JP6523032B2 - Aqueous drawing material composition - Google Patents

Description

  In the present invention, as in the conventional emulsion paint, after the coating film is dried, even if water droplets adhere to the coating film, no bleeding or dissolution occurs in the coating film, and the coating film is overlaid on the underlying film. Even if it is painted, it does not cause bleeding or dissolution to the substrate, that is, it has resistance to water wetting to such an extent that the substrate does not move, so it adheres to a pallet or paint brush and is removed by water washing even after drying. The present invention relates to an aqueous drawing material composition which can be excellent in the fixability of the coating film.

  Conventionally, an aqueous drawing material composition known as an emulsion paint is a kind of aqueous drawing material composition having water as a solvent, a pigment as a coloring agent, and a resin emulsion as a fixing agent, and drawing on a drawing surface Then, after the coating is formed, the solvent evaporates from the coating, and if the coating is dried, the resin in the emulsion forms a film, which is water insoluble on the drawing surface, and thus against water wetting Form a resistant coating.

  Such conventional emulsion paints, as described above, contain a large amount of resin emulsion so that the coating film is excellent in resistance to water wetting (see Patent Documents 1 and 2), so that they adhere to pallets and paint brushes. After being dried, it can not be removed by washing with water.

  Therefore, as in conventional emulsion paints, even if water droplets adhere to the dried coating, no bleeding or dissolution occurs in the coating, and even if it is overcoated on the underlying coating, Recently, an aqueous drawing material composition has been proposed which has water resistance to such an extent that the base does not move, and which can be easily removed by washing with water even after adhering to a pallet or a paint brush and drying (Patent Document 3) reference).

  However, the above-mentioned aqueous drawing material composition has a problem that the fixability of the coating film drawn on the drawing surface is inferior since the compounding amount of the resin emulsion is reduced so as to have the so-called special characteristics described above. That is, when the dried coating film is touched with the hand, at least the surface layer of the coating film is easily rubbed off, the coating film is damaged, and there is a problem that the drawn matter is stained and damaged.

Japanese Patent Application Publication No. 2003-221552 Japanese Patent Application Publication No. 2008-0379172 Unexamined-Japanese-Patent No. 2012-057042

  The present invention has been made to solve the above-mentioned problems in the conventional emulsion paints, and as in the case of the conventional emulsion paints, even if water droplets adhere to the coating after drying, it does not spread on the coating. There is no melting out, and even if it is overcoated on the base coat, the base is resistant to water wetting to such an extent that it does not move, so it adheres to the pallet or paint brush and is dried. It is an object of the present invention to provide an aqueous drawing material composition which can be removed even by washing with water, and moreover, is excellent in the fixability of the coating film.

  According to the present invention, in the aqueous drawing material composition containing water, a color pigment, a water-soluble resin and an acrylic resin emulsion, only the combination of hydroxyalkyl cellulose and anion-modified polyvinyl alcohol is contained as the water-soluble resin. An aqueous drawing material composition comprising the solid content in the range of 0.1% by weight or more and less than 5% by weight is provided.

  The aqueous drawing material composition according to the present invention contains, as the water-soluble resin, only a combination of hydroxyalkyl cellulose and anion-modified polyvinyl alcohol, and the acrylic resin emulsion has a solid content of 0.1% by weight or more and less than 5% by weight In the same manner as conventional acrylic resin emulsion paints, even if water droplets adhere to the coated film after drying, no bleeding or dissolution occurs in the coated film, and the film is overlaid on the base coated film, as in the case of the conventional acrylic resin emulsion paint. Even if it is coated, it has water resistance to such an extent that it does not move, so it adheres to a pallet or paint brush and can be easily removed by water washing even after drying, and moreover, the fixability of the coating is excellent. ing.

  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 does not bleed or dissolve, and the base The property of having resistance to water wetting to such an extent that the base does not move even if it is overcoated on a coating is called "water resistance", and after the water-based drawing material composition adheres to a pallet or a paint brush, it is dried. Also, the property that can be removed by washing the drawing composition with water is called "washable". 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, and is excellent in the fixing property of the coating film.

  An aqueous drawing material composition according to the present invention comprises an aqueous drawing material composition containing water, a color pigment, a water-soluble resin and an acrylic resin emulsion, and comprises only a combination of hydroxyalkyl cellulose and anion-modified polyvinyl alcohol as the water-soluble resin. The above resin emulsion is contained in the range of 0.1% by weight or more and less than 5% by weight in solid content.

(Pigment)
In the aqueous drawing material composition according to the present invention, a pigment is used as a colorant. The pigment is not particularly limited, and any conventionally known pigment may be used. For example, titanium oxide, zinc oxide, carbon black, iron black, aniline black, Hansa yellow, benzine yellow, tartrasine lake, permanent yellow toner, cadmium yellow, benzine orange, chrome vermillion, cadmium orange, permanent orange GTR, First Orange Lake, Lake Red C, Petal Pattern, Watching Red, Brilliant Carmine 6B, Permanent Red 2B, Permanent Red FRLL, Carmine Lake, Quinacridone Red, Methyl Violet Lake, First Violet B, Quinacridone Violet, Industlen Violet, Phthalocyanine Blue, Fast Sky Blue, Bitumen Blue, Ultramarine Blue, Victoria Blue Lake, Phthalocyanine Green, Over karite green lake, Pigment Green B, viridian, Shen'na can include amber, aluminum powder, bronze powder and the like, organic pigments, inorganic pigments and metal powder pigments.

  In addition to the above, as a colored pigment, a colored processed powder in which a dye or pigment is combined with a resin powder, a fluorescent pigment, a pigment in which the surface of natural mica is coated with a metal oxide, a metal oxide And pearl pigments coated with

  According to the present invention, the aqueous drawing material composition usually contains such a pigment in the range of 1 to 60% by weight, preferably in the range of 10 to 40% by weight. When the amount of the pigment in the aqueous drawing material composition is less than 1% by weight, there is a problem that the aqueous drawing material composition lacks coloring power. However, when it exceeds 60% by weight, the viscosity of the aqueous drawing material composition obtained becomes excessively high, and the drawing material composition has a poor elongation at the time of drawing, and the drawing property is poor.

  Further, according to the present invention, the aqueous drawing material composition may optionally contain an extender pigment in addition to the pigment as the colorant as described above. Examples of such an extender pigment include calcium carbonate, kaolin, talc, silica, aluminum silicate, alumina, barium sulfate and the like. Such an extender pigment is used, if necessary, in a range of 30% by weight or less, preferably 1 to 20% by weight.

(Thickener)
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 although it is not limited to these examples, among them, it has an appropriate thickening effect and can be obtained. Bentonite is particularly preferably used because it does not affect the water resistance and the water washability of the coating of the aqueous drawing material composition.

  In the present invention, the thickener is generally used in an aqueous drawing material composition in an amount of 10% by weight or less, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight. Used in the range of

(Water soluble resin)
In the aqueous drawing material composition according to the present invention, only a combination of hydroxyalkyl cellulose and modified polyvinyl alcohol is used as a water-soluble resin.

  In the present invention, the above hydroxyalkyl cellulose as the first water-soluble resin is used as a dispersing agent for dispersing the pigment in the aqueous drawing material composition in cooperation with the anion-modified polyvinyl alcohol described later, and also as an emulsion. In combination with resin and anion-modified polyvinyl alcohol, it is used as a fixing agent to fix the coating film on the drawing surface, and on the other hand, even when the aqueous drawing material composition adheres to the pallet or paint brush and is dried It is used to give an aqueous drawing material composition a water-washing property, ie, weak water solubility, to enable it to be removed by washing with water.

  As the hydroxyalkyl cellulose, preferably, at least one selected from hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl hydroxyethyl methyl cellulose is used. The aqueous drawing material composition according to the present invention contains such hydroxyalkyl cellulose in the range of 0.1 to 8% by weight, preferably in the range of 0.3 to 7% by weight.

  When the amount of hydroxyalkyl cellulose in the aqueous drawing material composition is less than 0.1% by weight, the coating after drying has a water-washing property, but the fixing property of the coating is insufficient at the time of drawing.

  However, when the amount of hydroxyalkyl cellulose in the aqueous drawing material composition is more than 8% by weight, the coating after drying does not have 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 at the time of drawing.

  Therefore, the aqueous drawing material composition according to the present invention contains an anion-modified polyvinyl alcohol as the second water-soluble resin, and an aqueous drawing material composition containing only the hydroxyalkyl cellulose as the water-soluble resin due to its excellent film forming property. In comparison with the above, the fixability of the coating film is excellent.

  Furthermore, the aqueous drawing material composition according to the present invention contributes also to the temporal stability of the aqueous drawing material composition by containing the above-mentioned anion-modified polyvinyl alcohol by its emulsifying action.

  The modified polyvinyl alcohol comprises a carboxy modified polyvinyl alcohol having a carboxyl group as a side chain and a sulfonic acid modified polyvinyl alcohol having a sulfonic acid group as a side chain, and in the present invention, a carboxyl group as a side chain as the modified polyvinyl alcohol Preferably, at least one selected from a carboxy-modified polyvinyl alcohol having the following formula and a sulfonic acid-modified polyvinyl alcohol having a sulfonic acid group as a side chain is preferably used. All such anion-modified polyvinyl alcohols can be obtained as commercial products.

  In general, polyvinyl alcohol is obtained by polymerizing vinyl acetate to obtain polyvinyl acetate, and this polyvinyl acetate can be obtained by saponification, that is, hydrolysis, and the degree of saponification is about 97 to 99%. Polyvinyl alcohols having various degrees of saponification are known, from saponification to partially saponified products having a degree of saponification of about 86 to 90%. The polyvinyl alcohol thus obtained, i.e. the usual or unmodified polyvinyl alcohol, generally has an aqueous solution acidity due to the hydroxy group it has.

  Thus, such conventional or unmodified polyvinyl alcohol may break the emulsion emulsification depending on the acrylic resin emulsion used.

  However, unlike the above-described normal or unmodified polyvinyl alcohol, the above-described anion-modified polyvinyl alcohol may break the emulsion of the acrylic resin emulsion even if it is blended in the aqueous drawing material composition containing the acrylic resin emulsion. On the contrary, the emulsion stability of the acrylic resin emulsion is excellent, and the excellent film-forming property allows the coating film of the aqueous drawing material composition according to the present invention to have excellent fixability.

  The aqueous drawing material composition according to the present invention contains such an anionically modified polyvinyl alcohol in the range of 0.5 to 8% by weight, preferably 1 to 6% by weight.

  When the proportion of the anion-modified polyvinyl alcohol in the aqueous drawing material composition is less than 0.5% by weight, the fixability of the coating film can not be improved, while when it is more than 8% by weight, it is obtained. The resulting aqueous drawing material composition is excellent in the fixability of the coating film, but the coating film after drying becomes inferior in water resistance, and the resulting aqueous drawing material composition has a viscosity too high. Therefore, the elongation of the aqueous drawing material composition is poor at the time of drawing.

(Acrylic resin emulsion)
As described above, the water-soluble resin contains only the combination of hydroxyalkyl cellulose and anion-modified polyvinyl alcohol, among which hydroxyalkyl cellulose gives weak water solubility to the dried coating of the aqueous drawing material composition, while, An acrylic resin emulsion is used to impart water resistance to the dried coating film of the same aqueous drawing material composition, and further, the anion-modified polyvinyl alcohol enhances the fixability of the coating film of the aqueous drawing material composition. There is.

  As a specific example of the said acrylic resin emulsion, Movinyl DM772 (made by Japan Synthetic Chemical Industry Co., Ltd.), TOCRYL W-168 (Toyo Ink Mfg. Co., Ltd.), Nicazole RX 866 D (Nippon Carbide Industries Ltd.) etc. are mentioned, for example. be able to.

  The aqueous drawing material composition according to the present invention contains such an acrylic resin emulsion in a range of 0.1% by weight or more and less than 5% by weight in terms of solid content, preferably 0.5-4 in solid content. It is contained in the range of 9% by weight, most preferably in the range of 0.5 to 4.5% by weight. When the content of the acrylic 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 furthermore, the fixing property is poor. The coated film after drying is inferior in water resistance. However, conversely, when the content of the acrylic resin emulsion in the aqueous drawing material composition is 5% by weight or more in solid content, it is difficult to wash the dried coating film with water.

(Wetting agent)
According to the present invention, the aqueous drawing material composition optionally contains a wetting agent to prevent its freezing and to delay drying. As the wetting agent, for example, besides polyhydric alcohol, urea or a derivative thereof is preferably used. Examples of the polyhydric alcohol include glycerin, ethylene glycol, propylene glycol, dipropylene glycol and sorbitol, and examples of the urea derivative include dimethylurea, tetramethylurea, tetraethylurea and thiourea. Etc. can be mentioned.

  Such a wetting agent is optionally used in the aqueous drawing material composition in the range of 20% by weight or less, preferably in the range of 1 to 15% by weight. If the content of the wetting agent in the aqueous drawing material composition is less than 1% by weight, in some cases, there is a problem that the coating film formed by the aqueous drawing material composition is brittle and is therefore brittle. 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 bad.

(Surfactant)
The aqueous drawing material composition according to the present invention may optionally contain a surfactant. As the surfactant, at least one selected from nonionic and anionic surfactants is used in a range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.

(Other additives)
According to the present invention, the aqueous drawing material composition is, if necessary, various additives conventionally used in the aqueous drawing material composition, for example, preservatives, fungicides, dispersants, antifoaming agents. Etc. may be included.

(Manufacturing)
The aqueous drawing material composition according to the present invention is not particularly limited in its production method. For example, a water-soluble resin, hydroxyalkyl cellulose and anion-modified polyvinyl alcohol, are dissolved in water, to which a color pigment, an extender and water, and if necessary, a wetting agent, surfactant, preservative, etc. After mixing and stirring until dispersion, dispersion treatment is performed using a roll mill, and then the acrylic resin emulsion is added to the mixture thus obtained, mixing, stirring and vacuum degassing, the present invention An aqueous drawing material composition according to

Example 1
An aqueous drawing material composition was prepared as described above using the components shown in Table 1 in the amounts shown in Table 1. The performance of the obtained aqueous drawing material composition, that is, the pallet washability, the paint brush washability, the water droplet water resistance, the double coatability, the fixability of the dried coating film and the temporal stability were evaluated as follows. The results are shown in Table 1.

Examples 2 to 4
An aqueous drawing material composition was prepared as described above using the components shown in Table 1 in the amounts shown in Table 1. The blending amount of the acrylic resin emulsion is an amount as an emulsion. With respect to the obtained aqueous drawing material composition, the pallet washability, the paint brush washability, the water droplet resistance, the overpaintability, the fixability of the dried coating film and the temporal stability were evaluated. The results are shown in Table 1.

Comparative Examples 1 to 8
An aqueous drawing material composition was prepared as described above using the components shown in Table 1 in the amounts shown in Table 1. With respect to the obtained aqueous drawing material composition, the pallet washability, the paint brush washability, the water droplet resistance, the overpaintability, the fixability of the dried coating film and the temporal stability were evaluated. The results are shown in Table 1. The details of each component used in Table 1 are as follows.

(component)
Tyrose H10000P2:
Hydroxyethyl cellulose (rotor 1 ° C 34 R, rotation speed 20 rpm, measurement time 3 minutes, measurement temperature 20 ° C. using an EHD viscometer, measured for a 1.5 wt% aqueous solution) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Viscosity 950 mPa · s)
Tyrose H22 P2:
Hydroxyethyl cellulose (rotor 1 ° C 34 R, rotation number 5 rpm, measurement time 3 minutes, measurement temperature 3 minutes, ELD viscosity meter under the conditions of 20 ° C using an ELD-type viscometer, the viscosity measured for a 1 wt% concentration aqueous solution) 20 mPa · s)

PVA AT-17:
Nippon Vida-Poval KK-made carboxy modified polyvinyl alcohol Gauceran L-3266:
Sulfonic acid modified polyvinyl alcohol PVA 403 manufactured by Nippon Synthetic Chemical Industry Co., Ltd .:
Kuraray's native polyvinyl alcohol

Plysurf A-212E:
Daiichi Kogyo Seiyaku Co., Ltd. nonion surfactant Sun eye bag SA:
Sanai Oil Co., Ltd. Preservative PC-700:
Shiroishi Kogyo Co., Ltd. calcium carbonate (body pigment)

Bentonite:
Hojun Co., Ltd. D Black:
Noma Chemical Industry Co., Ltd. black pigment Movinyl DM 772:
Nippon Synthetic Chemical Industry Co., Ltd. acrylic resin emulsion (solid content 46%)

(Performance evaluation)
Palette washability Five parts by weight of the aqueous drawing material composition was mixed with 1 part by weight of water to prepare a drawing material sample (the same applies hereinafter). The above drawing material sample was applied to pellets made of high impact polystyrene using a flat design brush, and then left to dry at room temperature for 1 week. As described above, the drawing material sample was adhered, and while the tap water was poured on the dried pallet, the adhered drawing material sample was rubbed with a flat design brush to wash the pallet. Thus, when 80% or more of the dried drawing material sample adhered to the pallet and was able to be washed away was A, the ratio of the drawing material sample which could be washed out was 30% or more and less than 80%. The time was B, and the time when the ratio of the drawing material sample which could be washed out was less than 30% was C.

Paint Brush Washability After uniformly drawing a drawing material sample on a wool flat brush, it was allowed to stand at room temperature for 1 week to dry. The sample of the drawing material was smeared in this way and washed with hand water while pouring tap water on the dried paint brush. In this way, when 80% or more of the drawing material sample that has been coated and dried can be washed away, A, the ratio of the drawing material sample that can be washed out is 30% or more and less than 80%. The time was B, and the time when the ratio of the drawing material sample which could be washed out was less than 30% was C.

Water Droplet Water Resistance A drawing material sample was overcoated on a drawing sheet three times using a flat design brush. The resulting coated film was dried at room temperature for 1 hour, and then 1 drop of tap water was dropped on the coated film using a 1 mL volume dropper, and left at room temperature for 6 hours to observe the state of the coated film. When no change was observed in the coating film, it was A, and when the coating film was cracked, decolorized and / or water marks were observed, it was C.

Overcoating Properties A drawing material sample was overcoated on the drawing paper three times using a flat design brush, and then the coating was dried at room temperature for 1 hour. Then, 5 parts by weight of an acrylic paint ("Acryl Gouache" manufactured by Sakura Crepas Co., Ltd.) was mixed with 1 part by weight of water, and this was applied three times in the longitudinal, transverse, and longitudinal directions on the coating film. At this time, when the acrylic paint can be overcoated without any problem on the previous coating (base), it is A, and when the previous coating (base) is moved or blurred, it is C.

Fixability A drawing material sample was overcoated on a drawing sheet three times using a flat design brush, and after the coating was dried at room temperature for 1 hour, the coating was traced with a finger. At this time, A was taken when the finger was not colored, and C was taken when the finger was colored.

Temporal stability The drawing material sample was stored in a polyethylene bottle at a temperature of 70 ° C. for 3 days, and then allowed to cool to room temperature. At this time, the time when no change was observed in the writing material sample was A, and the time when the writing material sample was thickened or gelled was C.

  As shown in Table 1, according to the present invention, a resin emulsion is contained in a range of 0.1 wt% or more and less than 5 wt%, and a hydroxyalkyl cellulose and an anion modified polyvinyl alcohol are respectively defined in the present invention as water soluble resins. In the same manner as the conventional emulsion paints, the dried coating film of the aqueous drawing material composition contained in the range is excellent in water droplet resistance, and bleeding or dissolution occurs even if water droplets adhere to the dried coating film. It does not occur, has a recoatability, and it can be removed by water-washing even when it adheres to a pallet or a paint brush and is dried, and furthermore, the aqueous drawing material composition according to the present invention fixes the dried coating It is excellent in sex.

  On the other hand, since the aqueous drawing material composition of Comparative Example 1 contains only the hydroxyalkyl cellulose as the water-soluble resin, the dried coating film is inferior in the fixing property. Then, although the aqueous | water-based drawing material composition of the comparative example 2 increases the compounding quantity of the hydroxyalkyl cellulose, the dry coating film is still inferior to fixability.

  Since the aqueous drawing material composition of Comparative Example 3 contains hydroxyalkyl cellulose and also contains unmodified polyvinyl alcohol, the dried coating film is excellent in fixability but inferior in stability over time.

  The aqueous drawing material composition of Comparative Example 4 contains an anionically modified polyvinyl alcohol, but the amount thereof is smaller than the amount specified in the present invention, so the dried coating is still inferior in fixability. However, in the aqueous drawing material composition of Comparative Example 5, the dry coating film is excellent in fixability since the compounding amount of the anionically modified polyvinyl alcohol is larger than the amount specified by the present invention, but the water resistance is improved. It is inferior.

  The aqueous drawing material composition of Comparative Example 6 contains neither an acrylic resin emulsion nor polyvinyl alcohol, and the dried coating film has no water resistance. Then, the aqueous | water-based drawing material composition of the comparative example 7 mix | blends an acrylic resin emulsion with the aqueous | water-based drawing material composition of the comparative example 6. FIG. Although the dried coating film is excellent in water resistance and stability over time, it is inferior in water washability.

  Thus, Comparative Example 8 is the aqueous drawing material composition of Comparative Example 7, in which the blending amount of hydroxyalkyl cellulose is increased. The dried coating film is excellent in water washability, but inferior in water resistance and fixability.

Claims (7)

An aqueous drawing material composition comprising water, a color pigment, a water-soluble resin and an acrylic resin emulsion, wherein the water-soluble resin contains only a combination of hydroxyalkyl cellulose and anion-modified polyvinyl alcohol, and the resin emulsion has a solid content of 0. 1 wt% or more, viewed contains within a range of less than 5 wt%, aqueous drawing material composition characterized contains Mukoto the anion-modified polyvinyl alcohol in the range of 0.5 to 8 wt%. The aqueous drawing material composition according to claim 1 , wherein the anion-modified polyvinyl alcohol is at least one selected from a carboxy-modified polyvinyl alcohol and a sulfonic acid-modified polyvinyl alcohol. The aqueous drawing material composition according to claim 1, wherein the hydroxyalkyl cellulose is in the range of 0.1 to 8% by weight. The aqueous drawing material composition according to claim 1 or 3 , wherein the hydroxyalkyl cellulose is at least one selected from hydroxyethyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose.   The aqueous drawing material composition according to claim 1, comprising bentonite as a thickener.   The aqueous drawing material composition according to claim 1, comprising an extender pigment. The aqueous drawing material composition according to claim 1, comprising at least one additive selected from a wetting agent, a surfactant and a preservative.