JPH11170686A - Image forming material and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording sheet, an ink jet recording liquid having excellent optical fastness and a method for forming an image. SOLUTION: An ink jet recording sheet contains a compound represented by a formula (wherein Y is a nonmetallic atom group necessary to form 5 to 7-membered ring, X is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, sulfinyl group, an oxyradical group, an alkoxy group, an aryloxy group, acyloxy group or a hydroxyl group, and R to R are each a hydrogen atom or an alkyl group.) and provided on a support in an ink receptive layer. An ink jet recording ink uses the compound. The method for forming an image uses the liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method excellent in light fastness of an image. Furthermore, the present invention relates to an image forming method using an ink jet recording and an ink jet printer.

[0002]

2. Description of the Related Art In recent years, with the spread of personal computers, printers such as ink-jet printers have rapidly become widespread. Further, with the spread of photo-quality scanners, photo CDs, and digital cameras, demand for a printing system for printing digitized photo images is rapidly increasing. Particularly, the spread of simple and inexpensive ink jet printers is remarkable, and the demand for image quality of the image is increasing year by year.

As an ink jet system, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. Many new methods have been proposed and put into practical use, such as a method using the above ink. In particular, recently, there is a tendency to eject a large amount of ink having a high print speed and a low density.

[0004] As a recording medium used in the ink jet recording method, a recording sheet having an ink receiving layer provided on a support called a normal paper or an ink jet recording sheet has conventionally been used. However, when these recording sheets are used, none of them can be used in the field of photographic image quality where high resolution and gloss are required, such as a lot of ink bleeding and low gloss.

In order to solve such a problem, a technique of an ink jet recording sheet using gelatin as an ink receiving layer on a resin-coated paper in which both sides of the paper are coated with a resin, that is, a so-called RC (resin-coated) paper as a support, is used. Kaihei 4-21
No. 6990, and No. 6-64306. Japanese Patent Application Laid-Open No. H7-179032 discloses a method for making the appearance and feel of an image output by an ink jet printer similar to those of a conventional photograph, in which a recording medium containing a synthetic hydrophilic resin in an ink receiving layer and an ink jet recording method using the same. A method is disclosed. Further, as a method of improving the image quality and stability of the image, Japanese Patent Application Laid-Open No.
No. 36 discloses a method of using a resin-coated support containing gelatin and a basic latex in an ink receiving layer.

[0006] With these improvements in systems and recording media, the image quality of ink jets has approached that of photographs.
For this reason, the performance other than the image quality has come to be compared with the photograph, and there has been a problem that the light fastness of the image is particularly poor.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming an image having excellent light fastness. In addition, printers that print digital image information such as inkjets, inkjet printers that have improved performance and increased printing speed, and inkjet printers that have improved image quality by ejecting many ink drops with low density, Another object of the present invention is to provide a method for forming an excellent image.

[0008]

The above object has been achieved by the following means. An ink jet recording paper comprising a compound represented by the following general formula (I) in an ink receiving layer provided on a support.

[0009]

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In the formula, Y represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered ring together with C and N. X represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group, an alkoxy group, an aryloxy group, an acyloxy group or a hydroxyl group. R ¹ , R ² , R ³ and R ⁴ are
They may be the same or different and each represents a hydrogen atom or an alkyl group. Here, any two groups of R ^{1 to} R ⁴ and Y may be bonded to each other to form a 5- to 7-membered ring. An ink jet recording paper, wherein the compound of the formula (I) has an anionic water-soluble group and has a total carbon number of 20 or less. An ink jet recording sheet comprising an ink receiving layer containing a compound represented by the above general formula (I) and a polymer mordant containing at least 60 mol% of a unit represented by the following general formula (II).

[0011]

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In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, and may be linear or branched. L represents a divalent linking group. p is 0 or 1 in an aqueous inkjet recording liquid containing a water-soluble dye, wherein the compound represented by the above general formula (I) is contained in an amount of 0.1 to 20% by weight based on the total amount of the recording liquid. Aqueous recording liquid for inkjet recording. A recording liquid for inkjet recording, wherein the compound of the above general formula (I) has an anionic water-soluble group and has a total carbon number of 20 or less. The compound represented by the general formula (I) is recorded on a recording medium having at least one layer containing a polymer mordant containing at least 60 mol% of the unit represented by the general formula (II) on a support. An image forming method for inkjet recording using an aqueous inkjet recording liquid characterized by containing 0.1 to 20% by weight based on the total amount of the liquid.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The general formula (I) that can be used in the present invention will be described in detail. In the formula (I), preferable examples of the 5- to 7-membered ring formed by Y include, for example, a pyrrolidine ring, a piperazine ring, a morpholine ring, a piperidine ring and the like.

Examples of the alkyl group represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a benzyl group, a hexadecyl group, Examples of the alkenyl group include an allyl group and an oleyl group, and examples of the alkynyl group include an ethynyl group and the like.
For example, phenyl group, naphthyl group, etc., as acyl group, for example, acetyl group, benzoyl group, pentanoyl group, etc., as sulfonyl group, for example, methanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc., as sulfinyl group, For example, a methanesulfinyl group, a benzenesulfinyl group and the like, and as the alkoxy group, for example, a methyloxy group, an ethyloxy group, an i-propyloxy group, an n-butyloxy group, a cyclohexyloxy group, an n-octyloxy group, a t-octyloxy group Benzyloxy group and the like; aryloxy group such as phenoxy group; and acyloxy group such as acetyloxy group and benzoyloxy group. Any of these groups may have a substituent, and examples of the substituent include a sulfonyl group, a carboxyl group, and a hydroxy group.

R¹~ R^FourIs a hydrogen atom or an alkyl group
(Selected from the same category as the alkyl group of X)
You. The compound represented by the general formula (I) is an anionic water
It preferably has a soluble group. Anionic water-soluble groups
pKa is a group having a dissociable group of 1 or more and 12 or less. This
The pKa value here is represented by the general formula (I) at room temperature.
The compound to be obtained is tetrahydrofuran (THF) / water = 6 /
4 shows the acid dissociation coefficient when dissolved in No. 4. Anionic water
The pKa of the soluble group is more preferably 3 or more and 12 or less.
Most preferably, it is 5 or more and 11 or less. Anio
Preferred examples of the water-soluble water-soluble group include -OH group, -SO
_ThreeH group, -NHSO_Two-Group, phenolic hydroxyl group, -C
ONHCO- group, -CONHSO_Two-Group, -CON
(R) -OH group, -COOH group, -SO _TwoNHSO_Two−
And groups containing groups. Among them, -NHSO_Two-Group,
Phenolic hydroxyl group, -CONHCO- group, -CONH
SO_Two-Group, -SO_TwoNHSO_Two-Groups are more preferred.
The compound represented by the general formula (I) has a total carbon number of
It is preferably 20 or less.

Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

[0017]

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[0018]

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[0019]

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The compound of the present invention can be prepared by the method described in
29 (4), 366 ('71), JP-A-49-5357.
No. 1, No. 49-53572, No. 49-53573,
No. 49-53574, JP-B-49-20974, EP-A-264,730, U.S. Pat.
It can be easily synthesized according to the method described in No. 9,415.

The method of incorporating the compound of the general formula (I) used in the present invention into the ink receiving layer of the ink jet recording paper is performed by dissolving the compound of the general formula (I) in a polar solvent such as water or methanol. A method for adding a compound molecule of the general formula (I) to a polymer mordant (such as copolymerization); a method for mordantizing a compound of the general formula (I) with a polymer mordant; A method of adding the compound to a water-soluble polymer, a method of combining the two, and an oil protection method described in JP-A-4-125559 are available. Most preferably, the compound is dissolved in water or a polar solvent such as methanol to receive the ink. This is a method of adding to a layer coating solution. The method of adding the compound of the general formula (I) used in the present invention to the recording liquid for ink jet recording can be carried out in exactly the same manner as the method for adding the compound to the ink receiving layer of the ink jet recording paper, and most preferably water or methanol. In this method, the ink is dissolved in such a polar solvent and added to the recording liquid for ink-jet recording.

The compound of the formula (I) to be added to the ink receiving layer and the ink jet recording liquid may be in the form of a precursor. The amount of the compound of the general formula (I) added to the ink receiving layer is preferably 0.1 to 100 times the number of moles of the dye forming the image. Specifically, 0.1 mmol / m ^{2 to} 100 mmol is contained in the ink receiving layer.
It is preferable to add 1 / m ² . More preferably 0.3m
^{mol / m 2 ~30mmol / m 2} . The most preferred range is
It is ^{0.5mmol / m 2 ~15mmol / m 2} .

General formula (II) which can be used in the present invention
Will be described in detail. The polymer mordant that can be used in the present invention contains at least 60 mol% of the unit represented by the general formula (II). In the general formula (II), R ¹ ,
R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, for example, a methyl group,
It represents an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group or the like, and a hydrogen atom, a methyl group, and an ethyl group are particularly preferable. L represents a divalent linking group having 1 to about 20 carbon atoms, for example, an alkylene group, a phenylene group, an arylene group and the like. Preferred specific examples of these divalent linking groups are shown below.

[0024]

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Preferred specific examples of the monomer unit represented by the general formula (II) of the present invention are shown below. However, it is not limited to these.

[0026]

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The polymer mordant which can be used in the present invention may contain a monomer unit other than the general formula (II). Preferred monomer units are, for example, pyrrolidones, acrylates (for example, n-butyl acrylate), Examples include methacrylic acid esters (for example, n-butyl methacrylate), acrylamides (for example, diacetone acrylamide), methacrylamides (for example, n-butyl methacrylamide), and styrenes (for example, styrene sulfinic acid). Further, JP-A-59-169042, JP-A-62-244036
May be contained. Further, two or more of these monomer units may be used.

The molecular weight of the polymer mordant which can be used in the present invention is preferably from 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer tends to move, and if the molecular weight is too large, coating may be hindered.

Preferred examples of the polymer mordant used in the present invention are shown below, but the present invention is not limited to these. Also, two or more kinds may be used in combination.

[0030]

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[0031]

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[0032]

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[0033]

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The synthesis method of the present invention is disclosed in
No. 44043, etc., and can be easily synthesized.

The amount of the polymer mordant to be applied can be easily determined by those skilled in the art according to the amount of the dye, the type and composition of the polymer mordant.
m ² is suitable, and it is particularly preferable to use 0.5 to 15 g / m ² . In that case, the film thickness is preferably 0.5 to 50 μm, more preferably 1 to 50 μm. The recording medium of the present invention may have at least one mordant layer,
If necessary, an auxiliary layer such as a protective layer, a layer having a fluorescent whitening agent for improving a white background, and an anti-curl layer can be provided. In particular, it is effective to provide a protective layer and a layer having a fluorescent whitening agent for improving a white background. The total thickness of the coating layer including the mordant layer and the auxiliary layer is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 25 μm or less.
Further, the coating layer may be provided not only on one side but also on both sides of the support.

An inorganic pigment can be used for the recording material of the present invention. The type of the inorganic pigment is not particularly limited, and any inorganic pigment can be used. For example, silica pigment, alumina pigment, titanium dioxide pigment, zinc oxide pigment, zirconium oxide pigment, mica-like iron oxide, lead white, lead oxide pigment, cobalt oxide pigment, strontium chromate, molybdenum pigment, smectite, magnesium oxide pigment, oxide Examples thereof include calcium pigments, calcium carbonate pigments, mullite, and the like, and one kind or two or more kinds can be used.

Among them, silica pigments and alumina pigments are preferred. The silica pigment may be spherical silica or amorphous silica, or may be synthetic silica by any of a dry method, a wet method, and an airgel method. Further, hydrophobic silica surface-treated with a trimethylsilyl group, silicone or the like may be used. These are preferably used as colloidal silica. The average particle size of the silica pigment used is preferably from 4 mμ to 120 mμ, more preferably from 4 mμ to 90 mμ. The silica pigment used in the present invention may or may not be porous, but is preferably porous, and the silica pigment particles have an average pore diameter of 50 to 500 and a pore volume of 0.5. It is preferably about 3 cc / g.

As the alumina pigment, both anhydrous alumina and alumina hydrate are preferably used. As anhydrous alumina, α-, β-, γ-, δ-, ζ-, η-, θ
-, Κ-, ρ-, and χ- can be used. As the alumina hydrate, both monohydrate and trihydrate can be preferably used. Examples of the monohydrate include pseudo-boehmite, boehmite and diaspore. Examples of the trihydrate include gibbsite and bayerite. Of these alumina pigments, alumina hydrate is preferably used. The average particle size of the alumina pigment used is 4 μm to 3 μm.
00 μm, more preferably 4 μm to 200 μm.
mμ. The alumina pigment used in the present invention may or may not be porous, but is preferably porous, and the average pore diameter of the alumina pigment particles is 50 to 500.
-The pore volume is preferably from 0.3 to 3 cc / g.

The method for synthesizing the alumina hydrate is not particularly limited, and for example, a sol-gel method in which ammonia is added to an aluminum salt solution to cause precipitation, a method in which alkali aluminate is hydrolyzed, and the like can be used. These can be dehydrated by heating and used as an anhydrous alumina pigment.

By including these inorganic pigments in the coating layer, the coating layer can be made porous and the ink absorption speed can be extremely increased. As a result, the image quality is improved, and the problem that the ink is transferred to another paper or another object on which ink is superimposed is solved.

The swelling ratio of the entire coating layer with water is 100%
It is desirably at least 1000% and preferably at most 150% and not more than 500%. Here, the swelling ratio is a value obtained by dividing the swelling value when water is dropped by the dry film thickness and multiplying by 100. Controlling the swelling behavior is extremely important in controlling ink seepage and spreading, and in preventing scratches and the like in the printer. The film surface pH of the recording medium is preferably 9 or less from the viewpoint of storage stability and safety of the recording medium. Here, the film surface pH is a value obtained by dropping 40 μl of water on the coated surface of the recording medium and measuring the pH one minute later.

As the binder for the mordant-containing layer and other layers constituting the recording medium, hydrophilic binders are preferably used. An example thereof is disclosed in JP-A-62-253159.
No. (26) to (28). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A-62-245260 and the like, that is, -COOM or-
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more kinds.

A binder may be added to the mordant layer of the recording medium of the present invention. As the binder used,
Although the above hydrophilic binder can be widely used,
Polyvinyl alcohol and derivatives thereof are preferred, and the degree of saponification of polyvinyl alcohol is particularly preferably 90% or less.

A matting agent can be used in the recording medium of the present invention. A conventionally known matting agent can be used. Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfate, calcium carbonate, etc.), and silver halide grains which do not form an image ( Silver chloride, silver bromide, etc., and a small amount of iodine atoms may be contained as a halogen component) or glass. In addition, West German Patent 2,529,321, British Patent 760,
Nos. 775 and 1,260,772, U.S. Pat.
01,905, 2,192,241, 3,05
3,662, 3,062,649, 3,25
7,206, 3,322,555, 3,35
No. 3,958, No. 3,370,951, No. 3,41
1,907, 3,437,484, 3,52
No. 3,022, No. 3,615,554, No. 3,63
5,714, 3,769,020, 4,02
Inorganic matting agents described in JP-A Nos. 1,245 and 4,029,504 can also be used.

Examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate propionate), cellulose ether (eg, ethyl cellulose), and synthetic resin. Examples of synthetic resins are water-insoluble or poorly soluble synthetic polymers, such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycysilyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), Acrylonitrile, olefins (eg, ethylene and the like), styrene, benzoguanamine, formaldehyde condensate, etc., alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl ( A polymer having a monomer component of a combination of (meth) acrylate, styrene sulfonic acid and the like can be used. In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole, polyvinylidene chloride, and the like can also be used. In addition, British Patent Nos. 1,055,713, U.S. Pat. Nos. 1,939,213 and 2,221,873
No. 2,268,662 and 2,322,037
No. 2,376,005, 2,391,181
Nos. 2,701,245 and 2,992,101
No. 3,079,257 and 3,262,782
No. 3,443,946, No. 3,516,832
Nos. 3,539,344 and 3,591,379
Nos. 3,754,924 and 3,767,448
And JP-A-49-106821 and 57-14835.
And the like.

Among them, polymethyl methacrylate (for example, SG-6 manufactured by Soken Chemical Co., Ltd.), benzoguanamine-formaldehyde condensation polymer (for example, eposter trade name; manufactured by Nippon Shokubai Chemical Co., Ltd .: existing chemical substance 7-3)
1), polyolefin (for example, Flowbeads L under the trade name)
E-1080, CL-2080, HE-5023; manufactured by Iron Chemical Co. or trade name Chemipearl V-100; manufactured by Mitsui Petrochemical), polystyrene beads (manufactured by Mortex),
Nylon beads (manufactured by Mortex), AS resin beads (manufactured by Mortex), epoxy resin beads (manufactured by Mortec), polycarbonate resins (manufactured by Mortec) and the like are preferable. JP-A-5353 as an alkali-soluble matting agent
No. 7231, No. 58-66937, No. 60-889
No. 4, an alkali-soluble matting agent such as an alkyl methacrylate / methacrylic acid copolymer described in JP-A-58-166.
No. 341, an alkali-soluble polymer having an anionic group can also be used. These matting agents may be used in combination. For example, a combination of two or more kinds of fine particle powders having different Mohs hardness, a combination of two or more kinds of spherical matting agents having different average particle diameters, an amorphous matting agent such as silica for the mordant layer and a polymethyl methacrylate for the back layer. Such a spherical matting agent is used in combination.

The constituent layers (including the back layer) of the recording medium of the present invention include silica, especially silica, for the purpose of improving adhesion resistance, improving film strength, improving curl balance, and improving ink absorption speed. Colloidal silica may be contained. The colloidal silica has an average particle diameter of 7 μm to 500 μm, the main component is silicon dioxide, and may contain alumina or sodium aluminate as a small component. In addition, these colloidal silicas may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide or an organic salt such as tetramethylammonium ion as a stabilizer. In particular, as a stabilizer for colloidal silica, colloidal silica comprising potassium hydroxide or ammonium hydroxide is preferable. These colloidal silicas are described, for example, in Egon Matijev.
ic), Surface and Colloid Science
6), pp. 3-100 (1973, John Wiley & Sans)
Sons)). Specific examples of colloidal silica include DuPont [E. I. do
pont Nemours & Co, (USA)]
From Ludox AM, Ludox AS, Ludox
Monsant Co, (U
SA) from Syton C-30, Syton 20
0, and Nalco Chem, CO (U
SA) from Nalcoag 1030, Nalcoa
g 1060, Nalcoag ID-21-64, and the like. The preferred use amount of the colloidal silica is 0.05 to 5.0 in terms of a dry weight ratio with respect to the solid content of the constituent layer, and particularly preferably 0.2 to 0.2.
２．５2.5.

In the present invention, it is preferable to use a germicidal and antibacterial agent for the recording medium in order to prevent decay of the dispersion or coating solution of various chemicals. The antibacterial and antibacterial agent used in the present invention may be any water-soluble one,
Specifically, thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothianoic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, Alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds,
Various antibacterial agents and antibacterial agents such as cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, active halobene compounds such as chlorinated isocyanuric acid, sodium, chelating agents, sulfite compounds, and penicillins. There are fungicides. In addition, other L. E West (LE Wes)
t), Water Quality Criteria (Wat
er Quality Criteria) Photo.
Sci. and Eng., Vol 9, No. 6 (196
5) The disinfectant described in JP-A-57-8542 and JP-A-58-8542.
No. 105145, No. 59-126533, No. 55-1
Various antibacterial agents described in Nos. 11942 and 57-157244; antibacterial antibacterial agents described in Hiroshi Horiguchi, "Chemistry of antibacterial and fungicide" (published by Sankyo Publishing Co., Ltd. in 1982) can be used.

The hardener used in the recording medium of the present invention is not particularly limited, and known hardeners such as aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and aziridines (for example, PB Report 19) , 9
21, U.S. Pat. Nos. 2,950,197 and 2,96
No. 4,404, No. 2,983,611, No. 3,2
Nos. 71,175, JP-B-46-40898
And isoxazole-based compounds (for example, those described in U.S. Pat.
1,609), epoxy type (for example, U.S. Pat. No. 3,047,394, West German Patent 1,0).
No. 35,663, British Patent No. 1,033,518, JP-B-48-35495, vinyl sulfones (for example, 1,3,5-triacrylonitrile-hexahydro-s) -Triazine,
Bis (vinylsulfonyl) methyl ether, N, N-ethylene-bis (vinylsulfonylacetamide) ethane,
N, N′-trimethylene-bis (vinylsulfonylacetamide) and the like, for example, PB reports 19, 920,
West German Patent Nos. 1,100,942 and 2,337,41
2, 2,545,722, 2,635,518
Nos. 2,742,308 and 2,749,260
No., UK Patent No. 1,251,091, Japanese Patent Application No. 45-5
Nos. 4236 and 48-110996, U.S. Pat.
Nos. 539,644 and 3,490,911), acryloyl-based (for example, Japanese Patent Application No.
8-27949, U.S. Pat. No. 3,640,720), carbodiimide-based (for example,
U.S. Pat. Nos. 2,938,892 and 4,043,818
Nos. 4,061,499, JP-B-46-
No. 38715, Japanese Patent Application No. 49-15095, triazines (for example, 2,4-dichloro-6-).
Hydroxy-S-triazine and the like, and also, for example, German Patent Nos. 2,410,973 and 2,553,915
No. 3,325,287, those described in JP-A-52-12722), N-methylols (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3 -Dihydroxydioxane, etc.), mucohalic acid type (mucochloric acid, mucophenoxycyclolic acid, etc.), dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, maleimide type, acetylene type, metasulfonic acid ester type hardened Membrane agents can be used.

Examples of the polymer hardener include polymers having an aldehyde group (eg, copolymers of acrolein) described in US Pat. No. 3,396,029, and US Pat. No. 3,362,827, Research. A polymer having a dichlorotriazine group described in Disclosure No. 17333 (1978); U.S. Pat. No. 3,623,8
No. 78, a polymer having an epoxy group, Research Disclosure 16725 (1978), U.S. Pat. No. 4,161,407, and JP-A-54-65033.
And polymers having an active vinyl group or a group that can be a precursor thereof described in JP-A-56-142524, and a polymer having an active ester group described in JP-A-56-66841. The addition amount of the hardener is optional, but usually about 0.01 to 30 wt% of the constituent materials which can react with the hardener, especially 0.1%.
10 to 10 wt% is appropriate.

In the constituent layers of the recording medium, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, and preventing static charge. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-18345.
No. 7, etc. Further, an organic fluoro compound may be included for the above purpose. Representative examples of the organic fluoro compound include JP-B-57-9053, Nos. 8-17.
Column, JP-A-61-20994, 62-135826
And hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

In the constituent layers of the recording medium, a high-boiling organic solvent can be used for the purpose of coating aid, improving releasability, improving slipperiness and preventing static charge. Specifically, JP-A-62-2
No. 53159, pp. (25) and 62-245253. Further, for the above purpose,
Various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. JP-A-62-215953 and 63-46
No. 449 is also effective.

The constituent layers (including the back layer) of the recording medium may contain various polymer latexes for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention and film crack prevention. . Specifically, Japanese Patent Application Laid-Open No. Sho 62
-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass point transition (40 ° C. or less) is used for the mordant layer, the mordant layer can be prevented from cracking and curl can be improved, and if a polymer latex having a high glass transition point is used for the back layer, An anti-curl effect is obtained.

In the constituent layers of the recording medium, an anti-fading agent may be used in combination with the compound represented by formula (I).
Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, Kuraman compounds, phenol compounds (eg, hindered phenols),
There are hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Patent Application Laid-Open No. 61-159
The compound described in No. 644 is also effective. Benzotriazole-based compounds (U.S. Pat.
Nos. 33,794), 4-thiazolidone-based compounds (US Pat. No. 3,352,681, etc.), benzophenone-based compounds (JP-A-46-2784, etc.), and other JP-A-54-48535, 62. -136641, 6
There are compounds described in 1-88256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. As the metal complex, US Pat. No. 4,24
No. 1,155, No. 4,245,018, columns 3 to 36,
No. 4,254,195, columns 3-8, JP-A-62-1
Nos. 74741 and 61-88256 (27) to (2)
9), pp. 63-199248, JP-A-1-75556.
No. 8, No. 1-74272 and the like.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). The anti-fading agent for preventing fading of the dye formed on the recording medium may be contained in the recording medium in advance, or may be contained in ink or the like and supplied from the outside to the recording medium. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

The recording medium may use a fluorescent whitening agent. In particular, it is preferable that a fluorescent whitening agent is incorporated in the recording medium, or it is contained in ink or the like and supplied from outside to the recording medium. As an example, K.K. Weenkataram
an "The Chemistry of Synt
Hetic Dyes ”, Vol. V, Chapter 8, JP-A-61-1
And the compounds described in US Pat. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor.

In the present invention, the support for the recording medium is not particularly limited.
Synthetic polymers (films) are mentioned. Specifically, it is made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper),
Metals, cloths, glasses and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, Japanese Patent Application Laid-Open No. 62-253159
The supports described in pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

In the present invention, a particularly preferred support is a paper or plastic support laminated on both sides with a polyolefin (eg, a homopolymer such as polyethylene, polystyrene, polyethylene terephthalate, polybutene, or a copolymer of any combination thereof). However, a white pigment such as titanium oxide and zinc oxide, and a coloring dye such as cobalt blue, ultramarine blue and neodymium oxide are preferably contained in the polyolefin.

The thickness of the polyolefin layer is not particularly limited, but is preferably from 10 to 100 microns, particularly preferably from 15 to 50 microns, and more preferably from 20 to 35 microns. The surface shape of the polyolefin can be any shape, such as a mirror surface, one with regular irregularities, one with irregular irregularities, etc., but the surface on which the constituent layers of the recording medium are applied is particularly a mirror surface. Is preferred. The surface of the polyolefin layer is subjected to a surface activation treatment such as a corona discharge treatment or a flame treatment, and if necessary, an undercoat layer is provided, and a constituent layer is applied thereon and used. There is no particular limitation on the white pigment that can be contained in the polyolefin on the coating surface side, but titanium oxide and zinc oxide are preferred, and anatase type titanium oxide is particularly preferred.
It is preferable to use it together with 0% or less of zinc oxide. The amount of the white pigment contained in the polyolefin is preferably 5% by weight or more, more preferably 10 to 50% by weight, and particularly preferably 15% to 30%.

The coloring pigment which can be contained in the polyolefin on the surface side is not particularly limited.
300 ° C for cobalt blue, ultramarine, neodymium oxide, etc.
Those that can withstand the above coating temperatures are desirable.
The amount of the tinting pigment used is 0.1 to 3% by weight based on the white pigment. In order to control the surface reflection characteristics, the selection and the amount of the tinting pigment are particularly important. Even in pigments referred to as ultramarine blue, colors vary greatly depending on the manufacturer and the production number. Therefore, it is desirable to mix and use various pigments so as to obtain necessary surface reflection characteristics. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer is preferably designed to have an antistatic function and to have a surface resistivity of 10 ¹² Ω · cm or less.

As the dye used in the recording liquid for ink jet recording of the present invention, for example, a dye described in JP-A-8-253593 or a dye described in JP-A-9-26985 can be used. These dyes can be used as inks as they are, or by dissolving them in an aqueous and / or organic solvent, or emulsifying and dispersing, or by encapsulating and dispersing with a polymer to form a liquid. The amount of these dyes added to the ink is determined in relation to the recording medium. For this reason, in the adjustment of the yellow, magenta, cyan and black inks, it is preferable to add 0.2 to 15% by weight, preferably 0.5 to 10% by weight, of each color ink.

Examples of solvents that can be used in the ink are as follows. The following solvents can be used as a mixture. For example; water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol , An alkyl alcohol having 1 to 10 carbon atoms such as decyl alcohol; for example, cyclopentane, hexane,
Aliphatic or aromatic hydrocarbon solvents represented by cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecanone, tetralin, decalin, benzene, toluene, xylene, etc .; for example, carbon tetrachloride, trichloroethylene, tetra Halogenated hydrocarbon solvents such as chloroethane, dichlorobenzene, etc .; for example, ether solvents such as ethyl ether, butyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, etc .; for example, acetone, methyl ethyl ketone, methyl propyl ketone, Ketone solvents such as methyl amyl ketone and cyclohexanone; for example, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate Esters, solvents such as ethylene glycol monoethyl ether acetate and ethyl lactate; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; other amines, amides and N-methyl-2- Various solvents such as nitrogen-containing heterocyclic systems such as pyrrolidone and 1,3-dimethyl-2-imidazolidinone, and oxycarboxylic acid-based intramolecular ester systems such as valerolactone and caprolactone are exemplified.

The method of forming an image using the ink-jet recording liquid of the present invention and the recording paper containing the polymer mordant of the present invention, when used in ink-jet printing, greatly exhibits the effects of the invention, but other methods can also obtain the effects.
As an example, the recording medium may be directly immersed in the ink, the ink may be sprayed onto the recording medium from the outside, or a coating containing the ink may be formed and the recording medium may be heated using heat. The dye may be transferred to the substrate (for example, sublimation type thermal transfer printing).

When the image of the present invention is formed by using the ink jet printing method, the recording liquid for ink jet recording of the present invention may contain a humectant and a solubilizer as needed. As these humectants and solubilizers, those described in JP-B-58-27762 are suitable. Specifically, at least one of a 5- to 7-membered nitrogen-containing heterocyclic ketone compound and an aliphatic sulfone compound,
Desirable is a combination with at least one alicyclic sulfone compound or alicyclic sulfoxide compound.

These compounds have remarkable effects as humectants and solubilizers, and include alkylene glycols, alkyl ethers of alkylene glycols, carboxylic acid amide derivatives, lactones, dioxyalkylene glycols as conventionally known hydrophilic organic solvents. Ethylene, sulfur compounds, alcoholamines, monohydric, dihydric or trihydric alcohols, carbonates, urea derivatives, ethylene oxide adducts, N-vinyl-2-pyrrolidone oligomers, cellulose derivatives such as hydroxypropylcellulose, etc. Do not show a decrease in their effect. Further, the humectant has an effect of preventing solidification of the dye and other compounds due to drying as one of causes of nozzle clogging.

Further, another cause of the clogging of the nozzle is considered to be the generation of fungi and the generation of aggregates due to the generation of fungi. A fungicide is also added. Molds and bacteria live in all parts of the ink jet printer, such as ink channels, storage tanks, and nozzles.
If conditions such as humidity are met, molds or bacteria will proliferate significantly, forming colonies, forming aggregates incorporating dyes and other compositions, and causing clogging.

When the ink jet printing method is used for the image forming method of the present invention, the method of the ink jet printing is not limited at all, and the image forming method of the present invention can be used regardless of a continuous type or an on-demand type. . The type of the ink jet head is not limited, and is preferably used for all printers including a piezo type, a bubble jet type, a thermal jet type, and a type using ultrasonic waves. Recent advances in ink-jet systems have been remarkable, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, a colorless method Many new methods, such as a method using transparent ink, have been proposed and put into practical use. Although the image forming method of the present invention is preferably used for any of these methods, the improvement effect is remarkable particularly in a printer that prints a large amount of ink having a high print speed and a low density to form an image close to a photograph. Be demonstrated.

[0068]

Embodiments of the present invention will be described below. In the examples, parts mean parts by weight. <Preparation of recording liquid 01 for inkjet recording> Dye 1 5 parts

[0069]

Embedded image

N-methylpyrrolidone 20 parts Diethylene glycol 20 parts Polyethylene glycol (PEG-300) 5 parts Water 50 parts The above composition mixture was heated and dissolved at 50 ° C.
The solution was filtered through an 8 μm microfilter to obtain 100 parts of the target recording liquid for ink jet recording.

<Preparation of Recording Paper 101> Pulp Mixing Ratio LB
Polyethylene was laminated on both sides of KP / NBSP = 6/4 high-quality paper (density 1.053, thickness 152 μm) at 300 ° C. by an extrusion coating method to prepare a reflective support. On the back surface, a mixture of titanium having a surface treatment as a white pigment in polyethylene having a density of 0.923 and ultramarine (blue mouth and red mouth) manufactured by Daiichi Kasei Co., Ltd. as a coloring pigment was used. The thickness of the front polyethylene was 36 μm, and the thickness of the back polyethylene was 27 μm. A sample 101 was prepared by coating the following coating layer on the above resin-coated support.
The main purpose of adding each compound is shown in parentheses.
The purpose of the addition is not limited to this.

First layer: alkali-treated gelatin 1.0 g / m ² compound UV-01 (fluorescent brightener) 0.03 g / m ² compound H-02 (hardener) 0.08 g / m ² metaboric acid Tetrahydrate salt (thickener) 0.10 g / m ² Compound W-04 (surfactant) 0.02 g / m ² Compound F-08 (preservative) 0.001 g / m ²

[0073]

Embedded image

Second layer: Polyvinyl alcohol Kuraray Co., Ltd. PVA420 7 g / m ² Compound W-04 (surfactant) 0.06 g / m ²

Third layer: alkali-treated gelatin 0.3 g / m ² SG-6 (matting agent) manufactured by Soken Chemical Co., Ltd. 0.18 g / m ² (polymethyl methacrylate average particle diameter 12 μm) Compound W-04 (interface (Activator) 0.02 g / m ² Compound W-07 (surfactant) 0.02 g / m ² Compound F-08 (preservative) 0.002 g / m ²

Next, recording liquid-01 for ink jet recording
In addition, the compounds of the general formula (I) (1), (2), (3),
In the same manner except that (4) is dissolved in water or methanol and added at 5% by weight of the ink jet recording amount, the recording liquid for ink jet recording-02, the recording liquid for ink ink jet recording-03, and the recording liquid for ink ink jet recording- 04, a recording liquid 05 for ink-jet recording was prepared.

A recording paper 102 was prepared in the same manner except that 2.0 g / m ² of the compound P-17 was added as a polymer mordant to the second layer of the recording paper 101. Further, the compound (1) of the general formula (I) is added to the second layer of the recording paper 102,
The recording media 103, 104, 105, and 1 were similarly prepared except that 1 mmol / m ^{2 of} (2), (3), and (4) was added.
06 was created.

After the recording papers 101 to 106 were applied and left at room temperature for one week, the recording papers were cut into a postcard size of 14.5 cm in length and 10 cm in width, and the recording liquid for ink jet recording-01 to 05 was used. A solid image was printed using the printer PM-700C.

The printed sample was obtained from Atlas C. I
Xenon light (85,000 lux) was irradiated for one week using a 65 weather meter. The image density before and after the irradiation with xenon light was measured using a reflection densitometer (X-Rite310TR), and the light fastness of the image was evaluated by determining the residual ratio of the dye. The residual dye ratio was determined according to the following equation.

Equation 1 The results are shown in Table 1.

Table 1 ────────────────────────────────── Inkjet Recording Inkjet Number for Ink Dye Residual Rate Recording Paper No. ────────────────────────────────── Comparative Example 01 101 40 Comparative Example 01 102 60 Invention 01 103 85 The present invention 01 104 82 The present invention 01 105 83 The present invention 01 106 81 The present invention 02 101 75 The present invention 02 102 80 The present invention 02 103 79 The present invention 02 104 78 The present invention 02 105 77 The present invention 02 106 79 The present invention 03 101 74 The present invention 03 102 84 The present invention 04 101 75 The present invention 04 102 83 The present invention 05 101 74 The present invention 05 102 84 ──────────────

[0082]

As described above, according to the present invention, an image having excellent light fastness can be obtained. In particular, with respect to an ink jet printer capable of obtaining image quality close to a photograph, the performance other than the image quality is compared with that of the photograph, and the excellent light fastness is a great invention result.

Claims (6)

[Claims] 1. An ink jet recording paper comprising a compound represented by the following general formula (I) in an ink receiving layer provided on a support. Embedded image In the formula, Y represents a nonmetallic atomic group necessary for forming a 5- to 7-membered ring together with C and N. X represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group, an alkoxy group, an aryloxy group, an acyloxy group or a hydroxyl group. R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group. Here, any one of R ^{1 to} R ⁴ and Y
Two groups may be linked together to form a 5- to 7-membered ring. 2. The ink jet recording paper according to claim 1, wherein the compound of the formula (I) has an anionic water-soluble group and has a total carbon number of 20 or less. 3. The ink jet recording paper according to claim 1, wherein the ink receiving layer contains a polymer mordant containing at least 60 mol% of a unit represented by the following general formula (II). Embedded image In the formula, R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or an alkyl group, and may be linear or branched. L represents a divalent linking group. p represents 0 or 1. 4. An aqueous ink jet recording liquid containing a water-soluble dye, wherein the compound represented by the general formula (I) is contained in an amount of 0.1 to 20% by weight based on the total amount of the recording liquid. Aqueous recording liquid for inkjet recording. 5. The recording liquid for ink-jet recording according to claim 4, wherein the compound of the formula (I) has an anionic water-soluble group and has a total carbon number of 20 or less. 6. The aqueous recording medium according to claim 4, wherein the recording medium has at least one layer containing a polymer mordant containing at least 60 mol% of the unit represented by the general formula (II) on a support. An image forming method for performing inkjet recording using an inkjet recording liquid.