JP2000141874A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink recording sheet of superior light fastness and water resistance of a recorded image and also of superior other properties such as the recording density, recording picture quality and the like. SOLUTION: An ink jet recording sheet is used for forming a recorded image formed by using an aqueous ink, and at least one kind of an ultraviolet absorbent represented by the formula N-2[3-(benzotriazol-2-Y1-5-tert-butyl-4- hydroxyphenyl propyonyl amino] ethyl-N,N,N-trimethyl ammonium chloride or the like (In the formula, R1, R2 and R3 represent a hydrogen atom, C1-C4 alkyl or a C1-C4 hydroxyalkyl and X represents an organic or an inorganic anion. (p) represents a 2-6 integer.) and a dimethyldiallyl ammonium amide copolymer as a cationic polymer are container in the recording sheet.

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 for use in printers, copiers and the like using an aqueous ink, and more particularly to an ink jet recording sheet having excellent light fastness of a recorded image.

[0002]

2. Description of the Related Art Ink jet recording systems are easy to achieve multi-color recording, have low noise, have relatively high recording speed,
It has advantages such as being able to record on a large area, and is currently widely used in various fields such as various printers, facsimile machines and computer terminals, and is rapidly spreading. In the inkjet recording method using an aqueous ink,
With the improvement of printer performance such as printing speed, resolution, gradation, etc., high-speed absorption of ink, high density, high image quality, water fastness of images, and light fastness of images, even for recording sheets Sex is also required.

[0003] In order to respond to such demands, there have been many proposals regarding sheets provided with an ink receiving layer mainly composed of a pigment and an adhesive on a support. For example, a coating layer composed of amorphous silica and a polymer binder (JP-A-55-51583, JP-A-57-157786, and JP-A-62-158084), and a coating layer containing an ink-absorbing pigment such as zeolite. (Japanese Patent Laid-Open No. 56-1441
No. 72), a coating layer composed of finely divided silicic acid and a water-soluble resin (JP-A-56-148583), and a coating layer containing a porous cationic alumina hydrate (JP-A-60-1985).
It is known to provide a support on a support.

Above all, amorphous silica is a pigment most suitable for ink jet recording because it has a high ink absorption speed, a large ink absorption capacity, can print with high image quality, and does not impair the coloring of the dye. It is considered. However, while the ink-receiving layer containing amorphous silica as a main component makes the coloring of the dye clear, it has the disadvantage that it promotes the decomposition of the dye by light and the recorded image is easily discolored or faded with time.

Further, from the viewpoint of improving the water resistance of printing, polycationic polymer electrolytes (JP-A-56-89992, JP-A-60-49990, and JP-A-61-125878).
Japanese Patent Application Laid-Open No. 57-36692), basic latex
Is known in the art. However, although the water resistance of the print is improved by the use of such a water resistance improver, the photodecomposition of the dye is promoted,
There is a problem that light resistance is reduced.

On the other hand, a general method for improving the light fastness of an image is to improve the light fastness of the ink. However, the ink used in the ink jet does not cause clogging of the nozzles and has a vivid color tone. It is indispensable to have dyes and pigments having good heat resistance, and it is not always possible to select dyes and pigments having excellent light resistance. At present, the light resistance of magenta ink is particularly insufficient.

As a method for improving the light fastness of an image from the surface of an ink jet recording sheet, at least one of a metal oxide such as phosphotungstic acid, phosphomolybdic acid, chromic dichloride, a metal chloride or tannic acid is used. (JP-A-57-87987),
A method of adding an antioxidant such as a hindered phenol (JP-A-57-74192), and a method of adding an ultraviolet absorber such as a benzophenone-based, benzotriazole-based or phenylsalicylic acid-based (JP-A-57-74193).
And JP-A-57-87988 and JP-A-63-222885) and a method of adding a hindered piperidine-based light stabilizer and the like (Japanese Patent Application Laid-Open No. 61-146591). However, none of the above-mentioned methods has provided sufficiently satisfactory light resistance and water resistance at present.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording sheet which is excellent in recording density and recording image quality and excellent in water resistance and light resistance of a recorded image.

[0009]

According to the present invention, there is provided an ink jet recording sheet for forming a recorded image using an aqueous ink, wherein the recording sheet contains at least one kind of an ultraviolet absorbent represented by the formula (1). And a dimethyldiallylammonium chloride-acrylamide copolymer as a cationic polymer.

[0010]

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Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group, and X ⁻ represents an organic or inorganic anion. . P represents an integer of 2 to 6. ]

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention has a significant feature in that the above-mentioned specific ultraviolet absorber and a dimethyldiallylammonium chloride-acrylamide copolymer are used in combination. By adopting such a configuration, with respect to the light fastness and water fastness of the image, a remarkable improvement effect is obtained that can be obtained by using each of them alone, and furthermore, the ink jet recording sheet excellent in the recording density and the recording quality. Is what you get.

The following are specific examples of the compound represented by the formula (1). N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4
-Hydroxyphenylpropionylamino] ethyl-
N, N-dimethylammonium chloride, N-2-
[3- (benzotriazol-2-yl) -5-tert-
Butyl-4-hydroxyphenylpropionylamino]
Ethyl-N, N, N-trimethylammonium chloride, N-2- [3- (benzotriazol-2-yl)
-5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N-dimethyl-N-2-hydroxyethylammonium chloride, N-2- [3-
(Benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N-di (2-hydroxyethyl) -N-methylammonium chloride, N-2- [3- ( Benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N-dimethyl-N-ethylammonium chloride, N-2-
[3- (benzotriazol-2-yl) -5-tert-
Butyl-4-hydroxyphenylpropionylamino]
Ethyl-N, N, N-trimethylammonium acetate, N-2- [3- (benzotriazol-2-yl)
-5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium bromide, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4- Hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium iodide, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N ,
N, N-trimethylammonium benzoate, N-2
-[3- (benzotriazol-2-yl) -5-tert
-Butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium sulfate, N-2- [3- (benzotriazole-2-
Yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium-p-toluenesulfate, N-2- [3
-(Benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N-dimethylammonium acetate, N-3
-[3- (benzotriazol-2-yl) -5-tert
-Butyl-4-hydroxyphenylpropionylamino] propyl-N, N, N-trimethylammonium chloride, N-4- [3- (benzotriazole-2-
Yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] butyl-N, N, N-trimethylammonium chloride, N-6- [3- (benzotriazol-2-yl) -5-tert-butyl- 4-hydroxyphenylpropionylamino] hexyl-N, N, N
-Trimethylammonium chloride and the like. Of course, it is not limited to these, and it is also possible to use two or more kinds in combination.

Further, a counter anion in the formula (1) X ^- Specific examples of, for example, chloride, bromide, iodide, phosphate ions, acetate ions, benzoate ions, sulfate ion, nitrate Ion, p-toluenesulfonic acid ion and the like.

The content of the ultraviolet absorbent represented by the formula (1) in the ink jet recording sheet is 0.1 to 3 g.
/ M ² , preferably 0.2 to 1 g / m ² . If the amount is less than 0.1 g / m ² , the effect of improving light resistance becomes insufficient, and if it is more than 3 g / m ² , the image quality may be deteriorated, which is not preferable.

Further, in the ink jet recording sheet, a phenol-based, thioether-based, phosphorus-based antioxidant, a hindered amine-based light stabilizer, a benzotriazole-based, and a benzophenone-based ultraviolet-absorbing agent are provided as long as the effects of the present invention are not impaired. It is also possible to add an agent, a singlet oxygen quencher and the like.

The dimethyldiallylammonium chloride / acrylamide copolymer used as the cationic polymer in the present invention is a copolymer comprising structural units represented by the following formulas (2) and (3), Any of a coalesced, block copolymer or graft copolymer may be used.

[0018]

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[0019]

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In such a copolymer, the molar ratio of the component of the formula (2) to the component of the formula (3) is in the range of 1: 0.02 to 1: 1, preferably 1: 0.05 to 1: 0.5. And the molecular weight is 10,000 or more, preferably 50,000 or more.

As a method for preparing the ink jet recording sheet of the present invention, for example, a method in which the above-mentioned specific cationic polymer and the ultraviolet absorbent are dissolved or dispersed in a base paper by a size press or the like in a paper making process. ,
The coating liquid for the ink-receiving layer obtained by mixing the ink-absorbing pigment, the adhesive, the cationic polymer and the ultraviolet absorber is coated on a support such as a high-quality paper, a synthetic paper, a film, or a nonwoven fabric using a coating machine. Examples include a method of forming an ink receiving layer by coating and drying, and a method of applying a coating liquid in which a cationic polymer and an ultraviolet absorber are dissolved or dispersed on the ink receiving layer formed of a pigment and an adhesive. Note that the ultraviolet absorber and the cationic polymer may be contained in separate layers.

Of these, the method of including an ultraviolet absorber and a cationic polymer in the ink receiving layer is particularly preferable because the effect is obtained by improving the light fastness of an image without deteriorating other qualities.

In the present invention, a dimethyldiallylammonium chloride / acrylamide copolymer is selectively used as the cationic polymer. However, if necessary, other known cationic polymers may be used as long as the effects of the present invention are not impaired. It is also possible to use a polymer in combination. The content of the cationic polymer is usually in the range of 0.1 to 4 g / m ² , preferably 0.2 to ² g / m ² .

Examples of the pigment contained in the ink receiving layer include zeolite, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide,
Zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, aluminum hydroxide, alumina, alumina hydrate, lithopone, urea-formalin resin filler, etc. is there. These may be used alone or in combination. Among these, synthetic amorphous silica, alumina and alumina hydrate are preferable because of their excellent ink receptivity.

The amount of the pigment used in the ink receiving layer is as follows:
It is about 20 to 90% by weight, preferably about 30 to 80% by weight, based on the ink receiving layer. If it exceeds 90% by weight, the coating strength of the ink receiving layer will be reduced, and if it is less than 20% by weight, the ink absorbency will be reduced, and the ink drying property after recording will be insufficient and the image quality may be degraded.

In the ink receiving layer, adhesives such as oxidized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein, gelatin, soy protein, complete (partial)
Aqueous solutions such as saponified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, styrene-maleic anhydride copolymer salts, styrene-butadiene latex, acrylic latex, polyester polyurethane latex, and vinyl acetate latex An adhesive or an organic solvent-soluble resin such as polymethyl methacrylate, a polyurethane resin, an unsaturated polyester resin, a vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and an alkyd resin is used singly or in combination. These adhesives are generally used in an amount of 5 to 120 parts by weight, preferably about 8 to 50 parts by weight, based on 100 parts by weight of the pigment.

Furthermore, a pigment dispersant,
Thickeners, crosslinkers, flow modifiers, defoamers, defoamers, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent brighteners, ultraviolet absorbers, antioxidants, preservatives An agent, an anti-binder, a water-proofing agent, and the like can be appropriately added.

The ink receiving layer comprises a coating liquid for an ink receiving layer,
A coating method such as a bar coater, a blade coater, an air knife coater, and a gravure coater is formed by applying and drying such that the applied amount after drying is at least about ² to 20 g / m ² on at least one surface of the support. . 2g /
When the amount is less than m ² , the recording image quality deteriorates, and 20 g / m ²
If the amount is larger than the above range, the strength of the coating film and the productivity may decrease. After the formation of the ink receiving layer, it is possible to impart surface smoothness by using, for example, a super calender or a gloss calender.

The aqueous ink for forming a recorded image is a recording liquid comprising the following colorant, liquid medium, and other additives. Colorants include direct dyes, acid dyes,
Various water-soluble dyes such as reactive dyes are exemplified. Examples of the liquid medium of the aqueous ink include water alone or a combination of water and a water-soluble organic solvent. Examples of various water-soluble organic solvents include monohydric alcohols such as ethyl alcohol and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol and glycerin, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether. And lower alkyl ethers of polyhydric alcohols. As additives, for example, pH adjusters, sequestering agents,
Anti-binder, viscosity modifier, surface tension modifier, surfactant,
And rust preventives.

[0030]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted to such specific Examples. In the examples, "parts" and "%" indicate parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 N-2- [3- (benzotriazol-2-yl) -5
-Tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium chloride 6 parts, synthetic amorphous silica (trade name: Fine Seal X45, manufactured by Tokuyama Soda) 100 parts, silicon-modified polyvinyl alcohol (Product name: R1130, made by Kuraray) 3
0 parts, 10 parts of a dimethyldiallylammonium chloride-acrylamide copolymer (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical Co., Ltd.) as a cationic polymer, and a solid concentration of 15% consisting of a small amount of an antifoaming agent, a dispersant, and water the ink receiving layer coating solution, by coating and drying a wire bar such that the 10 g / m ² on a solids to fine paper of 65 g / m ^2, after forming the ink receiving layer, and super calendered An ink jet recording sheet was prepared.

Example 2 In Example 1, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium Instead of chloride, N-2-
[3- (benzotriazol-2-yl) -5-tert-
Butyl-4-hydroxyphenylpropionylamino]
An ink jet recording sheet was prepared in the same manner as in Example 1 except that ethyl-N, N-dimethyl-N-hydroxyethylammonium chloride was used.

Example 3 In Example 1, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium Instead of chloride, N-2-
[3- (benzotriazol-2-yl) -5-tert-
Butyl-4-hydroxyphenylpropionylamino]
An ink jet recording sheet was prepared in the same manner as in Example 1 except that ethyl-N, N-dimethylammonium chloride was used.

Comparative Example 1 In Example 1, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium An ink jet recording sheet was prepared in the same manner as in Example 1 except that chloride was not used.

Comparative Example 2 In Example 1, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium An ink jet recording sheet was prepared in the same manner as in Example 1 except that 22 parts of the following additive dispersion liquid was added instead of chloride. [Preparation of additive dispersion] 2- (2'-hydroxy-5 '
A mixture of 15 parts of (-methylphenyl) benzotriazole), 10 parts of a 5% aqueous solution of polyvinyl alcohol, and 30 parts of water was pulverized with a sand mill until the average particle diameter became 1.0 μm to obtain a dispersion.

Comparative Example 3 In Example 1, N-2- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenylpropionylamino] ethyl-N, N, N-trimethylammonium Instead of chloride, methyl-3
Same as Example 1 except that a condensate of-[3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight: about 3000) was used. Thus, an ink jet recording sheet was prepared.

Comparative Example 4 In Example 1, dicyandiamide polyalkylene polyamine (trade name: Neofix E-) was used in place of dimethyl diallylammonium chloride-acrylamide copolymer (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical). 117, manufactured by Nikka Chemical Co., Ltd.), and an ink jet recording sheet was prepared in the same manner as in Example 1.

The following evaluations were performed on the ink jet recording sheets obtained in the above Examples and Comparative Examples. [Light resistance of image portion] Solid printing was performed on the ink jet recording sheet with magenta (M) ink using an ink jet printer (model name: BJC-420J, manufactured by Canon Inc.). Regarding the obtained image portion, a light source: xenon, 6
Weather meter set to 3 ゜ C, 40% RH (Model name: SUNSHINE XENON LONG LIFE WEATHER ME
TER, manufactured by Suga Test Instruments Co., Ltd.) for 72 hours, and the density before and after the irradiation is measured by a Macbeth densitometer (model: RD-914, using a magenta filter, manufactured by Macbeth Co.), and the image fading rate is calculated by the following equation. , Are shown in the table. Image fading rate (%) = [1- (density after irradiation) / (density before irradiation)] × 100

[Water Resistance of Image Area] The image area obtained by printing in the same manner as above was immersed in water at 25 ° C. for 5 minutes, and the density before and after immersion was measured with a Macbeth densitometer (model: RD-914, magenta filter). Used, manufactured by Macbeth Co., Ltd.), and the image fading rate was calculated from the following formula, and is shown in the table. Image fading rate (%) = [1- (density after immersion) / (density before immersion)] × 100

[0040]

[Table 1]

[0041]

As is clear from the table, the ink jet recording sheet of the present invention was a sheet excellent in light resistance and water resistance of an image.

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[Procedure amendment]

[Submission date] March 26, 1999 (1999.3.2
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

The following evaluations were performed on the ink jet recording sheets obtained in the above Examples and Comparative Examples. [Light resistance of image portion] Solid printing was performed on the ink jet recording sheet with magenta (M) ink using an ink jet printer (model name: BJC-420J, manufactured by Canon Inc.). Regarding the obtained image portion, a light source: xenon, 6
Weather meter set to 3 ゜ C, 40% RH (Model name: SUNSHINE XENON LONG LIFE WEATHER ME
Light irradiation with TER, manufactured by Suga Test Instruments Co., Ltd. for 72 hours, and Macbeth densitometer (model: RD-914, green ) before and after irradiation
( Using a filter , manufactured by Macbeth Co., Ltd.), and the image fading rate was calculated from the following formula, and is shown in the table. Image fading rate (%) = [1- (density after irradiation) / (density before irradiation)] × 100

Claims (1)

[Claims] 1. An ink jet recording sheet for forming a recorded image using an aqueous ink, wherein the recording sheet contains at least one ultraviolet absorbent represented by the formula (1), An ink-jet recording sheet comprising a dimethyldiallylammonium chloride-acrylamide copolymer as a polymer. Embedded image [Wherein, R ₁ , R ₂ , and R ₃ each represent a hydrogen atom, C _1-
An alkyl or hydroxyalkyl group C ₁ -C ₄ a C _4, X ^- represents an organic or inorganic anion. P represents an integer of 2 to 6. ]