JP2003266926A - Ink jet recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording material which shows a high coated layer strength of an ink receiving layer, a reliable continuous paper supply performance at an ink jet recording device and an outstanding yellowing resistance of a white paper part, in the ink jet recording material with an ink receiving layer formed on a support. <P>SOLUTION: In the ink jet recording material with an ink receiving layer formed on the support, the ink receiving layer contains a water-soluble polyvalent metallic salt and a polymer ultraviolet absorbent. The ink receiving layer can contain a fluorescent whitening agent and the water-soluble polyvalent metallic salt is preferably an organic acid metallic salt. The polymer ultraviolet absorbent is preferably a water dispersion fine particle or water-soluble. In addition, the support is preferably an acidic paper and a pigment used in the ink receiving layer is preferably amorphous silica. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inkjet recording material, and more particularly to an inkjet recording material having an ink receiving layer provided on a support.

[0002]

2. Description of the Related Art An ink jet recording system is a system in which minute droplets of ink are ejected according to various operating principles to adhere to a recording material such as paper to record an image or characters. The inkjet recording device used for inkjet recording is
The flexibility of the recording pattern is great, the high-speed printing property and the low noise property are excellent, and the features such as no development and fixing are required, and not only can complex images be formed accurately and quickly, but especially characters created by a computer and As a hard copy creating apparatus for image information such as various figures, it has become popular rapidly in recent years. It is also easy to perform multicolor recording using a plurality of ink nozzles. The color image formed by the multi-color inkjet recording method can obtain a recording comparable to that of the multi-color printing by the plate making method or the printing by the color photographic method. However, it is being widely applied because it is more economically advantageous than the printing method and the photographic method.

Further, with the diversification of applications, it has come to be used for large format posters, POP arts, and drawing applications. In these applications, the high sharpness of the ink jet is utilized and the excellent color property allows the formation of a good image, which has a great advertising effect. Adaptation to these is also a reason for diversifying inkjet recording materials because it is possible to easily obtain images with excellent image reproducibility and color reproducibility such as sharpness and color at the personal computer level. There is.

With the recent increase in the number of hard copies, such an ink jet recording apparatus is required to have a higher speed. Increasing the speed of ink jet recording apparatuses has been realized by improving ink ejection speed, arranging ink nozzles in parallel and increasing size, improving ink nozzle moving speed, and improving ink absorption speed of ink jet recording material. Due to the increase in the speed of the inkjet recording apparatus, the conveying speed of the inkjet recording material has increased, so that an inkjet recording material having excellent conveying properties corresponding to the increase has been required.

In general, such an ink jet recording material is provided with an ink receiving layer on a support in order to obtain excellent image reproducibility and color reproducibility. The coating layer strength of the ink receiving layer is one of the characteristics that affect the transportability of the inkjet recording material. In an inkjet recording device,
The inkjet recording material is conveyed mainly by a pickup roll-covering elastic body (paper feed roller). If the coating strength of the ink receiving layer is weak, the ink receiving layer peels from the support, and the powder of the ink receiving layer adheres to the paper feed roller when the ink receiving layer is conveyed by the inkjet recording device. When the amount of powder in the ink receiving layer adhering to the paper feed roller increases, the coefficient of friction between the inkjet recording material and the paper feed roller decreases, and continuous paper feeding causes paper feed failure and paper discharge failure.

There have been many proposals for increasing the coating strength of the ink receiving layer. The method of overcoating the ink receiving layer with a resin or the like or the method of curing the hydrophilic binder in the ink receiving layer lowers the ink absorbability of the ink receiving layer and causes bleeding at the print boundary. JP-A-5
JP-A-221115 discloses an inkjet recording material in which starch particles are added to an ink receiving layer, but the strength of the ink receiving layer itself is increased, but it is not satisfactory in terms of ink bleeding and transfer to other paper. Is enough.

Japanese Unexamined Patent Publication (Kokai) No. 6-278357 discloses a method using colloidal silica. When continuous paper feeding is carried out, the initial carrying property is good, but as the number of carried paper sheets increases, the ink jet ink is used. The coefficient of friction between the recording material and the paper feed roller tends to decrease, resulting in defective paper feeding and defective paper ejection.

On the other hand, in order to obtain the whiteness of the appearance of the ink receiving layer, a fluorescent whitening agent dye may be contained, but the fluorescent whitening agent dye is decomposed by light and its action is lowered,
There is a problem that the inkjet receiving layer is discolored.

Japanese Unexamined Patent Publication (Kokai) No. 8-169172 discloses a method of incorporating a UV-absorbing cationic polymer. Although it is effective in yellowing resistance to an antioxidant contained in a file, it has light resistance. The yellowing resistance of the white paper part is insufficient.

Japanese Unexamined Patent Publication No. 2000-103160 discloses a method of incorporating a polyvalent metal ion, but does not describe the interaction with a polymeric ultraviolet absorber and the yellowing resistance of a blank part.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink-jet coating which has a high coating strength of the ink-receiving layer, is excellent in continuous feeding property in an ink-jet recording apparatus, and is excellent in yellowing resistance of a blank portion. A recording material is provided.

[0012]

DISCLOSURE OF THE INVENTION The inventor of the present invention enhances the coating layer strength in order to provide an ink jet recording material which is excellent in continuous paper feeding property in an ink jet recording apparatus and is excellent in yellowing resistance of a white paper portion. The method and the method for improving the yellowing resistance of the white paper portion were intensively studied. As a result, in the ink jet recording material in which the ink receiving layer is provided on the support, the above problem was solved by containing the water-soluble polyvalent metal salt and the polymer ultraviolet absorber in the ink receiving layer.

In a preferred embodiment, the ink receiving layer contains a fluorescent whitening dye.

In a preferred embodiment, the water-soluble polyvalent metal salt is an organic acid metal salt.

In a preferred embodiment, the polymer ultraviolet absorber is water-dispersed fine particles or water-soluble.

In a preferred embodiment, the support is acid paper.

In a preferred embodiment, the pigment used in the ink receiving layer is made of amorphous silica.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The ink jet recording material of the present invention will be described in detail below.

The water-soluble polyvalent metal compound used in the present invention is a water-soluble metal selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten and molybdenum. The salt may be a salt. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, cupric chloride. ,
Ammonium chloride copper (II) dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium ammonium hexahydrate Hydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, Ferric chloride, ferrous sulfide, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc salicylate, zirconium acetate, zirconium chloride, zirconium chloride octadecahydrate, hydroxy Zirconium chloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate , Sodium phosphate, sodium tungsten citrate, 12 tungstophosphoric acid n-hydrate, dodecatungstosilicic acid 26-hydrate, molybdenum chloride, dodecamolybdophosphoric acid n-hydrate.

The water-soluble polyvalent metal salt used in the present invention is
Organic acid polyvalent metal salts are more preferred. Among the organic acid polyvalent metal salts, organic sulfonic acid metal salts, organic sulfuric acid ester metal salts are preferable, for example, benzene sulfonic acid metal salts, naphthalene sulfonic acid metal salts and the like are known, as the substituents to have these , Alkyl group, alkenyl group, hydroxyl group, mercapto group, nitro group, nitroso group,
Examples thereof include amino group, oxyamino group, hydrazino group, halogen group, aldehyde group, ketone group and carboxyl group. Further, it may have two or more different substituents. Of these, preferred are calcium toluene sulfonate, zinc toluene sulfonate, calcium phenol sulfonate, zinc phenol sulfonate, and zinc sulfosalicylate.

The water-soluble polyvalent metal salt used in the present invention means a polyvalent metal salt which is soluble in water at 20 ° C. in an amount of 1% by mass or more. The content of the water-soluble polyvalent metal salt used in the present invention in the ink receiving layer is preferably 0.1 to 50 mmol / m ^{2, and} more preferably 0.2 to 20 mmol / m ² . If it is less than 0.1 mmol / m ² , the effect is insufficient, and if it exceeds 50 mmol / m ² , the hue of the ink receiving layer changes or the hue balance of the image changes.

The high molecular weight ultraviolet absorber used in the present invention is preferably an acrylic polymer having a skeleton acting as an ultraviolet absorber in its side chain. Other monomer units that can be introduced into the copolymer composition together with an acrylic monomer having a skeleton acting as an ultraviolet absorber in the side chain,
Styrene and its derivatives, as various esters of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, other esters, or
(Meth) acrylic acid 2-hydroxyethyl ester,
(Meth) acrylic acid 2-hydroxypropyl ester,
Examples thereof include (meth) acrylic acid 2-methoxyethyl ester, various other (meth) acrylic acid esters, (meth) acrylamide and derivatives thereof, vinyl acetate, and many other monomers. These monomers are 1
One kind or two or more kinds can be copolymerized and used.

Examples of the skeleton which acts as an ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylic acid-based, cyanoacrylate-based and triazine-based skeletons, preferably benzophenone-based and benzotriazole-based. For example, the following can be illustrated.

The benzophenone type compounds include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4.
-Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,
4'-dimethoxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane,
2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) ethoxybenzophenone, 2-hydroxy-4-
(2-methacroyloxy) ethoxybenzophenone,
2-hydroxy-4- (2-methyl-2-acryloyloxy) ethoxybenzophenone and the like can be mentioned.

As the benzotriazole type, 2-
(2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-3 ', 5' -Di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,2'-methylenebis (4-t-octyl-6- Benzotriazole) phenol, 2- (2'-hydroxy-3 ', 5'
-Dicumylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-aminophenyl)
Benzotriazole, 2- {2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -tetrahydroftylimidomethyl) -5'-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- {2'-hydroxy-
5 '-(methacryloyloxy) phenyl} benzotriazole, 2- {2'-hydroxy-5'-(acryloyloxy) phenyl} benzotriazole, 2-
{2'-hydroxy-3'-t-butyl-5 '-(methacryloyloxy) phenyl} benzotriazole, 2
-{2'-hydroxy-3'-methyl-5 '-(acryloyloxy) phenyl} benzotriazole, 2-
{2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl} -5-chlorobenzotriazole,
2- {2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'
-Hydroxy-5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'- Hydroxy-3'-methyl-5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-
Hydroxy-5 '-(methacryloyloxypropyl)
Phenyl} -5-chlorobenzotriazole, 2-
{2'-hydroxy-5 '-(acryloyloxybutyl) phenyl} -5-methylbenzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-carboxyphenyl) benzotriazole, 2- {2'-hydroxy-5 '-(acryloyloxybutyl) phenyl} -5-methylbenzotriazole, {2- Hydroxy-3-t-butyl-5- (acryloyloxyethoxycarbonylethyl) phenyl} benzotriazole and the like can be mentioned.

Examples of the salicylic acid type include phenyl salicylate, pt-butylphenyl salicylate and p-octylphenyl salicylate.

Examples of cyanoacrylates include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, methyl-2-cyano-3-methyl-3. −
(P-Methoxyphenyl) acrylate and the like can be mentioned.

As the triazine type, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,2)
4-di-t-butylphenyl) -s-triazine, 2-
(2-Hydroxy-4-methoxyphenyl) -4,6-
Diphenyl-s-triazine, 2- (2-hydroxy-
4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-t-butylphenyl-s-triazine)
Etc.

The high molecular weight ultraviolet absorber used in the present invention has a molecular weight of 2000 or more. Further, the molecular weight is preferably 7,000 or more. When the molecular weight is 7,000 or more, long-term yellowing resistance of the white paper portion can be obtained. Molecular weight is 200
In the case of a low molecular weight UV absorber of about 500 to 500, the UV absorber itself lacks long-term stability, and bleed-out occurs from the ink receiving layer, which affects the hue of the image and long-term white paper resistance. No yellowing is obtained.

The polymer ultraviolet absorber used in the present invention is preferably water-dispersed fine particles or water-soluble. The average particle size of the water-dispersed fine particles is preferably 2 μm or less. There is no particular lower limit to the average particle size, and particles having a size of about 1 nm can be obtained. If the average particle size exceeds 2 μm, the printing density when printing with an inkjet recording device may decrease, which is not preferable.

Examples of water-dispersed fine particles of the polymer ultraviolet absorber are K-840 (manufactured by Chukyo Yushi Co., Ltd.) and Sun Life UA.
-20 (manufactured by Nichika Chemical Co., Ltd.), Eva Color (manufactured by Satoda Kako Co., Ltd.), UDouble Series (manufactured by Nippon Shokubai Chemical Co., Ltd.),
ULS series (manufactured by Yatasha Yushi Kogyo Co., Ltd.) and the like can be mentioned.

Examples of water-soluble polymeric UV absorbers include RUVA-CW21, NW18, 30W (Otsuka Chemical Co., Ltd.) and the like.

The polymeric ultraviolet absorbers used in the present invention may be used alone or in combination of two or more.
The content in the ink receiving layer is preferably 0.0001 to 1 g / m ² in terms of active ingredient. 0.000
If it is less than 1 g / m ² , the effect will be insufficient and 1 g / m ²
If the amount is larger, the effect is not improved so much, the hue of the ink receiving layer is changed, or the hue balance of the image is changed.

When both the water-soluble polyvalent metal salt used in the present invention and the polymer ultraviolet absorber are present in the ink receiving layer, the coating layer strength is increased and the yellowing resistance of the white paper portion is improved.
Although the reason is not clear, it is considered that there is an interaction between the metal ion of the metal salt and the structure of the polymer ultraviolet absorber. The effect is insufficient with a low molecular weight UV absorber.

Examples of the fluorescent whitening dye used in the present invention include stilbene-based, distilbene-based, benzoxazole-based, coumarin-based, imidazole-based, benzimidazole-based, and pyrazoline-based dyes, and the dye itself is preferable. It is a stilbene type with excellent stability.

The content of the fluorescent whitening dye in the ink receiving layer is 0.5 g / m ² or less, and may be omitted if the whitening effect is unnecessary. When the ink receiving layer contains a fluorescent whitening agent, the low molecular weight UV absorber was insufficient in the yellowing resistance of the white paper portion for a long period of time against light irradiation, but when the polymeric UV absorber of the present invention was used. Long-term resistance to yellowing of white paper can be obtained.

The support in the present invention is a paper containing pulp and a filler as main components. As natural pulp,
Chemical pulp such as LBKP, NBKP, GP, PGW, R
Examples include mechanical pulp such as MP, TMC, CTMP, CMP and CGP, semi-chemical pulp, waste paper pulp such as DIP, and also non-wood pulp such as kenaf, bacus and cotton, and synthetic pulp. . These are 1
One kind or a mixture of two or more kinds can be used.

The support in the present invention is preferably acidic base paper containing natural pulp as a main component, or neutral base paper with a sulfuric acid band liquid or the like on a tab size press, simsizer, air knife coater, blade coater, Pseudo-acidic base paper coated with a gate roll coater, bar coater, rod coater, roll coater, bill blade coater, short dwell blade coater, etc., among which acidic base paper is particularly preferable.

As a support for the ink jet recording material,
When so-called neutral paper containing natural pulp as the main component and mixed with heavy calcium carbonate or light calcium carbonate in the filler is used, the surface pH of the ink receiving layer shifts to the alkaline region with time. . This is because the filler is a solid alkali and affects the pH of the entire inkjet recording material including the ink receiving layer. The ink receiving layer is preferably acidic, that is, has a pH of 3 to 6.5. If the surface pH exceeds 6.5, the image storability is deteriorated. When an acidic base paper is used as the support in the present invention,
It is possible to obtain an inkjet recording material having high coating layer strength, excellent continuous feeding property, high yellowing resistance of a white paper portion, and good image storability.

In the present invention, the surface pH of the ink receiving layer
J. TAPPI paper pulp test method No. According to the method described in 6, a drop of a pH indicator is dropped on the surface of the test piece, and the color of the extract is measured by a standard color change table or a single drop extraction method in which the pH is determined by comparing with the pH standard color change solution.

The support used in the present invention includes, in addition to conventionally known fillers generally used in papermaking, a binder, an internally added sizing agent, a paper strength enhancer, an optical brightening agent, if necessary.
One or more kinds of various additives such as a yield improving agent and a coloring agent such as a dye or a pigment may be mixed.

When an internally added colorant is used in the support of the present invention, a water-soluble dye represented by a direct dye, a basic dye, a reactive dye, an edible dye or the like, a colored inorganic pigment such as a yellow red orange system, Pigments such as colored organic pigments and azo organic pigments are used, and yellow dyes and pigments are particularly preferable.

The ink-receiving layer according to the present invention is absorptive, image reproducible and colored for inks containing dyes and pigments used in commercially available ink jet recording devices (ink jet printers, ink jet plotters, ink jet proofers, etc.). It is composed of a composition mainly composed of a pigment and a binder satisfying the above characteristics. Further, in the case of being applied to an ink jet recording system in which dye ink is also used, it is preferable to contain a cationic compound in addition to the above. Further, as other additives, a pigment dispersant,
Thickeners, leveling agents, coloring dyes, coloring pigments, antioxidants, surfactants, defoamers, foam suppressors, foaming agents, penetrants, mold release agents, preservatives, antivibrating agents, water resistant agents, Wet strength agent,
Various additives such as a dry paper strength enhancer and a pH adjuster may be added in appropriate combination.

Examples of the pigment used in the ink receiving layer of the present invention include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, chisan white and silicic acid. Aluminum, diatomaceous earth, calcium silicate,
Magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, vapor phase silica, aluminum oxides such as α, β, γ, δ-, aluminum hydroxide, alumina, lithopone, zeolite, hydrohalloysite, One or more white pigments such as white inorganic pigments such as magnesium carbonate and magnesium hydroxide, styrene plastic pigments, acrylic plastic pigments, organic pigments such as polystyrene, urea resins and melamine resins can be used. Among them, porous inorganic pigments are preferable, and porous synthetic amorphous silica, porous magnesium carbonate, porous alumina and the like can be mentioned, and porous synthetic amorphous silica having a large pore volume is particularly preferable. Usually, the average particle size of these pigments is preferably in the range of 0.1 to 20 μm. When amorphous silica is used in the present invention, not only the coating layer strength is high, the continuous sheet feeding property is excellent, the image storability is good, and the high ink absorbency is obtained.

Examples of the binder used in the ink receiving layer of the present invention include natural polymer substances such as potato starch, sweet potato starch, wheat starch, tapioca starch, and starches such as cornstarch, laminaran, seaweed mannan, fuinori, Those obtained from algae such as Irish moss, agar, and alginate, grated yam, yam, mannan, quince seed, pectin, tragacanth gum, karaya gum, xanthine gum, guar gum, locust bean gum, tamarind seed gum, arabic gum, carob gum. , And vegetable mucilages such as benzoin gum, homopolysaccharides such as dextran, glucan, xanthan gum, and levan, and microbial mucilages such as succinoglucan, pullulan, curdlan, and heterosaccharides such as xanthan gum, glue, gelatin , Casein, and proteins such as collagen and the like.

As the semi-natural product (semi-synthetic product), propylene glycol alginate, viscose,
Fiber cellulose derivatives such as methyl cellulose, ethyl cellulose, methyl ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, carboxymethyl hydroxyethyl cellulose, and hydroxypropyl methyl cellulose phthalate, carboxymethyl guar gum, hydroxypropyl guar gum, and Examples thereof include modified gums such as hydroxyethyl guar gum, and processed or derivatives of the above natural polymer substances.

As the modified starch which is a semi-synthetic product, white dextrin, yellow dextrin, cultivated starch such as bridish gum, enzyme-modified dextrin such as enzyme dextrin and Schardinger dextrin, acid-decomposed starch such as solubilized starch, Oxidized starch such as dialdehyde starch, pregelatinized starch such as modified and non-modified pregelatinized starch,
Esterified starch such as starch phosphate, fatty acid starch, starch sulfate, nitrate nitrate, xanthate starch, and carbamic acid starch, hydroxyalkyl starch, carboxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamyl Etherified starch such as ethyl starch and dialkylamino starch, methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch, and crosslinked starch such as dicarboxylic acid crosslinked starch, starch polyacrylamide copolymer, starch polyacrylonitrile copolymer , Cationic starch polyacrylate copolymer,
Examples include cationic starch vinyl polymer copolymers, starch styrene maleic acid copolymers, starch graft copolymers such as starch polyethylene oxide copolymers, and the like.

As synthetic products, polyvinyl alcohol,
Silyl-modified polyvinyl alcohol, partially acetalized polyvinyl alcohol, allyl-modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isobutyl ether and other modified polyvinyl alcohol, polyacrylic acid salts, polyacrylic acid ester partially saponified products, polymethacrylic acid Salts, polyacrylic acid derivatives and polymethacrylic acid derivatives such as polyacrylic amide, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone vinyl acetate copolymer, styrene butadiene copolymer (SBR), nitrile butadiene copolymer ( NBR),
Examples thereof include a styrene acrylic acid ester copolymer, a styrene maleic acid copolymer, a styrene crotonic acid copolymer, and a vinyl chloride-containing copolymer. The above binders may be used alone or in combination of two or more.

The cationic compound used in the ink receiving layer of the present invention is a salt insoluble in the sulfonic acid group, carboxyl group, amine group, etc. in the water-soluble direct dye or water-soluble acid dye which is the water-soluble ink dye component. Secondary amine, which forms
Examples thereof include compounds containing a primary amino or quaternary ammonium salt. The cationic compounds may be used alone or in combination of two or more.

The layer structure of the ink receiving layer of the present invention may be a single layer or a laminated layer. In the case of a laminated structure, all layers may be layers having the same composition, or may be a laminated structure with layers composed of other components. In the case of stacking, the water-soluble polyvalent metal salt and the polymer ultraviolet absorber may be contained in any one layer, or may be contained in two or more layers. From the viewpoint of improvement, the outermost layer is preferable.

The coating amount of the ink receiving layer of the present invention is as follows.
It is preferably in the range of 1 to 40 g / m ² . If the coating amount is less than 1 g / m ² , the ink absorbability of the ink receiving layer is not sufficient, so that uneven absorption occurs and the ink jet performance is adversely affected. When it exceeds 40 g / m ² , the adhesive strength between the ink receiving layer and the support is lowered.

The ink receiving layer may be coated on the support according to the present invention by a slide popper coating method,
Curtain coating method, extrusion coating method, air knife coating method, blade coating method, roll coating method, rod bar coating method, and gravure coating method,
Examples include size press coating method and spray coating method. These coating methods can be performed on-machine or off-machine. Also,
After coating, it may be finished using a calendar. Examples of the calendar method include a machine calendar method, a TG calendar method, a super calendar method, a soft calendar method, an embossing calendar method and the like.

The thickness of the ink jet recording material of the present invention is preferably about 50 to 300 μm. If it exceeds 300 μm, the rigidity becomes high and the flexibility of the recording material is lacking, so that the transportability in the ink jet recording apparatus is deteriorated. If it is less than 50 μm, the printing characteristics (cockling, ink absorbency, etc.) may be adversely affected, and the rigidity of the ink jet recording material is lowered, so that the transportability in the ink jet recording apparatus is deteriorated.

The ink used for recording the ink jet recording material of the present invention is generally a recording liquid containing the following colorant, solvent and other additives.

Examples of the colorant for the ink include direct dyes, basic dyes, reactive dyes, dyes such as water-soluble dyes represented by food dyes, colored inorganic pigments such as carbon black, phthalocyanine organic pigments, and azo. Examples include pigments such as organic pigments.

The solvent of the ink is water and various water-soluble organic solvents. For example, alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, dimethylformamide, dimethylacetamide. Amides such as, ketones or ketone alcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol Alkylene such as 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol There 2-6 alkylene glycol, glycerol, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether, and the like. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferable. Other additives include, for example, a pH adjusting agent, a sequestering agent, an antifungal agent, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a surfactant, and a rust preventive agent.

[0057]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Also,
The parts and% shown in the examples are parts by mass and% by mass of solid content or substantial components, unless otherwise specified.

<Preparation of Support A> 80 parts of hardwood bleached kraft pulp (LBKP, freeness 370 mlcsf) and softwood bleached kraft pulp (NBKP, freeness 400 mlcs)
f) From a slurry prepared by mixing 20 parts, 13 parts of talc, 3 parts of sulfuric acid band, 0.2 part of a commercial rosin sizing agent and 0.3 part of cationic starch with water, a basis weight of 100 g /
and papermaking base paper of m ^2, and to produce a support A acidic base paper 2 g / m ² deposited was in a solid content of oxidized starch by a size press apparatus during papermaking. The pH of the surface of this base paper was 4.6.

<Preparation of Support B> 80 parts of broadleaf bleached kraft pulp (LBKP, freeness 370 mlcsf) and softwood bleached kraft pulp (NBKP, freeness 400 mlcs)
f) 20 parts, 13 parts ground calcium carbonate, 1 part cationic starch, 0.08 part alkyl ketene dimer sizing agent and polyalkylene polyamine epichlorohydrin resin 0.
Medium 4 parts from the slurry obtained by mixing the water and papermaking raw paper having a basis weight of 100 g / m ² at Fourdrinier and papermaking Size when not oxidized starch in solid with the press device 2 g / m ² is adhered to A base material B of a sex paper was manufactured. The pH of the surface of this base paper was 7.8.

<Ink Receiving Layer Coating Liquid A> Amorphous silica fine particles (Mizukasil P78A: as a pigment for the ink receiving layer).
Average particle size 3.3 μ: 100 parts by Mizusawa Chemical Co., Ltd., 20 parts by weight of polyvinyl alcohol (R1130: Kuraray Co., Ltd.), 20 parts of cationic dye fixing agent (SUMIREZ RESIN 1001: Sumitomo Chemical Co., Ltd.), and basic The content of polyaluminum hydroxide (Purachem WT: manufactured by Riken Green Co., Ltd.) when the ink receiving layer was dried was 0.5 mmol / m ² , and the water-dispersible polymer ultraviolet absorber (benzotriazole type, molecular weight 10).
(More than 0,000) (ULS-1700: manufactured by Yansha Yushi Kogyo Co., Ltd.)
Was dissolved in water so as to have a content of 0.8 g / m ² when the ink receiving layer was dried and mixed to prepare an ink receiving layer coating liquid A having a solid content of 15%.

<Ink Receiving Layer Coating Liquid B> Ink receiving layer coating liquid A is a basic polyaluminum hydroxide (Purachem W).
T: manufactured by Riken Green Co., Ltd.) with a solid content of 15% by replacing the content in the ink receiving layer when dried to 40 mmol / m ^2.
Ink receiving layer coating liquid B

<Ink Receiving Layer Coating Liquid C> Water-dispersible polymer ultraviolet absorber of ink receiving layer coating liquid A (benzotriazole type, molecular weight of 1,000,000 or more) (ULS-1700: manufactured by Yatasha Yushi Kogyo Co., Ltd.) Was replaced with a content of 0.01 g / m ² when the ink receiving layer was dried to obtain an ink receiving layer coating liquid C having a solid content of 15%.

<Ink receiving layer coating liquid D> Average particle diameter 10
-20 nm colloidal silica (Snowtex O: Nissan Chemical Co., Ltd.) 20 parts, amorphous silica fine particles (Mizukasil P78A: average particle diameter 3.3 μ: Mizusawa Chemical Co., Ltd.) 100
Part, fluorescent whitening dye (Brancophor Pliq.01: manufactured by Bayer) 3 parts, polyvinyl alcohol (PVA11
7: Kuraray Co., Ltd.) 20 parts, cationic dye fixing agent (Sumireds Resin 1001: Sumitomo Chemical Co., Ltd.) 20 parts, and
The content of basic polyaluminum hydroxide (Purachem WT: manufactured by Riken Green Co., Ltd.) when the ink receiving layer is dried is 20 mmol / m ² , and the water-dispersible polymer ultraviolet absorber (benzotriazole-based, molecular weight 1,000,000 or more) ( ULS-170
No. 0 (manufactured by Yushisha Kogyo Kogyo Co., Ltd.) was dissolved and mixed in water so that the content when the ink receiving layer was dried was 0.3 g / m ² , to prepare an ink receiving layer coating liquid D having a solid content of 15%. .

<Ink Receiving Layer Coating Liquid E> Amorphous silica fine particles (Mizukasil P78A:
Average particle size 3.3 μ: 100 parts by Mizusawa Chemical Co., Ltd., 20 parts by weight of polyvinyl alcohol (R1130: Kuraray Co., Ltd.), 20 parts of cationic dye fixing agent (SUMIREZ RESIN 1001: Sumitomo Chemical Co., Ltd.), and basic Polyaluminum hydroxide (Purachem WT: manufactured by Riken Green Co., Ltd.) has a content of 0.5 mmol / m ² when the ink receiving layer is dried, and a water-dispersible polymer ultraviolet absorber (benzophenone type, molecular weight of 1,000,000 or more) (ULS -383 MG: manufactured by Yushisha Kogyo Kogyo Co., Ltd.) was dissolved and mixed in water so that the content when the ink receiving layer was dried was 0.8 g / m ^2, and an ink receiving layer coating liquid E having a solid content of 15% was obtained. did.

<Ink Receiving Layer Coating Liquid F> Amorphous silica fine particles (Mizukasil P78A:
Average particle size 3.3 μ: 100 parts by Mizusawa Chemical Co., Ltd., 20 parts by weight of polyvinyl alcohol (R1130: Kuraray Co., Ltd.), 20 parts of cationic dye fixing agent (SUMIREZ Resin 1001: Sumitomo Chemical Co., Ltd.), and thiocyanic acid. The content of calcium tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) when the ink receiving layer is dried is 0.5 mmol / m ² , and the water-dispersible polymer ultraviolet absorber (benzophenone type, molecular weight of 1,000,000 or more) (ULS
-383 MG: manufactured by Yushisha Kogyo Kogyo Co., Ltd.) in water so that the content when the ink receiving layer is dried is 0.8 g / m ² .
The mixture was mixed to obtain an ink receiving layer coating liquid F having a solid content of 15%.

<Ink Receiving Layer Coating Liquid G> 100 parts of amorphous silica fine particles (Mizukasil P50: average particle size 9.5 μ: manufactured by Mizusawa Chemical Co., Ltd.) as a pigment for the ink receiving layer, fluorescent whitening dye (Brancophore Pliq) .01: manufactured by Bayer)
3 parts, polyvinyl alcohol (R1130: manufactured by Kuraray Co., Ltd.) 20 parts, cationic dye fixing agent (Sumireds resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) 20 parts, and water-soluble polymer ultraviolet absorber (benzotriazole type, molecular weight 1000)
(About 0) (RUV-NM18: manufactured by Otsuka Chemical Co., Ltd.) has a content of 0.8 g / m ² when the ink receiving layer is dried, and contains zinc p-phenolsulfonate (manufactured by Kishida Chemical Co., Ltd.) when the ink receiving layer is dried. It was dissolved and mixed in water to give an amount of 0.5 mmol / m ² to obtain an ink receiving layer coating liquid G having a solid content of 15%.

<Ink Receiving Layer Coating Liquid H> 100 parts of amorphous silica fine particles (Mizukasil P50: average particle size 9.5 μ: manufactured by Mizusawa Chemical Co., Ltd.) as a pigment for the ink receiving layer, fluorescent whitening dye (Brancophore Pliq) .01: manufactured by Bayer)
3 parts, polyvinyl alcohol (R1130: manufactured by Kuraray Co., Ltd.) 20 parts, cationic dye fixing agent (Sumireds resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) 20 parts, and water-soluble polymer ultraviolet absorber (benzotriazole type, molecular weight 1000)
(About 0) (RUV-NM18: Otsuka Chemical Co., Ltd.) has a content of 0.8 g / m ² when the ink receiving layer is dried, and zinc 5-sulfosalicylate (Kanto Chemical Co., Ltd.) has a content of the ink receiving layer when dried. Dissolved in water so that the concentration becomes 0.5 mmol / m ² ,
The mixture was mixed to obtain an ink receiving layer coating liquid H having a solid content of 15%.

<Ink Receiving Layer Coating Liquid I> Amorphous silica fine particles (Mizukasil P78A:
Average particle size 3.3 μ: 100 parts of Mizusawa Chemical Co., Ltd., 20 parts of polyvinyl alcohol (R1130: Kuraray Co., Ltd.), 20 parts of cationic dye fixing agent (SUMIREZ Resin 1001: Sumitomo Chemical Co., Ltd.) are dissolved in water. The mixture was mixed to obtain an ink receiving layer coating liquid I having a solid content of 15%.

<Ink receiving layer coating liquid J> Average particle diameter 10
-20 nm colloidal silica (Snowtex O: Nissan Chemical Co., Ltd.) 20 parts, amorphous silica fine particles (Mizukasil P78A: average particle diameter 3.3 μ: Mizusawa Chemical Co., Ltd.) 100
Part, fluorescent whitening dye (Brancophor Pliq.01: manufactured by Bayer) 3 parts, polyvinyl alcohol (PVA11
7: Kuraray Co., Ltd.) 20 parts, and a cationic dye fixing agent (Sumireds Resin 1001: Sumitomo Chemical Co., Ltd.) 20 parts were dissolved in water and mixed to prepare an ink receiving layer coating liquid J having a solid content of 15%.

<Ink Receiving Layer Coating Liquid K> Ink receiving layer coating liquid I was mixed with basic polyaluminum hydroxide (Purachem W).
(T: manufactured by Riken Green Co., Ltd.) was mixed so that the content when the ink receiving layer was dried was 0.5 mmol / m ² , and the solid content was 1
The coating liquid K was 5% of the ink receiving layer.

<Ink Receiving Layer Coating Liquid L> Ink receiving layer coating liquid I is a water-dispersible polymer ultraviolet absorber (benzotriazole type, molecular weight of 1,000,000 or more) (ULS-1700: manufactured by Yatasha Yushi Kogyo Co., Ltd.). Was mixed so as to have a content when dried of the ink receiving layer of 0.8 g / m ² to obtain an ink receiving layer coating liquid L having a solid content of 15%.

<Ink receiving layer coating liquid M> Amorphous silica fine particles (Finesil X60:
Average particle size 6.2μ: 100 parts by Tokuyama), fluorescent whitening dye (Brancophore Pliq.01: by Bayer) 3 parts, polyvinyl alcohol (PVA117: by Kuraray) 25 parts, cationic dye fixing agent ( Sumirezu Resin 1001: 20 parts by Sumitomo Chemical Co., Ltd., and a water-soluble low molecular weight ultraviolet absorber (benzotriazole type, molecular weight 20)
(Less than 00) (Seesorb 101: Shiraishi Calcium Co., Ltd.)
When the ink receiving layer is dried, its content is 0.8 g / m ² , p-
Zinc phenolsulfonate (manufactured by Kishida Chemical Co., Ltd.) was dissolved and mixed in water so that the content of the ink receiving layer when dried was 0.5 mmol / m ^2, and the coating liquid M for the ink receiving layer having a solid content of 15% was prepared. And

Examples 1 to 9 and Comparative Examples 1 to 5 The ink receiving layer shown in Table 1 was coated and dried on a support by a bar coater so that the dry coating amount was 15 g / m ² . 9 and Comparative Examples 1-5 were obtained.

The ink jet recording materials prepared in the above Examples and Comparative Examples were evaluated by the following evaluation methods, and the results are shown in Table 1.

(1) Coating Layer Strength (1-1) Measurement of Static Friction Coefficient of 100th Sheet between Ink Receiving Layer Side Surface of Inkjet Recording Material and Paper Feed Roller Friction Coefficient Measuring Device According to ASTM D-1894-63 (AB-401, manufactured by Tester Sangyo), 23 ° C
Under a 50% RH environment, the coefficient of static friction between the surface of the inkjet recording material on the ink receiving layer side and the paper feed roller was determined according to JIS P8147. An A4 size seed is used as the inkjet recording material, and an Epson inkjet printer (PM is used as the elastic sheet.
750C) paper feed roller processed into a sheet shape, and the inkjet recording material side is 1000 mm /
The static friction force (mN) of the 100th sheet after moving at the speed of minute
Was measured. The static friction coefficient was calculated by the following formula. Static friction coefficient = static friction force (mN) ÷ weight vertical load (g) x 9.8
If the static friction coefficient value exceeds 2, there is no problem in continuous sheet feeding.

(1-2) Falling of powder After the measurement of (1-1) above was carried out, the powder of the ink receiving layer attached to the paper feed roller was visually judged. ○: Almost no powder is observed. Δ: Some powder is observed. X: Adhesion of powder is clearly recognized. The powder drop that does not affect the continuous feeding property is evaluated as ◯ and Δ.

(2) Image hue Epson inkjet printer (PM750
Solid printing of BK, Y, M, and C was performed according to C), and the difference in color was visually determined using Comparative Example 1 as a reference (◯). ◯: Almost no difference in color is recognized. Δ: A slight difference in color is recognized. X: Clearly a difference in color is recognized. The difference in color has no problem in practical use in the evaluations of ◯ and Δ.

(3) Evaluation of yellowing resistance of white paper part The light resistance was evaluated as an evaluation of yellowing resistance of the white paper part.
600 with Atlas Suntest CPS photobleaching tester
After irradiating at W / m ² for 100 hours, L ^* a ^* b ^* (display method according to CIE) of a blank sheet before and after irradiation was measured by a color difference meter (Macbeth Spectral manufactured by Gretag).
o Eye). The degree of yellowing on the white paper is
It can be expressed by the difference in b ^* before and after irradiation (Δb ^* ), and the smaller this value is, the less yellowing is. ○: △ b ^* <3 Good yellowing resistance △: 3 ≤ △ b ^* ≤ 5 Yellowing resistance tolerance x: △ b ^* > 5 There is no problem in practical use as long as b ^* has no persistent yellowing resistance. It is an evaluation of ○ and △.

[0079]

[Table 1]

As is clear from Table 1 above, in Examples 1 to 9 containing the water-soluble polyvalent metal salt and the polymeric ultraviolet absorber, the coating layer strength was high and the static friction coefficient of the 100th sheet was high.
Also, it is excellent in yellowing resistance of the blank part. On the contrary,
In Comparative Examples 1 to 5 containing no water-soluble polyvalent metal salt and / or polymer ultraviolet absorber, the coating layer strength was not sufficient and 1
It can be seen that the static friction coefficient of the 00th sheet is low and the yellowing resistance of the white paper portion is insufficient.

[0081]

INDUSTRIAL APPLICABILITY By using the ink jet recording material of the present invention, the ink jet recording material has a high coating strength of the ink receiving layer, excellent continuous feeding property in an ink jet recording apparatus, and excellent yellowing resistance of a blank portion. It is now possible to provide wood.

Claims (7)

[Claims] 1. An inkjet recording material having an ink receiving layer provided on a support, wherein the ink receiving layer contains a water-soluble polyvalent metal salt and a polymeric ultraviolet absorber. Recording material. 2. The ink jet recording material according to claim 1, wherein the ink receiving layer contains a fluorescent whitening agent dye. 3. The ink jet recording material according to claim 1, wherein the water-soluble polyvalent metal salt is an organic acid metal salt. 4. The ink jet recording material according to any one of claims 1 to 3, wherein the polymer ultraviolet absorber is water-dispersed fine particles. 5. The ink jet recording material according to claim 1, wherein the polymeric ultraviolet absorber is water-soluble. 6. The ink jet recording material according to claim 1, wherein the support is acid paper. 7. The ink jet recording material according to claim 1, wherein the pigment used in the ink receiving layer is made of amorphous silica.