JPH07310040A - Colored specular ink - Google Patents

Abstract

PURPOSE:To produce a colored specular ink developing brilliant and beautiful specular color image and metallic color, giving extremely high specular gloss and printing suitability and having easy handleability by compounding a binder resin with leafing aluminum powder in combination with non-leafing aluminum powder. CONSTITUTION:This specular ink is produced by kneading (i) non-leafing type aluminum powder as a main component with (ii) leafing type aluminum powder and (iii) a binder resin and mixing (A) the obtained kneaded material with (B) a solvent and (C) a color pigment. The compounding ratios of (i):(ii):(iii) are preferably (5.2-10):1:(3-10) and the components (i) and (ii) each is used in the form of paste dispersed in a solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel color specular ink.

There are a vapor deposition method and a printing method as a method of decorating a material with a metallic color. The former has a major drawback in that the equipment cost is high because a vacuum device or the like must be used. On the other hand, a so-called silver ink in which a metal powder is used as a pigment is generally used in the printing method in order to give a metallic luster. Such a silver ink is one in which a paste prepared by dispersing aluminum powder in a petroleum solvent is mixed in a vehicle. There are conventionally two types of such silver inks, a leafing type and a non-leafing type.
The former uses a leafing type aluminum paste, in which scaly aluminum particles float and are arrayed on the ink film surface, and due to the irregular reflection, they appear to shine silvery, but the surface irregularities are severe. Therefore, the reality is that it is metallic rather than mirror-like. When the non-leafing type is used, the aluminum particles are dispersed in the ink film without floating on the film surface, so that the aluminum particle has a silver-white metallic appearance but is not specular.

In addition, all inks have an ink film surface with a strong metallic feeling, but since the basic color is silver, it does not change much like the vapor deposition method. To improve this, a leafing type pigment is used. Even if an attempt is made to add and color the pigment, the pigment sinks below the ink film surface, so the coloring effect of the pigment is hardly obtained, and if the addition amount of the pigment is increased, the metallic tone is lost. Further, in the non-leafing type, even if a pigment is added, the pigment is uniformly colored but dispersed, resulting in poor gloss. For these reasons, it has heretofore been difficult to form a mirror-like color surface having a composite of metallic luster and bright and beautiful coloring.

The present invention is intended to solve the above-mentioned problems, and its purpose is to provide a beautiful metallic color on one side and diffuse reflection of sunlight or artificial light on the other side. It is possible to create an excellent mirror surface color without press printing, and it is easy to handle and print properly, and to provide a color mirror ink with excellent characteristics such as discoloration resistance, fade resistance, weather resistance, and heat resistance. It is in. INDUSTRIAL APPLICABILITY The present invention is suitable as a printing ink for transparent materials such as home appliances, ornaments, arts and crafts, accessories such as watches and glasses, various plastic molded products and glass products, and printing inks for various paper products, Further, it can be used for coating metal products such as vehicles and parts thereof. The printing method can also be applied to any printing such as screen printing, letterpress printing, intaglio printing, lithographic printing, and transfer.

[0005]

In order to achieve the above object, the present invention mainly uses non-leafing type aluminum powder, and uses leafing type aluminum powder for this, and kneads these with a binder resin to obtain a coloring pigment or a A solvent is added. It is preferable that the non-leafing type aluminum powder, the leafing type aluminum powder, and the binder resin are mixed in a predetermined ratio, that is, the non-leafing type aluminum powder, the leafing type aluminum powder, and the binder resin are in a weight ratio (1.2 to 5). ): (1): (2.5-10)
The most preferable combination ratio is (1.2 ~
3): (1): (3 to 10). Although powders may be used as the non-leafing type aluminum powder and the leafing type aluminum powder, it is preferable to use paste made with a solvent or oil and fat.

[0006]

According to the color mirror surface ink of the present invention, the non-leafing aluminum powder and the leafing aluminum powder are uniformly dispersed in the binder resin, and the scale-like non-leafing aluminum particles are uniformly dispersed in the resin, and the leafing aluminum is The particles are arranged in order without agglomeration, and the surface of the leafing aluminum particles is coated with a very thin resin film. Due to the high concealing property due to the laminated structure of aluminum particles and the reflectivity due to the smoothness of the surface, an extremely glossy mirror surface is formed.
Especially, since the non-leafing aluminum powder is mixed in a larger amount than the leafing aluminum powder and the mixing ratio is (1.2 to 5): (1), the non-leafing aluminum powder is irregularly dispersed throughout the film. Since the gaps between the non-leafing aluminum powders are filled with the leafing aluminum powders, the layer has a high density, so that the surface smoothness becomes very high. Further, the leafing aluminum powder is arrayed on the film surface, and the array gap is filled with the non-leafing powder. Moreover, since the mixing ratio of the binder resin is set to a specific range, the color pigment fine particles are uniformly dispersed at a high concentration, and the color pigment fine particles adhere to the non-leafing aluminum particles and also to the leafing aluminum particles through a very thin resin film. Adhere to. Therefore, it is possible to create a beautiful metallic color or a color mirror surface having a vivid color tone.

The present invention will be described in detail below. The printing ink according to the present invention is basically a non-leafing type aluminum powder as a main component, to which a leafing type aluminum powder is added, and these are dispersed and kneaded in a binder resin. As the non-leafing type aluminum powder and the leafing type aluminum powder, scaly aluminum powder having an average particle size of 3 to 20 μm and whose surface is polished is preferably used. The non-leafing type aluminum powder and the leafing type aluminum powder may have the same particle size or different particle sizes. In the latter case, a leafing type aluminum powder having a finer particle size than that of the non-leafing type aluminum powder is preferably used. In the leafing type aluminum powder, the particle surface is coated with a fatty acid represented by stearic acid. Such non-leafing type aluminum powder and leafing type aluminum powder are not the powder itself, but preferably those obtained by removing the resin component from the vehicle component, that is, a paste-like substance dispersed in a mixture of oil and solvent or further a plasticizer. Things are used. In this case, it is suitable that the nonvolatile content is 60 to 80% and the fat and oil content is 7 to 0.1%.

As the oil, polymerized linseed oil, cinnamon oil,
Vegetable oil represented by castor oil, soybean oil, polymerized oil, processed oil represented by dehydrated castor oil, malein oil, urethane oil, vinylated oil, mineral oil represented by machine oil, spindle oil, etc. are selected. It As the solvent, any one of a low boiling point solvent, a medium boiling point solvent and a high boiling point solvent is adopted depending on the printing target and the printing method. Examples of the low boiling point solvent include aliphatic hydrocarbons represented by n-hexane and n-heptane, aromatic hydrocarbons represented by toluene and cyclohexane,
Alcohols represented by methyl alcohol, ethyl alcohol, n-propyl alcohol, IPA, n-butyl alcohol, isobutyl alcohol, esters represented by ethyl acetate, methyl acetate, isopropyl acetate, represented by acetone, MEK, MIBK. Examples include ketones. As the medium boiling point solvent, an aliphatic hydrocarbon represented by mineral spirit, xylene, solvent naphthalate, tetralin, an aromatic hydrocarbon represented by dipentende, cyclohexyl alcohol, an alcohol represented by 2-methylcyclohexyl alcohol, and butyl acetate. Represented by, cyclohexane, methylcyclohexane, DAA, ketone represented by isophorone, glycol represented by ethylene glycol, propylene glycol, glycol ether represented by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate represented by Glycol ether ester is used. As the high-boiling solvent, aliphatic hydrocarbons represented by high-boiling petroleum solvents, alcohols represented by tridecyl alcohol, glycols represented by diethylin glycol, glycol ethers represented by diethylin glycol monobutyl ether, and diethyl ether. A glycol ether ester represented by tylin glycol monobutyl ether acetate can be used.

The binder resin for dispersing the non-leafing type aluminum powder and the leafing type aluminum powder is not particularly limited. For screen printing, polyvinyl acetate and its copolymer resin, ethylene-
Vinyl acetate copolymer resin and vinyl chloride / vinyl acetate copolymer resin are preferable. In addition, rosin-modified phenol resin, urea resin and melamine resin, ketone resin, PVC,
Acrylic resin, polyester resin, alkyd resin, polyamide resin, epoxy resin, polyurethane, nitrocellulose, ethyl hydroxyethyl cellulose, cyclized rubber, chlorinated rubber, etc. are used alone or 2
One or more species can be used in combination. For letterpress and planographic printing,
Chroman-indene resin is preferable, and rosin-modified phenol resin, alkyd resin, epoxy resin and the like are preferable. These resins are appropriately selected by a combination of the pasty non-leafing type aluminum powder and the solvent used for the leafing type aluminum powder, and for example, the solvent is a low solvent such as methyl ethyl ketone, ethyl acetate, or toluene. In the case of a mixed solvent having a boiling point, polyvinyl acetate, a copolymer resin thereof, an ethylene-vinyl acetate copolymer resin, or a vinyl chloride / vinyl acetate copolymer resin is suitable.

According to the present invention, the non-leafing type aluminum powder, the leafing type aluminum powder and the binder resin are blended at a constant ratio.
This is a major feature. The weight ratio of non-leafing type aluminum powder: leafing type aluminum powder: binder resin is (1.2 to 10):
(1): (2.5 to 10). Leafing type aluminum powder must have a lower compounding ratio than non-leafing type aluminum powder, and even if the compounding ratio is the same, it is not possible. If there is a lot of leafing type aluminum powder, it will be arranged mainly on the printed film, and the non-leafing type aluminum powder in the film will disperse but will not be arranged regularly, so there will be gaps inside the film, The aluminum powder in the lower part of the film, that is, the substrate side, becomes coarse and the glossiness decreases, resulting in a metallic tone rather than a mirror surface.Because the leafing type aluminum powder will overlap on the printed film, this may also be uneven. This is because the color becomes violent, and it becomes difficult to arrange the pigment particles neatly on the printed film, so that a beautiful color metallic is not obtained.

The formulation examples of the present invention are as follows. In this formulation example, the non-leafing type aluminum powder is represented by A, the leafing type aluminum powder is represented by B, and the resin is represented by C. 1) A: B: C = (1.2-3): 1: (3-10) Specific example A: B: C = 1.5: 1: 5, 2: 1: 5, 2.
5: 1: 5, 1.5: 1: 7, 2: 1: 7, 2.5: 1:
7, 1.5: 1: 10, 1.5: 1: 3, 1.5: 1: 4 2: 1: 4, 2: 1: 6, 2) A: B: C = (3.2- 5): 1: (3 to 10) Specific example A: B: C = 5: 1: 3, 5: 1: 5,5:
1: 7, 5: 1: 10 3) A: B: C = (5.2-10): 1: (3-10) Specific examples A: B: C = 6: 1: 7, 7: 1: 8, 7:
1: 9, 10: 1: 10, particularly preferred of the above formulations are 1), then 2), and 3). The ratio of the binder resin is preferably higher than that of the non-leafing type aluminum powder, and if it is too low, the mirror surface characteristics tend to deteriorate. However, it is far better than the combination of leafing type aluminum powder and resin.

In the present invention, various organic or inorganic pigments are added for color mirror printing. Examples of the inorganic pigment include carbon black and titanium oxide, and as the organic pigment, cyanine-based, thioindigo maroon-based, quinophthalone-based, pinazoloquinadron-based, quinacridone-based, monoazo-based, disazo-based, etc. are selectively used. It For example, as the three primary colors, disazolo yellow, brilliant carmine 6B, phthalocyanine blue, etc. are used, and as high-grade pigments, yellow is condensed azo yellow, isoindolinone yellow, red is quinacridone red,
Condensed Azo Red, green is Phthalocyanine Green, brown is Benji, Benzimizolone Brown. This pigment may be added in an amount of about 3 to 7% with respect to the kneaded product of the above two kinds of aluminum powder and the binder resin. Then, in silk screen printing or the like, in order to improve the slip on the plate, a medium boiling point solvent may be added in an amount of about 5 to 10% to the above composition depending on conditions such as temperature conditions. In addition, depending on printability, improvement of film physical properties, etc., gelling agent, thixotropy imparting agent, thickening agent, antioxidant, dryer, crosslinking agent,
Additives such as a curing agent, a defoaming agent, a dispersant, and an ultraviolet absorber are selectively added.

In order to produce the color mirror ink according to the present invention, when the non-leafing type aluminum powder and the leafing type aluminum powder are pastes, these and the resin are sufficiently stirred and mixed with a mixer or the like,
A paste is obtained in which particles of non-leafing type aluminum powder and particles of leafing type aluminum powder are uniformly dispersed. After that, in order to adjust the fluidity, color, and drying property of the ink, it suffices to add a pigment, a solvent, and an additive to the two-type aluminum powder kneaded material. The solvent may be added to the second type aluminum powder paste, stirred and mixed, and then left for a predetermined time to remove the supernatant solvent. The solvent may of course be added little by little when obtaining the aluminum powder dispersion.

The color specular ink according to the present invention may be printed by any method such as screen printing, letterpress or transfer printing, and lithographic printing. In addition, the printing object is preferably a transparent plate, sheet, film, molded body such as plastic or glass from the viewpoint of exhibiting the characteristics of mirror color and metallic color, but in addition, paper, cloth, ceramics, wood ,
It can also be applied to metals and the like. Printing is also solid printing,
It is also possible to perform printing of a specific shape such as a character, a symbol, a figure, or a pattern, or multi-layer printing using a combination of solid printing and printing of a specific contour. In order to print on a transparent material, it is preferable to print on the back surface of the substrate, and in the case of multilayer printing, characters,
If the symbols, figures, patterns, etc. are printed in any color such as black using an ordinary ink by any method such as octopus printing, screen printing, transfer, etc., and then printing using the color specular ink according to the present invention. Good. Further, a release film is coated with a resin film, printing is performed using the ink of the present invention on the resin film and stop printing is performed thereon, and then the release paper is peeled off,
If the resin film surface is thermally transferred to a desired object, the mirror surface can be made the side opposite to the substrate. The drying method is arbitrary, such as natural drying or heat drying with hot air.

[0015]

[Example 1]

1) The present invention was applied to prepare three-color specular color ink for screen printing. As leafing aluminum powder (A), it has the characteristics of average particle size 7μm, nonvolatile content 72%, sieve residue (+ 44μm) trace%, water surface coverage area WCA30100cm ² / g, mixed solvent mineral spirits, oil content 6%. A paste was used. As non-leafing aluminum powder (B),
Average particle size 12 μm, non-volatile content 65%, residual residue (+44
μm) 1%, mixed solvent HOWS, and a paste having characteristics of 1% of oil and fat were used. A vinyl acetate copolymer was used as the resin (C). Ethyl acetate, toluene, cyclohexane, and isophorone were used as the solvent (D). As the color pigment (E), pigment red (red),
Pigment Yellow (yellow) and Hariogen Blue (blue) were used. 2) The composition was kneaded with 3 parts: 2 parts: 10 parts of A: B: C, and 20 parts of D and 1 part of E to 100 parts of this mixture.
0 part was added to obtain the target ink. The mixture had a syrup-like shape, and when D and E were added, the mixture had a plastic viscosity suitable for printing. 3) The resulting specular color ink was solid-printed on a polyester resin transparent substrate having a thickness of 75 μm using a screen of mesh 300, and dried with hot air at 100 ° C. for 20 minutes.

4) Beautiful metallic colors of red, yellow, and blue appeared on the printing surface of each of the three print samples obtained, and a beautiful color mirror surface appeared on the lower surface of the printing (substrate side). . As a result of performing an adhesion test with a cross cut tape of 24 mm on this printed sample, no abnormality was found, and 2 minutes of UV carbon and 18 minutes out of 120 minutes of water spraying time, 3
As a result of the accelerated weathering test at 00 hours, the ink film was peeled off, peeled off, and no blistering was observed. In addition, changes in discoloration and fading are also found in JIS L 0804 A 1411
According to the gray scale method specified in 1 above, the result was a good grade of 5. 5) Furthermore, in order to quantitatively examine the mirror surface degree according to the present invention, the glossiness was measured by the 20-degree mirror surface gloss prescribed in JIS Z8741. As the measuring device, GMX-202 manufactured by Murakami Color Research Laboratory was used. This measurement was made using only leafing aluminum powder (Comparative Example 1) and using only non-leafing aluminum powder.
In order to clarify the difference from (Comparative Example 2), a sample without addition of a coloring pigment was used. In Comparative Example 1, the A: C ratio was 3: 1.
The compounding ratio was 0, and in Comparative Example 2, B: C was 3:10.
The blending ratio of is. The light beam is incident from the mirror surface side, that is, the back surface side of the substrate, and is received by the light receiver. First, a substrate printed with black ink was measured to check the glossiness of the substrate. As a result, the glossiness was 126. Next, when the comparative example 1 was measured, it was 170 and the comparative example 2 was 155. Finally, when the measurement was performed on the product of the present invention, it exceeded 270 and scaled over. From this result, it can be seen that the present invention has an extremely high specularity.

6) In order to examine the reason why such measurement results were obtained, the surface texture was observed from the back side of the substrate with an electron microscope (magnification: 230). The results are shown in FIGS. 1 to 3. Figure 1
Is the product of the present invention, FIG. 2 is Comparative Example 1, and FIG. 3 is Comparative Example 2.
As is clear from them, in Comparative Examples 1 and 2, the distribution of aluminum particles is rough and the unevenness is remarkable. On the other hand, in the product of the present invention, the distribution of aluminum particles is dense and the irregularities are very small and smooth. It is clear that this is because the blending of the non-refining aluminum powder and the leafing aluminum powder is appropriate. 7) Moreover, the thing which made A: B: C 1: 1: 10 (Comparative Example 3) was also measured. The result is a gloss level of 147,
Compared with Comparative Examples 1 and 2, the specularity is lower, which means that it is not practical.

[Example 2] 1) A: B: C = 2.5: 1: 5 (invention product 2), A: B:
C = 1.5: 1: 5 (Invention 3), A: B: C = 2: 1:
5 (Invention product 4), A: B: C = 1.5: 1: 10 (Invention product 5)
In addition to the above, a specular color ink was prepared under the same conditions as in Example 1. Beautiful metallic colors of red, yellow, and blue appeared on the printed surface of each of these printed samples, and a beautiful colored mirror surface appeared on the lower surface of the printed sample. The printed sample was subjected to an adhesion test using a cross-cut tape of 24 mm, and there was no abnormality. The result of the accelerated weathering test (300 hours) showed that the ink film had peeled off, and peeling and blistering were not observed at all. Also, the change in discoloration and fading was a good result of 5th grade by the gray scale method. Furthermore, the results of measuring the specular gloss under the above conditions also showed good scale-over.

[0019]

According to the present invention described above, the leafing aluminum powder and the non-leaf aluminum powder are used in combination, and the mixture is mixed with the binder resin, and the coloring pigment is added thereto, so that press printing is not required. The excellent effect of being able to create a beautiful printed surface of a color mirror surface and metallic color is obtained. Especially, the compounding ratio of the leafing aluminum powder, the non-leaf aluminum powder and the binder resin is (1.2 to 10): (1):
In the case of (2.5 to 10), a vivid and beautiful color mirror surface and metallic color can be sufficiently revealed, the mirror surface can be made extremely high, and the printability is excellent and the handling is easy. That is an excellent effect.

[Brief description of drawings]

FIG. 1 is a micrograph showing a surface structure of a printed film using the ink of the present invention.

FIG. 2 is a micrograph showing a surface structure of a printed film printed with a printing ink obtained by using only leafing aluminum powder.

FIG. 3 is a micrograph showing a surface structure of a printed film printed with a printing ink obtained by using only non-leafing aluminum powder.

Claims (6)

[Claims] 1. A color specular ink comprising a non-leafing type aluminum powder as a main component, kneading a leafing type aluminum powder and a binder resin, and adding a solvent and a coloring pigment to the kneaded product. 2. The compounding ratio of the non-leafing type aluminum powder, the leafing type aluminum powder and the binder resin is (1.2 to 10) :( 1) :( 2.5 to 1).
0) The color specular ink according to claim 1. 3. The blending ratio of the non-leafing type aluminum powder, the leafing type aluminum powder and the binder resin is (1.2 to 3) :( 1) :( 3 to 10). Color mirror surface ink. 4. The compounding ratio of the non-leafing type aluminum powder, the leafing type aluminum powder and the binder resin is (3.2 to 5) :( 1) :( 3 to 10). Color mirror surface ink. 5. The compounding ratio of the non-leafing type aluminum powder, the leafing type aluminum powder and the binder resin is (5.2 to 10) :( 1) :( 3 to 10).
The color specular ink according to claim 1, wherein 6. The color specular ink according to claim 1, which is a paste in which non-leafing type aluminum powder and leafing type aluminum powder are respectively dispersed in a solvent.