JP5717321B2 - Aqueous paint composition and method for producing the same - Google Patents

Description

  The present invention relates to a water-based paint composition suitably used for watercolor paints, poster colors and the like.

  In general, water-based paint compositions such as watercolor paints and poster colors are compositions containing water, a water-soluble resin, and a coloring material, and are applied to paper or the like when drawing a picture. When drawing with a paint, take the paint from a tube or other container onto the palette, mix it with other colors of paint or water, and apply to the paper using a paintbrush. It is common.

  Patent Document 1 discloses that a paint film can be removed while washing the cloth while maintaining the paintability on paper or wooden cloth, and a paint film having water resistance and weather resistance is formed. Describes an aqueous paint composition containing spherical colored resin particles having an average particle diameter of 3 to 20 μm which are difficult to enter into the fiber of the clothes as a colorant and using a heat-crosslinkable water-soluble resin as a fixing agent.

JP 2002-265872 A

The palette that serves as a saucer for placing the paint on the brush is often white so that the color when the paper is colored can be confirmed. In particular, in the case of transparent watercolor paint, since the transmitted light of the background is also seen, it is difficult to distinguish the color of the paint when the palette is chromatic. In the case of an opaque paint, it is difficult to be influenced by the color of the background, but since the color condition around the placed paint is also important for the color discrimination of the paint, it can be said that a uniform color is preferable.
Usually, a palette of watercolor paints is repeatedly used after being used and washed with water to remove the aqueous paint composition. However, even if washed with water, the colorant remains as if the palette was thinly dyed, and it may not be possible to return it to the state before use. When placing a paint on the palette, it may be mixed with a paint of a new color. It may be visible and is a problem. This is because the coloring agent enters the surface of the pallet and gets stuck to the scratches attached to the pallet during repeated use.
In particular, when organic pigments with good color development and many types of colors are used, organic pigments have a fine particle size and many oleophilic properties. This hinders the dissolution of the conductive resin and makes it difficult to remove dirt from the pallet. In addition, if the organic pigment is first treated with a surfactant to make the organic pigment hydrophilic, the surfactant acts as a bridge between the palette and the organic pigment even if the water-soluble resin dissolves. Therefore, after all, the organic pigment may not leave the pallet and may contaminate the pallet more.
On the other hand, if the particle diameter of the pigment as the colorant is increased, the pigment does not enter the concavo-convex portion of the pallet and the stain becomes difficult to adhere, but there is a problem that the color development when painted is worsened.

The gist of the present invention is an aqueous paint composition containing only an organic pigment whose surface is covered with at least a left-rotating arabic gum film as a coloring material .

Left-handed optical gum arabic has a high proportion of sugars such as D-glucuronic acid that are easily soluble in water, and is bound to calcium and magnesium salts of arabic acid. Left-handed rotation refers to the property that linearly polarized light rotates to the left. The glucose skeleton having the carboxyl group of D-glucuronic acid absorbs right-handed rotation in linearly polarized light, so that only left-handed left-handed rotation is confirmed. The
Such left-rotating gum arabic is attached to the surface of organic pigments that are also difficult to adjust to water due to the existing saccharide components that are difficult to dissolve in water, and the surface of organic pigments is covered with components that are easily soluble in water. Since a film is formed and can be easily detached from the pallet by washing water and washed away, it is presumed that the pallet is less likely to remain dirty.

Water is used as the main solvent in the aqueous paint composition.
The gum arabic used in the present invention is a sap secreted from a tree of the genus Acacia and is a substance having optical activity. Optical rotation is a phenomenon in which polarized light rotates as it passes through an optical rotatory material. The optical rotation of gum arabic is obtained by dissolving 5 g of gum arabic in 100 ml of distilled water and separating the precipitate with a membrane filter or centrifugation. The remaining solution is measured with a polarimeter. The polarimeter is a device that irradiates a material to be measured plane-polarized light by a polarizer and detects the optical rotation generated at that time by rotating the analyzer. -300 type, JASCO Corporation make, polarimeter, P-2200, etc. can be used for the measurement. The result of the measurement is that the polarized light transmitted through the gum arabic faces the light traveling direction and the light rotates counterclockwise is called left-handed rotation.
The left-rotating gum arabic has a higher proportion of sugars such as glucuronic acid that are easily soluble in water, and a smaller proportion of sugars such as galactose that are less soluble in water than right-handed gum. Therefore, it is considered that levorotatory gum arabic is more soluble in water than right rotatory gum arabic, so when levorotatory gum arabic forms a film on the surface of an organic pigment, it is more soluble in water. Therefore, it is considered that the organic pigment can be prevented from adhering to the pallet. On the other hand, right-rotating gum arabic has many components that are difficult to dissolve in water, and the lipophilic nature of organic pigments cannot be sufficiently suppressed, so it is difficult to dissolve in water and prevents pallet contamination. Examples of left-handed optical rotation include gum arabic collected from Acacia Senegal. The amount used is preferably 1% to 40% by weight as the aqueous paint composition.

The organic pigment may be a conventionally known one. For example, Hansa Yellow-10G, 5G, 3G, 4, GR, A, G, Benzidine Yellow, Permanent Yellow NCG, Quinoline Yellow, Sudan 1, Permanent Orange 2G, Indanthrene Brilliant Orange GK, Vulcan Orange, Benzidine Orange HL, pyrazoline orange TMP, perinone orange, DPP orange, permanent brown FG, para brown, permanent red 4R, fire red, brilliant carmine BS, pyrazolone red, quinacridone red, Bordeaux 5B, thioindigo red, naphthol carmine HR , Nafsol Red F5RK, Nafsol Red F3RK-70, Permanent Red FGR, Permanent Carmine FB, Permanent Red 2B, Brilliantca Min 6B, perylene vermilion, perylene red, DPP Red, Fast Violet B, dioxazine violet, quinacridone magenta, alkali blue lake, copper phthalocyanine blue, indigo, Indus Ren blue, acid green lake, there is a copper phthalocyanine green and the like. Moreover, you may use the composite pigment which made the said organic pigment adhere to the surfaces, such as a calcium carbonate. Blue # 2400 (composite pigment made of copper phthalocyanine blue, calcium carbonate, silica, dioxin violet, and aluminum silicate) and blue # 2500 (composite pigment made of copper phthalocyanine blue, calcium carbonate, alumina silicate, and naphthol carmine HR) are commercially available. , Viridangulin P (composite pigment composed of copper phthalocyanine green, copper phthalocyanine blue, Hansa Yellow 10G, calcium carbonate, kaolin, silica), FS / NR 418 (composite composed of copper phthalocyanine blue, copper phthalocyanine green, calcium carbonate, aluminum silicate) Pigment) (above, manufactured by Noma Chemical Co., Ltd.), NSB A-25 (composite pigment made of copper phthalocyanine blue and calcium carbonate) (made by Dainichi Seika Kogyo Co., Ltd.) And the like. Among these organic pigments, an insoluble azo pigment monoazo or disazo pigment and a phthalocyanine pigment are preferable.
Monoazo-type and disazo-type insoluble azo pigments have a well-balanced benzene ring with azo groups in between, and phthalocyanine pigments have a symmetrical molecular structure. Is likely to be uniform.
These pigments may be used alone or in combination of two or more. The amount used is preferably 0.1% to 40% by weight as the aqueous paint composition. As a composite pigment, 0.1 to 40 weight% is preferable as an aqueous paint composition.

  As a coloring agent, a dye becomes a molecular level when dissolved in water and is dissolved in water or gum arabic and cannot be surface-treated. Therefore, it cannot be used because the dye penetrates into the material of the pallet.

In addition to the above components, various components can be blended as necessary.
As the water-soluble resin, natural water-soluble resins such as glue and dextrin, semi-synthetic water-soluble resins such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, and synthetic water-soluble resins such as polyvinyl alcohol and acrylic resins can be used.
Also, freeze stabilizers such as propylene glycol and ethylene glycol, phenol, chloroacetamide, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4 -Isothiazoline-3-one, 2-pyridinethiol-1-oxide sodium salt, sodium dehydroacetate, sodium benzoate, sodium sorbate, potassium sorbate, thiabendazole, phenoxyethanol, sodium fluoride, 4- (2-nitrobutyl) Preservatives and fungicides such as morpholine, 1,3-dimorpholino-2-ethyl-2-nitripropane, 2-bromo-2-nitropropane-1,3-diol, titanium dioxide, iron oxide, iron hydroxide, Ultramarine inorganic pigment, calcium carbonate and talc, White inorganic powder and rust inhibitor as an extender pigment such as squid, defoamers, of course it can be used in combination defoamers, and the like surfactants.

  In order to adjust the drying speed of the aqueous paint composition and improve the solubility in water, a water-soluble high-boiling solvent such as glycerin can also be used. The amount used is preferably 1 to 20% by weight as the aqueous paint composition.

The method for producing the aqueous paint composition of the present invention is as follows.
First, a solution in which a left-rotating gum arabic is added to a mixed solution of water and glycerin and stirred with a stirrer such as a turbo mixer is made. At this time, it may be dissolved by heating. Foreign matter such as dust mixed in gum arabic is filtered and removed. Add organic pigment to this solution and mix and stir with a turbo mixer or Henschel mixer to form a gum arabic film on the surface of the organic pigment.
Then, add a water-soluble resin, preservative / antifungal agent, inorganic pigment, extender pigment, etc. to a conventionally known stirrer / disperser such as turbo mixer, Henschel mixer, 3-roll mill, horizontal ball mill or horizontal bead mill. It can be easily obtained by mixing and dispersing.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example.

(Example 1) Watercolor paint 1) Arabic glue manufacturing process Water 35 parts by weight Acacia Senegal gum arabic (left-handed rotation) 17 parts by weight Glycerin 9 parts by weight The above ingredients are heated to 90 ° C. while stirring with a turbo mixer and dissolved. .
2) Pigment treatment step 61 parts by weight of the above gum arabic paste liquid Hansa Yellow 10G (CI Pigment Yellow 3) 2 parts by weight Disazo Yellow (CI Pigment Yellow 14) 1 part by weight Anisidine Yellow (CI Pigment Yellow 74) 2 parts by weight The above components are stirred for 5 minutes with a turbo mixer.
3) Paint production process 66 parts by weight The above pigment dispersion 66 parts by weight Light calcium carbonate 34 parts by weight Titanium dioxide 2 parts by weight Silica 4 parts by weight Dextrin 4 parts by weight Propylene glycol 0.1 part by weight Thiabendazole 0.1 part by weight Sodium fluoride 0.002 Part by weight Potassium sorbate 0.5 part by weight Sodium dehydroacetate 0.25 part by weight Sodium benzoate 1 part by weight Demol N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation)
0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a yellow watercolor paint.

(Example 2) Watercolor paint 1) Arabic glue manufacturing process Water 32 parts by weight Acacia Senegal gum arabic (left-handed) 16 parts by weight Glycerin 8 parts by weight The above ingredients are heated to 90 ° C. while stirring with a laboratory mixer and dissolved. .
2) Pigment treatment step 56 parts by weight of the above gum arabic glue solution Hansa Yellow 10G (CI Pigment Yellow 3) 2 parts by weight Phthalocyanine green (CI Pigment Green 7) 2 parts by weight The above ingredients are stirred for 5 minutes with a labbo mixer. .
3) Paint production process 60 parts by weight Pigment dispersion 15 parts by weight Light calcium carbonate 30 parts by weight Heavy calcium carbonate 30 parts by weight Alumina silica 3 parts by weight Propylene glycol 1 part by weight Thiabendazole 0.5 part by weight Sodium fluoride 0.001 part by weight Dehydro Sodium acetate 0.3 parts by weight Sodium benzoate 1 part by weight The above ingredients were stirred for 10 minutes with a lab mixer and then passed twice with a three-roll mill to obtain a green watercolor paint.

(Example 3) Watercolor paint 1) Arabic glue manufacturing process Water 40 parts by weight Acacia Senegal gum arabic (left-handed) 20 parts by weight Glycerin 11 parts by weight The above is heated to 90 ° C. with stirring in a laboratory mixer and dissolved.
2) Pigment treatment step 72 parts by weight of gum arabic glue solution Blue # 2500 (Copper phthalocyanine blue (CI Pigment Blue 15:
1), calcium carbonate, alumina silica and naphthol carmine HR (CI Pigme
nt Red150), 15 parts by weight carbon black (CI Pigment Black 7) 0.1 parts by weight The above components are stirred for 5 minutes in a labbo mixer.
3) Paint production process 87.1 parts by weight of the above pigment dispersion 24 parts by weight of light calcium carbonate 2 parts by weight of alumina silica Propylene glycol 0.2 parts by weight Thiabendazole 0.5 part by weight 2-bromo-2-nitropropane-1,3 -Diol 0.5 part by weight Sodium benzoate 1 part by weight Sodium dehydroacetate 0.3 part by weight Potassium sorbate 0.3 part by weight The above ingredients were stirred with a lab mixer for 10 minutes and then passed through a three-roll mill twice. After doing, I got indigo watercolor paint.

(Example 4) Watercolor paint 1) Arabic glue manufacturing process Water 33 parts by weight Acacia Senegal gum arabic powder (left-handed optical rotation) 16 parts by weight Glycerin 9 parts by weight The above ingredients are dissolved with stirring in a laboratory mixer.
2) Pigment processing step 58 parts by weight of the above gum arabic paste Vulcan orange (CI Pigment Orange 16) 3 parts by weight Permanent Red FGR (CI Pigment Red 112) 1 part by weight The above components are stirred with a turbo mixer for 5 minutes. To do.
3) Paint production process 62 parts by weight of the above pigment dispersion 42 parts by weight of light calcium carbonate 42 parts by weight of silica 5 parts by weight of carboxymethylcellulose 0.5 part by weight of propylene glycol 0.5 part by weight Thiabendazole 0.5 part by weight Sodium fluoride 0.001 part by weight Sodium dehydroacetate 0.3 parts by weight Suneye back sodium omazine (containing 2% 2-pyridinethiol-1-oxide sodium salt, manufactured by Sanai Oil Co., Ltd.) 0.4 parts by weight The above ingredients were stirred for 10 minutes with a laboratory mixer Then, after passing twice on a three-roll mill, a vermilion watercolor paint was obtained.

(Example 5) Watercolor paint 1) Arabic glue manufacturing process Water 35 parts by weight Acacia Senegal gum arabic (left-handed rotation) 17 parts by weight Glycerin 9 parts by weight The above ingredients are heated to 90 ° C. while stirring with a turbo mixer and dissolved. .
2) Pigment treatment step 61 parts by weight of gum arabic paste 61 parts by weight yellow 3G (CI Pigment Yellow 93) 4 parts by weight permanent carmine FB (CI Pigment Red 5) 1 part by weight To do.
3) Paint production process 66 parts by weight The above pigment dispersion 66 parts by weight Light calcium carbonate 40 parts by weight Titanium dioxide 1 part by weight Silica 4 parts by weight Dextrin 4 parts by weight Propylene glycol 0.1 part by weight Thiabendazole 0.1 part by weight Sodium fluoride 0.002 Part by weight Potassium sorbate 0.5 part by weight Sodium dehydroacetate 0.25 part by weight Sodium benzoate 1 part by weight Demol N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation)
0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain an orange watercolor paint.

(Example 4) Watercolor paint 1) Arabic glue manufacturing process Water 33 parts by weight Acacia Senegal gum arabic powder (left-handed optical rotation) 16 parts by weight Glycerin 9 parts by weight The above ingredients are dissolved with stirring in a laboratory mixer.
2) Pigment treatment step 58 parts by weight of gum arabic paste Permanent Red 2B (CI Pigment Red 48: 3) 2 parts by weight Naphthol Red 5R (CI Pigment Red 170) 2 parts by weight Stir for 5 minutes.
3) Paint production process 62 parts by weight of the above pigment dispersion 42 parts by weight of light calcium carbonate 42 parts by weight of silica 5 parts by weight of carboxymethylcellulose 0.5 part by weight of propylene glycol 0.5 part by weight Thiabendazole 0.5 part by weight Sodium fluoride 0.001 part by weight Sodium dehydroacetate 0.3 parts by weight Suneye back sodium omazine (containing 2% 2-pyridinethiol-1-oxide sodium salt, manufactured by Sanai Oil Co., Ltd.) 0.4 parts by weight The above ingredients were stirred for 10 minutes with a laboratory mixer Then, after passing twice on a three-roll mill, a vermilion watercolor paint was obtained.

(Comparative Example 1)
In Example 3, a watercolor paint was obtained in the same manner as in Example 1 except that Acacia Senegal gum arabic (left rotatory) was replaced with Acacia Sejar arabic gum tarfa grade (right rotatory).

(Comparative Example 2)
In Example 2, a watercolor paint was obtained in the same manner as in Example 2 except that Acacia Senegal gum arabic (left-handed rotation) was replaced with dextrin.

(Comparative Example 3)
In Example 4, all the components were put in a container at once, stirred for 30 minutes with a lab mixer, passed twice with a three-roll mill, and then a vermilion watercolor paint was obtained.

  Table 1 shows the results of confirming the detergency of the aqueous paint compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 on the plastic pallet.

Detergency measurement method 1 g is put on a palette (ZZL-31 (Pentel (manufactured) material: impact-resistant polystyrene obtained by copolymerization of styrene and polybutadiene)) with watercolor paint, 1 g of distilled water is added, and a paint brush (ZBNR-14 (Pentel After mixing well)), drying at room temperature for 30 minutes, washing the pallet surface with running brush (ZBNF-14, Pentel Co., Ltd.) for 15 seconds under running water. What was repeated 10 times was dried, and the Y value was measured with a spectroscopic color difference meter NF-777 (manufactured by Nippon Denshoku Industries Co., Ltd.) for the uncoated part (A) and the coating mark (B) on the pallet surface. The detergency for the pallet was set to a value of B / A × 100, and the larger the value, the better the detergency.

Claims (2)

An aqueous paint composition containing only an organic pigment whose surface is covered with a levorotatory gum arabic film at least as a colorant . 2. An organic pigment is mixed in a solution of at least water, glycerin and levorotatory gum arabic to form an organic pigment covered with a levorotatory gum arabic film, and mixed and dispersed with other compounds. A method for producing the aqueous paint composition as described .