JPS5829240B2 - Kirokuzai - Google Patents

Description

[Detailed description of the invention] The present invention relates to recording materials.

Conventionally, metal compounds that can react with specific organic compounds to produce chelate compounds, or chelate compounds that react with specific metal compounds, have been applied to the surface of fibrous materials such as pulp paper and substrates that are absorbent to liquids. A layer is formed for recording by chelate coloring, which is made of an organic compound that can generate compounds, and when printing, printing, writing, etc. is performed on this surface, it reacts with the metal compound or organic compound and chelates. A recording material that is printed, printed, written, etc. using a recording ink made of an aqueous solution containing an organic compound or an inorganic compound that can generate a compound, and is colored by the generation of a chelate compound to obtain a recorded image. Are known.

However, if the thickness of the layer used for recording by chelate coloring in such recording materials is thin, the recording ink may permeate into the base material, causing bleeding and making the recorded image unclear. If the layer for recording is thick due to chelate coloring, the absorption and drying properties of the recording ink will be poor, and if it comes in contact with fingers, etc., the recorded image will shift, which is a drawback. was difficult to obtain.

The purpose of the present invention is to solve the above-mentioned drawbacks, and it is possible to prevent the recording ink from permeating the base material and causing blurring of the recorded image, and to prevent the recording ink from penetrating into the base material and causing blurring of the recorded image. It is an object of the present invention to provide a recording material that is absorbed and dries, does not cause any deviation of the recorded image even when touched with fingers, and provides a recorded image with excellent resolution.

The gist of the present invention is that a non-absorbent layer is formed on at least a portion of the surface of the base material, and a layer selected from iron, vanadium, titanium, molybdenum, and tungsten is placed on the non-absorbent layer. an inorganic compound having at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten, or an organic compound capable of forming a color by forming a chelate compound with at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten; A recording material characterized in that a layer for recording is formed by chelate coloring made of a substance and a binder.

Next, the recording material of the present invention will be explained in more detail.

Examples of the base material in the recording material of the present invention include pulp paper,
Woven fabrics, nonwoven fabrics, leather, wood boards, synthetic paper, porous sheets, etc. are suitable, and an appropriate one is selected and used depending on the intended use of the recording material.

The base material may be made of an opaque material, or if the recording material of the present invention is used for purposes such as copying by a copying machine, a transparent or translucent material may be used.

The base material may be used in the form of a film or sheet, or may be used in the form of a bag or other form.

However, when a layer for recording is formed directly on the substrate by chelate coloring, when printing, printing, writing, etc. is performed using the recording ink, the recording ink reaches the substrate. However, in order to prevent the recording ink from penetrating into the base material, the present invention provides a layer that is non-absorbent to the liquid on the surface of the base material. The layer that is non-absorbent to liquids is preferably formed from materials such as thermoplastic resins, thermosetting resins, rubbery polymeric substances, celluloid, metals, glass, etc. .

In order to form the non-absorbent layer, appropriate means may be adopted depending on the type of material forming the layer, and suitable methods include coating, adhesion, etc.

According to the present invention, an inorganic compound having at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten, or iron, vanadium, etc. , titanium,
A layer for recording is formed by chelate coloring, which is composed of an organic compound capable of forming a chelate compound with at least one metal selected from molybdenum and tungsten to form a color, a fine powder substance, and a binder. There is.

The iron atom in the inorganic compound usually reacts with an organic compound to form a chelate compound when the valence is trivalent, and produces a color, and the vanadium atom and titanium atom usually react when the valence is tetravalent. A molybdenum atom and a tungsten atom usually react with an organic compound to produce a chelate compound and develop a color when the molybdenum atom and tungsten atom have a valence of 6.

Therefore, iron atoms in the inorganic compound are contained as compounds with a valence of 3, vanadium atoms and titanium atoms as compounds with a valence of 4, and molybdenum atoms and tungsten atoms as compounds with a valence of 6. It is better to

Suitable examples of such inorganic compounds include ferric chloride, sodium vanadate, vanadyl sulfate, titanium tetrasalt, sodium molybdate, and sodium tungstate.

In addition, examples of organic compounds that can form a chelate compound with at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten to form a color include dioxybenzene, isopropylcatechol, diisopropylcatechol, and tertiary-butylcatechol. , tert-butyl-
Methylcatechol, tertiary octylcatechol, tertiary octyl-methylcatechol, α-chloro-3,4-dioxyacetophenone, trioxyacetophenone, gallic acid, methyl gallic acid, gallic acid ester, dioxynaphthalene, dioxynaphthalene sulfone Acid salts, dioxyphenylacetic acid, etc. are suitable.

Fine powder substances include inorganic powders such as calcium carbonate, magnesium carbonate, diatomaceous earth, kaolin, clay, talc, silica, zeolite, titanium oxide, barium sulfate, mica powder, alumina, and zinc white, wood powder, and microcrystalline cellulose powder. , organic powders of insoluble cellulose derivatives such as cork powder, ebonite powder, lignin, pulp powder, and other inorganic or organic fibrous materials such as glass fibers, slag wolves, cellulose fibers, and synthetic fibers are cut into short pieces to form powders. It is preferable to use one or two types of
More than one species is selected and used.

When the inorganic powder or organic powder is used, the particle size is preferably 20 μm or less, most preferably 10 μm or less.

In addition, when using powdered inorganic or organic fibrous material cut into short lengths, it is preferable to use 150 meshes (Tyler decoration) or less, and optimally 200 meshes (Tyler decoration) or less. be.

The fine powder substance improves the absorbency of recording ink, the adhesion and drying properties of chelate colored images, and instantly removes recording ink when printing, printing, writing, etc. is performed using recording ink. Since it absorbs and dries, even if you touch the area with your fingers after printing, printing, writing, etc., the recorded image will not shift.

As a binder, polyvinyl alcohol, vinyl acetate resin, vinyl acetate-acrylic ester copolymer, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, polyacrylic ester resin,
Preferred are polyester resins, styrene-maleic acid copolymers, thermoplastic resins such as cellulose resins, various rubbery polymeric substances typified by styrene-butadiene copolymer rubber, starch, casein, gelatin, etc. One or more of these may be selected and used.

The binder binds the inorganic compound or the organic compound and the fine powder substance, and also firmly fixes the layer for recording by chelate coloring on the non-absorbing layer formed on the surface of the base material. have a property.

When the inorganic compound is used in the layer for performing recording by chelate coloring, the inorganic compound has a concentration of 0.2×10 −4 to 0.2×10 −4 to 0.2 Preferably, the organic compound is present in an amount of 0.3
-4 to 0.2 x 10' mol/weight is preferred.

Further, the ratio of the fine powder substance to the binder is 90:
10 to 30 near 0 is preferred, optimally 8
The ratio is 0:20 to 40:60.

In order to form a recording layer on the non-absorbing layer formed on the surface of the base material by chelate coloring consisting of the above-mentioned inorganic compound or the above-mentioned organic compound, a fine powder substance, and a binder, for example, The inorganic compound or the organic compound and the fine powder substance are mixed with a binder dissolved, swollen or dispersed in an organic solvent or water, and this is applied onto the non-absorbent layer formed on the surface of the base material. Preferably, it is attached.

For this purpose, it is preferable to apply using a blade coater, knife coater, roll coater, etc., to use means such as spraying or dipping, or to apply by solid printing or halftone printing. It is preferable to dry it naturally or by forced heating to volatilize the organic solvent or water.

The thickness of the layer for recording by chelate color development is preferably in the range of 5 to 20 microns.

In the recording material of the present invention, necessary information may be printed in advance with colored oil-based or water-based ink on the layer for recording by chelate coloring, and buttons may be attached to the layer for recording by chelate coloring. Necessary information may be printed in advance with colored oil-based or water-based ink on the surface of the base material other than the portion where the button is formed.

For the recording material of the present invention, as a recording ink for recording such as printing, printing, writing, etc., in the layer for recording by chelate coloring, the layer for recording by chelate coloring is inorganic. When a compound is present, a solution of an organic compound capable of reacting with a metal atom in the inorganic compound to produce a chelate compound and develop a color is used; A solution of an inorganic compound that can react with an organic compound to form a chelate compound and develop a color is used.

Water is most suitable as the solvent for the solution, but a mixture of water and an organic solvent is also suitable.

As the organic compound ◆ or inorganic compound used in the recording ink, those similar to the above-mentioned organic compounds or inorganic compounds that are present in the layer for recording by chelate coloring are suitable for use.

When the recording ink contains the organic compound, it is preferable that the organic compound is present in the recording ink in an amount of 0.4 x 10 to 20 mol/l; 0 in the recording ink when
．． It is preferable to prepare the amount so that it is present in an amount of 1×10 −3 to 0.5 mol/l.

The recording ink is normally a colorless liquid and does not stain the hands even if it gets on the fingers, and if it gets on the fingers it can be easily washed off with water.

When printing, printing, writing, etc. is performed using the recording ink on a layer for recording by chelate coloring, the inorganic compound or the organic compound present in the layer for recording by chelate coloring. The organic or inorganic compounds present in the recording ink react to form a chelate compound and develop a color to form a recorded image, and the tone of this recorded image is mainly black, black-blue, or sepia.

In the recording material of the present invention, a layer that does not absorb liquid is formed on at least a portion of the surface of the base material, and on the non-absorbent layer, a material selected from iron, vanadium, titanium, molybdenum, and tungsten is formed. an inorganic compound having at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten; Since a layer for winding the recording is formed by chelate coloring and a binder, a chelate compound is formed by reacting with the inorganic compound or organic compound on the layer for recording by chelate coloring. When printing, printing, writing, etc. is performed using a recording ink containing an organic or inorganic compound that develops color, the non-absorbent layer prevents the recording ink from penetrating into the base material. The image does not smear, and the layer used for recording by chelate coloring has excellent absorbency and drying properties for the recording ink, and as the recording ink is absorbed and dried instantly, there is no misalignment of the recorded image. This allows clear recorded images with good resolution to be obtained.

The recording material of the present invention can be used, for example, to display labels, labels, tags, recording sheets, and various display sheets for displaying product display, manufacturing loft number display, date display, quality display, measurement value, etc. , suitable for use in packaging products.

Examples of the present invention are described below.

Example 1 A column for printing, writing, etc. is formed on the upper part of a high-quality paper 1 with a thickness of 0.2 mm by printing 2, and a column made of polyethylene resin with a thickness of 20 μm and non-absorbent for liquid is formed on the lower part. Layer 3 was formed into a rectangular shape.

On this non-absorbent layer 3, 40 g/m of a dispersion consisting of 1 part of lauryl gallate, 15 parts of fine silica powder, 8 parts of vinyl acetate, and 200 parts of methyl ethyl ketone was applied and dried by heating to 90°C.

Thus, on the non-absorbing layer 3, a layer 4 for recording by chelate coloring made of lauryl gallate, fine silica powder, and vinyl acetate was formed, having a thickness of 5 μm.

On the display sheet obtained in this manner, five display columns of product name, date of manufacture, and manufacturing loft were printed using an aqueous solution of 0.05 mol of vanadyl sulfate dissolved in 11 parts of water as a recording ink.

The chelate colored image thus obtained was black and clear, and even when the chelate colored image was rubbed with a finger immediately after printing, no printing deviation occurred.

Example 2 A confectionery packaging bag 1' made of a woven fabric with a thickness of 1 mm has a printing 2' for displaying the product 6' on the upper part, and a printing bag 2' on the lower part made of urethane rubber with a thickness of 20 μm for liquids. Then, a non-absorbent layer 3' was formed by coating.

Next, on this non-absorbent layer 3', a dispersion of 200 parts of methyl ethyl ketone, 8 parts of ethylene-vinyl acetate copolymer resin, 15 parts of calcium carbonate, and 2 parts of 1.2 dioxynaphthalene was applied in an amount of 50 g/vol. It was dried by heating to ℃.

In this way, a layer 4' for recording by chelate coloring and having a thickness of 5 μm was formed, which was composed of 1,2-dioxynaphthalene, calcium carbonate, and vinyl acetate copolymer resin.

Next, 0.05 mol of titanium tetrachloride was added to the layer 4' for turning records by chelate coloring of the packaging bag 1'.
When the solution of step 4 dissolved in water was used as a recording ink and the product name, manufacturing loft number, manufacturing date, etc. 5' was printed using a rubber stamp, a clear sepia-colored printed image was obtained. Ta.

This chelate image did not cause any misprinting even when rubbed with fingers.

[Brief explanation of the drawing]

The drawings show an example of the recording material of the present invention, and FIG. 1 is a perspective view showing an example of the recording material being used as a display sheet.
FIG. 2 is a perspective view showing an example in which the recording material is used as a packaging bag, and FIG. 3 is a sectional view of the same. Explanation of symbols, 1...High quality paper, 1'...Packaging bag, 2
．． 2'...Printing, 3,3'...Layer non-absorbent to liquid, 4,4'...Layer for recording by chelate coloring, 5,5'...Display.

Claims (1)

[Claims] 1 A layer that does not absorb liquid is formed on at least a portion of the surface of the base material, and at least one type selected from iron, vanadium, titanium, molybdenum, and tungsten is formed on the non-absorbent layer. Chelate consisting of an inorganic compound having a metal atom or at least one metal atom selected from iron, vanadium, titanium, molybdenum, and tungsten, an organic compound capable of forming a chelate compound and coloring, a fine powder substance, and a binder. Recording material 0 characterized in that a layer is formed when the recording is wound due to color development.