JPH09176995A - Recording medium on which recording is carried out by ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recorded material having good image and suppressed in color bleeding of color image without unevenness of printing by injecting a specific ink composition by an ink jet method onto a recording medium on which a specific ink receiving layer is provided. SOLUTION: A coloring agent such as dye is blended with an organic solvent such as methanol and a resin emulsion of an acrylic, vinyl acetate-based, styrene-butadiene-based, vinyl chloride-based, acryl-butadiene-based, vinyl chloride-based, acryl-styrene-based, butadiene-based or styrene-based resin having <=150nm particle diameter and water to prepare an ink composition. An ink receiving layer containing <=0.001mol/m<2> , preferably >=0.003mol/m<2> and <=0.02mol/m<2> polyvalent metal ion selected from a group of Ca<2+> , Cu<2+> , Ni<2+> , Zn<2+> , Ba<2+> , Al<3+> , Fe<3+> and Cr<3+> is provided on a paper substrate using a blade coater to form the objective recording medium. The droplet of the ink composition is recorded onto the recording medium by an ink jet method to provide a recorded material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium on which recording is performed with an ink composition, and particularly to a recording medium preferably used for ink jet recording.

2. Description of the Related Art In order to obtain high-quality prints or images with an ink composition, efforts are mainly made from two aspects: improvement of the ink composition and improvement of the recording medium.

Further, the ink jet recording method as a recording method using the ink composition is characterized in that a high resolution and high quality image can be printed at a high speed by a relatively inexpensive apparatus. In ink jet recording, various improvements have been made from the viewpoints of an ink composition, a recording medium, a recording method, and the like, aiming at higher image quality and better printing stability.

Some of the inventors of the present invention have previously proposed an ink composition having good properties, particularly an ink composition preferably used in an ink jet recording method, which comprises a resin emulsion (special feature). Kaihei 6-21
2106).

[0005]

SUMMARY OF THE INVENTION The present inventors have recently combined an ink composition containing the above resin emulsion with a recording medium having an ink receiving layer containing a specific amount of polyvalent metal ions to obtain good image quality. I found that I can achieve it.

Therefore, an object of the present invention is to provide a recording medium which can realize good image quality.

The recording medium according to the present invention is used for recording with an ink composition containing a colorant, an organic solvent, water, and a resin emulsion, and contains 0.001 mol / polyvalent metal ion. A recording medium having an ink receiving layer containing m ² or more.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Recording Medium The recording medium according to the present invention is used in a recording system using an ink composition having a specific composition described below. Examples of the recording method using the ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, and various other printing methods. Further, the ink composition is not limited to the liquid ink, and includes a solid colorant and a colorant which is used by heating and melting. In particular, the recording medium according to the present invention is preferably used for an ink jet recording method.

The recording medium according to the present invention comprises an ink receiving layer, the ink receiving layer containing polyvalent metal ions of 0.0
01 or more, preferably 0.003 mol / m ² or more 0.0
The content is 2 mol / m ² or less.

In the present invention, preferred examples of polyvalent metal ions include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ and Zn.
²⁺ , Ba ^2+, etc. divalent metal ions Al ³⁺ , Fe ³⁺ , Cr
^Examples include trivalent metal ions such as ³⁺ .

A high quality image can be realized by recording on the recording medium according to the present invention with an ink composition having the composition described below. In particular, in addition to high print density and low print unevenness,
Bleeding, especially bleeding between colors (color bleed) in a color image can be suppressed. The present invention is not intended to be limitedly interpreted for the following reasons, but the reasons are expected to be as follows. That is, the ink composition contains a resin emulsion as described later. It is considered that this resin emulsion has the effect of suppressing the permeation of the coloring component by the interaction with the polyvalent metal ion and further promoting the fixing to the recording medium. Further, depending on the type of the resin emulsion, it is considered that it has the effect of forming a film on the recording medium and improving the abrasion resistance of the printed matter. From the above, it seems that good image quality is realized.

In the recording medium according to the present invention, the ink receiving layer may be provided on the substrate, or the ink receiving layer itself may be the recording medium. Examples of the latter include commonly used plain paper. As the ink receiving layer of the former recording medium, for example, a layer having a hydrophilic polymer or a water absorbing polymer provided on a substrate, or an inorganic pigment or an organic pigment together with a binder as a porous layer on the substrate And the like. Examples of hydrophilic polymers or water-absorbent polymers include agar, carrageenin, corn starch, guar gum, gum arabic, karaya gum, tragacanth gum, locust bean gum, tapioca starch, and other natural resins, cationic starch, dextran, hydroxyalkyl. Chemically modified natural resins such as starch, methyl cellulose, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, polyacrylamide, cationic resins, polyacrylic acid and its derivatives, polyethylene oxide, poly-N-vinyl-2-pyrrolidone, vinyl ether polymers , Synthetic polymers such as styrene-maleic anhydride copolymer and ethylene-maleic anhydride copolymer. Examples of inorganic pigments include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, and silica. Calcium acid, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-pemite, aluminum hydroxide,
Alumina, lithopone, zeolite, hydrohaloysite,
Examples of the organic pigment include magnesium carbonate and magnesium hydroxide, and examples of the organic pigment include styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, and melamine resin.

The substrate of the recording medium according to the present invention is not particularly limited as long as it can support the ink receiving layer and has strength as a recording medium, and it may be transparent or opaque. Examples of the opaque substrate include cloth, wood, metal plate, paper, and the like. Further, a opaque substrate obtained by subjecting a later-described transparent substrate to opacity treatment can also be used. As the transparent substrate, for example, polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane, film or plate such as cellulite, And a glass plate and the like.

Specifically, the recording medium according to the present invention may be the same as the recording medium having a known or commonly used ink receiving layer, except that the recording medium comprises polyvalent metal ions in the above range. Specific examples of such a recording medium include, for example, JP-A-60-222,281 and JP-A-6-62.
The recording media described in JP-A 1-89,082, JP-A-62-95,285, and JP-A-1-186,372 can be mentioned.

The method of incorporating polyvalent metal ions into the ink receiving layer is not particularly limited as long as the above content is realized. In the case of a recording medium in which an ink receiving layer is provided on a substrate, the composition for forming the ink receiving layer,
The polyvalent metal ion may be contained in the above amount, and the composition may be applied to a substrate and dried. When the base material also serves as the ink receiving layer, it may be produced by applying or impregnating the base material with an aqueous solution containing a polyvalent metal ion and then drying.

Specifically, in the production of a recording medium having a known or commonly used ink receiving layer as described above, the amount of polyvalent metal ions in the final ink receiving layer is set within the above range. It may be added and manufactured in the precursor composition to be the ink receiving layer.

Ink Composition The ink composition used in the present invention basically comprises a colorant, an organic solvent, water, and a resin emulsion.

Here, the resin emulsion means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. Examples of the resin component of the dispersed phase include acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, and styrene resin.

According to a preferred embodiment of the present invention, this resin is preferably a polymer having both a hydrophilic portion and a hydrophobic portion. Further, the particle size of these resin components is not particularly limited as long as an emulsion is formed.
It is preferably not more than about 5 nm, more preferably about 5 to 100 nm.

These resin emulsions can be obtained by mixing resin particles with water, optionally together with a surfactant. For example, an acrylic resin or styrene-acrylic resin emulsion is prepared by adding (meth) acrylic acid ester or styrene, (meth) acrylic acid ester, and optionally (meth) acrylic acid ester, and a surfactant to water. It can be obtained by mixing. The mixing ratio of the resin component and the surfactant is usually preferably about 10: 1 to 5: 1. When the amount of the surfactant used is in the above range, better water resistance and permeability of the ink can be obtained. The surfactant is not particularly limited, but preferred examples thereof include the surfactants described below.

The ratio of the resin as the dispersed phase component to water is 60 to 400 parts by weight of water, preferably 100 to 200 parts by weight, relative to 100 parts by weight of the resin.

It is also possible to use a commercially available resin emulsion, for example, Microgel E-100.
2, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001
(Acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.) Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, Nippon Zeon Co., Ltd.) Made), Cybinol S
K-200 (acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.) and the like.

The ink used in the present invention preferably contains a resin emulsion so that the resin component accounts for 0.1 to 40% by weight of the ink, and more preferably 1 to 2.
It is in the range of 5% by weight.

The colorant may be either a dye or a pigment.

As the dyes, direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes,
Various commonly used dyes such as soluble vat dyes and reactive disperse dyes can be used.

As the pigment, an inorganic pigment or an organic pigment can be used without particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. Examples of organic pigments include azo dyes (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.), and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc., dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

According to a preferred embodiment of the present invention, these pigments are preferably added to the ink as a pigment dispersion obtained by dispersing them in an aqueous medium with a dispersant. As a preferable dispersant, a dispersant which is commonly used for preparing a pigment dispersion liquid, for example, a polymer dispersant or a surfactant can be used. It will be apparent to those skilled in the art that the dispersant and the surfactant contained in this pigment dispersion will also function as the surfactant of the ink composition described later.

The amount of pigment added to the ink is 0.5 to 25.
% By weight, more preferably 2 to 15% by weight.
It is about.

The organic solvent is preferably a low boiling point organic solvent, and preferred examples thereof include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol and tert.
-Butanol, iso-butanol, n-pentanol and the like. A monohydric alcohol is particularly preferable. The low boiling point organic solvent has the effect of shortening the drying time of the ink.

The ink composition used in the present invention preferably further contains a high boiling point organic solvent. Preferred examples of the high boiling point organic solvent include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, triethylene glycol, triethylene glycol. Polyhydric alcohols such as methylolethane and trimethylolpropane;
Alkyl of polyhydric alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether Ethers, urea, 2-pyrrolidone, N-methyl-2
-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine and the like.

The addition amount of the low boiling point organic solvent is 0.5 of the ink.
10 to 10% by weight is preferable, and more preferably 1.5 to 6% by weight. The amount of the high boiling point organic solvent added is preferably 0.5 to 40% by weight of the ink, and more preferably 2 to 20% by weight.

The ink composition used in the present invention may contain a surfactant. Examples of this surfactant include anionic surfactants (for example, sodium dodecylbenzene sulfonate, sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfates, etc.), nonionic surfactants (for example, polyoxyethylene). Ethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, etc.), and these may be used alone or in combination of two or more. Can be used. Also,
Acetylene glycol (olefin Y, and Surfynol 82, 104, 440, 465, and 485
(All manufactured by Air Products and Chemicals Inc.) can also be used.

According to a preferred embodiment of the present invention, the ink composition preferably contains sugar. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosyl , Maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a sugar in a broad sense, and is used to include a substance widely existing in nature such as alginic acid, α-cyclodextrin, and cellulose.

The derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols (formula H
OCH ₂ (CHOH) n CH ₂ OH (where n = 2
Represented by an integer of 5), oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thiosugars and the like. In particular, sugar alcohols are preferred, and specific examples include maltitol and sorbitol.

The content of these saccharides is 0.1 to 0.1% of the ink.
A range of 40% by weight, preferably 0.5 to 30% by weight is suitable.

In addition, if necessary, a pH adjusting agent, a preservative, an antifungal agent, etc. may be added.

[0037]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

Black ink 1 Carbon black MA7 5% by weight (manufactured by Mitsubishi Kasei) Styrene-acrylic acid copolymer 1% by weight (dispersant) Boncoat 4001 3% by weight (acrylic resin emulsion, resin component 50%, MF)
T = 5 ° C., manufactured by Dainippon Ink and Chemicals, Inc.) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight 2-Pyrrolidone 2% by weight Ethanol 4% by weight Pure water remaining amount Carbon black and dispersant And were mixed and dispersed in a sand mill (Yasukawa Seisakusho) together with glass beads (diameter: 1.7 mm, 1.5 times amount (weight) of the mixture) for 2 hours. After that, the glass beads were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Color Ink A cyan ink composition, a magenta ink composition, and a yellow ink composition were prepared from the following colorants and liquid media in accordance with the production of the above black ink.

Cyan ink composition pigment KETBLUX-1 (manufactured by Dainippon Ink and Chemicals, Inc.) 2% by weight Magenta ink composition pigment KETRED309 (manufactured by Dainippon Ink and Chemicals, Inc.) 2% by weight Yellow ink composition pigment KETYELLOW403 (manufactured by Dainippon Ink and Chemicals, Inc.) 2% by weight liquid medium styrene-acrylic acid copolymer 1% by weight (dispersant) Boncoat 4001 3% by weight (acrylic resin emulsion, resin component 50%, minimum film formation) Temperature (MFT) = 5 ° C., manufactured by Dainippon Ink and Chemicals, Inc. Sucrose 0.7 wt% Maltitol 6.3 wt% Glycerin 10 wt% 2-Pyrrolidone 2 wt% Ethanol 4 wt% Ion-exchanged water Remaining amount coating composition 1 micronized silicic acid 15 wt% polyvinyl alcohol 7.5 wt% nitric acid magnesium Arm 10 wt% water balance coating composition 2 micronized silicic acid 15 wt% polyvinyl alcohol 7.5 wt% magnesium nitrate 5% by weight water balance coating composition 3 micronized silicic acid 15 wt% polyvinyl alcohol 7. 5% by weight Calcium chloride 5% by weight Water Remaining amount This coating composition was coated on a commercially available high-quality paper having a Stecht size degree of 20 seconds with a blade coater so that the coating amount was 15 g / m ² and dried. The recording medium of the example was obtained. Print Evaluation Test Evaluation 1: Print Quality (Bleed) Using an inkjet printer MJ-700V2C (manufactured by Seiko Epson Corporation), printing was performed on each of the following papers. As for printing, first, the first liquid was printed at 100% duty, and then characters were printed with black ink. After drying, the characters were examined for bleeding.

Xerox P paper (manufactured by Xerox Co., Ltd.) Ricopy 6200 paper (manufactured by Ricoh Co., Ltd.) Xerox 4024 paper (manufactured by Xerox Co., Ltd.) Neenah Bond paper (manufactured by Kimberley Clark Co.) Xerox R paper (manufactured by Xerox Co., Ltd.) ) Yamayuri Paper (Recycled paper manufactured by Honshu Paper Co., Ltd.) The results are shown in Table 1. In the table, clear printing without bleeding − ◎ When whisker-like bleeding occurs − ○ When bleeding occurs so that the outline of the character is not clear − × Evaluation 2: Printing quality (OD value) Printing with evaluation 1 Reflection O of printed matter obtained in the section of quality (bleeding)
The D value was measured with Machbeth PCMII (manufactured by Macbeth). The results were as shown in Table 1.

Evaluation 3: Printing unevenness With an ink jet printer MJ-700V2C, 100% duty printing of the black ink composition was performed on each of the following papers. The printing method was the same as the method shown in Evaluation 1 above, except that the black ink composition was used at 100% duty.

Ricopy 6200 paper (manufactured by Ricoh Co., Ltd.) Canon dry paper (manufactured by Canon Inc.) Machbeth PCMII was used to measure the OD value at any 5 points on the printed portion, and the average value was determined. This procedure was repeated five times, and the maximum value and the minimum value of the five average values were determined. If this difference is less than 0.4, there is no practical problem,
Furthermore, less than 0.3 is preferable. The results are as shown in Table 1. In the table, the difference in OD value is less than 0.3-A The difference in OD value is 0.3 or more and less than 0.4- ○ The OD value is 0.4 or more-X Evaluation 4: Clogging characteristics of inkjet printer MJ-700V2C The head was filled with a predetermined ink, and alphanumeric characters were printed continuously for 10 minutes. After that, stop the printer and leave it without the cap.
It was left for 1 week to 1 month in an environment of 0 ° C. and 25% Rh. After the standing, alphanumeric characters were printed again, and the number of clogging recovery operations required until printing equivalent to that before the standing was obtained was examined. The results are as shown in Table 1. In the table, printing that is equivalent to the initial printing is possible with 0 to 2 return operations.- ◎ Printing that is equivalent to the initial printing is possible with 3 to 5 recovery operations. Impossible − ×

[Table 1]

Claims (7)

[Claims] 1. Used for recording with an ink composition containing a colorant, an organic solvent, water, and a resin emulsion, and containing 0.001 mol / m ² or more of polyvalent metal ions. A recording medium having an ink receiving layer. 2. The recording medium according to claim 1, wherein the recording with the ink composition is an inkjet recording method. 3. A polyvalent metal ion is Ca ²⁺ , Cu ²⁺ , Ni.
^2. A compound selected from the group consisting of ²⁺ , Mg2 ⁺ , Zn2 ⁺ , Ba2 ⁺ , Al3 ⁺ , Fe3 ⁺ , and Cr3 ^+.
Or the recording medium according to 2. 4. The recording according to claim 1, wherein the polyvalent metal ion content of the ink receiving layer is 0.003 mol / m ² or more and 0.02 mol / m ² or less. Medium. 5. A droplet of an ink composition containing a colorant, an organic solvent, water, and a resin emulsion is formed, and the droplet is added to any one of claims 1 to 3. An inkjet recording method comprising the step of adhering to the recording medium described. 6. The resin component of the dispersed phase of the resin emulsion is acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, or styrene resin. The inkjet recording method according to claim 5, wherein 7. A recorded matter recorded by the ink jet recording method according to claim 5.