JPH06340164A - Ink jet recording medium - Google Patents

Abstract

PURPOSE:To improve a water resistance by a method wherein a water-soluble polymer for an ink accepting layer is prepared by mixing a monomer selected out of quaternary salt monomers shown by specific formulas, a monomer shown by a specific formula, a monomer selected out of specific compounds, and an epoxy or triazine curing agent each by specific parts by weight. CONSTITUTION:A water-soluble polymer for an ink accepting layer is prepared by mixing 10-50 pts.wt. monomer selected out of quaternary salt monomers shown by formulas I-III, 1-30 pts.wt. monomer shown by a formula IV, 20-80 pts.wt. monomer selected out of specific monomers, such as acrylamide, methacrylamide, and N-N-dimethyl acrylamide, and 0.1-30 pts.wt. epoxy or triazine curing agent per 100 pts.wt. of the water-soluble polymer. In the formulas, R1-R13 represent hydrogen atom, methyl group, ethyl group, and the like and may be the same or different; X is halogen ion and the like; Q is oxygen atom or NH group; and (n) is an integer 2 or 3.

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 recording using an aqueous ink, particularly paper, RC
The present invention relates to a recording medium suitable for color image recording using a water-based ink having paper or film as a support.

[0002]

2. Description of the Related Art The ink jet recording method is one in which minute droplets of ink are ejected by various operating principles and adhered to a recording medium to record characters, images, etc. It is rapidly becoming widespread as a hard copy output device because of its large size, easy multicoloring, and easy maintenance. In addition, ink recording media for overhead projectors that use a translucent film as a support are often used for meetings, lectures, briefing sessions, etc. along with photographic slides. Creating has many advantages.

[0003] Conventionally, as recording media for ink jet, efforts have been made from the viewpoint of equipment and ink composition to use high-quality paper or coated paper used for ordinary printing and writing, but speeding up of the equipment. The demand for recording media is becoming higher with the development of high definition images and full color images. That is, as a recording medium, the density of ink dots is high, the color tone is bright and vivid, and the ink absorption capacity is large and the absorption speed is fast, so even if ink dots overlap, ink bleeding and bleeding will occur. It is necessary that the ink dots do not occur, and that the shape of the ink dots is smooth and the periphery is not blurred. In order to meet these requirements, some proposals have been made in the past. For example, JP-A-53-49113 discloses an ink jet recording paper in which a sheet containing urea-formalin resin powder is impregnated with a water-soluble polymer. However, such a type of ink jet recording paper has dots. However, there is a drawback that the area around is easily blurred and the dot density is low.

Further, JP-A-55-5830 discloses an ink jet recording paper having a support surface provided with an ink-absorptive coating layer, and JP-A-55-51583 discloses a coating layer. An example of using amorphous silica powder as a pigment is further described in JP-A-59-174381 and JP-A-6-174381.
0-44389, 60-132785,
JP-A-60-171143 discloses an ink jet recording sheet provided with a transparent ink receiving layer. Although these coated paper type ink jet recording media have been improved in comparison with general paper type ink jet recording paper in terms of dot diameter, dot shape and print density, they are still insufficient in terms of ink absorption speed. Yes, especially when multi-color color recording etc., when multiple dots of water-based ink overlap, ink bleeding occurs, or the ink is not sufficiently dry or absorptive, so the ink may not reach the guide roller of the printer. Problems such as transfer and contamination of recorded images may occur.

On the other hand, regarding an ink jet recording medium for an overhead projector using a transparent support, the use of an ink-absorbing inorganic pigment generally impairs the transparency, so that it cannot be used in a large amount. In many cases, the property depends on the properties of the resin layer formed on the surface of the transparent support. Examples of resins conventionally used for such applications include, for example, JP-A-57-3818.
No. 5, polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, JP-A-60-
No. 234879, a copolymer of polyvinyl alcohol and an olefin or styrene and maleic anhydride; JP-A No. 61-74879 discloses a cross-linked product of polyethylene oxide and an isocyanate compound;
Blends of carboxymethyl cellulose and polyethylene oxide disclosed in JP-A 1-181679, JP-A-61-61
Various examples such as polymers obtained by grafting methacrylamide on polyvinyl alcohol in JP-A-132377 can be cited.

[0006]

In any of the above examples, when a large number of ink dots are printed on the surface of the recording medium at high speed, such as in the case of high speed multicolor color recording, the ink is used. Both the absorption speed and the ink absorption capacity are not sufficient, and dot bleeding, color unevenness and density unevenness due to ink mixing between adjacent dots, non-uniformity of the solid part, etc. There was a problem. Further, the water resistance of the recorded image is not sufficient, and there are problems that the ink dye flows out due to the adhesion of water droplets and the surface of the recording material is dissolved by water.

[0007]

The present invention discloses a specific method for solving the above problems.
At least one ink receiving layer provided on paper, RC paper (paper laminated on one or both sides with polyethylene), translucent support such as polyester sheet, or other support such as film support, is water-soluble. In an ink jet recording medium for forming a recorded image using a water-based ink containing a water-soluble dye, the ink-receiving layer contains a water-soluble polymer, and the water-soluble polymer is represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3. 10 to 50 parts by weight of a monomer selected from quaternary salt monomers and 1 to 30 parts by weight of a monomer represented by Chemical formula 4, and further acrylamide, methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide as a water-soluble monomer, Diacetone acrylamide, N-methylol acrylamide, 2
-Hydroxyethyl (meth) acrylate, a water-soluble polymer obtained by copolymerizing a monomer selected from N-vinylpyrrolidone in the range of 20 to 80 parts by weight, and an epoxy curing agent or triazine together with the water-soluble polymer. The water-soluble polymer 10
A crosslinked water-soluble polymer obtained by applying a liquid mixed in an amount of 0.1 to 30 parts by weight to 0 part by weight onto the support and drying the solution, The object of the present invention is achieved by using a recording medium.

In the chemical formula ₁ , R ₁ represents hydrogen or a methyl group, and Q represents oxygen or an NH group. R ₂ , R ₃ , R ₄
Represents a methyl or ethyl group and may be the same or different. X represents a halogen ion, a sulfonate ion, an alkylsulfonate ion, an acetate ion, or an alkylcarboxylate ion. N is 2 or 3
Represents the integer.

In Chemical Formula 2, R ₅ , R ₆ and R ₇ represent a methyl or ethyl group and may be the same or different.
X is the same as X in Chemical formula 1.

In the chemical formula 3, R ₈ , R ₉ and R ₁₀ represent a methyl, ethyl or allyl group and may be the same or different. X is the same as X in Chemical formula 1.

In the chemical formula 4, R ₁₁ and R ₁₂ represent hydrogen or a methyl group and may be the same or different. R ₁₃ represents hydrogen or a carboxylic acid group.

In the constitution of the above water-soluble polymer,
The monomer selected from Chemical formula 3 is characterized in that it is a quaternary salt, and the solubility in water of the polymer obtained by introducing such a monomer component into the copolymer composition in the range of 10 parts by weight or more and 50 parts by weight or less. It also has the function of improving the fixing property and water resistance of the ink for ink jet recording.

That is, in general ink for ink jet recording, an acid dye having a sulfonic acid group having good water solubility or an edible pigment is mainly used, and a polymer having a quaternary base is used on the recording medium. If present, it is considered that the polymer and the dye are chemically bonded by counter ion exchange, and as a result, the action of enhancing the fixability or water resistance of the recorded image can be exhibited.

The composition ratio of the quaternary salt type monomer selected from the chemical formulas 1 to 3 introduced into the water-soluble polymer as a copolymerization component in the water-soluble polymer is 10 parts by weight or more.
It is necessary to select within the range of 0 parts by weight or less, and 1
When the composition ratio is less than 0 parts by weight, the fixability to the dye in the ink is not sufficient, and washing the recorded image with water results in easy erasing of the image. Further, when the composition ratio exceeds 50 parts by weight, the film formed of such a water-soluble polymer has a very high hygroscopic property, and the surface becomes sticky or blocking easily occurs in a high humidity atmosphere. Cause problems.

Further, by introducing a carboxyl group-containing monomer represented by Chemical formula 4 into the water-soluble polymer according to the present invention in the range of 1 to 30 parts by weight into the water-soluble polymer, an epoxy curing agent or a triazine-based compound is introduced. The reaction site for the curing agent can be provided in the polymer,
When an epoxy curing agent or a triazine-based curing agent is added together with such a water-soluble polymer to form a film, the ink receiving layer having excellent water resistance can be formed by the progress of the crosslinking reaction. Preferred examples of such monomers include acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Examples thereof include, but are not limited to, itaconic acid and fumaric acid.

When the composition ratio of the monomer represented by Chemical formula 4 in the water-soluble polymer is less than 1 part by weight, the degree of crosslinking by the curing agent becomes insufficient and a water resistant film cannot be formed. Absent. Further, when the amount is more than 30 parts by weight, the effect of fixing the ink by the quaternary base is increased by the anionic property by the carboxyl group, so that the fixing property of the dye in the ink receiving layer is hindered and the dye is easily washed off with water. It is not preferable because it will end up.

In the case where the ink receiving layer contains a water-soluble polymer in which the monomer component represented by Chemical formula 4 is introduced into the water-soluble polymer in an amount of 1 to 30 parts by weight, an epoxy type curing agent or By using a triazine-based curing agent in combination, the water-soluble polymer can be cured, and the water resistance of the recorded image can be dramatically improved, blocking can be suppressed, surface stickiness can be prevented, and the ink absorption rate and absorption can be improved. It is particularly preferable because the effect of increasing the capacity is recognized.

Preferred examples of the epoxy-based curing agent include compounds represented by Chemical formulas 5 to 13, and examples of the triazine-based curing agent include those represented by Chemical formulas 14 and 15. .

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7] In Chemical formula 7, n represents an integer of 2 or 3.

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12] In Chemical formula 12, m represents an integer from 1 to 22.

[0027]

[Chemical 13] In Chemical formula 13, q represents an integer of 1 to 11.

[0028]

[Chemical 14]

[0029]

[Chemical 15]

The mixing ratio of the above epoxy-based curing agent or triazine-based curing agent to the water-soluble polymer is 0.1 to 30 parts with respect to 100 parts by weight of the water-soluble polymer.
It is preferable to select from the range of parts by weight, and if the mixing ratio is less than the above range, the water-soluble polymer film itself forming the ink receiving layer formed by the introduction of such a curing agent is not sufficiently crosslinked, and the water resistance of the film is reduced. Is insufficient,
It is not preferable because blocking is likely to occur. On the other hand, when such a curing agent is used in an amount exceeding 30 parts by weight, a sufficiently water-resistant polymer film is formed, but it becomes difficult to absorb the ink, and the overflowing ink is used as a guide for the ink jet recording apparatus. It is not preferable because it causes a problem of polluting the roller and a problem that the print quality is significantly deteriorated.

A mixture of the water-soluble polymer and the above curing agent may be applied as a coating liquid on a support such as paper or film and dried at a temperature of 50 ° C. to 130 ° C. Preferably, at a temperature lower than this, the crosslinking reaction between the curing agent and the water-soluble polymer does not proceed,
If the drying temperature is higher than 0 ° C, side reactions other than the curing reaction may occur and the coating may be colored, which is not preferable. Also,
If necessary, it is also preferable to further allow the curing reaction to proceed to a more complete degree by allowing it to stand at room temperature or higher for several days to one week after drying.

Acrylamide, methacrylamide, N, N-dimethylacrylamide, N are used as the third copolymerization component introduced into the water-soluble polymer according to the present invention.
A monomer selected from isopropyl acrylamide, diacetone acrylamide, N-methylol acrylamide, 2-hydroxyethyl (meth) acrylate and N-vinylpyrrolidone in the range of 20 to 80 parts by weight as a copolymerization component in the water-soluble polymer. It is necessary to copolymerize. By introducing these copolymerization components, it is said that the ink absorption of the formed film is increased, and in particular, the absorption of alcohols such as glycerin, isopropyl alcohol, and diethylene glycol that are usually added to the ink and other organic solvents are increased. Exerts a desirable effect. Moreover,
By introducing such a copolymerization component, the stickiness of the film can be suppressed, blocking can be prevented, the dot diameter of the printed part can be adjusted appropriately, the uniformity of the solid part can be improved, the sharpness of the image can be improved, the printing gloss and the surface can be improved. It works very effectively to improve gloss. When the composition ratio of the third component in the water-soluble polymer as described above is less than 20 parts by weight, it is not preferable because such a preferable effect is difficult to appear.
If the amount is more than parts by weight, the fixing property of the dye in the ink is impaired and the above-mentioned effects are not exhibited, which is not preferable.

The object relating to the present invention is achieved by introducing the water-soluble polymer having the above-mentioned structure into the ink receiving layer. The various monomers shown above as the copolymerization component in the water-soluble polymer are achieved. In addition to the above, it is also preferable to introduce various monomers so that the printing characteristics suitable for the characteristics of the ink jet recording apparatus used are exhibited. Such other monomer components include, for example, (meth) acrylic acid alkyl ester, styrene sulfonate, styrene, allyl sulfonate, methallyl sulfonate, vinyl acetate, etc. It can be used regardless of the purpose.

The water-soluble polymer solution is used alone to apply it to the surface of a support such as paper or film to form an ink-receiving layer, thereby improving good print quality and water resistance of recorded images. It is possible to achieve the object of the invention, and further, in addition to the water-soluble polymer, various water-soluble polymers, latexes, surfactants, inorganic pigments, polymer particles, and other additives are mixed or layered. It is also possible to do so. Alternatively, it is also possible to use a method in which the base paper is contained in the pulp slurry at the time of papermaking instead of the coating liquid.

For example, a water-soluble polymer such as polyvinyl alcohol, starch, carboxymethyl cellulose, cationized gelatin, cationized polyvinyl alcohol, and cationized starch may be mixed with the water-soluble polymer and used as a coating solution. In addition, addition of latex such as various acrylic latex, SBR latex, polyvinyl acetate latex, surfactant such as polyalkylene oxide, inorganic pigment such as alumina sol and cationic colloidal silica, polymer such as micron-sized polystyrene fine particles Inclusion of particles and the like in the ink receiving layer is also carried out for various purposes.

When the water-soluble polymer is used as a coating liquid, the amount of the water-soluble polymer in the ink receiving layer formed on the surface of the support is 0.1 g / m ² to 20 g / m ² in terms of solid content. It is preferable that the coating is performed in the range of ² , and
Good ink absorption is exhibited at a coating amount of 1 g / m ² or more. When the coating amount is more than 20 g / m ² , the function as an ink receiving layer does not change at all, but problems such as easy curling of the recording medium may occur.

As the water-soluble polymer disclosed in the present invention, a copolymer polymer having the above-mentioned composition is preferably used, but a polymer containing any component in the copolymer component as a graft chain is also preferable. used. For example, if a monomer component selected from Chemical Formulas 1 to 3 is 10 to 5
In the presence of a water-soluble polymer obtained by copolymerizing 0 part by weight and a monomer component represented by Chemical Formula 4 in the range of 1 to 30 parts by weight,
As a second monomer, a method of forming a graft polymer by polymerizing 20 to 80 parts by weight of the above-mentioned component monomers such as acrylamide and methacrylamide, or preliminarily synthesizing a macromonomer formed from any of the monomer components. Alternatively, the graft polymer can be synthesized by copolymerizing this with another monomer. The composition of the trunk or the branch portion in such a graft polymer can be synthesized in various combinations, but by using the graft polymer, the wettability of the ink-receiving layer surface to ink is appropriately controlled and the dot diameter is adjusted to a desired size. Controlling is also preferably performed. Such graft polymers can be used as homopolymers, copolymers, various water-soluble polymers described above, latexes, surfactants,
It can be used together with various additives such as inorganic pigments and polymer fine particles.

The ink for printing using the recording material for ink jet obtained by the present invention is not particularly limited as long as it is a water-based ink, but it is particularly preferable for the purpose of sufficiently securing the water resistance of a recorded image. Inks containing acid dyes and food dyes are preferably used.

[0039]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 Trimethylammonium propyl acrylamide chloride (monomer of Chemical formula 1) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser tube.
40 g of DMAPAA-Q), 10 g of acrylic acid (monomer of Chemical formula 4) and 50 g of acrylamide were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and a water bath at 50 ° C was used. Stir under nitrogen atmosphere above. 0.9 grams of V-50 on this
(2,2'-azobis (2-methylpropionamidine) dihydrochloride manufactured by Wako Pure Chemical Industries, Ltd.) was added to initiate polymerization, and heating and stirring was continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Synthesis Example 2 Trimethylammonium propyl acrylamide chloride (manufactured by Kojin, DMAP) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
45 g of AA-Q), 10 g of methacrylic acid (monomer of Chemical formula 4), and 45 g of diacetone acrylamide were introduced, and 200 g of distilled water and 100 g of ethanol were added to dissolve them, and the mixture was dissolved in a water bath at 50 ° C. The mixture was stirred under a nitrogen atmosphere. To this, 0.9 g of V-50 (Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to start polymerization, and the mixture was heated and stirred for 4 hours on a water bath. Continued. A colorless, viscous polymer solution was obtained.

Synthesis Example 3 Trimethylammonium propyl acrylamide chloride (manufactured by Kojin, DMAP) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
35 g of AA-Q), 8 g of methacrylic acid, and 57 g of N, N-dimethylacrylamide were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and the mixture was dissolved in a water bath at 50 ° C. under a nitrogen atmosphere. It was stirred. 0.9 grams of V-50 (Wako Pure Chemical, 2,
2'-azobis (2-methylpropionamidine) dihydrochloride) was added to initiate polymerization, and 4
The heating and stirring were continued for an hour. A colorless, viscous polymer solution was obtained.

Synthesis Example 4 Trimethylammonium propyl acrylamide chloride (manufactured by Kojin Co., Ltd., DMAP) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
35 grams of AA-Q), 15 grams of methacrylic acid,
Further, 50 g of N-vinylpyrrolidone was introduced, 200 g of distilled water and 100 g of ethanol were added to dissolve the solution, and a 2N aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7.0, followed by heating at 50 ° C. The mixture was stirred on a water bath under a nitrogen atmosphere. To this, 0.9 g of V-50 (Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to start polymerization, and the mixture was heated and stirred for 4 hours on a water bath. Continued. A colorless, viscous polymer solution was obtained.

Synthesis Example 5 In a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, trimethylammonium propyl acrylamide chloride (manufactured by Kojin, DMAP) was used.
45 g of AA-Q), 5 g of methacrylic acid, and 50 g of 2-hydroxyethyl methacrylate were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and the mixture was stirred on a water bath at 50 ° C. under a nitrogen atmosphere. did. 0.9 grams of V-50 (Wako Pure Chemical Industries,
2,2'-azobis (2-methylpropionamidine)
Dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Synthesis Example 6 Into a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 4 parts of ethyl trimethylammonium methacrylate chloride (monomer of Chemical formula 1) was added.
5 g of methacrylic acid, 5 g of methacrylic acid and 50 g of acrylamide were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and the mixture was stirred in a water bath at 50 ° C. under a nitrogen atmosphere. 0.9 grams of V-5
0 (manufactured by Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Synthesis Example 7 In a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux condenser, 40 g of ethyltrimethylammonium methacrylate methacrylate, 10 g of methacrylic acid, and N, N were added. -Introducing 50 g of dimethylacrylamide, adding 200 g of distilled water and 100 g of ethanol to dissolve it, and stirring the mixture in a water bath at 50 ° C under a nitrogen atmosphere. 0.9 grams of V-5
0 (manufactured by Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Synthesis Example 8 In a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 40 g of ethyltrimethylammonium methacrylate methacrylate, 10 g of methacrylic acid, and N, N were added. -Introducing 30 grams of dimethyl acrylamide, 20 grams of diacetone acrylamide, 200 grams of distilled water and 10 grams of ethanol.
0 g was added and dissolved, and the mixture was stirred on a water bath at 50 ° C. under a nitrogen atmosphere. To this, 0.9 g of V-50 (Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to start polymerization, and the mixture was heated and stirred for 4 hours on a water bath. Continued. A colorless, viscous polymer solution was obtained.

Synthesis Example 9 40 g of diallyldimethylammonium chloride (monomer of Chemical formula 3) and 10 g of methacrylic acid were placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. Further, 20 g of N, N-dimethylacrylamide and 30 g of acrylamide were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and the mixture was stirred on a water bath at 50 ° C under a nitrogen atmosphere. 0.9 grams of V-50 (Wako Pure Chemical Industries,
2,2'-azobis (2-methylpropionamidine)
Dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Synthesis Example 10 4-vinylbenzyltrimethylammonium chloride (monomer of Chemical formula 2) was added to a 4-liter 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux condenser.
2 g, methacrylic acid 8 g, N, N-dimethylacrylamide 30 g, 2-hydroxyethyl methacrylate 20 g were introduced, and distilled water 200
Gram and 100 grams of ethanol are added and dissolved,
The mixture was stirred under a nitrogen atmosphere on a water bath at 50 ° C. 0.9 for this
Gram V-50 (manufactured by Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Comparative Synthesis Example 1 Trimethylammonium propylacrylamide chloride (manufactured by Kojin Co., Ltd., DMAP) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
80 g of AA-Q) and 20 g of acrylamide were introduced, 200 g of distilled water and 100 g of ethanol were added and dissolved, and the mixture was stirred on a water bath at 50 ° C. under a nitrogen atmosphere. 0.9 grams of V-50 (Wako Pure Chemical Industries,
2,2'-azobis (2-methylpropionamidine)
Dihydrochloride) was added to initiate polymerization, and heating and stirring were continued for 4 hours on a water bath. A colorless, viscous polymer solution was obtained.

Comparative Synthesis Example 2 Trimethylammonium propylacrylamide chloride (manufactured by Kojin Co., Ltd., DMAP) was placed in a 1-liter 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
50 grams of AA-Q) and 50 grams of N-vinylpyrrolidone
Introduce 200 grams of distilled water and 1 gram of ethanol
00 g was added and dissolved, and the mixture was stirred on a water bath at 50 ° C under a nitrogen atmosphere. 0.9 g of V-50 (Wako Pure Chemical Industries, 2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added to this to initiate polymerization,
Heating and stirring were continued for 4 hours on the water bath. A colorless, viscous polymer solution was obtained.

Example 1 The polymer solution obtained in each of Synthesis Examples 1 to 10 was added in a solid content of 10
It is weighed out so as to be a weight part, and further, as an epoxy curing agent, Denacol EX-521 (manufactured by Nagase Chemical Industry Co., Ltd.
= 3 compounds) and the total solid concentration is 12
The solution was made into a weight% solution, and the pH of the solution was adjusted to 8.0 to obtain a coating liquid. These coating liquids were applied to a 100-micron-thick PET film that had been subjected to an aqueous undercoat treatment to give a dry thickness of 1
It was coated so as to have a thickness of 0 micron, and was dried by heating in a dryer adjusted to 75 ° C. for 3 hours. The obtained sheet was printed using an ink jet printer pixel jet manufactured by Canon Inc., and the results shown in Table 1 and Table 2 were obtained. The image density was evaluated for each color of black (Bk), yellow (Y), magenta (M) and cyan (C).

Example 2 In the same manner as in Example 1 except that the hydroxydichlorotriazine sodium salt shown in Chemical formula 14 was used instead of the epoxy curing agent, the same good result was obtained.

Example 3 The polymer solution obtained in each of Synthesis Examples 1 to 10 was used as a solid content.
It is weighed out so as to be a weight part, and further, as an epoxy curing agent, Denacol EX-512 (manufactured by Nagase Kasei Kogyo,
= 2 compounds) and the total solid concentration is 12
A solution of 10% by weight is added, 0.08 parts by weight of Newcol 707 (manufactured by Nippon Emulsifier) as a polyethylene glycol-based surfactant, and 0.02 parts by weight of 5 micron monodisperse polystyrene fine particles as a matting agent are added, and the pH of the solution
Was adjusted to 8.0 to obtain a coating liquid. These coating solutions have a dry film thickness of 12 on RC paper laminated with polyethylene.
It was coated to a micron size and heated and dried for 3 hours in a dryer adjusted to 75 ° C. The obtained sheet was printed using an ink jet printer pixel jet manufactured by Canon Inc., and the results shown in Tables 3 and 4 were obtained.

Comparative Example 1 The polymer solutions obtained in Comparative Synthesis Examples 1 and 2 were weighed so that the solid content was 10 parts by weight, and distilled water was added to make a total solid content concentration of 12% by weight. PH was adjusted to 8.0 to prepare a coating solution. 10 of these coating liquids
Coated to a dry film thickness of 10 microns on a 0-micron-thick aqueous PET film that has been subjected to an undercoating treatment, and then at 75 ° C.
It heat-dried for 3 hours in the dryer adjusted to. The obtained sheet was printed using an ink jet printer pixel jet manufactured by Canon Inc., and the results shown in Table 1 and Table 2 were obtained.

Comparative Example 2 The polymer solutions obtained in Comparative Synthesis Examples 1 and 2 were weighed so that the solid content was 10 parts by weight, and distilled water was added to make the total solid content concentration a 12% by weight solution. 0.08 parts by weight of Newcol 707 (manufactured by Nippon Emulsifier) as a glycol-based surfactant and 0.02 parts by weight of 5 micron monodisperse polystyrene fine particles as a matting agent were added to adjust the pH of the solution to 8.0. Coating solution. These coating solutions were coated on polyethylene-laminated RC paper so that the dry film thickness would be 12 microns, and heated and dried for 3 hours in a dryer adjusted to 75 ° C. The obtained sheet was printed using an ink jet printer pixel jet manufactured by Canon Inc., and the results shown in Tables 3 and 4 were obtained.

[0057]

[Table 1]

In Table 1, water resistance was evaluated using the printed sample as 4
It was immersed in warm water of 0 ° C., and when the printed image did not change, it was marked with ◯, and when not, it was marked with x. In addition, the evaluation of the uniformity of the solid portion was evaluated by visually observing the degree of print unevenness when a uniform solid image of each color was printed.

[0059]

[Table 2]

In Table 2, the ink absorbency was evaluated by touching the printed surface immediately after printing with a finger, marking the case where the ink was dried and the ink was not transferred to the finger, and marked the case where the ink was transferred. For the evaluation of blocking property, sample before printing or after printing
The samples were placed in a room where the temperature and humidity were adjusted to 5 ° C. and 80% and left, and left for 24 hours, and the case where the sample surfaces adhered after 24 hours was marked with X, and the case where the samples were easily separated without bonding was marked with ◯. The dot reproducibility was evaluated by observing the printed dots with an optical microscope and evaluating the dot diameter and the sharpness of the contour. When there is a change in the dot diameter due to ink bleeding between adjacent dots, or when there is a shade in the color density within the dots, mark x, and when there is no dot bleed and a uniform color density and dot diameter are shown. Was marked as ○.

[0061]

[Table 3]

In Table 3, the evaluation of water resistance and the uniformity of the solid portion were carried out in the same manner as in Table 1.

[0063]

[Table 4]

In Table 4, the evaluation of ink absorbency, the evaluation of blocking property, and the evaluation of dot reproducibility were performed in the same manner as in Table 2.

[0065]

INDUSTRIAL APPLICABILITY According to the present invention, a recording medium for an ink jet having excellent ink absorbability, sharp dots, and uniform solid area and good print quality can be obtained, and the water resistance of a printed image is significantly improved. It is possible to obtain a recording medium having an improved quality.

Claims (1)

[Claims] 1. An ink jet recording medium, wherein a water-based ink containing a water-soluble dye is used to form a recorded image on at least one ink receiving layer provided on a support, the ink receiving layer being water-soluble. 10 to 50 parts by weight of a monomer containing a polymer, wherein the water-soluble polymer is a monomer selected from the quaternary salt monomers represented by Chemical formula 1, Chemical formula 2, and Chemical formula 3.
1 to 30 parts by weight of the monomer represented by
A monomer selected from N, N-dimethyl acrylamide, N-isopropyl acrylamide, diacetone acrylamide, N-methylol acrylamide, 2-hydroxyethyl (meth) acrylate and N-vinylpyrrolidone is copolymerized in the range of 20 to 80 parts by weight. And a water-soluble polymer obtained by adding an epoxy-based curing agent or a triazine-based curing agent together with the water-soluble polymer in an amount of 0.1 to 3 with respect to 100 parts by weight of the water-soluble polymer.
A recording medium for an ink jet, which is the crosslinked water-soluble polymer obtained by applying a liquid mixed in an amount of 0 part by weight onto the support and drying the liquid. [Chemical 1] (In Chemical Formula 1, R ₁ represents hydrogen or a methyl group, Q represents an oxygen or NH group. R ₂ , R ₃ and R ₄ represent a methyl or ethyl group and may be the same or different. X represents a halogen ion, a sulfonate ion, an alkyl sulfonate ion, an acetate ion, or an alkyl carboxylate ion, and n represents an integer of 2 or 3.) (In Chemical Formula 2, R ₅ , R ₆ and R ₇ represent a methyl group or an ethyl group and may be the same or different. X is the same as X in Chemical Formula 1.) (In Chemical Formula 3, R ₈ , R ₉ and R ₁₀ represent a methyl, ethyl or allyl group and may be the same or different. X
Is the same as X in Chemical formula 1. ) [Chemical 4] (Wherein R ₁₁ and R ₁₂ represent hydrogen or a methyl group,
It may be the same or different. R ₁₃ represents hydrogen or a carboxylic acid group. )