタン、ソルビトール、マンノース、グルコース、ガラクトース、スクロース、ラクトース、ラフィノース、メレジトース、アカルボース、スタキオース等｝等が挙げられる。 Examples of the 4- to 14-valent polyol include polyglycerin {diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, undecaglycerin, dodecaglycerin, etc.} and sugars { Pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, sorbitol, mannose, glucose, galactose, sucrose, lactose, raffinose, melezitose, acarbose, stachyose, etc.}.
これらのうち、トリオール及び４〜８価のポリオールが好ましく、さらに好ましくはトリオール、特に好ましくはトリメチロールエタン、トリメチロールプロパン及びグリセリン、最も好ましくはグリセリンである。 Of these, triols and 4- to 8-valent polyols are preferable, triols are more preferable, trimethylolethane, trimethylolpropane, and glycerin are most preferable, and glycerin is most preferable.
脂肪酸としては、飽和脂肪酸及び不飽和脂肪酸が含まれる。
飽和脂肪酸としては、炭素数２〜３０の飽和脂肪酸が含まれ、直鎖飽和脂肪酸及び分岐飽和脂肪酸が使用できる。
Fatty acids include saturated fatty acids and unsaturated fatty acids.
As a saturated fatty acid, a C2-C30 saturated fatty acid is contained, and a linear saturated fatty acid and a branched saturated fatty acid can be used.
直鎖飽和脂肪酸としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、セロチン酸及びメリシン酸等が挙げられる。 Examples of the linear saturated fatty acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, and melicic acid.
分岐飽和脂肪酸としては、イソ酪酸、イソ吉草酸、ピバル酸及びイソステアリン酸等が挙げられる。 Examples of the branched saturated fatty acid include isobutyric acid, isovaleric acid, pivalic acid, and isostearic acid.
不飽和脂肪酸としては、炭素数３〜３０の直鎖不飽和脂肪酸が含まれ、直鎖不飽和脂肪酸及び分岐不飽和脂肪酸が使用できる。 As unsaturated fatty acid, a C3-C30 linear unsaturated fatty acid is contained, and a linear unsaturated fatty acid and a branched unsaturated fatty acid can be used.
直鎖不飽和脂肪酸としては、アクリル酸、クロトン酸、ヘプテン酸、ミリストレイン酸、パルミトレイン酸、オレイン酸及びトリアコンテン酸等が挙げられる。 Examples of the linear unsaturated fatty acid include acrylic acid, crotonic acid, heptenoic acid, myristoleic acid, palmitoleic acid, oleic acid and triacontenoic acid.
分岐不飽和脂肪酸としては、メタクリル酸、イソミリストレイン酸及びイソオレイン酸等が挙げられる。 Examples of branched unsaturated fatty acids include methacrylic acid, isomiristoleic acid and isooleic acid.
これらのうち、鏝捌き性及び耐水性の観点から、直鎖飽和脂肪酸及び直鎖不飽和脂肪酸が好ましく、さらに好ましくはラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、クロトン酸、ヘプテン酸、ミリストレイン酸、パルミトレイン酸及びオレイン酸、特に好ましくはミリスチン酸、パルミチン酸、ステアリン酸、ミリストレイン酸、パルミトレイン酸及びオレイン酸、最も好ましくはパルミチン酸、ステアリン酸、パルミトレイン酸及びオレイン酸である。 Of these, linear saturated fatty acids and linear unsaturated fatty acids are preferred from the viewpoints of water resistance and water resistance, more preferably lauric acid, myristic acid, palmitic acid, stearic acid, crotonic acid, heptenoic acid, myristolein. Acids, palmitoleic acid and oleic acid, particularly preferably myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid and oleic acid, most preferably palmitic acid, stearic acid, palmitoleic acid and oleic acid.
多価アルコール脂肪酸フルエステル（Ａ）は、多価アルコールと脂肪酸とから公知の方法（エステル化反応）で製造してもよいし、動植物に由来するものを使用してもよく、市場からも容易に入手できるものも少なくない。 The polyhydric alcohol fatty acid full ester (A) may be produced from a polyhydric alcohol and a fatty acid by a known method (esterification reaction), or may be derived from animals or plants and easily from the market. There are many things that can be obtained.
１種類の多価アルコールと複数種類の脂肪酸とのフルエステルとして、市場から入手できる商品としては、大豆油、ヤシ油、パーム油、アマニ油、綿実油及びナタネ油｛日清オイリオ株式会社｝等が挙げられる。 As a full ester of one kind of polyhydric alcohol and a plurality of kinds of fatty acids, products available from the market include soybean oil, palm oil, palm oil, linseed oil, cottonseed oil and rapeseed oil {Nisshin Oilio Co., Ltd.} Can be mentioned.
１種類の多価アルコールと１種類の脂肪酸とのフルエステルとして、市場から入手できる商品としては、トリミリスチン（グリセリンのミリスチン酸トリエステル）、トリステアリン（グリセリンのステアリン酸トリエステル）、トリオレイン（グリセリンのオレイン酸トリエステル）、トリパルミチン（グリセリンのパルミチン酸トリエステル）及びトリベヘニン（グリセリンのベヘニン酸トリエステル）{東京化成工業株式会社}等が挙げられる。 As a full ester of one kind of polyhydric alcohol and one kind of fatty acid, commercially available products include trimyristin (glycerol myristate triester), tristearin (glycerol stearate triester), triolein ( Glycerin oleic acid triester), tripalmitin (glycerin palmitic acid triester) and tribehenine (glycerin behenic acid triester) {Tokyo Chemical Industry Co., Ltd.}.
多価アルコール脂肪酸フルエステル（Ａ）の純度（重量％）は、多価アルコール脂肪酸フルエステルを主成分として含まれていれば制限はないが、８０以上が好ましく、さらに好ましくは９０以上、特に好ましくは９５以上である。この範囲であると、鏝捌き性がさらに良好となる。 The purity (% by weight) of the polyhydric alcohol fatty acid full ester (A) is not limited as long as it contains the polyhydric alcohol fatty acid full ester as a main component, but is preferably 80 or more, more preferably 90 or more, particularly preferably. Is 95 or more. Within this range, the sagability is further improved.
純度は、多価アルコール脂肪酸フルエステルの状態等によって定量方法が決定され、公知の定量方法（液体クロマトグラフィー法、ガスクロマトグラフィー法等）によって定量される。 The purity is quantified by a known quantification method (liquid chromatography method, gas chromatography method, etc.) depending on the state of the polyhydric alcohol fatty acid full ester and the like.
１種類の多価アルコールと複数種類の脂肪酸とのフルエステルの酸価（ｍｇＫＯＨ／ｇ）は、１５以下が好ましく、さらに好ましくは１０以下、特に好ましくは５以下、最も好ましくは２以下である。この範囲であると、鏝捌き性がさらに良好となる。 The acid value (mgKOH / g) of the full ester of one kind of polyhydric alcohol and a plurality of kinds of fatty acids is preferably 15 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. Within this range, the sagability is further improved.
酸価は、ＪＩＳ Ｋ００７０−１９９２の「３．１中和滴定」に準拠して測定される。 The acid value is measured according to “3.1 Neutralization titration” of JIS K0070-1992.
１種類の多価アルコールと１種類の脂肪酸とのフルエステルの水酸基価（ｍｇＫＯＨ／ｇ）は、１５０以下が好ましく、さらに好ましくは１００以下、特に好ましくは５０以下、つぎに好ましくは３０以下、さらに好ましくは１５以下、最も好ましくは１０以下である。この範囲であると、鏝捌き性がさらに良好となる。 The hydroxyl value (mgKOH / g) of the full ester of one kind of polyhydric alcohol and one kind of fatty acid is preferably 150 or less, more preferably 100 or less, particularly preferably 50 or less, and then preferably 30 or less, Preferably it is 15 or less, most preferably 10 or less. Within this range, the sagability is further improved.
水酸基価は、ＪＩＳ Ｋ００７０−１９９２の「７．１中和滴定法」に準拠して測定される。 The hydroxyl value is measured according to “7.1 neutralization titration method” of JIS K0070-1992.
本発明のセメント組成物用粘性調整剤には、さらに多孔質粉体（Ｂ）を含むことが好ましく、多孔質粉体（Ｂ）の含有量（重量部）は、多価アルコール脂肪酸フルエステル（Ａ）１００重量部に対して、４０〜９９００が好ましく、さらに好ましくは５０〜１９００、特に好ましくは６０〜９００である。多孔質粉体（Ｂ）を含むと、セメント組成物用粘性調整剤がスラリー状乃至粉体状になるためセメント等とさらに均一混合しやすくなる。 The viscosity adjusting agent for cement composition of the present invention preferably further contains a porous powder (B), and the content (parts by weight) of the porous powder (B) is a polyhydric alcohol fatty acid full ester ( A) 40-9900 are preferable with respect to 100 weight part, More preferably, it is 50-1900, Most preferably, it is 60-900. When the porous powder (B) is contained, the viscosity adjusting agent for the cement composition becomes a slurry or a powder, so that it becomes easier to uniformly mix with cement or the like.
多孔質粉体（Ｂ）としては、多孔質粉体であれば制限がないが無機多孔質粉体が好ましく、さらに好ましくは酸化ケイ素、酸化アルミニウム、炭酸カルシウム及び炭酸マグネシウムからなる群より選ばれる少なくとも１種の多孔質粉体、特に好ましくは酸化ケイ素及び炭酸カルシウム、最も好ましくは酸化ケイ素である。 The porous powder (B) is not limited as long as it is a porous powder, but is preferably an inorganic porous powder, more preferably at least selected from the group consisting of silicon oxide, aluminum oxide, calcium carbonate and magnesium carbonate. One kind of porous powder, particularly preferably silicon oxide and calcium carbonate, most preferably silicon oxide.
多孔質粉体（Ｂ）のフタル酸ジ−ｎ−ブチル（ＤＢＰ）吸油量（ｍｌ／１００ｇ）は、１０〜５００が好ましく、さらに好ましくは５０〜４００、特に好ましくは１００〜３００である。この範囲であると、セメント等とさらに均一混合しやすくなる。 The porous powder (B) has a di-n-butyl phthalate (DBP) oil absorption (ml / 100 g) of preferably 10 to 500, more preferably 50 to 400, and particularly preferably 100 to 300. Within this range, it becomes easier to mix more uniformly with cement and the like.
ＤＢＰ吸油量は、ＪＩＳ Ｋ５１０１−１９９１に準拠して、２５℃で測定される値である（多孔性粉体（Ｂ）にジブチルフタレート（ＤＢＰ）を滴下しつつ練り合わせ、全体がかたい１つの塊となる点を終点とする。）。 The DBP oil absorption is a value measured at 25 ° C. in accordance with JIS K5101-1991 (kneading while dripping dibutyl phthalate (DBP) into the porous powder (B), and the whole is a hard lump. The point that becomes is the end point.)
多孔質粉体（Ｂ）を含む場合、多価アルコール脂肪酸フルエステル（Ａ）及び多孔質粉体（Ｂ）を均一混合できれば、本発明のセメント組成物用粘性調整剤の製造方法に制限はなく、多価アルコール脂肪酸フルエステル（Ａ）及び多孔質粉体（Ｂ）を一括して混合する方法（１）、多価アルコール脂肪酸フルエステル（Ａ）に多孔質粉体（Ｂ）を少量ずつ連続又は分割して加えながら混合する方法（２）、多孔質粉体（Ｂ）に多価アルコール脂肪酸フルエステル（Ａ）を少量ずつ連続又は分割して加えながら混合する方法（３）、多価アルコール脂肪酸フルエステル（Ａ）と多孔質粉体（Ｂ）を少量ずつ連続又は分割して混合する方法（４）等が適用できる。これらのうち、製造効率の観点等から、方法（３）が好ましい。 When the porous powder (B) is contained, the method for producing the viscosity adjusting agent for cement composition of the present invention is not limited as long as the polyhydric alcohol fatty acid full ester (A) and the porous powder (B) can be mixed uniformly. , Method (1) of mixing the polyhydric alcohol fatty acid full ester (A) and the porous powder (B) at once, the polyhydric alcohol fatty acid full ester (A) and the porous powder (B) successively Alternatively, the method of mixing while adding divided (2), the method of mixing while adding the polyhydric alcohol fatty acid full ester (A) to the porous powder (B) in small portions continuously or divided (3), the polyhydric alcohol A method (4) or the like in which the fatty acid full ester (A) and the porous powder (B) are mixed little by little or continuously can be applied. Among these, the method (3) is preferable from the viewpoint of production efficiency.
多孔質粉体（Ｂ）を含む場合、多価アルコール脂肪酸フルエステル（Ａ）及び多孔質粉体（Ｂ）を混合する攪拌混合装置としては、公知の攪拌混合装置が使用でき、プロペラ型攪拌機、ディゾルバー、ホモミキサー、ボールミル、サンドミル、ニーダー、ラインミキサー、リボンミキサー、傾胴ミキサー、オムニミキサー及びヘンシェルミキサー等が挙げられる。 When the porous powder (B) is included, as a stirring and mixing device for mixing the polyhydric alcohol fatty acid full ester (A) and the porous powder (B), a known stirring and mixing device can be used, and a propeller type stirrer, Examples include a dissolver, a homomixer, a ball mill, a sand mill, a kneader, a line mixer, a ribbon mixer, a tilt cylinder mixer, an omni mixer, and a Henschel mixer.
本発明のセメント組成物用粘性調整剤は、セメント組成物（セメントペースト、モルタル、コンクリート、セメントプラスター、ポリマーセメント、ポリマーモルタル、ポリマーコンクリート等）用粘性調整剤として好適である。また、本発明のセメント組成物用粘性調整剤は、石膏、漆喰、ドロマイトプラスター、ぱて、（粘土、珪藻土、ラッカーパテ、エポキシパテ、ポリエステルパテ、ラッカーパテ、炭酸カルシウムパテ等）等のコテ塗りにより塗装する際にも使用できる。 The viscosity modifier for cement composition of the present invention is suitable as a viscosity modifier for cement compositions (cement paste, mortar, concrete, cement plaster, polymer cement, polymer mortar, polymer concrete, etc.). In addition, the viscosity adjusting agent for cement composition of the present invention is coated by iron coating such as gypsum, plaster, dolomite plaster, pallet (clay, diatomaceous earth, lacquer putty, epoxy putty, polyester putty, lacquer putty, calcium carbonate putty, etc.). Can also be used.
本発明のセメント組成物用粘性調整剤の使用量（重量％）は、多価アルコール脂肪酸フルエステル（Ａ）の重量がセメントの重量に基づいて、０．０１〜１０となる量が好ましく、さらに好ましくは０．０３〜５となる量、特に好ましくは０．０５〜３となる量である。この範囲であると、鏝捌き性がさらに良好となる。 The use amount (% by weight) of the viscosity adjusting agent for cement composition of the present invention is preferably such that the weight of the polyhydric alcohol fatty acid full ester (A) is 0.01 to 10 based on the weight of the cement. The amount is preferably 0.03 to 5, particularly preferably 0.05 to 3. Within this range, the sagability is further improved.
本発明のセメント組成物は、セメント、水及び上記のセメント組成物用粘性調整剤を含んでいれば、調製方法やその他の添加剤の有無、各含有量等は通常のセメント組成物と変わらない。 As long as the cement composition of the present invention contains cement, water, and the above viscosity modifier for cement composition, the preparation method, the presence or absence of other additives, each content, etc. are the same as those of a normal cement composition. .
セメントとしては、特に限定はなく、石膏及び／又はクリンカーを含んでいればよく、混合材料等を含んでいてもよい。 The cement is not particularly limited, and may include gypsum and / or clinker, and may include a mixed material.
セメント組成物には、骨材（砂、砂利等）や添加剤（ＡＥ剤、減水剤、ＡＥ減水剤、湿潤剤、膨張剤、防水剤、遅延剤、増粘剤、凝集剤、収縮低減剤、強度向上剤、硬化促進剤、消泡剤等）を含んでもよい。 For cement compositions, aggregates (sand, gravel, etc.) and additives (AE agent, water reducing agent, AE water reducing agent, wetting agent, swelling agent, waterproofing agent, retarder, thickener, flocculant, shrinkage reducing agent) , Strength improvers, curing accelerators, antifoaming agents, and the like.
以下、特記しない限り、部は重量部を意味する。
＜実施例１＞
多価アルコール脂肪酸フルエステル（Ａ１；トリオレイン、東京化成工業株式会社、グリセリンのオレイン酸トリエステル、ガスクロマトグラフィーによる純度８０重量％）をそのまま、本発明のセメント組成物用粘性調整剤（１）とした。
Hereinafter, unless otherwise specified, parts means parts by weight.
<Example 1>
Polyhydric alcohol fatty acid full ester (A1; Triolein, Tokyo Chemical Industry Co., Ltd., glycerin oleic acid triester, purity by gas chromatography 80% by weight) is used as it is, viscosity adjusting agent for cement composition of the present invention (1) It was.
＜実施例２＞
リボンミキサー（アルファー株式会社）を用いて、多孔質粉体（Ｂ１；Ｎｉｐｓｉｌ ＮＡ、東ソー・シリカ株式会社、酸化ケイ素、ＤＢＰ吸油量２５０ｍｌ／１００ｇ、「Nipsil」は同社の登録商標である。）６０部に、多価アルコール脂肪酸フルエステル（Ａ２；ナタネ油、酸価０．１ｍｇＫＯＨ／ｇ、日清オイリオ株式会社）１００部を少量ずつ滴下して、均一混合することにより、本発明のセメント組成物用粘性調整剤（２）を得た。
<Example 2>
Using a ribbon mixer (Alpha Co., Ltd.), porous powder (B1; Nipsil NA, Tosoh Silica Co., Ltd., silicon oxide, DBP oil absorption 250 ml / 100 g, “Nipsil” is a registered trademark of the company) 60 100 parts of polyhydric alcohol fatty acid full ester (A2; rapeseed oil, acid value 0.1 mg KOH / g, Nisshin Oilio Co., Ltd.) is added dropwise to a portion in small portions and uniformly mixed, whereby the cement composition of the present invention Viscosity modifier (2) was obtained.
＜実施例３＞
多孔質粉体（Ｂ１）６０部を、多孔質粉体（Ｂ２；Ｎｉｐｓｉｌ ＥＲ、東ソー・シリカ株式会社、酸化ケイ素、ＤＢＰ吸油量１８０ｍｌ／１００ｇ）９００部に変更したこと以外、実施例２と同様にして、本発明のセメント組成物用粘性調整剤（３）を得た。
<Example 3>
Example 2 except that 60 parts of the porous powder (B1) was changed to 900 parts of the porous powder (B2; Nipsil ER, Tosoh Silica Co., Ltd., silicon oxide, DBP oil absorption 180 ml / 100 g). Thus, a viscosity modifier (3) for a cement composition of the present invention was obtained.
＜実施例４＞
多価アルコール脂肪酸フルエステル（Ａ２）を多価アルコール脂肪酸フルエステル（Ａ３；大豆油、酸価０．１ｍｇＫＯＨ／ｇ、日清オイリオ株式会社）に変更したこと以外、実施例２と同様にして、本発明のセメント組成物用粘性調整剤（４）を得た。
<Example 4>
In the same manner as in Example 2, except that the polyhydric alcohol fatty acid full ester (A2) was changed to the polyhydric alcohol fatty acid full ester (A3; soybean oil, acid value 0.1 mg KOH / g, Nisshin Oilio Co., Ltd.) A viscosity modifier (4) for a cement composition of the present invention was obtained.
＜実施例５＞
多価アルコール脂肪酸フルエステル（Ａ２）を多価アルコール脂肪酸フルエステル（Ａ４；綿実油、酸価２ｍｇＫＯＨ／ｇ、日清オイリオ株式会社）に変更したこと以外、実施例２と同様にして、本発明のセメント組成物用粘性調整剤（５）を得た。
<Example 5>
In the same manner as in Example 2, except that the polyhydric alcohol fatty acid full ester (A2) was changed to a polyhydric alcohol fatty acid full ester (A4; cottonseed oil, acid value 2 mgKOH / g, Nissin Oilio Co., Ltd.) A viscosity modifier for cement composition (5) was obtained.
＜実施例６＞
多孔質粉体（Ｂ１）を、多孔質粉体（Ｂ３；ＳＩＬＹＳＩＡ ３７０、富士シリシア化学株式会社、酸化ケイ素、ＤＢＰ吸油量３００ｍｌ／１００ｇ、「SILYSIA」は有限会社ワイ・ケイ・エフの登録商標である。）に変更したこと以外、実施例２と同様にして、本発明のセメント組成物用粘性調整剤（６）を得た。
<Example 6>
Porous powder (B1), porous powder (B3; SILYSIA 370, Fuji Silysia Chemical Co., Ltd., silicon oxide, DBP oil absorption 300ml / 100g, "SILYSIA" is a registered trademark of WK FF Ltd. The viscosity adjusting agent for cement composition (6) of the present invention was obtained in the same manner as in Example 2 except that the above was changed.
＜実施例７＞
多孔質粉体（Ｂ１）を、多孔質粉体（Ｂ４；ＳＩＬＹＳＩＡ ７１０、富士シリシア化学株式会社、酸化ケイ素、ＤＢＰ吸油量１００ｍｌ／１００ｇ）に変更したこと以外、実施例２と同様にして、本発明のセメント組成物用粘性調整剤（７）を得た。
<Example 7>
Except that the porous powder (B1) was changed to a porous powder (B4; SILYSIA 710, Fuji Silysia Chemical Co., Ltd., silicon oxide, DBP oil absorption 100 ml / 100 g), the same procedure as in Example 2 was performed. A viscosity adjusting agent (7) for a cement composition of the invention was obtained.
＜比較例１＞
特許文献１の実施例４の記載に準拠して、リボンミキサー（アルファ株式会社）を用いて、水溶性セルロースエーテル（マーポローズ ９０ＭＰ−４０００、松本油脂製薬株式会社、ヒドロキシプロピルメチルセルロース）１００部及び水不溶性樹脂粒子{マツモトマイクロスフェアーＭ−１００、松本油脂製薬株式会社、ＰＭＭＡ樹脂、平均粒子径８μｍ、比重１．２０）５０部を均一混合して、比較用のセメント組成物用粘性調整剤（Ｄ１）を得た。
<Comparative Example 1>
In accordance with the description of Example 4 of Patent Document 1, 100 parts of water-soluble cellulose ether (Marporose 90MP-4000, Matsumoto Yushi Seiyaku Co., Ltd., hydroxypropylmethylcellulose) and a water-insoluble solution using a ribbon mixer (Alpha Corporation). 50 parts of resin particles (Matsumoto Microsphere M-100, Matsumoto Yushi Seiyaku Co., Ltd., PMMA resin, average particle diameter of 8 μm, specific gravity of 1.20) are uniformly mixed, and the viscosity adjuster for cement composition for comparison (D1) )
（鏝捌き性評価方法）
実施例で得たセメント組成物用粘性調整剤（１〜７）及び比較例で得たセメント組成物用粘性調整剤（Ｄ１）と下表の配合成分の配合量とを用いて、モルタルミキサーにて均一混合してセメント組成物（１〜７、Ｄ１）を調製した。
また、セメント組成物用粘性調整剤を水に変更したこと以外、同様にして、セメント組成物（ブランク）を調製した。
(Evaluation method for brilliance)
Using the viscosity adjusting agent for cement composition (1-7) obtained in Examples and the viscosity adjusting agent for cement composition (D1) obtained in Comparative Example and the blending amounts of the blending components shown in the table below, And uniformly mixed to prepare cement compositions (1-7, D1).
Further, a cement composition (blank) was prepared in the same manner except that the viscosity modifier for cement composition was changed to water.
使用する材料及び道具を２０℃に温度調整しこの温度で、３０×６０ｃｍのスレート板に厚さ１ｃｍになるように金鏝で調製した各セメント組成物を塗りつけて、次の基準で鏝捌き性を評価した。この結果を下表に示す。 Adjust the temperature of the materials and tools to be used to 20 ° C. At this temperature, apply each cement composition prepared with a hammer to a 30 × 60 cm slate plate to a thickness of 1 cm. Evaluated. The results are shown in the table below.
（鏝切れ）
○金鏝に試料が付着せず、平滑に塗りつけられた
△金鏝に試料が付着しないが、平滑に塗りつけられない
×金鏝に試料が付着する
(Cut out)
○ The sample does not adhere to the hammer and is applied smoothly △ The sample does not adhere to the hammer but cannot be applied smoothly × The sample adheres to the hammer
（鏝伸び）
○試料を容易に金鏝で押し広げることができ、平滑にできる
△試料を容易に鏝で押し広げることができるが、平滑にできない
×試料を容易に押し広げることができない
(Cradle growth)
○ The sample can be easily spread with a hammer and can be smoothed △ The sample can be easily spread with a hammer but cannot be smoothed × The sample cannot be easily spread
（耐水性評価）
調製した各セメント組成物（１〜７、Ｄ１、ブランク）をモールド（内寸１０×１０×１ｃｍ）に流し込み、振動を与え表面を水平にし、２０℃で1週間静置後、モールドを外して、１０×１０×１ｃｍの評価用硬化体を作製した。
評価用硬化体の表面に０．０２±０．００５ｍＬの脱イオン水を滴下し、１０秒後に水滴の接触角（度）を測定し、測定結果を下表に示す。接触角が大きいほど、水が表面に濡れにくいことを意味し、耐水性に優れている。なお、接触角の測定は協和化学株式会社製コンタクトアングルメーターＣＡＡを用いて２０℃温調室にて実施した。
(Water resistance evaluation)
Pour each prepared cement composition (1-7, D1, blank) into a mold (inner dimensions 10 x 10 x 1 cm), apply vibration, level the surface, leave it at 20 ° C for 1 week, then remove the mold. A cured body for evaluation of 10 × 10 × 1 cm was produced.
0.02 ± 0.005 mL of deionized water was dropped onto the surface of the evaluation cured body, and after 10 seconds, the contact angle (degree) of the water droplet was measured. The measurement results are shown in the table below. A larger contact angle means that water is less likely to get wet on the surface, and has better water resistance. The contact angle was measured using a contact angle meter CAA manufactured by Kyowa Chemical Co., Ltd. in a temperature controlled room at 20 ° C.
以上の通り、本発明のセメント組成物用粘性調整剤（１〜７）は、比較用のセメント組成物用粘性調整剤（Ｄ１）やブランクに比べて、鏝捌き性（鏝切れ性、鏝伸び性等）及び耐水性に優れていた。 As described above, the viscosity adjusting agent for cement composition (1 to 7) of the present invention is more flexible than the viscosity adjusting agent for cement composition (D1) or blank for comparison. Etc.) and water resistance.
Claims (5)
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