JPS63273673A - Stereoscopic ink and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled ink capable of giving stereoscopic characters, figures, etc., by film formation on expanded microcapsules with the liquid component in the other formulation ingredients followed by injecting the resultant microcapsules into the rest of the formulation ingredients and stirring. CONSTITUTION:In producing the objective ink from a binder, colorant and expanded microcapsules, film is formed on said microcapsules (pref., with a density 0.01-0.1g/cm<3>) with the liquid component in the other formulation ingredients followed by injecting the resultant microcapsules into the rest of the formulation ingredients and stirring, thus obtaining the objective ink.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a three-dimensional ink that can be used to write three-dimensional characters, nine figures, etc., and a method for producing the same, and in particular to three-dimensional inks that require special operations such as heating after writing. Without a word.

Three-dimensional ink that can simultaneously write on paper, cloth, wood, trees, plant branches and leaves, ceramics, synthetic resins with rough surfaces, and other harmful substrates, and obtain three-dimensional characters and shapes, etc. Regarding manufacturing methods.

(Prior Art) Conventionally, so-called foaming paints, which are heated and foamed after drawing, have been known as a method for obtaining three-dimensional characters and figures.

This foaming paint is made by mixing an organic or inorganic foaming agent into a resin, or by using thermally expandable microcapsules containing low-boiling hydrocarbons (Japanese Patent Laid-Open No. 59-15
No. 77), which is drawn on cloth or the like, dried, and then heated from the back side with an iron or the like to foam.

(Problems to be Solved by the Invention) In the case of the above-mentioned foam paint in which a foaming agent is mixed into the resin, the bonding force between the foam and the surface of the object to be drawn, such as cloth, is strong, and when the foam is foamed by heating, The body may be stretched, causing deformations such as wrinkles and kinks in the object to be drawn.

In order to overcome these drawbacks, foam paints using thermally expandable microcapsules containing the above-mentioned low-boiling hydrocarbons have been proposed.

However, both foam paints using thermally expandable microcapsules and foam paints made by mixing a foaming agent into the resin described above require heating after drawing, making them unsuitable for use by young children. In addition, there are restrictions such as it cannot be used unless there is a heating means, and the object to be painted must be able to withstand heating.In addition, whitening occurs due to foaming, and the color of the paint can be reproduced as it is in letters, shapes, etc. There is a problem that it cannot be done.

The present invention was proposed to solve these problems, and its purpose is to be able to be used safely and easily even by young children, and to be heat-resistant and capable of being used in any location. To provide a three-dimensional ink and a method for producing the same, which can obtain three-dimensional characters, two figures, etc., on a neutral base material at the same time as writing and with the same color of the ink.

(Means for Solving the Problems) In order to achieve the above object, the present invention uses foamed microcapsules instead of thermally expandable microcapsules that are foamed by heating after drawing.

By the way, the density of foamed microcapsules is 0.01
Because it is extremely low at ~0.1g/a#, it floats in the air and is difficult to handle in the air, and when mixed with other ingredients, it floats to the surface and the surfactant Alternatively, even if a high-speed stirrer is used, it is difficult to mix uniformly, and in particular, it is extremely difficult to uniformly disperse and mix expanded microcapsules in ink with a low viscosity comparable to ordinary writing ink.

As a result of repeated research in order to obtain an ink with a viscosity as low as that of ordinary writing ink, in which pre-foamed microcapsules are uniformly dispersed and mixed, the inventors of the present invention discovered that a liquid ink containing pre-foamed microcapsules and other ingredients was added to the pre-foamed microcapsules in advance. If a film is formed in advance and this is mixed with the remaining liquid component or other compounded components, a uniformly dispersed mixture of foamed microcapsules can be obtained, which is then mixed with a solvent component and a thinner (solid content concentration). By adding a substance that lowers the viscosity without significantly lowering the viscosity, it is possible to create an ink with a viscosity as low as that of ordinary writing ink while keeping the foamed microcapsules uniformly dispersed and mixed. I gained knowledge.

The present invention is based on this knowledge.

(1) An ink made by uniformly mixing a binder, an adhesive, and foamed microcapsules; and (2) a film formed by forming a film on the foamed microcapsules in advance with a liquid component among other ingredients; The present invention relates to a method for producing an ink that is poured into the remaining ingredients and stirred.

The foamed microcapsules of the present invention have extremely fine internal voids filled with polyester, polyacrylonitrile, polyvinylene chloride, acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-vinyl acetate copolymer resin,
It has a spherical shape covered with a film made of a foamed material such as acrylonitrile-methyl methacrylate copolymer resin, and as mentioned above, it has an extremely low density of 0.01 to 0.1 g/cyJ and is highly elastic.

In addition, as the binder in the present invention, a synthetic resin emulsion containing 15 to 70 vt% of resin such as urethane resin, acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl chloride resin 9-synthetic rubber latex, etc.
(including colloidal solutions) can be used.

Furthermore, as the coloring agent in the present invention, general organic pigments, inorganic pigments, and dyes can be used.

In the present invention, the blending ratio of the above-mentioned binder, expanded microcapsules, and colorant is preferably 10 to 35 vt% in terms of solid content in the total ink composition. When it is 100 parts by weight, it is 1 to 30 parts by weight, and the colorant is 0.01 to 5 parts by weight.
Preferably, the amount is 0 parts by weight.

If the binder is below the above-mentioned lower limit, other components such as foamed microcapsules cannot be fixed on the base material such as paper when writing is performed, resulting in a decrease in so-called image stability, and the above-mentioned Even if the upper limit of It will lower it.

If the foamed microcapsules are below the above-mentioned lower limit, it will not be possible to obtain three-dimensional characters, and on the other hand, if the foamed microcapsules are above the above-mentioned upper limit, phase separation will easily occur, reducing the stability of the ink and making writing difficult. In this case, the three-dimensional effect becomes excessive, resulting in problems such as a decrease in image stability.

If the amount of the colorant is less than the above-mentioned lower limit, the effect of the addition of the colorant disappears, and the characters etc. become colorless.

Conversely, even if the amount of the colorant exceeds the above-mentioned upper limit, the effect of adding the colorant will be saturated, which is not preferable in terms of cost.

In addition, in the present invention, additives such as a thickener, a thinner, a dispersant, an antifoaming agent, a wetting agent, a freeze stabilizer, a preservative, and an antifungal agent may be added as necessary.

The blending amount may be as long as the effect of each additive is produced.
Generally, the amount of each additive is from 0 to 20 parts by weight per 100 parts by weight of binder.

Furthermore, in the present invention, a solvent such as water, alcohols, aromatic hydrocarbons, halogenated hydrocarbons, etc. can be blended in order to adjust the viscosity and drying properties of the ink and to give the ink foaming properties. The amount to be added depends on the desired ink viscosity, dryness,
Although it varies depending on the degree of foaming, it is generally 0 to 300 parts by weight per 100 parts by weight of the binder. Note that the type of solvent is appropriately selected from the above depending on the binder used.

Furthermore, in the present invention, in order to reduce the amount of foamed microcapsules, or to prevent tackiness of the ink film, improve hiding power, make the ink film glossy, make the ink film matte, etc., calcium carbonate, Powder fillers such as aluminum hydroxide, talc, kaolin clay, waxite clay, colloidal silica, and finely divided benzoguanamine resin can be blended, and the blending amount varies depending on the above purpose, but generally 100 parts by weight of the binder is added. 0-10 against
It is 0 parts by weight.

The ink according to the present invention is produced by uniformly dispersing and mixing the above-mentioned ingredients by the above-described production method of the present invention. That is, first, foamed microcapsules are placed in, for example, a bag or a container with a lid, and a portion of a liquid component such as a binder or a solvent is injected into the bag.

Stir to form a liquid film on the surface of each expanded microcapsule to form a paste. Next, gradually add this mixture to a high-speed stirrer containing other ingredients and the rest of the liquid ingredient. Pour in and stir. Through this two-step operation, the liquid film formed on the surface of each capsule of the foamed microcapsules is mixed with the remaining liquid component charged in a high-speed stirrer or other components, and the foamed microcapsules are mixed with other components. can be uniformly dispersed and mixed.

At this time, if a suitable dispersant is added as an additive, a more uniform mixing state can be achieved.

Further, when lowering the viscosity, a solvent or a viscosity reducing agent may be added to the above-mentioned uniformly dispersed mixture and stirred.

(Function) When the ink according to the present invention is written on various base materials, a binder film is formed directly on the base material, and a filled layer of foamed microcapsules is formed on top of the binder film. A binder film is formed covering the cell filling layer, resulting in a three-dimensional character 9 figure etc. with flexibility and elasticity.

At this time, unlike the above-mentioned conventional foam paint, there is no need for heating after writing, and a binder film incorporating the above-mentioned foamed microcapsule filling layer is formed at the same time as writing, so three-dimensional characters etc. The color of the colorant in the ink can be obtained without any whitening phenomenon caused by foaming.

In addition, in the foamed microcapsule filled layer, since the liquid film described above is formed on each part of the foamed microcapsules that make up this layer, the adhesion of each particle to each other is high.
The ink does not come off even if you scratch it with your fingernail.

Further, by blending the filler with the foamed microcapsules while adjusting the particle size distribution or blending amount as appropriate, it is possible to obtain a three-dimensional character 2 figure with a matte or glossy surface.

In addition, the ink according to the present invention can be produced in a range from 100 cps to
A wide range of viscosities can be obtained, up to 100,000 cps, and the drying speed can also be adjusted by selecting the type of solvent.

It is possible to adjust the absorbency to the base material, etc., and it can be loaded into a normal pen-shaped container and used in the same way as normal writing ink.

The above-described ink of the present invention is produced by forming a film in advance on foamed microcapsules with part of a liquid component such as a binder or solvent, and then injecting the film into the remaining amount of the colorant or binder and stirring. Because it is manufactured in a two-step process, the above-mentioned film acts to activate the interface between the expanded microcapsules and other ingredients such as the binder.
Foamed microcapsules having an extremely low density of g/ad are produced in a uniformly dispersed and mixed state without floating on the ink surface.

Further, the viscosity of the ink can be easily reduced by adding a solvent or a viscosity reducing agent to the ink thus produced and stirring the ink.

(Example) Polyurethane aqueous dispersion with a resin content of 49.5% as a binder (Daiichi Kogyo Seiyaku ■ Product name on the back: Superflex E)
-2000) 100 parts by weight (hereinafter referred to as "parts"), 5 parts of plastic microballoons with a density of 0.03 g/a as expanded microcapsules (Daiichi Kogyo Seiyaku ■Reverse product name Superflex DE), pigment content 21vt% as a coloring agent.
Water-dispersed pigment (manufactured by Fuji Shiki ■ Part name: Fuji 5P-B
2 parts of 20% magnesium sulfate aqueous solution as a thinner, 50 parts of isopropyl alcohol as a solvent, and 20 parts of aluminum hydroxide as a filler were uniformly mixed to produce a cream-like ink.

That is, the entire amount of previously developed microcapsules is placed in a container with a lid, half of the binder is gradually poured into the container, and the mixture is stirred.
A binder film was formed on the foamed microcapsules to form a paste. This was poured into the stirrer containing the other ingredients mentioned above and stirred uniformly.

The viscosity of this ink is approximately 3,000 cps, and when it is loaded into an extrusion tube-shaped container that can draw lines 2 m thick and drawn on paper while being extruded, three-dimensional figures are immediately obtained in the same color tone as the ink. I was able to do that. It took about 5 minutes for this figure to dry.

Furthermore, when the amount of isopropyl alcohol was increased to 200 parts, the viscosity decreased to about 150 cps.

It was about the same as normal writing ink. This item was loaded into a pen-shaped container and characters were written on paper.

It was possible to immediately obtain three-dimensional characters with the same usability as ordinary writing ink. In this case, because the amount of ink used was small, the three-dimensional characters dried in a few seconds.

An acrylic resin emulsion with a resin content of 45 wt% (trade name Ultrasol K-50 manufactured by Takeda Pharmaceutical @) is used as the main binder.
) 100 parts, Example 1 as foamed microcapsules
Same as 1.5 parts 1 paint as colorant (Hodogaya Chemical ■
1 part (product name: 5PILON-REI)), 10 parts of water, calcium carbonate as a filler (product name: S from Takehara Chemical Co., Ltd.)
A-200) 20 parts were uniformly mixed in the same manner as in Example 1 to produce a cream ink.

The viscosity of this ink was about 3000 cps, and Example 1
When I drew a figure on a cloth by loading it into the same extruded tube-like container used in the ink, I was able to immediately obtain a three-dimensional figure in the same color tone as the ink.It took about 5 minutes for each figure to dry. did.

This cloth was washed in a washing machine for about 10 minutes, but no peeling or deterioration of the three-dimensional pattern was observed. Further, even after drying in a dryer, no single figure peeled off or deteriorated.

Synthetic rubber latex with a resin content of 40 wt% as a binder (product name Crossren NA-10 manufactured by Takeda Pharmaceutical Company Limited) 10
0 parts of foamed microcapsules, 2 parts of EXPANCEL-DE manufactured by Kema Nord, and 2 parts of a water-dispersed pigment with a pigment content of 25% as a coloring agent (part name: Fuji 5P-Black 8122 manufactured by Fuji Shiroki ■). , Nippon Acrylic Chemical as a thickener ■Back side product name Primal As
Three parts of E-60 were uniformly mixed in the same manner as in Example 1 to produce a cream ink.

The viscosity of this ink was about 8000 cps, and Example 1
When we loaded it into the same extruded tube-shaped container as used in , and drew letters on the leaves and trunks of trees, we were able to immediately obtain three-dimensional letters.

Even after one month, the letters did not peel off and remained in good condition (effects of the invention) As described above, according to the ink of the present invention, at the same time as writing,
It is possible to obtain three-dimensional character figures with low specific gravity and high volume in which foamed microcapsules are incorporated into the film formed by the binder. No manipulation is required.

Therefore, it is safe and easy to handle, making it suitable for use by young children, etc., and the writing base does not require heat resistance, and can be used with various bases such as paper, cloth, trees, plant leaves, plastic, etc. You can easily write on the material.

Furthermore, unlike conventional foaming paints, which do not foam after being written, no whitening phenomenon occurs, and it is possible to obtain three-dimensional characters with the same color tone as the ink.

The written three-dimensional characters have the physical properties of the binder and will not collapse even if a small amount of force is applied, and each part of the expanded microcapsules is covered with a film of the binder. Because of this, the individual particles of the foamed microcapsules have a high degree of adhesion to each other, and will not fall off even when scratched with a fingernail.Depending on the binder selected, there is also a certain degree of washing fastness, and it can be used to harden objects such as 3D letters written on cloth. It will not peel off or deteriorate after several washes.

Furthermore, if a fluorescent or phosphorescent coloring agent is used and three-dimensional characters are drawn on trees in a forest, etc., they can be seen from a distance and can be used as various signs.

Claims (4)

[Claims] (1) A three-dimensional ink characterized by containing a binder, a colorant, and expanded microcapsules. (2) Density of foamed microcapsules is 0.01 to 0.1
The three-dimensional ink according to claim 1, which has a particle size of g/cm^3. (3) When producing a three-dimensional ink containing a binder, a colorant, and expanded microcapsules, a film is formed on the expanded microcapsules in advance with a liquid component among the other ingredients;
A method for producing a three-dimensional ink, characterized in that the foamed microcapsules on which the film has been formed are then injected into the remaining other ingredients and stirred. (4) Density of foamed microcapsules is 0.01 to 0.1
The method for producing a three-dimensional ink according to claim 3, wherein the ink is g/cm^3.