JP2002293003A - Recording medium and recorded matter using the same, and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording medium, by which the image quality and preservability of an image to be recorded are improved by a method wherein dye molecules are prevented from contacting with the oxygen molecules in the air dye is prevented from acting as the sensitizer of a singlet oxygen, and a recorded matter using the recording medium and a recording method. SOLUTION: In order to obtain this recording medium, an ink accepting layer formed on a support and a surface layer formed on the ink accepting layer and including a latex turning into a coating film under heat are equipped. By the adhesion of an ink including a specified dye onto the recording medium, at least some part of a recording image is formed. With the ink, a recorded matter having the image formed on the recording medium and a method for recording on the recording medium are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium on which an image is recorded by dropping a dye ink, a recorded matter having a recorded image formed by the dye ink, and a recording method.

[0002]

2. Description of the Related Art Conventionally, an ink jet recording system for forming an image of a character, a picture, or the like by flying fine droplets of ink has been obtained at a high speed, at a high resolution, and easily at multicolor. Performances such as good light fastness, preservability and color reproducibility of the recorded matter (printed matter), difficulty in clogging of nozzles, and safety in terms of odor and fire hazard are required.

As proposals for achieving such a demand, for example, conventional examples described in JP-A-59-196285, JP-A-59-222381, and JP-A-11-5362 are disclosed. is there.

In a method for treating a recording medium described in JP-A-59-196285, an ink receiving layer comprising a thermoplastic organic polymer and an adhesive is provided on a support, and ink jet recording is performed on the ink receiving layer. Later, a plasticizer is applied,
The thermoplastic organic polymer is melted by heating to form a film. According to this method, it is possible to eliminate a void in the ink receiving layer and form a transparent film in which ink is trapped in the layer.

The recording medium described in JP-A-59-222381 has a layer containing a thermoplastic resin as a surface layer of an ink receiving layer in order to improve the water resistance and light resistance of an image of a recorded matter. After the image formation, the surface layer is formed into a film. The ink-receiving layer of this recording medium is mainly composed of a second layer in which a pigment having a large specific surface area, which has a high ability to absorb and retain ink and is applied together with an adhesive, and a fine-grained thermoplastic organic polymer as a main pigment. And an outermost layer coated and dried with the addition of an adhesive.

[0006] The recording medium described in JP-A-11-5362 has a porous outermost layer containing a thermoplastic resin having a ΔE of 20 or less after light exposure on a base material. Discoloration does not occur even during long-term storage, and a printed matter having high ink absorbency and high image density can be obtained.

Here, when forming a color image, it is common to use at least three colors of magenta ink, yellow ink and cyan ink. In particular, in the ink jet recording system, the ratio of the color mixture is adjusted by controlling the ejection of each ink by an electric signal using these three colors and, in some cases, the four colors to which the black ink is added, so that the multi-color expression is performed. It is carried out. For example, red is formed by magenta ink and yellow ink. The color mixture ratio changes depending on the ejection ratio of the magenta ink and the yellow ink, and a subtle red gradation can be expressed. Similarly, blue is represented by a mixed color of cyan ink and magenta ink, and green is represented by a mixed color of yellow ink and cyan ink.

However, it is known that the dye contained in the ink is deteriorated by visible light and ultraviolet light in sunlight, and causes discoloration. Therefore, various dyes, additives, and the like have been studied to improve light resistance.

The deterioration of an image due to visible light is considered to be due to discoloration and fading of the dye due to visible light. Specifically, it is considered that the dye is deteriorated or decomposed by photo-oxidation or photo-reduction. In particular, oxygen molecules in the air become singlet oxygen ( ¹ O ₂ ) due to the interaction with the dye molecules, which may attack the dye molecules to cause degradation and decomposition. That is, certain dyes themselves act as singlet oxygen sensitizers in the presence of light and oxygen. As a result, singlet oxygen is generated, and the dye is deteriorated by a self-sensitized photooxidation reaction in which the dye itself is oxidized by the singlet oxygen. In the case where inks of different hues are ejected and multi-color expression is performed by an ejection ratio (that is, a mixture ratio) as in an ink jet recording method, a certain dye acts as a singlet oxygen sensitizer, that is, a catalyst. It is conceivable that the generated singlet oxygen reacts with other adjacent or mixed dyes to cause discoloration and discoloration of the dye (catalyst discoloration), that is, a phenomenon of promoting deterioration and decomposition.

[0010]

Generally, a copper phthalocyanine dye is used as a colorant for a cyan ink from the viewpoints of light fastness, water fastness, coloring and sharpness.

However, the copper phthalocyanine dye acts as a sensitizer for singlet oxygen, and some coloring materials, especially magenta dyes, are easily degraded by this singlet oxygen.
As a result, there is a problem that the discoloration and fading become remarkable in a portion adjacent to or mixed with the cyan ink and the magenta ink.

Magenta dyes which are liable to undergo discoloration due to singlet oxygen are particularly azo dyes. On the other hand, magenta dyes represented by the formula (1) and magenta dyes represented by the formula (2) Many of the specific magenta dyes are excellent in sharpness and light resistance in a single color of the magenta ink, but in a mixed color portion with an ink containing a copper phthalocyanine dye, catalyst fading is remarkable. That is, the light resistance of the entire color image is poor. Further, specific dyes such as the magenta dye represented by the formula (1) and the magenta dye represented by the formula (2) have poor gas resistance.

SUMMARY OF THE INVENTION An object of the present invention is to solve such a conventional problem. By preventing the dye molecules from coming into contact with oxygen molecules in the air, the dye can be converted to singlet oxygen. It is an object of the present invention to provide a recording medium which prevents it from acting as a sensitizer and has improved image quality and storability of a recorded image, a recorded matter using the same, and a recording method.

[0014]

According to the present invention, there is provided an ink receiving layer formed on a support, comprising:
A magenta dye represented by the formula (1) or a formula (2) or a formula (3) shown below, comprising a surface layer containing a latex which is formed on the ink receiving layer and is formed into a film by heating. Magenta dye, and C.I. I. Direct Blue 199 and C.I. I. An object of the present invention is to provide a recording medium on which at least a part of a recorded image is formed by attaching an ink containing a specific dye such as a copper phthalocyanine dye such as Direct Blue 86.

[0015]

Embedded image However, R ₃ and R ₄ are independently hydrogen or a substituent of OH, CO
OM or SO ₃ M is a substituted alkyl having 2 or 3 carbon atoms, wherein R ₇ is hydrogen, CH ₂ CH ₂ CN or CH ₂ CH
₂ COOM, where M is hydrogen, alkali metal or ammonium ion.

In the recording medium having these structures, the ink adhering to the ink receiving layer can be covered by the coated surface layer, so that the ink is prevented from coming into contact with oxygen in the air. it can. Therefore, it is possible to prevent the dye contained in the ink from acting as a singlet oxygen sensitizer.

Further, the present invention provides an ink receiving layer provided on a support, a dye ink which adheres to the ink receiving layer to form a recorded image, and an ink receiving layer on which the recorded image is formed. And a formed surface layer, wherein the surface layer contains latex coated by heating,
At least a part of the recorded image includes a magenta dye represented by Formula (1) or a magenta dye represented by Formula (2) or Formula (3); I. Direct Blue 199 and C.I.
I. An object of the present invention is to provide a recorded matter formed from an ink containing at least a specific dye such as a copper phthalocyanine dye such as Direct Blue 86.

In the recorded matter having the above-mentioned structure, since the coated surface layer is formed on the ink attached to the ink receiving layer, the ink is prevented from coming into contact with oxygen in the air. be able to. Therefore, it is possible to prevent the dye contained in the ink from acting as a singlet oxygen sensitizer.

Further, the present invention provides a recording apparatus comprising: an ink receiving layer formed on a support; and a surface layer containing a latex formed on the ink receiving layer and formed into a film by heating. In the medium, a magenta dye represented by the formula (1) or a magenta dye represented by the formula (2) or the formula (3); I. Direct Blue 199 and C.I. I. An object of the present invention is to provide a recording method for forming at least a part of a recorded image by using an ink containing at least a specific dye such as a copper phthalocyanine dye such as Direct Blue 86.

According to this recording method, after the ink is attached to the ink receiving layer, a surface layer formed into a film can be formed thereon, thereby preventing the ink from coming into contact with oxygen in the air. can do. Therefore, it is possible to prevent the dye contained in the ink from acting as a singlet oxygen sensitizer.

The ink receiving layer can be of a microporous type. The term “microporous” as used herein refers to a layer in which the ink receiving layer has a large number of voids for absorbing and retaining ink. In such a layer, ink absorption is good and high-speed printing is appropriate. And a high-quality image can be recorded with less bleeding at the boundary.

In the above formula (2), R ₁ is hydrogen,
X, n, R _{3 to} R ₇ and M can be as described above.

In the above formula (2), n is 2 or 3, R ₃ and R ₄ are independently hydrogen, alkyl having 1 to 6 carbon atoms, and the substituent is OH, OCH ₃ , COOM or SO _3. a is either a substituted alkyl of 2 to 6 carbon atoms M, or R ₃ and R ₄ forms a 5- or 6-membered ring with or without heteroatoms, R ₅ substituents are OH , COOM or SO ₃ M, a substituted alkyl having 1 to 4 carbon atoms,
₆ is hydrogen, CH ₃ or CH ₂ CH ₃ , and R ₇ and M
However, it can be as described above.

In the above formula (2), R ₇ is hydrogen, alkyl having 1 to 3 carbons or a substituent is CN or CO
It can be a substituted alkyl having 2 or 3 carbon atoms which is OM.

Further, in the above formula (2), R ₅ is C
H ₂ CH ₂ OH, CH ₂ COOM or (CH ₂ ) ₃ SO
₃ M, R ₆ is hydrogen, and M can be hydrogen, an alkali metal atom, ammonium or ammonium substituted with alkyl of 1 or 2 carbon atoms or with H ₂ CH ₂ OH.

The voids preferably have a porosity of 30 to 80%, more preferably 40 to 70%, according to J. TAPPI No. 48-85. If the porosity is less than 30%, the quick drying property, absorption speed, absorption capacity, etc. of the ink may decrease. There is a risk of clogging. Examples of a method for controlling the porosity of the ink receiving layer within the above range include a method of controlling the ratio of the pigment and the binder, a method of physically forming a void, and a calendering treatment.

Further, the surface layer may be formed so as to form a film by the heating.

Further, the recording medium according to the present invention can be used for an ink jet recording system. Further, the recorded matter can be obtained by an inkjet recording method. Furthermore, the recording method can form the recorded image by an inkjet recording method.

Hereinafter, materials and production methods which can be suitably used in the present invention will be described more specifically.

[0030]Cyan ink  Cyan inks that can be suitably used in the present invention include:
At least copper phthalocyanine dye, water and organic solvent
At least one that comprises.

[0031]Copper phthalocyanine dye  As a copper phthalocyanine dye suitably used in the present invention
Is a copper phthalocyanine bone represented by the following formula (4):
Compounds having a case are exemplified.

[0032]

Embedded image Examples of the copper phthalocyanine dye suitably usable in the present invention include C.I. I. Direct Blue 86, 87, 1
99, and a water-soluble copper phthalocyanine dye represented by the following formula (5).

[0033]

Embedded image In the formula (5), CuPc represents a phthalocyanine skeleton, and R ¹ represents a hydrogen atom, a C _1-10 alkyl group, a C _1-10
1-10 alkoxy group or a _{hydroxy, C 1 -10,}
Represents an alkyl group, R ² is a C _1-10 alkylene group,
A C _1-10 alkyleneoxy C _1-10 alkylene group,
Represents a substituted triazine group, wherein M is lithium, sodium, potassium, ammonium, or mono- or di-C
Represents _1-6 alkylamino, n and m represent an integer of 0 to 4, and n + m is an integer of 4 or less.

Preferred specific compounds of the formula (5) include the following.

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image The amount of the copper phthalocyanine dye added is preferably in the range of 0.1 to 20% by weight based on the weight of the cyan ink.

The copper phthalocyanine dye may be used alone or as a mixture with another water-soluble dye used in an ink jet printer. Examples of the other dyes include the following.

C. I. Direct Blue 1,
2,6,8,15,22,25,34,69,70,7
1,72,75,76,78,80,81,82,8
3,90,98,106,108,110,120,1
23,158,163,165,192,193,19
4,195,196,200,201,202,20
3,207,218,236,237,239,24
6,258; C.I. I. Acid Blue 1,7,
9, 22, 23, 25, 27, 29, 40, 41, 4
3,45,49,51,53,55,56,59,6
2,78,80,81,83,90,92,93,10
2,104,111,113,117,120,12
4,126,145,167,171,175,18
3,229,234,236 As the other components, an imidazole derivative or a water-soluble organic nickel compound, an antioxidant, a sugar, or the like may be added alone or in combination as necessary.

[0041]Magenta ink  The magenta ink that can be preferably used in the present invention includes magenta ink.
It should contain at least a zeta dye, water and an organic solvent.
Ink composition.

The magenta dye may be used alone or in combination with other water-soluble dyes used in ink jet printers, and specific examples thereof include the following.

C. I. Direct Red 1,
2,4,8,9,11,13,17,20,23,2
4,28,31,33,37,39,44,46,4
7, 48, 51, 59, 62, 63, 73, 75, 7
7,80,81,83,84,85,90,94,9
9, 101, 108, 110, 145, 189, 19
7,220,224,225,226,227,23
0; I. Acid Red 1,4,6,8,13,
14, 15, 18, 19, 21, 26, 27, 30, 3
2,34,35,37,40,42,51,52,5
4,57,80,82,83,85,87,88,8
9,92,94,97,106,108,110,11
5,119,129,131,133,134,13
5,154,155,172,176,180,18
4,186,187,249,254,256,31
7,318 Particularly preferred magenta dyes include the following formula (1)
Or a magenta dye represented by the formula (2) or (3).

[0044]

Embedded image In the formula (1), R ⁴ represents a sulfonyl group or a carboxyl group, R ⁵ represents a triazine group which may be substituted, M represents lithium, sodium, potassium, ammonium, or mono- or di-C Represents _1-6 alkylamino.

The following are specific examples of the compound represented by the formula (1).

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded imageNote that in the formula (2), R₁Is hydrogen or C1-C6 fat
And n is 2, 3, or 4, and X is NR₃R₄
(Where R₃And R₄Is independently hydrogen, an alkyl having 1 to 6 carbons
Kill, substituent is OH, OCH₃, COOM or SO₃M
Substituted alkyl having 2 to 6 carbon atoms, aralkyl, not substituted
Substituted aryl or COOM or SO₃Ally substituted with M
And R₃And R₄Contains or does not contain heteroatoms
Or X may be SR₅
(Where R₅Is an alkyl having 1 to 6 carbon atoms or a substituent of O
H, OCH₃, COOM or SO₃M having 2 to 2 carbon atoms
6 is substituted alkyl) or X is OR
₆(Where R₆Is hydrogen or an aliphatic group having 1 to 6 carbon atoms.
R)₇Is hydrogen, alkyl having 1 to 6 carbons,
Substituents are CN, COOM, OH, COOCH₃, COOC
H₂CH₃Or COCH ₃Is a substituted aryl group having 2 to 6 carbon atoms
Alkyl, unsubstituted aryl, or CH₃Or halogen
Where M is hydrogen, a metal atom, ammonia
Or an alkyl, a, each having 1 to 12 carbon atoms.
Substituted with alkoxyalkyl or hydroxyalkyl
Ammonium.

[0050]

Embedded imageNote that in the equation (3), R₃And R₄Is independently hydrogen or a substituent
Is OH, COOM or SO₃M having 2 or 3 carbon atoms
A substituted alkyl,₇Is hydrogen, CH₂CH ₂CN
Is CH₂CH₂COOM, M is hydrogen, alkali gold
Genus or ammonium ion.

The following are specific examples of the compound represented by the formula (3).

[0052]

Embedded image The amount of the magenta dye added is desirably in the range of 0.1 to 20% by weight based on the magenta ink. Further, as other components, an imidazole derivative or a water-soluble organic nickel compound, an antioxidant, a saccharide or the like may be added alone or in combination, if necessary.

[0053]Water, organic solvent  Further, the ink according to the present invention has water and an organic solvent as a solvent.
And may be included. The organic solvent is preferably water-soluble
Organic solvent, for example,
It is preferable to select a low volatile solvent for the purpose of preventing clogging.
Good. Preferred specific examples include ethylene glycol
, Diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, 1,
3-propanediol, 1,5-propanediol,
1,2-hexanediol, 1,2,6-hexanetri
Polyhydric alcohols such as all and glycerin; ethylene glycol
Recall monomethyl ether, ethylene glycol mono
Butyl ether, diethylene glycol monobutyl acrylate
Ter, triethylene glycol monoethyl ether, g
Polyethylene glycol monobutyl ether, propylene
Glycol monomethyl ether, propylene glycol
Monobutyl ether, dipropylene glycol monomethyl
Glycol ethers such as toluene ether; formamide,
Dimethylformamide, diethanolamine, trieta
Nolamine, 1,3-dimethyl-2-imidazolidino
, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like
Nitrogen-containing solvent: thiodiglycol, dimethyl sulfoxide
And the like.

These solvents may be used alone or in combination of two or more. The addition amount of the solvent may be appropriately determined as desired, but is generally in the range of 40% by weight or less, preferably in the range of 3 to 30% by weight based on the ink.

Further, according to a preferred embodiment of the present invention, in a color ink jet system using multiple colors, from the viewpoint of preventing bleeding between adjacent color inks, a nonionic interface of glycol ethers or acetylene glycol is used. The addition of an activator is preferred. More preferably, by including both a glycol ether and an acetylene glycol-based nonionic surfactant, a very clear color image can be obtained. Particularly preferred are diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and the like. The amount added to the ink is preferably about 3 to 30% by weight. As the acetylene glycol-based nonionic surfactant, a commercially available product can also be used, and examples thereof include Olfin E1010, Olfin E104, and Olfin STG (all products of Nissin Chemical Co., Ltd.). The amounts of these additives may be appropriately determined as desired, but are preferably 3.0% by weight or less based on the ink.

Further, in order to prevent clogging, urea,
It is also preferable to add a solid wetting agent at room temperature having a hygroscopic property, such as trimethylolethane or trimethylolpropane. The addition amount may be appropriately determined as desired, but is preferably 20% by weight or less, more preferably 5 to 10% by weight based on the ink.

Further, in order to promote the drying property of the ink after image formation, anionic surfactants such as lower alcohols such as ethanol, 1-propanol and 2-propanol, fatty acid salts, alkyl sulfate salts and the like; It is preferable to add a nonionic surfactant such as acetylene glycols, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters. The content of lower alcohols in the ink is generally 10% by weight or less, and preferably in the range of 2 to 6% by weight. The content of the surfactant may be appropriately determined as desired, but is preferably in the range of 2% by weight or less based on the ink.

The ink used in the present invention can be manufactured by a general method. For example, there is a method in which the components are sufficiently mixed and dissolved, and the mixture is filtered under pressure with a membrane filter having a pore diameter of 0.8 μm, and then deaerated using a vacuum pump to prepare an ink.

[0059]Ink set  The ink set used in the present invention is the above-described cyan ink.
, Magenta ink, yellow ink, and
And black ink.

According to the ink jet recording method using the ink set according to the present invention, it is possible to realize an extremely good color image without discoloration due to visible light.

It is also possible to use an ink set containing two ink compositions of the same color but having different color densities. Specifically, for example, an ink set consisting of five colors of yellow ink, two types of magenta inks having different color densities, and two types of cyan inks having different color densities, or six colors obtained by adding black ink to the ink set is used. It can also be used. With such a combination of inks, a good image having excellent reproducibility of the intermediate color can be obtained.
Here, different color densities mean that, for the same colorant, the colorant concentration of the ink is different, and for similar colorants, the color saturation formed by the ink is different. Means

The concentration of the colorant in the low-concentration ink is not particularly limited, and may be any concentration, but may be about 1/10 to 2/3 of the concentration of the high-concentration colorant. preferable.

[0063]Recording media (inkjet media)  Further, the recording medium according to the present invention includes a support (substrate)
On at least one side of the substrate by, for example, a laminating means such as a coating method.
And at least one ink receiving layer.
May have a plurality of ink receiving layers. (1) Support The support according to the present invention comprises, in addition to the ink receiving layer, a back coat.
Layer may be provided. This support is transparent,
Any of transparent can be used, for example, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
Mechanical pulp such as MP, CMP and CGP, waste paper such as DIP
Pulp, wood pulp, synthetic fiber paper such as polyethylene fiber
Pigment, sizing agent and fixing agent, yield
Refining agents, paper strength enhancers, etc.
Seed additives are mixed as necessary, fourdrinier paper machine, round paper machine
Raw materials manufactured by various devices such as paper machines and twin wire paper machines.
Paper and base paper with starch, polyvinyl alcohol, etc.
Base paper with ispress or anchor coat layer
Paper, coated paper, cast with a coat layer on top
Coated paper such as coated paper, high quality paper, medium quality paper, bond paper, cash register
Coated paper, baryta paper, radiation curable resin coated paper, etc.
Papers can also be used. Such base paper and coated paper
May be provided with an ink receiving layer as it is.
Calendars such as calendars, TG calendars, and soft calendars
ー After smoothing the device before the ink receiving layer coating
May be used. Further, as a support, on the base paper
May be provided with a polyolefin resin layer.
, Polypropylene, polyester, nylon, rayo
Of synthetic resins such as polyurethane and polyurethane, and mixtures of these.
Film material or a medium formed by fiberizing these synthetic resins.
Body materials can also be used. Also, polyethylene teref
Talate, diacetate, triacetate, polycarbonate
Plastics such as acrylate, polyethylene, polyacrylate, etc.
A film made of a film can be used.

The use of a smooth and high-density support (resin-coated paper) such as that used for a photographic support can provide an image comparable to silver halide photography. Especially preferred.

The resin layer of the support (resin-coated paper) having a smooth and high density used herein is preferably made of polyethylene, and desirably contains titanium oxide in order to increase whiteness. (2) Pigment In the present invention, one or more pigments generally insoluble or hardly soluble in water can be used in the ink receiving layer. Examples of the pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide,
Zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohalo Site, white inorganic pigments such as magnesium carbonate and magnesium hydroxide, styrene plastic pigments, acrylic plastic pigments, and organic pigments such as polyethylene, urea resin, and melamine resin.

Among the above-mentioned pigments, as the white pigment contained as a main component in the ink receiving layer, a porous inorganic pigment is preferable because it is excellent in drying property and absorbency as an ink for an ink jet recording system. , Porous synthetic amorphous silica, porous magnesium carbonate, porous alumina and the like. Among these, in the present invention, the porous amorphous silica and the particle size satisfying both print quality and storage stability (water resistance, abrasion resistance, light resistance, indoor storage stability, storage stability against direct sunlight) It is preferable to use silica or porous alumina having a small particle size. The proportion of the pigment in the ink receiving layer is preferably from 5 to 70%. (3) Binder resin In the present invention, as a binder resin contained in the ink receiving layer, a polyvinyl alcohol-based water-soluble resin such as completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, and silyl-modified polyvinyl alcohol is used. , Vinyl acetate, oxidized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, soybean protein, silyl-modified polyvinyl alcohol; maleic anhydride resin, styrene-butadiene copolymer, methylmethacrylate-butadiene copolymer Conjugated diene copolymer latex such as polymer; acrylic polymer latex such as acrylic acid ester and methacrylic acid ester polymer or copolymer; ethylene vinyl acetate Vinyl-based polymer latex such as copolymer; or functional group-modified polymer latex with functional group-containing monomer such as carboxyl group of various polymers; aqueous solution of thermosetting synthetic resin such as melamine resin and urea resin Adhesives: Synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and alkyd resin, and these binder resins may be used alone or in combination of two or more. It can also be used.

Further, the mixing ratio of the pigment and the binder resin in the ink receiving layer is as follows: binder resin: pigment = 1: 1.
１ ： 1: 15 is preferable, and 1: 2２〜1: 10 is particularly preferable. (4) Other additives Further, in the ink receiving layer, other additives such as a cationic dye fixing agent, a light fastness improver, a pigment dispersant, a thickener, a pH adjuster, a lubricant, and a fluidity improver ( Denaturing agents, surfactants, defoamers, foam inhibitors, release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent brighteners, antioxidants, ultraviolet absorbers, light stabilizers, preservatives An agent, a water-proofing agent, a hardening agent and the like can be appropriately compounded as needed. (5) Formation of Ink Receiving Layer (Production Method) The ink receiving layer is formed by dissolving or dispersing the above-described material for forming an ink receiving layer in a suitable solvent such as water or an alcohol in which the material is dissolved, and applying a coating liquid. Adjust and form this by applying it on a support, for example, using various blade coater, roll coater, air knife coater, bar coater, rod blade coater, size press, etc. on or off machine as appropriate. can do.

The ink absorbing layer may be provided as a single layer or as two or more layers. The coating amount of the ink receiving layer is preferably 5 to 40 g / m ² . If the coating amount is less than this range, the ink absorbency and the fixing agent may not be sufficiently obtained, and if it is too large, problems such as powder dropout, productivity reduction and cost increase may be caused.

After the application of the ink receiving layer, finishing may be performed using a calender such as a machine calender, a TG calender, a super calender, and a soft calender.

[0070]Latex layer  (1) Configuration of Latex Layer The surface layer containing the latex according to the present invention is made of thermoplastic resin.
A porous layer containing a resin is provided.
Ink through this porous layer to the underlying layer, e.g.
Layer, or ink-absorbing substrate
An image is formed, and the outermost layer is heated to form a film.
By doing so, printed matter with excellent weather resistance can be obtained.
You.

In the present invention, by using a porous layer containing a thermoplastic resin which does not deteriorate the resin after light exposure and does not change its color as the outermost layer, the discoloration can be maintained even after long-term storage. It is possible to form a recording medium which does not easily occur and has excellent ink permeability. (2) Materials As the thermoplastic resin used in the present invention, any resin having the above-mentioned properties can be used. Examples thereof include vinyl chloride, vinylidene chloride, styrene, acrylic, and urethane. , Polyester-based, ethylene-based material or vinyl chloride-vinyl acetate, vinyl chloride-acrylic, vinyl chloride-vinylidene chloride,
Latexes such as vinylidene chloride-acrylic, SBR-based, and NBR-based latexes, and latexes of two or more copolymers thereof, for example, latexes such as SBR-based / NBR-based mixtures and vinyl chloride-acrylic-vinyl acetate-based mixtures. Can be

Further, the film has good long-term storage properties, scratch resistance, etc., and considering the weather resistance after nonporous treatment, the mechanical strength, water resistance, acid resistance, alkali resistance, oil resistance, and organic resistance of the film. A thermoplastic resin having at least one vinyl chloride monomer excellent in a solvent or the like is preferably used.

More preferably, a thermoplastic resin which is a copolymer of a vinyl chloride monomer and one or more other monomers is used. Since vinyl chloride alone is a very hard film having a certain degree of molecular arrangement, the resin is plasticized by copolymerizing one or more other polymerizable monomers, and the Tg or non-porosity of the thermoplastic resin is increased. The tempering temperature can be lowered.

It is preferable that at least one of the other polymerizable monomers to be copolymerized is an unsaturated carboxylic acid ester such as an acrylate ester or a fatty acid vinyl ester. The other at least one type of polymerizable monomer to be copolymerized is more preferably vinyl acetate from the viewpoint of easy copolymerization with vinyl chloride and ease of handling. For example, a latex comprising a vinyl chloride-vinyl acetate-based binary or tertiary or higher copolymer is particularly preferably used.

Further, the emulsion state of the latex is stabilized, the adhesion between the particles and the lower layer in the porous layer containing the latex obtained by using the latex is improved, and the affinity with the ink is appropriately increased, so that the ink permeation is improved. The latex used is at least one kind of vinyl chloride monomer and at least one kind of acrylic acid ester or fatty acid ester because the property for improving the property and the temperature for the non-porous treatment can be lowered. More preferably, it is a ternary or higher copolymer containing at least one or more polymerizable monomers having a carboxyl group.
For example, a latex composed of a copolymer of three or more vinyl chloride-vinyl acetate-acrylic acids is particularly preferably used.

The porous layer containing such a thermoplastic resin needs to have a certain level of mechanical strength so as not to be easily peeled off from the substrate or the pigment layer provided thereon. In order to increase the adhesion (rub resistance) of the layer, it is desirable to partially fuse the thermoplastic resin. Such partial fusion is performed by performing a heat treatment at a temperature not lower than the glass transition temperature (Tg) of the thermoplastic resin and not higher than the minimum film forming temperature. A very small amount of a binder, for example, polyvinyl alcohol may be added. The temperature of partial fusion is
The glass transition temperature is preferably at least 10 ° C, more preferably at least 20 ° C, and still more preferably at least 40 ° C. When two or more thermoplastic resins are used, the glass transition temperature refers to the glass transition temperature of the thermoplastic resin having the lowest glass transition temperature.

In order to improve the ink absorption rate and obtain an appropriate print dot diameter, it is important to adjust the average particle diameter of the thermoplastic resin used and its particle size distribution. Particle size is 0.1-15.0 μm
Is more preferable, more preferably 0.1 to 3 μm, and still more preferably 0.2 to 2 μm. When the average particle diameter is less than 0.1 μm, the absolute pore volume of the thermoplastic resin layer becomes small, and even at a temperature near Tg, the thermoplastic resin layer may begin to soften and block the pores. Tends to decrease. Further, the average particle diameter is 15.0 μm.
If it exceeds m, the surface becomes difficult to smoothen and the glossiness is liable to decrease when a nonporous treatment is performed after printing.

Further, the porous layer containing a thermoplastic resin may contain metal oxide fine particles, an ultraviolet absorber or a light stabilizer. When metal oxide fine particles are contained,
This is preferable because the beading resistance when recording with an ink jet printer is significantly improved and the resolution is improved. As the metal oxide particles, silica particles are preferably used. When silica particles are used, transparency can be maintained when the porous layer is densified by heat treatment. Further, by including an ultraviolet absorber or a light stabilizer, discoloration of the thermoplastic resin as well as discoloration of the image formed by the ink can be further suppressed. (3) Forming method The porous layer containing the thermoplastic resin is made of a thermoplastic resin,
It can be obtained by applying the composition to a base material or a pigment layer provided thereon and heat-treating it preferably at Tg or less of the thermoplastic resin.

The coating amount of the thermoplastic resin is required to be thick enough to impart surface gloss by post-printing treatment, not to exhibit interference colors, and to sufficiently exhibit the function as a protective film. It is preferably applied so that the thickness is usually 2 to 10 μm. Further, a latex layer may be provided on a commercially available recording medium for inkjet.

[0080]

Next, an embodiment according to the present invention will be described in detail. (Example 1) (1) Ink composition An ink composition having the composition shown in the following table was prepared. The following abbreviations were used in the table.

DEGmBE: diethylene glycol monobutyl ether Olfin E1010, Olfin STG, and Olfin E104 were acetylene glycol surfactants manufactured by Shin-Etsu Chemical Co., Ltd., and Proxel XL-2 was a preservative manufactured by Zeneca. The ink composition was adjusted to 100% by weight by adding ion-exchanged water.

[0082]Yellow ink  C. I. Acid Yellow 97 2.5% by weight C.I. I. Direct Yellow 86 2.5% by weight 2-Ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 12.0% by weight Diethylene glycol 3.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.5% by weight Proxel XL-2 0.3% by weightCyan ink  C. I. Direct Blue 87 3.5% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 10.0% by weight Diethylene glycol 2.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.5% by weight Triethanolamine 1.0% by weight Proxel XL-2 0.3% by weightLight cyan ink  C. I. Direct Blue 87 0.5% by weight 2-Ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 12.0% by weight Diethylene glycol 8.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.0% by weight Triethanolamine 0.2% by weight Proxel XL-2 0.3% by weightMagenta ink  Dye (shown in formula 12) 2.0% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 10.0% by weight Diethylene glycol 5.0% by weight DEGmBE 7. 0% by weight Olfine E1010 1.5% by weight Triethanolamine 0.9% by weight Proxel XL-2 0.3% by weightLight magenta ink  Dye (shown in formula 12) 0.2% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Trimethylolethane 12.0% by weight Diethylene glycol 8.0% by weight DEGmBE 7.0% by weight Olfin E1010 1.0% by weight Potassium hydroxide 0.03% by weight Proxel XL-2 0.3% by weight (2) Formation of recording medium The support was weighed at 90 g / m.²High-quality paper of this support
A coating liquid in which a material having the following composition is dissolved and dispersed in water is sequentially applied to one side.
By coating and drying, ink-receiving layer, latek
And a layer containing copper is provided at a temperature of about 70 ° C.
Heating was performed for 60 seconds to obtain an ink jet recording medium.

The ratios given in the examples are weight ratios of dry solids. The coating amount was 20 g / m ² for the ink receiving layer and 10 g / m ² for the surface layer containing the latex, unless otherwise specified.

[0084]Ink receiving layer  Binder resin Fully saponified PVA (Kuraray: PVA-117) 25% by weight Pigment silica (Tokuyama: X-37B) 70% by weight Cationic dye fixing agent Polyallylamine (Nittobo: PAS-H) 5 Weight%Latex-containing surface layer  SBR latex (Nipol LX407K, manufactured by Zeon Corporation) 100% by weight (Example 2) (1) Ink composition The same ink composition as in Example 1 was used. (2) Formation of recording medium A method similar to that of Example 1 was used except that a material having the following composition was used.
Formed.

[0085]Ink receiving layer  Binder resin Fully saponified PVA (Kuraray PVA-117) 25% by weight Pigment silica (Tokuyama: X-37B) 70% by weight Cationic dye fixing agent Polyallylamine (Nittobo: PAS-H) 5% by weightLatex-containing surface layer  SBR latex (manufactured by Zeon Corporation: Nipol LX407K) 70% by weight Silica sol (manufactured by Catalysis Kasei Kogyo Co., Ltd .: Cataloid S1-80P) 30% by weight (Example 3) (1) Ink composition The same ink composition as in Example 1 was used. Was. (2) Formation of recording medium A method similar to that of Example 1 was used except that a material having the following composition was used.
Formed.

[0086]Ink receiving layer  Binder resin Fully saponified PVA (Kuraray PVA-117) 25% by weight Pigment silica (Tokuyama: X-37B) 70% by weight Cationic dye fixing agent Polyallylamine (Nittobo: PAS-H) 5% by weightLatex-containing surface layer  SBR latex (Nihon Zeon: Nipol LX407K) 65% by weight Silica sol (Catalyst Kasei Kogyo: Cataloid S1-80P) 30% by weight Ultraviolet absorber (Nihon Ciba Geigy: TINUVIN 328) 5% by weight (Example 4) (1) Ink compositionYellow ink  The same one as in Example 1 was used.

[0087]Cyan ink  The same one as in Example 1 was used.

[0088]Light cyan ink  The same one as in Example 1 was used.

[0089]Magenta ink  Dye (shown in formula 13) 2.0% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 10.0% by weight Diethylene glycol 5.0% by weight DEGmBE 7. 0% by weight Olfine E1010 1.5% by weight Triethanolamine 0.9% by weight Proxel XL-2 0.3% by weightLight magenta ink  Dye (shown in formula 13) 0.2% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Trimethylolethane 12.0% by weight Diethylene glycol 8.0% by weight DEGmBE 7.0% by weight Olfin E1010 1.0% by weight Potassium hydroxide 0.03% by weight Proxel XL-2 0.3% by weight (2) Formation of recording medium The recording medium was formed in the same manner as in Example 1. (Example 5) (1) Ink composition The same composition as in Example 4 was used. (2) Formation of recording medium A recording medium was formed in the same manner as in Example 2. Example 6 (1) Ink Composition The same composition as in Example 4 was used. (2) Formation of recording medium A recording medium was formed in the same manner as in Example 3. Comparative Example 1 (1) Ink Composition An ink composition having the composition shown in the following table was prepared.
Was. The abbreviations and the like in the table are the same as in Example 1.
You.

[0090]Yellow ink  C. I. Acid Yellow 97 2.5% by weight C.I. I. Direct Yellow 86 2.5% by weight 2-Ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 12.0% by weight Diethylene glycol 3.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.5% by weight Proxel XL-2 0.3% by weightCyan ink  C. I. Direct Blue 87 3.5% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 10.0% by weight Diethylene glycol 2.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.5% by weight Triethanolamine 1.0% by weight Proxel XL-2 0.3% by weightLight cyan ink  C. I. Direct Blue 87 0.5% by weight 2-Ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 12.0% by weight Diethylene glycol 8.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.0% by weight Triethanolamine 0.2% by weight Proxel XL-2 0.3% by weightMagenta ink  C. I. Direct Red 227 2.0% by weight 2-ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Glycerin 10.0% by weight Diethylene glycol 5.0% by weight DEGmBE 7.0% by weight Olphin E1010 1.5% by weight Triethanolamine 0.9% by weight Proxel XL-2 0.3% by weightLight magenta ink  C. I. Direct Red 227 0.2% by weight 2-Ethyl-4-methylimidazole 15.0% by weight Sodium L-ascorbate 5.0% by weight Trimethylolethane 12.0% by weight Diethylene glycol 8.0% by weight DEGmBE 7.0% by weight % Orfin E1010 1.0% by weight Potassium hydroxide 0.03% by weight Proxel XL-2 0.3% by weight (2) Formation of recording medium The same medium as in Example 1 was used. Comparative Example 2 (1) Ink Composition An ink having the same composition as in Example 1 was prepared. (2) Formation of recording medium A method similar to that of Example 1 was used except that a material having the following composition was used.
Formed.

[0091]Ink receiving layer  Binder resin Completely saponified PVA (Kuraray: PVA-117) 25% by weight Pigment silica (Tokuyama: X-37B) 70% by weight Cationic dye fixing agent Polyallylamine (Nittobo: PAS-H) 5 % By weight (Comparative Example 3) (1) Ink Composition An ink having the same composition as in Comparative Example 1 was prepared. (2) Formation of recording medium The same one as in Comparative Example 2 was used. (Evaluation method) Examples 1 to 6 and Comparative examples 1 to
A commercially available ink was added to the ink jet recording medium obtained in Example 3.
Jet printer (Seiko Epson: PM-80)
0C), color patches, portrait images, etc.
After printing the object to be evaluated, the obtained recording medium is
Heat at a temperature of 20 ° C. for about 60 seconds to coat the surface layer
You.

When performing this heat treatment, a laminator may be used to make the outermost surface smoother. Further, when the film is passed through the laminator, the film may be placed on the printing surface, passed simultaneously, and then formed into a film by a method such as peeling off the film.

[0093] When a recorded matter (printed matter) on which a recorded image was formed was prepared in this manner, good images were obtained in all cases. Next, using the recorded matter on which these images were formed, evaluation was performed by the following method. Table 1 shows the results. (1) Light fastness test 1 (Xenon lamp acceleration test) Using the above-mentioned ink jet printer, magenta (M) and cyan having an optical density of 1.0 were applied to the ink jet recording media obtained in each of Examples and Comparative Examples. (C), solid printing of blue (B) was performed. Next, using a xenon weatherometer (Ci-5000, manufactured by ATLAS), the black panel temperature was 35 ° C., the relative humidity was 60%, and 340 nm.
An exposure test of 45 KJ / m ² was performed at an ultraviolet irradiation intensity of 0.18 W / m ² .

Next, using a spectrophotometer (GRETAG SPM50, manufactured by Gretag Macbeth), the optical density of each color patch printed on these recording media was measured before and after the exposure test, whereby the exposure test was performed. The light resistance was evaluated according to the following evaluation criteria by obtaining the residual rate (%) of the optical density afterward.

A: Residual rate of optical density exceeds 90% B: Residual rate of optical density exceeds 80% and less than 90% C: Residual rate of optical density exceeds 70% and less than 80% D: The residual ratio of the optical density is less than 70%. (2) Light fastness test 2 (accelerated fluorescent lamp test) The light fastness of the ink jet recording medium obtained in each of the above Examples and Comparative Examples. As in Test 1, solid printing of magenta (M), cyan (C), and blue (B) with an optical density of 1.0 was performed. Then, using a fluorescent lamp acceleration tester (HPUV, manufactured by ATLAS), about 6 W / m ²
The exposure test was performed by irradiation with only a white fluorescent lamp for 100 hours in the ultraviolet wavelength range of 300 to 400 nm.

Next, the light resistance was evaluated in the same manner as in the light resistance test 1. (3) Water resistance test Using the inkjet printer, the inkjet recording media obtained in each of the examples and comparative examples were used for yellow (Y), magenta (M), cyan (C), and blue (B). Solid printing was performed. Next, one drop of water was attached to the printed portion with a dropper, and the state after air drying was evaluated according to the following evaluation criteria.

A: No dye flow out B: Dye flow out, but legible C: Legible (4) Moisture resistance test Obtained in each of the Examples and Comparative Examples using the inkjet printer. On an inkjet recording medium, yellow (Y), magenta (M), cyan (C), blue (B) line lines, images, white lines during solid printing, and solid printing with an optical density of 1.0 Was done. Next, these were subjected to an exposure test for 3 days using a thermo-hygrostat at 32 ° C. and a relative humidity of 85%.

For each of the examples and comparative examples, before and after the exposure test, the line thickness, the thinning of the white line (white outline), the bleeding of the outline of the image, and the discoloration of each color patch were evaluated. The color change of each color patch is described in the light resistance test 1
Was evaluated in the same manner as described above. (5) Scratch resistance test A 500 g weight was placed on the recording medium obtained in each of the examples and comparative examples, rubbed, and evaluated according to the following evaluation criteria.

A: no scratch B: slightly scratched C: many scratches (6) Gas resistance test For the ink jet recording medium obtained in each of the above Examples and Comparative Examples. In the same manner as in the light resistance test 1, solid printing of magenta (M), cyan (C), and blue (B) with an optical density of 1.0 was performed. Next, a simple gas (O ₃ , NO _X , SO _X , H ₂ S) generator was used to conduct an exposure test at a concentration of about 1 ppm for 72 hours. Next, evaluation was performed in the same manner as in the light resistance test 1. (7) Print density test Black (B)
k), yellow (Y), magenta (M), cyan (C)
Was performed, and the density of this portion was evaluated using SPM-50 manufactured by Gretag Macbeth. (8) Image sharpness test Using the inkjet printer, a black (B)
k), yellow (Y), magenta (M), cyan (C)
Was performed, and whether or not the colors were blurred or mixed unevenly at the boundary between each color and multiple colors was evaluated according to the following criteria.

A: No bleeding B: Color bleeding or non-uniformly mixed parts are slight, but there is no practical problem C: Color bleeding or non-uniformly mixed parts are conspicuous and practical D: severe bleed (9) Color reproducibility test
k), yellow (Y), magenta (M), cyan (C)
Is printed, and the area is determined from the a ^* b ^* chromaticity diagram.
The evaluation was performed according to the following evaluation criteria, with the area obtained in Comparative Example 1 as 100%.

A: The area ratio is 130% or more. B: The area ratio is 110% or more and less than 130%. C: The area ratio is 100% or more and less than 110%. D: The area ratio is less than 100%. Yes (10) Gloss test According to the measurement method defined in JIS Z8741
The degree of specular gloss was measured. The higher the numerical value, the higher the gloss and the more preferable.

[0102]

[Table 1] From the results shown in Table 1, it can be seen that the recording medium according to the present invention obtained good results in all test items.

This is because the surface layer containing the latex blocks oxygen molecules in the air and dye molecules, and prevents the dye contained in the ink from acting as a singlet oxygen sensitizer. Because you can.

[0104]

As described above, according to the present invention,
Since the ink adhering to the ink receiving layer can be covered by the coated surface layer, the ink can be prevented from coming into contact with oxygen in the air. Therefore,
The dye contained in the ink can be prevented from acting as a singlet oxygen sensitizer. As a result, of course, it is excellent in color development, density and color reproducibility,
It is possible to provide a recording medium excellent in storability, a recorded matter using the same, and a recording method.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 35/029 C09B 35/26 35/26 47/24 47/24 C09D 11/00 C09D 11/00 B41J 3 / 04 101Y F term (reference) 2C056 EA13 FC06 2H086 BA13 BA15 BA56 4J039 BA29 BC07 BC12 BC16 BC19 BC20 BC33 BC40 BC52 BC54 BC60 BC65 BC73 BC77 BC79 BE02 CA03 CA06 EA15 EA16 EA34 EA42 GA24

Claims (20)

[Claims] An ink receiving layer formed on a support,
It is formed on the ink receiving layer and is heated to
Comprising a surface layer containing a latex to form a film,
The magenta dye represented by the formula (1) shown below or
Magenta dye represented by formula (2) and copper phthalocyanine
Ink supplied from an ink set comprising a dye
Is attached, at least a part of the recorded image is
The recording medium to be formed. Embedded imageHowever, in the formula (1), R⁴Is a sulfonyl group or a carboxy group
Represents a xyl group;⁵Is an optionally substituted triazine
M represents lithium, sodium, potassium, a
Ammonium or mono or di C_1-6Alkylam
Which represents noHowever, in the formula (2), R₁Is hydrogen or C1-C6 fat
And n is 2, 3, or 4, and X is NR₃R₄
(Where R₃And R₄Is independently hydrogen, an alkyl having 1 to 6 carbons
Kill, substituent is OH, OCH₃, COOM or SO₃M
Substituted alkyl having 2 to 6 carbon atoms, aralkyl, not substituted
Substituted aryl or COOM or SO₃Ally substituted with M
And R₃And R₄Contains or does not contain heteroatoms
Or X may be SR₅
(Where R₅Is an alkyl having 1 to 6 carbon atoms or a substituent of O
H, OCH₃, COOM or SO₃M having 2 to 2 carbon atoms
6 is substituted alkyl) or X is OR
₆(Where R₆Is hydrogen or an aliphatic group having 1 to 6 carbon atoms.
R)₇Is hydrogen, alkyl having 1 to 6 carbons,
Substituents are CN, COOM, OH, COOCH₃, COOC
H₂CH₃Or COCH ₃Is a substituted aryl group having 2 to 6 carbon atoms
Alkyl, unsubstituted aryl, or CH₃Or halogen
Where M is hydrogen, a metal atom, ammonia
Or an alkyl, a, each having 1 to 12 carbon atoms.
Substituted with alkoxyalkyl or hydroxyalkyl
Ammonium. 2. The recording medium according to claim 1, wherein said ink receiving layer is of a microporous type. 3. The recording medium according to claim 1, which is used for an ink jet recording system. 4. The recording medium according to claim 1, wherein in the formula (2), R ₁ is hydrogen, and X, n, R _{3 to} R ₇ and M are as defined in claim 1. 5. In the formula (2), n is 2 or 3, R ₃ and R ₄ are independently hydrogen, alkyl having 1 to 6 carbons, and the substituent is OH, OCH ₃ , COOM or SO _3. a is either a substituted alkyl of 2 to 6 carbon atoms M, or R ₃ and R ₄ forms a 5- or 6-membered ring with or without heteroatoms, R ₅ substituents are OH , COOM or SO ₃ M, a substituted alkyl having 1 to 4 carbon atoms,
₆ is hydrogen, CH ₃ or _CH 2 CH _3, recording medium according to claim 4, wherein _{R 7} and M are as according to claim 1, wherein. 6. The recording medium according to claim 5, wherein in the formula (2), R ₇ is hydrogen, alkyl having 1 to 3 carbons, or substituted alkyl having 2 or 3 carbons wherein the substituent is CN or COOM. . 7. In the above formula (2), R ₅ is CH ₂ C
H ₂ OH, CH ₂ COOM or (CH ₂ ) ₃ SO ₃ M, R ₆ is hydrogen and M is hydrogen, an alkali metal atom, ammonium or alkyl having 1 or 2 carbon atoms, or H ₂ CH ₂ OH 7. Ammonium substituted with:
The recording medium according to the above. 8. An ink receiving layer provided on a support,
A dye which adheres to the ink receiving layer to form a recorded image;
Ink on the ink receiving layer on which the recorded image was formed.
And a surface layer, wherein the surface layer is formed into a film by heating.
Containing latex, at least the recorded image
Some are magenta dyes represented by the following formula (1)
Or a magenta dye represented by the following formula (2):
Provided from an ink set comprising copper phthalocyanine dye
Recorded matter formed from supplied ink. Embedded imageHowever, in the formula (1), R⁴Is a sulfonyl group or a carboxy group
Represents a xyl group;⁵Is an optionally substituted triazine
M represents lithium, sodium, potassium, a
Ammonium or mono or di C_1-6Alkylam
Which represents noHowever, in the formula (2), R₁Is hydrogen or C1-C6 fat
And n is 2, 3, or 4, and X is NR₃R₄
(Where R₃And R₄Is independently hydrogen, an alkyl having 1 to 6 carbons
Kill, substituent is OH, OCH₃, COOM or SO₃M
Substituted alkyl having 2 to 6 carbon atoms, aralkyl, not substituted
Substituted aryl or COOM or SO₃Ally substituted with M
And R₃And R₄Contains or does not contain heteroatoms
Or X may be SR₅
(Where R₅Is an alkyl having 1 to 6 carbon atoms or a substituent of O
H, OCH₃, COOM or SO₃M having 2 to 2 carbon atoms
6 is substituted alkyl) or X is OR
₆(Where R₆Is hydrogen or an aliphatic group having 1 to 6 carbon atoms.
R)₇Is hydrogen, alkyl having 1 to 6 carbons,
Substituents are CN, COOM, OH, COOCH₃, COOC
H₂CH₃Or COCH ₃Is a substituted aryl group having 2 to 6 carbon atoms
Alkyl, unsubstituted aryl, or CH₃Or halogen
Where M is hydrogen, a metal atom, ammonia
Or an alkyl, a, each having 1 to 12 carbon atoms.
Substituted with alkoxyalkyl or hydroxyalkyl
Ammonium. 9. The recorded matter according to claim 8, wherein said ink receiving layer is of a microporous type. 10. The recorded matter according to claim 8, wherein said recorded image is formed by an ink jet recording system. 11. The recorded matter according to claim 8, wherein in the formula (2), R ₁ is hydrogen and X, n, R _{3 to} R ₇ and M are as defined in claim 8. 12. In the formula (2), n is 2 or 3.
R ₃ and R ₄ are independently hydrogen, alkyl having 1 to 6 carbon atoms, and the substituent is OH, OCH ₃ , COOM or SO ₃ M
Or a substituted alkyl having 2 to 6 carbon atoms, or R ₃
And R ₄ are 5- or 6-, with or without a heteroatom.
R ₅ is a substituted alkyl having 1 to 4 carbon atoms having a substituent of OH, COOM or SO ₃ M;
R ₆ is hydrogen, CH ₃ or CH ₂ CH ₃ , and R ₇ and M
The recorded matter according to claim 11, which is as described in claim 8. 13. In the formula (2), R ₇ is hydrogen,
Alkyl or a substituent having 1 to 3 carbon atoms is CN or COOM
13. A substituted or unsubstituted alkyl having 2 or 3 carbon atoms.
The recorded matter described. 14. In the formula (2), R ₅ is CH ₂
CH ₂ OH, CH ₂ COOM or (CH ₂ ) ₃ SO ₃ M
R ₆ is hydrogen and M is hydrogen, an alkali metal atom, ammonium or ammonium substituted with alkyl having 1 or 2 carbon atoms or H ₂ CH ₂ OH.
3. The recorded matter according to 3. 15. An ink receiving layer formed on a support
Formed on the ink receiving layer and heated
A surface layer containing a latex to form a film.
A magenta dye represented by the following formula (1) is recorded on a recording medium.
Or magenta represented by the following formula (2)
Using an ink containing a dye and copper phthalocyanine dye
Recording method for forming at least a part of a recorded image. Embedded imageHowever, in the formula (1), R⁴Is a sulfonyl group or a carboxy group
Represents a xyl group;⁵Is an optionally substituted triazine
M represents lithium, sodium, potassium, a
Ammonium or mono or di C_1-6Alkylam
Which represents noHowever, in the formula (2), R₁Is hydrogen or C1-C6 fat
And n is 2, 3, or 4, and X is NR₃R₄
(Where R₃And R₄Is independently hydrogen, an alkyl having 1 to 6 carbons
Kill, substituent is OH, OCH₃, COOM or SO₃M
Substituted alkyl having 2 to 6 carbon atoms, aralkyl, not substituted
Substituted aryl or COOM or SO₃Ally substituted with M
And R₃And R₄Contains or does not contain heteroatoms
Or X may be SR₅
(Where R₅Is an alkyl having 1 to 6 carbon atoms or a substituent of O
H, OCH₃, COOM or SO₃M having 2 to 2 carbon atoms
6 is substituted alkyl) or X is OR
₆(Where R₆Is hydrogen or an aliphatic group having 1 to 6 carbon atoms.
R)₇Is hydrogen, alkyl having 1 to 6 carbons,
Substituents are CN, COOM, OH, COOCH₃, COOC
H₂CH₃Or COCH ₃Is a substituted aryl group having 2 to 6 carbon atoms
Alkyl, unsubstituted aryl, or CH₃Or halogen
Where M is hydrogen, a metal atom, ammonia
Or an alkyl, a, each having 1 to 12 carbon atoms.
Substituted with alkoxyalkyl or hydroxyalkyl
Ammonium. 16. The recording method according to claim 15, wherein in the formula (2), R ₁ is hydrogen, and X, n, R _{3 to} R ₇ and M are as defined in claim 15. 17. In the formula (2), n is 2 or 3.
R ₃ and R ₄ are independently hydrogen, alkyl having 1 to 6 carbon atoms, and the substituent is OH, OCH ₃ , COOM or SO ₃ M
Or a substituted alkyl having 2 to 6 carbon atoms, or R ₃
And R ₄ are 5- or 6-, with or without a heteroatom.
R ₅ is a substituted alkyl having 1 to 4 carbon atoms having a substituent of OH, COOM or SO ₃ M;
R ₆ is hydrogen, CH ₃ or CH ₂ CH ₃ , and R ₇ and M
17. The recording method according to claim 16, wherein is as described in claim 15. 18. In the formula (2), R ₇ is hydrogen,
Alkyl or a substituent having 1 to 3 carbon atoms is CN or COOM
18. A substituted alkyl having 2 or 3 carbon atoms, which is
The recording method described. 19. In the formula (2), R ₅ is CH ₂
CH ₂ OH, CH ₂ COOM or (CH ₂ ) ₃ SO ₃ M
R ₆ is hydrogen and M is hydrogen, an alkali metal atom, ammonium or ammonium substituted with alkyl having 1 or 2 carbon atoms or H ₂ CH ₂ OH.
8. The recording method according to item 8. 20. The recording method according to claim 15, wherein the recording image is formed by an ink jet recording method.