JP2000280614A - Sheet coated with powdery coating material and its utilization and manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a sheet coated with a powdery coating material formed by coating the dry coating on a base composed of a resin without deforming the base, heat melting and fixing the coating material thereon, particularly manufacture an aqueous ink jet recording material of superior absorbability of an aqueous jet ink having its base composed of a resin, and forming a sharp and high density image as the utilization of the sheet coated with the powdery coating material and also provide a manufacturing method thereof. SOLUTION: An aqueous ink jet recording material with a base composed of a resin and provided with ink acceptive layers thereon fusion bonded one another while having partially spaces in a powdery coating material, and the surfaces of water absorption resin particles and hydrophobic resin particles are coated respectively with hydrophilic inorganic fine particles in the powdery coating material, and the base of the aqueous ink jet recording material is composed of a resin having both of the glass transition temperature and the softening point higher than those of the hydrophobic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder paint coated sheet having a resin coating film obtained by dry-coating a powder coating on a base material made of a resin, melting by heating, and fixing the powder coating. More specifically, the present invention relates to a powder coating sheet which can be suitably used as an aqueous ink jet recording material or a sublimation thermal transfer recording material, and to its production.

In particular, the present invention relates to an aqueous ink jet recording material whose base material is a resin and a method for producing the same.
While having excellent absorbency of aqueous inkjet ink,
The present invention relates to an aqueous inkjet recording material having a base material made of a resin and capable of forming a clear and high-density image, and a method for producing the same.

[0003]

2. Description of the Related Art Conventionally, various recording systems have been known. In recent years, aqueous ink jet recording systems in which aqueous ink is ejected directly from nozzles onto a recording sheet, and is adhered for recording have been widely used. Has reached.

[0004] This aqueous ink jet recording material has conventionally been
In addition to a water-soluble or water-swellable resin, an aqueous coating liquid containing a pigment and other additives is wet-coated on a water-absorbing substrate such as paper, and the aqueous solvent is removed and dried. Forming a layer comprising the resin layer in which the pigment is dispersed as an ink receiving layer, adsorbing the colorant in the ink to the pigment, and absorbing the water in the ink into the resin, An image is formed thereon.

However, when the substrate is made of a hydrophobic resin, such a method causes various problems. That is, the water-soluble or water-swellable resin, pigments, depending on the solvent for the aqueous coating liquid blended with other additives,
It may attack the hydrophobic resin forming the base material. In addition, when the above-mentioned aqueous coating liquid is applied on a substrate made of such a resin, it takes time to form the ink receiving layer because the substrate is unlikely to absorb the aqueous solvent. However, if the coating liquid is applied to a substrate and then heated and dried rapidly, the ink receiving layer will crack. Furthermore, according to the method as described above, the aqueous coating liquid is wet-coated on a substrate,
Because it is dried to form an ink receiving layer,
In removing the solvent, not only environmental considerations are required, but also the manufacturing cost of the ink jet recording material must be increased.

Further, in the ink jet recording material obtained by the conventional method as described above, the surface of the ink receiving layer is generally covered with a continuous resin layer.
Ink-jet inks have low absorptivity and are inferior in dryness of the ink, and therefore, the substrate used is also limited to those having a high water absorption. I have. Further, according to the receiving layer as described above, the coloring property of the ink is not sufficient.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in a powder coating coated sheet as a conventional recording material, particularly, an aqueous ink jet recording material. It is an object of the present invention to provide an aqueous inkjet recording material having a base material of resin, which is excellent in the absorbability of an aqueous inkjet ink and can form a clear and high-density image, and a method for producing the same.

[0008]

According to the present invention, there is provided a powder coating material having a resin coating film formed on a resin base material and having a resin coating film which is mutually fused while a powder coating material has partial voids therebetween. In the body paint coated sheet, the powder paint is formed by coating the surface of resin particles with inorganic fine particles, and the resin forming the base material has both a glass transition temperature and a softening point lower than the resin constituting the powder paint. A powder paint coated sheet characterized by comprising a high resin as a main component is provided.

In particular, according to the present invention, there is provided an aqueous ink jet recording material having an ink receiving layer fused to each other on a base material made of a resin, with a powder coating having partial voids therebetween. The above-mentioned powder coating is obtained by coating the surfaces of the water-absorbent resin particles and the hydrophobic resin particles with hydrophilic inorganic fine particles, respectively, and the resin forming the base material has a glass transition temperature and a softening point higher than the hydrophobic resin. An aqueous ink jet recording material is provided, both of which are made of a high resin.

Further, according to the present invention, there is provided an aqueous ink-jet recording material having an ink-receiving layer formed by fusing with each other on a base material made of a resin, with a powder coating having partially voids therebetween. The powder coating is formed by coating the surfaces of water-absorbent resin particles and hydrophobic resin particles with first inorganic fine particles, respectively, and the resin forming the base material has a glass transition temperature and a softening point lower than those of the hydrophobic resin. Are both made of high resin,
Further, there is provided an aqueous inkjet recording material in which a layer made of hydrophilic second inorganic fine particles is formed on the ink receiving layer.

Further, according to the present invention, there is provided an aqueous ink jet recording material having an ink receiving layer fused to each other on a base material made of a resin while a powder coating material partially has a gap therebetween. The above-mentioned powder coating, while partially exposing the hydrophilic first inorganic fine particles to the surface thereof, covers the hydrophobic resin composition particles contained therein and the surface of the hydrophobic resin composition particles. A water-based ink jet recording material comprising a hydrophilic second inorganic fine particle and a resin constituting the base material having a higher glass transition temperature and a higher softening point than the hydrophobic resin is provided.

Further, according to the present invention, there is provided an aqueous ink-jet recording material having an ink-receiving layer formed by fusing with each other on a base material made of a resin, with a powder coating having partially voids therebetween. The above-mentioned powder coating, while partially exposing the hydrophilic first inorganic fine particles to the surface thereof, covers the hydrophobic resin composition particles contained therein and the surface of the hydrophobic resin composition particles. Consisting of hydrophilic second inorganic fine particles, the resin constituting the base material is made of a resin having a higher glass transition temperature and a higher softening point than the above-mentioned hydrophobic resin, and further,
An ink jet recording material is provided in which a layer composed of hydrophilic third inorganic fine particles is formed on the ink receiving layer.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a resin substrate (hereinafter simply referred to as a substrate resin) is a resin film or sheet or a resin itself such as a molded product. Alternatively, the surface may be a resin, such as a laminate of a resin film and paper, metal, or wood. However, according to the present invention, the base resin needs to be a resin having both a higher glass transition temperature and a higher softening point than the hydrophobic resin described below.

According to the present invention, there is provided a powder coating sheet having a resin coating film formed on a base material made of a resin and having a resin coating film which is mutually fused while having a partial gap between the powder coating materials. The powder coating is obtained by coating the surface of resin particles with inorganic fine particles, and the resin forming the base material has a glass transition temperature and a softening point higher than those of the resin constituting the powder coating as a main component. Powder coating sheet is provided.

[0015] In particular, according to the present invention, as an application of such a powder coating coated sheet, an ink receiving layer formed by fusing the powder coating to each other while having a partial gap therebetween is used. In an aqueous inkjet recording material having a base material made of a resin, the powder coating is obtained by coating the surfaces of water-absorbent resin particles and hydrophobic resin particles with hydrophilic inorganic fine particles, respectively, and the resin forming the base material is An aqueous inkjet recording material comprising a resin having both a higher glass transition temperature and a higher softening point than the hydrophobic resin is provided.

In the present invention, the main component or the main component refers to a component occupying 50% by weight or more of the component.

First, a preferred embodiment of the first aqueous inkjet recording material according to the present invention will be described. This first
The aqueous inkjet recording material of the above, wherein the powder coating material has an ink receiving layer formed by fusing each other on a base material made of a resin, while the powder coating partially has a gap therebetween, The coating is such that the surfaces of the water-absorbent resin particles and the hydrophobic resin particles are each coated with hydrophilic first inorganic fine particles, and the resin forming the base material has a glass transition temperature and a softening point lower than those of the hydrophobic resin. Both are made of high resin.

The powder coating used for producing such a first aqueous ink jet recording material has an average particle size of 0.1 to 50 μm.
Water-absorbing resin particles and hydrophobic resin particles having an average particle size of 1 nm
To 5 μm of the first inorganic fine particles, and the respective surfaces are coated with the first inorganic fine particles. According to the present invention, the hydrophobic resin is a resin having both a lower glass transition temperature and a lower softening point than the base resin.

The above-mentioned water-absorbing resin is not particularly limited in a polymer material constituting the water-absorbing resin, but is preferably a chemically cross-linkable water-absorbing resin, and the water absorption of deionized water per unit weight of the resin. Amount is 100-100
Those in the range of 0 g / g are preferable, and particularly, 300 to
Those in the range of 1000 g / g are preferred. Examples of such a water-absorbing resin include a crosslinked product of polyacrylic acid partial sodium salt (for example, Aqualic (registered trademark) CA manufactured by Nippon Shokubai Co., Ltd., Sun Fresh ST-500MPS manufactured by Sanyo Chemical Industry Co., Ltd.), and the like. , Starch / acrylic acid graft polymer partial sodium salt (for example, Sanfresh ST-500S or 100 manufactured by Sanyo Chemical Industries, Ltd.)
Can be mentioned.

In addition, a crosslinked isobutylene-sodium maleate copolymer, a crosslinked styrene-sodium maleate copolymer, a starch-sodium polyacrylate grafted product, a saponified starch-polyacrylonitrile grafted product, cellulose-polystyrene Examples thereof include a grafted product of sodium acrylate and a vinyl alcohol-sodium (meth) acrylate copolymer. Commercially available products can be obtained for such a chemically crosslinked type water absorbent resin.

However, in the present invention, the water-absorbing resin particles are formed into a powder coating together with the hydrophobic resin particles, and the powder coating is dry-coated on a base material.
It is preferably in the range of 50 μm, especially 0.5 to 30 μm.
It is preferably in the range of μm. If the average particle size exceeds 50 μm, uneven coating may occur when dry-coated on a substrate. In particular, in the present invention, the water-absorbent resin preferably has an average particle size in the range of 1 to 20 µm.

Further, according to the present invention, the water-absorbent resin is dry-coated on the substrate, and then heated together with the hydrophobic resin particles,
The softening point is 70-100 for fusing together.
It is preferably in the range of ° C. When the softening point is lower than 70 ° C., it is easy to coagulate at room temperature and it is difficult to perform dry coating. However, when the softening point exceeds 100 ° C., it is not preferable because it is difficult to fuse them together.

According to the present invention, the hydrophobic resin has a lower glass transition temperature and a lower softening point than the base resin, and the deionized water absorption is 0.1 times or less of its own weight.
In particular, various types can be used without limitation. Examples of such a hydrophobic resin include a saturated polyester resin, a styrene-acryl copolymer resin, an ethylene-vinyl acetate copolymer resin, a styrene-butadiene copolymer resin, and the like.

Commercial products can be suitably used as the saturated polyester resin. Such commercial products include, for example, Byron 103, 200, 290, 600
(Manufactured by Toyobo Co., Ltd.), KA-1038C (manufactured by Arakawa Chemical Co., Ltd.), TP-220, 235 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Diacron ER-101, ER-50
1, FC-172, FC-344, FC-714 (manufactured by Mitsubishi Rayon Co., Ltd.), Tufton NE-382, 111
0, 2155 (manufactured by Kao Corporation) and the like.

The styrene-acrylic copolymer resin is a copolymer of styrene and (meth) acrylic acid ester. Specifically, the (meth) acrylic acid ester includes, for example, ethyl acrylate and butyl acrylate. , Methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

As such a styrene-acrylic copolymer resin, various commercially available products can be suitably used. Commercially available products include, for example, Hymer UNI-3000, TB
-1800, TBH-1500 (Sanyo Chemical Industry Co., Ltd.)
CPR-100, 600B, 200, 300, X
PA4799, 4800 (manufactured by Mitsui Chemicals, Inc.) and the like.

Therefore, in the present invention, the base resin is
The resin may be thermoplastic or thermosetting, and examples thereof include polyethylene terephthalate resin, polyethylene naphthylate resin, polyvinyl chloride resin, polycarbonate resin, acrylic resin, and phenol resin.
If necessary, the surface of the resin substrate may be subjected to a corona discharge treatment or a primer treatment in order to enhance the adhesiveness with the powder coating forming the ink receiving layer.

According to the present invention, the hydrophobic resin is melt-kneaded, if necessary, with a colorant or an anti-offset agent, cooled, pulverized, and then classified to obtain a desired average particle size. You can have it.

The colorant is preferably a white colorant. For example, titanium oxide is preferably used, but is not limited thereto. The colorant gives the substrate the required ground color. The white colorant gives the substrate a white ground color. The colorant is usually 1 to 50 with respect to the hydrophobic resin.
%, Preferably in the range of 5 to 40% by weight.

As will be described later, the anti-offset agent is obtained by dry-coating a powder coating material on a substrate, and then heating and partially melting the coating material to form a gap therebetween. It is blended with the hydrophobic resin so as not to cause offset when forming the ink receiving layer which is fused. As the anti-offset agent, usually, various waxes having a melting point in the range of 50 to 150 ° C. are preferably used. In particular,
Examples thereof include paraffin wax, polyolefin wax such as polyethylene and polypropylene, fatty acid metal salts, fatty acid esters, higher fatty acids, higher alcohols, and the like. Such an anti-offset agent is usually
0.1 to 20% by weight based on the hydrophobic resin, preferably
It is used in the range of 0.5 to 10% by weight.

As described above, in order to form a hydrophobic resin into which a coloring agent or an anti-offset agent is blended as necessary, particles are mixed with the hydrophobic resin and the coloring agent or the anti-offset agent, usually at 100 to 200 ° C. It can be obtained by melt-kneading at about the temperature, cooling, pulverizing and classifying. According to the present invention, such hydrophobic resin particles are not particularly limited, but preferably have an average particle size close to the water-absorbing resin particles used together, usually 0.1 to 0.1.
The particles are classified so as to have an average particle size of 50 μm, preferably 0.5 to 20 μm.

Further, according to the present invention, after the hydrophobic resin is dry-coated on the substrate, it is heated together with the water-absorbing resin particles,
The softening point is 70-120 for fusing together.
It is preferably in the range of ° C. When the softening point is lower than 70 ° C., it is easy to coagulate at room temperature and it is difficult to perform dry coating. However, when the softening point exceeds 120 ° C., it is difficult to fuse them together and it is difficult to fix them to the substrate, which is not preferable.

According to the present invention, the surfaces of the water-absorbent resin particles and the hydrophobic resin particles are each coated with hydrophilic first inorganic fine particles to form a powder coating, which is then dry-coated on a resin substrate. Then, by heating, an ink receiving layer is formed on the resin base material in which the powder coating material is fused to each other while having a partial gap therebetween.

The hydrophilic first inorganic fine particles include, for example, silica, alumina, calcium carbonate,
Fine particles of titanium oxide or the like are preferably used, and such hydrophilic first inorganic fine particles are formed of water-absorbing resin particles so that the surfaces of the water-absorbing resin particles and the hydrophobic resin particles can be sufficiently coated. It is desirable that the average particle diameter of the resin particles is sufficiently smaller than the average particle diameter of each of the hydrophobic resin particles. In view of this point, those having an average particle diameter of 5 μm or less, preferably 1 nm to 1 μm are preferably used. Also,
The hydrophilic first inorganic fine particles may be about 1/3 of the average particle diameter of the water-absorbing resin particles or the hydrophobic resin particles, but are preferably 1/10 or less, particularly preferably 1/100 or less.
It is as follows.

Such hydrophilic first inorganic fine particles include:
Commercial products can be easily obtained. Specific examples of commercially available products include, for example, Aerosil (registered trademark) 50, 90G, 13 which is anhydrous silica manufactured by Nippon Aerosil Co., Ltd.
0, 200, 200V, 200CF, 200FAD, 3
00, 300CF, 380, OX50, TT600, M
OX80, MOX170, COK84, etc., aluminum oxide C, titanium dioxide P25, etc., Carplex (registered trademark) silica FPS-2, FPS, manufactured by Shionogi & Co., Ltd.
-3, FPS-4, FPS-5, FPS-101, CS
-5, CS-7, BS-304F, BS-304N, etc.
Further, anhydrous silica S13 manufactured by Clariant Japan,
V15, N20, T30, T40, Callite KT which is calcium carbonate manufactured by Shiraishi Industry Co., Ltd., and the like.

According to the present invention, such a hydrophilic first
The inorganic fine particles are used in an amount of 3 to 12 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the total amount of the water-absorbing resin particles and the hydrophobic resin particles. That is, 3 to 12 parts by weight of the hydrophilic first inorganic fine particles are mixed with 100 parts by weight of the total amount of the water-absorbing resin particles and the hydrophobic resin particles, and the surfaces of the respective particles are coated. Dry coating is applied to the resin base material and heated to partially melt the powder coating, so that the powder coating can be mutually melted while having partial voids between them. Let me wear
A resin layer having a gap between each other is formed on a resin substrate as an ink receiving layer.

In the present invention, the thickness of such an ink receiving layer is usually in the range of 2 to 80 μm, preferably in the range of 5 to 50 μm. According to the present invention,
As described above, since the water-absorbing resin particles and the hydrophobic resin particles whose surfaces are coated with the hydrophilic first inorganic fine particles form the ink receiving layer, the surface of the receiving layer also has the hydrophilic first inorganic fine particles. Coated with inorganic fine particles.

Therefore, when the amount of the hydrophilic first inorganic fine particles is less than 3 parts by weight based on 100 parts by weight of the total amount of the water-absorbing resin particles and the hydrophobic resin particles, the surface of each of the resin particles is hydrophilic. The surface of the ink receiving layer is not sufficiently covered by the first inorganic fine particles having a hydrophilic property.
Is not sufficiently coated with the inorganic fine particles, the obtained ink jet recording material has insufficient color developability and cannot form a clear and high-density image. On the other hand, hydrophilic first inorganic fine particles are composed of water-absorbent resin particles and hydrophobic resin particles 10.
When more than 12 parts by weight relative to 0 parts by weight,
It is difficult for the hydrophobic resin particles to come into direct contact with the resin base material, and even when such a powder coating is heated, it is difficult to sufficiently fix the resin coating to the resin base material. Inhibits adhesion.

Further, according to the present invention, the ratio of the water-absorbent resin to the hydrophobic resin is preferably in the range of 5 to 50% by weight of the water-absorbent resin and 95 to 50% by weight of the hydrophobic resin. When the proportion of the water-absorbent resin particles is less than 5% by weight, the ink receiving layer does not have sufficient water absorbency and the ink absorbency is not sufficient. On the other hand, the ratio of the water-absorbing resin particles is 50% by weight.
If the amount is larger than the above, there is a possibility that when the ink adheres to the ink receiving layer, the ink receiving layer swells, then dries and shrinks, and the surface (and thus the image) cracks.

According to the present invention, when the ratio of the water-absorbing resin to the hydrophobic resin is within the above range, when the ink adheres to the ink receiving layer, the ink, particularly
Immediately absorbs moisture to ensure the absorbability of the inkjet ink and minimizes swelling at that time, thus minimizing shrinkage when dried, effectively preventing cracks in the image. Can be prevented.

According to the present invention, a layer composed of hydrophilic second inorganic fine particles can be provided on such an ink receiving layer. The hydrophilic second inorganic fine particles may be the same as or different from the first hydrophilic inorganic fine particles for coating the water-absorbent resin and the hydrophobic resin, respectively, to obtain a powder coating, and accordingly, As the hydrophilic second inorganic fine particles, for example, silica, alumina, calcium carbonate,
Fine particles such as titanium oxide can be used. Such hydrophilic second inorganic fine particles have an average particle size of 1 nm.
To 1 μm, preferably 1 nm to 50 nm. The most preferred hydrophilic second inorganic fine particles have an average particle diameter in the range of 5 to 30 nm.

As described above, the ink jet recording sheet provided with the ink receiving layer having such a two-layer structure covers the water-absorbent resin particles and the hydrophobic resin particles with the first hydrophilic inorganic fine particles, respectively. The resulting powder coating is dry-coated on a resin substrate, heated and fixed to form a powder coating layer, and then a hydrophilic second coating is formed on the powder coating layer.
The inorganic fine particles are dry-coated and heated under pressure to fix the layer composed of the hydrophilic second inorganic fine particles on the powder coating layer, and thus the powder coating is formed on the resin substrate. By forming an ink receiving layer that is fused to each other while partially forming a gap therebetween, and by forming a layer made of the hydrophilic second inorganic fine particles on the ink receiving layer, Obtainable.

However, according to the present invention, if necessary,
A powder coating obtained by coating each of the water-absorbent resin particles and the hydrophobic resin particles with the first hydrophilic inorganic fine particles is dry-coated on a resin substrate to form a powder coating layer. Dry-coating of hydrophilic second inorganic fine particles on the powder coating layer to form a layer made of hydrophilic second inorganic fine particles, and then of the above hydrophilic second inorganic fine particles The powder coating layer having a layer thereon is heated under pressure, thus forming an ink receiving layer that is fused together on the substrate while the powder coating has a partial gap therebetween. It can also be obtained by forming a layer made of the hydrophilic second inorganic fine particles on the ink receiving layer.

The average particle diameter of the hydrophilic second inorganic fine particles is 1
When larger than μm, when inkjet recording is performed on a recording sheet having such a layer of inorganic fine particles on the surface, an obtained image may lack accuracy, and an inkjet recording material that gives a high quality image may be used. I can't get it. On the other hand, the hydrophilic second inorganic fine particles may have an average particle diameter smaller than 1 nm, but it is sufficient to use those having an average particle diameter of 1 nm or more from the viewpoint of availability.

According to the present invention, the thickness of the layer composed of the hydrophilic second inorganic fine particles is usually in the range of 10 nm to 10 μm, and particularly preferably in the range of 20 nm to 5 μm. According to the present invention, when the layer made of the second hydrophilic inorganic fine particles is formed on the receiving layer, the powder coating for forming the receiving layer includes the water-absorbing resin particles and The surface of 100 parts by weight of the total amount of the hydrophobic resin particles may be coated with 3 to 12 parts by weight, preferably 5 to 10 parts by weight of hydrophobic inorganic fine particles. Further, the powder coating for forming the receiving layer, the surface of 100 parts by weight of the total amount of the water-absorbent resin particles and the hydrophobic resin particles, the first hydrophilic inorganic fine particles and the hydrophobic inorganic fine particles. 3 to 12 parts by weight, preferably 5-1
It may be coated with 0 parts by weight.

According to such an ink-jet recording material, when the ink-jet ink adheres to the ink, the colorant in the ink is captured by the hydrophilic second inorganic fine particles, so that a clear and high-density image is obtained. On the other hand, the water in the ink is quickly filtered by the hydrophilic second inorganic fine particles, penetrates into the receiving layer, is quickly absorbed into the gap between the powder coatings, and When the water-absorbent resin particles and the hydrophobic resin particles are coated with the hydrophilic first inorganic fine particles, they are adsorbed to the first inorganic fine particles.

Such hydrophobic inorganic fine particles should also be sufficiently smaller than the average particle size of each of the resin particles so that the surfaces of the water-absorbent resin particles and the hydrophobic resin particles can be sufficiently covered. Is desirable, and considering this point,
Usually, the average particle size is 5 μm or less, preferably 1 nm to
Those having a thickness of 1 μm are preferably used. The hydrophobic inorganic fine particles may be about 1/3 of the average particle diameter of each of the water-absorbent resin particles and the hydrophobic resin particles, but are preferably 1/10 or less, and particularly preferably 1/100 or less. .

Such a hydrophobic inorganic fine particle can be easily obtained as a commercial product. Specific examples of commercially available products include, for example, Aerosil (registered trademark) R972, R972V, and R97, which are anhydrous silicas of Nippon Aerosil Co., Ltd.
2CF, R974, R202, R805, R812S,
Titanium dioxide T805, RX200, RY200, etc.,
Anhydrous silica H15, H2 manufactured by Clariant Japan
0, H30, H2000, H2000 / 4, H300
4, H2015EP, H2050EP and the like.

FIG. 1 schematically shows a cross section of an embodiment of the ink jet recording sheet according to the present invention. The surface of each of the water-absorbent resin particles 11a and the hydrophobic resin particles 11b is coated with the hydrophilic first inorganic fine particles 12 to form a powder coating 13, and these powder coatings are
The ink receiving layer 16 is formed by being fused to each other and partially fixed on the resin base material 15 while partially having a gap 14 therebetween.

FIG. 2 schematically shows a cross section of another embodiment of the ink jet recording sheet according to the present invention. As in the embodiment shown in FIG. 1, the powder coating material 23 is formed by covering the respective surfaces of the individual water-absorbent resin particles 21a and the hydrophobic resin particles 21b with the first hydrophilic inorganic fine particles 22. The particles of the powder coating are mutually fused and fixed on the resin base material 25 while partially forming the gaps 24 therebetween, thereby forming the ink receiving layer 26. In this embodiment, a layer 28 made of second inorganic fine particles 27 is further formed on the ink receiving layer 26, and the ink receiving layer has a two-layer structure.

In the present invention, dry coating of a powder coating on a substrate can be performed, for example, by electrostatic coating such as electrostatic spraying or electrostatic immersion, spraying, spray coating, dispersion, or the like. Powder coating method such as powder fusion lamination method, dusting method, cascade method, magnetic brush development method, powder cloud method, open chamber method, liquid development method, fur development method, printing development method, development method by electrostatic induction, etc. An electrophotographic method can be used.

However, among these dry coatings, in the present invention, for example, the electrostatic spray method can be preferably used. This electrostatic spraying method is a kind of powder coating. Specifically, the powder paint is conveyed to the tip of the spray gun by air, and a negative electrode is attached to a needle electrode incorporated in the tip of the spray gun. High voltage (for example, -50 to
-90 kV) to negatively charge the powder coating,
On the other hand, along with the grounded electrode on the back of the substrate, thus,
An electric field existing between the spray gun and the grounded electrode carries the negatively charged powder coating material to the base material and electrostatically attaches it.

Next, a preferred embodiment of the second aqueous ink jet recording material according to the present invention will be described. This second
The aqueous inkjet recording material of the above, wherein the powder coating material has an ink receiving layer formed by fusing each other on a base material made of a resin, while the powder coating partially has a gap therebetween, The coating contains a part of the hydrophilic first inorganic fine particles having an average particle diameter of 1 μm to 5 μm and exposes the surface to the surface thereof, and contains the hydrophobic resin composition particles having an average particle diameter of 5 to 30 μm; A hydrophilic second inorganic fine particle having an average particle diameter of 1 nm to 1 μm covering the surface of the hydrophilic resin composition particles, wherein the resin forming the base material has a glass transition temperature and a softening point higher than the hydrophobic resin. Are both made of high resin.

The powder coating used for producing such a second aqueous ink jet recording material is composed of a hydrophobic resin and an average particle diameter of 1: 1.
Melt and knead with hydrophilic first inorganic fine particles of 5 μm to 5 μm, pulverized to have an average particle size of 5 to 30 μm,
A part of the hydrophilic first inorganic fine particles is exposed to the surface of the hydrophobic resin particles, and the resulting hydrophobic resin composition particles are used as the hydrophobic resin composition particles. It can be obtained by mixing with the second inorganic fine particles and coating the surface of the hydrophobic resin composition particles with the hydrophilic second inorganic fine particles.

According to the present invention, the hydrophobic resin has a lower glass transition temperature and a lower softening point than the base resin, and the deionized water absorption is 0.1 times or less of its own weight.
In particular, various types can be used without limitation. Examples of such a hydrophobic resin include a saturated polyester resin, a styrene-acryl copolymer resin, an ethylene-vinyl acetate copolymer resin, a styrene-butadiene copolymer resin, and the like.

The hydrophilic first inorganic fine particles used in the second aqueous inkjet recording material according to the present invention are:
The average particle diameter is in the range of 1 μm to 5 μm, and a commercially available product can be suitably used. Examples of such commercially available products include silica such as Carplex manufactured by Shionogi & Co., Ltd., Mizukasil manufactured by Mizusawa Chemical Industry Co., Ltd., and Fine Seal X-37, 40, 70, 80 manufactured by Tokuyama Corporation. ED-I, ED-III, E manufactured by Yonesho Lime Industry Co., Ltd.
DV, calcium carbonate such as Callite KT manufactured by Shiraishi Calcium Co., Ltd., and the like.

According to the present invention, such a hydrophilic first
5-30% by weight of the inorganic fine particles based on the hydrophobic resin
These are melt-kneaded, cooled, and then pulverized to have an average particle size of 5 to 30 μm, whereby a part of the hydrophilic first inorganic fine particles is converted to hydrophobic resin particles. The hydrophobic resin composition particles dispersed and contained in the hydrophobic resin particles while being exposed on the surface of the resin can be obtained.

According to the present invention, the hydrophobic resin and the hydrophilic first inorganic fine particles having an average particle diameter in the range of 1 μm to 5 μm are melt-kneaded, cooled, and then cooled to an average particle diameter of 5 to 3 μm.
When crushed to have a particle size of 0 μm, the hydrophilic first
Since the inorganic fine particles of the above have a large average particle size, the kneaded material is cracked mainly at the interface between the hydrophobic resin and the inorganic fine particles, and the inorganic fine particles having such a large particle size are formed on the surface of the hydrophobic resin particles. Part, exposed hydrophobic resin composition particles can be obtained. When the average particle diameter of the hydrophilic first inorganic fine particles is smaller than 1 μm, the kneaded material is uniformly dispersed and contained in the hydrophobic resin particles, and the kneaded material is hardly cracked at the interface. On the other hand, when the average particle diameter of the hydrophilic first inorganic fine particles is larger than 5 μm, the inorganic fine particles are present as independent particles together with the hydrophobic resin composition particles. When dry coating is performed on a base material and heated for fixing, there is a concern that good fixing may be impaired.

As described above, according to the present invention, the hydrophobic resin and the hydrophilic first inorganic fine particles having an average particle size of 1 μm to 5 μm are melt-kneaded, cooled, and pulverized so as to have an average particle size of 5 to 30 μm. By dispersing the inorganic fine particles in hydrophobic resin particles, by containing, the inorganic fine particles,
Some are exposed on the surface of the hydrophobic resin particles, and thus,
By imparting hydrophilicity to the hydrophobic resin particles, it is possible to impart ink absorption and color development to the ink receiving layer formed therefrom.

According to the present invention, as described above, an appropriate amount of a colorant or an anti-offset agent is added to the hydrophobic resin composition particles.
You may mix.

The powder coating used for the production of the second aqueous ink jet recording material according to the present invention generally comprises a hydrophobic resin and hydrophilic first inorganic fine particles having an average particle diameter of 1 μm to 5 μm. After being melt-kneaded at a temperature of about 100 to 200 ° C., cooled, and then pulverized so as to have an average particle diameter of 5 to 30 μm to obtain hydrophobic resin composition particles. It can be obtained by mixing with the hydrophilic second inorganic fine particles and coating the surface of the hydrophobic resin composition particles with the hydrophilic second inorganic fine particles.

The average particle diameter of the hydrophilic second inorganic fine particles is 1
When it is larger than μm, even if such inorganic fine particles are mixed with the hydrophobic resin composition particles and the surface of the hydrophobic resin composition particles is coated, the hydrophobic resin composition particles can be uniformly coated. It is difficult to increase the proportion of the surface not covered with the hydrophilic second inorganic fine particles. As a result, the hydrophobic resin composition particles do not have sufficient hydrophilicity. It is difficult to form an ink receiving layer having excellent ink absorbency and color development.

Such hydrophilic second inorganic fine particles include:
Commercial products can be easily obtained. Specific examples of commercially available products include, for example, Aerosil (registered trademark) 50, 90G, 13 which is anhydrous silica manufactured by Nippon Aerosil Co., Ltd.
0, 200, 200V, 200CF, 200FAD, 3
00, 300CF, 380, OX50, TT600, M
OX80, MOX170, COK84, etc., aluminum oxide C, titanium dioxide P25, etc., anhydrous silica S13, V15, N20, T30 manufactured by Clariant Japan,
T40 and the like can be mentioned.

According to the present invention, such a hydrophilic second
The inorganic fine particles are used in an amount of 3 to 12 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the hydrophobic resin composition particles. That is, the hydrophobic resin composition particles 10
The second inorganic fine particles having a hydrophilic content of 3 to 12 relative to 0 parts by weight.
By weight, the surface of the hydrophobic resin composition particles is coated, and this is used as a powder coating, and is dry-coated on a resin substrate and heated to partially melt the powder coating. By doing so, the powder coatings are mutually fused while having a gap therebetween, and a resin layer having a gap between them is formed on a resin base material as an ink receiving layer. The voids between the powder coatings are usually between 1 nm and 200 nm.
Range. In the present invention, the thickness of such an ink receiving layer is usually in the range of 2 to 80 μm, preferably in the range of 5 to 50 μm.

According to the present invention, while the first hydrophilic fine inorganic particles are partially exposed on the surface, dispersion,
To form a hydrophobic resin composition particle, and a powder coating obtained by coating the surface of the hydrophobic resin composition particle with hydrophilic second inorganic fine particles forms an ink receiving layer. The surface of the ink receiving layer also has the hydrophilic first property.
And second inorganic fine particles.

Therefore, when the amount of the hydrophilic second inorganic fine particles is less than 3 parts by weight with respect to 100 parts by weight of the hydrophobic resin composition particles, the surface of the hydrophobic resin composition particles becomes hydrophilic. And the surface of the ink receiving layer is also not sufficiently coated with the hydrophilic inorganic fine particles, so that the obtained ink jet recording material has insufficient color developability, and provides a clear and high-density image. Cannot be formed. On the other hand, when the hydrophilic second inorganic fine particles are more than 12 parts by weight based on 100 parts by weight of the hydrophobic resin composition particles, particularly, the hydrophobic resin composition particles are less likely to directly contact the base material, Even if such a powder coating is heated, it is difficult to sufficiently fix it to the substrate.

According to the second aqueous ink jet recording material of the present invention, a layer composed of hydrophilic third inorganic fine particles can be provided on such an ink receiving layer. As the hydrophilic third inorganic fine particles, usually, the same as the hydrophilic second inorganic fine particles used in the production of the second aqueous inkjet recording material are used,
The type does not need to be the same as the hydrophilic second inorganic fine particles. Accordingly, the hydrophilic third inorganic fine particles may have an average particle diameter in the range of 1 nm to 1 μm, but preferably have an average particle diameter in the range of 1 nm to 50 nm.
Most preferably, the average particle size is in the range of 5 to 30 nm.

The ink jet recording sheet provided with such an ink receiving layer having a two-layer structure is prepared by dry-coating the powder coating on a resin substrate as described above,
Is fixed to form a powder coating layer, and then the hydrophilic third inorganic fine particles are dry-coated on the powder coating layer, and heated under pressure to form a hydrophilic third inorganic fine particle. A layer composed of inorganic fine particles is fixed on the powder coating layer, thus forming an ink receiving layer formed by fusing each other on the resin substrate while the powder coating partially has a gap therebetween. It can be obtained by forming a layer composed of the hydrophilic third inorganic fine particles on the ink receiving layer.

However, according to the present invention, if necessary,
The powder coating is dry-coated on a resin substrate to form a powder coating layer, and then a hydrophilic third coating is formed on the powder coating layer.
Is applied by dry coating to form a layer made of hydrophilic third inorganic fine particles, and then a powder coating layer having a layer made of the hydrophilic third inorganic fine particles thereon is added. Heating under pressure, thus forming an ink receiving layer that is fused to each other on the base material while the powder coating material has a partial gap therebetween, and the It can also be obtained by forming a layer composed of hydrophilic third inorganic fine particles.

The third hydrophilic inorganic fine particles have an average particle size of 1
When larger than μm, when inkjet recording is performed on a recording sheet having such a layer of inorganic fine particles on the surface, an obtained image may lack accuracy, and an inkjet recording sheet that gives a high quality image may be obtained. I can't get it. On the other hand, the hydrophilic third inorganic fine particles may have an average particle size smaller than 1 nm, but it is sufficient to use those having an average particle size of 1 nm or more from the viewpoint of availability.

As described above, in the ink jet recording sheet having the layer composed of the hydrophilic third inorganic fine particles on the receiving layer, when the ink jet ink adheres to the ink jet recording sheet, the colorant in the ink becomes Since it is captured by the layer of the third inorganic fine particles, a clear and high-density image is formed. On the other hand, the water in the ink is quickly filtered by the layer of the hydrophilic third inorganic fine particles to form a receiving layer. It penetrates into it and is quickly adsorbed by the voids between the powder coatings, and is also adsorbed by the hydrophilic inorganic fine particles on its surface.

According to the present invention, the thickness of the layer composed of the hydrophilic third inorganic fine particles is usually in the range of 10 nm to 10 μm, particularly preferably in the range of 20 nm to 5 μm.

According to the present invention, when a layer composed of hydrophilic third inorganic fine particles is formed on the receiving layer, the powder coating for forming the receiving layer is formed of the above-mentioned average particle size. The surface of 100 parts by weight of the hydrophobic resin composition particles having a diameter of 5 to 20 μm may be coated with 3 to 12 parts by weight, preferably 5 to 10 parts by weight of hydrophobic inorganic fine particles. Further, the powder coating for forming the receiving layer, the surface of 100 parts by weight of the hydrophobic resin composition particles having an average particle size of 5 to 20 μm, the second hydrophilic inorganic fine particles and the hydrophobic inorganic fine particles 3 to 12 parts by weight of the mixture, preferably 5 to 1
It may be coated with 0 parts by weight.

According to such an ink jet recording sheet, when the ink jet ink adheres to the sheet, the colorant in the ink is captured by the layer of the hydrophilic third inorganic fine particles. On the other hand, the water in the ink is quickly filtered by the layer of the hydrophilic third inorganic fine particles, penetrates into the receiving layer, and is quickly adsorbed in the gap between the powder coatings. When the hydrophobic resin composition particles have hydrophilic inorganic fine particles on their surfaces, they are adsorbed to the particles.

The hydrophobic inorganic fine particles are also desirably sufficiently smaller than the average particle diameter of the hydrophobic resin composition particles so that the surface of the hydrophobic resin composition particles can be sufficiently covered. Considering this point, usually, those having an average particle size of 5 μm or less, preferably 1 nm to 1 μm are preferably used. The hydrophobic inorganic fine particles may be about １ ／ of the average particle diameter of the hydrophobic resin composition particles,
Preferably it is 1/10 or less, particularly preferably 1
/ 100 or less.

Commercially available products can also be suitably used for such hydrophobic inorganic fine particles. Examples of such commercially available products include, for example, Aerosil (registered trademark) R972, R972V, and R97, which are anhydrous silicas of Nippon Aerosil Co., Ltd.
2CF, R974, R202, R805, R812S,
Titanium dioxide T805, RX200, RY200, etc.,
Anhydrous silica H15, H2 manufactured by Clariant Japan
0, H30, H2000, H2000 / 4, H300
4, H2015EP, H2050EP and the like.

The powder coating sheet according to the present invention can be suitably used as a sublimation type thermal transfer recording material. That is, the average particle size of the hydrophobic resin is 0.1 to 30 μm.
A powder coating obtained by coating the surface of the resin particles of the above with hydrophobic inorganic fine particles having an average particle diameter of 5 μm or less, preferably 1 nm to 1 μm, dry-coating on a resin substrate, heating and melting and fixing. Thus, it is possible to obtain a sublimation thermal transfer recording material having, as an ink receiving layer, a resin coating film formed by fusing the powder coating materials to each other with a partial gap therebetween. Here, according to the present invention, a resin having a higher glass transition temperature and a higher softening point than the hydrophobic resin is used as the resin forming the base material.

A colorant, an anti-offset agent, and other appropriate additives may be added to the resin particles in advance to have a required average particle size. Further, the hydrophobic inorganic fine particles, based on 100 parts by weight of such resin particles,
Usually, it is used in the range of 3 to 12 parts by weight, preferably 5 to 10 parts by weight.

An ink sheet having information on a sublimable dye is superimposed on such a sublimable thermal transfer recording material, and the sublimable dye is sublimated by heating the ink sheet. The ink receiving layer is diffused and absorbed, forming not only a high-density thermal transfer image on the recording material in accordance with the information but also the hydrophobic inorganic fine particles covering the surface of the resin particles. On the other hand, it has a high release property.

Further, according to the present invention, on such an ink receiving layer, in the same manner as described above, it is composed of hydrophobic inorganic fine particles having an average particle diameter of 1 nm to 1 μm, preferably 1 to 50 nm. By providing a layer, the ink sheet has higher releasability.

[0081]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 (Preparation of Powder Coating) 80 parts by weight of styrene / acrylic copolymer resin (Hymer UNI-3000 manufactured by Sanyo Chemical Industries, Ltd., glass transition temperature 58 ° C., softening point 98 ° C.) and titanium oxide Pigment (Taipage A220 manufactured by Ishihara Sangyo Co., Ltd.) 2
0 parts by weight are melt-kneaded, cooled, pulverized and classified,
Hydrophobic resin particles having an average particle size of 11.0 μm were prepared.

85 parts by weight of the hydrophobic resin particles and 15 parts by weight of water-absorbing resin particles having an average particle size of 10 μm (Aqualic CA ML10 manufactured by Nippon Shokubai Co., Ltd., water absorption 300 to 400 g / g, softening point 89 ° C.) 5 parts by weight of hydrophilic silica fine particles (200 manufactured by Nippon Aerosil Co., Ltd., average particle size: 12 nm) were mixed and stirred to prepare a powder coating.

(Preparation of Inkjet Recording Material) Polycarbonate resin subjected to corona discharge treatment (glass transition temperature 15
(0 ° C., softening point: 220 to 230 ° C.) The above-mentioned powder coating is sprayed onto the entire surface of the film using a commercially available electrostatic spraying device and adhered, and then heated to about 80 to 100 ° C. under pressure. The powder coating was fixed on the substrate at the same time as the powder coating particles were partially fused to each other to form a 20 μm thick resin layer having voids between the particles as an ink receiving layer. The ink jet recording material thus obtained was evaluated for the ink jet recording characteristics and the presence or absence of deformation of the base material as follows.

(Inkjet Recording Characteristics) Using a commercially available inkjet printer (Epson PM-750C), inkjet recording was performed on the above inkjet recording material, and the ink absorbency and color development were examined. Immediately after ink jet recording of the color chart prescribed by the Japan Standards Association on recording paper, the dryness of the ink was touched with the fingertip on the image, and when the ink did not adhere to the fingertip, it was evaluated as ○, and the ink partially adhered to the fingertip The time was indicated by x. The color developability of the ink was determined by measuring the darkest part of the color chart with a Macbeth densitometer, and was evaluated as ◎ when yellow 1.2 or more, magenta 1.0 or more, and cyan 0.6 or more, and yellow 1.0 or more. ~ 1.2,
○ for magenta 0.9-1.0, cyan 0.5-0.6, yellow 0.8-1.0, magenta 0.8-0.9, cyan 0.4-
When the value was 0.5, the result was Δ, and when the value was yellow 0.8 or less, magenta 0.8 or less, and cyan 0.4 or less, the result was x.

(Deformation of Base Material) The deformation was visually inspected.

Table 1 shows the results.

Example 2 (Preparation of Powder Coating) 80 parts by weight of styrene-acrylic copolymer resin (Hymer UNI-3000 manufactured by Sanyo Chemical Industries, Ltd., glass transition temperature 58 ° C., softening point 98 ° C.) and titanium oxide Pigment (Taipage A220 manufactured by Ishihara Sangyo Co., Ltd.) 2
0 parts by weight are melt-kneaded, cooled, pulverized and classified,
Hydrophobic resin particles having an average particle size of 11.0 μm were prepared.

85 parts by weight of the hydrophobic resin particles and 15 parts by weight of water-absorbing resin particles having an average particle size of 10 μm (Aqualic CA ML10 manufactured by Nippon Shokubai Co., Ltd., water absorption 300 to 400 g / g, softening point 89 ° C.) 5 parts by weight of hydrophobic silica fine particles (R972, manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) were mixed and stirred to prepare a powder coating.

(Preparation of Inkjet Recording Material) Example 1
In the same manner as in the above, an ink receiving layer having a thickness of 20 μm having voids between the particles was formed on the same polycarbonate resin film as in Example 1, and hydrophilic silica fine particles (200 manufactured by Nippon Aerosil Co., Ltd.) were formed on the ink receiving layer. , Average particle size 1
2 nm) using a commercially available electrostatic spray device,
After attaching, heat under pressure to about 80-100 ° C,
A layer of the hydrophilic silica having a thickness of 3 μm was fixed on the ink receiving layer to prepare an ink jet recording material. With respect to this ink jet recording material, the ink jet recording characteristics and the presence or absence of deformation of the substrate were examined in the same manner as in Example 1. Table 1 shows the results.

Example 3 (Preparation of Powder Coating) 80 parts by weight of styrene / acrylic copolymer resin (Hymer SBM100 manufactured by Sanyo Chemical Industries, Ltd., glass transition temperature 42 ° C., softening point 71 ° C.) and titanium oxide pigment ( Twenty parts by weight of Ishihara Sangyo Co., Ltd. (Taipaek A220) were melt-kneaded, cooled, pulverized and classified to prepare hydrophobic resin particles having an average particle size of 11.0 μm.

85 parts by weight of the hydrophobic resin particles and 15 parts by weight of water-absorbing resin particles having an average particle size of 10 μm (Aqualic CA ML10 manufactured by Nippon Shokubai Co., Ltd., water absorption 300 to 400 g / g, softening point 89 ° C.) 5 parts by weight of hydrophilic silica fine particles (200 manufactured by Nippon Aerosil Co., Ltd., average particle size: 12 nm) were mixed and stirred to prepare a powder coating.

(Preparation of Ink-Jet Recording Material) As a substrate, a primer-treated soft vinyl chloride resin (glass transition temperature: 50 ° C., softening point: 80 to 85 ° C.) was used.
Using a commercially available electrostatic spraying device, the above powder coating is sprayed onto the entire surface of the film and adhered thereto, and then heated under pressure to about 80 to 100 ° C. to apply the powder coating to the above base material. The powder coating particles were partially fused to each other at the same time as the toner particles were fixed thereon, to form a 20 μm thick resin layer having voids between the particles as an ink receiving layer. The ink-jet recording material thus obtained was examined for ink-jet recording characteristics and the presence or absence of deformation of the substrate. Table 1 shows the results.

Comparative Example 1 (Preparation of Powder Coating) 300 parts by weight of saturated polyester resin (manufactured by Toyobo Co., Ltd., Byron 28SS (solid content: 30%)) and hydrophilic silica fine particles (20 manufactured by Nippon Aerosil Co., Ltd.)
(0, average particle size: 12 nm) was dispersed and dissolved in a mixed solvent of toluene / methyl ethyl ketone to prepare an oily coating solution.

(Preparation of Inkjet Recording Material) This oily coating liquid was applied onto a polycarbonate resin film which had been subjected to the same corona discharge treatment as in Example 1, heated to 120 ° C. and dried to prepare an inkjet recording material. With respect to this ink jet recording material, the ink jet recording characteristics and the presence or absence of deformation of the substrate were examined in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 Styrene / acrylic copolymer resin (Sanyo Chemical Industries, Ltd.)
Hymer UNI-3000, glass transition temperature 58 ° C,
80 parts by weight of a softening point (98 ° C.) and 20 parts by weight of a titanium oxide pigment (Taipe A220, manufactured by Ishihara Sangyo Co., Ltd.) are melt-kneaded, cooled, pulverized and classified to obtain an average particle size of 11.0 μm.
Was prepared.

85 parts by weight of the hydrophobic resin particles and 15 parts by weight of water-absorbing resin particles having an average particle diameter of 10 μm (Aqualic CA ML10 manufactured by Nippon Shokubai Co., Ltd., water absorption 300 to 400 g / g, softening point 89 ° C.) 5 parts by weight of hydrophobic silica fine particles (R202 manufactured by Nippon Aerosil Co., Ltd., average particle size: 14 nm) were mixed and stirred to prepare a powder coating.

(Preparation of Ink-Jet Recording Material) Using this powder coating, an ink-receiving layer was formed on a corona-discharge-treated polycarbonate resin film in the same manner as in Example 1, and the ink-jet recording material thus obtained was obtained. Regarding the recording material, the ink jet recording characteristics and the presence or absence of deformation of the base material were examined. Table 1 shows the results.

Comparative Example 3 In the same manner as in Example 1, a film having a thickness of 20
A μm ink receiving layer is formed on a polycarbonate resin film, and hydrophilic silica fine particles (X-60 manufactured by Tokuyama Corporation, average particle diameter: 10 μm) are formed on the ink receiving layer using a commercially available electrostatic spray device. After spraying and adhering, the ink was heated to about 80 to 100 ° C. under pressure to fix a layer of hydrophilic silica having a thickness of 15 μm on the ink receiving layer to prepare an ink jet recording material. About this inkjet recording material, similarly to Example 1,
The ink jet recording characteristics and the presence or absence of deformation of the substrate were examined.
Table 1 shows the results.

Comparative Example 4 A primer-treated vinyl chloride resin (glass transition temperature: 50 ° C., softening point: 80 to 85 ° C.) film was used as a substrate, and a commercially available electrostatic spraying device was used on the entire surface of the film. Then, after the powder coating is sprayed and adhered, the powder coating is heated to about 80 to 100 ° C. under pressure to fix the powder coating on the base material and at the same time partially separate the powder coating particles from each other. Fused, thickness 20μ with voids between particles
m of the resin layer was formed as an ink receiving layer. The ink-jet recording material thus obtained was examined for ink-jet recording characteristics and the presence or absence of deformation of the substrate. Table 1 shows the results.

[0101]

[Table 1]

[0102]

According to the first aqueous ink jet recording material of the present invention, a powder coating obtained by coating the surfaces of water-absorbent resin particles and hydrophobic resin particles with hydrophilic inorganic fine particles is dry-coated on a resin substrate. By heating and heating, the powder coating is partially melted, so that the powder coating has partially voids therebetween, and the ink receiving layer, which is mutually fused, is formed on the resin base material. Here, according to the present invention, according to the present invention, a dry coating is performed on the base resin by using a powder coating mainly composed of a hydrophobic resin having both a lower glass transition temperature and a lower softening point than the base resin. Then, the ink is heated and melted to form an ink receiving layer, so that a high-performance ink jet recording material can be obtained easily and at low cost without deformation of the base material and in comparison with the conventional wet method.

Further, according to the present invention, since the water-absorbing resin particles and the hydrophobic resin particles whose surfaces are coated with the hydrophilic first inorganic fine particles form the ink receiving layer, the surface of the receiving layer also has , Coated with hydrophilic first inorganic fine particles.
Therefore, according to such an aqueous inkjet recording material, the colorant in the ink is quickly captured by the first hydrophilic inorganic fine particles coating the surface of the ink receiving layer, and the water is Through the voids between the body paint particles,
Since the ink is quickly absorbed by the water-absorbing resin, the ink absorbability is excellent.

Further, according to the aqueous ink jet recording material of the present invention, the resin component in the ink receiving layer is composed of a water absorbing resin and a hydrophobic resin. In particular, by absorbing moisture and suppressing swelling at that time, and thereby suppressing shrinkage upon drying, it is possible to effectively prevent the image from being cracked.

According to the ink jet recording material having the layer made of the second hydrophilic inorganic fine particles on the ink receiving layer, the colorant in the ink is more quickly formed by the layer made of the second hydrophilic fine inorganic particles. Since the image is captured, a clear image with high density and no bleeding can be formed.

The second aqueous ink-jet recording material according to the present invention is characterized in that the hydrophilic first inorganic fine particles are partially exposed on the surface thereof while containing the hydrophobic resin composition particles.
A powder coating consisting of hydrophilic second inorganic fine particles covering the surface of the hydrophobic resin composition particles is dry-coated on a resin substrate and heated to partially coat the powder coating. By melting, the powder coating has an ink receiving layer formed by fusing each other on a metal substrate while partially having a gap therebetween, and the present invention relates to the present invention. According to
The base resin is dry-coated with a powder coating mainly composed of a hydrophobic resin whose glass transition temperature and softening point are lower than those of the base resin, and heated and melted to form an ink receiving layer. And a high-performance ink jet recording material can be obtained simply and inexpensively as compared with the conventional wet method.

When the aqueous ink-jet ink adheres to such an aqueous ink-jet recording material, the colorant in the ink is quickly captured by the first and second hydrophilic inorganic fine particles of the ink receiving layer, and the colorant in the ink is absorbed. Is not only quickly captured by such hydrophilic inorganic fine particles, but also penetrates into the voids between the powder coating particles and is captured.

Further, by forming a layer composed of hydrophilic inorganic fine particles on the ink receiving layer according to the present invention, the colorant in the ink is more quickly captured by the layer composed of the hydrophilic inorganic fine particles. A clear image can be formed at a high density without bleeding.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of one embodiment of an ink jet recording sheet according to the present invention.

FIG. 2 is a schematic view showing a cross section of another embodiment of the ink jet recording sheet according to the present invention.

[Explanation of symbols]

11a, 21a: water-absorbing resin particles, 11b, 21b: hydrophobic resin particles, 12, 22: hydrophilic first inorganic fine particles, 13, 23: powder coating, 14, 24: void, 15,
25: base material made of resin, 16, 26: ink receiving layer,
27: hydrophilic second inorganic fine particles, 28: hydrophilic second fine particles
A layer composed of inorganic fine particles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 B41J 3/04 101Y F-term (Reference) 2C056 FC06 2H086 BA19 BA31 BA33 BA41 BA45 4D075 AA09 BB29Z CA35 DA11 DC27 EA02 EB01 EB31 EB53 EB57 4J038 CB051 CB132 CC022 CC041 CC051 CE022 CG092 CP012 DD011 HA216 HA286 HA446 KA15 KA20 MA01 MA03 MA12 MA13 MA14 NA03 PA02 PB11 PC08

Claims (18)

[Claims] 1. A powder paint-coated sheet having a resin coating film formed on a base material made of a resin and having a resin coating film fused to each other while the powder coating material partially has a gap therebetween. The coating is obtained by coating the surface of resin particles with inorganic fine particles, and the resin forming the base material is mainly composed of a resin having both a higher glass transition temperature and a higher softening point than the resin forming the powder coating. Powder coating sheet. 2. A water-based ink jet recording material having an ink receiving layer fused to each other on a base material made of a resin, with the powder coating having a partial gap therebetween. The surfaces of the water-absorbent resin particles and the hydrophobic resin particles are each coated with hydrophilic inorganic fine particles, and the resin forming the base material is made of a resin having both a higher glass transition temperature and a higher softening point than the hydrophobic resin. An aqueous ink jet recording material characterized by the following. 3. The powder coating has a surface of 5 to 50% by weight of water-absorbent resin particles having an average particle size of 0.1 to 50 μm and a surface of 50 to 95% by weight of hydrophobic resin particles having an average particle size of 0.1 to 50 μm. The aqueous inkjet recording material according to claim 2, wherein the aqueous inkjet recording material is coated with hydrophilic inorganic fine particles having an average particle size of 1 nm to 5 µm. 4. The powder coating according to claim 2, wherein the powder coating comprises 100 parts by weight of a total of water-absorbent resin particles and hydrophobic resin particles coated with 3 to 12 parts by weight of hydrophilic inorganic fine particles. Aqueous inkjet recording material. 5. The water-absorbent resin has a deionized water absorption in the range of 100 to 1000 g / g, and has a water absorption of 70 to 100 ° C.
The aqueous ink jet recording material according to any one of claims 2 to 4, wherein the aqueous resin has a softening point in the range of 70 to 120C. 6. The aqueous ink jet recording material according to claim 2, wherein the hydrophilic inorganic fine particles are silica, alumina, titanium oxide or calcium carbonate. 7. An aqueous ink jet recording material having an ink receiving layer fused to each other on a base material made of a resin while the powder coating material partially has a gap therebetween. The surface of each of the water-absorbent resin particles and the hydrophobic resin particles is coated with first inorganic fine particles, and the hydrophobic resin is made of a resin having a lower glass transition temperature and a lower softening point than the resin forming the base material. An aqueous ink jet recording material, further comprising a layer made of hydrophilic second inorganic fine particles formed on the ink receiving layer. 8. The powder coating composition has a surface of 5 to 50% by weight of water-absorbent resin particles having an average particle size of 0.1 to 50 μm and a surface of 50 to 95% by weight of hydrophobic resin particles having an average particle size of 0.1 to 50 μm. The aqueous inkjet recording material according to claim 7, wherein the aqueous inkjet recording material is coated with first inorganic fine particles having an average particle size of 1 nm to 5 µm. 9. The powder coating composition according to claim 7, wherein a total of 100 parts by weight of the water-absorbent resin particles and the hydrophobic resin particles is coated with 3 to 12 parts by weight of the first inorganic fine particles. Aqueous ink jet recording material. 10. The water-absorbent resin has a water absorption of deionized water in the range of 100 to 1000 g / g, and 70 to 100 g / g.
C. in the range of 70 to 120.degree.
The aqueous ink jet recording material according to any one of claims 7 to 9, which has a softening point in the range of: 11. The method according to claim 1, wherein the hydrophilic second inorganic fine particles have a particle diameter of 1 nm to 1 nm.
The aqueous ink jet recording material according to claim 7, having an average particle size in a range of µm. 12. The aqueous ink jet recording material according to claim 7, wherein the first and / or second inorganic fine particles are silica, alumina, titanium oxide or calcium carbonate. 13. An aqueous ink jet recording material having a powder coating having an ink receiving layer fused to each other on a base material made of a resin while having a gap partially between the powder coating and the base material.
The powder coating, while partially exposing the hydrophilic first inorganic fine particles to the surface, covers the hydrophobic resin composition particles contained therein and the surface of the hydrophobic resin composition particles. 2. A water-based ink jet recording material comprising: hydrophilic second inorganic fine particles, wherein the hydrophobic resin comprises a resin having both a lower glass transition temperature and a lower softening point than the resin forming the base material. 14. A powder coating material having an average particle size of 1 μm to 5 μm.
5 to 30% by weight of hydrophobic resin composition particles having an average particle diameter of 5 to 30 μm while partially exposing the hydrophilic first inorganic fine particles of the above, and the hydrophobic resin composition The aqueous ink jet recording material according to claim 13, comprising hydrophilic second inorganic fine particles having an average particle diameter of 1 nm to 1 µm covering the surface of the particles. 15. A powder coating composition comprising the hydrophobic resin composition particles 100.
15. The aqueous ink jet recording material according to claim 13, wherein the water-based ink-jet recording material is obtained by coating a weight part with 3 to 12 weight parts of hydrophilic second inorganic fine particles. 16. The aqueous ink jet recording material according to claim 13, wherein the hydrophilic first or second inorganic fine particles are silica, alumina, titanium oxide or calcium carbonate. 17. The aqueous ink jet recording material according to claim 13, wherein a layer comprising hydrophilic third inorganic fine particles is formed on the ink receiving layer. 18. The method according to claim 1, wherein the hydrophilic third inorganic fine particles have a particle diameter of 1 nm to 1 nm.
18. The aqueous inkjet recording material according to claim 17, having an average particle size in the range of [mu] m.