JPH09286944A - Ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image of good quality with improved dry to touch and resistances to abrasion, water and light by applying a first solution containing a polyvalent metallic salt to a recording medium, then printing the ink composition on this recording medium. SOLUTION: (A) A recording medium is treated with a first solution containing a polyvalent metallic salt (preferably a salt of Ca<2+> or Mg<2+> with nitrate or carboxylic ion). Then, the treated recording medium is printed with (B) an ink composition of (i) a colorant, (ii) a resin emulsion, (iii) an organic solvent, (iv) water, and further, (v) an epoxy group-containing compound bearing functional group reactive with epoxy group and/or an epoxy group-containing organic compound having no above-described functional group. The component A preferably contains an epoxy-curing agent.

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 method, and more particularly, an ink jet recording method in which a first liquid containing a polyvalent metal salt is adhered to a recording medium and then an ink composition is printed on the recording medium. Regarding the method.

2. Background Art Ink jet recording method by ejecting droplets of an ink composition is a printing method for printing by adhering to a recording medium such as paper. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. In general, an ink composition used for ink jet recording contains water as a main component, and contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

On the other hand, as an ink jet recording method, a method of applying a polyvalent metal salt solution to a recording medium and then applying an ink composition containing a dye material having at least one carboxyl group has recently been proposed. (For example,
JP-A-5-202328). According to this method, an insoluble complex is formed from a polyvalent metal ion and a dye, and the presence of this complex can provide a high-quality image having water resistance and no color bleed.

[0004] Further, by using a color ink containing at least a surfactant or a penetrating solvent for imparting permeability and a salt, and a black ink which thickens or aggregates by the action of the salt, an image is formed. It has been proposed that a high-quality color image having a high density and no color bleed can be obtained (Japanese Patent Laid-Open No. 6-10673).
No. 5). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids of a first liquid containing a salt and an ink composition.

[0005]

SUMMARY OF THE INVENTION The present inventors have recently found that in an ink jet recording method for printing such two liquids, the ink composition contains an epoxy group-containing compound and / or an epoxy group having a functional group capable of reacting with an epoxy group. It has been found that good printing can be realized by containing an epoxy group-containing compound having no reactive functional group and by making the first liquid contain a polyvalent metal salt. The present invention is based on this finding.

Therefore, it is an object of the present invention to provide a method capable of realizing a good image in an ink jet recording method for printing two liquids. In particular, an object of the present invention is to provide a method for improving the finger corrosion resistance and scratch resistance of printed matter, and also improving the water resistance and light resistance of the printed matter.

The ink jet recording method according to the present invention is an ink jet recording method in which a first liquid containing a polyvalent metal salt is attached to a recording medium, and then the ink composition is printed on the recording medium. The ink composition contains a colorant, a resin emulsion, an organic solvent, and water, and further contains an epoxy group-containing compound having a functional group capable of reacting with an epoxy group and / or a functional group capable of reacting with an epoxy group. A method comprising an epoxy group-containing compound which does not have.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The ink jet recording method according to the present invention comprises a step of adhering a first liquid essentially containing a polyvalent metal salt to a recording medium, and thereafter printing an ink composition on the recording medium. It consists of Further, in the present invention, a liquid containing a polyvalent metal salt is used as the first liquid, and a liquid containing at least a resin emulsion and an epoxy group-containing compound is used as the ink composition.

Epoxy group-containing compound and epoxy curing
Agent With the epoxy group-containing compound used in the present invention,
It has at least two epoxy groups in its molecular structure, and means a resin (that is, a polymer having a high molecular weight) that undergoes a crosslinking reaction involving the epoxy groups. In the present invention, an epoxy group-containing compound that gives a print having good abrasion resistance and water resistance can be used without particular limitation in the inkjet recording method described below.

The epoxy group-containing compound used in the present invention includes a compound having an epoxy group and further having a functional group capable of reacting with the epoxy group, and a functional group having an epoxy group but capable of reacting with the epoxy group. Compounds that do not have.

Here, the functional group capable of reacting with an epoxy group means a group which reacts with an epoxy group to cause a crosslinking reaction thereof, and examples thereof include a hydroxyl group, a carboxyl group and a sulfonic acid group. In the present invention, when an epoxy group-containing compound having a functional group capable of reacting with an epoxy group is further used, the addition of the epoxy curing agent to the first liquid as described later can be omitted. On the other hand, when an epoxy group-containing compound having a functional group capable of reacting with an epoxy group is used and an epoxy curing agent is further added to the first liquid, the fixing speed of printing can be further improved. Which advantage is obtained can be appropriately selected.

The mechanism by which an epoxy group-containing compound is added to the ink composition in the present invention to obtain good printing as described above is considered as follows. However, this mechanism is merely an assumption, and the present invention should not be construed as being limited to this mechanism.

In the method according to the present invention, first, the first liquid is attached to the recording medium. Next, the ink composition is attached to the recording medium to which the first liquid is attached. When the ink composition adheres to the recording medium, aggregation occurs due to the interaction between the polyvalent metal ion of the polyvalent metal salt in the first liquid and the colorant and / or the resin emulsion in the ink composition (see below). In the case where the epoxy group-containing resin emulsion also serves as the resin emulsion, aggregation occurs due to the interaction between the epoxy group-containing resin emulsion and the polyvalent metal ion). Here, when the first liquid contains an epoxy curing agent, a crosslinking reaction of the epoxy groups of the epoxy group-containing compound occurs and resinification proceeds. In addition, when a compound having a functional group capable of reacting with an epoxy group is used as the epoxy group-containing compound, it is considered that the resin formation proceeds by the following mechanism despite the absence of the epoxy curing agent. That is, with the polyvalent metal salt in the first liquid,
When the distance between the epoxy group-containing compounds becomes extremely small due to aggregation with the colorant and / or the resin emulsion, a phenomenon occurs in which an epoxy group and a functional group capable of reacting with the epoxy group react between adjacent epoxy group-containing compounds. is expected. It is considered that this reaction causes a cross-linking reaction between the epoxy group-containing compounds to form a resin. By the resinization as described above, the printing firmly adheres to the recording medium, and the resin film is further formed on the printing surface. It is considered that such printing has good abrasion resistance, water resistance, and light resistance.

It is obvious that it is not preferable that the epoxy group-containing compound having a functional group capable of reacting with the epoxy group reacts with each other in the ink composition. It is preferable to avoid utilization.

Examples of the epoxy group-containing compound preferably used in the present invention include epoxy group-containing resin emulsions and water-soluble epoxy compounds.

According to a preferred embodiment of the present invention, the epoxy group-containing resin emulsion has a continuous phase of water and a dispersed phase of the following formulas (I) and (II):

[0017]

Embedded image (In the formula, R ¹ and R ³ independently represent H or CH ₃ , and R ² is an alkyl group (preferably C ₁ to
₂₁ alkyl), a hydroxyl group, a carboxyl group and a sulfonic acid group, which represents one or more groups), and an epoxy group-containing acrylic resin containing a copolymer containing a repeating unit represented by Examples include emulsions. This resin is not limited depending on the mode of copolymerization, and can be, for example, a block copolymer or a random copolymer.

The end of such a copolymer does not have an essential effect on the properties of the copolymer because it is a polymer, but in general, a segment of a polymerization initiator is bound to it. Will be Examples of such a section of a polymerization initiator include sections of a polymerization initiator such as ammonium persulfate and potassium persulfate, specifically —OSO ₃ H.

Preferred examples of R ² are --OH and --C.
OOH, —COO—R (wherein R represents a linear or branched alkyl group, preferably a C _1-12 alkyl group, and one or more hydrogen atoms on the alkyl group are a hydroxyl group or a phosphono group. Or optionally substituted with a sulfonic acid group) and an aryl group substituted with a sulfonic acid group (eg, a phenyl group, a tolyl group). Specific examples of the group represented by R ² include —OH, —COOH,
_{-COOCH 2 CH 2 OH, -COOCH 2} CH (CH
_{3) OH, -COOCH 2 CH 2} PO (OH) 2, -C
₆ H ₅ SO ₃ H, -COOCH ₂ CH ₂ SO ₃ H, -C
_{OOCH 3, -COOC 2 H 5,} -COOC 4 H 9, -
COOC ₆ H ₁₃ , -COO (CH ₂ ) ₁₁ CH, -COO
_{CH 2 CH (CH 3) CH} 2 C (CH 3) 3 and the like. Here, the hydroxyl group, carboxyl group, or sulfonic acid group that may be contained in R ² is a functional group capable of reacting with the epoxy group. Therefore, when R ² contains only an alkyl group and when R ² contains a hydroxyl group, a carboxyl group, or a sulfonic acid group but does not substantially react with the epoxy group, the resin emulsion reacts with the epoxy group. It has no possible functional groups. When R ² contains a hydroxyl group, a carboxyl group, or a sulfonic acid group in addition to the alkyl group, the resin emulsion has a functional group capable of reacting with the epoxy group.

It is also possible to use a commercially available resin emulsion, for example, Almatex Z116 (manufactured by Mitsui Toatsu Chemical Co., Inc.), Newcoat S-2170 and S-1080 (Shin-Nakamura Chemical). Industrial Co., Ltd.), Vanatex # 952 and HG-9.
(Manufactured by Shin-Nakamura Chemical Co., Ltd.), Pietex B-
3 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The water-soluble epoxy compound preferably contains two or more epoxy groups reactive with the epoxy curing agent described later in one molecule, and is typically a water-soluble diepoxide. . Examples of the water-soluble epoxy compound preferably used in the present invention include those represented by the following formula.

[0022]

Embedded image (In the formula, n represents a natural number of 4 to 9) A preferred example of the water-soluble epoxy compound is polyethylene glycol glycidyl ether. As a commercially available product, Epolite 400E (polyethylene glycol # 400 glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.),
Epolite 200E (Polyethylene glycol # 200
Glycidyl ether, Kyoeisha Chemical Co., Ltd., Epolite 80
Examples include MF (glycerin diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.), Epiol G-100 (glycerin diglycidyl ether, manufactured by NOF CORPORATION), and Denacol (manufactured by Nagase Kasei Co., Ltd.).

The epoxy group-containing compound having a functional group reactive with the epoxy group, which is preferably used in the present invention, is, for example, at least part of R ^{2 in} the epoxy group-containing resin emulsion reacts with the epoxy group. Examples thereof include a functional group capable of being selected, that is, a functional group selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. A part of R ² is an alkyl group (preferably C ₁ to
C ₂₁ alkyl) and does not contain a functional group capable of reacting with an epoxy group. As a commercially available product, Almatex Z116 (manufactured by Mitsui Toatsu Chemicals, Inc.) can be mentioned.

The content of the epoxy group-containing compound in the ink composition according to the present invention is preferably about 1 to 10% by weight of the ink composition, more preferably 1 to 5% by weight.

The ink composition used in the present invention contains a resin emulsion as described later. When the epoxy group-containing compound is an epoxy group-containing resin emulsion, the epoxy group-containing compound is It also doubles as a resin emulsion,
Further, the resin emulsion of another component may not be included.
However, according to a preferred embodiment of the present invention, it is preferable to add a resin emulsion in addition to the epoxy group-containing resin emulsion.

In the present invention, an epoxy curing agent may be preferably contained in the first liquid. This epoxy curing agent
It means a compound that promotes resinification (polymerization) of the epoxy group-containing compound by a crosslinking reaction together with the epoxy group-containing compound contained in the above-mentioned ink composition. In the present invention, an epoxy curing agent which gives good abrasion resistance and water resistance in the ink jet recording method described below can be used without particular limitation.

The epoxy hardeners preferably used in this invention are typically water soluble. Such curing agents include amine compounds such as ethylenediamine,
Diethylaminopropylamine, N-aminoethylpiperazine, trimethylhexamethylenediamine, modified aliphatic amines, water-soluble polyamines, water-soluble room temperature curing catalysts other than amines, for example aromatic sulfonic acids such as P-phenol sulfonic acid, for epoxy emulsions A curing agent is included. It is also possible to use a commercially available curing agent, for example, ALMATEX H700.
(Mitsui Toatsu Chemical Co., Ltd.) and Epoki-H (Mitsui Toatsu Chemical Co., Ltd.).

The concentration of such an epoxy curing agent in the first liquid is preferably about 0.1 to 40% by weight, more preferably about 1 to 20% by weight.

In the present invention, when the ink composition is printed on the recording medium to which the first liquid is adhered, the epoxy curing agent contained in the first liquid and the epoxy group containing in the ink composition are contained. The compound reacts, and the crosslinking reaction of the epoxy group-containing compound proceeds. The reaction is represented as follows, for example.

[0030]

Embedded image As a result, the conversion of the epoxy group-containing compound into a resin (in the case of a resin emulsion, higher molecular weight) is promoted. By such resin formation during printing formed on the recording medium, the printing firmly adheres to the recording medium, and a resin film is further formed on the printing surface. Such printing has good abrasion resistance,
It has water resistance and light resistance.

Ink Composition The ink composition used in the present invention comprises a colorant and
It comprises at least a resin emulsion, an organic solvent, water, and the aforementioned epoxy group-containing compound.

The resin emulsion preferably used in the present invention is one in which the continuous phase is water and the resin component of the dispersed phase does not contain an epoxy group. As described above, when the epoxy group-containing compound is an epoxy group-containing resin emulsion, addition of this resin emulsion is not essential. Such resin components include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins,
Examples thereof include butadiene resin and styrene resin.

Further, as a commercially available resin emulsion,
For example, Microgel E-1002, 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, manufactured by Zeon Corporation), Cybinol SK-200 (acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.), and the like.

According to a preferred embodiment of the present invention, these resins are preferably polymers having both a hydrophilic portion and a hydrophobic portion. The particle size of these resin components is not particularly limited as long as it forms an emulsion,
nm or less is preferable, and more preferably 5 to 100 n
m.

These resin emulsions can be obtained by adding a surfactant and water to a polymer obtained by the polymerization reaction to emulsify it, or by emulsion-polymerizing a monomer in water in the presence of the surfactant. it can. For example,
The acrylic resin emulsion or the styrene-acrylic resin emulsion can be obtained by emulsion polymerization of (meth) acrylic acid ester or styrene and (meth) acrylic acid ester in the presence of an emulsifier such as a surfactant. . 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 preferable examples include anionic surfactants (eg, alkyl sulfate, alkylallyl sulfonate, dialkyl succinate, alkylnaphthalene sulfonate, etc.), nonionic surfactants having an HLB of 10 or more (eg, polyoxyethylene sulfonate). Ethylene alkyl ether, polyoxyethylene alkyl allyl ether, etc., and these may be used alone or in combination of two or more.

The ratio of the resin as the disperse 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.

The ink composition used in the present invention comprises a resin emulsion having a resin component of 0.1 to 0.1%.
The content is preferably 40% by weight, more preferably 1 to 25% by weight.

Both the resin emulsion containing an epoxy group and the resin emulsion not containing an epoxy group suppress the permeation of the coloring component due to the interaction with the polyvalent metal ion and further fix it to the recording medium. Has the effect of promoting

The colorant contained in the ink composition used in the present invention may be either a dye or a pigment.

Examples of dyes include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes,
Various dyes usually used for ink jet recording, such as a soluble vat dye and a reactive disperse dye, 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 pigments (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, 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 composition is 0.5.
Is preferably about 25 to 25% by weight, more preferably 2 to 15
It is about% by weight.

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 ink drying time.

The ink composition used in the present invention may contain a surfactant. Examples of surfactants include:
The above-mentioned surfactant and acetylene glycol (olefin Y, and Surfynol 82, 104, 44
0, 465, and 485 (all Air Products and
Chemicals Inc.))).

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, glucicyl. , (Sorbit), maltose, cellobiose,
Lactose, sucrose, trehalose, maltotriose, etc. can be mentioned. 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 above-mentioned saccharides (for example, sugar alcohol (general 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 appropriately in the range of 0.1 to 40% by weight, preferably 0.5 to 30% by weight of the ink composition.

According to a preferred embodiment of the present invention, it is preferable that the ink composition used in the present invention further contains a high boiling point organic solvent as a wetting agent. Preferred examples of the high-boiling organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, Polyhydric alcohols such as trimethylolethane and trimethylolpropane, 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 Alkyl ethers of polyhydric alcohols such as urea, 2-pyrrolidone, N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine and the like.

The amount of these wetting agents added is preferably 0.5 to 40% by weight of the ink composition, more preferably 2 to 2%.
The range is 0% by weight. The addition amount of the low boiling point organic solvent is preferably 0.5 to 10% by weight of the ink composition, and more preferably 1.5 to 6% by weight.

In addition, a pH adjusting agent, an antiseptic agent, an antifungal agent, etc. may be added to the ink composition, if necessary, in order to improve the storage stability.

Among these, examples of the pH adjusting agent include potassium hydroxide, sodium hydroxide and triethanolamine.

First Liquid The first liquid used in the present invention basically comprises a polyvalent metal salt, water, and preferably the above-mentioned epoxy curing agent.

In the present invention, the polyvalent metal salt contained in the first liquid is composed of polyvalent metal ions having a valence of 2 or more and preferably nitrate ions or carboxylate ions which bind to these polyvalent metal ions, It is soluble in water.

Here, the carboxylate ion is preferably derived from a carboxylic acid selected from the group consisting of a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms and a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. It is something. Carbon number 1
Preferred examples of the saturated aliphatic monocarboxylic acid of to 6 include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid and hexanoic acid. Particularly, formic acid and acetic acid are preferable.

The hydrogen atom on the saturated aliphatic hydrocarbon group of this monocarboxylic acid may be substituted with a hydroxyl group, and lactic acid is a preferred example of such a carboxylic acid.

Further, preferred examples of the carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid, and more preferred is benzoic acid.

On the other hand, specific examples of polyvalent metal ions include:
Examples thereof include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ and Ba ^2+, and trivalent metal ions such as Al ³⁺ , Fe ³⁺ and Cr ³⁺ .

In particular, the metal salt composed of the above-mentioned anion and Ca ²⁺ or Mg ²⁺ gives preferable results from the two viewpoints of the pH of the first liquid and the quality of the obtained printed matter.

The concentration of these polyvalent metal salts in the first liquid may be appropriately determined within a range where printing quality and the effect of preventing clogging can be obtained, but it is preferably about 0.1 to 40% by weight, and It is preferably about 5 to 25% by weight.

In the present invention, the first liquid preferably contains a wetting agent such as a high boiling point organic solvent. Preferred examples of the high boiling point organic solvent include those described in the section of the ink composition. The high-boiling organic solvent prevents head clogging by preventing the first liquid from drying.

The amount of the high boiling point organic solvent added is not particularly limited, but is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.

According to a preferred embodiment of the present invention, it is preferable to add triethylene glycol monobutyl ether and glycerin as the high boiling point organic solvent. When these are added in combination, the addition amounts of triethylene glycol monobutyl ether and glycerin are 10
It is preferably about 20 to 20% by weight and about 1 to 15% by weight.

Further, the first liquid may be colored by adding a color coloring agent and have the function of the ink composition.

In addition, in order to improve the storage stability, a pH adjusting agent, an antiseptic agent, an antifungal agent and the like may be added to the first liquid, if necessary.

Among these, examples of the pH adjusting agent include potassium hydroxide, sodium hydroxide and triethanolamine. When triethanolamine is added, its amount is preferably about 0 to 2.0% by weight.

Inkjet recording method and recording apparatus An inkjet recording method according to the present invention and an inkjet recording apparatus for carrying out the method will be described below with reference to the drawings.

The ink jet recording apparatus of FIG. 1 is an embodiment in which the ink composition and the first liquid are stored in a tank, and the ink composition and the first liquid are supplied to the recording head through the ink tube. That is, the recording head 1 and the ink tank 2 are connected by the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and the ink composition,
In some cases, a plurality of color ink composition chambers and a first liquid chamber are provided.

The recording head 1 is arranged along the carriage 4.
It is moved by the timing belt 6 driven by the motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by the platen 8 and the guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is supplied to the waste ink tank 13 via the tube 12.
Is stored in.

An enlarged view of the nozzle surface of the recording head 1 is shown in FIG. The portion indicated by 1b is the nozzle surface of the first liquid, and the nozzle 21 for discharging the first liquid is provided in the vertical direction. On the other hand, the portion indicated by 1c is the nozzle surface of the ink composition, and from the nozzles 22, 23, 24, and 25, the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are respectively provided. Discharged.

Further, an ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG. The recording head 1 moves in the direction of arrow A. During that move,
The first liquid is ejected from the nozzle surface 1b to form a band-shaped first liquid adhesion region 31 on the recording medium 7. Next, the recording medium 7 is transported by a predetermined amount in the paper feed direction arrow B. During that time, the recording head 1 moves in the direction opposite to the arrow A in the figure, and returns to the position on the left end of the recording medium 7. Then, the ink composition is printed on the first liquid adhering area where the first liquid is already adhering, and the printing area 32 is formed.

Further, as shown in FIG. 4, in the recording head 1, it is possible to arrange all the nozzles in the lateral direction. In the figure, 41a and 41b are discharge nozzles of the first liquid, respectively, from the nozzles 42, 43, 44 and 45, a yellow ink composition, a magenta ink composition,
A cyan ink composition and a black ink composition are ejected. In the recording head of such a mode, the recording head 1 can print on both the forward path and the return path that reciprocate on the carriage, and at a speed faster than that when the recording head shown in FIG. 2 is used. Printing can be expected.

Further, in some ink jet recording apparatuses, replenishment of the ink composition is performed by replacing the cartridge which is the ink tank. This ink tank may be integrated with the recording head.

A preferred example of an ink jet recording apparatus using such an ink tank is shown in FIG. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 5, the recording heads 1a and 1b
Is integrated with the ink tanks 2a and 2b.
The recording head 1a or 1b discharges the ink composition and the first liquid, respectively. The printing method may be basically the same as that of the apparatus shown in FIG. In this aspect, the print head 1a, the ink tank 2a, the print head 1b, and the ink tank 2b move together on the carriage 4.

Regarding the adhesion of the first liquid to the recording medium, either the method of selectively adhering the first liquid only to the place where the ink composition is adhered or the method of adhering the first liquid to the entire surface of the paper is used. It may be a mode. The former is economical because it can minimize the consumption of the first liquid,
A certain degree of accuracy is required for the position where both the first liquid and the ink composition are attached. On the other hand, in the latter, the requirement for the accuracy of the adhesion position of the first liquid and the ink composition is relaxed compared to the former, but a large amount of the first liquid is adhered to the entire surface of the paper, and the paper curls during drying. Cheap. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the first liquid.

[0076]

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 Raven 1080 5% by weight (Colombyan Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Microgel E-5002 10% by weight (styrene-acrylic resin emulsion, resin component 29 0.2%, MFT = about 80 ° C., manufactured by Nippon Paint Co., Ltd.) Almatex Z116 4% by weight (epoxy group-containing acrylic resin emulsion, resin component 50%, manufactured by Mitsui Toatsu Chemicals, Inc.) Sucrose 0.7% by weight mulch Thor 6.3 wt% Glycerin 10 wt% 2-Pyrrolidone 2 wt% Ethanol 4 wt% Pure water Remaining amount

Black ink 2 carbon black Raven 1080 5% by weight (Colombian Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Microgel E-5002 10% by weight (styrene-acrylic resin emulsion, Resin component 29.2%, MFT = about 80 ° C., manufactured by Nippon Paint Co., Ltd.) Epolite 400E 2% by weight (water-soluble epoxy compound, polyethylene glycol # 400 glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) 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

Black ink 3 carbon black Raven 1080 5% by weight (Colombyan Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight ALMATEX Z116 4% by weight (epoxy group-containing acrylic resin emulsion, resin component) 50%, manufactured by Mitsui Toatsu Chemicals, Inc.) Epolite 400E 2% by weight (water-soluble epoxy compound, Kyoeisha Chemical Polyethylene glycol # 400 glycidyl ether) 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

Black ink 4 Carbon black MA7 5% by weight (manufactured by Mitsubishi Kasei Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight ALMATEX Z116 3.0% by weight (epoxy group-containing acrylic resin emulsion, resin) Ingredients 50%, manufactured by Mitsui Toatsu Chemicals, Inc. Triethanolamine (pH adjuster) 0.9 wt% KOH (pH adjuster) 0.1 wt% Sucrose 0.7 wt% Maltitol 6.3 wt% Glycerin 10 wt% 2-pyrrolidone 2 wt% Ethanol 4 wt% Pure water Remaining amount

Black Ink 5 Carbon Black Raven 1080 5% by weight (Colombyan Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Microgel E-5002 10% by weight (styrene-acrylic resin emulsion, Resin component 29.2%, MFT = about 80 ° C., manufactured by Nippon Paint Co., Ltd.) 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 The carbon black and the dispersant 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. The above ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

A first liquid having the following composition was prepared by mixing the following components, stirring at room temperature for 1 hour, and then suction-filtering the composition at room temperature with a 5 μm membrane filter. First liquid 1 Magnesium nitrate hexahydrate 25% by weight Triethylene glycol monobutyl ether 10% by weight Glycerin 20% by weight Triethanolamine 0.9% by weight Pure water Remaining amount

First liquid Magnesium nitrate hexahydrate 25% by weight Water-soluble polyamine: Almatex H700 (epoxy curing agent) 2% by weight Triethylene glycol monobutyl ether 10% by weight Glycerin 20% by weight Triethanolamine 0 9.9% by weight pure water remaining amount

Printing evaluation test Printing method Printing was performed on each of the following papers with an inkjet printer MJ-700V2C (manufactured by Seiko Epson Corporation).
For printing, first print the first liquid at 100% duty, and then
Printed letters with black ink. The discharge amount of both the first liquid and the ink is 0.07 μg / dot, and the density is 360 dpi.
And

Printing test paper 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.)・ Recycled paper) Yamayuri paper (Recycled paper manufactured by Honshu Paper Co., Ltd.)

Evaluation 1 : Print quality (OD value) The reflection OD value of the printed matter is Macbeth PCMII (manufactured by Macbeth Co.).
It was measured at. The results were as shown in Table 1.

Evaluation 2 : Abrasion resistance test (line marker resistance) The printed matter was printed immediately after the printing and one day after the printing, in two states, yellow water-based ZEBRA PE manufactured by Zebra.
Using N2 (trademark), press the print characters with a pen pressure of 4.9 × 10.
Rubbing was carried out at ⁵ N / m ² , and the degree of stain on the yellow part was examined and evaluated as follows.

Immediately after printing, even if it is rubbed twice, no stain occurs. ◎ After 1 day, rubbing twice does not stain at all. ○ After 1 day, rubbing does not occur until rubbing once, but there is paper that stains after 2 times or more. △ Rub once after 1 day. There is paper that stains with ×

The results are shown in Table 1. Table 1 Evaluation 1 Evaluation 2 Scratch resistance 1st liquid black Printing quality (Line ink (OD value) Marker property) Example 1 1 1 1.53 ○ 2 1 2 1.48 ○ 3 1 3 1.55 ○ 4 1 4 1.50 ○ 5 2 1 1.53 ◎ 6 2 2 1.48 ◎ 7 2 3 1.55 ◎ 8 2 4 1.50 ◎ Comparative Example 1 1 5 1.40 △

[Brief description of drawings]

FIG. 1 is a diagram showing an inkjet recording apparatus for carrying out a method according to the present invention, in which a recording head and an ink tank are independent from each other, and an ink composition and a first liquid are formed by an ink tube. Is supplied to.

FIG. 2 is an enlarged view of the nozzle surface of the recording head, showing 1b.
Is the nozzle surface of the first liquid, and 1c is the nozzle surface of the ink composition.

FIG. 3 is a diagram illustrating inkjet recording using the recording head of FIG. 2; In the figure, reference numeral 31 denotes a first liquid adhering area, and reference numeral 32 denotes a printing area where the ink composition is printed on the first liquid adhering.

FIG. 4 is a diagram showing another aspect of the recording head, in which all the ejection nozzles are arranged in the horizontal direction.

FIG. 5 is a view showing an ink jet recording apparatus for carrying out the method according to the present invention. In this embodiment, the recording head and the ink tank are integrated.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording head 2 Ink tank 3 Ink tube 21 First liquid discharge nozzle 22, 23, 24, 25 Ink composition discharge nozzle 31 First liquid adhesion area 32 Printing area

Claims (8)

[Claims] 1. An ink jet recording method for depositing a first liquid containing a polyvalent metal salt on a recording medium, and thereafter printing the ink composition on the recording medium, wherein the ink composition comprises a colorant. An epoxy group-containing compound comprising a resin emulsion, an organic solvent, and water, and further containing an epoxy group-containing compound having a functional group capable of reacting with an epoxy group and / or an epoxy group-containing compound having no functional group capable of reacting with an epoxy group. The method that consists of. 2. The method of claim 1, wherein the first liquid further comprises an epoxy hardener. 3. The method according to claim 1, wherein the epoxy group-containing compound is an epoxy group-containing resin emulsion and / or a water-soluble epoxy compound. 4. The epoxy group-containing resin emulsion,
The method according to claim 3, which comprises a copolymer comprising repeating units represented by the following formulas (I) and (II). Embedded image (In the formula, R ¹ and R ³ independently represent H or CH ₃ , and R ² contains one or more groups selected from an alkyl group, a hydroxyl group, a carboxyl group, and a sulfonic acid group in its structure. Represents a group). 5. The method according to claim 3, wherein the water-soluble epoxy compound is represented by the following formula. Embedded image (In the formula, n represents a natural number of 4 to 9) 6. The ink composition further comprises a resin emulsion containing no epoxy groups.
5. The method according to any one of 5 above. 7. The method of claim 2, wherein the epoxy hardener is a water soluble polyamine. 8. A recorded matter recorded by the method according to claim 1.