JP2001293948A - Ink jet recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording medium having excellent gloss feeling and ink water resistance of a printed part after recording on a surface of the medium at a low cost. SOLUTION: The ink jet recording medium comprises an accepting layer containing a cationic silica obtained by polymerizing a quaternary ammonium salt compound having an ethylenic unsaturated group in a silica sol on a base material. The recording medium also comprises an accepting layer containing a cationic silica obtained by polymerizing an amine compound having an ethylenic unsaturated group in a silica sol and at least one type of polymer compound selected from the group consisting of an amine cyclized polymer, amine condensation polymer and polyamine derivative on a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording medium, and more particularly, to an ink jet recording medium having good glossiness on the surface of the recording medium and good water resistance of the ink in a printed portion after recording.

[0002]

2. Description of the Related Art An ink jet recording system is a system in which ink droplets ejected from a nozzle at a high speed are adhered to a recording material for recording, and has features such as easy full-color printing and low printing noise. . In this method, conditions such as not causing clogging of the ink jet nozzle and having a vivid color tone are required.Therefore, the dyes of the ink used are many acid dyes and direct dyes, and dyes having excellent water resistance are not necessarily required. Currently, it is not possible to select.

[0003] Ink jet recording papers are commercially available, such as high quality papers devised so as to be rich in ink absorptivity and coated papers whose surfaces are coated with a porous pigment such as silica. When these papers are immersed in water or the like, there is a problem that ink oozes out. Therefore, there is a strong demand for ink jet recording papers having excellent water resistance.

[0004] Coated paper coated with a mixed solution of a porous pigment such as silica and a cationic polymer for the purpose of improving water resistance is commercially available. However, a porous pigment such as silica and a cationic polymer are commercially available. However, there is a problem that a porous pigment such as silica aggregates during mixing, the particle diameter increases, and the glossiness of the recording medium surface decreases. Particularly, strong cationic polymers having high ink fixing performance, such as diallyldimethylammonium salt polymer, dimethylamine-epichlorohydrin condensed polymer, and polyacrylpolyamine-epichlorohydrin, have a strong tendency.

For the purpose of improving glossiness, it has been attempted to pulverize aggregates after mixing a porous pigment such as silica with a cationic polymer over a long period of time to form fine particles. Is difficult and the cost required for grinding is high. Therefore, there is a strong demand for cationized silica microparticles of ink jet recording paper that can be manufactured at low cost without re-milling, and have both excellent glossiness on the surface of the recording medium and excellent water resistance of the ink in the printed area after recording. I have.

JP-A-11-58942 discloses that inorganic fine particles having an acrylic group bonded by a covalent bond by the reaction of inorganic fine particles with a silane coupling agent having an acrylic group are synthesized. Inorganic fine particles comprising an organic cationic polymer covalently bonded to inorganic fine particles via a silane coupling agent by copolymerizing inorganic fine particles having a quaternary ammonium salt with inorganic fine particles having a quaternary ammonium salt. Are described.

However, since the above-mentioned invention uses an expensive silane coupling agent having an acrylic group, and the reaction steps are complicated and the number of steps is large, the production cost of the obtained cationic inorganic fine particles is considerably high. Guessed.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and provides an inexpensive ink jet recording medium which is excellent in both glossiness on the surface of the recording medium and ink water resistance of a printed portion after recording. is there.

[0009]

The present invention employs the following configuration to solve the above-mentioned problems. That is, the first invention of the present invention is "an ink jet recording material containing a cationized silica obtained by polymerizing a quaternary ammonium salt compound having an ethylenically unsaturated group in a silica sol in a receptor layer". .

[0010] The second invention of the present invention is directed to "a silica sol containing a quaternary ammonium salt compound having an ethylenically unsaturated group in an amount of 0.1 part by weight per 100 parts by weight of silica.
To 40 parts by weight according to the first aspect of the present invention ".

[0011] The third invention of the present invention relates to a method comprising the steps of: "cationizing silica obtained by polymerizing an amine compound having an ethylenically unsaturated group in a silica sol, amine-based cyclized polymer, amine-based condensed polymer, And an ink jet recording medium containing at least one polymer compound selected from the group consisting of polyamine derivatives in the receptor layer.

The fourth invention of the present invention is directed to "(a) polymerization of an amine compound having an ethylenically unsaturated group in the cationized silica, an amine-based cyclized polymer, an amine-based condensation polymer, The sum of the weight with the polyamine derivative is 0.1 to 40 parts by weight with respect to 100 parts by weight of silica, and (b) the weight of the amine cyclized polymer, the amine polycondensate and the polyamine derivative is The sum is 1 to 10,000 parts by weight based on 100 parts by weight of a polymerized amine compound having an ethylenically unsaturated group. "

The fifth invention of the present invention relates to "an ink jet recording material according to the third invention of the present invention, wherein the amine cyclized polymer is a homopolymer and / or a copolymer of diallyldimethylammonium salt". is there.

The sixth invention of the present invention relates to an inkjet recording method according to the third invention, wherein the amine-based condensation polymer is a dimethylamine-epichlorohydrin condensation polymer and / or a dicyandiamide-polyalkylenepolyamine condensation polymer. Body ".

[0015] A seventh invention of the present invention is the "ink jet recording material according to the third invention of the present invention, wherein the polyamine derivative is a polyacrylpolyamine / epichlorohydrin reactant".

An eighth invention of the present invention is the "ink-jet recording material according to the first or third invention of the present invention, wherein the silica sol has a pH of 6 or less".

The present inventors have conducted various studies to obtain an inexpensive ink jet recording medium which is excellent both in glossiness on the surface of the recording medium and ink water resistance in a printed portion after recording. As a result, when the pH of the silica sol exceeds 6, if the pH is adjusted to 6 or less with an acid or a cation exchange resin, a quaternary ammonium salt compound having an ethylenically unsaturated group in the silica sol can be easily mixed. Then, by continuously polymerizing a quaternary ammonium salt compound having an ethylenically unsaturated group in the silica sol, fine particles of the cationized silica sol can be easily obtained without aggregation of the silica in the silica sol. And completed the first invention of the present invention.

Next, diallyldimethylammonium salt polymer, dimethylamine-epichlorohydrin condensed polymer, polyacrylpolyamine-epichlorohydrin, etc., as described in the prior art, are used in silica sol by the same method as in the first invention. It is also conceivable to carry out the polymerization by the method described above. Therefore, instead of the amine compound having an ethylenically unsaturated group, which is a raw material component of the cationized silica sol,
Cyclopolymerization or polycondensation of diallyldimethylammonium chloride or dimethylamine / epichlorohydrin was attempted in silica sol. As a result, it was found that the polymerization efficiency was extremely low. In addition, as in the prior art, an aqueous solution of polydiallyldimethylammonium chloride or an aqueous solution of a polycondensed dimethylamine / epichlorohydrin polymer was directly mixed into the silica sol while dripping, but the entire system gelled and the fluidity disappeared. However, even when pulverized, only cationized silica having a larger particle size than the initial silica sol particle size was obtained, and it was found that it was impossible to obtain a recording medium having a good surface glossiness.

As a result of further intensive studies, an amine compound having an ethylenically unsaturated group was polymerized in the silica sol,
By cationizing the particle surface, an aqueous solution of an amine-based cyclized polymer, an amine-based condensed polymer, and a polyamine-based derivative can be dropped into a cationized silica sol and mixed without gelation. Heading, the second of the present invention
Completed the invention.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The recording layer of the present invention will be described in detail below. The quaternary ammonium salt compound having an ethylenically unsaturated group used in the first invention of the present invention is a compound represented by the following general formulas (1), (2) and (3). However, the present invention is not particularly limited to these.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

In the formula, R _{1 ,} R _{5 and} R ₆ are each a hydrogen atom or C ₁ -C
_Represents an alkyl group of ₄ , preferably a hydrogen atom or a methyl group. R _{2 ,} R _{3 ,} R _{4 ,} R _{6 ,} R _{7 ,} R _{8 ,} R ₁₀ are a hydrogen atom or a C ₁ -C ₁₀ alkyl group, a benzyl group, an allyl group,
It represents an acetyl group or the like, and is preferably a hydrogen atom or a methyl group. A represents an oxygen atom or a nitrogen atom. B represents a divalent linking group, for example, an ethylene group, a propylene group, or a phenylene group. X ⁻ represents an anion, for example, a halogen ion or an alkyl sulfate ion. n represents an integer of 1 to 4.

The general formulas (1), (2) and (3)
Examples of the monomer represented by are shown below.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

The silica sol used in the first invention of the present invention is not particularly limited in the method for producing the silica sol and the particle size. Silica sol with small particle size is cationic polymer
When the present invention is used for a silica sol having a small particle diameter, it is particularly suitable when the present invention is used for a silica sol having a small particle diameter because of a strong tendency to agglomerate when mixed. Regarding the particle state of the silica sol, there is no problem in either the primary particle system or the secondary particle system.

In the polymerization of the cationized silica used in the first invention of the present invention, a quaternary silica having an ethylenically unsaturated group is used.
The amount of the quaternary ammonium salt compound is 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of silica. If the amount of the quaternary ammonium salt compound having an ethylenically unsaturated group is more than 40 parts by weight, the resulting cationized silica aggregates to increase the particle diameter, and the glossiness of the recording medium surface is reduced. Further, the pores between the cationized silica particles become smaller, making it difficult to obtain an ink absorption rate, and lowering the water resistance of the receiving layer itself. On the other hand, if the amount of the quaternary ammonium salt compound having an ethylenically unsaturated group is less than 0.1 part by weight, the water resistance of the printed portion after printing is insufficient, so that when wet with water, the ink elutes into the water. The printed part may disappear.

Further, when polymerizing a quaternary ammonium salt compound having an ethylenically unsaturated group in a silica sol,
Other compounds having an ethylenically unsaturated group, such as butyl acrylate, butyl methacrylate, butoxyethyl acrylate, 1,6-hexanediol diacrylate, vinyl benzene, divinyl benzene, styrene, and vinyl acetate may also be copolymerized. it can.

The polymerization method used in the present invention is a general radical polymerization method in which polymerization is initiated with a radical polymerization initiator and a redox initiator system. As the polymerization initiator, a radical polymerization initiator such as potassium persulfate, ammonium persulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride can be used. The polymerization procedure is not particularly limited, but the amine compound having an ethylenically unsaturated group is stirred and mixed in the silica sol, and the temperature is adjusted to 60 to 70 ° C. under stirring and a nitrogen stream, and the mixture is stirred for about 1 hour. Thereafter, a radical polymerization initiator is added, and after stirring for several hours, the polymerization is terminated. The pH range of the silica sol used in the present invention is p
H6 or less. Preferably, the pH is 4 or less.

As the amine compound having an ethylenically unsaturated group used in the third invention of the present invention, the compounds of the above-mentioned general formulas (1) to (3) can be used, and the following general formula (4) ), (5) and (6). However, the substituents of R _{1 to} R ₁₀ used in the general formulas (4) to (6) are the same as those in the general formulas (1) to (3).
The meaning is the same as that used in.

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

The general formulas (4), (5) and (6)
Examples of the monomer represented by are shown below.

[0040]

Embedded image

[0041]

Embedded image

The silica sol used in the second invention of the present invention is the same as that of the first invention.

The polymerization method used in the second invention is the same as that in the first invention.

The amine-based cyclized polymer, amine-based condensed polymer and polyamine-based derivative used in the third invention of the present invention are not limited to the polymers exemplified below. Conventionally known ones are used. For example, homopolymers and copolymers of diallyldimethylammonium salt, dimethylamine-epichlorohydrin condensation polymers, dicyandiamide-polyalkylenepolyamine condensation polymers, and polyacrylpolyamine-epichlorohydrin reactants.

In the polymerization of the cationized silica used in the fourth invention of the present invention, an amine compound polymer having an ethylenically unsaturated group in the cationized silica, an amine-based cyclized polymer and an amine-based condensation polymer are used. And the sum of the weights of the polyamine derivatives is 0.1 to 4 with respect to 100 parts by weight of silica.
0 parts by weight, preferably 0.3 to 30 parts by weight, and the total ratio of the weight of the amine-based cyclized polymer, amine-based condensation polymer and polyamine-based derivative is an amine compound polymer having an ethylenically unsaturated group 1 to 1000 for 100 parts by weight
0 parts by weight, preferably 10 to 1000 parts by weight.

The total amount of the amine compound polymer having an ethylenically unsaturated group, the amine-based cyclized polymer, the amine-based condensation polymer and the polyamine-based derivative was 10%.
If the amount is more than 40 parts by weight with respect to 0 parts by weight, the resulting cationized silica aggregates to increase the particle size, and the glossiness of the recording layer surface is reduced. The pores between the cationized silica particles become small, making it difficult to obtain an ink absorption rate, and reducing the water resistance of the receiving layer itself. On the other hand, when the amount of addition is 0.1.
If the amount is less than 3 parts by weight, the water resistance of the printed portion after printing becomes insufficient, and if water is applied to the printed portion, the ink in the printed portion may elute into the water and the recording may be lost.

If the amount of the amine compound polymer having an ethylenically unsaturated group is too small relative to silica, then the following addition of the amine-based cyclized polymer, amine-based condensation polymer and polyamine-based derivative occurs. The following adverse effects occur. Gelation occurs when the amine-based cyclized polymer, amine-based condensed polymer and polyamine-based derivative are added, and the glossiness of the surface of the produced recording medium is reduced. On the other hand, if the added amount of the amine-based cyclized polymer, amine-based condensed polymer and polyamine-based derivative is too small, the water resistance of the printed portion after printing becomes insufficient, and when the water is applied to the printed portion, the ink in the printed portion becomes insoluble. The record may be partially eluted in water and the record may bleed.

As the binder resin used in the present invention, the above-mentioned cationic resin has the same effect, but other known water-soluble resins can also be used. For example, as a water-soluble resin, polyvinyl alcohol (hereinafter referred to as PVA), casein, soybean protein, synthetic proteins, starch, gelatin, cellulose derivatives such as carboxymethylcellulose and methylcellulose, styrene-butadiene copolymer, styrene-maleic anhydride Coated copolymer, ethylene-maleic anhydride copolymer, methyl methacrylate-butadiene copolymer conjugated diene polymer latex, acrylic polymer latex, styrene-vinyl acetate copolymer, etc. Known binder resins used can be used. These resins are used alone or in combination. It is not particularly limited to these.

The weight ratio of the solid content of the cationized silica to the binder resin used in the present invention is 10%.
2 to 100 parts by weight, preferably 5 to 5 parts by weight per 0 parts by weight
0 parts by weight. If the amount of the binder resin is more than 100 parts by weight, the pores between the cationized silica particles become small, and it is difficult to obtain an ink absorption rate. On the other hand, if the added amount of the binder resin is less than 2 parts by weight, large cracks may occur in the recording layer, and the image quality and print density may be reduced.

In order to increase the light fastness after fixing the ink, a light fastness improver such as an antioxidant and an ultraviolet absorber is added to the recording layer of the present invention, which is generally used as a means. Is also possible.

The antioxidants used in the present invention include:
Phenol type, phosphorus type which prevents oxidation by heat and oxygen,
And sulfur-based antioxidants. It is not particularly limited to these. For example, as phenolic antioxidants, monophenol-based: 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, bisphenol-based: 2,2 '-Methylenebis (4-methyl-6-t-butylphenol),
2,2'-methylenebis (4-ethyl-6-t-butylphenol) and the like. High molecular phenol type: 1,1,3-
Tris (2-methyl-4-hydroxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tocophenols and the like. Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate and the like. Examples of the phosphorus antioxidant include known ones such as triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (mono and / or dinonyl phenyl) phosphite, and diisodecyl pentaerythritol diphosphite. .

As the ultraviolet absorber used in the present invention, an organic or inorganic one is appropriately selected. In addition to these, conventionally known ones are used. It is not particularly limited to these. Salicylic acids (phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, etc.) and benzophenones (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, etc.), benzotriazole
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-ter
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, etc., cyanoacrylate (2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3) '-Diphenyl acrylate and the like).

As the inorganic ultraviolet absorber, zinc oxide,
Transition metal oxides such as cerium oxide, titanium oxide, and yttrium oxide are appropriately used. It is not particularly limited to these.

The ink jet recording medium of the present invention has an ink receiving layer provided on the following various supports. The support used in the present invention is not particularly limited, and may be transparent or opaque. For example, plastic films such as cellophane, polyethylene, polypropylene, soft polyvinyl chloride, hard polyvinyl chloride, polyester, etc., high quality paper, art paper, coated paper, cast coated paper, foil paper, kraft paper, polyethylene laminated paper, impregnated Conventionally known materials such as paper, metallized paper, synthetic paper and the like, such as paper, vapor-deposited paper, and water-soluble paper, are appropriately used.

In addition, various auxiliaries such as a dispersant, a thickener, a defoamer, a colorant, an antistatic agent and a preservative used in the production of general coated paper are appropriately added.

As the coating method, known coating means such as a bar coating method, a roll coating method, a blade coating method, an air knife coating method, a gravure coating method, a die coating method and a curtain coating method can be used. This is not the case.

The coating amount of the recording layer used in the present invention is not particularly limited, but is 3 to 60 g / m ² , preferably 10 to 50 g / m ² .

The ink used in the ink jet recording method of the present invention comprises, as essential components, a dye for forming an image and a liquid medium for dissolving or dispersing the dye.
If necessary, the composition is adjusted by adding various dispersants, surfactants, viscosity adjusters, specific resistance adjusters, pH adjusters, fungicides, dissolution or dispersion stabilizers for recording agents, and the like.

Examples of the recording agent used in the ink include direct dyes, acid dyes, basic dyes, reactive dyes, edible dyes, disperse dyes, oil dyes, and various pigments. Can be used without. The content of such a dye is determined depending on the type of the liquid medium component, the characteristics required for the ink, and the like, but in the case of the ink of the present invention, the composition as in the conventional ink, that is, There is no particular problem in use at a ratio of about 0.1 to 20% by weight.

Examples of the solvent for the ink used in the present invention include water and various water-soluble organic solvents, for example, alkyl alcohols having 1 to 4 carbon atoms such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol. , Ketones such as diacetone alcohol or ketone alcohols, polyethylene glycol,
Polyalkylene glycols such as polypropylene glycol, ethylene glycol, triethylene glycol,
Examples thereof include alkylene glycols having 2 to 6 alkylene groups such as diethylene glycol, amides such as dimethylformamide, ethers such as tetrahydrofuran, and lower alkyl ethers of polyhydric alcohols such as glycerin and triethylene glycol monomethyl ether.

In addition, it is also possible to add an antioxidant, an ultraviolet absorber and the like.

[0062]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples below, but it is needless to say that the present invention is not limited thereto. Unless otherwise specified, parts and% in the examples are solid contents excluding water, and represent parts by weight and% by weight, respectively.

<Example 1> (Preparation of cationized silica) In 500 g of silica sol A (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with a cation exchange resin), ]
20 g of a 50% aqueous solution of a cationic monomer (M-1) represented by the formula (1) is added, and the mixture is heated to an internal temperature of 70 ° C. under stirring and a nitrogen stream. Thereafter, 4 g of a 5% aqueous potassium persulfate solution was added, and the polymerization reaction was performed for 5 hours.
1) was obtained. The average particle diameter of the resulting cationized silica (S-1) was 120 nm, and no aggregation of particles was observed.

(Preparation of Coating Solution for Recording Layer) Next, 100 parts of the cationized silica (S-1) obtained above and PV
A (product name: PVA R-1130, manufactured by Kuraray Co., Ltd.) 25
Were mixed to prepare a recording layer coating liquid.

(Preparation of Inkjet Recording Sheet) A commercially available coated paper (trade name: OK coat, 127.9 g / m) was prepared by applying the above coating solution to a dry weight of 20 g / m ^2.
m ² , manufactured by Oji Paper Co., Ltd.) using a die coater and dried to produce an ink jet recording medium of the present invention. The water resistance of the printed portion of this ink jet recording medium and the glossiness of the recording medium surface were evaluated by the following methods. The evaluation results are shown in Table 1.

[Evaluation Method of Inkjet Recording Material] An ink jet printer (trade name: PM-
700C, manufactured by EPSON).

[Evaluation of Water Resistance] After standing for 24 hours after printing, water droplets were dropped. One minute later, the water droplets were wiped off, and the condition of the portion was visually evaluated in the following two stages. ：: almost no change visually. X: Ink was completely removed.

[Evaluation of Glossiness of Recording Material Surface] The glossiness of the recording material surface was visually evaluated for each of the black, yellow, cyan, and magenta printed portions from the lateral angle in the following three stages. . ：: The same level of glossiness as a silver halide color photograph was obtained. ：: Inferior to silver salt type color photograph, but high glossiness. Δ: Glossiness comparable to commercially available coated paper or art paper.

[Evaluation of Aggregation of Sol] The aggregation of the sol was visually evaluated in the following two stages. ：: No sol aggregation. X: There is sol aggregation.

<Example 2> In the preparation of the cationized silica of Example 1, silica sol B was used instead of silica sol A.
(Adjusted to a primary particle diameter of 11 nm, an average secondary particle diameter of 100 nm, a concentration of 20%, and a pH of 4 with an aqueous hydrochloric acid solution) using a cationic monomer represented by the compound [Chemical Formula 5] instead of the cationic monomer (M-1) (M- Using 2), cationized silica (S-2) was obtained. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

<Example 3> In the preparation of the cationized silica of Example 1, silica sol C was used instead of silica sol A.
(Synthetic amorphous silica having an average particle size of 3 μm (trade name: Nip
(sil HD-2, primary particle diameter 11 nm, manufactured by Nippon Silica Industry Co., Ltd.) was adjusted to pH 4 with an aqueous hydrochloric acid solution, pulverized and dispersed by a sand grinder, and further pulverized and dispersed by a pressure-type homogenizer to obtain an average particle diameter of 70 nm. The process of pulverization and dispersion was repeated until the concentration became 10%.)
Was used in place of the cationic monomer (M-1) to obtain a cationized silica (S-3) using the cationic monomer (M-3) represented by [Formula 6]. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

<Example 4> (Preparation of cationized silica) In 500 g of silica sol B (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with hydrochloric acid aqueous solution), 5 g of a 50% aqueous solution of the represented cationic monomer (M-6)
And heated to an internal temperature of 70 ° C. under stirring and a nitrogen stream. Thereafter, 4 g of a 5% aqueous potassium persulfate solution was added,
The polymerization reaction was performed for 5 hours. Next, 25 g of a 20% aqueous solution of a dimethyleneamine / epichlorohydrin condensed polymer was added with stirring to obtain a cationized silica (S-4) of the present invention. The resulting cationized silica (S-4) has an average particle size of 12
0 nm and no aggregation was observed. A recording medium of the present invention was produced in the same manner as in Example 1, except that the recording medium was used.
evaluated. Table 2 shows the evaluation results.

Example 5 (Preparation of cationized silica) In 500 g of silica sol A (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with a cation exchange resin),
10 g of a 50% aqueous solution of the cationic monomer (M-1) represented by the formula (1) is added, and the mixture is heated to an internal temperature of 70 ° C. under stirring and a nitrogen stream. Thereafter, 4 g of a 5% aqueous potassium persulfate solution was added, and a polymerization reaction was performed for 5 hours. Next, 25 g of a 20% aqueous solution of polydiallyldimethylammonium chloride was added with stirring to obtain a cationized silica (S-5) of the present invention.
The resulting cationized silica (S-5) has an average particle size of 1
20 nm and no aggregation was observed. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 2 shows the evaluation results.

<Comparative Example 1> In the preparation of the cationized silica of Example 1, only the silica sol A was used, but no cationization was performed. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

<Comparative Example 2> (Preparation of cationized silica) In 500 g of silica sol A (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with a cation exchange resin), 500 g of a cationic polymer (namely, When 50 g of a polymer of the cationic monomer (M-1) represented by Chemical Formula 4 (concentration: 25%) was added, the viscosity increased and aggregation was observed. The aggregate is pulverized and dispersed by a sand grinder, and has an average particle diameter of 800 nm.
Was prepared. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

Comparative Example 3 (Preparation of Cationized Silica) In 500 g of silica sol B (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with hydrochloric acid aqueous solution), 500 g of the cationic polymer (namely, The cationic monomer (M-
When 50 g of the polymer of 2) (concentration 25%) was added,
Viscosity increased and aggregation was observed. The aggregate was pulverized and dispersed by a sand grinder to prepare a cationized silica (SB) having an average particle diameter of 800 nm. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

Comparative Example 4 (Preparation of Cationized Silica) Silica Sol C (average particle size 3
μm synthetic amorphous silica (trade name: NipsilHD-
2, primary particle size 11 nm, manufactured by Nippon Silica Industry Co., Ltd.), adjusted to pH 4 with hydrochloric acid aqueous solution, pulverized and dispersed by a sand grinder, and repeated the pulverization / dispersion process until the average particle diameter becomes 70 nm, prepared at a concentration of 10%. 1000g
40 g of a cationic polymer (that is, a polymer of the cationic monomer (M-2) represented by Chemical Formula 5; concentration: 25%)
Was added, the viscosity increased and aggregation was observed. The aggregate was pulverized and dispersed by a sand grinder to prepare a cationized silica (SC) having an average particle diameter of 600 nm. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 1 shows the evaluation results.

<Comparative Example 5> (Preparation of cationized silica) A cationized silica (SD) was prepared in the same manner as in Example 4 except that the dimethylamine-epichlorohydrin polycondensate was not added. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 2 shows the evaluation results.

Comparative Example 6 (Preparation of Cationized Silica) Polydiallyldimethylammonium in 500 g of silica sol A (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with a cation exchange resin) When 50 g of a 20% aqueous chloride solution was added, the viscosity increased and aggregation was observed. The aggregate was pulverized and dispersed by a sand grinder to prepare cationized silica (SE) having an average particle diameter of 800 nm. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 2 shows the evaluation results.

<Comparative Example 7> (Preparation of cationized silica) Dimethylamine / epichlorohydrin was condensed in 500 g of silica sol B (primary particle diameter 11 nm, average secondary particle diameter 100 nm, concentration 20%, adjusted to pH 4 with aqueous hydrochloric acid). 50 g of 20% aqueous solution of polymer
Upon addition, the viscosity increased and aggregation was observed. The aggregate was pulverized and dispersed by a sand grinder to prepare cationized silica (S-F) having an average particle diameter of 800 nm.
A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used. Table 2 shows the evaluation results.

<Comparative Example 8> (Preparation of cationized silica) Silica sol C (average particle size 3
μm synthetic amorphous silica (trade name: NipsilHD-
2, primary particle size 11 nm, manufactured by Nippon Silica Industry Co., Ltd.), adjusted to pH 4 with hydrochloric acid aqueous solution, pulverized and dispersed by a sand grinder, and repeated the pulverization / dispersion process until the average particle diameter becomes 70 nm, prepared at a concentration of 10%. 1000g
When 50 g of a 20% aqueous solution of a dicyandiamide / polyalkylene polyamine polycondensate was added thereto, the viscosity increased,
Aggregation was observed. The aggregate was pulverized and dispersed by a sand grinder to prepare a cationized silica (SG) having an average particle diameter of 600 nm. A recording medium of the present invention was manufactured and evaluated in the same manner as in Example 1 except that the recording medium was used.
Table 2 shows the evaluation results.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

Industrial Applicability The present invention relates to an ink jet recording medium, and particularly to an ink jet recording medium having excellent image quality, which is excellent in glossiness of the recording medium surface and water resistance of a printed portion after printing without deteriorating printing quality. Was done. As is clear from Table 1, Examples 1 to 3 were excellent in all evaluation items. The print water resistance of Comparative Example 1 was inferior. In Comparative Examples 2 to 4, sol aggregation occurred, and the sol was pulverized again. However, the glossiness of the recording medium surface was reduced. As is clear from Table 2, Examples 4 to 5 in which the cationized silica of the present invention obtained by polymerizing a cation monomer in a silica sol were contained in a receptor layer of an ink jet recording material.
Was excellent in all evaluation items. On the other hand, in Comparative Example 5 in which the cationized silica to which no cationic polymer was added was contained in the receiving layer of the ink jet recording medium, the water resistance of the printed portion was poor. Comparative Example 6 in which a cationized silica of a conventional formulation obtained by mixing a cationic polymer with a silica sol was contained in a receiving layer of an ink jet recording material.
No. 8 to 8 were inferior in glossiness of the recording medium surface.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA13 FB01 FB04 FC06 2H086 BA01 BA15 BA21 BA33 BA37 BA41

Claims (8)

[Claims] 1. An ink jet recording material comprising a receiving layer containing cationized silica obtained by polymerizing a quaternary ammonium salt compound having an ethylenically unsaturated group in a silica sol. 2. The silica sol according to claim 1, wherein the quaternary ammonium salt compound having an ethylenically unsaturated group is 0.1 to 40 parts by weight based on 100 parts by weight of the silica. The ink-jet recording medium according to the above. 3. A cationized silica obtained by polymerizing an amine compound having an ethylenically unsaturated group in a silica sol, and a cyclized polymer, an amine-based condensation polymer, and a polyamine-based derivative. An ink jet recording medium containing at least one polymer compound to be formed in a receptor layer. 4. A polymer obtained by polymerizing an amine compound having an ethylenically unsaturated group in the cationized silica,
The sum of the weight of the amine-based cyclized polymer, the amine-based condensed polymer and the polyamine-based derivative is 0.1 to 40 parts by weight with respect to 100 parts by weight of silica, and (b) the amine-based cyclized polymer , The sum of the weights of the amine-based polycondensate and the polyamine-based derivative is 1 to 10,000 based on 100 parts by weight of the polymerized amine compound having an ethylenically unsaturated group.
4. The ink jet recording material according to claim 3, wherein the content is part by weight. 5. The ink jet recording material according to claim 3, wherein the amine-based cyclized polymer is a homopolymer and / or a copolymer of diallyldimethylammonium salt. 6. The amine-based condensation polymer is dimethylamine.
4. The ink jet recording material according to claim 3, wherein the recording material is an epichlorohydrin condensation polymer and / or a dicyandiamide / polyalkylene polyamine condensation polymer. 7. The ink jet recording material according to claim 3, wherein the polyamine derivative is a polyacryl polyamine / epichlorohydrin reactant. 8. The ink jet recording medium according to claim 1, wherein the silica sol has a pH of 6 or less.