JP2001138624A - Medium to be recorded - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medium to be recorded having a high image density of a printed product without adverse influence of an ink to the hue of a dye, an image having a clear color tone and high resolution and excellent ink absorbability and image preservability by improving a light resistance and discoloring and fading resistances of an ink jet image. SOLUTION: The medium to be recorded comprises an ink receiving layer containing a compound represented by formula ((wherein X- is a monovalent metal complex anion, R1 to R8 are each a hydrogen atom or a monovalent organic residue, wherein at least one of R1 to R8 is a monovalent organic residue selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkinyl group and a substituted or unsubstituted aralkyl group, and n is 1 or 2.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium particularly suitable for ink-jet recording using an aqueous ink.
The present invention relates to a recording medium in which an image recorded on the recording medium has a clear color tone, a high resolution, a high image density, and is excellent in ink absorbency and preservability of a recorded image.

[0002]

2. Description of the Related Art Ink-jet recording is a method in which fine droplets of ink are caused to fly according to various operating principles and adhere to a recording medium such as paper to record images and characters. Because of its excellent features such as high speed, low noise, easy multi-coloring, great flexibility in recording patterns, and no need for development and fixing, it is used in various applications such as information equipment as various image recording devices. Are rapidly spreading. Further, the image formed by the multi-color ink jet method can obtain a record comparable to that of the multi-color printing by the plate making method and the printing by the color photographic method, and when the number of copies is small, Is widely used in the field of full-color image recording because it is cheaper than ordinary multicolor printing and printing. In addition, recording devices and recording methods have been improved with improvements in recording characteristics such as higher recording speed, higher definition, and full color printing. However, advanced characteristics are also required for recording media. It is becoming.

In order to solve such a problem, various types of recording media have been proposed. For example,
JP-A-52-53012 discloses an ink-jet paper in which a low-size base paper is impregnated with a paint for surface treatment. Also, JP-A-53-49113 discloses that
There is disclosed an inkjet paper in which a sheet containing urea-formalin resin powder is impregnated with a water-soluble polymer. JP-A-55-5830 discloses an ink-jet recording sheet provided with an ink-absorbing coating layer on the surface of a support, and JP-A-55-146786 discloses an amorphous silica in a layer to be coated. JP-A-55-146786 discloses an example using a water-soluble polymer coating layer.

In recent years, a recording medium having a coating layer using an alumina hydrate having a boehmite structure has been proposed, for example, US Pat. No. 4,879,166,
No. 5,104,730, JP-A-2-276620, JP-A-4-37576, and JP-A-5-32037. Recording media using these alumina hydrates have good fixation of ink dyes and obtain good color images because alumina hydrate has a positive charge. In terms of image quality and gloss in an image, it has advantages such as being better than a conventional recording medium.

[0005]

However, in the case of a full-color image, a multi-color recorded image, that is, usually, cyan,
Since the recording is performed in four colors of magenta, yellow, and black, there is a problem that the degree of permissibility of discoloration or fading (fading) is smaller than in the case of a single-color recorded image, and the image is significantly deteriorated. In inkjet recording,
In most cases, the ink used is an aqueous solution of a dye, and pigments requiring a binder are rarely used due to the fineness of the inkjet nozzle. Dyes used in ink jet recording have a problem that light fastness is lower than conventional color pigments and light resistance of formed images is poor.

On the other hand, the most common method for improving the light fastness of an image is to use a dye having excellent light fastness as a dye used in an ink.
However, the ink used for ink jet recording is required to have conditions such as not causing clogging of the ink jet nozzle and having a vivid color tone. Therefore, it is not always possible to select a dye having excellent light fastness. is the current situation.

To improve the light fastness, for example, Japanese Patent Application Laid-Open Nos. Sho 54-68303 and 54-8580.
Nos. 4 and 56-18151 disclose examples in which an ultraviolet absorber is added to an ink liquid. However, there is a problem that these ultraviolet absorbers reduce the jetting stability of the ink and cannot be added in large amounts due to low solubility, and the effect is small when added in small amounts. or,
As another solution, JP-A-57-74192, JP-A-57-74193 and JP-A-57-87988 disclose examples in which a medium contains a benzophenone-based or benzotriazole-based ultraviolet absorber. It has been disclosed.
However, these ultraviolet absorbers have a problem that they cause yellowing of the recording paper, change the hue of the printed ink, or have a poor light fastness improvement effect depending on the color of the ink.

Japanese Patent Application Laid-Open No. 61-14659, 6
JP-A-4-36480 and JP-A-3-13376 disclose examples in which a hindered phenol-based or hindered amine-based antioxidant is contained in a medium. These are also similar to the ultraviolet absorbers and are effective for fading indoors (dark areas), but have a poor effect on light resistance.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above-mentioned prior art, and it is an object of the present invention to provide a recording medium having improved light fastness and discoloration fastness to an ink jet recorded image. . Another object of the present invention is to provide:
Without adversely affecting the hue of the dye constituting the ink, the formed recorded image (printed matter) has a high image density, a clear color tone and a high quality image with high resolution, It is an object of the present invention to provide a recording medium having excellent recorded image storability.

[0010]

The above object is achieved by the present invention described below. That is, the present invention is a recording medium having an ink receiving layer containing a compound represented by the following general formula (I).

Further, the recording medium of the present invention has an ink receiving layer containing a compound represented by the following general formula (II).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The present inventors have solved the above-mentioned problems of the prior art, and when printed and recorded by inkjet recording or the like, have excellent ink absorbency,
Without adversely affecting the color development of the obtained printed matter, a high image density and a high-resolution printed matter having a clear color tone can be obtained, and the printed matter has sufficient light resistance, discoloration and fading. As a result of diligent studies on the recording medium excellent in the storage stability of the recorded image is suppressed, in the ink receiving layer,
The present invention has been found that it has been found that the recording medium can be imparted with performance meeting the above-mentioned purpose by adding the compound represented by the general formula (I) or the general formula (II). That is, the compound represented by the general formula (I) or the general formula (II) is effective in improving the light fastness of the formed image, but hardly absorbs in a visible region, and thus is contained in the ink receiving layer. In this case, the recording paper is not yellowed or the color tone of the printed ink is not changed, so that the color development is not adversely affected. As a result, the recording medium has a light fastness and an anti-fading color of the image. It is considered that a high-quality color image having excellent properties can be formed.

The recording medium of the present invention is characterized in that a double salt compound of an aminium salt cation and a metal complex anion represented by the general formula (I) or (II) is contained in the ink receiving layer. . Hereinafter, these compounds will be described. First, the compound represented by the following formula (I) will be described. In the general formula (I), X ⁻ is a metal complex anion, and R _{1 to} R ₈ of the aminium salt cation represent a hydrogen atom or a monovalent organic residue. Further, at least one of R _{1 to} R ₈ is selected from a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aralkyl group. It is preferably a valent organic residue.

In the aminium salt compound represented by the above general formula (I), specific examples of preferred monovalent organic residues as R _{1 to} R ₈ are shown below. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, a t-butyl group, and an n-amyl group , T-amyl group, n-hexyl group, n-octyl group,
t-octyl group and the like. Further, examples of the alkyl group having a substituent include a 2-hydroxyethyl group,
Hydroxyalkyl groups such as 3-hydroxypropyl group and 4-hydroxybutyl group, 2-acetoxyethyl group, 2
Acetoxyalkyl group such as acetoxyprol group, carboxymethyl group, 2-carboxyethyl group, carboxyalkyl group such as 3-carboxypropyl group, for example, methoxymethyl group, 2-methoxyethyl group, 3-methoxydipropyl group , 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxypentyl, 4-methoxypentyl, 3-methoxypentyl, 2-methoxypentyl, 6 -Methoxyhexyl group, ethoxymethyl group, 2-
Ethoxyethyl group, 3-ethoxydipropyl group, 2-ethoxypropyl group, 4-ethoxybutyl group, 3-ethoxybutyl group, 5-ethoxypentyl group, 4-ethoxypentyl group, 6-ethoxyhexyl group, propoxymethyl group An alkoxyalkyl group such as a 2-propoxyethyl group, a 3-propoxypropyl group, a 4-propoxybutyl group, and a 5-propoxypentyl group; for example, a substituted alkoxyalkyl group such as a dichloromethoxymethyl group or a 2-difluoromethoxyethyl group; No. Examples of the unsubstituted alkenyl group include a vinyl group, a propenyl group,
Examples thereof include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Examples of the substituted alkenyl group include a 1,2-dichlorovinyl group and a 2,3-dibromopropenyl group. Furthermore, examples of the unsubstituted alkynyl group include a propargyl group, a butynyl group, a pentynyl group, and a hexynyl group.Examples of the substituted alkynyl group include 2,3-dichloropropargyl and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, and the like.Examples of the substituted aralkyl group include a carboxybenzyl group, a sulfobenzyl group, and a p-methylbenzyl group. Motoki is fisted.

Further, the monovalent organic residue of R _{1 to} R ₈ is an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group).
-Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc., substituted alkyl groups (for example, 2-hydroxyethyl group, 3- A hydroxypropyl group, etc.)
_At least _{one of} R _{1 to} R ₈ , especially R ₁ and R ₂ , R ₃ and R ₄ ,
At least two of the combinations of organic residues of R ₅ and R ₆ and R ₇ and R ₈ are a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group It is preferable to use a compound that is a monovalent organic residue selected from a substituted or unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. Further, all of R _{1 to} R ₈ are the above-mentioned substituted or unsubstituted alkoxyalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group,
And 1 selected from substituted or unsubstituted aralkyl groups
When a compound that is a valent organic residue is used, a recording medium that is preferable in terms of storage stability can be obtained. In particular, a substituted or unsubstituted alkoxyalkyl group is preferable because the solubility of the double salt compound can be further improved. In the present invention, as R _{1 to} R ₈ , it is preferable to use a compound having an organic residue having 2 to 8, particularly 3 to 8 carbon atoms.

Next, a double salt compound of an aminium salt cation and a metal complex anion having a structure represented by the following general formula (II) used in the recording medium of the present invention will be described.

In the above general formula (II), X ⁻ is a metal complex anion, and R ′ of the aminium salt cation
_{1 to} R ′ ₈ are combinations of R ′ ₁ and R ′ ₂ , R ′ ₃ and R ′ ₄ , R ′ ₅ and R ′ _6, and R ′ ₇ and R ′ ₈ , at least one of which is combined with a nitrogen atom A group of atoms necessary to form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring is shown. Examples of the 5-membered ring include a pyrrolidine ring and the like, examples of a 6-membered ring include a piperidine ring, a morpholine ring and a tetrahydropyridine ring, and examples of a 7-membered ring include a cyclohexylamine ring and the like. Can be And R ' _m and R'
_When the combination of _{m + 1} (where m = 1, 3, 5, 7) is an atomic group constituting a morpholine ring, the solubility of the double salt compound can be further improved. preferable.

Further, in the general formula (II), R ′ ₁
And R ' ₂ , R' ₃ and R ' ₄ , R' ₅ and R ' _6, and R' ₇ and R '
It is preferable to use a compound having a structure in which a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring is formed in at least two of the combinations of _8. , R ′ _m and R ′ _{m + 1} (where m = 1,
It is preferable to use a compound having a structure in which a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring is formed in all the combinations of 3, 5, and 7).

All the aromatic rings of the compounds represented by formulas (I) and (II) are a lower alkyl group having 1 to 5 carbon atoms, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group and the like. It may be substituted. In the general formulas (I) and (II), n is 1 or 2.

Next, specific examples of the aminium salt cation used in the compounds represented by formulas (I) and (II) of the present invention are shown in Tables 1-1 and 1-2. However, for simplicity, it is displayed as follows. For example, the general formula (I)
When the aminium salt cation therein is n = 1, R _{1 to} R ₄ are ethyl groups, and R _{5 to} R ₈ are propenyl groups, the display format is as follows.

The aminium salt cation represented by the general formula (II) has n = 2, and R ′ ₁ and R ′ ₂ , R ′ ₃ together with a nitrogen atom.
And R _'4, R' when forming each 5-membered ring is ₅ and R _'6 and R' ₇ and the combination of R _'8 is indicated as follows.

[0022]

[0023]

Next, the metal complex anion paired with the above-mentioned aminium salt cation constituting the double salt compound represented by the general formula (I) or (II) used in the present invention will be described. Various metals can be used as the metal complex used as the counter anion in the present invention, and examples thereof include metal complex compounds represented by the general formulas (III) to (IX). However, in the following general formulas (III) to (IX), M is N
i represents a transition metal atom such as Co, Mn, Cu, Pb, and Pt.

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

R _{9 to} R in the above general formulas (III) to (VII)
₂₈ , the substituted or unsubstituted alkyl group includes, for example, methyl group, ethyl group, n-propyl group, iso-
Propyl group, n-butyl group, sec-butyl group, iso
-Butyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl, t-octyl and the like. Examples of the substituted or unsubstituted alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, and an iso-propyloxy group.

Also, R _{9 to} R ₁₂ , R _{17 to} R ₂₀ , R _{21 to} R ₂₄
And R _{25 to} R ₂₈ , examples of the substituted amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, an acetylamino group, and a benzoylamino group. Also, R _{13 to} R ₁₆ , R _{17 to} R ₂₀ , R _{21 to} R ₂₄ and R
In ₂₅ to R _28, examples of the substituted or unsubstituted aryl group, e.g., phenyl, tolyl, xylyl,
Examples include an ethylphenyl group, a chlorophenyl group, a nitrophenyl group, a methoxyphenyl group, a dimethoxydiphenyl group, a trimethoxyphenyl group, and an ethoxyphenyl group.

Next, specific examples of suitable metal complex anions represented by the above general formulas (III) to (IX) are shown in Tables 2-1 to 2-1.
It is shown in Table 2-6.

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

The general formulas (I) and (II) used in the present invention
Is a double salt compound in which an aminium salt cation exemplified in Table 1 described above and a metal complex compound exemplified in Table 2 described above form a salt, and specific examples thereof are shown below. It is shown in Table 3.

[0043]

In the recording medium of the present invention, R _{13 to} R
A double salt compound using a metal complex having at least one of _{16 as} an alkoxy-substituted aryl group as an anion, or
It is particularly preferable to use a double salt compound using a metal complex in which at least one of R _{9 to} R ₁₂ is a halogen atom. These compounds are excellent in solubility, can improve light fastness without adversely affecting the hue of the dye when contained in the ink receiving layer, and can effectively suppress deterioration of a recorded image. From this point, the general formulas (III) and (IV)
The double salt compounds using the metal complex anions shown in Table 2 are preferable. Further, (III) -5 shown in Table 2-1 and Table 2
The double salt compound using the metal complex anion of (IV) -5 shown in -2 is particularly preferable.

Next, a method for synthesizing the compounds represented by the general formulas (I) and (II) exemplified above will be described.
First, an aminium salt compound having an acid anion (for example, a perchlorate ion, an iodine ion, a chloride ion, a hexafluoroantimonate ion, etc.) as a counter ion is synthesized. This aminium salt compound is disclosed in U.S. Pat. No. 3,251,881 and U.S. Pat.
No. 71, U.S. Pat. No. 3,484,467 and JP-A-61-69991, etc., and can be synthesized, for example, as follows.

[0046]

The amino compound obtained by the above-mentioned Ullmann reaction and reduction reaction is substituted by alkylation, alkoxyalkylation, alkenylation, and aralkylation by selective substitution, and then the aminium salt compound of the general formula (I) is oxidized. Can be obtained. or,
When R _{1 to} R ₈ are asymmetric, it is necessary to carry out this selective substitution in multiple steps, so that R ₁ to R ₈ are cost-effective.
It is preferred that R ₈ be the same.

Further, the aminium salt cation of the aminium salt compound of the general formula (II) is converted to R ′ in the step of the selective substitution reaction according to the method for synthesizing the aminium salt cation of the aminium salt compound of the general formula (I). _m and R ' _{m + 1} (however,
m = 1, 3, 5, 7) is an alkylating agent suitable for obtaining a substituted or unsubstituted 5-membered ring, substituted or unsubstituted 6-membered ring, substituted or unsubstituted 7-membered ring together with N. Just use it.

For example, to form a pyrrolidine ring,
1,4-dibromobutane, 1,4-dichlorobutane,
It can be formed by alkylation with 1,4-diiodobutane or the like. For the piperidine ring, 1,5-dibromopentane, 1,5-dichloropentane, 1,5-diiodopentane or the like is used. To form a morpholine ring, first, after hydroxyethylation with 2-bromoethanol or the like, a morpholine ring can be formed by dehydration by acid treatment, and a tetrahydropyridine ring is obtained after methacrylation with methacrylic bromide or the like. And cyclization by acid treatment. In the cyclohexylamine ring, cyclization is performed with 1,6-difluorohexane or the like. In particular, in the cyclization reaction of an amino group, the reaction proceeds more quickly than in the alkylation, the yield is good, and the production advantage is greater than that of a conventional propyl-form or butyl-form.

On the other hand, an anion-type metal complex whose counter ion is a cation is described, for example, in Journal of American Chemical Society (Journal of A).
merchandise Chemical Society)
It can be obtained according to the method of Schrauzer et al. Described in Vol. 87, p. 1483, 1965, and can be synthesized, for example, according to the following steps.

[0051]

The neutral metal complex obtained by the above reaction 1) or 2) is converted into an anion by adding p-phenylenediamine in dimethyl sulfoxide, and then a quaternary alkyl ammonium salt is added in alcohol to form a metal. A complex anion is obtained. In addition, as the cation in this case,
Tetraalkylammoniums as exemplified below are preferred.

[0053]

Next, equimolar amounts of the aminium salt compound and the anionic metal complex are dissolved in a polar solvent. As the polar solvent to be used, N, N-dimethylformamide and the like are preferable. The concentration may be about 0.01 mol / l. Thereafter, an aqueous solvent, particularly water, is added thereto to cause double decomposition to obtain a precipitate. The amount of water to add
The excess may be 10 times or more. The reaction temperature is preferably from room temperature to about 90 ° C. Next, both liquid phases are separated, filtered and dried, and if necessary, this is repeated two to three times. If recrystallization is performed with DMF-ethanol or the like, the double salt compound used in the present invention is obtained. .

In addition to the above-mentioned method, a neutral one, which is an intermediate of the metal complex anion, is dissolved in methylene chloride or the like, and this is combined with an acid anion. The double salt compound used in the present invention can also be obtained by adding an equimolar amount of an aminium salt compound, concentrating and recrystallizing. Alternatively, in addition to the above method, a neutral metal complex anion intermediate may be dissolved in methylene chloride or the like, an aminium salt compound may be added in an equimolar amount, concentrated, and recrystallized.

The double salt compound of the aminium salt cation and the metal complex anion exemplified above has a maximum absorption wavelength of 90.
It has a large absorption peak with a molar absorption coefficient of about tens of thousands to hundreds of thousands. However, since there is almost no absorption in the visible region, even when a recording medium for a full-color image is used, there is almost no change in the hue of the ink or the possibility of fading of the formed image. Further, in addition to the double salt compound of the aminium salt cation and the metal medium anion, when forming an ink receiving layer, a hindered phenol-based or hindered amine-based antioxidant, a benzotriazole-based or benzophenone-based ultraviolet absorber Etc. may be used together.

The double salt compound used in the present invention is
When used by dissolving in a coating liquid for forming an aqueous ink receiving layer (hereinafter, simply referred to as a receiving layer coating liquid),
It is preferable to use a polar organic solvent in combination. in this case,
It is preferable that at least a part of R _{1 to} R ₈ of the compound represented by the general formula (I) is a compound having an alkoxyalkyl group such as a methoxyethyl group and an ethoxyethyl group because of relatively high solubility. When used by dissolving in an organic solvent or when used in a dispersed state, of course, any compound can be used.

In particular, when a compound in which all of R _{1 to} R ₈ are the same alkyl group is used, if an aqueous receiving layer coating liquid is used when forming the ink receiving layer, the solubility is poor. It is preferable to use a compound having an asymmetric structure in combination with a different alkyl group or another organic substituent because solubility and dispersibility are increased. In this case, even an alkyl group alone can be applied to an ink receiving layer system mainly composed of a water-soluble binder. Since the coating liquid for the porous ink receiving layer is a dispersion system, the present invention is not limited thereto, and all compounds represented by the general formulas (I) and (II) can be applied. It is more preferable to use an organic solvent in combination with water since dissolution and dispersion can be performed uniformly.

The organic solvent which can be used in combination with water or other than water depends on whether the compounds represented by the general formulas (I) and (II) are dispersed or dissolved. In general, for example, alcohols such as methanol, ethanol, isopropanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, N, N-dimethylformamide,
Amides such as N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate and butyl acetate, chloroform, methylene chloride, Aliphatic halogenated hydrocarbons such as chloroethylene, carbon tetrachloride, and trichloroethylene; aromatics such as benzene, toluene, xylene, monochlorobenzene, and dichlorobenzene; or aliphatics such as n-hexane, cyclohexanone, and ligroin Hydrocarbons and fluorine-based solvents such as tetrafluoropropanol and pentafluoropropanol can be used.

The content of the compound of the general formula (I) or (II) used in the ink receiving layer of the recording medium of the present invention is 0.1.
1 to 100 mmol / m ² , preferably 0.5 to 50
mmol / m ² . At less than 0.1 mmol / m ² ,
The improvement of the light fastness of the formed recorded image is small,
When the amount is more than mmol / m ² , the absorptivity of the ink receiving layer decreases, which is not preferable.

The method for producing the recording medium of the present invention containing the compound of the general formula (I) or (II) in the ink receiving layer includes the following methods (1) to (3). (1) When a pulp fiber is disintegrated into a slurry and then formed into a slurry by a paper machine, a coating solution in which the compound (I) or (II) is dissolved or dispersed is dipped or applied by a size press device or the like provided in the middle. Method to be contained. (2) A coating liquid comprising an ink-absorbing pigment containing the compound (I) or (II) and a binder is applied to a support using a usual coating apparatus, and the compound (I) or (II)
A method of providing an ink receiving layer containing (3) Compound (I) or (II) dissolved or dispersed on an ink receiving layer composed of an ink-absorbing pigment and a binder
How to apply. In this case, it can be used in combination with commonly used pigments, binders and other additives. Also, if it is necessary to impart further water resistance to the image, 4
It is also possible to use a cationic resin such as a polyalkylene polyamine dicyandiamide ammonium salt condensate polydiamine derivative having a quaternary ammonium group.

In a preferred embodiment of the recording medium of the present invention, as shown in FIG. 1, a general formula (I) or (II)
Is formed, and the ink receiving layer 2 is mainly composed of a pigment and a binder. In this case, especially in the case of those used for full-color printing, unlike the case of document printing, four colors of ink are printed on the entire surface. It is preferable that an ink-absorptive pigment is used in terms of image properties and color developing properties (color density). Of course, ordinary plain paper and a medium having an absorbing layer such as polyvinyl alcohol-sodium acrylate copolymer or cation-modified polyvinyl alcohol on a support as a receiving layer are also applicable. However, the latter has a problem in that the ink absorption speed is slow and drying is difficult, and ink before fixing is likely to be aggregated to cause beading (uneven printing). Therefore, in the recording medium of the present invention, as the pigment to be contained in the ink receiving layer, an inorganic pigment type such as alumina hydrate or silica, which makes the ink receiving layer porous when added, may be used. More preferred.

[0063] The porous ink receiving layer may be formed mainly of thermoplastic resin particles. The resin particles used to form the porous ink-receiving layer are used as an aqueous or non-aqueous dispersion or suspension in the form of a colloidal solution in a solvent or water. Examples of such resin particles include, for example, polyester, polyethylene, polyurethane, styrene-acryl copolymer, polyacrylate, polymethacrylate, ethylene-vinyl acetate copolymer, polystyrene, polyvinyl chloride and the like. No. However, it is not limited to these resins, and those obtained by modifying these resins and those obtained by copolymerizing monomers can also be used. These resin particles can be used alone or in combination as desired. The shape of the resin particles used may be spherical or acicular, but in order to form a porous polymer resin ink-receiving layer having more uniform pores, it is preferable to use resin particles having a shape close to true sphere. .

The resin particles have an average of 10 nm to 1 nm.
It is preferable to use one having a particle size of 00 nm, preferably 200 nm or less. If the particle size of the resin particles exceeds 200 nm, the pores of the ink receiving layer become too large, so that scattered light increases and haze increases. For this reason, when printed, the ink sinks without being caught in the vicinity of the surface of the ink receiving layer, but the dye of the ink sinking in the ink receiving layer is smeared, so that the formed image has a low color density. It will be something.

The minimum film forming temperature of the resin particles is from 40 ° C. to 150 ° C.
It is preferable to use one in the range of ° C. Here, the minimum modeling temperature is a minimum temperature at which a uniform film can be formed when the resin particles are heated to form a film. In the present invention, since it is preferable to form a porous polymer resin ink receiving layer by heating after uniformly coating thermoplastic resin particles on a support, it is not necessary to form a dense film, but It is preferable to heat and dry the resin particles under such conditions that the resin particles are fused and bonded to each other to such an extent that the film has the above-mentioned film strength and a porous matrix structure is formed.

Here, the pore diameter of the porous polymer resin ink receiving layer is preferably about 3 nm to 100 nm. This is because it is difficult to increase the ink absorption speed with pores having a diameter of 3 nm or less, and the haze increases when pores having a diameter of more than 100 nm exist.

The diameter distribution was measured by drying a recording medium having a porous polymer resin layer formed on a PET film in a vacuum state for at least 24 hours and then applying a mercury intrusion method (for example, E.I.
W. WASHIBURN, Proc. Natl. Aca
d. Sci. 7, p. 115 (1921) etc.). In addition, in the calculation of the pore diameter,
The method of Barrett et al. May be used (J. Am. C.).
hem. SOc. 73.373 (1951)). The pores of the porous polymer resin ink receiving layer as described above can be obtained by optimizing the relationship between the type of polymer resin particles used, the particle diameter, drying conditions, film pressure, and the like. For example, polymer resin particles in a coating liquid emulsion are agglomerated and gelled while maintaining their particle state, and dried and formed into a film at a temperature of MFT (minimum film forming temperature) or lower. Many pores are formed and maintained. At this time, an inorganic pigment such as alumina hydrate or silica described below may be used in combination to improve the ink absorption and the fixability of the dye.
It may be used in combination with another binder described later.

The ink receiving layer of the recording medium of the present invention is preferably formed so that the total pore volume is in the range of 0.1 to 1.0 ml / g. When the pore volume of the ink receiving layer is larger than the above range,
If the cracking or powder drop occurs and the size is smaller than the above range, the ink absorption becomes poor. In particular, when performing multi-color printing, the ink overflows from the ink receiving layer and bleeding is likely to occur in the image.

The BET specific surface area of the ink receiving layer is preferably in the range of 20 to 450 m ² / g. If it is smaller than this range, the glossiness of the ink receiving layer is lost,
Further, the haze increases, so that the image has a white haze. On the other hand, if it is larger than the above range, cracks are likely to occur in the ink receiving layer. The BET specific surface area and the pore volume can be determined by a nitrogen adsorption / desorption method after deaeration at 120 ° C. for 24 hours.

The pigment used in the ink receiving layer constituting the recording medium of the present invention includes, for example, calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titania, zinc oxide, zinc carbonate, aluminum silicate, alumina Inorganic pigments such as hydrate, silicic acid, sodium silicate, magnesium silicate, calcium silicate, and silica, organic pigments such as plastic pigment and urea resin pigment, and a combination thereof can be used. In particular, silica and alumina hydrate are preferable pigments from the viewpoint of image suitability such as ink absorption and resolution.

As the silica, natural silica, synthetic silica, amorphous silica, and chemically modified silica compounds can be used. Particularly, silica having a positive charge is preferable. For example, trade name “Atellite CT- 100 "
(Made by Asahi Denka Kogyo Co., Ltd.), "Snowtex AK"
(Manufactured by Nissan Chemical Industry Co., Ltd.) and the like are commercially available, available and preferably used.

Alumina hydrate has a positive charge, so that the dye in the ink can be fixed well.
It is more preferable as a pigment to be used in the ink receiving layer because a high gloss, transparent and good color development image can be obtained, and it can be applied to a high gloss photographic medium and a transparent OHP sheet.

The alumina hydrate suitably used in the present invention is represented by the following general formula. In the formula, n represents any of the integers of 0, 1, 2 or 3, and m represents a value of 0 to 10, preferably 0 to 5. m
Since H ₂ O often represents a removable hydration that does not participate in the formation of a crystal lattice, m can take a non-integer value. Also, when this type of alumina hydrate is calcined, m can reach a value of zero.

The alumina hydrate suitable for carrying out the present invention is an amorphous alumina hydrate analyzed by an X-ray diffraction method. In particular, Japanese Patent Application Nos. Hei.
No. 125438, No. 5-125439, No. 6
It is preferable to use the alumina hydrate described in -114571.

In the production process of the alumina hydrate, the pore properties are adjusted. However, in order to satisfy the BET specific surface area and the pore volume of the ink receiving layer, the pore volume is 0.1 to 0.1. It is preferred to use 1.0 ml / g of alumina hydrate. When the pore volume of the alumina hydrate is out of the above range, it is difficult to make the pore volume of the ink receiving layer fall within the above specified range. It is preferable to use alumina hydrate having a BET specific surface area of 40 to 500 m ² / g. When the BET specific surface area of the alumina hydrate is out of the above range, it is difficult to make the specific surface area of the ink receiving layer within the specified range.

In forming the ink receiving layer of the recording medium of the present invention, the binder used in combination with the above pigment is preferably a water-soluble polymer. For example, polyvinyl alcohol or a modified product thereof (cation modified, anionic modified, silanol modified), starch or a modified product thereof (oxidation, etherification), gelatin or a modified product thereof, casein or a modified product thereof, carboxymethyl cellulose, gum arabic, hydroxy Cellulose derivatives such as ethylcellulose and hydroxypropylmethylcellulose, urethane emulsion, polyester emulsion, acrylic emulsion, SBR latex, NBR latex, conjugated diene copolymer latex such as methyl methacrylate-butadiene copolymer, functional group modified polymer latex, ethylene acetate Vinyl copolymer latex such as vinyl copolymer, polyvinylpyrrolidone, maleic anhydride or its copolymer, acrylate copolymer, acrylamide type維等 is preferable. When an organic solvent is used, polyamide-based fibers, polyutarene-based fibers, polyester-based fibers, polyvinyl acetal-based fibers, acrylic-based fibers, and the like can be used. These binders can be used alone or in combination of two or more.

As long as the BET specific surface area and the pore volume of the ink receiving layer are satisfied, the mixing ratio of the pigment and the binder is 1: 1 to 30: 1 by weight, preferably 5: 1 to 20: You can arbitrarily select between 1. If the amount of the binder is less than the above range, the mechanical strength of the ink receiving layer is insufficient, cracking or powder drop occurs, and if it is more than the above range, the pore volume is reduced and the ink absorption is poor. Become.

The dispersion containing the pigment and the binder may contain, if necessary, a dispersion, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a waterproofing agent, Foaming agent,
A release agent, a foaming agent, a penetrant, a coloring dye, a fluorescent whitening agent, an ultraviolet absorber, an antioxidant, a preservative, and an antibacterial agent can be added as necessary. As the waterproofing agent, any known material such as a quaternary ammonium halide salt and a quaternary ammonium salt polymer can be freely selected and used.

As a support for forming the ink receiving layer having the above-mentioned structure, papers such as appropriately sized paper, non-size paper, resin-coated paper, and sheet-like materials such as thermoplastic films can be used. Materials and fabrics can be used, and there is no particular limitation. In the case of a thermoplastic film, for example, a transparent film of polyester, polystyrene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polyethylene, polycarbonate, etc., or alumina hydrate, opaque by filling or fine foaming of titanium white. Sheets can also be used. When resin-coated paper is used for the support, it has the same touch as a normal photo print,
The texture is obtained, and the recording medium of the present invention has a high glossiness in the ink receiving layer, which is very similar to a normal photographic print.

In order to improve the adhesion between the support and the ink receiving layer, a surface treatment such as a corona treatment or a flame treatment may be performed, or an easy-adhesion layer may be provided as an undercoat layer. Further, in order to prevent curling, a curling preventing layer such as a resin layer or a pigment layer may be provided on the back surface of the support or at a predetermined site.

The ink receiving layer is formed by applying a dispersion containing a pigment and a binder such as polyvinyl alcohol using a coating apparatus.
It is formed by a method of coating and drying on a support. As a coating method, a blade coat method, an air knife method, a roll coat method, a brush coat method, a gravure coat method, a kiss coat method, an extrusion method, a slide hopper (slide bead) method, a curtain coat method, a spray method, or the like is used. be able to.

Examples of the apparatus for drying the applied coating liquid include hot air dryers such as a linear tunnel dryer, an arch dryer, an air loop dryer, and a sine curve air float dryer, and a dryer using an infrared ray, a heat dryer, a microwave, or the like. And various drying apparatuses. The coating amount of the dispersion is 0.5 to 60 g / m ² in terms of dry solid content,
The thickness is more preferably 5 to 45 g / m ² , but in order to obtain good ink absorbency and resolution, the thickness of the ink receiving layer must be 15 μm or more, preferably 20 μm or more, and more preferably 25 μm or more. is there.

The dispersion used in the present invention has a ratio (viscosity over time / initial viscosity) of the viscosity at the initial stage immediately after dispersion to the viscosity after standing and stored for 10 days is 0.5 to 3. Is a preferable range. Outside this range, the pot life of the dispersion becomes short, which causes problems in coating stability and storage stability of the dispersion. A more preferred range is 0.5-2.
5, and within this range, the defoaming of the dispersion liquid is easy, so that the productivity is improved and, at the same time, coating defects can be prevented. ADVANTAGE OF THE INVENTION According to this invention, the stability with time and the preservability of a dispersion liquid are excellent, and a stable dispersion state can be maintained over a long period of time.

The ink receiving layer in the present invention may have a single-layer structure or a multilayer structure. Examples of the multilayer structure include those described in JP-A-57-89954, JP-A-60-224578, and JP-A-61-12388. For example, an ink permeable layer described in JP-A-61-12388 may be further provided on the ink-receiving layer of the present invention. The ink receiving layer is provided on at least one side of the support, but may be provided on both sides of the support for the purpose of preventing curling, ink jet recording on both sides, and the like.

The sheet simply coated on the support can be used as it is as the recording medium of the present invention. For example, the sheet is passed through a roll nip under heating and / or pressure with a super calender, gloss calender or the like. It is also possible to give the smoothness of. In this case, excessive processing by the super calendering reduces the ink absorbency due to the space between the formed particles, so that the degree of processing may be limited. Note that the recording medium of the present invention is not necessarily colorless, and may be a colored recording medium.

The ink used for forming an image on the recording medium of the present invention may be a known ink component itself. For example, as a coloring material, a direct dye, an acid dye, a basic dye, Water-soluble dyes such as reactive dyes and food coloring agents can be used. Particularly, it is suitable as an ink of an ink jet recording system, and has a light fastness in combination with the general formulas (I) and (II) to be contained in the ink receiving layer and in combination with a recording medium having the ink receiving layer. Examples of color materials that provide images having required properties such as properties, stability, color development, and sharpness include, for example,
The following are mentioned.

The direct dyes include: C.I. I. Direct Black; 2, 4, 9, 1
1, 14, 19, 22, 27, 32, 36, 38, 4
1, 48, 49, 51, 56, 62, 71, 74, 7
5, 77, 78, 80, 105, 106, 107, 10
8, 112, 113, 117, 132, 146, 15
4, 194

C. I. Direct Yellow;
1, 2, 4, 8, 11, 12, 24, 26, 27, 2
8, 33, 34, 39, 41, 42, 44, 48, 5
0, 51, 58, 72, 85, 86, 87, 88, 9
8, 100, 110, 142 C.I. I. Direct Orange 6, 8, 10,
26, 29, 34, 39, 41, 44, 46, 49, 5
1, 60, 102

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, 230 C.I. I. Direct Violet; 1, 7, 9,
12, 35, 47, 47, 51, 90, 94

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, 86, 90, 98, 106, 108, 110, 12
0, 123, 158, 163, 165, 192, 19
3, 194, 195, 196, 199, 200, 20
1, 202, 203, 207, 218, 236, 23
7, 239, 246, 258 C.I. I. Direct Green; 1, 6, 8, 2
8, 33, 37, 59, 63, 64 C.I. I. Direct Braun; 1A, 2, 6,
25, 27, 44, 58, 95, 100, 101, 10
6, 109, 112, 173, 194, 195, 20
9, 210, 211

The acid dyes include: C.I. I. Acid Black; 1, 2, 7, 16,
17, 24, 26, 28, 31, 41, 48, 52, 5
8, 60, 63, 94, 107, 109, 112, 11
8, 119, 121, 122, 131, 155, 156 C.I. I. Acid Yellow; 1, 3, 4, 7,
11, 12, 13, 14, 17, 18, 19, 23, 2
5, 29, 34, 36, 38, 40, 41, 42, 4
4, 49, 53, 55, 59, 61, 71, 72, 7
6, 78, 99, 111, 114, 116, 122, 1
35, 161, 172

C. I. Acid Orange; 7,
8, 10, 19, 33, 56, 64 C.I. 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, 243, 249, 254, 25
6, 260, 289, 315, 317, 318 C.I. I. Acid Violet; 7, 11, 15,
34, 35, 41, 43, 49, 75

C. 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
6, 145, 167, 171, 175, 183, 22
9, 234, 236 C.I. I. Acid Green; 3, 12, 19, 2
7, 41, 9, 16, 20, 25 C.I. I. Acid Braun; 4, 14

The basic dyes include: C.I. I. Basic Black; 2, 8 C.I. I. Basic Yellow; 1, 2, 11,
12, 14, 21, 32, 36 C.I. I. Basic Orange; 2, 15, 2
1, 22 · C.I. I. Basic Red; 1, 2, 9, 12, 1
3, 14, 37 C.I. I. Basic Violet; 1, 3, 7, 1
0, 14, 27 C.I. I. Basic Blue; 1, 3, 5, 7,
9, 24, 25, 26, 28, 29 C.I. I. Basic Green; 1, 4 C.I. I. Basic Braun; 1, 12

The reactive dyes include: C.I. I. Reactive Black; 1, 3,
5, 6, 8, 12, 14 C.I. I. Reactive Yellow; 1, 2,
3, 13, 14, 15, 17 C.I. I. Reactive Orange; 2, 5,
7, 16, 20, 24 C.I. I. Reactive Red; 6, 7, 11,
12, 15, 17, 21, 23, 24, 35, 36, 4
2, 63, 66 C.I. I. Reactive Violet; 2, 4,
5, 8, 9 C.I. I. Reactive Blue; 2, 5, 7,
12, 13, 14, 15, 17, 18, 19, 20, 2
1, 25, 27, 28, 37, 38, 40, 41, 71 I. Reactive Green; 5, 7 C.I. I. Reactive Braun; 1, 7, 1
6

Further, as food colorants, there are: I. Food Black; 1, 2, C.I. I. Food Yellow; 3, 4, 5 • C.I. I. Food Red; 2, 3, 7, 9, 14,
52, 87, 92, 94, 102, 104, 105, 1
06 C.I. I. Food Violet; 2 C.I. I. Food Blue; 1, 2, C.I. I. Food Green; 2, 3

The examples of the dyes described above are particularly preferable as the coloring material of the ink used when forming an image on the recording medium of the present invention. Such water-soluble dyes are generally used in conventional inks at a ratio of about 0.1 to 20% by weight.

The solvent used in the ink used in the present invention is
Water, or a mixed solvent of water and a water-soluble organic solvent, particularly suitable is a mixed solvent of water and a water-soluble organic solvent. It contains alcohol. As the water, it is preferable to use deionized water instead of general water containing various ions. As the water-soluble organic solvent used by mixing with water, for example, methyl alcohol,
C 1-4 alkyl alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol;
Amides such as dimethylformamide and dimethylacetamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol and butylene Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl (or ethyl) ) Ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl)
Lower alkyl ethers of polyhydric alcohols such as ethers; N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone and the like. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred.

The content of the water-soluble organic solvent in the ink is generally from 0 to 95% by weight based on the total weight of the ink.
%, Preferably 10 to 80% by weight, more preferably 20 to 50% by weight. In addition, the ink used in the present invention may contain, in addition to the above components, a surfactant, a viscosity modifier, a surface strength modifier, a pH regulator, a fungicide, a rust inhibitor and the like, depending on the application.

The above-described various water-soluble materials were added to the recording medium for ink jet recording of the present invention in which the ink receiving layer contained the near-infrared absorbing compound having the structure of the general formulas (I) and (II) described above. When recording is performed using an aqueous ink containing a dye, light fastness and discoloration fastness of an image are improved. Although the reason is not clear, it is thought that the discoloration or fading of the dye due to light is due to photo-oxidation.However, the light with the wavelength at the main absorption peak in the visible region of the dye itself is more than the fading due to ultraviolet light. The near-infrared absorbing compounds having the structures of general structural formulas (I) and (II) used in the present invention are:
Since it has a lower energy level than the dye contained in the ink, it is considered that the dye is prevented from being excited, and as a result, the photooxidation reaction is suppressed.

[0101]

Next, an embodiment of the present invention will be described. The parts are based on weight. <Synthesis Example 1> 0.1 mol of P-phenylenediamine, p-
0.5 mol of nitrochlorobenzene, 0.24 mol of anhydrous potassium carbonate and 2 parts (by weight) of copper powder were placed in 130 parts of dimethylformamide, and refluxed for 4 days with stirring. After the reaction, the reaction mixture was filtered, and the residue was thoroughly washed with dimethylformamide, water and acetone, and then dried.
And reddish-brown tetrakis (p-nitrophenyl)-
26 parts of 1,4-phenylenediamine were obtained. 24 parts of the compound obtained above were added to an autoclave together with 1.5 parts of a dimethylformamide palladium-carbon hydrogenation catalyst (100 parts), and hydrogen gas was applied to the autoclave at 5.0 kg / cm ^2.
The mixture was stirred at 0 ° C to 100 ° C until hydrogen absorption ceased.

After the reaction, the reaction solution was filtered, the residue was washed with dimethylformamide, and the filtrate was poured into 360 parts of ice water. After stirring for a while, the precipitate was collected by filtration. Recrystallization was performed with a mixed solvent of ethanol and dimethylformamide to obtain 10 parts of tetrakis (p-aminophenyl) -1,4-phenylenediamine. The purity was measured by high performance liquid chromatography to be 98.5%.

(Aminium compound No. 1 shown in Table 1)
Synthesis of 02) 4 parts of the amino compound obtained above were combined with 24 parts of dimethylformamide, 0.7 parts of anhydrous sodium hydrogencarbonate and 4.0 parts of 2-methoxyethyl bromide in 10 parts.
The mixture was heated and stirred at 0 ° C to 130 ° C. After reacting for 36 hours, the reaction solution was poured into 150 parts of ice water and extracted with ethyl acetate. After drying, it was purified on a silica gel column. The amount obtained was 3.1 parts. Here, by infrared absorption analysis, N
The disappearance of absorption due to H stretching vibration was confirmed.

Next, 1 part of this compound was dispersed in 20 parts of acetone, and an equimolar amount of silver perchlorate was added with stirring. After reacting at room temperature for 1 hour, the precipitated silver was separated by filtration, the filtrate was diluted with isopropyl ether, allowed to stand, and the precipitated crystals were collected by filtration. The amount obtained was 0.6 parts. Compound No. having the following structure synthesized as described above. 102 is
It was a compound having a large absorption region in the infrared region having an absorption maximum wavelength of 1,010 nm and an absorption coefficient of 29,000.

[0105]

The above-described example is for the case where the anion is perchloric acid. However, in the case where another anion is used, the target compound can be easily obtained by using the corresponding silver salt. For example, AgSbF ₆ , AgBF ₄ ,
AgSO ₄ , AgNO ₃ , AgSO ₃ C ₆ H ₄ CH ₃ , AgS
A silver salt such as O ₃ CF ₃ can be used. Alternatively, it can be obtained by electrolytic oxidation.

(Double salt compound No. (I)-shown in Table 3)
4) Next, the aminium compound N obtained above
o. No. 102 and the double salt compound No.
(I) -4 was synthesized. First, nickel (II) bisdithiobenzyl (trade name: MIR-101 Midori Kagaku)
1.4 g and 1.8 g of p-phenylenediamine were dissolved in 10 ml of dimethyl sulfoxide. A solution of 3.2 g of tetrabutylammonium bromide in ethanol 6
0 ml was added dropwise. Upon further stirring, red needles precipitated, which were collected by filtration, washed with water and purified by recrystallization.
0.8 g of nickel (II) bisdithiobenzyltetrabutylammonium of the metal complex (IV) -1 shown in FIG. As a result of measuring the absorption spectrum of this crystal, the MIR
Λ _max 930nm of -101 is, has been shifted to the long wavelength side of 950nm, it was confirmed that became the anion body.

[0108]

Compound No. synthesized above was used. Bis (4- [bis (2-methoxyethyl) amino] phenyl) [N, N, -bis (4- [bis (2-methoxyethyl) amino] phenyl) -4-aminophenyl] aminium perchlorate To a solution of 0.5 g in 50 ml of DMF was added 0.5 g of nickel bisdithiobenzyltetrabutylammonium obtained above, and the mixture was heated and stirred at 50 ° C. for 3 hours. The reaction solution was poured into water, and the obtained precipitate was washed with water and dried, and then recrystallized to obtain a double salt compound 0.7.
g was obtained. When the differential scanning calorimetry of the obtained compound was measured, disappearance of the peak of perchlorate at 270 ° C. was recognized. The results of the elemental analysis were as shown in Table 4 below. From these results, it was confirmed that the target double salt compound was obtained.

[0110]

(Synthesis Example 2) (Synthesis of double salt compound No. (I) -15 shown in Table 3)
First, Compound No. having the following structure, which was synthesized in the same manner as in Synthesis Example 1, was prepared. 117 in a solution prepared by dissolving 1.0 g of bis (p-dipropenylaminophenyl) [N, N, -bis (p-dipropenylaminophenyl) -p-aminophenyl] aminium perchlorate in 90 ml of DMF.
0.7 g of nickel-bis (trichlorobenzenedithiol) tetra (n-butyl) ammonium (trade name: PA-1006; manufactured by Mitsui Toatsu Fine Co., Ltd.) of compound (III) -5 having the following structure was added, 3 hours at 50 ° C,
The mixture was heated and stirred. The reaction solution was poured into water, and the obtained precipitate was washed with water, dried, and then recrystallized to obtain a double salt compound 0.1.
95 g were obtained.

[0112]

When the differential scanning calorimetry of the obtained compound was measured, the disappearance of the peak of perchlorate at 270 ° C. was recognized. The results of the elemental analysis were as shown in Table 5 below. From these results, it was confirmed that the target double salt compound was obtained.

[0114]

(Synthesis Example 3) (Synthesis of Double Salt Compound No. (II) -4 shown in Table 3) First, Compound No. 2 having the following structure, which was synthesized in the same manner as in Synthesis Example 1, was prepared. 203 g of bis [4- (2-methylpyrrolidino) phenyl] (N, N, -bis [4- (2-methylpyrrolidino) phenyl] -p-aminophenyl) aminium perchlorate in 70 ml of DMF 0.68 g of compound (IV) -5 nickel-bis (trimethoxybenzenedithiol) tetra (n-butyl) ammonium having the following structure was added to the solution dissolved in
For 3 hours. The reaction solution was poured into water, and the obtained precipitate was washed with water and dried, and then recrystallized to obtain a double salt compound.

[0116]

[0117]

When the differential scanning calorimetry of the obtained compound was measured, disappearance of the peak of perchlorate at 270 ° C. was observed. The results of the elemental analysis were as shown in Table 6 below. From these results, it was confirmed that the target double salt compound was obtained.

(Synthesis Example 4) In the same manner as described above, a double salt compound composed of each combination of an aminium salt compound cation and a metal complex anion shown in Table 3 was prepared.
(I) -1, (I) -2, (I) -3, (I) -5,
(I) -8, (I) -9, (I) -10, (I) -1
1, (I) -12, (I) -13, (I) -14, (I
Nos. I) -2, (II) -3, (II) -5 and (II)-
No. 6 was synthesized.

(Production of Alumina Hydrate) Aluminum dodexide was produced by the method described in US Pat. No. 4,242,271. Next, the aluminum dodoxide was hydrolyzed by the method described in U.S. Pat. No. 4,202,870 to produce an alumina slurry. Water was added to the alumina slurry until the alumina hydrate solid content became 7.9%. The pH of the alumina slurry to which water was added was 9.5. A 3.9% nitric acid solution was added to the slurry to adjust the pH, thereby obtaining a colloidal sol. The colloidal sol was spray-dried at 75 ° C. to obtain alumina hydrates (A and B). With respect to these alumina hydrates, the BET specific surface area and the pore volume were determined by the following methods, and the results are shown in Table 7.

Evaluation Items 1) Pore volume (PV) After deaeration at 120 ° C. for 24 hours, the pore volume (PV) was measured by a nitrogen adsorption / desorption method using “Auto Soap I” (trade name) manufactured by Kantachrome. 2) BET specific surface area (SA) The BET specific surface area was calculated using the method of Brunauer et al.

[0122]

<Example 1> Coating liquid 1-100 parts by weight of alumina hydrate A-Compound No. 1 (I) -1 0.08 parts by weight ・ 100 parts by weight of aqueous solution of polyvinyl alcohol and gohsenol NH-23 (Nippon Synthetic Chemical Industry Co., Ltd.) ・ 60% aqueous solution of water-soluble melamine resin (Smileds Resin 613SP) 4 Parts by weight ・ ion exchange water 300 parts by weight ・ DMF 100 parts by weight

The liquid having the above formulation was stirred at a rotation speed of 1450 rpm for 3 hours using a disperser (Satake Chemical Machinery Co., Ltd., trade name: portable mixer A510, using DS impeller blades) to obtain a coating liquid. . In addition, Compound No.
(I) -1 was dissolved in DMF and then added with stirring. White polyester film (manufactured by DuPont, trade name: Melinex 339, 125 μm) as a support
Thickness), the coating liquid 1 obtained above was kiss-coated at a speed of 10 m / min and dried at 145 ° C. to obtain a dry coating thickness of 40 μm.
Was formed to obtain a recording medium of this example. Various physical properties of the obtained recording medium were measured and evaluated by the following methods. Table 8 shows the results.

Hereinafter, the measurement and evaluation methods performed above will be described. 1) Printing characteristics A drop-on-demand type ink jet head having 128 nozzles at a nozzle interval of 16 nozzles per 1 mm was used with an ink jet printer provided with four colors of Y, M, C, and Bk. Ink jet recording was performed with the ink, and the ink absorbency, image density, bleeding, and beading were evaluated. This evaluation was performed under normal temperature and normal humidity (23 ° C., 60% RH).

The composition of the ink used at this time is shown below. Ink composition・ Ink dye (Y, M, C, Bk) 3 parts ・ Thiodiglycol 10 parts ・ Diethylene glycol 10 parts ・ Water 77 parts As a colorant of each of the above inks, C.I. I. Direct Yellow 86, and magenta (M) ink for C.I. I. Acid Red 3
5 for cyan (C) ink. I. Direct Blue 199, and C.I. I. Each dye of Food Black 2 was used.

A) Image Density The image density of an image solid-printed with the M ink having the above composition was determined as follows.
Evaluation was performed using a reflection densitometer 310TR manufactured by X-Rite. The reason why the M ink was used as the evaluation target was that the image density of M among the four colors was the lowest in any of the examples. )

B) Light fastness (%) Atlas fade meter Ci-35 (Atlas El)
electric Devices Co. Made)
A xenon lamp with an illuminance of 0.39 W / m ² was irradiated for 30 hours, a light stability test was performed, and image densities before and after the test were measured. From these values, light resistance was determined by the following equation. That is, the image density residual ratio after the light resistance test was defined as light resistance. In any of the examples, the light fastness of the M image among the four colors was the lowest, so the image printed with the M ink was also evaluated here.

[0129]

C) Ink Absorbability Immediately after solid printing of the Y, M, C, and Bk inks of the above composition in a single color or multiple colors, the drying state of the ink on the surface of the recording medium is examined by touching the recording portion with a finger. Evaluation was made according to the following criteria.
30 ng of ink is applied to the ink receiving layer at a rate of 32 per mm ^2.
× The ink amount for printing 32 dots is 400%. The ink amount in single-color printing is 100%, ◎ indicates that the ink does not adhere to the finger at 300% ink amount, ○ indicates that the ink does not adhere to the finger at 200% ink amount, Those that did not adhere were evaluated as Δ.

D) Bleeding, Beading Bleeding and beading on the surface of the recording medium after solid printing of Y, M, C, and Bk inks of the following composition in a single color or multicolors were visually observed and evaluated. 100 ink amount for single color printing
%, No bleeding or beading was generated at an ink amount of 300%, ○ was given when the ink amount was not 200%, and △ was given at 100% of the ink amount.

<Examples 2 to 5 and Comparative Example 1> The alumina hydrate A and the compound (I) -1 used in Example 1 are shown in Table 8.
The recording media of Examples 2 to 5 and Comparative Example 1 were obtained in the same manner as in Example 1 except that the combinations and addition amounts shown in Table 1 were used. And it evaluated by the method similar to Example 1, and the result was shown in Table 8.

<Examples 6 and 7 and Comparative Example 2> Instead of alumina hydrate A of Example 1, silica (trade name: Mizukasil P-78F, manufactured by Mizusawa Chemical Industry Co., Ltd., BET specific surface area: 390 m ²⁾ / G, BET pore volume 1.69 ml / g) and the recording media of Examples 6, 7 and Comparative Example 2 in the same manner as in Example 1 except that the combination and the addition amount shown in Table 8 were used. I got And it evaluated by the method similar to Example 1, and the result was shown in Table 8.

[0134]

Example 8 A paper serving as a support was prepared with the following composition. (Pulp)-NBKP (softwood kraft pulp) compounding ratio 30%-LBKP (hardwood bleached kraft pulp) compounding ratio 70% (additive)-Shinryo (talc) 4.0% by weight-Sizing agent (alkylene ketene dimer) 0 0.4% by weight ・ Cationized starch 0.5% by weight ・ Size press coating amount (polyacrylamide) 2.5% by weight After forming paper having a basis weight of 127 g / m ^{2 under} the above papermaking conditions,
Flattening was performed using a calender. The Stöckicht sizing degree was 100 seconds. In addition, the measurement of the degree of Stekigt sizing was performed by the method shown in JIS P8122. The thickness of the support was 145 μm.

Coating liquid 2-Amorphous silica: P-78A (manufactured by Mizusawa Chemical Industry Co., Ltd., BET specific surface area: 350 m ² / g, BET pore volume: 1.53 ml / g) 75 parts by weight-As described above 25 parts by weight of prepared alumina hydrate B Compound No. having the constitution shown in Table 3 (I) -3 0.10 part by weight ・ Waterproofing agent (benzethonium chloride): 20 parts by weight of Hyamine 1622 (trade name: manufactured by Sankyo Chemical Industry Co., Ltd.) ・ Waterproofing agent (benzalkonium chloride): cation 08B 50% aqueous solution (Morin Chemical Industry Co., Ltd.) 40 parts by weight ・ Binder (polyvinyl alcohol): 10% aqueous solution of PVA-117 (Kuraray Co., Ltd.) 500 parts by weight ・ Ink set 50% by weight of 30% Sumireze Resin 1001 (manufactured by Sumitomo Chemical Co., Ltd.)-650 parts by weight of water (ion-exchanged water)-50 parts by weight of meta-modified ethanol

A liquid having the above formulation was dispersed in a dispersing machine (trade name: Portable Mixer A510, DS, manufactured by Satake Chemical Machinery Co., Ltd.)
The mixture was stirred for 3 hours at a rotation speed of 1450 rpm using an impeller blade) to obtain a coating liquid 2. One surface of the support prepared above was coated with the above coating liquid 2 by air knife, and then dried at 100 ° C. for 5 minutes to obtain a recording medium of the present invention having a coating amount of 5.2 g / m ² . . The obtained recording medium was measured and evaluated in the same manner as in Example 1. Table 9 shows the results. As a colorant for each of the above inks, C.I. I. Direct Yellow 86, and magenta (M) ink for C.I. I. Acid Red 14 and C.I. for cyan (C) ink. I. Direct Blue 199 to Black (Bk)
For ink, C.I. I. Each dye of Direct Black 154 was used.

<Examples 9, 10 and Comparative Example 3> Example 8
Double salt compound No. used in A recording medium was obtained in the same manner as in Example 8, except that (I) -3 was used in the combination and addition amount shown in Table 9.

<Example 11> (Porous polymer resin ink-receiving layer) Aqueous polycarbonate polyurethane-based resin dispersion (average particle diameter of emulsion resin: 135 µm, minimum film formation temperature (MFT): 90 ° C, glass transition temperature: 64 ° C) , Solids concentration 30.0%): 100
To 15 parts by weight of an aqueous dispersion of the above-mentioned alumina hydrate B (solid content concentration: 20%) was added 15 parts by weight of Compound No. (I) -9 [Aminium compound No. 114 and the metal complex anion No. 114
(IV) -4 double salt compound] in DMF (solids concentration 3
%): 1 part by weight to obtain a coating liquid. Die-coated on a white polyester film (Melinex 339, 125 μm thickness, manufactured by DuPont) as a support,
After drying at 5 ° C., a porous polymer resin ink receiving layer having a thickness of 35 μm was formed to obtain a recording medium of this example. At this time, the pore diameter of the coating layer was 14 μm. The obtained medium was measured and evaluated in the same manner as in Example 8. Table 9 shows the results.

<Examples 12 and 13 and Comparative Example> Example 1
Compound No. 1 A recording medium was obtained in the same manner as in Example 11, except that (I) -9 was used in the combinations and addition amounts shown in Table 9. Table 9 shows the results.

[0141]

<Example 14> As raw material pulp, 370 ml of hardwood bleached kraft pulp (LBKP) having 370 ml of freeness (CSF) and 20 parts of softwood kraft pulp (NBKP) having 410 ml were used. Alumina hydrate A as a filler was mixed with 11% by weight based on the pulp solid content, and a double salt compound N having the composition shown in Table 3 was added.
o. (I) -2 was added in an amount of 0.1
2% by weight, and a cationized starch (CATOF, manufactured by Oji National Co., Ltd.) was added as a retention aid in an amount of 0.3% by weight based on the solid content of the pulp, and a polyacrylamide-based yield was obtained immediately before papermaking. 0.05% by weight of an enhancer (PARK FLOCK FR-X, manufactured by Hoshi Kogyo Kogyo)
The mixture was added and the paper was weighed to 70 g / m ² using a TAPPI standard sheet former. Next, a solution of oxidized starch having a concentration of 2% (MS3800, manufactured by Nippon Shokuhin Co., Ltd.) was applied by a size press and dried at 100 ° C. to obtain a recording medium of this example. Example 8 for the obtained recording medium
The measurement and evaluation were performed in the same manner as described above. Table 10 shows the results.

<Examples 15 and 16 and Comparative Example 5> A recording medium was obtained in the same manner as in Example 14, except that (I) -2 was used in the combinations and addition amounts shown in Table 10.
Table 10 shows the results.

[0144]

<Example 17> (Non-porous) polyvinyl acetal resin (KX-1, water / isopropyl alcohol = 50/40, solid content 79%, manufactured by Sekisui Chemical Co., Ltd.): 100 parts by weight, Alumina hydrate A: 0.5 part by weight, double salt compound No. (I)-
10: 0.07 parts by weight of a dispersing machine (Tokusai Kika Kogyo
K, ROBO MICS, using homodisper blades) at a transfer speed of 500 rpm for 1 hour. The obtained coating liquid was applied to a white polyester film (Dupont, Melinex 339, 125 μm thick) using a wire bar so as to have a dry coating thickness of 15 μm.
After drying at 0 ° C. for 5 minutes, a recording medium was obtained. The obtained recording medium was measured and evaluated in the same manner as in Example 8. The results are shown in Table 11.

<Examples 18 to 19 and Comparative Example 6> A recording medium was obtained in the same manner as in Example 17 except that the compound of Example 17 was used in combination as shown in Table 11. Table 11 shows the results.

[0147]

[0148]

As described above, according to the present invention, 1) it is possible to provide a recording medium with improved light fastness and discoloration fastness of an ink jet recorded image. 2) It is possible to obtain a recording medium having a high density of recorded images, a clear color tone, a high resolution, and excellent ink absorption and preservability of recorded images without adversely affecting the hue of the dye.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a recording medium of the present invention.

Continued on front page F-term (reference) 2H086 BA14 BA15 BA21 BA31 BA33 BA34 4J038 BA021 BA091 BA191 CA061 CA071 CA081 CB022 CC032 CC062 CD032 CE021 CG001 CG142 CG151 CJ032 CK031 DD001 DD002 DG001 DG002 HA166 HA38 JB06 JB06

Claims (39)

[Claims] 1. A recording medium having an ink receiving layer containing a compound represented by the following general formula (I). 2. R _{1 to} R ₈ in the general formula (I) each have 2 carbon atoms.
2. The recording medium according to claim 1, wherein the number of organic residues is from eight to eight. 3. The compound of the formula (I) wherein R _{1 to} R ₈ have 3 carbon atoms.
3. The recording medium according to claim 2, wherein the number of organic residues is from eight to eight. 4. R ₁ and R ₂ , R ₃ and R ₄ in the general formula (I),
All of the substituents of at least two of the combinations of organic residues R ₅ and R ₆ and R ₇ and R ₈ are substituted or unsubstituted alkoxyalkyl groups, substituted or unsubstituted alkenyl groups, substituted or The recording medium according to claim 1, wherein the recording medium is a monovalent organic residue selected from an unsubstituted alkynyl group and a substituted or unsubstituted aralkyl group. 5. In the formula (I), all of R _{1 to} R ₈ are a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group and a substituted or unsubstituted group. 2. The recording medium according to claim 1, wherein the recording medium is a monovalent organic residue selected from the group consisting of: 6. The metal complex anion (X) in the general formula (I)
^The recording medium according to claim 1, wherein-) is represented by the following general formula (III). 7. The recording medium according to claim 6, wherein the metal complex anion (X ⁻ ) represented by the general formula (III) has the following structure. 8. The metal complex anion (X) in the general formula (I)
^The recording medium according to claim 1, wherein-) is represented by the following general formula (IV). 9. The recording medium according to claim 8, wherein at least one of the substituents R _{13 to} R _{16 in} the general formula (IV) is an alkoxy-substituted aryl group. 10. The recording medium according to claim 8, wherein the metal complex anion (X ⁻ ) in the general formula (I) has the following structure. 11. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is represented by the following general formula (V). 12. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is represented by the following general formula (VI). 13. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is represented by the following general formula (VII). 14. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is represented by the following general formula (VIII). 15. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is represented by the following general formula (IX). 16. The recording medium according to claim 1, wherein the metal complex anion (X ⁻ ) in the general formula (I) is a nickel complex anion. 17. The compound represented by the formula (I) wherein R ₁ , R ₂ , R ₃ ,
2. The recording medium according to claim 1, wherein at least one of R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is an alkoxyalkyl group. 18. A recording medium having an ink receiving layer containing a compound represented by the following general formula (II). 19. The recording medium according to claim 18, wherein when the five-membered ring is included in the general formula (II), the five-membered ring is a pyrrolidine ring. 20. The recording medium according to claim 18, wherein when the six-membered ring is included in the general formula (II), the six-membered ring is any of a piperidine ring, a morpholine ring and a tetrahydropyridine ring. 21. The recording medium according to claim 18, wherein when the 7-membered ring is included in the general formula (II), the 7-membered ring is a cyclohexylamine ring. 22. R ′ ₁ and R ′ ₂ , R ′ _{3 in the} general formula (II)
And R ′ ₄ , R ′ ₅ and R ′ _6, and R ′ ₇ and R ′ ₈ , at least two of which are substituted or unsubstituted 5-membered rings or substituted or unsubstituted 6-membered rings. The recording medium according to claim 18, wherein the recording medium is a ring, a substituted or unsubstituted 7-membered ring. 23. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (III). 24. The recording medium according to claim 23, wherein the metal complex anion (X ⁻ ) in the general formula (II) has the following structure. 25. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (IV). 26. The recording medium according to claim 25, wherein at least one of the substituents R _{13 to} R _{16 in} the general formula (IV) is an alkoxy-substituted aryl group. 27. The recording medium according to claim 26, wherein the metal complex anion in the general formula (II) has the following structure. 28. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (V). 29. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (VI). 30. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (VII). 31. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (VIII). 32. The recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is represented by the following general formula (IX). 33. The optical recording medium according to claim 18, wherein the metal complex anion in the general formula (II) is a nickel complex anion. 34. R ′ in the general formula (II)₁, R '_Two,
R '_Three, R '_Four, R '_Five, R '₆ , R '₇, R '₈Of the combinations
2. The method according to claim 1, wherein at least one pair forms a morpholine ring.
9. The optical recording medium according to 8. 35. The recording medium according to claim 1, wherein the ink receiving layer is a porous layer. 36. The recording medium according to claim 35, wherein the porous layer mainly comprises alumina hydrate. 37. The recording medium according to claim 35, wherein the porous layer is mainly composed of silica. 38. The recording medium according to claim 35, wherein the porous layer is mainly composed of thermoplastic polymer particles. 39. The recording medium according to claim 1, wherein the ink receiving layer is internally added to paper.