JP2001105717A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording material adapted to be used particularly in an outdoor by incorporating good ink absorbability, fixability, excellent printing quality level, weather resistance and water resistance, and good surface strength. SOLUTION: In the recording material having an ink receiving layer on at least one side surface of a base material, the layer contains a non-water soluble resin, a pigment, a water soluble cationic resin and a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink absorbing property,
The present invention relates to a recording material having good fixability, excellent print quality, excellent weather resistance and water resistance and excellent surface strength, and particularly to a recording material suitable for use in the field.

[0002]

2. Description of the Related Art In recent years, with the improvement of computer performance and the spread of computers, hard copy technology has rapidly developed. As a hard copy recording method, a method such as a thermal transfer recording method, an electrophotographic method, and an ink jet method are known.

[0003] Ink jet printers are
In this method, ink droplets are ejected from a nozzle toward a recording material at a high speed. In recent years, printing apparatuses such as offices, homes, and personal computers are rapidly spreading because of easy coloration and low printing noise. Furthermore, the application to industrial fields such as large signboards is also expected because of the improvement in printing quality and the ease of upsizing approaching silver halide photography.
Recently, with the improvement of printer and ink performance,
Recording materials are also required to have improved clarity of images, high color density, ink drying properties, water resistance, weather resistance, and surface strength.

Some proposals have conventionally been made to satisfy these characteristics. For example, a method of providing a porous ink receiving layer mainly composed of a pigment on a base material (JP-A-52-9)
Nos. 074, 55-51583 and 55-1
44172, 55-150395 and 5
Nos. 6-157, 56-148582 and 5
JP-A-65-148583, JP-A-57-107880, JP-A-58-136481, etc.), and a method of providing an ink receiving layer mainly composed of a water-soluble resin on a substrate (JP-A-59-45188; No. 60-44386)
And various methods for further improving the performance such as printing characteristics and water resistance by these methods have been proposed (JP-A-56-86789, JP-A-57-64591, and JP-A-57-64591). 87987, 58-89391, 59-20696, 60-49990
JP-A-60-56587, JP-A-60-1711
Nos. 90, 61-47290, 61-89
082). In many cases, improvement in water resistance by using a mixture of a water-soluble resin and a water-insoluble resin has been proposed (Japanese Patent Publication No. 5-88678, Japanese Patent Application Laid-Open No. 10-2784).
No. 11, JP-A-10-157286, JP-A-9-11613, JP-A-6-8618, JP-A-10-264511, JP-A-10-2728
No. 32, JP-A-9-156209, JP-A-1
0-287036, JP-A-63-307979, JP-A-9-295391).

[0005] In addition, there is an example in which improvement of water resistance and weather resistance is proposed by using a water-insoluble resin alone or as a main component, or in combination with a pigment or the like (JP-A-10-181).
189, JP-A-4-364947, JP-A-7-3058, JP-B-4-142933,
JP-A-7-9756, JP-A-7-156536, JP-A-8-197834, JP-A-8-31
No. 0111, Japanese Patent Application Laid-Open No. 7-9775, Japanese Patent Application Laid-Open
JP-147885, JP-A-147886, JP-A-6-227114, JP-A-6-239015
JP, JP-A-9-99633, JP-A-8-11
JP-A-8792, JP-A-7-40647, JP-A-9-169085, JP-A-8-216504, JP-A-9-296067, JP-A-6-328
JP-A-836, JP-A-9-99632, JP-A-7-99632.
JP-A-323656, JP-A-1-229684, JP-B-63-252779, JP-A-1-13
No. 3779, Japanese Patent Publication No. 6-62002, Japanese Patent Publication No. 6-69753, Japanese Patent Application Laid-Open No. Sho 56-148586, Japanese Patent Application Laid-Open No. 58-134784, Japanese Patent Application Laid-Open No. 58-1
No. 34785, JP-A-58-134786,
JP-A-58-134787, JP-A-58-132
No. 585, JP-A-59-11284, JP-A-62-140875, JP-A-62-222884.
JP-A-63-173678, Japanese Patent Publication No.
No. 188387)

However, in any of the above methods, it is difficult to obtain a highly balanced recording material having good ink absorption and fixing properties, excellent print quality, weather resistance and water resistance, and good surface strength. Can not.

[0007]

SUMMARY OF THE INVENTION The present invention relates to an ink jet recording system such as an ink jet printer, an ink jet plotter or the like, which can record a high-quality image with high coloration and no bleeding at a high speed, as well as water resistance, weather resistance and surface resistance. It is to provide a recording material having excellent strength.

[0008]

According to the present invention, there is provided a recording material having an ink receiving layer on at least one side of a base material. It is characterized by containing a water-soluble resin, a pigment, a water-soluble cationic resin and a surfactant.

In general, the absorption of ink by a recording material composed of a pigment and a resin is caused by the fact that the ink adhered to the surface of the ink receiving layer of the recording material enters into fine voids in the structure of the ink receiving layer mainly by dissolution or swelling action. This is done by:
Factors that greatly affect the ink absorption of such an ink receiving layer include the structure of the ink receiving layer and the physical properties of the material constituting the ink receiving layer.

That is, the structure of the ink receiving layer is such that the ink easily penetrates, and the ink receiving layer has a space suitable for absorbing and storing the ink. It is important that the material constituting has affinity for the ink. Therefore, when the ink used is water-based, it is necessary to use a material having a hydrophilic property for absorbing and receiving the ink of the recording material, that is, for forming the ink receiving layer, in order to obtain excellent ink absorbability. Is effective. However, on the other hand, when a highly hydrophilic material such as a water-soluble resin is used as a main component, there is a disadvantage that the water resistance is poor. Even when a water-soluble resin is crosslinked to compensate for this drawback, the water resistance and weather resistance are still insufficient.

When a water-insoluble resin is used as a main component in order to improve the water resistance and weather resistance, the affinity for ink is inferior, so that the print quality and ink absorbability are reduced.

Further, if a water-insoluble resin and a hydrophilic resin are used in a mixture in order to increase the affinity with the ink, the ink absorbency, print quality, water resistance and weather resistance cannot be well balanced.

As a result of intensive studies, the present inventor has found that the ink receiving layer contains a water-insoluble resin, a pigment, a water-soluble cationic resin and a surfactant so that a high-quality image with high color and no bleeding can be obtained. It has been found that absorption, water resistance, weather resistance and surface strength can be highly balanced.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention relates to a recording material having an ink receiving layer provided on a substrate, and an undercoat layer is appropriately provided between the substrate and the ink receiving layer. As the substrate used in the present invention,
Fine paper, Kent paper, general paper such as coated paper, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, or their foams, calcium carbonate,
A plastic film such as an inorganic pigment mixture such as titanium oxide can be used. Among them, a plastic film base is preferable in terms of water resistance.

The water-insoluble resin in the ink receiving layer in the present invention is not particularly limited, but polyester resins,
Examples thereof include polyvinyl chloride resin, polystyrene resin, polymethyl methacrylate resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, acrylic acid copolymer resin, and polyvinyl butyral resin. Among them, acrylic acid-based copolymer resins are preferred in terms of weather resistance. As the acrylic acid-based copolymer resin, a cationic emulsion type is desired in view of the stability of the coating solution and the suitability for coating. The content in the ink receiving layer is preferably from 10 to 50% by weight, and more preferably from 20 to 40% by weight. If it is 10% by weight or less, the surface strength tends to be particularly poor, and if it is 40% by weight or more, the ink absorption tends to be particularly poor. In the present invention, a water-soluble resin or a suitable amount of a water-soluble resin and a crosslinking agent may be contained to such an extent that the water resistance is not remarkably reduced.

The pigment in the ink-receiving layer in the present invention is not particularly limited, but common organic pigments and inorganic pigments such as silica, clay, talc, diatomaceous earth, calcium carbonate, calcined kaolin, titanium oxide and zinc oxide are used. Although inorganic pigments are preferable in terms of ink absorbability, amorphous synthetic silica, calcium carbonate, and the like are particularly preferable. The content in the ink receiving layer is preferably from 20 to 70% by weight, and more preferably from 30 to 50% by weight. 2
If the content is 0% by weight or less, the ink absorption tends to be particularly poor,
If it is 70% by weight or more, the surface strength tends to be particularly poor.

The water-soluble cationic resin in the ink-receiving layer in the present invention is not particularly limited, but is not particularly limited. And compounds such as polyethyleneimine and dimethyl methacrylate, and copolymers and modified products.

The content of the water-soluble cationic resin in the ink receiving layer is preferably from 5 to 30% by weight, more preferably from 10 to 20% by weight. If it is less than 5% by weight, the printing quality is particularly poor, and if it is more than 30% by weight, the ink absorbency is particularly poor.

The surfactant in the ink receiving layer in the present invention is not particularly limited, but is preferably a fluorine-based or silicon-based surfactant, or a mixture thereof.

The content of the surfactant in the ink receiving layer is preferably 5 to 30% by weight, more preferably 10 to 30% by weight.
20% by weight. If it is less than 5% by weight, the print quality is particularly poor, and if it is more than 30% by weight, the ink absorbency is particularly poor.

The reason for the excellent effects of the present invention is that water-soluble resins are mainly used to improve water resistance and weather resistance, and the disadvantages of ink absorption and printing quality are reduced by water-soluble cations. It is presumed that it could be prevented by adding the resin and the surfactant. That is, a synergistic effect occurs due to the fixing property of the ink by the water-soluble cationic resin and the improvement of the ink permeability by the surfactant, and the suitable ink dots spread on the surface of the ink receiving layer and the rapid ink absorption into the image receiving layer. I guess it was because it was realized.

In the present invention, various additives may be added to the ink receiving layer to such an extent that ink absorbency and other physical properties are not impaired. For example, pigment dispersants, defoamers, colorants,
Examples include an antioxidant, a fluorescent brightener, a plasticizer, an ultraviolet absorber, a viscosity adjuster, a crosslinking agent, and a PH adjuster.

The method for providing the ink receiving layer is not particularly limited, but includes a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, a bar coating method and the like. A commonly used method can be applied. The coating amount is not particularly limited, but is 1
Is preferably 0~50g / m ^2, more preferably from 15 to 35 g / m ^2. At 10 g / m ² , the ink absorption tends to be poor. If it is 50 g / m ² or more, the surface strength tends to decrease.

In the present invention, it is preferable to provide an anchor layer between the substrate and the ink receiving layer. Due to the effect of the anchor layer, the adhesion between the substrate and the ink-receiving layer is improved, and good surface strength is obtained. The resin constituting the anchor layer preferably contains at least one selected from a polyester resin, a polyurethane resin, an acrylic resin, a melamine resin and a vinylidene chloride resin. Further, in the anchor layer, a pigment dispersant, an antifoaming agent,
A coloring agent, an antioxidant, a fluorescent brightener, a plasticizer, an ultraviolet absorber, a viscosity modifier, a crosslinking agent, and the like are appropriately used as needed.

In the present invention, an antistatic layer or an adhesive layer may be provided on the surface opposite to the surface on which the ink receiving layer is provided, from the viewpoint of handleability during post-processing.

The ink used for the recording material of the present invention is not particularly limited, but a pigment type is preferred in terms of weather resistance.

The recording material thus obtained has good ink absorbency and fixability, is excellent in print quality, weather resistance and water resistance, and has good surface strength.

[0028]

Next, Examples and Comparative Examples of the present invention will be described.
The present invention is not limited by this. The measurement / evaluation method used in the present invention will be described below. In addition, color density and bleeding were evaluated as print quality.

(1) Ink absorbency CJ-70 (manufactured by Roland), Cyan, Magenta, Ye
llow, Red, Green, Blue, Black (hereinafter abbreviated as B:
(Lack is abbreviated as K.) After printing the solid portion of each color, the time from when the ink did not adhere to the finger even when the finger was touched was measured. 3 minutes or less: ○ 3 to 10 minutes: Δ 10 minutes or more: × 10 minutes or more results in poor practicality.

(2) Coloring Density The density of the solid K portion in (1) is measured using a Macbeth densitometer (TR92).
7: manufactured by Sakata Inx Co., Ltd.).

(3) A pattern in which C, M, and Y lines (width: 5 mm) are drawn and printed on the solid portion of each color in (1), and the blur condition at the boundary between the solid portion and the line of each color. Was visually determined. The boundary is sharp when the bleed is 0.5 mm or less: ○ The boundary is slightly unclear when the bleed is 0.5 to 1 mm: The boundary is unclear when the bleed is 1 mm or more: ×

(4) Water resistance After immersing the image of (1) in water of 30 ° C. for 24 hours,
The change (α) in color density due to (3) of the naturally dried product was determined by the following equation. Note that a Macbeth densitometer (TR927) was used for the density measurement. α = color density after immersion for 24 hours / color density before immersion × 1
00 α ≧ 95 is a good standard.

(5) Weather resistance Test conditions of the exposure test method using an open frame carbon arc lamp according to JIS A1415: WS-A: 50
The change (β) in the color density after 0 hour was determined by the following equation.
Note that a Macbeth densitometer (TR927) was used for the density measurement. β = color density after 500 hours / color density before test × 10
0 In addition, the decrease in the surface strength of the unprinted portion was judged by touching with a finger. The receiving layer is not damaged even if rubbed lightly: ○ The receiving layer is brittle and peeled off even if rubbed lightly: ×

(6) Surface Strength The scratch resistance was measured by scratching with a nail. Does not hurt unless strongly scratched: ○ Slightly hurt even if scratched: △ easily scratched and has practical problems: ×,

Example 1 Substrate 1 80% by weight of a polyethylene terephthalate resin having an intrinsic viscosity of 0.62 as a raw material, 15% by weight of a polystyrene resin for general use (T575-57U manufactured by Mitsui Toatsu Chemicals, Inc.), and an average particle diameter of 0.1%. Using 5% by weight of 35 μm anatase type titanium dioxide (TA-300 manufactured by Fuji Titanium Co., Ltd.) as a raw material, it is charged into a twin screw extruder, melt-extruded from a T-die at 290 ° C., and electrostatically cooled and rotated. And an unstretched sheet of a polymer mixture was obtained. Subsequently, the unstretched sheet was longitudinally stretched 3.5 times at 80 ° C. with a roll stretching machine, then transversely stretched 3.8 times at 125 ° C. with a tenter, and then heat-treated at 235 ° C. while relaxing by 4%. Apparent specific gravity containing many cavities 1.15, thickness 100
μ of a white polyester film was obtained.

Anchor Layer The following solution was prepared, applied to the above-mentioned base film so as to have a dry weight of about 0.05 g / m ^2, and dried in an oven maintained at 160 ° C. for 60 seconds. An anchor layer was formed.・ Water 62.00 g ・ Isopropyl alcohol 25.98 g ・ Water-dispersed polyester resin 9.00 g (Toyobo Co., Ltd. Vironal MD-16) ・ Block isocyanate 2.00 g (Daiichi Kogyo Seiyaku Co., Ltd. Elastron BN-) 11) ・ 10% by weight aqueous solution of zinc borofluoride (manufactured by Hashimoto Chemical Co., Ltd.) 0.02 g ・ Organic particles (Nippon Shokubai Co., Ltd. Eposter MA1002) 3.00 g

Ink receiving layer A composition having the following composition is prepared as a coating liquid. As a procedure for liquid preparation, for example, a predetermined amount of a pigment dispersed in water with a homogenizer or the like is transferred to a container equipped with a stirrer. The stirrer is continuously stirred at such a speed that the components in the container can be sufficiently stirred. A predetermined amount of the water-insoluble resin is transferred there. In this case, the stirring time and the like are sufficiently adjusted so that the coating liquid does not aggregate. A predetermined amount of a water-soluble cation resin is added thereto, and the mixture is similarly sufficiently stirred while paying attention to aggregation of the coating liquid. Further, a surfactant is added thereto and sufficiently stirred. The water-insoluble resin, the water-soluble cationic resin, and the surfactant may be appropriately diluted with water or, in some cases, alcohol or the like in advance so as to be easily dispersed in the coating solution. The coating solution thus prepared was applied onto the anchor layer so that the weight after drying was 25 g / m ^2, and dried in an oven maintained at 120 ° C. for 180 seconds to obtain a recording material. 40% by weight of pigment (amorphous synthetic silica) (Sylysia 450, manufactured by Fuji Silysia Ltd.) 30% by weight of water-insoluble resin (cationic acrylic emulsion) (SFC54, manufactured by Dainippon Ink and Chemicals, Inc.) 15% by weight of a water-soluble cationic resin (polyallylamine hydrochloride) (PAA-HCL-3L, manufactured by Nitto Boseki Co., Ltd., solid content concentration: 50% by weight) ・ 15% by weight of a surfactant (silicone surfactant: water dispersion) % (Paintad 57 manufactured by Dow Corning Asia Co., Ltd.)

Example 2 A recording material was obtained in the same manner as in Example 1 except that the ink receiving layer was in the following mode. A coating solution having the following composition was applied on the anchor layer of the ink receiving layer so that the weight after drying was 30 g / m ^2, and dried in an oven maintained at 100 ° C. for 180 seconds to obtain a recording material. -Pigment (amorphous synthetic silica) 50% by weight (Sylysia 440, manufactured by Fuji Silysia Ltd.)-Water-insoluble resin (ethylene / vinyl acetate copolymer) 20% by weight (S-305, manufactured by Sumitomo Chemical Co., Ltd.)・ Water-soluble cationic resin (quaternary ammonium compound derivative) 10% by weight (Parafix EH manufactured by Ohara Palladium Chemical Co., Ltd.) ・ Surfactant (silicone type surfactant) 20% by weight (Dow Corning Asia ( Co., Ltd. Painted 32)

Example 3 A void-containing polyester film (Crisper G232)
3: An ink receiving layer was formed on 50 μm (manufactured by Toyobo Co., Ltd.) in the following manner.

Ink receiving layer The following solution was applied so that the weight after drying was 20 g / m ^2, and dried in an oven maintained at 100 ° C. for 150 seconds to obtain a recording material. -Pigment (amorphous synthetic silica) 30% by weight (BS304F manufactured by Shionogi Pharmaceutical Co., Ltd.)-Water-insoluble resin (acrylate copolymer resin) 35% by weight (DINAL RS- manufactured by Dainippon Ink and Chemicals, Inc.) 308) ・ Water-soluble cationic resin (quaternary ammonium-based compound derivative) 14% by weight (Parafix EH manufactured by Ohara Palladium Chemical Co., Ltd.) ・ Surfactant (fluorine-based surfactant) 21% by weight (Dainippon Ink (MegaFac F-144D manufactured by Chemical Industry Co., Ltd.)

Example 4 The water-soluble cationic resin used in Example 1 was as follows. Copolymer of diallyldimethylammonium chloride and diallylamine Kayafix UR manufactured by Nippon Kayaku Co., Ltd.

Comparative Example 1 The water-insoluble resin in Example 1 was a water-soluble resin mixture having the following composition ratio. Fully saponified polyvinyl alcohol Kuraray Co., Ltd. PVA117 85% by weight Melamine resin Sumitomo Chemical Co., Ltd. M-30W 15% by weight

Comparative Example 2 In the ink receiving layer of Example 1, a coating liquid was prepared by recalculating the proportions of the other components by weight without adding a water-soluble cationic resin so that the total weight was 100% by weight. Thus, a recording material was obtained in the same manner as in Example 1.

COMPARATIVE EXAMPLE 3 In the ink receiving layer of Example 2, a coating liquid was prepared by recalculating the proportions of the other components in a proportion of 100% by weight without adding a surfactant. A recording material was obtained in the same manner as in Example 1.

Comparative Example 4 In Example 3, the water-insoluble resin was a mixture of a water-soluble resin and a water-insoluble resin having the following composition ratio. Water-soluble resin (fully saponified polyvinyl alcohol) Nippon Synthetic Chemical Industry Co., Ltd. (NH-18 50% by weight) Non-water-soluble resin (acrylic acid ester copolymer resin) Dainippon Ink and Chemicals, Inc. DICNAL RS-308) 50% by weight %

[0046]

[Table 1]

[0047]

[Table 2]

As can be seen from Tables 1 and 2, the recording materials obtained according to the examples had ink absorbency, print quality, weather resistance,
Excellent in water resistance and surface strength with good balance. In contrast, Comparative Example 1 had poor surface strength, and Comparative Examples 2 and 3 had poor print quality. When a water-soluble resin is used as in Comparative Example 4, the water resistance and weather resistance are particularly poor, and the balance of the quality as a whole is not good.

[0049]

The recording material of the present invention has good ink absorbency and fixability, and has excellent print quality, weather resistance, water resistance and good surface strength, and is particularly suitable for use in the field. It is a thing.

Continued on front page F-term (reference) 2C056 EA05 EA13 FB01 FC06 2H086 BA15 BA31 BA33 BA36 BA51 BA55 4J002 BC03W BD04W BD08W BE06W BG00W BG06W BG07X BJ00X CF00W CG00W CH04X CK00W CM00X DE106 DJ136DE36 DJ36

Claims (4)

[Claims] 1. A recording material having an ink receiving layer on at least one surface of a substrate, wherein the ink receiving layer contains a water-insoluble resin, a pigment, a water-soluble cationic resin, and a surfactant. Recording material. 2. The recording material according to claim 1, wherein the surfactant is fluorine-based, silicon-based, or a mixture thereof. 3. The recording material according to claim 1, wherein the water-insoluble resin is a cationic acrylic emulsion. 4. The recording material according to claim 1, wherein said recording material is used in ink jet recording using a pigment ink.