WO2013133296A1 - Aqueous painting material composition - Google Patents
Aqueous painting material composition Download PDFInfo
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- WO2013133296A1 WO2013133296A1 PCT/JP2013/056072 JP2013056072W WO2013133296A1 WO 2013133296 A1 WO2013133296 A1 WO 2013133296A1 JP 2013056072 W JP2013056072 W JP 2013056072W WO 2013133296 A1 WO2013133296 A1 WO 2013133296A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or 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 aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
- C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/06—Artists' paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- such an aqueous drawing material composition preferably contains hydroxyalkyl cellulose in the range of 0.1 to 10% by weight.
- GTR First Orange Lake, Lake Red C, Petite, Watching Red, Brilliant Carmine 6B, Permanent Red 2B, Permanent Red FRLL, Carmine Lake, Quinacridone Red, Methyl Violet Lake, First Violet B, Quinacridone Violet, Induslen Violet, Phthalocyanine blue, first sky blue, bitumen, ultramarine, Victoria blue lake, phthalocyanine Lee , It may be mentioned marker light green lake, Pigment Green B, viridian, Shen'na, amber, aluminum powder, bronze powder and the like, organic pigments, inorganic pigments and metal powder pigments.
- resin emulsions include, for example, acrylic resin emulsions such as Mobile DM772 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), TOCRYL W-168 (Toyo Ink Manufacturing Co., Ltd.), Nicazole RX866D (Nihon Carbide). Kogyo Co., Ltd.) and the like.
- acrylic resin emulsions such as Mobile DM772 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), TOCRYL W-168 (Toyo Ink Manufacturing Co., Ltd.), Nicazole RX866D (Nihon Carbide). Kogyo Co., Ltd.) and the like.
- vinyl acetate-acrylic resin emulsion for example, Movinyl DM-5 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be mentioned, and as acrylic-styrene resin emulsion. Examples thereof include Polysol AP-1900 (
- a high-boiling organic solvent is usually used so that the above-described resin emulsion can be dried to form a continuous coating film containing the above-described colorant and water-soluble resin.
- An appropriate amount of a film-forming aid may be included.
- the aqueous drawing material composition according to the present invention may contain a surfactant, if necessary.
- a surfactant at least one selected from nonionic and anionic surfactants is used in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Inorganic Chemistry (AREA)
Abstract
(Problem) Provided is an aqueous painting material composition that does not undergo bleeding or dissolution of the paint film even when water droplets adhere to the dried paint film, and has resistance to wetting by water to such an extent that the base coat does not move even when overpainted on the paint film of a base coat, in the same way as conventional emulsion paints, that nevertheless can be removed by washing with water even when it has long been adhered to and dried on a palette or paint brush.
(Solution) Provided is an aqueous painting material composition containing water, coloring pigment, and water-soluble resin and resin emulsion containing hydroxyalkyl cellulose and water-soluble styrene-acrylic resin, characterized in that the water-soluble styrene-acrylic resin is contained within a range of 0.5-6.5 wt% calculated for styrene-acrylic resin and the resin emulsion is contained within a range of from 0.1 wt% to less than 5 wt% in terms of solid content.
Description
本発明は、従来のエマルジョン絵具と同様に、塗膜が乾燥した後は、その塗膜に水滴が付着しても、塗膜に滲みや溶け出しが起こらず、また、下地の塗膜に重ね塗りしても、その下地に滲みや溶け出しが起こらない、即ち、下地が動かない程度に水濡れに対する抵抗性を有し、それでいて、パレットや絵筆に付着し、乾燥して、長期間経過した後にも、水洗いによって取り除くことができる水性描画材組成物に関する。
In the present invention, as in the case of conventional emulsion paints, after the coating film is dried, even if water droplets adhere to the coating film, the coating film does not bleed or dissolve, and the coating film is overlaid on the underlying coating film. Even if it is painted, the base does not bleed or dissolve, that is, it has resistance to water so that the base does not move, yet it adheres to the palette or paintbrush, dries, and has passed for a long time. The present invention also relates to an aqueous drawing material composition that can be removed later by washing with water.
従来、エマルジョン絵具として知られている水性描画材組成物は、水を溶媒とし、顔料を着色剤とし、樹脂エマルジョンを定着剤として有する一種の水性描画材組成物であって、描画面上に描画して、塗膜を形成した後、その塗膜から溶媒が蒸発し、塗膜が乾燥すれば、エマルジョン中の樹脂が造膜して、描画面上に水不溶性、従って、水濡れに対して抵抗性を有する塗膜を形成する。
An aqueous drawing material composition conventionally known as an emulsion paint is a kind of aqueous drawing material composition having water as a solvent, a pigment as a colorant, and a resin emulsion as a fixing agent. Then, after the coating film is formed, if the solvent evaporates from the coating film and the coating film dries, the resin in the emulsion is formed into a film, which is insoluble on the drawing surface, and therefore against water wetting. A coating film having resistance is formed.
このような従来のエマルジョン絵具は、上述したように、塗膜が水濡れに対する抵抗性にすぐれるように、樹脂エマルジョンを多く含むので（特許文献１及び２参照）、パレットや絵筆に付着して、乾燥した後には、水洗いによって取り除くことができない。
As described above, such a conventional emulsion paint contains a large amount of resin emulsion so that the coating film has excellent resistance to water wetting (see Patent Documents 1 and 2). Once dried, it cannot be removed by washing with water.
本発明は、従来のエマルジョン絵具における上述した問題を解決するためになされたものであって、従来のエマルジョン絵具と同様に、乾燥後の塗膜に水滴が付着しても、塗膜に滲みや溶け出しが起こらず、また、下地の塗膜上に重ね塗りしても、その下地が動かない程度に水濡れに対する抵抗性を有し、それでいて、パレットや絵筆に付着し、乾燥して、長期間が経過した後であっても、水洗いによって取り除くことができる水性描画材組成物を提供することを目的とする。
The present invention has been made to solve the above-described problems in conventional emulsion paints, and, as with conventional emulsion paints, even if water droplets adhere to the dried paint film, It doesn't melt out, and even if it's overcoated on the underlying film, it has resistance to water so that the base doesn't move, yet it adheres to the palette and paintbrush, dries, An object of the present invention is to provide an aqueous drawing material composition that can be removed by washing even after the period has elapsed.
本発明によれば、水、着色顔料、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂を含む水溶性樹脂及び樹脂エマルジョンを含む水性描画材組成物において、上記水溶性スチレン－アクリル樹脂をスチレン－アクリル樹脂換算で０．５～６．５重量％の範囲で含み、上記樹脂エマルジョンを固形分にて０．１重量％以上、５重量％未満の範囲にて含むことを特徴とする水性描画材組成物が提供される。
According to the present invention, in the aqueous drawing material composition comprising water, a color pigment, a water-soluble resin containing hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin, and a resin emulsion, the water-soluble styrene-acrylic resin is converted into a styrene-acrylic resin. An aqueous drawing material composition comprising 0.5 to 6.5% by weight in terms of conversion and containing the resin emulsion in a range of 0.1% by weight or more and less than 5% by weight in terms of solid content Is provided.
本発明によれば、このような水性描画材組成物は、ヒドロキシアルキルセルロースを０．１～１０重量％の範囲で含むことが好ましい。
According to the present invention, such an aqueous drawing material composition preferably contains hydroxyalkyl cellulose in the range of 0.1 to 10% by weight.
本発明による水性描画材組成物は、樹脂エマルジョンを固形分にて０．１重量％以上、５重量％未満の範囲にて含むと共に、水溶性樹脂として、水溶性スチレン－アクリル樹脂０．５～６．０重量％とヒドロキシアルキルセルロースを含むので、従来のエマルジョン絵具と同様に、乾燥後の塗膜に水滴が付着しても、塗膜に滲みや溶け出しが起こらず、また、下地の塗膜の上に重ね塗りしても、その下地が動かない程度に耐水性を有し、それでいて、パレットや絵筆に付着し、乾燥して、長期間が経過した後であっても、水洗いによって取り除くことができる。
The aqueous drawing material composition according to the present invention contains a resin emulsion in a range of 0.1% by weight or more and less than 5% by weight in terms of solid content, and water-soluble styrene-acrylic resin 0.5 to Since it contains 6.0% by weight and hydroxyalkyl cellulose, as with conventional emulsion paints, even if water droplets adhere to the dried coating film, the coating film does not bleed or dissolve, and the base coating Even if it is overcoated on the film, it has water resistance to the extent that its base does not move, yet it adheres to the palette and paintbrush, dries, and even after a long time has passed, it is removed by washing with water be able to.
以下、本発明において、簡単のために、水性描画材組成物の塗膜が乾燥した後、この塗膜に水滴が付着しても、塗膜の滲みや溶け出しが起こらず、また、下地の塗膜の上に重ね塗りしても、その下地が動かない程度に水濡れに対する抵抗性を有する性質を「耐水性」といい、水性描画材組成物がパレットや絵筆に付着し、乾燥した後にも、その描画組成物を水洗いによって取り除くことができる性質を「水洗い性」という。即ち、本発明による水性描画材組成物が形成した塗膜は、乾燥した後、耐水性と水洗い性を兼ね備えている。
Hereinafter, in the present invention, for the sake of simplicity, after the coating film of the aqueous drawing material composition is dried, even if water droplets adhere to the coating film, the coating film does not bleed or dissolve, The property that has resistance to water wetting to the extent that the base does not move even if it is overcoated on the coating is called "water resistance", and after the aqueous drawing material composition adheres to the palette or paintbrush and dries However, the property that the drawing composition can be removed by washing with water is called “washing property”. That is, the coating film formed by the aqueous drawing material composition according to the present invention has both water resistance and water washability after drying.
本発明による水性描画材組成物は、水、着色顔料、ドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂を含む水溶性樹脂及び樹脂エマルジョンを含む水性描画材組成物において、上記水溶性スチレン－アクリル樹脂をスチレン－アクリル樹脂換算で０．５～６．５重量％の範囲で含み、上記樹脂エマルジョンを固形分にて０．１重量％以上、５重量％未満の範囲にて含む。
The aqueous drawing material composition according to the present invention is an aqueous drawing material composition comprising water, a color pigment, a water-soluble resin containing droxyalkyl cellulose and a water-soluble styrene-acrylic resin, and a resin emulsion. Is contained in the range of 0.5 to 6.5% by weight in terms of styrene-acrylic resin, and the resin emulsion is contained in the range of 0.1 to 5% by weight in terms of solid content.
更に、本発明による水性描画材組成物は、ヒドロキシアルキルセルロースを０．１～１０重量％の範囲で含むことが好ましい。
Furthermore, the aqueous drawing material composition according to the present invention preferably contains hydroxyalkyl cellulose in the range of 0.1 to 10% by weight.
即ち、本発明による水性描画材組成物は、水溶性樹脂として、ヒドロキシアルキルセルロースを０．１～１０重量％とスチレン－アクリル樹脂換算で水溶性スチレン－アクリル樹脂０．５～６．５重量％の組み合わせを含むことが好ましい。特に、本発明によれば、水性描画材組成物は、水溶性樹脂として、上記ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂の組み合わせのみを含むことが好ましい。
That is, the aqueous drawing material composition according to the present invention comprises 0.1 to 10% by weight of hydroxyalkyl cellulose as a water-soluble resin and 0.5 to 6.5% by weight of water-soluble styrene-acrylic resin in terms of styrene-acrylic resin. It is preferable that the combination of these is included. In particular, according to the present invention, the aqueous drawing material composition preferably contains only the combination of the hydroxyalkyl cellulose and the water-soluble styrene-acrylic resin as the water-soluble resin.
（顔料）
本発明による水性描画材組成物において、着色剤には顔料が用いられる。この顔料は、特に限定されるものではなく、従来、知られている顔料であれば、いずれでも用いられる。具体例として、例えば、酸化チタン、酸化亜鉛、カーボンブラック、鉄黒、アニリンブラック、ハンザイエロー、ベンジジンイエロー、タートラジンレーキ、パーマネントイエロートナー、カドミウムイエロー、ベンジジンオレンジ、クロムバーミリオン、カドミウムオレンジ、パーマネントオレンジＧＴＲ、ファーストオレンジレーキ、レーキレッドＣ、弁柄、ワッチングレッド、ブリリアントカーミン６Ｂ、パーマネントレッド２Ｂ、パーマネントレッドＦＲＬＬ、カーマインレーキ、キナクリドンレッド、メチルバイオレットレーキ、ファーストバイオレットＢ、キナクリドンバイオレット、インダスレンバイオレット、フタロシアニンブルー、ファーストスカイブルー、紺青、群青、ビクトリアブルーレーキ、フタロシアニングリーン、マーカライトグリーンレーキ、ピグメントグリーンＢ、ビリジアン、シェンナー、アンバー、アルミニウム粉末、ブロンズ粉末等、有機顔料、無機顔料及び金属粉顔料を挙げることができる。 (Pigment)
In the aqueous drawing material composition according to the present invention, a pigment is used as the colorant. The pigment is not particularly limited, and any conventionally known pigment can be used. Specific examples include, for example, titanium oxide, zinc oxide, carbon black, iron black, aniline black, Hansa yellow, benzidine yellow, tartrazine lake, permanent yellow toner, cadmium yellow, benzidine orange, chrome vermillion, cadmium orange, and permanent orange. GTR, First Orange Lake, Lake Red C, Petite, Watching Red, Brilliant Carmine 6B, Permanent Red 2B, Permanent Red FRLL, Carmine Lake, Quinacridone Red, Methyl Violet Lake, First Violet B, Quinacridone Violet, Induslen Violet, Phthalocyanine blue, first sky blue, bitumen, ultramarine, Victoria blue lake, phthalocyanine Lee , It may be mentioned marker light green lake, Pigment Green B, viridian, Shen'na, amber, aluminum powder, bronze powder and the like, organic pigments, inorganic pigments and metal powder pigments.
本発明による水性描画材組成物において、着色剤には顔料が用いられる。この顔料は、特に限定されるものではなく、従来、知られている顔料であれば、いずれでも用いられる。具体例として、例えば、酸化チタン、酸化亜鉛、カーボンブラック、鉄黒、アニリンブラック、ハンザイエロー、ベンジジンイエロー、タートラジンレーキ、パーマネントイエロートナー、カドミウムイエロー、ベンジジンオレンジ、クロムバーミリオン、カドミウムオレンジ、パーマネントオレンジＧＴＲ、ファーストオレンジレーキ、レーキレッドＣ、弁柄、ワッチングレッド、ブリリアントカーミン６Ｂ、パーマネントレッド２Ｂ、パーマネントレッドＦＲＬＬ、カーマインレーキ、キナクリドンレッド、メチルバイオレットレーキ、ファーストバイオレットＢ、キナクリドンバイオレット、インダスレンバイオレット、フタロシアニンブルー、ファーストスカイブルー、紺青、群青、ビクトリアブルーレーキ、フタロシアニングリーン、マーカライトグリーンレーキ、ピグメントグリーンＢ、ビリジアン、シェンナー、アンバー、アルミニウム粉末、ブロンズ粉末等、有機顔料、無機顔料及び金属粉顔料を挙げることができる。 (Pigment)
In the aqueous drawing material composition according to the present invention, a pigment is used as the colorant. The pigment is not particularly limited, and any conventionally known pigment can be used. Specific examples include, for example, titanium oxide, zinc oxide, carbon black, iron black, aniline black, Hansa yellow, benzidine yellow, tartrazine lake, permanent yellow toner, cadmium yellow, benzidine orange, chrome vermillion, cadmium orange, and permanent orange. GTR, First Orange Lake, Lake Red C, Petite, Watching Red, Brilliant Carmine 6B, Permanent Red 2B, Permanent Red FRLL, Carmine Lake, Quinacridone Red, Methyl Violet Lake, First Violet B, Quinacridone Violet, Induslen Violet, Phthalocyanine blue, first sky blue, bitumen, ultramarine, Victoria blue lake, phthalocyanine Lee , It may be mentioned marker light green lake, Pigment Green B, viridian, Shen'na, amber, aluminum powder, bronze powder and the like, organic pigments, inorganic pigments and metal powder pigments.
また、上記以外にも、着色顔料として、染料や顔料を樹脂粉体と組み合わせた着色加工粉体、蛍光顔料、天然マイカの表面を金属酸化物で被覆した顔料、合成マイカの表面を金属酸化物で被覆したパール顔料等をも挙げることができる。
In addition to the above, as colored pigments, colored processed powders combining dyes and pigments with resin powders, fluorescent pigments, pigments with natural mica surfaces coated with metal oxides, and synthetic mica surfaces with metal oxides Examples thereof include pearl pigments coated with.
本発明によれば、水性描画材組成物は、このような顔料を、通常、１～４０重量％の範囲で含み、好ましくは、１０～３０重量％の範囲で含む。水性描画材組成物における顔料の量が１重量％よりも少ないときは、水性描画材組成物として、着色力に欠ける不具合がある。しかし、４０重量％を越えるときは、得られる水性描画材組成物の粘度が過度に高くなって、描画に際して、描画材組成物の伸びが悪く、描画性に劣る。
According to the present invention, the aqueous drawing material composition usually contains such a pigment in the range of 1 to 40% by weight, preferably in the range of 10 to 30% by weight. When the amount of the pigment in the aqueous drawing material composition is less than 1% by weight, the aqueous drawing material composition has a problem of lacking coloring power. However, when the amount exceeds 40% by weight, the viscosity of the resulting aqueous drawing material composition becomes excessively high, and the drawing material composition is poorly stretched during drawing, resulting in poor drawing performance.
更に、本発明によれば、水性描画材組成物は、上述したような着色剤としての顔料のほかに、必要に応じて、体質顔料を含んでいてもよい。このような体質顔料として、例えば、炭酸カルシウム、カオリン、タルク、シリカ、ケイ酸アルミニウム、アルミナ、硫酸バリウム等を挙げることができる。このような体質顔料は、必要に応じて、３０重量％以下、好ましくは、１～２５重量％の範囲で用いられる。
Furthermore, according to the present invention, the aqueous drawing material composition may contain extender pigments as necessary in addition to the pigment as the colorant as described above. Examples of such extender pigments include calcium carbonate, kaolin, talc, silica, aluminum silicate, alumina, and barium sulfate. Such extender pigments are used in an amount of 30% by weight or less, preferably 1 to 25% by weight, if necessary.
本発明による水性描画材組成物は、好ましくは、増粘剤を含む。増粘剤としては、例えば、ベントナイト、金属石鹸、ウレタンブロックポリマー等が用いられ、また、これら例示に限定されるものではないが、なかでも、適度の増粘効果を有し、しかも、得られる水性描画材組成物の塗膜の耐水性と水洗い性に影響を与えないことから、ベントナイトが特に好ましく用いられる。
The aqueous drawing material composition according to the present invention preferably contains a thickener. As the thickener, for example, bentonite, metal soap, urethane block polymer, and the like are used, and the thickener is not limited to these examples. Bentonite is particularly preferably used because it does not affect the water resistance and water washability of the coating film of the aqueous drawing material composition.
本発明において、増粘剤は、水性描画材組成物において、通常、１０重量％以下の範囲で用いられ、好ましくは、０．１～１０重量％、特に好ましくは、０．５～５重量％の範囲で用いられる。
In the present invention, the thickener is usually used in the range of 10% by weight or less in the aqueous drawing material composition, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight. It is used in the range.
（水溶性樹脂）
本発明による水性描画材組成物は、水溶性樹脂として、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂を含む。 (Water-soluble resin)
The aqueous drawing material composition according to the present invention contains hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as water-soluble resins.
本発明による水性描画材組成物は、水溶性樹脂として、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂を含む。 (Water-soluble resin)
The aqueous drawing material composition according to the present invention contains hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as water-soluble resins.
本発明において、ヒドロキシアルキルセルロースは、水性描画材組成物において顔料を分散させるための分散剤として機能すると共に、エマルジョン樹脂と共同して塗膜を描画面に定着させるための定着剤として機能し、そして、一方において、水性描画材組成物がパレットや絵筆に付着し、乾燥した場合にも、水洗いによって、これを取り除くことを可能とするための水洗い性、即ち、弱い水溶性を水性描画材組成物に与えるように機能する。
In the present invention, the hydroxyalkyl cellulose functions as a dispersant for dispersing the pigment in the aqueous drawing material composition, and also functions as a fixing agent for fixing the coating film on the drawing surface in cooperation with the emulsion resin. On the other hand, even when the water-based drawing material composition adheres to the palette or paintbrush and is dried, the water-based drawing material composition has a water-washing property for allowing it to be removed by washing with water, that is, weak water solubility. It works to give things.
本発明において、上記ヒドロキシアルキルセルロースとしては、好ましくは、ヒドロキシエチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシエチルエチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルヒドロキシエチルメチルセルロースから選ばれる少なくとも１種が用いられる。
In the present invention, the hydroxyalkyl cellulose is preferably at least one selected from hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl hydroxyethyl methyl cellulose.
本発明による水性描画材組成物は、このようなヒドロキシアルキルセルロースを０．１～１０重量％の範囲、好ましくは、０．１～８重量％の範囲で含む。水性描画材組成物におけるヒドロキシアルキルセルロースの量が０．１重量％よりも少ないときは、乾燥後の塗膜は水洗い性を有するものの、描画に際して、塗膜の定着性が不十分である。しかし、水性描画材組成物におけるヒドロキシアルキルセルロースの量が１０重量％よりも多いときは、乾燥後の塗膜が耐水性をもたず、また、得られる水性描画材組成物が過度に高い粘度を有し、描画に際して、水性描画材組成物の伸びが悪い。
The aqueous drawing material composition according to the present invention contains such a hydroxyalkyl cellulose in the range of 0.1 to 10% by weight, preferably in the range of 0.1 to 8% by weight. When the amount of hydroxyalkyl cellulose in the aqueous drawing material composition is less than 0.1% by weight, the coating film after drying has water washability, but the fixing property of the coating film is insufficient when drawing. However, when the amount of hydroxyalkyl cellulose in the aqueous drawing material composition is more than 10% by weight, the coating film after drying does not have water resistance, and the resulting aqueous drawing material composition has an excessively high viscosity. In drawing, the aqueous drawing material composition has poor elongation.
本発明において、上記水溶性スチレン－アクリル樹脂は、スチレン－アクリル酸共重合体によって代表される共重合体樹脂であって、アクリル酸を単量体成分として有する。そこで、このスチレン－アクリル樹脂を水溶性とするに足りる量のスチレン－アクリル樹脂中のアクリル酸単位を水酸化ナトリウムや水酸化カリウム等の水酸化アルカリ金属類、アンモニア、又はアルキルアミンやアルカノールアミンのような有機アミン類にて塩構造とすることによって水溶性としたものである。本発明による水性描画材組成物において、水溶性スチレン－アクリル樹脂の含有量は、スチレン－アクリル樹脂中のアクリル酸単位をアクリル酸塩単位とする前のスチレン－アクリル樹脂換算の量であり、本発明による水性描画材組成物は、水溶性スチレン－アクリル樹脂をスチレン－アクリル樹脂換算にて０．５～６．５重量％の範囲で含み、好ましくは、０．５～５．５重量％の範囲で含む。
In the present invention, the water-soluble styrene-acrylic resin is a copolymer resin represented by a styrene-acrylic acid copolymer, and has acrylic acid as a monomer component. Therefore, the acrylic acid unit in the styrene-acrylic resin in an amount sufficient to make the styrene-acrylic resin water-soluble is converted to an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, ammonia, or an alkylamine or alkanolamine. It is made water-soluble by making it into a salt structure with such organic amines. In the aqueous drawing material composition according to the present invention, the content of the water-soluble styrene-acrylic resin is an amount in terms of styrene-acrylic resin before the acrylic acid unit in the styrene-acrylic resin is converted to an acrylate unit. The aqueous drawing material composition according to the invention contains a water-soluble styrene-acrylic resin in a range of 0.5 to 6.5% by weight in terms of styrene-acrylic resin, preferably 0.5 to 5.5% by weight. Include in range.
本発明において、水溶性スチレン－アクリル樹脂は、前記ヒドロキシアルキルセルロースと同様に、水性描画材組成物において顔料を分散させるための分散剤としてと共に、エマルジョン樹脂と共同して塗膜を描画面に定着させるための定着剤として機能するが、特に、水性描画材組成物がパレットや絵筆に付着し、乾燥して、長期間経過した後にも、水洗いによって、これを取り除くことを可能とするための水洗い性を水性描画材組成物に与えるように機能する。
In the present invention, the water-soluble styrene-acrylic resin is used as a dispersant for dispersing the pigment in the aqueous drawing material composition as well as the hydroxyalkyl cellulose, and the coating film is fixed on the drawing surface in cooperation with the emulsion resin. In particular, the water-based drawing material composition adheres to the palette or paintbrush, dries, and even after a long period of time, it can be removed by washing with water. It functions to impart properties to the aqueous drawing material composition.
従って、本発明においては、水性描画材組成物における水溶性スチレン－アクリル樹脂の量がスチレン－アクリル樹脂換算で０．５重量％よりも少ないときは、水性描画材組成物がパレットや絵筆に付着し、乾燥して、長期間が経過した後の水洗い性を水性描画材組成物に有効に与えることができない。
Therefore, in the present invention, when the amount of water-soluble styrene-acrylic resin in the aqueous drawing material composition is less than 0.5% by weight in terms of styrene-acrylic resin, the aqueous drawing material composition adheres to the palette or paintbrush. However, it is not possible to effectively give the water-based drawing material composition the water-washing property after drying for a long time.
しかし、水性描画材組成物における水溶性スチレン－アクリル樹脂の量がスチレン－アクリル樹脂換算で６．５重量％よりも多いときは、塗膜が十分に乾燥しきらず、また、乾燥したとしても、その塗膜が十分な耐水性をもたず、また、得られる水性描画材組成物が過度に高い粘度を有し、描画に際して、水性描画材組成物の伸びが悪い。
However, when the amount of the water-soluble styrene-acrylic resin in the aqueous drawing material composition is more than 6.5% by weight in terms of styrene-acrylic resin, the coating film is not fully dried. The coating film does not have sufficient water resistance, and the resulting aqueous drawing material composition has an excessively high viscosity, and the drawing of the aqueous drawing material composition is poor during drawing.
本発明によれば、水性描画材組成物は、このように、水溶性樹脂として、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂との組み合わせを含み、これらの樹脂の組み合わせによって、水性描画材組成物の乾燥後の塗膜に弱い水溶性を与えると共に、特に、水溶性樹脂として、ヒドロキシアルキルセルロースと共に水溶性スチレン－アクリル樹脂を含むことによって、水性描画材組成物がパレットや絵筆に付着し、乾燥して、長期間が経過した後であっても、それを水洗いによって取り除くことができる。
According to the present invention, the aqueous drawing material composition thus includes a combination of a hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as a water-soluble resin, and an aqueous drawing material composition is obtained by combining these resins. In addition to imparting weak water-solubility to the dried coating film, and especially including a water-soluble styrene-acrylic resin together with hydroxyalkyl cellulose as the water-soluble resin, the aqueous drawing material composition adheres to the palette or paintbrush and is dried. Thus, even after a long period of time, it can be removed by washing with water.
特に、本発明によれば、水性描画材組成物は、水溶性樹脂として、ヒドロキシアルキルセルロース０．１～１０重量％と水溶性スチレン－アクリル樹脂０．５～６．５重量％の組み合わせのみを含むことが好ましい。即ち、本発明による水性描画材組成物は、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂以外には、水溶性樹脂を含まない。
In particular, according to the present invention, the aqueous drawing material composition comprises only a combination of 0.1 to 10% by weight of hydroxyalkyl cellulose and 0.5 to 6.5% by weight of a water-soluble styrene-acrylic resin as a water-soluble resin. It is preferable to include. That is, the aqueous drawing material composition according to the present invention contains no water-soluble resin other than hydroxyalkyl cellulose and water-soluble styrene-acrylic resin.
（樹脂エマルジョン）
本発明による水性描画材組成物においては、前述したように、水溶性樹脂として、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂との組み合わせを含み、これらの組み合わせによって、水性描画材組成物の乾燥後の塗膜に弱い水溶性を与えるが、一方、その同じ水性描画材組成物がその乾燥後の塗膜に耐水性を有するように、樹脂エマルジョンを含む。 (Resin emulsion)
In the aqueous drawing material composition according to the present invention, as described above, the water-soluble resin includes a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin. While providing a weak water solubility to the coating film, a resin emulsion is included so that the same aqueous drawing material composition has water resistance to the dried coating film.
本発明による水性描画材組成物においては、前述したように、水溶性樹脂として、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂との組み合わせを含み、これらの組み合わせによって、水性描画材組成物の乾燥後の塗膜に弱い水溶性を与えるが、一方、その同じ水性描画材組成物がその乾燥後の塗膜に耐水性を有するように、樹脂エマルジョンを含む。 (Resin emulsion)
In the aqueous drawing material composition according to the present invention, as described above, the water-soluble resin includes a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin. While providing a weak water solubility to the coating film, a resin emulsion is included so that the same aqueous drawing material composition has water resistance to the dried coating film.
本発明において、上記樹脂エマルジョンは、特に限定されるものではないが、アクリル樹脂、酢酸ビニル樹脂、アクリル－スチレン樹脂、酢酸ビニル－アクリル樹脂、エチレン－酢酸ビニル樹脂、酢酸ビニル－バーサティック酸ビニルエステル樹脂、エチレン－塩化ビニル樹脂、アクリル－ベオバ樹脂、塩化ビニル樹脂、塩化ビニル－塩化ビニリデン樹脂、スチレン樹脂等の合成樹脂のエマルジョンが好ましく用いられる。
In the present invention, the resin emulsion is not particularly limited, but acrylic resin, vinyl acetate resin, acrylic-styrene resin, vinyl acetate-acrylic resin, ethylene-vinyl acetate resin, vinyl acetate-vinyl versatic acid ester. Resins, emulsions of synthetic resins such as ethylene-vinyl chloride resins, acrylic-belova resins, vinyl chloride resins, vinyl chloride-vinylidene chloride resins, styrene resins are preferably used.
特に、本発明によれば、水性描画材組成物における顔料の分散性や水性描画材組成物の製造費用等を考慮すると、アクリル樹脂エマルジョン、酢酸ビニル樹脂エマルジョン又は酢酸ビニル－アクリル樹脂エマルジョンが最も好ましく用いられる。
In particular, according to the present invention, an acrylic resin emulsion, a vinyl acetate resin emulsion, or a vinyl acetate-acrylic resin emulsion is most preferable in consideration of the dispersibility of the pigment in the aqueous drawing material composition and the production cost of the aqueous drawing material composition. Used.
このような樹脂エマルジョンの具体例として、例えば、アクリル樹脂エマルジョンとして、例えば、モビニールＤＭ７７２（日本合成化学工業（株）製）、ＴＯＣＲＹＬ Ｗ－１６８（東洋インキ製造（株））、ニカゾールＲＸ８６６Ｄ（日本カーバイド工業（株））等を挙げることができ、酢酸ビニル－アクリル樹脂エマルジョンとして、例えば、モビニールＤＭ－５（日本合成化学工業（株）製）を挙げることができ、また、アクリル－スチレン樹脂エマルジョンとして、例えば、ポリゾールＡＰ－１９００（昭和電工（株））等を挙げることができる。
Specific examples of such resin emulsions include, for example, acrylic resin emulsions such as Mobile DM772 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), TOCRYL W-168 (Toyo Ink Manufacturing Co., Ltd.), Nicazole RX866D (Nihon Carbide). Kogyo Co., Ltd.) and the like. As vinyl acetate-acrylic resin emulsion, for example, Movinyl DM-5 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be mentioned, and as acrylic-styrene resin emulsion. Examples thereof include Polysol AP-1900 (Showa Denko Co., Ltd.).
本発明による水性描画材組成物は、このような樹脂エマルジョンを固形分にて０．１重量％以上、５重量％未満の範囲で含み、好ましくは、固形分にて０．２～４．９重量％の範囲で含む。水性描画材組成物における樹脂エマルジョンの含有量が固形分にて０．１重量％よりも少ないときは、描画面上に形成した塗膜がひび割れることがあるうえに、定着性が十分でなく、更に、乾燥後の塗膜が耐水性に劣る。しかし、反対に、水性描画材組成物における樹脂エマルジョンの含有量が固形分にて５重量％以上であるときは、乾燥後の塗膜を水洗いし難い。
The aqueous drawing material composition according to the present invention contains such a resin emulsion in the range of 0.1 wt% or more and less than 5 wt% in solid content, preferably 0.2 to 4.9 in solid content. Including in the range of wt%. When the content of the resin emulsion in the aqueous drawing material composition is less than 0.1% by weight in solid content, the coating film formed on the drawing surface may be cracked, and the fixability is not sufficient, Furthermore, the coating film after drying is inferior in water resistance. However, on the contrary, when the content of the resin emulsion in the aqueous drawing material composition is 5% by weight or more in solid content, it is difficult to wash the coated film after drying.
特に、本発明によれば、好ましくは、水性描画材組成物が樹脂エマルジョンを上記範囲で含むと共に、前記スチレン－アクリル樹脂／樹脂エマルジョン固形分重量比０．２２～５の範囲、より好ましくは、０．５～４．５の範囲であるように、最も好ましくは、１．０～２．０の範囲となるように含むとき、乾燥塗膜に耐水性と長期間にわたるすぐれた水洗い性を共に有せしめることができる。
In particular, according to the present invention, the aqueous drawing material composition preferably contains the resin emulsion in the above range, and the styrene-acrylic resin / resin emulsion solid content weight ratio is in the range of 0.22 to 5, more preferably When it is included so that it is in the range of 0.5 to 4.5, most preferably in the range of 1.0 to 2.0, the dry coating film has both water resistance and excellent water washability over a long period of time. You can have it.
本発明によれば、上述した樹脂エマルジョンが乾燥して、前述した着色剤や水溶性樹脂を含む連続した塗膜を形成することができるように、必要に応じて、通常、高沸点有機溶剤である造膜助剤の適宜量を含んでもよい。
According to the present invention, if necessary, a high-boiling organic solvent is usually used so that the above-described resin emulsion can be dried to form a continuous coating film containing the above-described colorant and water-soluble resin. An appropriate amount of a film-forming aid may be included.
（湿潤剤）
本発明によれば、水性描画材組成物は、その凍結を防止し、また、乾燥を遅延させるために、必要に応じて、湿潤剤を含む。この湿潤剤としては、例えば、多価アルコールのほか、尿素やその誘導体が好ましく用いられる。上記多価アルコールとしては、例えば、グリセリン、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ソルビトール等を挙げることができ、また、尿素誘導体としては、例えば、ジメチル尿素、テトラメチル尿素、テトラエチル尿素、チオ尿素等を挙げることができる。 (Wetting agent)
According to the present invention, the aqueous drawing material composition includes a wetting agent, if necessary, to prevent freezing and to delay drying. As this wetting agent, for example, urea and its derivatives are preferably used in addition to polyhydric alcohols. Examples of the polyhydric alcohol include glycerin, ethylene glycol, propylene glycol, dipropylene glycol, and sorbitol. Examples of the urea derivative include dimethylurea, tetramethylurea, tetraethylurea, and thiourea. Etc.
本発明によれば、水性描画材組成物は、その凍結を防止し、また、乾燥を遅延させるために、必要に応じて、湿潤剤を含む。この湿潤剤としては、例えば、多価アルコールのほか、尿素やその誘導体が好ましく用いられる。上記多価アルコールとしては、例えば、グリセリン、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ソルビトール等を挙げることができ、また、尿素誘導体としては、例えば、ジメチル尿素、テトラメチル尿素、テトラエチル尿素、チオ尿素等を挙げることができる。 (Wetting agent)
According to the present invention, the aqueous drawing material composition includes a wetting agent, if necessary, to prevent freezing and to delay drying. As this wetting agent, for example, urea and its derivatives are preferably used in addition to polyhydric alcohols. Examples of the polyhydric alcohol include glycerin, ethylene glycol, propylene glycol, dipropylene glycol, and sorbitol. Examples of the urea derivative include dimethylurea, tetramethylurea, tetraethylurea, and thiourea. Etc.
このような湿潤剤は、必要に応じて、水性描画材組成物において、２０重量％以下の範囲で用いられ、好ましくは、１～１０重量％の範囲で用いられる。水性描画材組成物における湿潤剤の含有量が１重量％よりも少ないときは、場合によっては、水性描画材組成物が形成した塗膜が乾燥した後、脆いという問題がある。しかし、水性描画材組成物における湿潤剤の含有量が２０重量％を越えるときは、水性描画材組成物が形成した塗膜の乾燥性が悪い。
Such a wetting agent is used in an aqueous drawing material composition in an amount of 20% by weight or less, preferably 1 to 10% by weight, if necessary. When the content of the wetting agent in the aqueous drawing material composition is less than 1% by weight, there is a problem that the coating film formed by the aqueous drawing material composition is brittle after drying. However, when the content of the wetting agent in the aqueous drawing material composition exceeds 20% by weight, the drying property of the coating film formed by the aqueous drawing material composition is poor.
（界面活性剤）
本発明による水性描画材組成物は、必要に応じて、界面活性剤を含んでいてもよい。界面活性剤としては、ノニオン及びアニオン界面活性剤から選ばれる少なくとも１種が０．１～５重量％、好ましくは、０．５～３重量％の範囲にて用いられる。 (Surfactant)
The aqueous drawing material composition according to the present invention may contain a surfactant, if necessary. As the surfactant, at least one selected from nonionic and anionic surfactants is used in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
本発明による水性描画材組成物は、必要に応じて、界面活性剤を含んでいてもよい。界面活性剤としては、ノニオン及びアニオン界面活性剤から選ばれる少なくとも１種が０．１～５重量％、好ましくは、０．５～３重量％の範囲にて用いられる。 (Surfactant)
The aqueous drawing material composition according to the present invention may contain a surfactant, if necessary. As the surfactant, at least one selected from nonionic and anionic surfactants is used in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
（その他の添加剤）
本発明によれば、水性描画材組成物は、必要に応じて、従来、水性描画材組成物において用いられている種々の添加剤、例えば、防腐剤、防黴剤、分散剤、消泡剤等を含んでいてもよい。 (Other additives)
According to the present invention, the water-based drawing material composition can be prepared by adding various additives conventionally used in the water-based drawing material composition, for example, preservatives, antifungal agents, dispersing agents, antifoaming agents. Etc. may be included.
本発明によれば、水性描画材組成物は、必要に応じて、従来、水性描画材組成物において用いられている種々の添加剤、例えば、防腐剤、防黴剤、分散剤、消泡剤等を含んでいてもよい。 (Other additives)
According to the present invention, the water-based drawing material composition can be prepared by adding various additives conventionally used in the water-based drawing material composition, for example, preservatives, antifungal agents, dispersing agents, antifoaming agents. Etc. may be included.
（製造）
本発明による水性描画材組成物は、その製造方法において特に限定されるものではない。本発明による水性描画材組成物の製造方法の一例を挙げれば、例えば、ヒドロキシアルキルセルロースを水に溶解させ、これに着色顔料と体質顔料と水溶性スチレン－アクリル樹脂、水、必要に応じて、湿潤剤や界面活性剤、防腐剤等を加え、均一になるまで、混合、攪拌した後、ロールミルを用いて、分散処理し、次いで、このようにして得られた混合物に樹脂エマルジョンを加えて、混合、攪拌し、真空脱泡すれば、本発明による水性描画材組成物を得る。 (Manufacturing)
The aqueous drawing material composition according to the present invention is not particularly limited in its production method. An example of a method for producing an aqueous drawing material composition according to the present invention is, for example, by dissolving hydroxyalkyl cellulose in water, coloring pigment, extender pigment, water-soluble styrene-acrylic resin, water, if necessary, Add a wetting agent, surfactant, preservative, etc., mix and stir until uniform, then disperse using a roll mill, then add the resin emulsion to the mixture thus obtained, When mixed, stirred and vacuum degassed, an aqueous drawing material composition according to the present invention is obtained.
本発明による水性描画材組成物は、その製造方法において特に限定されるものではない。本発明による水性描画材組成物の製造方法の一例を挙げれば、例えば、ヒドロキシアルキルセルロースを水に溶解させ、これに着色顔料と体質顔料と水溶性スチレン－アクリル樹脂、水、必要に応じて、湿潤剤や界面活性剤、防腐剤等を加え、均一になるまで、混合、攪拌した後、ロールミルを用いて、分散処理し、次いで、このようにして得られた混合物に樹脂エマルジョンを加えて、混合、攪拌し、真空脱泡すれば、本発明による水性描画材組成物を得る。 (Manufacturing)
The aqueous drawing material composition according to the present invention is not particularly limited in its production method. An example of a method for producing an aqueous drawing material composition according to the present invention is, for example, by dissolving hydroxyalkyl cellulose in water, coloring pigment, extender pigment, water-soluble styrene-acrylic resin, water, if necessary, Add a wetting agent, surfactant, preservative, etc., mix and stir until uniform, then disperse using a roll mill, then add the resin emulsion to the mixture thus obtained, When mixed, stirred and vacuum degassed, an aqueous drawing material composition according to the present invention is obtained.
実施例１
表１に示す成分を表１に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物の性能、即ち、パレット洗浄性、水滴耐水性及び重ね塗り性を下記のようにして評価した。結果を表１に示す。 Example 1
Using the components shown in Table 1 in the amounts shown in Table 1, an aqueous drawing material composition was prepared as described above. The performance of the obtained aqueous drawing material composition, that is, pallet washability, waterdrop water resistance and overcoatability was evaluated as follows. The results are shown in Table 1.
表１に示す成分を表１に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物の性能、即ち、パレット洗浄性、水滴耐水性及び重ね塗り性を下記のようにして評価した。結果を表１に示す。 Example 1
Using the components shown in Table 1 in the amounts shown in Table 1, an aqueous drawing material composition was prepared as described above. The performance of the obtained aqueous drawing material composition, that is, pallet washability, waterdrop water resistance and overcoatability was evaluated as follows. The results are shown in Table 1.
実施例２～６
表１に示す成分を表１に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物について、パレット洗浄性、水滴耐水性及び重ね塗り性を評価した。結果を表１に示す。 Examples 2 to 6
Using the components shown in Table 1 in the amounts shown in Table 1, an aqueous drawing material composition was prepared as described above. About the obtained water-based drawing material composition, palette washing | cleaning property, water-drop water resistance, and recoating property were evaluated. The results are shown in Table 1.
表１に示す成分を表１に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物について、パレット洗浄性、水滴耐水性及び重ね塗り性を評価した。結果を表１に示す。 Examples 2 to 6
Using the components shown in Table 1 in the amounts shown in Table 1, an aqueous drawing material composition was prepared as described above. About the obtained water-based drawing material composition, palette washing | cleaning property, water-drop water resistance, and recoating property were evaluated. The results are shown in Table 1.
比較例１～６
表２に示す成分を表２に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物について、パレット洗浄性、水滴耐水性及び重ね塗り性を評価した。結果を表２に示す。 Comparative Examples 1-6
Using the components shown in Table 2 in the amounts shown in Table 2, an aqueous drawing material composition was prepared as described above. About the obtained water-based drawing material composition, palette washing | cleaning property, water-drop water resistance, and recoating property were evaluated. The results are shown in Table 2.
表２に示す成分を表２に示す量で用いて、上述したようにして、水性描画材組成物を調製した。得られた水性描画材組成物について、パレット洗浄性、水滴耐水性及び重ね塗り性を評価した。結果を表２に示す。 Comparative Examples 1-6
Using the components shown in Table 2 in the amounts shown in Table 2, an aqueous drawing material composition was prepared as described above. About the obtained water-based drawing material composition, palette washing | cleaning property, water-drop water resistance, and recoating property were evaluated. The results are shown in Table 2.
表１及び表２において用いた各成分の詳細は以下のとおりである。
（成分）
着色顔料：
「グンジョウ＃３０００」：第一化成工業（株）製群青
体質顔料：
炭酸カルシウム：白石工業（株）製軽微性炭酸カルシウム
ＳＩＰＥＲＮＡＴ ８２０Ａ：デグサジャパン（株）製ケイ酸アルミニウム
増粘剤：
ベントナイト：（株）ホージュン製ベントナイト
水溶性樹脂：
「チローゼＨ１００００Ｐ２」：日本合成化学工業（株）製ヒドロキシエチルメチルセルロース（ローター１°Ｃ３４Ｒ、回転数２０ｒｐｍ、測定時間３分、測定温度２０℃の条件下にＥＨＤ型粘度計を用いて、１．５重量％濃度水溶液について測定した粘度９５０ｍＰａ・ｓ） Details of each component used in Table 1 and Table 2 are as follows.
(component)
Color pigment:
“Gunjo # 3000”: Ultramarine extender pigment manufactured by Daiichi Kasei Kogyo Co., Ltd .:
Calcium carbonate: Slight stone calcium carbonate manufactured by Shiroishi Kogyo Co., Ltd. SIPERNAT 820A: Degussa Japan Co., Ltd. aluminum silicate thickener:
Bentonite: Hojun Co., Ltd. bentonite water-soluble resin:
“Tyroze H10000P2”: hydroxyethyl methylcellulose manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (rotor 1 ° C. 34R, rotation speed 20 rpm, measurement time 3 minutes, measurement temperature 20 ° C. using an EHD viscometer 1.5 (Viscosity 950 mPa · s measured for a weight% concentration aqueous solution)
（成分）
着色顔料：
「グンジョウ＃３０００」：第一化成工業（株）製群青
体質顔料：
炭酸カルシウム：白石工業（株）製軽微性炭酸カルシウム
ＳＩＰＥＲＮＡＴ ８２０Ａ：デグサジャパン（株）製ケイ酸アルミニウム
増粘剤：
ベントナイト：（株）ホージュン製ベントナイト
水溶性樹脂：
「チローゼＨ１００００Ｐ２」：日本合成化学工業（株）製ヒドロキシエチルメチルセルロース（ローター１°Ｃ３４Ｒ、回転数２０ｒｐｍ、測定時間３分、測定温度２０℃の条件下にＥＨＤ型粘度計を用いて、１．５重量％濃度水溶液について測定した粘度９５０ｍＰａ・ｓ） Details of each component used in Table 1 and Table 2 are as follows.
(component)
Color pigment:
“Gunjo # 3000”: Ultramarine extender pigment manufactured by Daiichi Kasei Kogyo Co., Ltd .:
Calcium carbonate: Slight stone calcium carbonate manufactured by Shiroishi Kogyo Co., Ltd. SIPERNAT 820A: Degussa Japan Co., Ltd. aluminum silicate thickener:
Bentonite: Hojun Co., Ltd. bentonite water-soluble resin:
“Tyroze H10000P2”: hydroxyethyl methylcellulose manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (rotor 1 ° C. 34R, rotation speed 20 rpm, measurement time 3 minutes, measurement temperature 20 ° C. using an EHD viscometer 1.5 (Viscosity 950 mPa · s measured for a weight% concentration aqueous solution)
水溶性スチレン－アクリル樹脂水溶液：
水溶性スチレン－アクリル樹脂水溶液１：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６９０」（重量平均分子量１６５００、酸価２４０ｍｇＫＯＨ／ｇ）を水酸化ナトリウムで中和して得られた共重合体樹脂含有量２０重量％の水溶液 Water-soluble styrene-acrylic resin aqueous solution:
Water-soluble styrene-acrylic resin aqueous solution 1: obtained by neutralizing styrene-acrylic acid copolymer resin “Jonkril 690” (weight average molecular weight 16500, acid value 240 mgKOH / g) manufactured by BASF Japan Ltd. with sodium hydroxide Aqueous solution having a copolymer resin content of 20% by weight
水溶性スチレン－アクリル樹脂水溶液１：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６９０」（重量平均分子量１６５００、酸価２４０ｍｇＫＯＨ／ｇ）を水酸化ナトリウムで中和して得られた共重合体樹脂含有量２０重量％の水溶液 Water-soluble styrene-acrylic resin aqueous solution:
Water-soluble styrene-acrylic resin aqueous solution 1: obtained by neutralizing styrene-acrylic acid copolymer resin “Jonkril 690” (weight average molecular weight 16500, acid value 240 mgKOH / g) manufactured by BASF Japan Ltd. with sodium hydroxide Aqueous solution having a copolymer resin content of 20% by weight
水溶性スチレン－アクリル樹脂水溶液２：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６７」（重量平均分子量１２５００、酸価２１３ｍｇＫＯＨ／ｇ）を水酸化ナトリウムで中和して得られた共重合体樹脂含有量２０重量％の水溶液
Water-soluble styrene-acrylic resin aqueous solution 2: Obtained by neutralizing styrene-acrylic acid copolymer resin “Joncrill 67” (weight average molecular weight 12500, acid value 213 mgKOH / g) manufactured by BASF Japan Ltd. with sodium hydroxide. Aqueous solution having a copolymer resin content of 20% by weight
水溶性スチレン－アクリル樹脂水溶液３：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６７８」（重量平均分子量８５００、酸価２１５ｍｇＫＯＨ／ｇ）を水酸化ナトリウムで中和して得られた共重合体樹脂含有量２０重量％の水溶液
Water-soluble styrene-acrylic resin aqueous solution 3: obtained by neutralizing styrene-acrylic acid copolymer resin “Joncrill 678” (weight average molecular weight 8500, acid value 215 mgKOH / g) manufactured by BASF Japan Ltd. with sodium hydroxide Aqueous solution having a copolymer resin content of 20% by weight
水溶性スチレン－アクリル樹脂水溶液４：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６８０」（重量平均分子量４９００、酸価２１５ｍｇＫＯＨ／ｇ）を水酸化ナトリウムで中和して得られた共重合体樹脂含有量２０重量％の水溶液
Water-soluble styrene-acrylic resin aqueous solution 4: Obtained by neutralizing styrene-acrylic acid copolymer resin “Joncrill 680” (weight average molecular weight 4900, acid value 215 mgKOH / g) manufactured by BASF Japan Ltd. with sodium hydroxide. Aqueous solution having a copolymer resin content of 20% by weight
水溶性スチレン－アクリル樹脂水溶液５：ＢＡＳＦジャパン（株）製スチレン－アクリル酸共重合体樹脂「ジョンクリル６９０」をアンモニアで中和して得られた共重合体樹脂含有量２８重量％の水溶液。
Water-soluble styrene-acrylic resin aqueous solution 5: An aqueous solution having a copolymer resin content of 28% by weight, obtained by neutralizing styrene-acrylic acid copolymer resin “Joncrill 690” manufactured by BASF Japan Ltd. with ammonia.
樹脂エマルジョン：
モビニールＤＭ７７２：日本合成化学工業（株）製アクリル樹脂エマルジョン（固形分４６重量％） Resin emulsion:
Mobile DM772: Nippon Synthetic Chemical Industry Co., Ltd. acrylic resin emulsion (solid content 46% by weight)
モビニールＤＭ７７２：日本合成化学工業（株）製アクリル樹脂エマルジョン（固形分４６重量％） Resin emulsion:
Mobile DM772: Nippon Synthetic Chemical Industry Co., Ltd. acrylic resin emulsion (solid content 46% by weight)
界面活性剤：
「プライサーフＡ－２１２Ｅ」：第一工業製薬（株）製ノニオン界面活性剤
「プライサーフＡ－２１２Ｃ」：第一工業製薬（株）製ノニオン界面活性剤
「ノプコ８０３４－Ｌ」：サンノプコ（株）製ノニオン界面活性剤
防腐剤：
「サンアイバックＳＡ」：三愛石油（株）製
造膜助剤：
「テキサノール」：イーストマンケミカル製 Surfactant:
“Plysurf A-212E”: Nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Plisurf A-212C”: Nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Nopco 8034-L”: San Nopco Co., Ltd. Nonionic surfactant preservative made by:
“Suneye Back SA”: Sanai Oil Co., Ltd. Manufacturing Membrane Auxiliary:
“Texanol”: Eastman Chemical
「プライサーフＡ－２１２Ｅ」：第一工業製薬（株）製ノニオン界面活性剤
「プライサーフＡ－２１２Ｃ」：第一工業製薬（株）製ノニオン界面活性剤
「ノプコ８０３４－Ｌ」：サンノプコ（株）製ノニオン界面活性剤
防腐剤：
「サンアイバックＳＡ」：三愛石油（株）製
造膜助剤：
「テキサノール」：イーストマンケミカル製 Surfactant:
“Plysurf A-212E”: Nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Plisurf A-212C”: Nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Nopco 8034-L”: San Nopco Co., Ltd. Nonionic surfactant preservative made by:
“Suneye Back SA”: Sanai Oil Co., Ltd. Manufacturing Membrane Auxiliary:
“Texanol”: Eastman Chemical
（性能評価）
パレット洗浄性
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。ポリプロピレン製のペレットに平型デザイン筆を用いて上記描画材試料を塗布した後、室温で１か月間放置して乾燥させた。このように描画材試料を付着させ、乾燥させたパレットに水を十分に含ませた平型デザイン筆で擦ってパレットを洗浄した。このようにして、パレットに付着し、乾燥した描画材試料の８０％以上を洗い流すことができたときをＡ、洗い流すことができた描画材試料の割合が３０％以上、８０％未満であったときをＢ、洗い流すことができた描画材試料の割合が３０％未満であったときをＣとした。 (Performance evaluation)
Pallet detergency A drawing material sample was prepared by mixing 5 parts by weight of the aqueous drawing material composition with 1 part by weight of water. The above drawing material sample was applied to a polypropylene pellet using a flat design brush, and then allowed to stand at room temperature for 1 month to dry. The drawing material sample was adhered in this manner, and the pallet was washed by rubbing with a flat design brush sufficiently containing water in the dried pallet. In this way, A was when 80% or more of the dried drawing material sample adhered to the pallet could be washed away, and the ratio of the drawing material sample that could be washed away was 30% or more and less than 80%. The time was designated as B, and the time when the proportion of the drawing material sample that could be washed out was less than 30% was designated as C.
パレット洗浄性
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。ポリプロピレン製のペレットに平型デザイン筆を用いて上記描画材試料を塗布した後、室温で１か月間放置して乾燥させた。このように描画材試料を付着させ、乾燥させたパレットに水を十分に含ませた平型デザイン筆で擦ってパレットを洗浄した。このようにして、パレットに付着し、乾燥した描画材試料の８０％以上を洗い流すことができたときをＡ、洗い流すことができた描画材試料の割合が３０％以上、８０％未満であったときをＢ、洗い流すことができた描画材試料の割合が３０％未満であったときをＣとした。 (Performance evaluation)
Pallet detergency A drawing material sample was prepared by mixing 5 parts by weight of the aqueous drawing material composition with 1 part by weight of water. The above drawing material sample was applied to a polypropylene pellet using a flat design brush, and then allowed to stand at room temperature for 1 month to dry. The drawing material sample was adhered in this manner, and the pallet was washed by rubbing with a flat design brush sufficiently containing water in the dried pallet. In this way, A was when 80% or more of the dried drawing material sample adhered to the pallet could be washed away, and the ratio of the drawing material sample that could be washed away was 30% or more and less than 80%. The time was designated as B, and the time when the proportion of the drawing material sample that could be washed out was less than 30% was designated as C.
水滴耐水性
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。平型デザイン筆を用いて、上記描画材試料を画用紙上に３回重ね塗りした。得られた塗膜を室温で１時間乾燥させた後、１ｍＬ容量のスポイトを用いて、上記塗膜上に水道水を一滴落として、室温で６時間放置して、塗膜の状態を観察した。塗膜に変化がみられなかったときをＡとし、塗膜上に目立たない水滴跡が僅かにみられたときをＢとし、塗膜にひび割れ、色落ち及び／又は水滴痕の発生がみられたときをＣとした。 Water Drop Water Resistance 5 parts by weight of an aqueous drawing material composition was mixed with 1 part by weight of water to prepare a drawing material sample. Using a flat design brush, the drawing material sample was applied three times on drawing paper. After the obtained coating film was dried at room temperature for 1 hour, a drop of tap water was dropped on the coating film using a 1 mL capacity dropper and left at room temperature for 6 hours to observe the state of the coating film. . When no change was observed in the coating film, A was designated, and when an inconspicuous water droplet trace was found on the coating film, B was designated, and the coating film was cracked, discolored and / or generated. C was the time when
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。平型デザイン筆を用いて、上記描画材試料を画用紙上に３回重ね塗りした。得られた塗膜を室温で１時間乾燥させた後、１ｍＬ容量のスポイトを用いて、上記塗膜上に水道水を一滴落として、室温で６時間放置して、塗膜の状態を観察した。塗膜に変化がみられなかったときをＡとし、塗膜上に目立たない水滴跡が僅かにみられたときをＢとし、塗膜にひび割れ、色落ち及び／又は水滴痕の発生がみられたときをＣとした。 Water Drop Water Resistance 5 parts by weight of an aqueous drawing material composition was mixed with 1 part by weight of water to prepare a drawing material sample. Using a flat design brush, the drawing material sample was applied three times on drawing paper. After the obtained coating film was dried at room temperature for 1 hour, a drop of tap water was dropped on the coating film using a 1 mL capacity dropper and left at room temperature for 6 hours to observe the state of the coating film. . When no change was observed in the coating film, A was designated, and when an inconspicuous water droplet trace was found on the coating film, B was designated, and the coating film was cracked, discolored and / or generated. C was the time when
重ね塗り性
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。平型デザイン筆を用いて、上記描画材試料を画用紙上に３回重ね塗りした後、塗膜を室温で１時間乾燥させた。次いで、上記と同じ描画材試料を上記塗膜上に縦、横及び縦方向に３回塗布した。このとき、先の塗膜（下地）上に問題なく重ね塗りすることができたときをＡとし、先の塗膜（下地）が動いたり、滲んだりしたときをＣとした。 Overcoatability 5 parts by weight of an aqueous drawing material composition was mixed with 1 part by weight of water to prepare a drawing material sample. The above-mentioned drawing material sample was applied three times on drawing paper using a flat design brush, and then the coating film was dried at room temperature for 1 hour. Next, the same drawing material sample as described above was applied three times in the vertical, horizontal and vertical directions on the coating film. At this time, A was defined as the time when the previous coating film (underground) could be overcoated without any problem, and C as defined when the previous coating film (underground) moved or oozed.
水性描画材組成物５重量部を水１重量部と混合して、描画材試料を調製した。平型デザイン筆を用いて、上記描画材試料を画用紙上に３回重ね塗りした後、塗膜を室温で１時間乾燥させた。次いで、上記と同じ描画材試料を上記塗膜上に縦、横及び縦方向に３回塗布した。このとき、先の塗膜（下地）上に問題なく重ね塗りすることができたときをＡとし、先の塗膜（下地）が動いたり、滲んだりしたときをＣとした。 Overcoatability 5 parts by weight of an aqueous drawing material composition was mixed with 1 part by weight of water to prepare a drawing material sample. The above-mentioned drawing material sample was applied three times on drawing paper using a flat design brush, and then the coating film was dried at room temperature for 1 hour. Next, the same drawing material sample as described above was applied three times in the vertical, horizontal and vertical directions on the coating film. At this time, A was defined as the time when the previous coating film (underground) could be overcoated without any problem, and C as defined when the previous coating film (underground) moved or oozed.
これに対して、比較例１による水性描画材組成物は、水溶性樹脂としてヒドロキシアルキルセルロースを含むが、水溶性スチレン－アクリル樹脂を含まないので、パレット洗浄性に劣る。
On the other hand, the aqueous drawing material composition according to Comparative Example 1 contains hydroxyalkyl cellulose as a water-soluble resin, but does not contain a water-soluble styrene-acrylic resin, and therefore has poor pallet washability.
比較例２による水性描画材組成物は、水溶性樹脂としてヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂の組み合わせを含むが、水溶性スチレン－アクリル樹脂の含有量が本発明で規定する範囲よりも少ないので、パレット洗浄性に劣る。
The aqueous drawing material composition according to Comparative Example 2 contains a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as a water-soluble resin, but the content of the water-soluble styrene-acrylic resin is less than the range specified in the present invention. So it is inferior in pallet cleanability.
反対に、比較例３による水性描画材組成物は、水溶性樹脂としてヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂の組み合わせを含むが、水溶性スチレン－アクリル樹脂の含有量が本発明で規定する範囲よりも多いので、塗膜は、耐水性と重ね塗り性に劣っている。
On the contrary, the aqueous drawing material composition according to Comparative Example 3 contains a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as a water-soluble resin, but the content of the water-soluble styrene-acrylic resin is within the range specified by the present invention. Therefore, the coating film is inferior in water resistance and overcoatability.
比較例４による水性描画材組成物は、水溶性樹脂としてヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂の組み合わせを含むが、樹脂エマルジョンを含まないので、パレット洗浄性はよいが、塗膜は、耐水性と重ね塗り性に劣っている。
The aqueous drawing material composition according to Comparative Example 4 contains a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as a water-soluble resin, but does not contain a resin emulsion, so that the pallet washability is good. Inferior in properties and overcoatability.
The aqueous drawing material composition according to Comparative Example 4 contains a combination of hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin as a water-soluble resin, but does not contain a resin emulsion, so that the pallet washability is good. Inferior in properties and overcoatability.
Claims (7)
- 水、着色顔料、ヒドロキシアルキルセルロースと水溶性スチレン－アクリル樹脂を含む水溶性樹脂及び樹脂エマルジョンを含む水性描画材組成物において、上記水溶性スチレン－アクリル樹脂をスチレン－アクリル樹脂換算で０．５～６．５重量％の範囲で含み、上記樹脂エマルジョンを固形分にて０．１重量％以上、５重量％未満の範囲にて含むことを特徴とする水性描画材組成物。 In an aqueous drawing material composition comprising water, a color pigment, a water-soluble resin containing a hydroxyalkyl cellulose and a water-soluble styrene-acrylic resin, and a resin emulsion, the water-soluble styrene-acrylic resin is converted to 0.5 to 0.5 in terms of styrene-acrylic resin. An aqueous drawing material composition comprising 6.5 wt% and containing the resin emulsion in a solid content of 0.1 wt% or more and less than 5 wt%.
- ヒドロキシアルキルセルロースを０．１～１０重量％の範囲で有する請求項１に記載の水性描画材組成物。 The aqueous drawing material composition according to claim 1, comprising hydroxyalkylcellulose in a range of 0.1 to 10% by weight.
- 水溶性スチレン－アクリル樹脂と樹脂エマルジョンをスチレン－アクリル樹脂／樹脂エマルジョン固形分重量比が０．２２～５の範囲であるように含む請求項１に記載の水性描画材組成物。 The aqueous drawing material composition according to claim 1, comprising a water-soluble styrene-acrylic resin and a resin emulsion so that the weight ratio of solid content of styrene-acrylic resin / resin emulsion is 0.22 to 5.
- ヒドロキシアルキルセルロースがヒドロキシエチルセルロース、ヒドロキシエチルメチルセルロース及びヒドロキシプロピルメチルセルロースから選ばれる少なくとも１種である請求項１に記載の水性描画材組成物。 The aqueous drawing material composition according to claim 1, wherein the hydroxyalkylcellulose is at least one selected from hydroxyethylcellulose, hydroxyethylmethylcellulose and hydroxypropylmethylcellulose.
- 体質顔料を含む請求項１に記載の水性描画材組成物。 The aqueous drawing material composition according to claim 1, comprising an extender pigment.
- 増粘剤としてベントナイトを含む請求項１に記載の水性描画材組成物。 The aqueous drawing material composition according to claim 1, comprising bentonite as a thickener.
- 湿潤剤、界面活性剤及び防腐剤から選ばれる少なくとも１種の添加剤を含む請求項１に記載の水性描画材組成物。
The aqueous drawing material composition according to claim 1, comprising at least one additive selected from a wetting agent, a surfactant, and a preservative.
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| JP2012050901A JP5827582B2 (en) | 2012-03-07 | 2012-03-07 | Aqueous drawing material composition |
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| CN104151903B (en) * | 2014-08-21 | 2016-03-23 | 宁波高新区康大美术新材料有限公司 | High gloss acrylic paints of a kind of graphene-containing and preparation method thereof |
| JP6730564B2 (en) * | 2016-08-04 | 2020-07-29 | 株式会社サクラクレパス | Erasable colorant composition |
| JP6713376B2 (en) * | 2016-08-04 | 2020-06-24 | 株式会社サクラクレパス | Erasable colorant composition |
| CN108410236B (en) * | 2017-02-09 | 2020-06-09 | 株式会社樱花彩色笔 | Solid watercolor pigment composition |
| KR20190068054A (en) | 2017-12-08 | 2019-06-18 | 롯데정밀화학 주식회사 | Water-based paint composition having excellent water resistance and water-based paint prepared therefrom |
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| WO2012033074A1 (en) * | 2010-09-08 | 2012-03-15 | 株式会社サクラクレパス | Aqueous painting material composition |
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| US5743946A (en) * | 1995-12-18 | 1998-04-28 | Asahi Glass Company Ltd. | Water-color ink composition and process for forming an inorganic coating film |
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| CN101215787B (en) * | 2007-12-26 | 2010-12-08 | 宋健 | Water polyurethane latex composite compounding color coat art canvas and producing technique thereof |
| CN101215784B (en) * | 2008-01-18 | 2010-06-02 | 宁波康大美术用品有限公司 | Nano composite painting canvas dope |
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| JPH07102191A (en) * | 1993-09-30 | 1995-04-18 | Pentel Kk | Aqueous pigment composition |
| JPH1095932A (en) * | 1996-09-25 | 1998-04-14 | Sakura Color Prod Corp | Black paint |
| JP2007077339A (en) * | 2005-09-16 | 2007-03-29 | Sakura Color Prod Corp | Color |
| WO2007097448A1 (en) * | 2006-02-27 | 2007-08-30 | Sakura Color Products Corporation | Eliminable colorant composition |
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| CN104271681B (en) | 2017-03-08 |
| CN104271681A (en) | 2015-01-07 |
| JP2013185055A (en) | 2013-09-19 |
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