JP2901743B2 - Bright printing ink composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a printing ink, and more particularly, to a method of using a specific plate-like iron oxide as a coloring pigment to obtain a metallic-like glittering texture. The present invention relates to a brilliant printing ink composition applied to printed matter such as paper and decorative boards.

(Prior Art) Conventionally, aluminum powder, bronze powder, and titanium dioxide-coated mica have been used as pigments for printing inks in order to provide a lustrous printed surface having a metallic luster. Further, a colored dye or pigment is further used in combination with the metal powder or mica, and printing is performed by offset printing, gravure printing, flexographic printing, screen printing, or the like.

(Problems to be Solved by the Invention) As the metallic glossy printing ink, as described above, there are those in which a normal iron oxide pigment is blended with a metal powder such as aluminum or mica coated with titanium dioxide. In the case of a compound containing an ordinary iron oxide pigment, the specular reflection due to the metal powder or the like is reduced by the diffuse reflection of the iron oxide pigment, so that a printed material having a sufficiently satisfactory glitter texture cannot be obtained.

Further, the conventional metallic printed matter has a performance that substantially satisfies the market requirements in terms of durability, but does not yet provide a soft glittering texture with satisfactory aesthetics.

The present inventors have conducted intensive research to eliminate the above-described conventional defects, and as a result, the average diameter is 0.5 to 5.0 μm, the thickness is 0.00
Plate-like iron oxide particles having a plate-like ratio of 5 to 0.05 μm and a plate-like ratio of 50: 1 to 500: 1 may be used alone as a pigment for a printing ink, or may be used in combination with a coloring pigment, a mica pigment and a metal powder pigment. The present invention has been found that, by using the above, a printed matter having a soft brilliant texture that cannot be obtained by a printing ink using a conventional metal powder pigment or mica pigment can be obtained.

(Means for Solving the Problems) That is, the present invention provides a sheet iron oxide alone having an average diameter of 0.5 to 5.0 μm, a thickness of 0.005 to 0.05 μm, and a sheet ratio of 50: 1 to 500: 1, or the sheet iron oxide. One or more pigments selected from the group consisting of color pigments, mica pigments and metal powder pigments, and these are dispersed in an ink varnish mainly composed of a varnish resin and a solvent. It is a printing ink composition.

 Hereinafter, the present invention will be described in detail.

Plate-like iron oxide powder used in the present invention, for example, ferric salt,
In a method of producing a matite particle powder into a plate by hydrothermally treating an alkaline suspension having a pH of 9 or more containing either hydrous ferric oxide particles or FeOx · Fe ₂ O ₃ (0 ≦ × ≦ 1) particles A water-soluble salt having a ratio of 0.1 to 15.0 mol per mol of Fe and a compound containing 1.5 to 20.0 mol% of Si in terms of Si with respect to Fe are added to the alkaline suspension in advance, followed by hydrothermal treatment. Can be obtained by

As the ferric salt, ferric chloride, ferric sulfate, ferric nitrate and the like can be used.

The hydrous ferric oxide may be in the form of any particle such as a needle or a spindle obtained by various known reactions, and the reaction mother liquor containing hydrous ferric hydroxide as it is, washing the reaction mother liquor with water, A wet cake obtained by filtration and a dried product of the wet cake can be used.

FeOx · Fe ₂ O ₃ (0 ≦ × ≦ 1) particles are obtained by washing and filtering a reaction mother liquor containing granular or cubic magnetite particles obtained by reacting a ferrous salt with an aqueous alkaline solution. Needle cake or spindle-like FeOx.Fe obtained by reducing the wet cake and the dried product of the wet cake and the above-mentioned needle-like or spindle-like hydrous ferric oxide particles, or further oxidizing as necessary.
₂ O ₃ (0 ≦ × ≦ 1) particles and the like can be used.

The pH of the alkaline suspension is 9 or higher. If it is less than 9, needle-like hydrous ferric oxide particles or particulate FeO _x · Fe ₂ O ₃ particles are mixed in the plate-like hematite particles.

Hydrothermal treatment uses an autoclave device, usually 150 to 3
Perform in a temperature range of 30 ° C. Generally, as the alkali concentration becomes higher, the reaction temperature at which plate-like hematite particles are formed tends to be lower. When the temperature is lower than 150 ° C., hydrous ferric oxide or FeO _x · Fe ₂ O ₃ remains as it is, and no plate-like hematite particles are generated. When the temperature exceeds 330 ° C., plate-like hematite particles can be generated, but the upper limit of the temperature is 330 ° C. in consideration of safety on the apparatus.

Examples of the water-soluble salts include sulfates, nitrates, chlorides, and acetates of alkali metals.

The addition amount of the water-soluble salt is 0.1 to 15.0 mol per 1 mol of Fe.
Ratio. If the amount is less than 0.1 mol, the color of the resulting plate-like hematite particles, particularly the hue and saturation, will be small, and the desired plate-like hematite particles cannot be obtained. Even if it exceeds 15 mol, the target plate-like hematite particles can be obtained,
There is no point in adding more than necessary.

Compounds containing Si used include potassium and sodium silicates, colloidal silica, and the like.

The amount of the compound containing Si is 1.5 to 2 in terms of Si with respect to Fe.
0.0 mol%. When the content is less than 1.5 mol%, the thickness of the resulting plate-like hematite particles is only 500 mm or more, and as a result, the plate-like ratio becomes small, and a black-purple color is exhibited. 20mo
If it exceeds 1%, the thickness of the plate-like hematite particles is 50
As a result, the fragmentation phenomenon of the particle form is likely to occur.

The compound containing water-soluble salt and Si affects the particle morphology and surface properties of the resulting plate-like hematite particles, and therefore, must be added before the formation reaction of the plate-like hematite particles is started. And the order of addition may be either earlier or simultaneously.

As the addition amount of the water-soluble salt increases, the average diameter of the generated plate-like hematite particles tends to increase, and as the addition amount of the compound containing Si increases, the thickness of the generated plate-like hematite particles decreases. The plate ratio tends to increase.

The above-mentioned plate-like iron oxide particles contained 1 in 100 parts by weight of the ink composition.
Used in the range of 5 to 38 parts by weight.

The color pigment used in combination with the above-mentioned plate-like iron oxide in the present invention is one used in ordinary printing inks, and specifically, for example, an azo pigment, an anthraquinone pigment,
Organic pigments such as isoindolinone pigments, perylene pigments, quinacridone pigments, thioindigo pigments, copper phthalocyanine pigments and metal complex pigments, and examples of inorganic pigments include titanium dioxide pigments, cobalt blue pigments , Yellow lead, navy blue, ultramarine, iron black carbon black, zinc white, and the like.

Examples of the extender include calcium carbonate, barium sulfate, barium carbonate, talc, clay, alumina white, and silica.

The above color pigment is used in an amount of 0.2 to 6 parts by weight based on 100 parts by weight of the ink composition.

As the mica pigment used in combination with the plate-like iron oxide in the present invention, conventionally known mica pigments can be widely used, and examples thereof include transparent pearl mica, colored mica, and interference mica. The above mica pigment is the ink composition 10
It is used in the range of 0.1 to 7 parts by weight in 0 parts by weight.

Furthermore, the metal powder pigment used in combination with the plate-like iron oxide in the present invention, for example, aluminum powder, brass powder,
Examples include stainless steel powder and copper powder.

These metal powder pigments are used in 100 parts by weight of the ink composition.
Used in the range of 0.1 to 5 parts by weight.

Next, as the type of printing ink containing the plate-like iron oxide of the present invention, there are conventionally known various types, for example, letterpress ink, planographic ink, intaglio gravure ink,
A stencil screen ink and the like, and from a solvent system, an oil ink, a solvent ink, a water-based ink and the like.

The varnish resin component used in the ink composition of the present invention is a conventionally known varnish resin component, and as the resin for aqueous printing ink, casein, hydroxyethyl cellulose, a water-soluble salt of a styrene-maleic acid ester-based copolymer,
Water-soluble salts of (meth) acrylic ester (co) polymers,
Water-soluble salt of styrene- (meth) acryl ester latex, water-soluble alkyd resin, styrene-butadiene copolymer latex, (meth) acryl ester polymer latex, styrene- (meth) acryl ester copolymer latex , Ethylene-vinyl acetate copolymer latex, polyethylene dispersion, ethylene copolymer dispersion, and the like.

The varnish resin component of the oil-based printing ink includes cellulose acetate butyrate, nitrocellulose, vinyl acetate (co) polymer, styrene (co) polymer, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer Copolymer, polyvinyl butyral, alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, amino alkyd resin, polyester polymer, polyurethane polymer, acrylic polyol urethane polymer, soluble polyamide polymer Phenolic resin, rosin-modified phenolic resin, rosin-modified maleic resin, and the like.

The varnish resin is 5 to 5 parts by weight in 100 parts by weight of the ink composition.
Used in the range of 2 parts by weight.

Examples of the solvent that dissolves or disperses the varnish resin include those commonly used in printing inks such as water, alcohols, esters, ketones, aromatic hydrocarbons, and petroleum solvents. These solvents are used in the range of 19 to 70 parts by weight based on 100 parts by weight of the ink composition.

In the ink composition of the present invention, other additives, a dryer, a wax, a plasticizer, a dispersant, and the like are appropriately compounded and used.

As the print-receiving material used in the present invention, conventionally known printable or coatable articles such as paper, chemical fiber mixed paper, synthetic paper, plastic film, plastic sheet and the like are used. Among them, various kinds of papers, such as high quality paper, art paper, coated paper, lightweight coated paper, offset rotary printing paper, matte coated paper, and paper changing, are appropriately used.

(Function of the Invention) The most important point in the present invention is that the average diameter in the ink is
Plate-like iron oxide particles having a plate-like ratio of 0.5 to 5.0 µm, a thickness of 0.005 to 0.05 µm and a plate-like ratio of 50: 1 to 500: 1 are blended. As a result, it is a fact that it is possible to obtain a printed matter having a soft and metallic brilliant texture.

Regarding the reason why the printing ink according to the present invention can form a surface with excellent glitter texture on a printing material, the present inventor has reported that plate-like iron oxide particles contained in the printing ink have a specific form. This is considered to be due to the occurrence of specular reflection.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In Examples and Comparative Examples, parts and% are based on weight.

Example 1 Plate-like hematite (plate-like ratio: 104: 1, average particle diameter 2.5 μm,
27 parts 20% nitrified cotton dope 57 parts Butyl acetate 3 parts Propylene glycol methyl ether 4 parts Toluene 5 parts DOP 3 parts Silica 1 part Disperse the above composition with a paint shaker for 60 minutes, and apply printing ink. Obtained.

Using the ink obtained above, decorative paper was dried in a gravure printing method and solid-coated to 5 g / m ² to obtain a printed matter.

Table 1 shows the results of evaluating the aesthetics of the obtained printed matter.

Comparative Example 1 27 parts granular hematite (average particle size 0.2 μm) 20% nitrified cotton dope 57 parts butyl acetate 3 parts propylene glycol methyl ether 4 parts toluene 5 parts DOP 3 parts silica 1 part A print was obtained in the same manner.

Table 1 shows the results of evaluating the aesthetics of the obtained printed matter.

Example 2 Plate-like hematite (plate-like ratio: 104: 1, average particle diameter 2.5 μm,
Thickness 0.024) 27 parts Copper phthalocyanine blue 5 parts 20% nitrified cotton dope 52 parts Butyl acetate 3 parts Propylene glycol methyl ether 4 parts Toluene 5 parts DOP 3 parts Silica 1 part In the same manner as in Example 1 using the ink having the above composition. To obtain a printed matter. Table 1 shows the evaluation of the obtained printed matter.

Comparative Example 2 A printed matter was obtained in the same manner as in Example 2, except that the granular hematite particles (average particle diameter: 0.2 μm) were used instead of the plate-like hematite of Example 2.

 Table 1 shows the results of evaluation of the obtained printed matter.

Example 3 Plate-like hematite (plate-like ratio 69: 1, average particle size 2.4 μm,
23 parts Aluminum paste (product name; Altop 15T, a product of Toyo Aluminum Co., Ltd.) 3 parts Polyurethane polyurea resin 50 parts (resin solid content 30% toluene solution) Isopropyl alcohol 10 parts Methyl ethyl ketone 14 parts Was charged into a ball mill and kneaded for 10 hours to obtain an ink composition.

Next, this ink composition was printed on a stretched polypropylene film using a bar coater (No. 8), and dried at room temperature for 1 hour to obtain a printed matter. Table 1 shows the results of evaluation of the obtained printed matter.

Comparative Example 3 A printed material was obtained in the same manner as in Example 3 except that spindle-shaped hematite (long axis: 0.07 μm, axial ratio (long axis: short axis) 5: 1) was used instead of the plate-like hematite of Example 3. Was.

 Table 1 shows the results of evaluation of the obtained printed matter.

Example 4 Plate-like hematite (plate-like ratio 69: 1, average particle diameter 2.4 μm,
27 parts Mica pigment (Product name: Iriodin 300 Gold Pearl Merck) 7 parts 20% nitrified cotton dope 50 parts Butyl acetate 3 parts Propylene glycol methyl ether 4 parts Toluene 5 parts DOP 3 parts Silica 1 part Above A printed material was obtained in the same manner as in Example 1 using the ink having the composition. Table 1 shows the evaluation of the obtained printed matter.

Comparative Example 4 A printed material was obtained in the same manner as in Example 4 except that the plate-like hematite of Example 4 was replaced with a plate-like hematite having a plate ratio of 30: 1, an average particle diameter of 30.0 μm, and a thickness of 1.0 μm. . Table 1 shows the results of evaluation of the obtained printed matter.

Example 5 Plate-like hematite (plate-like ratio: 104: 1, average particle diameter 2.5 μm,
18.6 parts Quinacridone pigment 5.4 parts Mica pigment (Product name: Iriodin 300 Gold Pearl Merck Co., Ltd.) 3.0 parts Preparation varnish for offset lithography 70.8 parts (ink solvent 29.5%) 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 part Ink solvent 1.0 part An offset lithographic ink was obtained from the above components according to a conventional method.

Table 1 shows the evaluation of printed matter obtained by printing on high quality paper with an offset printing machine using the ink obtained above.

Comparative Example 5 A printed material was obtained in the same manner as in Example 5 except that the plate-like hematite of Example 5 was replaced with a plate-like hematite having a plate ratio of 30: 1, an average particle diameter of 30.0 μm, and a thickness of 1.0 μm. .

 Table 1 shows the results of evaluation of the obtained printed matter.

 The evaluation was performed on a five-point scale, and was evaluated as excellent 5 → 1 poor.

In addition, the brilliant feeling referred to herein is a functional value proportional to the amount of positive reflected light with respect to incident light, and is generally a glittering feeling.

The directionality referred to here is a difference between a color tone in a positive reflected light region with respect to incident light and a color tone in a negative reflected light region with respect to incident light, that is, a color difference.

In addition, the soft feeling here is the texture of the brilliant feeling, and is a functional value related to the distribution state of the positive reflected light in the physical property value. wide. This is a so-called sensory value that can be said to be a dense feeling of glitter.

The numerical value of L ^* 45 / L ^* -45 was measured by a goniospectrophotometer of Murakami Color Research Laboratory Co., Ltd.

At an incident angle of 70 °, an L value is expressed as −45 ° when viewed from 45 ° from the incident side and + 45 ° when viewed from 45 ° when light is reflected.

(Effect of the Invention) Since the printing ink of the present invention uses plate-like iron oxide particles having a specific form as the pigment of the ink, metal powder pigments or mica pigments may be used without using them at all in some cases. To give a soft printed matter having a brilliant feeling.

In particular, paper products and wood products can be printed with the appearance of metal, so that they have great application value to building materials, upholstery and the like.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuro Toda 4-1-2, Funariminami, Naka-ku, Hiroshima-shi, Hiroshima Prefecture Toda Kogyo Co., Ltd. ⁶ , DB name) C09D 11/00-11/14

Claims (7)

(57) [Claims] An average diameter of 0.5 to 5.0 μm and a thickness of 0.005 to 0.05
μm and a plate-like iron oxide having a plate-like ratio of 50: 1 to 500: 1 alone or in combination with one or more kinds of pigments selected from color pigments, mica pigments and metal powder pigments in the plate-like iron oxide, A glittering printing ink composition characterized by dispersing this in an ink varnish containing a varnish resin and a solvent as main components. 2. The method according to claim 1, wherein the plate-like iron oxide is 15 parts by weight in 100 parts by weight of the ink composition.
2. The brilliant printing ink composition according to claim 1, which occupies about 38 parts by weight. 3. The color pigment is used in an amount of 0.2 to 100 parts by weight of the ink composition.
The glitter printing ink composition according to claim 1, which occupies 6 parts by weight. 4. The method according to claim 1, wherein the mica pigment is contained in an amount of 0.1 to 100 parts by weight of the ink composition.
The brilliant printing ink composition according to claim 1, which occupies -7 parts by weight. 5. The method according to claim 1, wherein the metal pigment is 0.1 to 100 parts by weight of the ink composition.
The glitter printing ink composition according to claim 1, which occupies 5 parts by weight. 6. A varnish resin containing 5 parts by weight of the ink composition in 100 parts by weight.
2. The brilliant printing ink composition according to claim 1, which occupies about 52 parts by weight. 7. The bright printing ink composition according to claim 1, wherein the solvent accounts for 19 to 70 parts by weight based on 100 parts by weight of the ink composition.