JPH02142865A - Brilliant ink - Google Patents

Abstract

PURPOSE:To obtain the title ink improved in brilliancy and metallic luster by adding a specified primary coloring metallic pigment to an ink. CONSTITUTION:A double bond-containing carboxylic acid is thermally polymer ized to obtain a carboxylic acid (b) having at least one double bond and two carboxyl groups. A metallic pigment (a) is mixed with 0.2-10 pts.wt. component (b) per 100 pts.wt. component (a) of 1m<2>/g in an organic solvent (c) in an amount to give 10-25 pts.wt. component (a) per 100 pts.wt. component (c) at 60 deg.C or below, and the mixture is filtered to obtain a cake. This cake is kneaded or mixed by agitation with 1-50 pts.wt. coloring pigment (d) per 100 pts.wt. metal of component (a), for example, in the case where component (a) is an Al pigment having a mean particle diameter of 22mum and water-coated surface area of an Al powder of 7400cm<2>/g in the presence of component (c), and excess compo nent (c) is removed to obtain a primary coloring metallic pigment composed of component (a) and component (d) chemisorbed by the surface of component (a) through component (b). A mixture of additives such as a binder, a solvent, a plasticizer and a dispersant is mixed with 0.1-50 pts.wt. said pigment.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to printing inks and writing inks, and more specifically, the present invention relates to printing inks and writing inks, and more specifically, inks that have a metallic color appearance by containing a colored metallic pigment as a glittering pigment. This invention relates to a glitter ink.

[Prior Art] Conventionally, expensive gold powder and silver powder have rarely been used in inks with metallic luster, and metal powders such as brass powder and aluminum powder have been used exclusively as substitutes. The colors of inks that use only these metal powders as pigments are limited to gold or silver, which is quite different from the original gold or silver, but in order to express various colors with a metallic feel, As is done in metallic painting, achromatic metal powder such as aluminum powder and dyes and pigments of various colors are mixed in ink. In addition, in order to express various colors with metallic hues, including golden yellow, there are also inks that use crushed powder, which is made by lining both sides of an aluminum vapor-deposited layer with transparent colored resin layers, as a pigment. These inks have advantages and disadvantages and have not been widely used.

・[Problems to be solved by the invention] In other words, is the method of mixing dyes and coloring pigments with metal powder the most commonly used method, or is it necessary to use a large amount of dyes and pigments to express the imaged color? There are problems such as the brightness inevitably decreases, or the more you mix dyes and pigments of the three primary colors to express an intermediate color, the brightness decreases and the color becomes darker. Currently, there is no choice but to use colors selected from among the many dyes and pigments available. In addition, there is a crushed powder that does not have these drawbacks, but it is difficult to make fine powder with a sharp particle size distribution, and it is difficult to make a fine powder with a sharp particle size distribution, so it is difficult to make a fine powder with a sharp particle size distribution, and it is difficult to make a fine powder with a sharp particle size distribution. It can be used when powder is required, but it is difficult to use when fine powder is required, such as in writing ink. In addition, these crushed powders have poor weather resistance and heat resistance, so they are not suitable for applications that require weather resistance, such as color printing of posters.
Practically unusable.

[Means for solving the problem] As mentioned above, we are conducting intensive research to overcome the drawbacks of conventional metal powders and improve the beauty, gloss, weather resistance, dispersibility, and stability of ink with metallic luster. As a result, it was found that by incorporating in the ink a primary or secondary colored metallic pigment, which is a colored pigment chemically adsorbed through a carboxylic acid, all of the drawbacks of conventional metal powders mentioned above can be overcome. , we have completed the present invention.

The glitter ink of the present invention is obtained by uniformly dispersing a colored metal pigment together with a binder in an organic solvent or a water-soluble solvent. Each family will be explained below.

(Regarding the Pigment) The primary colored metallic pigment used in the present invention is a carboxylic acid (hereinafter referred to as thermal It is produced by treating a polymeric carboxylic acid (called a polymerized carboxylic acid) and a metallic pigment with an autogenous solvent, and then removing the excess organic solvent.

In addition, secondary colored metallic pigments are produced by stirring thermally polymerized carboxylic acid and metallic pigments in an organic solvent, then filtering the cake and blue pigment in the presence of an organic solvent, kneading or stirring-mixing them, and then mixing them with an organic solvent. After adding a radically polymerizable unsaturated carboxylic acid while dispersing and stirring in a solvent, a monomer having three or more radically polymerizable double bonds and a polymerization initiator are added and polymerized, and excess organic solvent is removed from this. It is made by

(- Regarding suboptimal color metallic pigments) - Coloring pigments used for deposited colored metallic pigments, etc. may be either organic or inorganic pigments as long as they do not dissolve in the white organic solvent used. Coloring pigments must be stably adsorbed on metallic pigments that have been subjected to thermally polymerized carboxylic acid adsorption treatment.
Perinone pigments, perylene pigments, phthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, etc., cobalt blue,
Carbon black, titanium oxide, etc.

Examples of organic solvents include aliphatic hydrocarbons such as hexane, heptane, octane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, solvent naphtha, and xylene; esters such as ethyl acetate and butyl acetate; tetrahydrofuran and diethyl ether. Examples include ethers such as These organic solvents are usually used alone or in combination, but when producing a secondary colored metallic pigment, it is desirable to use the same organic solvent as used in producing the deposited colored metallic pigment.

Further, as the thermally polymerized carboxylic acid, for example, a thermally polymerized carboxylic acid obtained by thermally polymerizing linseed oil fatty acid or soybean oil fatty acid, a thermally polymerized carboxylic acid obtained by thermally polymerizing linseed oil fatty acid or soybean oil fatty acid and acrylic acid, etc. are used. .

The amount of thermally polymerized carboxylic acid to be used varies depending on the surface area of the metallic pigment used and the amount of colored pigment used when producing the secondary colored metallic pigment, but it is 0 to 100 parts by weight of the lrd/gr metallic pigment. .2 to 10 parts by weight, especially 1 to 3 parts by weight are preferred.

In order to produce a primary colored metallic pigment using the above-mentioned raw materials, first, the metallic pigment and the thermally polymerized carboxylic acid are added to an organic solvent, heated, and thoroughly stirred. The amount of organic solvent can be determined by vigorous stirring, and is not critical as long as the thermally polymerized carboxylic acid is evenly adsorbed onto the surface of the metallic pigment.

Approximately 1 to 3 parts by weight of the metallic pigment is used per 100 parts by weight of the organic solvent. The temperature is preferably 60℃ or higher, and 60℃
Above this, the chemical adsorption rate becomes too fast and it becomes difficult to achieve uniform adsorption. The time tends to be shorter as the temperature is higher, and is selected appropriately.

After the above operation, it is filtered using a filter press or the like, and the metallic pigment having a layer of thermally polymerized carboxylic acid formed on its outer surface is recovered as a filter cake.

Next, the recovered thermally polymerized carboxylic acid-treated metallic pigment is placed in a container, and a colored pigment that has been dispersed and stirred with an organic solvent is added to the container using a pot mill (small ball mill) containing chrome steel balls, etc., and then kneaded and mixed. Stir to mix.

The optimal conditions for dispersing and stirring colored pigments differ for each pigment, but
The organic solvent may be used in an amount of 1 to 5 parts by weight per 1 part by weight of the colored pigment. Further, when 0.02 parts by weight of a pigment dispersant is added, the dispersion becomes even better.

At this time, if the amount of the organic solvent is too large, the chemical adsorption of the colored pigment to the thermally polymerized carboxylic acid-treated metallic pigment will be poor, and if the amount is too small, mixing and stirring will become difficult.

The organic solvent that is contained in the thermally polymerized carboxylic acid-treated metallic pigment paste and the one used for dispersing and stirring the colored pigment are inevitably used, but including the total amount of these, the metal content of the metallic pigment 10 per 100 parts by weight
~200 parts by weight is preferred.

In addition, the amount of coloring pigment varies depending on the surface area of the metallic pigment (actually, there is an inverse correlation with the particle size, so the particle size is used as a substitute), but the average particle size is 22 μm, and the WCA (water covered surface area of aluminum powder) of aluminum is 7400 c♂/gr. In the case of pigments, the metal content is 100j+! It is preferably 1 to 50 parts by weight, particularly 5 to 20 parts by weight.

If the amount of the colored pigment is less than 1 part by weight, the color appearance will deteriorate, and if it exceeds 50 parts by weight, the amount of adsorption will be too large, which will not only impair the metallic feel, but also leave unadsorbed color pigments, which is uneconomical.

If the average particle size is coarser than the above, the surface area will be smaller and the amount of coloring pigment used must be reduced accordingly; conversely, if the average particle size is finer than the above, the surface area will always be larger. , color pigments should also be used accordingly.

The above operation is performed at 60° C. or lower, and the time is appropriately selected depending on the respective temperature. When the temperature exceeds 60℃,
The adsorption speed becomes too fast, making it difficult to be evenly adsorbed.

Instead of adsorbing the color pigment by stirring in the container, the color pigment can be dispersed and mixed using the Bot mill, and a thermally polymerized carboxylic acid-treated metallic pigment can be added thereto. At this time, the amount of organic solvent used can be minimized.

When using the primary colored metallic pigment obtained by the above method as a pigment, the organic solvent is separated and used.
When used as a raw material for a secondary colored metallic pigment, it is used in a state in which an organic solvent is retained.

In either of these cases, unadsorbed colored pigments may be removed by decantation or the like using an organic solvent.

The above-mentioned sub-colored metallic pigments have coloring pigments chemically adsorbed onto the metallic pigment surface via thermally polymerized carboxylic acid, and are not physically fixed by coating with resin, etc., so they cannot be used in ink, etc. When using the product, the chemically adsorbed coloring pigments described above may be desorbed if vigorous stirring is performed or if a considerable amount of thermally polymerized carboxylic acid or a substance equivalent to it is present in the system. The feature of the invention is lost.

However, there is no intense agitation as mentioned above, and the ink can be applied and desorbed smoothly. Furthermore, since there is no decrease in light reflectance due to the resin coating layer, it exhibits an excellent metallic color feeling.

(Regarding secondary colored metallic pigments) - Fixed colored metallic pigments cannot be vigorously stirred, but by further processing them, water resistance,
A secondary colored metallic pigment with excellent chemical resistance and metallic color feeling can be obtained.

Examples of radically polymerizable unsaturated carboxylic acids used to produce secondary colored metallic pigments include trimethylolpropane triacrylate, trimethylolpropane triacrylate, and trimethylolpropane triacrylate. Examples include methylolpropane trimethacrylate, tetramethylolmethane triacrylate, and tetramethylolmethanetetraacrylate.

The polymerization initiator may be one that is generally known as a radical generator, such as peroxides such as benzoyl peroxide, lauroyl peroxide, isobutyl peroxide, methyl ethyl ketone, and azobisisobutyroyl peroxide. Examples include nitrile.

To make secondary colored metallic pigments using these,
Add the above organic solvent and primary colored metallic pigment to a sufficiently stirrable amount of the organic solvent 1. After adding the radically polymerizable unsaturated carboxylic acid with vigorous stirring, add the radically polymerizable unsaturated carboxylic acid having three or more radically polymerizable double bonds. Monomers and polymerization initiators are added and polymerized. If the amount of the above organic solvent is too small, the viscosity of the reaction system will become too high once polymerization starts, making it difficult to coat each colored metallic particle with resin, and multiple particles will overlap and become coated with resin. , which causes lumps to form when converted into ink. If the amount of the above-mentioned autogenous solvent is too large, production efficiency will deteriorate. Through the above polymerization operation, the fixed colored metallic pigment is coated with a highly crosslinked three-dimensional resin layer, resulting in stable water resistance,
A secondary colored metallic pigment with excellent chemical resistance is formed,
By separating excess organic solvent by filtration, drying, etc., a secondary colored metallic pigment can be obtained.

In the above reaction, it is preferable to replace the reaction system with an inert gas such as nitrogen or argon.

In addition, the time from adding the above-mentioned radically polymerizable unsaturated carboxylic acid until adding S, a monomer having three or more radically polymerizable double bonds, and a polymerization initiator should be Preferably, there is an interval of at least 5 minutes to achieve coalescence. The temperature of the polymerization reaction varies depending on the type of polymerization initiator, but is between 30 and 150°C, and the reaction time is appropriately selected depending on the temperature, but is between 30 minutes and 1 hour.
The range is 0 hours.

If the above polymerization reaction is carried out using only a monomer having three or more radically polymerizable double bonds and a polymerization initiator without using a radically polymerizable unsaturated carboxylic acid, the polymerization system will not only become viscous and unable to be stirred, but also become unstable. A strong film cannot be obtained.

This indicates that it is not necessary to cover the surface of the secondary coloring metallic pigment with a radically polymerizable unsaturated carboxylic acid in advance.

The size of the primary or secondary colored metallic pigment used in the present invention varies depending on the type of ink, and in the case of printing ink, the length and width range from 0.5 to 200 am.
A material having a thickness of 0.3 to 5 tlrrI is used. In this case, if the length and width are less than 0.5 μs, the reflection area will be small and there will be almost no glitter, and if it is more than 200 kon, it cannot be applied to gravure printing. In the case of writing ink, it is desirable that its length and width do not exceed 20 mm. If there are more than 20 containers, the weight will be large and the fluidity will be reduced.
Preservability deteriorates, leading to ink fading and ink clogging. For the same reason, it is desirable that the thickness does not exceed 1 μn1.

- The amount of secondary or secondary colored pigments used is 0 in the printing ink.
A content of 1 to 30% by weight is preferable; less than 0.1% is too small, resulting in poor coverage and no effect. If it exceeds 30%, the dispersibility is poor and the viscosity increases significantly, making printing difficult. In the case of writing ink, it is preferable to include 10 to 60% by weight in the ink. Content: 10% by weight
If it is less than that, it is difficult for the pigment to be distributed uniformly, the written characters become mottled, and the metallic luster also becomes mottled. If it exceeds 60%, the fluidity will be low, causing ink blurring and ink clogging.

(Regarding the binder) As the binder resin, rosin-modified maleic acid resin, polymerized rosin, maleic acid resin, polyvinyl alcohol, gum arabic, vegetable oil, polyamide resin, ethyl cellulose, etc. are used.

(Regarding solvents) Solvents include ethyl cellosolve, butyl cellosolve, isopropyl alcohol, butyl alcohol, butyl acetate,
Methyl isobutyl ketone, glycerin, hexylene glycol, toluene, water, or a mixture thereof may be used as appropriate.

(Regarding other compounding agents) Plasticizers, dispersants, stabilizers, viscosity modifiers, surfactants, etc. are used as appropriate.

Further, extender pigments such as silica gel and magnesium carbonate may be mixed mainly with the printing ink.

[Function] In the present invention, individual pigment particles are given glitter, so even when used as printing ink or writing ink, the glitter will not be lost at all. Maintains brilliance over a wide range of tones.

The present invention will be illustrated by giving examples below.

Example 1 Mineral spirit 4 in a 1000 ml Sannoro flask
Add 00 ml of aluminum pigment (manufactured by Showa Aluminum Powder ■, high brightness grade flaky aluminum paste 725N, metal content 85.5%, average particle size 22).
140 g of acrylic acid and 2.4 g of a carboxylic acid with double bonds (manufactured by Harima Kasei Kogyo ■, Diazid) were added, and the temperature was raised to 55°C without introducing N2 gas. The mixture was stirred vigorously for 1 hour, cooled to room temperature, and filtered to obtain a thermally polymerized carboxylic acid-treated aluminum pigment. The amount of diazid adsorbed on this aluminum was 2.2 g.

In addition, 150 ml of xylene and a yellow pigment (manufactured by Ciba Geigy, C1nquasia
FastGold YT-915-D) 24g and pigment dispersant (Kao ■, homogenol L-100) 0.
48 g was added and rotated at 30 rpm for 16 hours to disperse and pulverize the yellow pigment.

Next, the aluminum pigment on which Diazid was adsorbed was put into a pot mill that had finished dispersing and pulverizing the yellow pigment, and the pot mill was further rotated at 3 Orpm for 3 minutes to cause the yellow pigment to be adsorbed on the surface of Diazid. From this, remove the excess mineral spirit and get the primary golden color.
I got the pigment.

Using the primary golden pigment thus obtained, a gravure printing ink was prepared in the following manner.

The mixing ratio of raw materials was as follows.

-Flame gold pigment 15 parts by weight Polyamide resin 20/Methane 1
8 / Ethyl alcohol 14 Isopropyl alcohol 23 The above raw materials were placed in a kneader and kneaded for 1 hour to obtain a printing ink.

Furthermore, at the time of use, 10 parts by weight of toluene and 10 parts by weight of ethyl alcohol are added to this to adjust the viscosity, and printing
In all halftone prints, glittering prints with golden metallic luster were obtained.

Example 2 150 g of the Ikkashinkin-colored P-ki-ke balls, pigments, and Net prepared in Example 1 were placed in a Sannoro flask containing 1,600 ml of mineral spirit without removing the mineral spirit, and 3.0 g of acrylic acid was added. The mixture was added and stirred for 15 minutes at a temperature of 60°C. Next, 30 g of trimethylolpropane trimethacrylate was added and the temperature was raised to 100° C. over 3 hours to polymerize, resulting in -Flame Dye A-Yo→4. The surface of the pigment was coated with resin. This is filtered to remove excess mineral spirits, giving it a secondary golden color.

Created a pigment.

Using the thus obtained secondary golden pigment, an ink for felt-tip pens was prepared as follows.

The mixing ratio of raw materials was as follows.

Secondary golden pigment 35 parts by weight Polymerized rosin
1B ” Maleic acid resin 5 //Kijirol
15〃 n-Butyl alcohol 5 // Toluene 10” Butyl acetate
13'' Surfactant 1 // The above raw materials were charged into a mixed wire mold and stirred and mixed for 1 hour at 1° to obtain an ink for dispersed pens.

When I wrote on art paper with the obtained signboard ink, I was able to write letters with a golden luster and a sense of brilliance.

Example 3 Mineral spirit 4 in a 1000 ml Sannoro flask
00 ml of aluminum pigment (manufactured by Showa Aluminum Powder ■, high brightness grade flaky aluminum paste 574P S,
105 g of acrylic acid (metal content: 85.5%) and 2.4 g of a carboxylic acid having a double bond (manufactured by Harima Kasei Kogyo ■, Diazid) obtained by thermally polymerizing acrylic acid and soybean oil fatty acid were added, and N2 gas was introduced. After stirring vigorously for 1 hour while maintaining the temperature at 55° C., the mixture was cooled to room temperature and filtered to obtain a thermally polymerized carboxylic acid-treated aluminum pigment. The amount of diazid adsorbed on this aluminum was 2.2 g.

In addition, 30ml of mineral spirit was added to a pot mill containing a 6m+m diameter chromium steel ball in a 250ml glass bottle.
and red pigment (manufactured by Dainippon Ink & Chemicals, Co1o)
f'ine Red 238A) 24g and pigment dispersant (Kao, homogenol L-100) 0.48g
was added and rotated at 30 rpm+n for 16 hours to disperse and pulverize the red pigment.

Next, the aluminum pigment adsorbed with Diazid and the dispersed and pulverized red pigment were placed in a 500 ml Sannoro flask together with 80 ml of mineral spirit.
A water-based flexographic ink was made as follows using a 10 minute vacuum at room temperature while introducing N2.

Ethyl cellulose 30/l water 437/denatured alcohol 10//surfactant 2〃 were added thereto, 3.0 g of acrylic acid was added, and the mixture was stirred at a temperature of 80° C. for 15 minutes. Next, 4.2 g of trimethylolpropane trimethacrylate-1-Bog and azobisisobutyronitrile dissolved in 170 ml to 150 ml of Mineral StA-pirit were added to obtain a good ink. When this ink was used to print on a polypropylene film in the same manner as in Example 1, the results were as follows: 0.5 mm wide line printing, solid printing,
In all halftone prints, bright prints with red metallic luster were obtained.

Example 4 A blue pigment was used instead of a red pigment (a water-based ink manufactured by Dainippon Ink) was used.

Gum arabic 3 // Polyvinyl alcohol 1 // Glycerin 1 Surfactant 5 ... Salicylic acid 1 // Water 54 ... The above raw materials were charged into a kneading mold and mixed for 2 hours to be uniformly dispersed and mixed with the water-based ink. did.

When the obtained water-based ink was written on plain paper with a T-pen pen, it was possible to write bright characters with a blue metallic luster.

When used with rosin-modified maleic acid resin, ethyl cellulose, isopropyl alcohol, ethyl cellosolve, butyl acetate, toluene, and surfactant (Ryu φ Ana), a shiny line with a red metallic luster was drawn.

Claims (2)

[Claims] (1) A coloring pigment is chemically adsorbed onto the surface of a metallic pigment via a carboxylic acid having at least one double bond and two carboxyl groups, which is obtained by thermally polymerizing one or more carboxylic acids having a double bond. 1. A glittering ink comprising 0.1 to 50 parts by weight of a primary colored metallic pigment. (2) A secondary colored metallic pigment obtained by coating the primary colored metallic pigment according to claim (1) with a polymer comprising a radically polymerizable unsaturated carboxylic acid and a monomer having three or more radically polymerizable double bonds. of,
A glitter ink characterized by containing 0.1 to 60 parts by weight in the ink.