JP2002069355A - Ink composition for intaglio printing and printed matter using the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for intaglio printing having depth and exhibiting strong brightness and its printed matter in order to solve a problem in which printed surface obtained by using ink composition containing a conventional gloss pigment exhibits certain degree of brightness, but the brightness is not sufficient. SOLUTION: This ink composition for intaglio printing comprises gloss pigment obtained by coating flake-like glass with a metal oxide having higher refractive index than that of metal or glass and having 0.3-1.5 μm average thickness and 10-60 μm average particle diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prints on printing paper such as art paper or coated paper, laminated paper, resin film, etc., and has high glitter and high quality.
In addition, the present invention relates to an intaglio printing ink composition from which a printed matter having excellent cosmetic properties can be obtained.

[0002]

2. Description of the Related Art An intaglio printing ink composition comprises a vehicle resin, a pigment, a solvent, an additive and the like. For example, it is manufactured by adding and mixing a pigment in a vehicle resin so as to be 10 to 30% by weight, and further adding a solvent to adjust the viscosity to a viscosity suitable for printing. When a glossy material such as flake aluminum powder or titanium dioxide-coated mica powder is used as the pigment, the printed surface using the ink composition has a glittering appearance. For example, JP-A-6-255234 describes an intaglio printing ink composition containing a colored glowing pearl pigment.

[0003]

The brightness of the printed surface formed by using such a glossy material, although exhibiting a certain degree of glitter, is not yet in a satisfactory state. An object of the present invention is to provide an intaglio printing ink composition which exhibits a deeper and more brilliant luster than conventional ones, and a printed material using the same.

[0004]

The ink composition for intaglio printing of the present invention comprises a flake-like gloss pigment in which the surface of a flake-like glass is coated with a metal or a metal oxide layer having a higher refractive index than glass. is there. This gloss pigment is based on flaky glass whose surface is extremely smooth, and since each particle functions like a fine mirror,
Its brilliancy is significantly better than conventional ones. Therefore, the intaglio printing ink composition presents a clear and brilliant print finish that has never been seen before.

[0005] Further, a coat layer may be provided on the printed surface using a transparent material. In this case, the reflected light emitted from the glossy pigment shines strongly and forms a beautiful printed appearance. Further, a dye or other pigment may be blended as a coloring material, and a colored intaglio printing ink composition may be used.

The metals used for coating include gold, silver,
Platinum, palladium, titanium, cobalt, nickel, or alloys thereof are exemplified. Among them, silver, nickel or an alloy thereof, which is excellent in cost and quality, is preferable. When coating the metal on the flake glass, the thickness of the coating film is preferably 0.04 to 0.2 μm. If the thickness is less than 0.04 μm, the original luster of the metal is significantly reduced, and the function as a luster pigment is lost. on the other hand,
If the thickness exceeds 0.2 μm, the brilliancy will not be improved in spite of the amount of metal used, which is a problem in terms of cost.

The metal oxide used for coating preferably has a high refractive index, and examples thereof include anatase type titanium dioxide, rutile type titanium dioxide and iron oxide. Among these, anatase-type titanium dioxide and rutile-type titanium dioxide are preferable from the viewpoint of chemical durability and cost. Especially, rutile type titanium dioxide is preferable. The coating film of the metal oxide is appropriately adjusted depending on the type of the metal oxide, the required degree of brilliancy, the interference color, or the like.
m, particularly preferably 0.03 to 0.8 μm. If the coating film is too thin, sufficient gloss cannot be obtained, while if it is too thick, economic efficiency is impaired.

[0008] The refractive index of this metal oxide must be higher than the refractive index of glass as a substrate. When the refractive index of the metal oxide is high, total reflection from the particle surface of the gloss pigment is easily caused, and higher glitter can be obtained. Since the refractive index of glass is generally about 1.5 to 1.6, an anatase type titanium dioxide having a refractive index of about 2.5 or a rutile type titanium dioxide having a refractive index of about 2.7 is preferable. Strong brilliancy due to total reflection is obtained. In addition, since the coating film of titanium dioxide functions as an interference filter,
By changing the thickness, glitter of various colors can be obtained. That is, by adjusting the thickness of the coating film of the metal oxide, it is possible to impart subtle chromatic glitter to the printed appearance, and to further enhance the sense of quality. When the titanium dioxide coating film is around 0.05 μm, it exhibits a silver color, when it is about 0.14 μm, it has a reddish purple color, and when it is about 0.2 μm, it has a yellow-green reflective color. The brilliancy of the chromatic color is remarkably superior to the printing surface using a conventional coloring material, for example, pearl mica, and a rich appearance with a sense of depth is formed.

[0009] The shape of the gloss pigment must be a flake having a large specific surface area in order to obtain higher glitter. In consideration of the applicability and fluidity to the printing plate in intaglio printing, and the uniform dispersibility of the gloss pigment in the ink composition, the average thickness of the gloss pigment is 0.3 to 1.5 μm, and the average particle diameter is 10 μm.で 60 μm. If the average particle size exceeds 60 μm, the print finish will be poor,
On the other hand, when the thickness is less than 10 μm, the glitter is significantly reduced. When the average thickness is less than 0.3 μm, it is easily crushed. On the other hand, when the average thickness is more than 1.5 μm, the printing finish becomes uneven and the appearance is likely to be poor.

The above-mentioned interference filter function of the coating film is largely affected by the smoothness of the surface of the coating film and the contact surface with the substrate. That is, as these surfaces are smoother, scattering of the reflected light is suppressed, the interference filter functions effectively, and extremely strong reflected light is generated in one direction. Therefore, flaky glass excellent in surface smoothness is optimal for the base material.

The luster pigment is produced by coating the surface of a flake glass with a metal by a usual electroless plating method or powder sputtering method. For example, Japanese Patent Application Laid-Open No. 2-58582 describes a method of applying a metal coating to the surface of flake glass having an average particle size of 40 μm and a thickness of 3 μm by an electroless plating method. JP-A-60-86177 describes a method of applying a metal coating to flake glass having a thickness of about 3 μm and a particle size of about 300 to 700 μm by a sputtering method.

On the other hand, as a method for coating flake glass with a metal oxide, a method is known in which a metal hydroxide is coated on the surface of the flake glass by a sol-gel method or a liquid phase method and then heated and dehydrated. For example, as an example of the sol-gel method, JP-A-9-176515 discloses a flaky glass coated with a metal oxide having an average shape ratio (average thickness / average particle size) of 1 / 9-1 and an average particle size of 25-500 μm. Is described. As an example of the liquid phase method, US Pat. No. 5,753,371 discloses that a glass flake glass made of C glass is dispersed in an acidic aqueous solution, and then a TiCL ₄ aqueous solution is poured while adjusting the pH. A method is described in which the reaction is completed, the resultant is washed with filtered water, and then heated and calcined at a predetermined temperature. By further developing this liquid phase method, a method for uniformly and stably coating a metal hydroxide (hereinafter referred to as “p
We have developed a "liquid phase method." That is,
As a pretreatment operation, the glass flakes are surface-treated with tin chloride in an aqueous hydrochloric acid solution and then treated with hexachloroplatinic acid. The pre-treated glass flakes are added to an aqueous hydrochloric acid solution adjusted to about pH 1.0, the temperature of the slurry is raised to 75 ° C., and an aqueous solution of TiCL ₄ is added while adjusting the pH to pH 1. When the predetermined interference color is reached, the reaction is terminated. The reaction product is filtered, washed with water, and calcined at a predetermined temperature, for example, 600 ° C. According to the p liquid phase method, a metal oxide-coated product can be obtained uniformly and stably without unevenness as compared with the method of US Pat. No. 5,753,371.

The chemical composition of the flake glass is not particularly limited, and contains silicon dioxide as a main component and aluminum oxide, calcium oxide and sodium oxide in a considerable amount. The type of glass is not particularly limited. For example, E-glass and C
Glass, other alkali-resistant glass, high-strength glass, silica glass, boron-free E glass, boron-free alkali glass, soda-lime glass (A glass), and the like. The typical content of these components is shown in Table 1 below.

[0014]

[Table 1]

The content of the gloss pigment in the intaglio printing ink composition is preferably from 3 to 40% by weight. If the content is less than 3% by weight, the amount of gloss pigment is too small, and the glitter on the printed surface tends to be insufficient. On the other hand, if it exceeds 40% by weight, the fluidity of the ink composition decreases, and the dispersibility of the gloss pigment in the ink composition decreases, so that aggregation tends to occur.

The gloss pigment may be coated with a protective film on the outermost surface thereof for the purpose of improving uniform dispersibility and / or durability in the ink composition. For this protective film, for example, an organic material such as an acrylic resin or a polyester resin, or an inorganic material such as silicon dioxide or aluminum oxide can be used. Further, if necessary, the surface of the protective film may be treated with a surface treating agent such as a coupling agent. Specific means for improving the durability and the like in this manner are disclosed in, for example,
-91567, JP-A-7-268241 or U.S. Pat. No. 5,436,077.

The vehicle resin in the intaglio printing ink composition is not particularly limited, and may contain an auxiliary agent and an extender pigment as long as the gloss of the gloss pigment is not reduced. Such vehicle resins include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin ester, maleic resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate,
Ethyl cellulose, chlorinated rubber, cyclized rubber, resin such as ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin or alkyd resin or a mixture thereof, or resin comprising water-soluble water-soluble resin or aqueous emulsion resin of the above resin And solvent groups such as hydrocarbons, alcohols, ketones, ethers, esters and water. And as an extender, barium sulfate, barium carbonate, calcium carbonate,
Examples thereof include gypsum, alumina white, talc, calcium silicate, and precipitated magnesium carbonate. Further, examples of the auxiliary agent include a plasticizer, an antioxidant, an ultraviolet inhibitor, and an antistatic agent.

When a gloss pigment is mixed or dispersed in a vehicle resin to produce the intaglio printing ink composition, a paint conditioner, dissolver, high speed mixer, homomixer, kneader, roll mill or sand mill is used as a mixing and dispersing machine. It is preferable to use such as. The intaglio printing ink composition is printed on the surface of a base material such as printing paper such as art paper or coated paper, laminated paper, resin film or metal using a known gravure printing machine or the like. Further, if necessary, the printing surface may be protected by a transparent vehicle resin. The intaglio printing ink composition gives a printed surface such as a packaging paper, a plastic bag for packaging, various cans, a label such as a bottle or a plastic bottle, or a poster or the like, a rich appearance exhibiting high glitter by a known means. be able to.

[0019]

The present invention will be described in more detail with reference to the following examples. In addition, "part" described below represents a weight part.

(Production Examples 1 and 2) The soda-lime glass (I) (A glass) or the C glass (II) in the above “Table 1” was
It was formed into a glass film having a thickness of 1 μm by using a prototype flake-like glass facility described in Japanese Utility Model Application Laid-Open No. 59-69930. This glass film was crushed and classified to obtain a predetermined flaky glass. The shape of the glass flakes was measured, and the results are shown in Table 2 below.

(Production Example 3) A non-crystalline flake-like silica coarse powder was produced using the method for producing flake-like glass described in JP-A-6-191868. The material used was a mixture of commercially available silicon tetramethoxide, ethanol and 0.1 N nitric acid in a volume ratio of 1: 2: 1 and reacted at room temperature for 3 hours. This silica coarse powder was pulverized and classified to form a predetermined flaky silica, and the shape was measured. Table 2 below shows the measurement results.
Shown in

[0022]

[Table 2]

EXAMPLE 1 1 g of stannous chloride dihydrate and 1 ml of hydrochloric acid were added to 500 ml of purified water while stirring. 50 g of the flaked glass of Production Example 1 was added to this solution.
Was added with stirring, and the mixture was treated at room temperature for 2 minutes. After that, washing and filtration were performed well to obtain a wet cake. Next, 50 g of silver nitrate was dissolved in 1 L of purified water, and 25 g of sodium hydroxide was added thereto to precipitate the contained components. Ammonia water was added until the precipitate disappeared. This solution is designated as solution A. In addition, 90 g of sucrose was dissolved in 1 L of water, 1 ml of nitric acid was added, and the mixture was boiled for about 5 minutes. Then, immediately after cooling, 170 ml of ethanol was added. This solution is designated as solution B. The above wet cake was added to 500 ml of the liquid A while stirring, and the mixture was uniformly dispersed. Then, 140 ml of the liquid B was added, followed by stirring for 15 minutes. Thereafter, the reaction solution was filtered, washed with water,
The filtrate was dried at 105 ° C. to obtain a silvery white flaky glossy pigment having a slightly yellowish color. When the average thickness of this gloss pigment was measured by an optical microscope-image analysis method, it was 1.4 μm. The average particle diameter measured by a laser scattering method was 24.1 μm. This gloss pigment was evaluated according to the following printed surface appearance test method. As a result, the dispersibility of this gloss pigment is good,
A printed matter with an elegant appearance showing a strong glitter with a sense of depth was obtained. The results are shown in Table 3 below.

<< Printed Surface Appearance Test Method >> 15 parts of a gloss pigment is added to 80 parts of a vehicle resin having the following composition component content, and dispersed for 30 minutes by a paint conditioner to produce an intaglio printing ink composition. Using this ink composition, printing is performed on a black colored paper, and the appearance (dispersibility, depth feeling and glitter) of the obtained printed surface is visually observed under natural light.

<Incorporation of Vehicle Resin for Intaglio Printing Ink> Nitrocellulose 5.5 parts Ethyl acetate 4.0 Part Isopropyl alcohol 2.0 parts Ethanol 20.0 parts Plasticizer 1.0 part ----

[Examples 2 and 3] A glossy pigment was produced in the same manner as in Example 1 except that the flake glass of Production Example 2 or 3 was used, and a printed matter was obtained. The results are shown in Table 3 below.

Comparative Example 1 A printed material was obtained in the same manner as in Example 1, except that a commercially available flake aluminum was used instead of the gloss pigment. The results are shown in Table 3 below.

[0028]

[Table 3]

Example 4 Stannous chloride and 1 L of purified water
Dissolve 0.2 g of dihydrate and add dilute hydrochloric acid to pH 2.5
The flaked glass 1 of Production Example 1 was added to the solution adjusted to
Add 00g with stirring, stir for 10 minutes and filter.
Was. Next, hexachloroplatinic acid / hexahydrate was added to 1 L of purified water.
Was dissolved in 0.02 g of the filtered
After adding the glass with stirring and stirring for 10 minutes
And filtered. Hydrochloric acid was added to 1 L of purified water to pH 0.7,
The flaked glass pretreated as above is added to this hydrochloric acid solution.
The solution was charged with stirring, and the temperature of the solution was raised to 75 ° C.
Add titanium tetrachloride (TiCL _Four) Solution converted to Ti 0.0
Add at a rate of 2g / min, so that the pH does not change
Add sodium hydroxide at the same time and neutralize
Titanium (TiO_Two) Or its hydrate on flaked glass
Was precipitated. Titanium dioxide on this flaky glass
When the layer thickness shows the specified interference color, the titanium tetrachloride
The addition of the liquid and sodium hydroxide was stopped. Then filtration,
After washing with water and allowing the filtrate to air dry, bake at 600 ° C.
Thus, a gloss pigment was obtained. This luster pigment (titanium dioxide coating
X-ray diffractometer (XD-D1 type island)
(Manufactured by Tsu Works Co., Ltd.)
It was confirmed that the titanium oxide was of a rutile type. Ma
To an electron microscope (S-4500, manufactured by Hitachi, Ltd.)
When the film formation state of titanium dioxide was examined further,
It was confirmed that a dense film was formed. Also optical
Using a microscope-image analysis method, the average thickness of the gloss pigment was calculated.
The measured value was 1.4 μm. Also laser
As a result of measuring the average particle size by a scattering method, it was found that the average particle size was 24.3 μm.
there were. About this gloss pigment, the above printing surface appearance test
Evaluated according to the law. As a result, the dispersibility of the gloss pigment
Excellent transparency with good luminosity with depth
Printed matter was obtained.

Examples 5 and 6 In the same manner as in Example 4 except that the glass flakes of Production Example 1 were replaced with those of Production Examples 2 and 3, glossy pigments were produced and printed matters were obtained. This printed matter was evaluated according to the above-described printed surface appearance test method. The results are shown in Table 4 below.

Comparative Example 2 A printed product was obtained in the same manner as in Example 4, except that a commercially available pearl mica was used in place of the gloss pigment. This printed matter was evaluated according to the above-described printed surface appearance test method. The results are shown in Table 4 below.

[0032]

[Table 4]

[0033]

As described in detail above, according to the intaglio printing ink composition, it is possible to obtain a printed matter having a sense of depth and a sense of quality, exhibiting a strong glitter, and being extremely excellent in cosmetics. That is, printing paper such as art paper and coated paper,
By forming an intaglio image on the surface of laminated paper, resin film, metal, etc., it gives high glitter to packaging paper, packaging resin bags, various cans, labels and posters such as bottles and PET bottles, The commercial value can be increased.

Claims (3)

[Claims] An average thickness of a flake glass coated with a metal or a metal oxide having a refractive index higher than that of glass is from 0.3 to 0.3.
An intaglio printing ink composition containing a gloss pigment having a size of 1.5 μm and an average particle size of 10 to 60 μm. 2. An intaglio printing ink composition containing the gloss pigment in an amount of 3 to 40% by weight. 3. A printed matter using the ink composition for intaglio printing according to claim 1 or 2.