JP2001150825A - Image receiving resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image receiving resin sheet suitable for writing by a water base ink pen, a pencil or the like and capable of printing or image forming by a printer. SOLUTION: The image receiving resin sheet comprises a resin sheet base material 11, and writable image receiving and writing layers 12 formed on both front and rear surfaces of the material 11 and receiving a color material to be image receivable and writable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image receiving resin sheet capable of printing or printing characters, pictures, photographs and the like using a thermal transfer printer or the like.

[0002]

2. Description of the Related Art Conventionally, an image receiving resin sheet which has higher durability and water resistance than a paper sheet and can receive a printed image has been widely used. In this type of image receiving resin sheet,
A color material receiving layer is formed on one side with a polyester resin having an affinity for the sublimable color material. When printing an image, a sublimable color material was formed by thermal transfer.

[0003]

The required number of such image-receiving resin sheets can be printed using a printer, and the images are also beautiful and have a high-class appearance. There are many. However, the above-mentioned conventional image-receiving resin sheet has no water-absorbing property because the colorant-receiving layer is formed of a polyester-based resin, and cannot be written with an aqueous pen. Further, the coloring material receiving layer was hard and had a smooth surface, and thus was not suitable for writing with a pencil. Because of the limitations of writing utensils, it was difficult to write a message when handing a toy business card, or to write down a note when it was received.

An object of the present invention is to provide an image-receiving resin sheet which can be printed and printed by a printer and is suitable for writing with an aqueous pen or pencil.

[0005]

The present invention solves the above-mentioned problems by the following means. In addition, in order to make it easy to understand, description is given with reference numerals corresponding to the embodiment of the present invention, but the present invention is not limited to this. In order to solve the above-mentioned problem, an invention according to claim 1 is provided on both front and back surfaces of a resin sheet substrate (11) and the resin sheet substrate (11), and can receive a color material and receive an image. And a writable image receiving / writing layer (12).

According to a second aspect of the present invention, there is provided the image receiving resin sheet according to the first aspect, wherein the image receiving / writing layer (12) receives a dye that has been melt-transferred.

[0007] The third aspect of the present invention is the first or second aspect.
5. The image receiving resin sheet according to item 1, wherein the image receiving / writing layer (12) contains hydrophilic porous microsilica.

According to a fourth aspect of the present invention, in the image receiving resin sheet according to the third aspect, the image receiving / writing layer is (12) a first layer (12a) containing hydrophilic porous microsilica;
An image receiving resin sheet having a second layer (12b) containing cellulose acetate.

According to a fifth aspect of the present invention, in the image receiving resin sheet according to the third aspect, the image receiving / writing layer (12) contains hydrophilic porous microsilica and cellulose acetate. It is.

According to a sixth aspect of the present invention, in the image receiving resin sheet according to the third aspect, the image receiving / writing layer (12) is a hydrophilic porous micro silica having a pore volume of 0.2 to 0.9 ml / g. And a hydrophilic porous microsilica having a pore volume of 1.2 to 3.0 ml / g.

[0011]

Embodiments of the present invention will be described below in more detail with reference to the drawings. (First Embodiment) FIG. 1 is a view showing a first embodiment of an image receiving resin sheet according to the present invention, and FIG.
1B is a rear view, and FIG. 1C is a cross-sectional view of FIG.
It is sectional drawing. The image receiving resin sheet 10 includes a resin sheet base material 11 and an image receiving / writing layer 12.

(Resin sheet substrate) Resin sheet substrate 11
While holding the image receiving and writing layer 12, withstands the heat applied at the time of image formation, it is preferable to have a mechanical strength that does not hinder handling, if it has such performance, The material is not particularly limited. For example, various plastic laminated papers, synthetic papers such as polyolefin or polystyrene or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, poly Acrylonitrile,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyetheretherketone, polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkylvinylether copolymer, polyvinyl fluoride,
Tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer,
Various plastic films or sheets such as polychlorotrifluoroethylene or polyvinylidene fluoride can be used, and a white opaque film or foam formed by adding a white pigment or a filler to these plastics or forming a film. A foam sheet or the like can also be used.

Further, a laminate in which the above-mentioned materials are arbitrarily combined may be used. Examples of typical combinations of laminates include a laminate of cellulose fiber paper and synthetic paper, a laminate of cellulose fiber paper and a plastic film or sheet, a laminate of plastic films or sheets of different types or grades, and the like. . Such a laminated body may be a two-layered body, but in order to obtain the texture and texture of the base material, a coated paper or a white or transparent plastic film is used as a core material, and synthetic paper or a foamed plastic film is laminated on both surfaces thereof. A three-layer body or a laminate of three or more layers can also be used. The thickness of these resin sheet substrates is not particularly limited, but is usually 50
A thickness of about 800 μm is appropriate. In the case where the resin sheet substrate as described above has a poor adhesion to a layer formed on the surface, a corona discharge treatment, a plasma treatment, various types of primer coating, or the like can be applied to the surface.

(Image Receiving / Writing Layer) The image receiving / writing layer 12 is formed on both surfaces of the resin sheet substrate 11, receives the transferred color material, and is a commonly used writing instrument, a pencil.・ Includes mechanical pencils, fountain pens, water-based pens such as water-based pens, and oil-based writing tools such as ball-point pens and oil-based pens, and allows stamps to adhere well so that they can be used as postcards. It has a proper releasability, is smoothly discharged from the printer, and has the performance of not being contaminated by the coloring material of another sheet even when it is stacked. The image receiving and writing layer 12 is composed of a thermoplastic resin serving as a binder and a hydrophilic porous microsilica manufactured by a wet method dispersed in the first resin 12 as a main component.
a and a second layer 1 composed mainly of cellulose acetate
2b. As a method for transferring an image to the image receiving / writing layer 12, a heat-sensitive fusion transfer method is preferable. In the thermal fusion transfer method, a printer having a thermal head that generates heat in response to a recording signal is used to transfer a melt transfer sheet (ribbon) having a coloring material such as a pigment or a dye to an image receiving / writing layer 12.
This is a method of transferring an image in accordance with a recording signal by superimposing the image on the recording medium.
Since the image is transferred by the thermal fusion transfer method in this manner, printing can be performed even on microsilica, and the choice of thermoplastic resin for the binder is wide. In the present embodiment, as shown in FIGS. 1A and 1B, a dog illustration a1, a name a2, and a telephone number a3 are printed on the surface,
A floral pattern a4 is printed on the back surface.

The micro-silica forms fine irregularities on the surface of the image-receiving resin sheet 10 to impart pencil writability, and the -SiOH group (hydrophilic group) on the surface of the micro-silica allows the writability with an aqueous pen to be improved. The purpose is to give the adhesiveness of the stamp. The above minute uneven shape is
The degree of unevenness is determined by the average particle size of the microsilica. That is, if the particle size is too small, sufficient fine irregularities cannot be obtained, and the writing performance with a pencil or a mechanical pencil is reduced. On the other hand, if the particle size is too large, it affects the surface friction characteristics, and an appropriate slip property cannot be obtained. Further, when an aqueous writing instrument is used, bleeding easily occurs. Furthermore,
Images cannot be transferred clearly. For the above reasons, the average particle size of the microsilica used in the present invention is preferably about 1 to 10 μm.

The amount of microsilica to be added to the thermoplastic resin binder is preferably in the range of about 0.1 to 3 and more preferably about 0.15 to 2 in the mass ratio of the total amount of microsilica / the thermoplastic resin. It is particularly preferred that it is within the range. When the mass ratio is less than 0.1, sufficient writing suitability and stamp adhesiveness cannot be obtained, and when the mass ratio exceeds 3, the coating suitability decreases and the coating film strength decreases, When writing with a writing instrument, problems such as the coating film being easily peeled off occur, which is not preferable.

In the present invention, as described above, hydrophilic porous microsilica produced by a wet method is used. Microsilica is also produced by a dry method, but in the dry method, silicon tetrachloride is produced by burning and hydrolyzing in the gas phase. Have no. Such silica has low water absorption and is not suitable for applications requiring high hydrophilicity and water absorption as in the present invention. In this regard, the micro silica produced by the wet method (gel method) is an aqueous sodium silicate solution,
Since the silica sol produced by the reaction with sulfuric acid or hydrochloric acid is produced by gelling, it becomes porous. And since such a silica is porous and has a silanol group (-SiOH) which is a hydrophilic functional group on the surface at the same time, the silica has a higher hydrophilicity and water absorption compared to a normal hydrophilic filler. It is suitable for improving the writing properties and stamp adhesiveness of the aqueous pen. Some silicas manufactured by a wet method have been subjected to a surface treatment with an organic or inorganic substance in order to lower the hydrophilicity. However, hydrophilicity is important in the present invention, and it is preferable to use silica that has not been subjected to such treatment.

As the binder of the first layer 12a, various thermoplastic resins (for example, polyvinyl acetate, polyvinyl chloride, polyvinyl butyral, polyethylene, polyamide, hydroxyethyl cellulose, methyl cellulose,
Nitrocellulose, polystyrene, polyester, etc.
Polyacrylate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-organic acid copolymer, vinyl chloride-vinylidene chloride copolymer, etc.)
In addition to the function as a fixing agent, it is particularly preferable to use polyvinyl butyral in order to further improve the stain resistance due to a coloring material and the like, and also, together with polyvinyl butyral, a curing agent It is more preferable to use an isocyanate compound or a chelating agent in combination.

The first layer 12a is formed by dissolving microsilica, a thermoplastic resin and necessary additives in a suitable organic solvent or water.
The dispersed solution / dispersion is formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate. The thickness is generally about 0.2 to 20 μm. In forming the first layer 12a, a cross-linking agent such as a polyisocyanate or a chelating agent is added to the coating solution to make the formed layer a cross-linked body. Strength and the like can be further improved.

The second layer 12b is a layer formed on the surface of the first layer 12a and contains cellulose acetate as a main component. The second layer 12b imparts necessary surface friction characteristics and releasability to the image receiving / writing layer 12. Cellulose acetate varies in solubility and releasability in a solvent depending on the degree of acetylation and the degree of polymerization, and the degree of oxidation is good when the degree of oxidation is in the range of about 40 to 60%. Those having a range of about 100 to 300 are preferable. If the degree of polymerization is too low, the releasability decreases, and if the degree of polymerization is too high, processing suitability (solvent solubility) decreases, which is not preferable. The second layer 12b is formed by dissolving and dispersing cellulose acetate and necessary additives in an appropriate organic solvent or water, for example, by a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. It is formed by applying and drying by such forming means as above. By the formation of the second layer 12b, appropriate surface friction characteristics and releasability are obtained for the image receiving and writing layer 12, and the transportability in the printer is improved, the blocking resistance is improved, and the printed matter is further improved. When stacked, the problem of set-off that the color material forming the image is transferred to the image receiving / writing layer 12 and the image receiving / writing layer 12 is stained is also solved at the same time. The thickness of the second layer 12b is preferably about 0.01 to 1 μm. When the thickness is less than 0.01 μm, the above-mentioned properties, particularly the releasability, cannot be obtained. When the thickness exceeds 1 μm, the surface of the image receiving / writing layer 12 becomes too smooth, and is provided by the micro silica in the first layer 12a. This is because the writing property and the sticking property of the stamp are deteriorated.

(How to Use) FIG. 2 is a diagram showing a method of using the first embodiment of the image receiving resin sheet according to the present invention. The image receiving resin sheet 10 is used as follows. An unused image-receiving resin sheet 10 is prepared (FIG. 2 (A)), and the illustration a1 of the dog is placed on the image-receiving and writing layer 12 on both sides by a printer.
Are printed to produce a toy business card (FIG. 2B). When handing the business card, add the message b1 (FIG. 2)
(C)). The recipient who has received the business card makes a note of the necessary items b2 (FIG. 2D).

According to the present embodiment, the image receiving / writing layer 12
Are formed on both sides of the resin sheet substrate 11,
You can print on a printer without worrying about the front and back. In addition, the image receiving / writing layer 12 can be image-printed by a heat-sensitive melt transfer method, and can be easily written with a hydrophilic porous microsilica contained in the first layer 12a using a pencil, an aqueous pen or the like. . Further, the second layer 12
Since b is provided, the transportability in the printer is improved, and there is no offset of the color material.

(Second Embodiment) FIG. 3 is a sectional view showing an image receiving resin sheet according to a second embodiment of the present invention. In each of the embodiments described below, parts that perform the same functions as those in the first embodiment described above are denoted by the same reference numerals, and
Duplicate description will be omitted as appropriate. The image receiving / writing layer 12 contains microsilica and cellulose acetate dispersed in a thermoplastic resin as a binder. As the microsilica and the thermoplastic resin, those similar to those of the first embodiment can be used. Cellulose acetate resin is used for image receiving and writing layer 1
2 to give good releasability and reduce the decrease in the density of the printing screen and the transfer of color materials, and prevent the printing screen from being contaminated even when the prints are stacked and stored. The degree of polymerization is preferably 100 to 400, and the degree of acetylation is about 30 to 63% by mass. Further, the average degree of polymerization is 100 to 200, and the degree of acetylation is 53 to 5 based on the solubility and the dissolution concentration of the general solvent.
Those having about 7% by mass are particularly preferred. The degree of acetylation is
FIG. 2 shows the content of acetic acid bound in cellulose acetate by mass percentage.

According to the present embodiment, the image receiving / writing layer 12
Contains microsilica and cellulose acetate dispersed in a thermoplastic resin as a binder, so that it can be applied and formed in one step, and the production cost can be reduced.

(Third Embodiment) The configuration of the third embodiment is as follows.
Since it is the same as the image receiving resin sheet of the second embodiment, FIG.
The drawings corresponding to are omitted. The image receiving / writing layer 12 is mainly composed of a thermoplastic resin serving as a binder and at least two kinds of hydrophilic porous microsilica having a different pore volume and manufactured by a wet method and dispersed therein.
In the present embodiment, the pore volume is 0.2 to 0.9 ml /
g of microsilica and a pore volume of 1.2-3.0 ml /
g of micro silica is used in combination. In general, the larger the pore volume, the larger the surface area and the amount of silanol groups per unit volume, which increases the hydrophilicity and water absorption, and improves the fixability and stamp adhesion of water-based inks such as fountain pens and water-based pens. Is preferred. However, 3.0
If the amount exceeds ml / g, on the contrary, the hydrophilicity becomes too high, and the aqueous ink bleeds, or the voids in the microsilica particles become too large, resulting in problems such as reduced hardness and reduced pencil writing. Not preferred. On the other hand, when the pore volume is less than 0.2 ml / g, the hardness is sufficient,
Although the pencil writing property is good, it is not preferable because the hydrophilicity and the water absorption are reduced, and the fixability of the aqueous ink and the adhesiveness of the stamp are reduced.

According to the present embodiment, the image receiving / writing layer 12
Contains hydrophilic porous microsilica having different pore volumes, so that writing can be performed even more clearly using a pencil or an aqueous pen.

(Fourth Embodiment) FIG. 4 is a sectional view showing an image receiving resin sheet according to a fourth embodiment of the present invention. In the present embodiment, an intermediate layer 13 is provided between the resin sheet substrate 11 and the image receiving / writing layer 12. Middle layer 13
Is a layer for improving the adhesion of the image receiving / writing layer 12 to the resin sheet substrate 11. The intermediate layer 13 is formed by adding a vinyl acetate resin or a vinyl acetate copolymer resin to a base resin having good adhesiveness to the resin sheet substrate 11, and further adding microsilica as necessary. The addition amount of the vinyl acetate resin, the vinyl acetate copolymer resin and the microsilica varies depending on the selection of the resin sheet substrate 11 and the base resin to be used, but the total amount of the vinyl acetate resin, the vinyl acetate copolymer resin and the microsilica is 5%. It is preferably about 50% by mass. When a resin (for example, polyurethane resin) having good adhesiveness to various resin sheet base materials 11 is used as the base resin, vinyl acetate resin or microsilica may not be added. Also,
If necessary, additives such as a whitening agent such as calcium carbonate or titanium oxide, a fluorescent whitening agent, an antistatic agent or other pigments may be added. Specific examples of the coating solution for the intermediate layer 13 include 5 parts by mass of a polyurethane resin [N-5199 Nippon Polyurethane Co., Ltd.], 10 parts by mass of titanium oxide [TCA-888, Tochem Products Co., Ltd.], and methyl ethyl ketone. / Toluene / isopropyl alcohol (mass ratio 2: 2: 1) to 7
Examples of the composition include 0 parts by mass.

According to the present embodiment, since the intermediate layer 13 is provided, the image receiving / writing layer 12 can be securely adhered to the resin sheet substrate 11.

(Modifications) Various modifications and changes are possible without being limited to the above-described embodiments, and these are also within the equivalent scope of the present invention. For example, the image receiving / writing layer 12 may be added with additives such as a whitening agent such as calcium carbonate or titanium oxide, a fluorescent whitening agent, an antistatic agent and other pigments. By doing so, the image receiving / writing layer 12 can more clearly receive an image. The image receiving / writing layer 12 may contain a nylon filler. Nylon filler has a high melting point, is thermally stable, has good oil resistance, chemical resistance, etc., so it is difficult to be dyed by coloring materials, and has self-lubricating properties, low friction coefficient, and wear. Therefore, the transportability of the image receiving resin sheet 10 in the printer is improved. In addition, as the nylon filler to be contained,
It is preferably spherical with a molecular weight of 100,000 to 900,000 and having an average particle diameter of about 0.01 to 30 μm, and particularly preferably has a molecular weight of 100,000 to 500,000 and an average particle diameter of 0.01 to 10 μm.
Are more preferred. As for the type of nylon filler, nylon 12 filler is more preferable than nylon 6 or nylon 66 because it has excellent water resistance and does not change its properties due to water absorption.

[0030]

As described above in detail, according to the first aspect of the present invention, since the resin sheet substrate has the image receiving and writing layers on both the front and back surfaces, the color material can be received on any surface. And can be written.

According to the second aspect of the present invention, since the image receiving / writing layer receives the dye that has been melt-transferred, the resin material can be selected in a wide range.

According to the third aspect of the present invention, since the image receiving / writing layer contains hydrophilic porous microsilica, it can be written with a pencil, an aqueous pen or the like.

According to the fourth aspect of the present invention, since the image receiving / writing layer has the first layer containing hydrophilic porous micro silica and the second layer containing cellulose acetate, it is possible to write with a pencil, an aqueous pen or the like. It is possible and the transportability in the printer is good.

According to the fifth aspect of the present invention, since the image receiving / writing layer contains hydrophilic porous microsilica and cellulose acetate, it can be formed by coating in a small number of steps, and the production cost is low.

According to the sixth aspect of the present invention, since the image receiving / writing layer contains two kinds of hydrophilic porous microsilica having different pore volumes, it is possible to use either a pencil or an aqueous pen. Can be written more clearly.

[Brief description of the drawings]

FIG. 1 is a diagram showing a first embodiment of an image receiving resin sheet according to the present invention.

FIG. 2 is a diagram illustrating a method of using a first embodiment of an image receiving resin sheet according to the present invention.

FIG. 3 is a sectional view showing a second embodiment of the image receiving resin sheet according to the present invention.

FIG. 4 is a sectional view showing a fourth embodiment of the image receiving resin sheet according to the present invention.

[Explanation of symbols]

 Reference Signs List 10 Image receiving resin sheet 11 Resin sheet base material 12 Image receiving / writing layer 12a First layer 12b Second layer 13 Intermediate layer

Claims (6)

[Claims] 1. An image-receiving resin sheet comprising: a resin sheet base; and a layer formed on both front and back surfaces of the resin sheet base, capable of receiving a color material and being capable of receiving an image, and being writable. 2. The image receiving resin sheet according to claim 1, wherein the image receiving and writing layer receives a dye that has been melt-transferred. 3. The image-receiving resin sheet according to claim 1, wherein the image-receiving and writing layer contains hydrophilic porous microsilica. 4. The image receiving resin sheet according to claim 3, wherein the image receiving / writing layer has a first layer containing hydrophilic porous microsilica and a second layer containing cellulose acetate. Image receiving resin sheet. 5. The image receiving resin sheet according to claim 3, wherein the image receiving / writing layer contains hydrophilic porous microsilica and cellulose acetate. 6. The image receiving resin sheet according to claim 3, wherein the image receiving / writing layer has a pore volume of 0.2 to 0.9 ml / g.
With a hydrophilic porous microsilica having a pore volume of 1.2 to
An image receiving resin sheet comprising 3.0 ml / g of hydrophilic porous microsilica.