JPS6144667B2 - - Google Patents

Description

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

In recent years, with the rapid spread of electronic computers, automatic recording devices, recorded image reading devices, facsimile machines, etc., there has been a demand for recording materials for terminal recording devices that have quick-drying ink and high resolution. . When recording on the recording material installed in the terminal recording device of these devices, in order to obtain a steady recorded image and to ensure good workability at the beginning of use, oil-based or water-based non-volatile Liquid ink is used, but when pulp paper is used as a recording material, the ink seeps into the gaps between the fibers, resulting in low resolution.
Commercially available synthetic papers have the disadvantage of poor ink fixation and quick drying properties, and with conventional recording materials, the benefits of using high-performance equipment have been reduced.

The present invention eliminates the drawbacks of conventional recording materials, and provides a recording material that has excellent ink fixation and quick drying properties when recorded with non-volatile liquid ink, and has a high resolution. The purpose is to

The gist of the present invention is to provide a printing material in which a coating layer made of inorganic fine powder with a particle size of 5 microns or less and a binder is formed on at least one side of a base material layer that does not have absorbency for non-volatile liquid ink, The coating layer has a thickness of 5 microns or more, and the oil absorption of the coating layer [measured value according to Japanese Industrial Standard P8130 (paper and paperboard oil absorption test method)] is 200 seconds or less, and the coating layer has a thickness of 200 seconds or less. The surface smoothness of the surface is 3000
It is from 10,000 seconds to 10,000 seconds. It consists in recording materials for non-volatile liquid ink recording. Next, the recording material of the present invention will be explained in more detail. The base material layer in the present invention may be any material as long as it does not have absorbency to non-volatile liquid ink, and when recording with non-volatile liquid ink, the ink will not bleed and the printed image will not bleed. Examples of the material for such a base material include thermoplastic resin, thermosetting resin,
Metals, glass, etc. can be used, including olefin resins, styrene resins, vinyl chloride resins, vinyl acetate resins, polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, polyacrylate resins, and phenoxy resins. Thermoplastic resins such as resins and cellulose resins are optimal.

If the base material layer is made of thermoplastic resin or thermosetting resin and has poor opacity, the resin 100%
It is possible to add an inorganic filler in an amount of about 1 to 50 parts by weight per part by weight. Such inorganic fillers include calcium carbonate, magnesium carbonate,
Calcined gypsum, talc, barium sulfate, kaolin, silica, titanium oxide, zinc sulfide, etc. are suitable, and one type may be used alone or two or more types may be used in combination.

The base layer may be entirely formed of the above-mentioned materials, but for example, the surface of the pulp paper is made of a material that does not absorb non-volatile liquid ink, such as thermoplastic resin or thermosetting resin. It may be formed by thinly coating or impregnating pulp paper, or by laminating a metal foil such as aluminum foil on the surface of pulp paper.

The thickness of the base material layer is preferably about 30 to 1000 microns.

A coating layer made of inorganic fine powder and a binder is formed on at least one side of the base layer. The inorganic fine powder includes calcium carbonate, magnesium carbonate,
Calcined gypsum, talc, barium sulfate, kaolin, silica, titanium oxide, zinc sulfide, etc. are suitable, and one type may be used alone or two or more types may be used in combination. The coating layer in the recording material of the present invention must have excellent ink drying properties, excellent fixation properties, uniform ink penetration, and high resolution. For good application, the particle size of the inorganic fine powder is preferably limited to 5 microns or less. Particle size of inorganic fine powder is 5
The term "micron or less" refers to particles having a particle size that can pass through a sieve with an opening of 5 microns.

However, if the particle size of the inorganic fine powder becomes larger than 5 microns, the ink absorption, drying and fixing properties of the coating layer will be reduced, the ink will not bleed uniformly, and the coating layer will not absorb evenly. Surface smoothness decreases,
The resolution of the recorded image becomes poor, and this tendency becomes more severe as the grain size becomes larger.

Examples of the binder include polyvinyl chloride, polyvinyl alcohol or its acetal, vinylidene chloride-vinyl chloride copolymer, vinyl chloride-
Suitable examples include vinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer, acrylonitrile-vinyl acetate copolymer, polyethylene, polyethylene terephthalate, polyamide, polyacrylonitrile, cellulose acetate polymer, vinyl acetate-acrylic acid ester copolymer, etc. Therefore, even if only one type is used, 2
You may use more than one species in combination. It is preferable to use such a thermoplastic resin in a state in which it is dissolved or swollen in a liquid in which it can be dissolved or swelled, or in a state in which it is dispersed in a liquid in which it can be dispersed into an emulsion.

These liquids include benzene, toluene,
xylene, ethyl acetate, methyl acetate, methanol, ethanol, isopropyl alcohol, n-
Butanol, isobutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, n-hexane, n-heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dioxane,
Methyl cellosolve, ethyl cellosolve, chloroform, carbon tetrachloride, methylene chloride, trichlene, etc. are suitable, and water can also be used as a dispersion medium.

To form the coating layer, for example, 70 to 130 parts of inorganic fine powder is added to the binder solution, swelling liquid, or emulsion dispersion per 100 parts by weight of the thermoplastic resin.
It is preferable to apply a dispersion in which the weight part is dispersed and dry it. Before forming the coating layer, the surface of the base layer may be subjected to a treatment such as corona discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone oxidation treatment, electron beam irradiation treatment, etc. to improve the adhesion strength of the coating layer. Moreover, when the base material layer is formed of metal, a degreasing treatment can also be performed.

Therefore, it is preferable to use 70 to 130 parts by weight of inorganic fine powder per 100 parts by weight of the binder in the coating layer when recording is performed using an oil-based or water-based non-volatile liquid ink. This is because the absorbency is excellent and the liquid ink permeates uniformly, resulting in excellent resolution. However, if the amount of inorganic powder is less than 70 parts by weight per 100 parts by weight of the thermoplastic resin, the ink absorbency of the coating layer will be poor, and if the recorded image is touched with a finger, ink shift will easily occur, resulting in a recorded image with excellent resolution. It is easy to lose the ability to gain. Furthermore, if the amount of the inorganic fine powder is more than 130 parts by weight per 100 parts by weight of the thermoplastic resin, the adhesion strength of the coating layer to the base material layer will decrease, and the surface strength required as a recording material will not be obtained, causing the coating layer to rub. There is a risk that the ink may peel off, and when the ink bleeds, the lines of the recorded image become thicker and the resolution tends to decrease.

If necessary, additives such as plasticizers, stabilizers, antistatic agents, dyes, pigments, antioxidants, and ultraviolet absorbers may be present in small amounts in the coating layer. The thickness of the coating layer is 5 microns or more.
The reason why it is necessary to have a thickness of 5 microns or more is that the base material layer is not absorbent to non-volatile liquid ink so that the resolution does not deteriorate due to ink seepage.
It is necessary that the ink be completely absorbed in the coating layer, and in order to obtain good resolution, the ink must be absorbed in the thickness direction, and for this purpose, a thickness of at least 5 microns is required. Depends on what you have to have. However, if the thickness of the coating layer is less than 5 microns, the ink cannot be completely absorbed by just absorbing it in the thickness direction, and the absorption must spread in the plane direction, resulting in a significant decrease in resolution. There will be some drawbacks.

Oil absorption of the coating layer in the present invention [Japanese Industrial Standards
P8130 (oil absorption test method for paper and paperboard) measured value is 200 seconds or less. Recording is performed on the coating layer using oil-based or water-based non-volatile liquid ink, and whether the non-volatile liquid ink is oil-based or water-based, it has excellent ink absorption and quick drying properties. It is necessary for both of these non-volatile liquid inks to exhibit satisfactory ink absorption and quick drying properties, and that the ink does not aggregate on the surface of the coating layer and does not cause ink shading. In order to obtain good resolution, the oil absorption of the coating layer is made to be 200 seconds or less.

Next, conditions for measuring oil absorption in the present invention will be explained with reference to FIG. 1.

Take a test piece 1 with a size of 65 mm x 200 mm and weigh it.
An oil film of polybutene oil having a viscosity of 230±10 centiboads (20° C.) is applied to the surface of the coating layer 11 using a 5.70±0.05 kg roller.

6 volt, 8 watt tungsten light bulb,
The light is projected from the light projecting section 2, which consists of a condensing lens and an aperture, to the center of the coating section 3 at an angle of 75 degrees to the normal, and the irradiated surface is adjusted to be a rectangle of 22 mm x 16 mm. is received by a light receiving section 4 consisting of a laminated photovoltaic cell, the amount of light is exchanged into an electric current, and the amount of specularly reflected light is determined by a galvanometer 5 with a 5 micron ampere and 100 scale. In this case, the amount of reflected light from the oil film decreases as the oil is absorbed by the coating layer 11, and the pointer of the galvanometer 5 decreases to a point close to the amount of specularly reflected light from the coating layer 11 when no oil film is present. .
The oil absorption end point is defined as the point at which the pointer value of the galvanometer 5 when no oil film is present on the coating layer 11 has dropped to the point where 5 scales have been added. In this way, an oil film is formed on the surface of the coating layer 11, and the time from the time when the amount of specularly reflected light increases and the pointer of the galvanometer 5 rises until reaching the absorption end point is measured with a second clock, and the time is measured using a second clock. However, the recording material of the present invention has an oil absorption of 200 seconds or less.

In the recording material of the present invention, when polybutene oil with a viscosity of 230±10 centipoise (20°C) is used as the test oil, the oil absorption is 200 seconds or less, but when polybutene oil is used instead of polybutene oil at 15±3 centipoise (20°C) When glycerin oil is used, the oil absorption is preferably 200 seconds or less. In this way, when the oil absorption for glycerin oil is 200 seconds or less, it means that the absorbency of liquid substances with many hydrophilic groups such as glycerin is excellent, especially for water-based liquids. As for ink, it does not aggregate on the surface of the coating layer or cause shading due to uneven seepage, and has excellent ink absorption and quick-drying properties, and the resolution of recorded images is excellent. Become something.

However, in the present invention, the oil absorption of the coating layer is 200
If it is larger than 2 seconds, the absorbency for oil-based and water-based liquid inks will decrease, and the quick drying properties will be poor, and the ink may remain aggregated on the surface of the coating layer or spread horizontally and be absorbed. This results in disadvantages such as poor resolution due to the increase in image quality.

In the recording material of the present invention, the surface smoothness of the coating layer is 3,000 to 10,000 seconds. Beck smoothness is a value measured by a Beck smoothness measuring device, and is generally used to express the smoothness of paper. However, the smoothness of pulp paper is 500 even for high-quality paper.
The surface smoothness is extremely low, and the accuracy of coordinate positions and plate reproducibility are impaired when recording is performed using liquid ink.

However, since the recording material of the present invention has a base surface smoothness of the surface of the coating layer of 3000 to 10000 seconds,
When recording is performed on the surface of the coating layer, accurate coordinate positions and plate reproducibility are obtained, resulting in an excellent recorded image.

When recording on the surface of the coating layer in the recording material of the present invention, a nonvolatile liquid ink that is oil-based or water-based is used. Various inks ranging from those with a viscosity close to that of water to those with a high viscosity, including those with no volatile components at all and those in which a small amount of volatile components evaporate over a very long period of time. can be used.

As a recording method, printing methods such as letterpress, flat plate, or concave plate may be used, or writing methods using a pen may be used, or low viscosity water-based ink may be sprayed in a dotted manner. However, an inkjet printing method may be adopted in which characters, figures, symbols, etc. are recorded by forming lines that are visible continuously to the naked eye.
However, even when recording is performed using such a recording method, the recording material of the present invention has excellent ink absorption and quick drying properties, and can provide a recorded image with excellent resolution.

When recording with oil-based or water-based nonvolatile liquid ink on the coating layer of the recording material of the present invention, the recorded image depends on factors such as line image reproducibility, gradation reproducibility, edge changeability, and solid printing density. However, these properties of the recording material of the present invention are significantly superior. In terms of line image reproducibility, the recording material of the present invention has less ink bleeding and less thick lines, and in terms of gradation reproducibility, the results obtained by measuring with a reflection densitometer are not reproducible. This shows high reproducibility when halftone dot printing is performed using metal letterpress, and the results are excellent. Also, from the results of measuring edge changeability, that is, the slope of change in ink density at the ends of a recorded image, it is confirmed that there is little ink bleeding and that the resolution is excellent. All of these properties are far superior to those of pulp paper.

In the recording material of the present invention, a coating layer made of inorganic fine powder with a particle size of 5 microns or less and a binder is formed on at least one side of the base material layer that does not have absorbency for nonvolatile liquid ink, and the coating layer is It has a thickness of 5 microns or more, and the oil absorption of the coating layer [measured value according to Japanese Industrial Standard P8130 (paper and paperboard oil absorption test method)] is 200 seconds or less,
The surface smoothness of the coating layer is 3000 to 10000.
The coating layer can completely absorb the non-volatile liquid ink, and the non-volatile liquid ink has excellent ink absorption and quick drying properties whether the non-volatile liquid ink is oil-based or water-based. It does not aggregate on the surface and does not cause ink shading.
When recording, the coordinate position is accurate and the plate reproducibility is excellent, and an excellent recorded image with high resolution can be obtained.

Examples of the present invention are described below. In the examples, "parts" simply refer to parts by weight.

Example 1 An impact-resistant polystyrene resin film having a thickness of 80 microns and a width of 1000 mm was molded using an extruder. Next, the film was used as a base layer, and on one side, 12 parts of calcium carbonate fine powder with a particle size of 4.5 microns, 12 parts of polyvinyl acetate, 30 parts of toluene,
A dispersion consisting of 50 parts of methanol and 25 parts of isopropyl alcohol was applied and dried by standing in a hot air drying oven at 100° C. for 2 minutes to form a coating layer consisting of fine powder of calcium carbonate and polyvinyl acetate. The thickness of the coating layer was 10 microns.

Further, the oil absorption of the coating layer measured by the method described in the text was 30 seconds. The oil absorption of the coating layer for Glyalin oil also showed similar results. In addition, the coating layer has excellent surface smoothness, and the Beck smoothness measured by a Beck surface smoothness measuring device is
It was 3000 seconds.

When recording is performed using oil-based non-volatile ink on the surface of the coating layer, the ink absorbency and quick drying properties are excellent, and the ink does not aggregate on the surface of the coating layer or cause ink shading. Absorbed uniformly and completely. This property was the same even when recording was performed with aqueous nonvolatile ink.

In order to check the resolution of the coating layer, printing was performed using a metal letterpress plate with a width of 50μ, and a line image with a width of 93μ was obtained.Also, when halftone dot printing was performed using a 54% halftone plate, a line image with a width of 58% was obtained. A halftone printed image was obtained, and the edge change was measured with a microdensitometer, and the slope width from density level 0.2 to 0.7 was 16.5 μ, indicating excellent resolution.

Example 2 A composition consisting of 100 parts of high-impact polystyrene, 10 parts of ethylene-vinyl acetate copolymer, 20 parts of calcium carbonate, and 0.01 part of an antistatic agent was kneaded for 15 minutes using a Banbury mixer, and the mixture was charged into an extruder.
A film having a thickness of 80 microns and a width of 1000 mm was formed, and one side of the film was subjected to a corona discharge treatment.

Next, the film was used as a base material layer, and 100 parts of silicic anhydride fine powder (particle size 2.1 microns), 100 parts of acrylic acid ester-vinyl acetate copolymer, 200 parts of toluene, and 280 parts of methanol were applied to the surface subjected to corona discharge treatment.
A dispersion of 180 parts of methyl cellosolve and 180 parts of isopropyl alcohol was applied and dried by leaving it in a hot air drying oven at 120°C for 30 seconds to form a coating made of fine silicic anhydride powder and acrylic ester-vinyl acetate copolymer. formed a layer.

Furthermore, the oil absorption of the coating layer measured by the method described in the text was 40 seconds, and similar results were obtained for the oil absorption of glycerin oil. In addition, the coating layer has excellent surface smoothness, with a Beck smoothness of 3000 as measured by a Beck surface smoothness meter.
It was hot in seconds.

When recording is performed using oil-based nonvolatile ink on the surface of the coating layer, the ink absorption and ink drying properties are excellent, and the ink does not aggregate on the surface of the coating layer or cause ink shading. , uniformly completed and absorbed. This property was the same when recording was performed with aqueous nonvolatile ink.

In addition, in order to check the resolution of the coating layer, when printed with a metal letterpress plate consisting of a 50μ width plate, a 90μ width line image was obtained.Also, when halftone dot printing was performed with a 54% halftone letterpress plate, a line image with a width of 90μ was obtained.
A halftone printing machine with a dot density of 58% was obtained, and when edge change was measured with a microdensitometer, the density level was
The slope width from 0.2 to 0.7 was 14 μ, and the resolution was excellent.

Example 3 One side of a polyethylene resin film with a thickness of 80 microns and a width of 1000 mm was subjected to corona discharge treatment. Next, using the film as a base material layer, 100 parts of water was added to 100 parts of an aqueous emulsion in which 50% by weight of acrylic acid ester was dispersed, and 50 parts of silicic anhydride was mixed with the mixture while stirring with a homomixer. The dispersion was applied to the corona discharge treated surface of the base layer and dried by leaving it in a hot air drying oven at 110° C. for 1 minute to form a coating layer consisting of silicic anhydride and acrylic ester. The thickness of the coating layer was 10 microns.

Furthermore, the oil absorption of the coating layer measured by the method described in the text was 60 seconds, and similar results were obtained for the oil absorption of glycerin oil. In addition, the coating layer has excellent surface smoothness, with a Beck smoothness of 3000 as measured by a Beck surface smoothness meter.
It was hot in seconds.

When recording is performed using oil-based non-volatile ink on the surface of the coating layer, the ink absorbency and quick drying properties are excellent, and the ink does not aggregate on the surface of the coating layer or cause ink shading. Absorbed uniformly and completely. This property was the same even when recording was performed with aqueous nonvolatile ink.

In order to investigate the resolution of the coating layer, when printing was performed using a metal letterpress plate with a width of 50μ, a line image with a width of 9.5μ was obtained, and when halftone dot printing was performed using a letterpress with 54% halftone dots, a line image with a width of 60% was obtained. A halftone printed image was obtained, and when the edge change was measured using a microdensitometer, the slope width from the density level 0.2 to 0.7 was 18μ.
It had excellent resolution.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing an example of an oil absorption measuring device. Explanation of symbols, 1... Test piece, 2... Light projecting section, 3
...Coated part, 4... Light receiving part, 5... Galvanometer, 11
...covering layer.

Claims (1)

[Scope of Claims] 1. A coating layer consisting of an inorganic fine powder with a particle size of 5 microns or less and a binder is formed on at least one side of a base material layer that does not have absorbency for non-volatile liquid ink, and the coating layer is It has a thickness of 5 microns or more, and the oil absorption of the coating layer [Japanese Industrial Standards]
P3130 (oil absorption test method for paper and paperboard)] is 200 seconds or less, and the surface smoothness of the coating layer is 3000 to 10000 seconds, a recording material for non-volatile liquid ink recording.