JPH10157282A - Material to be recorded for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material to be recorded for ink jet recording by providing satisfactory printing image quality, excellent ink absorbing capacity and fixability, satisfactory surface gloss, satisfactory water resistance and light resistance of an image part with ink dye after printing, and no aging deterioration such as discoloring of a non-printed part. SOLUTION: The material to be recorded for ink jet recording having an ink receptive layer on a support comprises a polymer having a functional group represented by a formula and a crosslinker for making the receptive layer water resistance in the receptive layer. Formula (where R1 , R2 , R3 each indicates alkyl group, substituted alkyl group, aryl group, or substituted aryl group, which may be the same or different, and X indicates anion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium for water-based ink using an ink jet recording method, and more particularly to a recording material for ink jet recording using paper, resin-coated paper, film or the like as a support.

[0002]

2. Description of the Related Art In recent years, quality requirements for recording materials have become more and more severe with the increase in speed of ink jet recording apparatuses, higher definition of recorded images, and full color.
Furthermore, among the various inkjet printers that have been developed for full-color recording, models with the capability to output high-definition images that are comparable in quality to conventional silver halide photographic color images are being developed. In order to obtain a sufficient image density, the amount of droplets ejected as ink dots on the surface of a recording material is increasing, and the ink absorption capacity of the recording material is, for example, 20 to 30 per square meter.
It has been required that the ink absorb up to about gram of ink and no ink remains on the surface.

In order to absorb such a large amount of ink, it is effective to provide an ink absorbing layer, form a porous structure such as a pigment in the ink absorbing layer, and absorb the ink in the voids. In the ink absorbing layer having such a configuration, the gloss of the coating layer surface is usually significantly reduced due to the light scattering of the pigment, and further, the image quality may be deteriorated due to the disorder of the shape of the ink dots.

[0004] As an attempt to realize a good ink absorption capacity while having a surface gloss comparable to that of a silver halide photograph as an ink jet recording material, when forming an ink absorption layer, the surface gloss is reduced. It has been proposed that the polymer itself as a binder has such an ink absorbing property without introducing fine particles such as pigments, which are the main factor, into the ink absorbing layer. Although it is also used as a sheet, for example, JP-A-61-19389, JP-A-61-277483, JP-A-61-287778, JP-A-62-9988, JP-A-63-207681, and JP-A-Hei1 No. 146784,
As described in JP-A-1-280581 and JP-A-7-323656, examples of ink absorbing layers mainly composed of various natural or synthetic polymers are described.

When an ink-absorbing layer mainly composed of the above-described polymer is formed, a recording material having excellent gloss or light-transmitting properties can be obtained, but when the water resistance of the polymer itself is not sufficient, Alternatively, there is a problem that the water resistance of a recorded image cannot be ensured due to a lack of a function of fixing a printed ink dye.

As described above, the requirements for a recording material for realizing high-quality ink jet recording against silver halide photography include a sufficient ink absorption capacity and a surface gloss as good as color paper. In addition to the above, it is required that the storability of the recorded image be good. This requires that the recorded image has good water resistance, light resistance and the like, and that the non-printed portion does not deteriorate with time such as discoloration.

In an ink jet recording system using a water-based ink, since a water-soluble dye is mainly used as a coloring material for forming a printed image at present, such a water-soluble dye in a printed portion is removed in some form. Unless insolubilized or fixed, water resistance of the image cannot be realized. Conventionally, various systems have been proposed as a waterproofing agent or a fixing agent for such a dye. For example, as an example using an amine polymer such as an amino group, JP-A-7-304982 describes an example of substituted polyethyleneimine as a mordant, and JP-A-7-2666.
No. 89 discloses polyallylamine and Japanese Patent Application Laid-Open No.
JP-A-849992, JP-A-57-36692, JP-A-Showa-6
Nos. 1-72581, 61-74880, 61-2
No. 7279, JP-A-63-264391, JP-A-64-64391
-8085, JP-A-7-290817, JP-A-7-
Many amine-based polymers are described as dye fixing agents as seen in JP-A-125411.

The above amine fixing agent forms a salt with the dye to form a water-insoluble or sparingly soluble salt, or has an effect of being immobilized on a polymer, thereby reducing the water resistance of the recorded image. Although enhanced, the storage stability of the recorded image, for example, oxygen in the atmosphere, nitrogen oxides are preferably subjected to a chemical change due to various factors, such as yellowing of the non-printed portion or fading of the dye is promoted. In some cases, no effect was observed.

Examples of fixing agents other than amine-based fixing agents are described in, for example, JP-A-7-1830, examples of low-molecular-weight phosphonium compounds, and examples of inorganic fixing agents are described in JP-A-3-215081 and JP-A-3-215081. And cationic inorganic fine particles such as alumina sol described in JP-A-67684. Even in such a system, various problems occur in terms of the storability of the recorded image and the like. For example, when the recorded image is stored in an atmosphere under a high humidity, the dye diffuses in the recording layer, thereby causing image bleeding. For example, the dye fixability was not sufficient.

A polymer having a phosphonium base in the side chain has been conventionally found to be effective as a mordant in, for example, the field of photographic light-sensitive materials.
Nos. 29839, 3547649 and 48552
All patents, such as No. 11, describe examples of polymers having a phosphonium base. Also in these cases, since the compound having a phosphonium base is polymerized, the diffusion of such a polymer in the layer is smaller than that of the low molecular compound, and the diffusion of the dye after dyeing (mordanting) is low. The advantage is that the color bleeding is improved because it can be further suppressed.However, since such a polymer itself is water-soluble, it is not possible to obtain a sufficient effect in terms of water resistance of a recorded image at present. Was.

[0011]

As described above, an object of the present invention is to provide good print image quality, excellent ink absorption capacity, and good surface gloss, and use of the ink dye after printing. An object of the present invention is to provide a recording material that has good water resistance and light resistance in an image area, and is free from deterioration over time such as discoloration in a non-printed area. In the prior art, there is no system that satisfies all of the above items at the same time, and there is a long-awaited need for a solution. In particular, there is no satisfactory improvement method for the problem of light fastness such as fading of a printed portion or yellowing of a non-printed portion which occurs when an inkjet recording material after image formation is left outdoors or indoors under a fluorescent lamp. Was.

[0012]

The above objects are achieved by the present invention described below. That is, the invention according to claim 1 is characterized in that the ink receiving layer contains a polymer having a phosphonium base represented by Chemical Formula 1 and a crosslinking agent for making the ink receiving layer water resistant.

According to a second aspect of the present invention, the ink receiving layer contains a polymer having a phosphonium base represented by Chemical Formula 1 and a cross-linking agent for cross-linking the polymer to make it water-resistant.
That is, the polymer has a functional group that reacts with the crosslinking agent.

According to a third aspect of the present invention, there is provided the method of the second aspect, wherein the monomer having a phosphonium base represented by the general formula (1) and a hydroxy group, a carboxy group,
It contains a polymer obtained by copolymerizing at least a monomer having a functional group selected from amino groups, and a crosslinking agent capable of crosslinking the polymer.

The invention according to claim 4 is characterized in that the ink receiving layer contains a polymer having a repeating unit represented by the formula (2).

According to a fifth aspect of the present invention, there is provided the polymer according to the fourth aspect, further comprising a polymer having both the repeating unit represented by the formula (2) and a repeating unit selected from a hydroxy group, a carboxy group and an amino group. It contains a crosslinking agent capable of crosslinking the polymer.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A solution containing a polymer having a functional group represented by the above formula 1 and a crosslinking agent is coated on a support, or a solution containing a polymer having a repeating unit shown in the above formula 2 Is applied on a support to exert a fixing effect on the dye. Examples of the support include paper mainly composed of wood pulp and various films such as a polyester-based film and a cellulose acetate-based film, and those obtained by laminating polyethylene, polypropylene, and the like on paper, and the like. In such a case, it is preferable to apply it to the surface before use.

In Chemical Formula 1, R ₁ , R ₂ and R ₃ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, which may be the same or different. X is an anion, a halogen ion or a sulfonate anion,
It represents an arylsulfonate anion, an acetate anion, an alkyl carboxylate anion, or the like.

The polymer having a functional group represented by the following chemical formula 1 is
Since it has an effect of binding to a dye in a commonly used aqueous ink, it is effective as a fixing agent for the dye,
In addition, since the polymer has a large number of functional groups having such a fixing action in the molecule, the bonding speed to the dye is high, and thus it has an advantage that the fixing action is developed immediately after printing. Japanese Patent Application Laid-Open No. Hei 7-1830 which was mentioned as an example earlier
The publication discloses examples of low-molecular-weight phosphonium compounds.Although these low-molecular-weight phosphonium compounds themselves naturally have a binding property to dyes, dyes are required to exhibit a fixing action and exhibit water resistance of recorded images. It is necessary that the bound low molecular phosphonium compound is water-insoluble or hardly soluble. It is necessary to take some measures to prevent the low-molecular-weight phosphonium compound bound to the dye in the printed area and the low-molecular-weight phosphonium compound in the non-printed area from falling off the substrate, but usually the phosphonium compound itself is water-soluble. Since the phosphonium compound which does not bind to the dye easily falls off the substrate, there is a concern that a safety or environmental problem may occur such as transfer to a user's skin by contact with a finger or the like. Similarly, it can be easily imagined that the low-molecular-weight phosphonium compound bonded to the dye in the printed portion easily falls off the recording material by physical contact or friction unless the film itself is formed. Furthermore, the low molecular phosphonium compound has a problem that it easily bleeds out to the surface, and the surface of the recording material becomes sticky or blocked due to moisture in the air.

In the present invention, the use of a polymer having a phosphonium group imparts adhesion to a support. One of the effects is to prevent such a fixing agent from separating from the support. Can be The water resistance of the recorded image can be further increased by making the ink receiving layer containing the polymer having the functional group of Formula 1 water-resistant with a crosslinking agent. In particular, it was an unexpected effect that the combination of the polymer having the functional group of Chemical Formula 1 and the cross-linking agent significantly improved the light resistance of the printed portion and the non-printed portion.

In the present invention, the ink-receiving layer containing the polymer having the functional group of the formula (1) is cross-linked by a cross-linking agent. 2) an embodiment in which the polymer having the functional group of formula 1 is crosslinked positively and water-resistant, that is, a functional group which reacts with a crosslinking agent, for example, a hydroxyl group. , A carboxy group, an amino group and the like.

In the present invention, the embodiment 2) is preferred, and among them, the copolymerization of a monomer having a functional group of the formula 1 with a monomer having a functional group selected from a hydroxyl group, a carboxy group and an amino group is particularly preferred. It is preferable to use coalescence. Further, a mode in which 1) and 2) are combined is also preferable.

In the present invention, as a crosslinking agent (waterproofing agent) for crosslinking a polymer, for example, epoxy curing agent, aziridine curing agent, formalin, glyoxal, N-methylolated product (trimethylolated urea, poly (N-methylolacrylamide) ), Aldehydes such as dialdehyde starch, dichlorotriazine-based curing agents, vinyl sulfones, active ester-type curing agents, mucochloric acid-based curing agents, and the like. One of the features is that the water resistance of the recorded image can be further enhanced, and the fixing agent can be prevented from falling off from the non-printed portion. In particular, as described above, there is a remarkable effect on light resistance.

US Pat. No. 3,429,839, referred to above,
The polymers having a phosphonium base shown in JP-A Nos. 3547649 and 4855211 do not disclose any knowledge on crosslinking water resistance, and are simply applied to a recording material to be subjected to inkjet recording using such a water-soluble polymer. It was also found that the present invention could not solve the problems of water resistance and color bleeding of a recorded image, which are one of the objects of the present invention.
Furthermore, when a polymer having a phosphonium base that is not cross-linked and water-resistant is used in a recording material, moisture absorption is remarkable due to atmospheric moisture as in the case of a low molecular weight phosphonium compound, and stickiness and blocking of the surface are reduced. Although it often occurred, it was found that such a problem was avoided when a crosslinked water-resistant polymer was used.

As a method for forming a polymer having a functional group represented by the chemical formula 1, a monomer having a functional group represented by the chemical formula 1 is synthesized in advance, and this is mixed with another copolymerizable monomer to carry out polymerization. And a method of bonding a compound having a functional group represented by Chemical Formula 1 to a polymer formed in advance.

As described above, it is very effective to introduce a functional group for further reacting with a crosslinking agent into a polymer having a functional group represented by Chemical Formula 1 to make the polymer itself crosslinked and water-resistant. As such a functional group, a hydroxy group, a carboxy group, and an amino group are preferably selected. When the polymer has such a functional group, it is particularly preferable that the curing agent as described above is used as a crosslinking agent or a water-proofing agent, since the polymer can be effectively crosslinked and water-resistant.

Examples of the monomer having a hydroxy group, a carboxy group or an amino group include, but are not limited to, the following. 4-hydroxystyrene, 4-carboxystyrene, 4-aminostyrene, methacrylic acid, acrylic acid, methacrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl methacrylate, 2-N, N-dimethylaminoethyl methacrylate, crotonic acid, maleic acid, fumaric acid, monoalkyl maleate, allylamine, diallylamine and the like. I can do it.

Specific examples of monomers for obtaining a polymer having a functional group represented by Chemical formula 1 include the following compounds, but are not limited thereto.

[0029]

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[0030]

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[0031]

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The monomers as mentioned in the above examples are used alone,
Alternatively, a polymer having the effects aimed at by the present invention can be obtained by copolymerizing with another monomer copolymerizable therewith. Examples of such copolymerizable monomers include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, styrene derivatives such as 4-methoxystyrene, methyl methacrylate, Ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, etc .; alkyl methacrylates; aryl methacrylate or alkyl aryl esters such as phenyl methacrylate, benzyl methacrylate; , 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methoxydiethylene glycol methacrylate monoester, methoxypolyethylene methacrylate Methacrylic esters having an alkyleneoxy group such as coal monoester and polypropylene glycol methacrylate monoester, and amino group-containing methacrylic esters such as 2-dimethylaminoethyl methacrylate and 2-diethylaminoethyl methacrylate, or acrylic esters Examples similar to the corresponding methacrylic acid esters, or acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, monomers having a carboxy group such as fumaric acid monoalkyl ester, Amino group-containing monomers such as allylamine and diallylamine, or vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, methallyl sulfonic acid and its salts, styrene sulfonic acid and its , Monomers having 2-acrylamido-2-methylpropane sulfonic acid and sulfonic acid groups of salts thereof,
Monomers having a nitrogen-containing heterocycle such as 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, or 4-vinylbenzyltrimethylammonium chloride, acryloyloxyethyl as a monomer having a quaternary ammonium base Trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, quaternary product of dimethylaminopropylacrylamide with methyl chloride, quaternary product of N-vinylimidazole with methyl chloride, 4-vinylbenzylpyridinium chloride, etc., or acrylonitrile, methacrylonitrile, Also, acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, N-isopropylacrylamide De, diacetone acrylamide, N
-Acrylamide or methacrylamide derivatives such as methylol acrylamide and N-methoxyethyl acrylamide, and further vinyl esters such as acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl stearate and vinyl benzoate And also methyl vinyl ether,
Vinyl ethers such as butyl vinyl ether, and others,
Various monomers such as N-vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl methacrylate, vinyl chloride, vinylidene chloride, allyl alcohol, vinyltrimethoxysilane, and glycidyl methacrylate can be appropriately used as a copolymerization monomer. Among these various monomers, it is particularly preferable to select a monomer having a hydroxy group, a carboxy group or an amino group, which is particularly effective when the above-mentioned various crosslinking agents are added to make the polymer crosslinked and water-resistant.

In the polymer having the functional group represented by Chemical formula 1, the composition ratio of Chemical formula 1 in the polymer is as follows:
It is preferable to synthesize the copolymer at a ratio occupying 1 part by weight or more in 0 parts by weight, and when a repeating unit represented by Chemical Formula 1 is introduced into the copolymer at a ratio of less than this,
Since the obtained copolymer has a reduced binding property to the dye, it is not preferable when used as a dye fixing agent because a large amount is required or the fixing function is deteriorated. The composition ratio of Chemical Formula 1 in the copolymer is preferably 1 part by weight or more and 100 parts by weight or less, and more preferably the effect of the present invention is most remarkably exhibited when used in a proportion of 5 parts by weight or more and 100 parts by weight or less. In the case where a component having a hydroxy group, a carboxy group or an amino group is introduced as a copolymer component other than the chemical formula 1, the ratio of the latter component in the copolymer is from 0.1 part by weight to 3 parts by weight.
The range of 0 parts by weight is preferably used. In this range, a good crosslinked film is formed in combination with the crosslinking agent, and the advantage is that the ink absorbency of the crosslinked film is not impaired. If the proportion is less than the above range, a crosslinked film may not be formed even when a crosslinking agent is added, which is not preferable.On the contrary, if a copolymer is formed beyond the above range, the addition of the crosslinking agent Is not preferable because the ink absorbability of the crosslinked film is impaired.

Preferred examples of the copolymer according to the present invention are shown below, but are not limited thereto. The numbers in the chemical formulas indicate parts by weight.

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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When a polymer having a functional group represented by Chemical Formula 1 is impregnated or coated on a support, the amount of the polymer required to exhibit a desired effect is determined by the following formula: 0.1 g or more per square meter 2
The amount is preferably 0 g or less, and when used in an amount less than this range, the effect of adding the polymer is hard to be recognized, and even when used in excess of 20 g, only an excess of the polymer is present, which is preferable. Absent.

Since the polymer represented by the formula (1) alone has a function as a binder alone, it does not particularly require an additive as another binder. However, if necessary, another optional binder may be used. Can be used together. As such a binder, for example, as a cellulose derivative, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, diethylaminoethylcellulose, diethylammonium chloride hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride hydroxyethylcellulose, etc., starch, cationic starch, Various modified starches such as hydroxypropyl starch, or chitosan, carrageenan, acid-treated gelatin, alkali-treated gelatin, various modified gelatins, and further, as a vinyl polymer, polyvinyl alcohol, polyvinyl acetal, polyvinylpyrrolidone, polyacrylamide, sodium polyacrylate, polyvinylpyrolate Don - can be used various synthetic polymers such as vinyl acetate copolymer. When such a binder is used in combination with a polymer having a functional group represented by Chemical Formula 2, the amount of the binder added is not particularly limited, but may be, for example, more than 100 times the amount of the polymer having a functional group represented by Chemical Formula 2. When a binder is used, the effect of the present invention is hardly exhibited, which may be undesirable.

In addition to the polymer represented by Chemical formula 1, inorganic ultrafine particle dispersions such as colloidal silica and alumina sol, and synthetic fine particle silica such as titanium oxide, zinc oxide, calcium carbonate, amorphous silica and amorphous silica ,
Furthermore, various synthetic latex, polystyrene beads,
Polymer fine particles such as polymethyl methacrylate beads can be used in combination for various purposes such as prevention of blocking, surface modification, and improvement of hiding degree.

In the case where a surface gloss is required as an ink jet recording material such as a photographic color paper, the ink receiving layer is mainly composed of a binder, and the above-mentioned pigment components such as inorganic and organic fine particles are used. Is preferably minimized or not used. In such a case, it is required that the ink receiving layer mainly composed of the binder has a sufficient ink absorption capacity, a high absorption speed, and a dry printed surface immediately after printing. Further, it is practically required that the dye in the printed portion has water resistance, and has properties such that the ink is not transferred immediately after printing, for example, by tracing the printed surface with a finger.

The ink receiving layer composed of the polymer having a crosslinked water-resistant phosphonium base obtained in the present invention has good ink absorption performance despite being crosslinked. It is characterized in that sufficient ink jet recording can be performed by using the ink receiving layer alone without the need to add a pigment or a binder.

As described above, it is important to use a cross-linking agent in combination in order to increase the water resistance of the recorded image. Preferred examples of the cross-linking agent include specific examples shown in Chemical formulas 15 to 25. But are not limited to these examples.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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Further, even in the case where the above-mentioned other binder is used in combination with the polymer according to the present invention, it is preferable to use the above-mentioned crosslinking agent together. It is particularly preferable that the binder used together is also crosslinked and water-resistant by the crosslinking agent. As examples of preferred binders used in such a case, various binders such as the above-mentioned various cellulose derivatives, gelatins, and polyvinyl alcohol can be preferably used.

The amount of the cross-linking agent used is not particularly limited depending on the degree of water resistance, but excessive use may impair ink absorbability. There is. The optimum amount of the crosslinking agent to be added to the entire polymer to be water-resistant, including the polymer or all binders used in combination with the polymer, is from 0.1 to 20 parts by weight based on 100 parts by weight of the entire polymer. When the amount of the cross-linking agent used is less than this, the effect of the addition may not be observed in some cases, which is not preferable. When the water-proofing agent is used in an amount exceeding 20 parts by weight, the ink absorption capacity decreases and the printing surface May overflow with ink, which is not preferable.

The molecular weight of the polymer having a functional group represented by Chemical Formula 1 is preferably in the range of about 10,000 to 1,000,000 in weight average molecular weight, and if the molecular weight is lower than this range, the dye fixing property is low. In some cases, it is not sufficient, and the dye in the printed area may flow out due to contact with water, or the printed surface may be sticky. Further, when the molecular weight is higher than the above molecular weight range, because the solution viscosity is extremely high, because the viscosity of the solution when performing coating or impregnation treatment is too high, there is a case where it may interfere with processing is not preferred .

Next, a polymer having a repeating unit represented by Chemical Formula 2 and an ink receiving layer containing the polymer will be described.

In Chemical Formula 2, R ₄ represents hydrogen or a methyl group, A represents a divalent linking group, and n represents 0 or 1. Q represents an unsubstituted alkylene group having 2 or more carbon atoms, an alkyleneoxy group, an alkylene group having a quaternary ammonium base or an alkyleneoxy group. Also,
R ₅ , R ₆ and R ₇ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, which may be the same or different. X is an anion, and represents a halogen ion, a sulfonate anion, an arylsulfonate anion, an acetate anion, an alkyl carboxylate anion, or the like.

In Chemical formula 2, preferred examples of the divalent linking group A include a COO group, a CONH group, a phenylene group, and a straight-chain divalent linking group linked thereto. Typical examples are shown in the exemplified compound section below.

[0067]

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[0068]

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[0069]

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[0070]

Embedded image n represents an integer of 1 to 12.

[0071]

Embedded image m represents an integer of 1 to 12.

[0072]

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[0073]

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[0074]

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[0075]

Embedded image l represents an integer of 1 to 50.

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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The monomers as mentioned in the above examples are used alone,
Alternatively, a polymer exhibiting the effects aimed at by the present invention can be obtained by copolymerization with another monomer copolymerizable therewith. Examples of the copolymerizable monomer include those described in the description of the polymer having the functional group of Chemical formula 1.

In the polymer having the repeating unit represented by Chemical formula 2, the composition ratio of Chemical formula 2 in the polymer is 1 part by weight or more in 100 parts by weight of the copolymer. Preferably, when a repeating unit represented by the formula (2) is introduced into the copolymer at a ratio below this, the resulting copolymer has reduced binding property to the dye. It is not preferable because a large amount is required and the fixing function is deteriorated. The composition ratio of Chemical Formula 2 in the copolymer is preferably 1 part by weight or more and 100 parts by weight or less, and more preferably the effect of the present invention is most remarkably exhibited when used in a proportion of 5 parts by weight or more and 100 parts by weight or less.

Preferred examples of the polymer having the repeating unit of Chemical formula 2 are shown below, but the invention is not limited thereto. The numbers in the chemical formulas indicate parts by weight.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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The above-mentioned polymer is novel in a recording material for ink-jet recording, and exhibits superior ink absorbency, ink fixing property, water resistance, light resistance, film strength, etc. as compared with a conventional polymer having a phosphonium base. I do. In particular, it is possible to achieve both ink absorption and ink fixability, which are difficult to achieve. Therefore, there is no problem even when an ink jet printer having a relatively large amount of ink is used.

As described above, the above polymer is preferably used in combination with a cross-linking agent, but when no cross-linking agent is used, for example, when a pigment such as amorphous silica is used as in Example 3 described below. Also show superior performance compared to conventional polymers.

When a polymer having a repeating unit represented by the following formula (2) is impregnated or coated on a support, the amount of the polymer required for exhibiting a desired effect is determined based on the surface area of the support. The amount is preferably 0.1 g or more and 20 g or less per square meter. When used in an amount less than this range, the effect of the addition of the polymer is hard to be recognized. Is only present, which is not preferable.

In the present invention, a polymer having a phosphonium group is used in the form shown in Chemical formula 2 to impart adhesion to a support, and the separation of such a fixing agent from the support is prevented. This is one of the effects.
Further, it is extremely preferable to further increase the water resistance of the recorded image by positively making the polymer itself crosslinked and water-resistant. As the crosslinking agent (waterproofing agent), the above-mentioned curing agent is used. One of the features is that by using these curing agents together, the polymer can be made water resistant, the water resistance of the recorded image can be further enhanced, and the fixing agent can be prevented from dropping out of the non-printed area. It is.

As a functional group for reacting with the above-mentioned cross-linking agent to make the polymer itself cross-linked and water-resistant, a hydroxy group, a carboxy group and an amino group are preferably selected. Examples of the monomer having a hydroxy group, a carboxy group or an amino group include those described in the description of the polymer having a functional group of Chemical formula 1.

Preferred examples of the copolymer according to the present invention are shown below, but it should not be construed that the invention is limited thereto.
The numbers in the chemical formulas indicate parts by weight.

[0104]

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[0105]

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[0115]

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The molecular weight of the polymer having a functional group represented by Chemical formula 2 is preferably in the range of about 10,000 to 1,000,000 in weight average molecular weight, and if the molecular weight is lower than this range, the dye fixing property is low. In some cases, it is not sufficient, and the dye in the printed area may flow out due to contact with water, or the printed surface may be sticky. Further, when the molecular weight is higher than the above molecular weight range, because the solution viscosity becomes extremely high, because the viscosity of the liquid when performing coating or impregnation treatment is too high, there is a case where it may interfere with processing, which is not preferable. .

The ink-receiving layer composed of a polymer having a repeating unit represented by Chemical formula 2 obtained in the present invention has good ink absorption performance. A good result can be obtained by forming the ink receiving layer in any combination of the above and the polymer alone. When the ink receiving layer is formed of the polymer alone, it is preferable to use a cross-linking agent in combination and form the ink receiving layer with a cross-linked film. It is also preferable to use the agent appropriately.

In addition to the polymer represented by the chemical formula 2, inorganic fine particle dispersions such as colloidal silica and alumina sol, and titanium oxide, zinc oxide, calcium carbonate, or synthetic fine particle silica such as amorphous silica and amorphous silica ,
Furthermore, various synthetic latex, polystyrene beads,
Polymer fine particles such as polymethyl methacrylate beads can be used in combination for various purposes such as prevention of blocking, surface modification, and improvement of hiding degree.

Hereinafter, a synthesis example of a polymer having a repeating unit represented by Chemical formula 2 will be described. Synthesis Example 1 (Synthesis example 28) 525 g (2 mol) of triphenylphosphine and 250 g (2 mol) of β-chloroethoxyethanol
The mixture was heated and stirred at 110 ° C. for 24 hours in a nitrogen atmosphere. After cooling to room temperature, 1 liter of acetone was added, and the precipitated white powder was sufficiently washed and dried under reduced pressure. 309.5 g (0.8 mol) of β-hydroxyethoxyethyltriphenylphosphonium chloride (purity confirmed by H ¹ -NMR) obtained in a yield of about 75% was dissolved in 2 liters of dichloromethane, and poly ( 100 g of 4-vinylpyridine) cross-linked beads (manufactured by Acros Organics) are added with stirring, and 83.6 g (0.8 mol) of methacrylic acid chloride is gradually dropped from a dropping funnel on an ice-cooled bath at 0 ° C. did. After completion of the dropwise addition, stirring was further continued at room temperature for one day, and then the filtered filtrate was distilled off under reduced pressure. The obtained oily substance was washed with ether and dried under vacuum to obtain the desired compound.
Was obtained (95% yield). Other monomers were synthesized in a similar manner.

Synthesis Example 2 (Synthesis example of polymer represented by Chemical Formula 54) In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 40 g of the monomer represented by Chemical Formula 28 and acrylic acid 5 g and 55 g of dimethylacrylamide were introduced, 200 g of water and 100 g of ethanol were added, and the mixture was stirred on a 70 ° C. water bath while introducing nitrogen gas. As initiator, 2,
2'-azobis (2,4-dimethylvaleronitrile)
(V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and polymerization was started by adding 1 gram, followed by heating and stirring for 6 hours to obtain a viscous polymer solution. Other polymers were synthesized in the same manner.

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【Example】

Example 1 A coating liquid having a solid content concentration of 10% by weight was prepared according to the formulation shown in Table 1, and a wet coating amount of 100 g was applied on a photographic base paper coated with polyethylene using a doctor bar.
/ M ² , dried with a 70 ° C. hot air drier, and stored in a 40 ° C. drier for 24 hours to produce a recording sheet. In a similar manner, Table 2 was used as a comparative sample.
The recording sheets for comparison prepared with the formulations shown in Table 1 were respectively prepared. The obtained recording sheet is cut into A4 size,
BJC- manufactured by Canon as an inkjet printer
Printing was performed using 600 J, and the following items were evaluated.

(1) Print quality: It was evaluated whether or not the ink density was uniform in a 2-cm square fill pattern composed of a single color and a mixed color. The case where a pattern was drawn at a uniform density over the entire area where printing was performed was evaluated as ○, the case where the printing density was partially uneven was evaluated as Δ, and the case where printing unevenness occurred over the entire surface was evaluated as x.

(2) Ink Absorption: The above-mentioned print pattern was printed, and after printing, the PPC paper was pressed against the print surface to evaluate whether or not ink transfer occurred. The case where the transfer of the ink to the PPC paper does not occur immediately after the printing is indicated by ○, the case where the transfer occurs slightly within a few minutes immediately after the printing, and the case where the transfer does not occur within a few minutes is indicated by の. The case where transfer occurred was evaluated as x.

(3) Ink fixability: After printing the above-mentioned print pattern, water droplets were dropped on a print portion and left for 10 minutes. When the water droplets are wiped off, the dye in the printed area flows out, and the density of the image decreases and the ink spreads around the printed area.Then, the dye is not eluted and the ink spreads around the image area. The case where no occurrence occurred was represented by ○, and the middle between the two was represented by △.

(4) Water resistance: After printing the above-described print pattern, the recording sheet was immersed in warm water at 40 ° C.
It was left for 30 minutes. In either the printed part or the non-printed part, the case where it was dissolved or dropped from the support was marked as X, the case where there was no effect even after immersion was ◎, the case where slight color blurring occurred ○, the case where partial dissolution etc. occurred △.

(5) Storage property under high humidity: After printing the above print pattern, the sample was stored for one week in an atmosphere of 30 ° C. and 85% relative humidity. When the spreading of the printing pattern due to the diffusion of the dye or blocking occurred, the evaluation was evaluated as x, when both the blocking and the diffusion of the dye were mild, and evaluated as ○.

(6) Light fastness: The sheet on which the above-described print pattern was printed was left for one week in a room under irradiation of a fluorescent lamp, and color change such as fading of a printed portion and yellowing of a non-printed portion, and change in density were measured. . A case where marked color change or fading, yellowing of the printed part, etc. was observed as x, and although a slight density change was observed, the change in the color tone itself was slight or no change was observed, even in the non-printed part The case where no yellowing was observed was marked with と し, and the middle between the two was marked with △. When the evaluation was ○, the sample was further left for one week continuously, and when no change was observed, the evaluation was ◎.

(7) Gloss: With respect to the sheet on which the above-described print pattern was printed, a sheet having good gloss in both the non-printed portion and the printed portion was marked with ○, and a sheet having poor gloss in both was marked with x, The middle point between the two was marked with △.

Based on the above evaluation criteria, Tables 1 and 2
Tables 3 and 4 summarize the evaluation results of the recording sheets prepared by the blending of the above.

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[Table 1]

The numerical values in parentheses in Table 1 represent parts by weight. A coating solution was prepared so that the total polymer was 100 parts by weight and the content was 10% by weight. P1 = 1: 1 of gelatin and carboxymethylcellulose
Mixture P2 = Polymer represented by formula P3 = Polymer represented by formula P4 = Gelatin

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As a comparative sample, a coating liquid based on the following composition was prepared, and a recording sheet was prepared in the same manner.

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[Table 2]

The numerical values in parentheses in the table indicate parts by weight. A coating liquid was prepared so that the total content was 100 parts by weight, and the solid content concentration was 10% by weight. The coating liquid was similarly coated and dried to prepare a recording sheet. T1 = Compound represented by Chemical Formula 68 T2 = Homopolymer of Chemical Formula 3 T3 = Polymer represented by Chemical Formula 69 T4 = Polymer represented by Chemical Formula 70

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[Table 3]

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[Table 4]

As is clear from the above results, the combination of the polymer having a phosphonium base of the present invention and a crosslinking agent is as follows:
It almost satisfies all of the performances required for the recording material for ink jet. In particular, the improvement of light resistance and water resistance is very significant because the present invention has not been satisfactorily improved. In particular, a combination of a copolymer of a monomer having a phosphonium base and a monomer having a functional group which can be crosslinked by a crosslinking agent, and a crosslinking agent are preferable.

Example 2 A coating solution having a solid content of 10% by weight was prepared according to the formulation shown in Table 5, and wet coating was carried out on a photographic base paper coated on polyethylene with a doctor bar. Is 100g
/ M ² , dried with a 70 ° C. hot air drier, and stored in a 40 ° C. drier for 24 hours to produce a recording sheet. In a similar manner, Table 6 was used as a comparative sample.
The recording sheets for comparison prepared with the formulations shown in Table 1 were respectively prepared. The obtained recording sheet is cut into A4 size,
Using an ink jet printer, MJ-910C manufactured by Seiko Epson Co., Ltd., which has a relatively large amount of ink, printing was performed at the maximum print density, and the results were evaluated based on the evaluation criteria of Example 1. Table 7 summarizes the results.

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[Table 5]

The numerical values in parentheses in Table 5 represent parts by weight. A coating solution was prepared so that the total polymer was 100 parts by weight and the content was 10% by weight.

As a comparative sample, a coating liquid based on the following composition was prepared, and a recording sheet was prepared in the same manner.

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[Table 6]

The numerical values in parentheses in the table indicate parts by weight. A coating liquid was prepared so that the total polymer content was 100 parts by weight, and the solid content concentration was 10% by weight. The coating liquid was similarly coated and dried to prepare a recording sheet.

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[Table 7]

Sample No. 1 which is a combination of a copolymer of a monomer having a repeating unit of Chemical Formula 2 and a monomer having a functional group which can be crosslinked by a crosslinking agent, and a crosslinking agent. 1 to 15
Has excellent ink absorbency and fixability despite the large amount of ink.

Example 3 Synthetic amorphous silica (Fine Seal X-37 manufactured by Tokuyama)
B) 20 parts of water were dispersed by using 80 parts of water, and polyvinyl alcohol having a saponification degree of 97% (Kuraray-made PVA) was added thereto.
117) 70 parts of a 10% solution, 2 parts of an optical brightener (Kycoll BBL manufactured by Nippon Soda, 50% of active ingredient) are added, and 10% of a polymer solution or a comparative compound according to the present invention is further added.
30 parts of the solution was added to make a coating solution, which was 92 g / m2 in basis weight.
Use wire bar onto ² of the base paper was coated to a wet coating weight of about 150 g / m ^2, dried in a hot-air drier, to the front and back once by one calender treatment at a linear pressure of 49N / cm Thus, an inkjet recording medium was prepared. Print evaluation using an ink jet printer was performed in the same manner as in Example 2.

The obtained ink-jet recording material was evaluated for ink absorption, fixability and water resistance according to the evaluation criteria of Example 1. Table 8 shows the results.

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[Table 8]

As is clear from the above results, the polymer having the repeating unit of the formula (2) has excellent ink absorbency, fixability and water resistance as compared with other polymers even in a system containing no crosslinking agent. You can see that there is.

[0155]

According to the first, second and third aspects of the present invention, various properties required for an ink jet recording material, that is, print quality, ink absorption, ink fixability, surface gloss, water resistance, Almost satisfactory performance can be obtained in both light resistance and light resistance. In particular, improvement in light resistance, which has been a problem in the past, is achieved.

According to the fourth and fifth aspects of the present invention, in addition to the same effects as described above, in particular, both ink absorption and fixing can be achieved. Therefore, it is suitable for an ink jet printer having a large amount of ink.

Claims (5)

[Claims] 1. An ink-jet recording material having an ink receiving layer on a support, comprising: a polymer having a functional group represented by Chemical Formula 1 in the ink receiving layer; and a crosslinking agent for making the ink receiving layer water resistant. An ink jet recording material characterized by containing. Embedded image (In Chemical Formula 1, R ₁ , R ₂ , and R ₃ represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and these may be the same or different. X represents an anion.) 2. An ink-jet recording material having an ink-receiving layer on a support, wherein the polymer having the functional group represented by the chemical formula 1 in the ink-receiving layer and a cross-linking agent for cross-linking the polymer to make it water-resistant. An inkjet recording material comprising: 3. The polymer obtained by copolymerizing at least a monomer having a functional group represented by the above formula 1 and a monomer having a functional group selected from a hydroxyl group, a carboxy group and an amino group. An ink jet recording material comprising an ink receiving layer formed by adding a cross-linking agent capable of cross-linking the polymer to form an ink receiving layer. 4. An ink-jet recording material having an ink-receiving layer on a support, wherein the ink-receiving layer contains a polymer having a repeating unit represented by Chemical Formula 2. Embedded image (Wherein R ₄ represents hydrogen or a methyl group;
Represents a divalent linking group, and n represents 0 or 1. Q represents an unsubstituted alkylene group having 2 or more carbon atoms, an alkyleneoxy group, an alkylene group having a quaternary ammonium base or an alkyleneoxy group. R ₅ , R ₆ , R ₇
Represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, which may be the same or different.
X represents an anion. ) 5. The polymer according to claim 4, wherein a polymer having both a repeating unit represented by the formula (2) and a repeating unit selected from a hydroxyl group, a carboxy group or an amino group is used, and a crosslinking agent for crosslinking the polymer is added. An ink-jet recording material comprising an ink-receiving layer formed by cross-linking and water-resistant.