JP2002144716A - Ink jet recording medium and coating liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording medium excellent in ink absorbency, film forming properties and transparency and a coating liquid therefor. SOLUTION: In the ink jet recording medium, an ink absorbing layer includes an inorganic porous substance having fine pores with pore diameters of 1 to 200 nm in the pore diameter distribution obtained by a nitrogen adsorption method, alumina hydrate and a latex polymer. In addition, the coating liquid for the ink jet recording medium is disclosed.

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 paper used for ink jet printing and recording.
The present invention relates to an ink jet recording medium such as a sheet, a film, and a cloth, and a coating liquid for an ink jet recording medium used for manufacturing the same.

[0002]

2. Description of the Related Art The ink jet recording system has been used in a wide range of fields because of low noise at the time of recording, easy coloration, and high speed recording. However, high-quality paper and the like used for general printing have poor ink absorbency and drying properties, and have poor image quality such as resolution.Therefore, special papers that have improved these properties have been proposed. Recording paper coated with various inorganic pigments such as amorphous silica in order to increase the printing quality is disclosed. (JP-A-55-51583, JP-A-56-1485)
85, etc.) However, with the recent progress in the performance of ink jet printers, further improvement in the performance of the recording medium has been required, and satisfactory performance has not always been obtained with the above technology alone. In particular, insufficient ink absorptivity and bleeding due to an increase in the amount of ink ejected per unit area of the recording medium in order to obtain a high image quality comparable to a silver halide photograph are raised. Further, if the amount of the binder is reduced in order to increase the ink absorbency, the film-forming properties tend to be deteriorated, and there has not been obtained a film which sufficiently satisfies both. Furthermore, the transparency of the ink absorbing layer and the water resistance of the printed portion are required for high image quality and color density development comparable to silver halide photography.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording medium excellent in ink absorbency, film formability, transparency and water resistance, and a coating liquid for the ink jet recording medium.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems. As a result, the following ink-jet recording containing a specific inorganic porous material, alumina hydrate, and latex polymer was carried out. Media was found and the present invention was made. That is, the present invention is as follows. (1) In an ink jet recording medium provided with one or more ink absorbing layers on a support, at least one of the ink absorbing layers has a pore diameter of 1 to 200 nm in a pore diameter distribution determined by a nitrogen adsorption method. An ink jet recording medium containing an inorganic porous material having pores, alumina hydrate, and a latex polymer. (2) The ink jet recording medium according to (1), wherein the inorganic porous substance is substantially silicon oxide.

(3) The volume average particle diameter DL of the inorganic porous substance measured by the dynamic light scattering method is 10 to 200 nm.
And the difference SB-SL between the converted specific surface area SL of the inorganic porous substance obtained from the DL and the nitrogen adsorption specific surface area SB by the BET method is 100 m ² / g or more (1) to (2).
3. The ink jet recording medium according to claim 1. (4) The ink jet recording medium according to any one of (1) to (3), wherein the ink absorption layer contains polyvinyl alcohol or a polyvinyl alcohol derivative. (5) Ingredients of the ink absorbing layer according to (1) to (4),
And an ink jet recording medium coating solution containing a solvent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the invention, at least one ink absorbing layer is provided on the support. If necessary, two or more ink absorbing layers can be provided. As described above, by forming the ink absorbing layer into multiple layers, it is possible to share functions such as imparting gloss to the surface to each layer. The inorganic porous material, alumina hydrate, and latex polymer of the present invention must be contained in at least one layer.

The inorganic porous material used in the present invention has a pore diameter of 1 to 200 nm in a pore diameter distribution determined by a nitrogen adsorption method.
More preferably, it is a crystalline or amorphous porous substance made of an inorganic substance having pores at 2 to 100 nm. That the inorganic porous material has pores with a predetermined pore size distribution,
It can be confirmed that the pore diameter giving the maximum value observed in the pore diameter distribution diagram of the inorganic porous substance is within a predetermined range. If the pores are less than this range, the ink absorbency decreases, and if the pores are larger than this range, the transparency of the ink absorbing layer decreases, which is not preferable. The inorganic substance is not particularly limited, but for example, silicon, aluminum, zirconium, titanium, tantalum, niobium, tin, metal oxides such as tungsten,
Examples include metal phosphates such as aluminum, vanadium, zirconium, and tungsten, and silicon oxide is particularly preferably used. A substance whose surface has been modified by substituting a part of the inorganic substance with another element or modifying it with an organic substance can also be used. 1 to 200 by nitrogen adsorption method
It is not particularly limited as long as it is a porous substance in which pores are detected in nm, but mesoporous silica synthesized using a surfactant or the like as a template (US Pat. No. 3,556,725, JP-A-5-503499, JP-A-5-503499, And other mesoporous materials. Mesoporous silica is a porous silica material having an average pore size in a mesopore region of 2 to 50 nm, which has a regular structure in powder X-ray diffraction and has a substantially uniform pore size. In the present invention, not only a substance in which the arrangement of pores of the porous substance has regularity in X-ray diffraction but also a substance in which regularity is not recognized in X-ray diffraction can be used. .

In the present invention, the inorganic porous material has a volume average particle diameter DL of 10 to 10 as measured by a dynamic light scattering method.
Converted specific surface area SL and BE obtained from DL at 200 nm
The difference SB-SL from the nitrogen adsorption specific surface area SB by the T method is 1
A substance having a content of at least 00 m ² / g is preferably used from the viewpoint of the transparency of the ink absorbing layer. The converted specific surface area SL (m ² / g) calculated from the volume average particle diameter DL (nm) measured by the dynamic light scattering method assumes that the particles are spherical, and SL = 6 × 10 ³ / ( Density (g / cm ³ ) × DL). The substance has a small particle size and thus has excellent transparency of the ink absorbing layer, and has pores not only between particles but also inside the particles, which is preferable in terms of ink absorbability.
When the DL is less than 10 nm, the ink absorbency decreases, and
If it is larger than nm, the transparency of the ink absorbing layer is undesirably reduced. SB-SL is 10 in terms of ink absorbency.
It is preferably 0 m ² / g or more, more preferably 250 m ² / g or more, and if it is less than 100 m ² / g, the ink absorbency decreases, which is not preferable. The BET specific surface area (nitrogen adsorption specific surface area SB) of the substance is preferably from 200 to 1500 m ² / g, and the pore volume is preferably from 0.5 to 4 ml / g.

As a method for synthesizing the inorganic porous material, for example,
(A) SiO of silicon source_TwoBalance to reduced mass
Weight ratio of rate in the range of 0.01 to 30, template
The weight ratio of water to the weight of
Mixing silicon source and template to produce composite
And (b) removing a template from the complex.
It can be synthesized from the process. Template used here
Nonionic surfactants are preferably used as
Structural formula HO (C_TwoH_FourO)_a− (C_ThreeH₆O)_b− (C _TwoH
_FourO)_cH (however, a and c are 10 to 110, b is 30 to 7
Non-ionic surfactants represented by 0) are particularly preferred.
It is used well. Specifically, Pluronic P103,
P123 and P85 (manufactured by Asahi Denka). pore
To change the diameter, as an organic auxiliary, e.g. carbon number
6-20 aromatic hydrocarbons, alicyclic carbons having 5-20 carbon atoms
Hydrogen, aliphatic hydrocarbons having 3 to 16 carbon atoms,
Min and halogen substitutions should be used with the template.
Can be. Increase the pore size by using the organic auxiliary in combination
It is possible to The reaction between the silicon source and the template is
Dissolve and disperse silicon source in solvent and template
The mixture is dissolved and dispersed in a solvent and mixed and stirred.
Water or organic solvent
The reaction temperature is not particularly limited, but 5 to 150 ° C.
The reaction time is preferably 0.5 to 100 hours.
Can be.

In general, as a method for removing the template from the inorganic porous material-template complex, there are a method of firing the complex at a high temperature and a method of extracting it with a solvent. The method of extracting with a solvent is preferable in that the aggregation of particles can be suppressed and the template can be reused. For example, a method of extracting and removing a template with a solvent such as water or alcohol using an ultrafiltration device is suitably used. The content of the inorganic porous material in the ink absorbing layer is not particularly limited, but is preferably 10 to 99% by weight based on each ink absorbing layer containing the inorganic porous material. Also, 1 to 99% by weight based on the whole ink absorbing layer
It is preferred to contain. If the content is low, the ink absorbency decreases, which is not preferable.

The ink absorbing layer of the present invention needs to contain a latex polymer as a binder which does not impair the ink absorbency of the inorganic porous material. Such a latex polymer is, for example, a resin particle component in a resin dispersion obtained by emulsion polymerization of a polymerizable monomer.
The use of a latex polymer improves ink absorbency.

The latex polymer used in the present invention is not particularly limited. Examples thereof include vinyl acetate polymer latex, styrene-isoprene copolymer latex, styrene-butadiene copolymer latex, methyl methacrylate butadiene copolymer latex, acrylic Acid ester copolymer latexes, and functional group-modified polymer latexes obtained by modifying these copolymers with functional group-containing monomers such as carboxyl groups, amino groups, and quaternary ammonium bases. Examples of monomers used for the latex polymer include vinyl acetate, styrene, α-methylstyrene, ethylene, isoprene, butadiene, vinyl chloride,
Methacrylic acid, methacrylic acid ester such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, acrylic acid, ethyl acrylate, butyl acrylate, acrylic acid ester such as acrylic acid (2-ethylhexyl), amide derivative such as acrylamide, Acrylonitrile, methacrylonitrile and the like can be mentioned. One or more of these polymerizable monomers can be used.

When only a water-soluble binder such as a conventional polyvinyl alcohol is used as the binder for the inorganic porous material of the present invention, the ink absorption is reduced at a level where the film formability is good, and the amount of the ink used is reduced. When the amount is reduced, the ink absorbency is improved, but the film formability is reduced. On the other hand, when the inorganic porous substance of the present invention is used in combination with a latex polymer, it is possible to achieve both ink absorption and film formation. Although the reason for this is not clear, it is speculated that in the ink absorption layer, the particle diameter of the latex polymer is larger than the pores of the porous substance, so that the pores are not closed, and good ink absorbency is exhibited. I have.

The glass transition point and average particle size of the latex polymer used in the present invention are not particularly limited, but those having a glass transition point of -30 to 100 ° C. and an average particle size of 10 to 200 nm are preferably used. The content of the latex polymer used in the present invention is not particularly limited, but is preferably 5 to 400 parts by weight, particularly preferably 5 to 100 parts by weight, based on 100 parts by weight of the inorganic porous material. If the content is small, the film-forming property is reduced, and if the content is large, the ink absorbency is reduced, which is not preferable.

The ink absorbing layer of the present invention needs to contain alumina hydrate together with an inorganic porous substance and a latex polymer. By containing alumina hydrate, the water resistance of the printed portion is improved. The alumina hydrate used in the present invention is not particularly limited, but may have the general formula Al ₂ O ₃
A boehmite-structured alumina hydrate represented by nH ₂ O, wherein n is 1; a pseudo-boehmite-structured alumina hydrate, wherein n is greater than 1 and less than 3; Alumina hydrate having a porous structure is used, and alumina hydrate having a pseudo-boehmite structure is preferably used. One or more of these alumina hydrates are used. The alumina hydrate of the present invention can be synthesized by, for example, a method of hydrolyzing an aluminum alkoxide such as aluminum isopropoxide, neutralizing an aluminum salt with an alkali, or hydrolyzing an aluminate. The particle size of the alumina hydrate used in the present invention is not particularly limited,
Those having a thickness of 200 nm are preferably used. The amount of the alumina hydrate of the present invention is not particularly limited, but is preferably 1 to 900 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the inorganic porous material of the present invention. If the amount used is low, the water resistance is undesirably reduced.

In the present invention, it is preferable to use polyvinyl alcohol or a polyvinyl alcohol derivative in combination with a latex polymer in the ink absorbing layer in order to impart a better film-forming property. Examples of the polyvinyl alcohol derivative include cationically modified polyvinyl alcohol and silanol-modified polyvinyl alcohol. The content of the polyvinyl alcohol or the polyvinyl alcohol derivative used in the present invention is preferably 1 to 400 parts by weight based on 100 parts by weight of the latex polymer.
It is particularly preferred that the content be contained in an amount of from 100 to 100 parts by weight. If the content is small, the effect is not sufficient, and if the content is large, the ink absorbency decreases, which is not preferable.

In the present invention, there is also provided an ink jet recording medium coating liquid comprising the components of the ink absorbing layer described in (1) to (4) and a solvent. The solvent used is not particularly limited, but water-soluble solvents such as alcohols, ketones and esters, and / or water are preferably used. Further, a pigment dispersant, a thickener, a flow regulator, an antifoaming agent, a foam inhibitor, a release agent, a foaming agent, a colorant, and the like can be added to the coating liquid as needed. In the present invention, other organic binders can be used in combination. For example, polyvinyl acetates, polyvinylpyrrolidones, polyacetals, polyurethanes, polyvinylbutyrals, poly (meth) acrylic acids (esters), polyamides, polyacrylamides, polyester resins, urea resins, melamine resins, natural high Examples include starch and starch derivatives derived from molecules, cellulose derivatives such as carboxymethylcellulose and hydroxyethyl, casein, gelatin and the like.

In the present invention, at least one of the ink absorbing layers preferably contains a cationic polymer. By containing the cationic polymer, the water resistance of the printed portion is improved. The cationic polymer is not particularly limited as long as it shows cationicity, and primary amine, secondary amine, tertiary amine substituent and salts thereof,
Those containing at least one quaternary ammonium salt substituent are preferably used. For example, dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride-acrylamide copolymer, alkylamine polymer, polyaminedicyan polymer, polyallylamine hydrochloride and the like can be mentioned. The molecular weight of the cationic polymer is not particularly limited, but the weight average molecular weight is 1,000.
~ 200,000 are preferably used.

In the present invention, at least one of the ink absorbing layers preferably contains an ultraviolet absorber, a hindered amine light stabilizer, a singlet oxygen quencher, and an antioxidant. The light resistance of the printed portion is improved by containing the substance. The UV absorber is not particularly limited, but may be a benzotriazole-based, benzophenone-based, titanium oxide,
Cerium oxide, zinc oxide and the like are preferably used. The hindered amine light stabilizer is not particularly limited, but the N atom of the piperidine ring is NR (R is a hydrogen atom, an alkyl group, a benzyl group, an allyl group, an acetyl group, an alkoxyl group, a cyclohexyl group, a benzyloxy group). Are preferably used. The singlet oxygen quencher is not particularly limited, but aniline derivatives, organic nickel compounds, spirochromane compounds, and spiroindane compounds are preferably used. The antioxidant is not particularly limited, but includes phenol-based, hydroquinone-based, organic sulfur-based, phosphorus-based,
An amine type is preferably used.

In the present invention, at least one of the ink absorbing layers preferably contains an alkaline earth metal compound. By containing an alkaline earth metal compound, light resistance is improved. As the alkaline earth metal compound, magnesium, calcium and barium oxides, halides and hydroxides are preferably used. The method for incorporating the alkaline earth metal compound into the ink absorbing layer is not particularly limited. It may be added to the coating liquid slurry, or may be added at the time of synthesizing the inorganic porous substance or after the synthesis, and may be used by adhering and containing. The amount of the alkaline earth metal compound to be used is from 0.5 to 0.5 in terms of oxide based on 100 parts by weight of the inorganic porous material.
20 parts by weight are preferred.

In the present invention, at least one of the ink absorbing layers preferably contains a nonionic surfactant. Image quality by containing nonionic surfactant,
Light resistance is improved. The nonionic surfactant is not particularly limited, but a higher alcohol, an ethylene oxide adduct of a carboxylic acid, an ethylene oxide-propylene oxide copolymer is preferably used, and an ethylene oxide-propylene oxide copolymer is more preferably used. . The method for incorporating the nonionic surfactant into the ink absorbing layer is not particularly limited. It may be added to the coating liquid slurry, or may be added at the time of synthesizing the inorganic porous substance or after the synthesis, and may be used by adhering and containing.

In the present invention, at least one of the ink absorbing layers preferably contains an alcohol compound. By containing an alcohol compound, image quality and light resistance are improved. The alcohol compound is not particularly limited, but an aliphatic alcohol, an aromatic alcohol, a polyhydric alcohol, and a hydroxyl group-containing oligomer are preferably used, and a polyhydric alcohol is more preferably used. The method for including the alcohol compound in the ink absorbing layer is not particularly limited.
It may be added to the coating liquid slurry, or may be added at the time of synthesizing the inorganic porous substance or after the synthesis, and may be used by adhering and containing.

In the present invention, it is preferable that at least one of the ink absorbing layers contains colloidal silica and / or dry silica, whereby the image quality is improved and gloss is imparted by containing colloidal silica and / or dry silica. it can. The colloidal silica is not particularly limited, and may be a common anionic colloidal silica, a cationic colloidal silica obtained by a method of reacting a polyvalent metal compound such as an aluminum ion, or a bead-like connected and / or branched shape. Colloidal silica or the like is used. The fumed silica is not particularly limited, but fumed silica synthesized by burning silicon tetrachloride with hydrogen and oxygen is preferably used. The dry-process silica may be used as it is, or may be one whose surface is modified with a silane coupling agent or the like.

In the present invention, a gloss layer can be provided as the outermost layer. The means for providing the glossy layer is not particularly limited, but a method of containing an ultrafine particle pigment such as colloidal silica and / or dry silica, a super calender method, a gloss calender method, a casting method, and the like are used. The support used in the present invention is not particularly limited, but paper,
Polymer sheets, polymer films, and cloths are preferably used. These supports may be subjected to a surface treatment such as corona discharge, if necessary. The thickness of the ink absorbing layer is not particularly limited, but is 1 to 100 μm, and the coating amount is 1 to 100.
g / m ² is preferred. The coating method of the coating liquid is not particularly limited, but a blade coater, an air knife coater, a roll coater, a brush coater, a curtain coater, a bar coater, a gravure coater, a spray, or the like can be used.

Next, the present invention will be described based on embodiments.
The pore distribution, pore volume, and specific surface area were measured with Nitro using Autosorb-1 manufactured by Qantachrome. The pore size distribution was calculated by the BJH method. The specific surface area was determined by the BET method. The volume average particle diameter by the dynamic light scattering method is Lee
It was measured by a Microtrac UPA particle size distribution meter manufactured by ds & Northrup. X-ray powder analysis diagram is RIKEN RI
The measurement was performed using NT2500.

Evaluation of printing characteristics was performed using a commercially available inkjet printer (PM-800C manufactured by Seiko Epson) using yellow, magenta, cyan, black, green,
Red and blue solid prints were used. Evaluation items are shown below. (1) Ink absorbency: Judgment was made based on the degree of ink transfer after printing, and the degree of ink transfer, with the printed portion being pressed with white paper immediately after printing. ：: good, Δ: slightly good, ×: poor (2) Film-forming property: Cracking and adhesion of the coating film were visually judged. ：: good, Δ: somewhat good, ×: poor (3) Water resistance: The printed recording sheet was immersed in running water for 10 minutes, and then the degree of ink bleeding and loss was visually determined. : No ink flow, Δ: Partial ink flow, ×: Large ink flow

[0027]

Examples 1 to 3 Cation exchange resin (Amberlite, IR-120B) 100 previously converted to H @ + type
g of water was dispersed in 100 g of water.
O ₂ = 29% by weight, Na ₂ O = 9.5% by weight) 33.3
g is diluted with 66.7 g of water. After sufficiently stirring this, the cation exchange resin was separated by filtration to obtain 200 g of an active silica aqueous solution. This activated silica aqueous solution is SiO ₂
Was 5.0% by weight. 5 g of Pluronic P103 (ethylene oxide-propylene oxide copolymer) manufactured by Asahi Denka Co., Ltd. was dissolved in 1360 g of water, and 60 g of the above-mentioned active silica aqueous solution was added while stirring in a 35 ° C water bath. Further, 20 ml of a 0.015 mol / l NaOH aqueous solution was added. The pH of this mixture was 7.5. The mixture was stirred at 35 ° C. for 15 minutes, and then allowed to stand at 80 ° C. and reacted for 24 hours. The Pluronic P103 was removed from this solution using an ultrafiltration device to obtain a transparent porous substance sol solution having a SiO ₂ concentration of 4% by weight. The volume average particle diameter of the sample in this solution measured by the dynamic light scattering method was 60 nm, and the converted specific surface area was 45 m ² / g. This solution was dried at 105 ° C. to obtain a porous substance. No peak was observed in the X-ray diffraction pattern of this sample. The maximum value in the pore diameter distribution diagram of this sample was observed at a pore diameter of 8 nm, and the pore volume was 1.21 ml / g. BET
The nitrogen adsorption specific surface area by the method was 720 m ² / g, and the difference from the converted specific surface area was 675 m ² / g.

An alumina hydrate and a latex polymer were mixed with the porous material sol solution at a ratio shown in Table 1 with respect to 100 parts by weight of SiO ₂ to prepare a coating liquid. The above coating liquid is applied to a polyethylene terephthalate sheet (thickness: 100 μm) with a bar coater and dried to a thickness of about 25 μm.
The recording sheet provided with the ink absorbing layer was obtained. All of the obtained recording sheets were transparent. Table 1 shows the evaluation results of these sheets.

[0029]

Example 4 A recording sheet was obtained in the same manner as in Example 1 except that silanol-modified polyvinyl alcohol was mixed with the sol solution of the porous substance in the ratio shown in Table 1. The obtained recording sheet was transparent. Table 1 shows the evaluation results of this sheet.

[0030]

Comparative Examples 1 and 2 Example 1 was repeated except that only the polyvinyl alcohol and the silanol-modified polyvinyl alcohol were mixed in the sol solution of the porous material at the ratios shown in Table 1.
A recording sheet was obtained in the same manner as described above. All of the obtained recording sheets were transparent. Table 1 shows the evaluation results of these sheets.

[0031]

[Table 1]

[0032]

The ink jet recording medium of the present invention has excellent effects on ink absorption, film forming properties, transparency and water resistance.

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Claims (5)

[Claims] In an ink jet recording medium provided with one or more ink absorbing layers on a support, at least one of said ink absorbing layers has a pore diameter of 1 to 3 in a pore diameter distribution determined by a nitrogen adsorption method. An ink jet recording medium comprising: an inorganic porous material having pores of 200 nm; alumina hydrate; and a latex polymer. 2. The ink jet recording medium according to claim 1, wherein the inorganic porous substance is substantially silicon oxide. 3. The inorganic porous material has a volume average particle diameter DL of 10 to 200 nm measured by a dynamic light scattering method, and the reduced specific surface area S of the inorganic porous material determined from the DL.
Difference between L and the specific surface area SB of nitrogen by the BET method SB−
The inkjet recording medium according to claim 1, wherein SL is 100 m ² / g or more. 4. An ink absorbing layer comprising polyvinyl alcohol,
4. The ink jet recording medium according to claim 1, further comprising a polyvinyl alcohol derivative. 5. A coating liquid for an inkjet recording medium, comprising the components of the ink absorbing layer according to claim 1 and a solvent.