JP2003291519A - Ink jet recording sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording sheet especially excellent in the water resistance of an image while having fundamental characteristics of a conventional ink jet recording sheet and suitable for use in the outdoors like a poster or the like. <P>SOLUTION: The ink jet recording sheet is constituted by providing an ink receiving layer on a support. The ink receiving layer contains at least a cationic resin selected from a polymer of dimethylamine and epichlorohydrin, a polyallylamine and a diallylamine/allylamine copolymer and silica with a particle size distribution d10/d90 of 0.22 or more. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording sheet, and more specifically, it has an ink receiving layer on a substrate and is excellent in water resistance of images, and is particularly suitable for outdoor use such as posters. The present invention relates to an inkjet recording sheet.

[0002]

2. Description of the Related Art In recent years, due to the widespread use of computers, it has become common to print out materials created by computers using printers and the like. As a printer used at that time,
Examples include dot impact printers, laser printers, thermal printers, inkjet printers, and the like, but inkjet printers are widely used because they have almost no mechanical noise during printout and the running cost associated with printout is low.

In such an ink jet recording system, a recording sheet having an ink receiving layer provided on a base material is used. With the expansion of applications, not only image accuracy but also water resistance is required. ing. In order to prevent image bleeding, it has been attempted to contain a polymer of dimethylamine and epichlorohydrin or a polymer of diallylamine as a raw material in the ink receiving layer, but as a poster or the like,
Image water resistance is not always sufficient for outdoor use. (For example, see Patent Document 1)

[0004]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-160440

[0005]

SUMMARY OF THE INVENTION In such a situation, the present invention provides an ink jet recording sheet which has the basic characteristics of a conventional ink jet recording sheet, but is particularly excellent in water resistance of an image. It is intended to be provided.

[0006]

As a result of intensive studies to develop an ink jet recording sheet having the above-mentioned excellent properties, the present inventor has found that a specific cationic resin and a silica having a specific particle size distribution are used. It was found that the one provided with the ink receiving layer containing and can meet the purpose. The present invention has been completed based on such findings. That is, according to the present invention, an ink receiving layer is provided on a substrate, and the ink receiving layer is selected from a polymer of dimethylamine and epichlorohydrin, a polyallylamine, and a copolymer of diallylamine and allylamine. 1 or more cationic resins and a particle size distribution d10 / d90 of 0.
The present invention provides an inkjet recording sheet containing 22 or more silica. However, d
10 means the maximum particle size when the particle size is added from the smaller side and the cumulative volume becomes 10% of the whole, and d
90 means the maximum particle size when the particle size is added from the smaller side and the cumulative volume becomes 90% of the whole, and the particle size distribution here is the value of d10 divided by the value of d90. Is.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The ink jet recording sheet of the present invention has an ink receiving layer on at least one surface of a substrate. In the present invention, the base material is not particularly limited as long as it is in the form of a sheet.
Various materials such as plastic films, papers, non-woven fabrics and the like can be used, but plastic films are particularly preferable from the viewpoint of water resistance. The material of the plastic can be selected from general thermoplastic resin films such as vinyl chloride, polyethylene terephthalate, polypropylene, polystyrene and polycarbonate, or those in which inorganic powder such as calcium carbonate is internally added. .
Also, a foamed plastic film can be used. Here, the foamed plastic film refers to a plastic film having cracks or voids formed on the surface or inside of the film, or fine bubbles or cavities, and these bubbles or cavities include those such as calcium carbonate. A film containing inorganic powder is stretched to be generated around the inorganic powder (micro void film), or a film containing a foaming agent is formed by foaming a foaming agent. The form of formation of bubbles or cavities does not matter. The plastic film referred to here also includes what is called synthetic paper. The base material may have a single-layer structure or a multi-layer structure. As the multi-layer structure, for example, a method in which layers are bonded together via an adhesive,
Any known method such as a so-called co-extrusion method in which a plurality of raw materials are extruded from a plurality of extruders to join together to form a film, a so-called extrusion laminating method in which a film is directly laminated on the film while being extruded from an extruder, and a so-called extrusion laminating method. What was formed can also be used.

In the present invention, the ink receiving layer provided on at least one surface of the substrate is a polymer of dimethylamine and epichlorohydrin, polyallylamine,
And one or more cationic resins selected from copolymers of diallylamine and allylamine and silica as a filler. Among the above-mentioned cationic resins, it is preferable to use a polyallylamine or a copolymer of diallylamine and allylamine because it is excellent in preventing migration (bleeding of an image with time). Further, as a cationic resin contained in the ink receiving layer, a polymer of dimethylamine and epichlorohydrin, polyallylamine,
It is preferable to add polydiallylamine together with one or more cationic resins selected from the copolymers of diallylamine and allylamine, because the light resistance of the image is improved. The ratio of the polydiallylamine to the other cationic resin is preferably such that the weight ratio of the former to the latter is in the range of 1: 9 to 9: 1, and the form of the water-soluble salt is easy to handle.

Further, in the present invention, it is necessary that the particle size distribution d10 / d90 of silica is 0.22 or more. The particle size distribution can be measured using a laser diffraction type particle size distribution measuring device. This specific particle size distribution of silica and the specific cationic resin can be combined to improve the surface strength of the ink receiving layer and improve the water resistance of the image. This silica is preferably one having a particle size of 1 μm or more produced by a gel method and having a micron size. When the particle size of silica is micron size, it is possible to improve the printing suitability when printing with a pigment type ink. Further, a filler other than silica may be used in combination in the ink receiving layer as long as the effect of the present invention is not impaired.
The amount of the filler is 25% or less with respect to the weight of silica having a particle size distribution d10 / d90 of 0.22 or more. The substances that can be used are not limited to organic and inorganic substances, and examples thereof include calcium carbonate, talc, clay, diatomaceous earth, aluminum hydroxide, polystyrene, polymethacrylate, titanium oxide, and calcined kaolin.

The binder (binder) used in the ink receiving layer is not particularly limited, and examples thereof include polyvinyl alcohol, polyvinyl butyral, gelatin, polyvinyl acetal, carboxymethyl cellulose, polyvinyl pyrrolidone, polyester, acrylic resin, urethane resin. , Chlorinated polypropylene, polymerization or copolymer of vinyl versatate, styrene-acrylic copolymer,
Examples thereof include ethylene-vinyl acetate copolymer and styrene-butadiene rubber. These may be used alone or in combination of two or more. Among these, silanol-modified polyvinyl alcohol is more preferable because it improves the strength of the ink receiving layer. Further, the acrylic resin is more preferable because it further improves the water resistance of the image.

The content of silica, the binder, and the cationic resin in the ink receiving layer (solid content in the ink receiving layer) is 40 to 65% by weight, especially 4% for silica.
5 to 60% by weight is preferable, and the binder is 20 to
50% by weight, especially 25 to 45% by weight is preferable, and 5 to 15% by weight, especially 6 to 13% by weight is preferable for the cationic resin. When the amount of silica is less than this range, the ink absorbency, the drying property, and the water resistance of the image tend to be lowered,
On the other hand, if the amount is more than this range, the strength of the ink receiving layer tends to decrease. When the amount of the binder is less than this range, the strength of the ink receiving layer tends to decrease, and conversely, when the amount is more than this range, the ink absorbency, the drying property and the water resistance of the image tend to decrease. If the amount of cationic resin is less than this range,
Image bleeding tends to occur, and the water resistance of the image tends to decrease. On the contrary, when the amount is more than this range, the light resistance and the strength of the ink receiving layer tend to decrease. In the ink receiving layer, a water-soluble cationic substance other than the above-mentioned cationic resin such as a water-soluble aluminum salt, or a defoaming agent, which improves color development, if necessary, within a range not impairing the object of the present invention. , Antistatic agent, ultraviolet absorber, optical brightener,
Various additives such as antiseptics, pigment dispersants and thickeners can be contained. The thickness of this ink receiving layer is 25-
A range of 50 μm, particularly 25 to 40 μm is preferable. When the thickness is less than this range, the ink absorbency, the drying property, and the water resistance of the image are easily deteriorated, and the image bleeding is likely to occur. On the contrary, when the thickness is more than this range, banding is likely to occur and the dot The diameter tends to be small, and the image density tends to be low.

The ink jet recording sheet of the present invention comprises:
A layer other than the ink receiving layer may be provided as long as the object of the present invention is not impaired. For example, an anchor coat layer may be provided in order to improve the adhesion between the base material and the ink receiving layer. The ink-receiving layer can be formed by applying a coating liquid in which the constituent components are dissolved or dispersed in a suitable solvent by a known method such as reverse roll coating, air knife coating, gravure coating or blade coating. . When the surface smoothness of the ink receiving layer in the inkjet recording sheet of the present invention according to the Beck method is 10 seconds or more, the water resistance of the image is further improved, which is preferable. As a method of adjusting the surface smoothness, the ratio of the filler to the binder is made small (when the weight ratio is 1.0 or less, the smoothness tends to be 10 seconds or more), and the dispersion of the particle size distribution of the filler is made small. However, the particle size of the filler may be reduced, and the particle size of the filler may be adjusted depending on the kind of the filler or the binder.

[0013]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The particle size distribution of silica d10 / d
90 is a laser diffraction particle size distribution analyzer SA manufactured by Shimadzu
The performance of the inkjet recording sheet produced by measuring with LD-2000A was evaluated according to the following procedure. (1) Surface smoothness A Beck smoothness tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) was used to measure three times under the following conditions to obtain an average value. Environment: 23 ° C., 50% RH Sample humidity: 23 ° C., 50% RH for 2 hours Volume switching: 1 cc (2) Water resistance of image Print cyan, magenta, yellow and black mixed color (black), After 5 minutes from printing, one drop of distilled water was dropped on the printed portion with a dropper, and the degree of outflow of each color ink when the distilled water was completely absorbed was visually observed and evaluated according to the following criteria. ◎: No spill ○: Slightly spilled, but practically unaffected △: Spilled, practically hindered ×: Many spilled, practically hindered (3) Surface layer strength Ink receiving layer Cellophane tape (trade name: CT405A-18, manufactured by Nichiban Co., Ltd., length 10 cm) was attached by 3 reciprocations of a pressure roll of 2 kg, and the degree of peeling when pulled backward at an angle of 45 ° was visually observed. It evaluated by the judgment standard of. ◯: Area of coating layer adhered to cellophane tape is 20% or less Δ: Area of coating layer adhered to cellophane tape is more than 20% and 60% or less ×: Area of coating layer adhered to cellophane tape is 60% Super

Example 1 As a base material, a white foamed polypropylene film having a thickness of 80 μm (micro void film manufactured by YUPO Corporation, trade name: YUPO FPG80) was used. A uniform mixture of the following components was used as an anchor coating liquid. (a) Anionic acrylic resin [manufactured by BASF Dispersion Co., Ltd., trade name: ACRONAL YJ-6221D,
Solid content concentration 49% by weight] 60 parts by weight (b) Aragonite type calcium carbonate [manufactured by Shiraishi Central Research Laboratory, trade name: Callite SA, solid content concentration 100% by weight] 10 parts by weight (c) water 30 parts by weight ink receiving layer A uniform mixture of the following components was used as a coating liquid for use. (1) Silica [manufactured by Grace Davison, trade name: SYLOJET-P412, solid content concentration 100% by weight, average particle size 7.5 μm, particle size distribution (d10 / d9)
0) 0.27] 16. 92 parts by weight (2) Silanol-modified polyvinyl alcohol [Kuraray Co., Ltd., trade name: R polymer R-1130, solid content concentration 100% by weight] 8.06 parts by weight (3) Defoaming agent [San Nopco Co., Ltd.] , Product name: SN deformer 480, solid content concentration 100% by weight] 0.34 parts by weight (4) Polymer of dimethylamine and epichlorohydrin [Nika Chemical Co., Ltd., product name: Neofix RE, solid content concentration 40% by weight] 8.75 parts by weight (5) Fibrous hydrated aluminum oxide [manufactured by Nissan Chemical Industries, Ltd., trade name: alumina sol 200, solid content concentration 1
0% by weight] 5.40 parts by weight (6) 160.53 parts by weight of water A coating solution for anchor coating is applied on a substrate to give a thickness of 5
An ink jet recording sheet is formed by forming an anchor coat layer having a thickness of 30 μm (after drying) and applying a coating liquid for the ink receiving layer thereon to form an ink receiving layer having a thickness of 30 μm (after drying). Was produced. The surface smoothness of the obtained ink jet recording sheet was 41 seconds.

Example 2 An ink jet recording sheet was produced in the same manner as in Example 1 except that the ink receiving layer coating liquid was a mixture of the following components. The surface smoothness of the obtained ink jet recording sheet was 198 seconds. (1) Silica [manufactured by Grace Davison, trade name: SYLOJET-P412, solid content concentration 100% by weight, average particle size 7.5 μm, particle size distribution (d10 / d9)
0) 0.27] 10. 60 parts by weight (2) silica [manufactured by Fuji Silysia Chemical Ltd., trade name: Sylysia 440, solid content concentration 100% by weight, average particle diameter 3.5 μm, particle size distribution (d10 / d90) 0.35] 2
4.75 parts by weight (3) Cationic acrylic resin [Shin-Nakamura Chemical Co., Ltd.
Product name: NK polymer AC-11, solid content concentration 3
6% by weight] 98.22 parts by weight (4) Antifoaming agent [manufactured by San Nopco Ltd., trade name: SN deformer 480, solid content concentration 100% by weight] 0.20 parts by weight (5) Dimethylamine and epi Polymerization with chlorohydrin [Nippa Kagaku Co., Ltd., trade name: Neofix RE, solid content concentration 40% by weight] 16.23 parts by weight (6) Fibrous hydrated aluminum oxide [NISSAN CHEMICAL INDUSTRIES ( Ltd., trade name: Alumina sol 200, solid content concentration 1
0 wt%] 5.00 parts by weight (7) Water 45.00 parts by weight

Example 3 Instead of 8.75 parts by weight of the polymer of dimethylamine and epichlorohydrin in the coating liquid for the ink receiving layer in Example 1, a mixture of polydiallylamine and polyallylamine [Nikka] Made by Kagaku Co., Ltd., product name: Neofix RX
-100, solid content concentration 19% by weight, mixed aqueous solution of polyallylamine salt and polydiallylamine salt] 18.42 parts by weight were used to prepare an ink jet recording sheet in the same manner as in Example 1. The surface smoothness of the obtained ink jet recording sheet was 42 seconds.

Example 4 In place of 16.23 parts by weight of the polymer of dimethylamine and epichlorohydrin in the coating liquid for the ink receiving layer in Example 2, a mixture of polydiallylamine and polyallylamine [Nikka] Made by Kagaku Co., Ltd., product name: Neofix R
X-100, solid content concentration 19% by weight, mixed aqueous solution of polyallylamine salt and polydiallylamine salt] 34.16
An ink jet recording sheet was produced in the same manner as in Example 2 except that the amount of water used was 20.00 parts by weight. The surface smoothness of the obtained ink jet recording sheet was 186 seconds.

Example 5 Instead of 8.75 parts by weight of the polymer of dimethylamine and epichlorohydrin in the coating liquid for the ink receiving layer in Example 1, polyallylamine [manufactured by Nikaka Chemical Co., Ltd., Product name: Neofix RD-5, solid content concentration 32% by weight]
An inkjet recording sheet was produced in the same manner as in Example 1 except that 10.94 parts by weight was used. The surface smoothness of the obtained ink jet recording sheet was 40 seconds.

Example 6 Instead of 8.75 parts by weight of the polymer of dimethylamine and epichlorohydrin in the coating liquid for the ink receiving layer in Example 1, a copolymer of diallylamine and allylamine [Nitto Boseki] Product name: PAA-D11-HC
L, solid content concentration 40% by weight] An ink jet recording sheet was produced in the same manner as in Example 1 except that 8.75 parts by weight was used. The surface smoothness of the obtained ink jet recording sheet was 64 seconds.

Comparative Example 1 Silica 1 in the coating liquid for the ink receiving layer in Example 1
Silica [Misawa Chemical Industry Co., Ltd.] in place of 6.92 parts by weight
Product name: Mizukasil P-78F, solid content concentration 100
% By weight, average secondary particle size 12.5 μm, particle size distribution (d1
0 / d90) 0.12] 16.92 parts by weight were used to prepare an ink jet recording sheet in the same manner as in Example 1. The surface smoothness of the obtained ink jet recording sheet was 4.1 seconds.

Comparative Example 2 An ink jet recording sheet was produced in the same manner as in Example 1 except that the ink receiving layer coating liquid was a mixture of the following components. The surface smoothness of the obtained ink jet recording sheet was 190 seconds. (1) Silica [manufactured by Mizusawa Chemical Industry Co., Ltd., trade name: Mizukasil P-78F, solid content concentration 100% by weight, particle size distribution (d10 / d90) 0.12] 35.35 parts by weight (2) cationic Acrylic resin [Shin-Nakamura Chemical Co., Ltd.
Product name: NK polymer AC-11, solid content concentration 3
6% by weight] 98.22 parts by weight (3) Antifoaming agent [manufactured by San Nopco Ltd., trade name: SN deformer 480, solid content concentration 100% by weight] 0.20 parts by weight (4) Dimethylamine and epi Polymerization with chlorohydrin [Nippon Kagaku Co., Ltd., trade name: Neofix RE, solid content concentration 40% by weight] 16.23 parts by weight (5) Fibrous hydrated aluminum oxide [NISSAN CHEMICAL INDUSTRIES ( Ltd., trade name: Alumina sol 200, solid content concentration 1
0 wt%] 5.00 parts by weight (6) Water 45.00 parts by weight

Comparative Example 3 Instead of 8.75 parts by weight of the polymer of dimethylamine and epichlorohydrin in the coating liquid for the ink receiving layer in Example 1, a dicyandiamide condensate [manufactured by Nika Kagaku Co., Ltd.] was used. ,
Product name: Neofix E-117, solid content concentration 50% by weight] An inkjet recording sheet was produced in the same manner as in Example 1 except that 7.00 parts by weight was used. The surface smoothness of the obtained ink jet recording sheet was 51 seconds.

For each of the ink jet recording sheets obtained in Examples 1 to 5 and Comparative Examples 1 and 2, an ink jet printer [manufactured by Seiko Epson Corp.] using surface strength and a commercially available genuine pigment type ink was used. The water resistance of the image when printed with a model name: MC9000] was evaluated. The results are shown in Table 1 together with the surface smoothness.

[0024]

[Table 1]

[0025]

According to the present invention, one or more cationic resins selected from a polymer of dimethylamine and epichlorohydrin, a polyallylamine, and a copolymer of diallylamine and allylamine, and a specific particle size distribution. By providing an ink-receiving layer containing silica with, it has the basic characteristics of a conventional inkjet recording sheet, but is particularly suitable for outdoor use such as posters, which has excellent image water resistance. In addition, an inkjet recording sheet can be provided.

Claims (5)

[Claims] 1. An ink receiving layer is provided on a substrate, and the ink receiving layer is selected from a polymer of dimethylamine and epichlorohydrin, polyallylamine, and a copolymer of diallylamine and allylamine. An ink jet recording sheet comprising one or more cationic resins and silica having a particle size distribution d10 / d90 of 0.22 or more. 2. The ink jet recording sheet according to claim 1, wherein the ink receiving layer further contains polydiallylamine. 3. The ink jet recording sheet according to claim 1, wherein the ink receiving layer has a smoothness according to the Beck method of 10 seconds or more. 4. The ink receiving layer comprises silanol-modified polyvinyl alcohol as a binder.
5. The inkjet recording sheet according to any one of 1. 5. The ink jet recording sheet according to claim 1, wherein the ink receiving layer uses acrylic resin as a binder.