JPH09254528A - Jet printing method for notice printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording medium good in the close adhesiveness to a plastic base material, not generating the blur of ink caused by ink jetting and good in water resistance immediately after printing and a jet printing method for notice printed matter good in light fastness. SOLUTION: A poly(meth)acrylic acid copolymer being a component of an ink receiving layer is based on methyl methacrylate, ethyl acrylate and a radical polymerizable monomer having a carboxyl group. In this case, printed matter excellent in water resistance after printing, light fastness and printing quality can be obtained by a printing method using ink prepared by dispersing colored particles obtained by coating the peripheries of resin particles with an average particle size of 50-300nm with org. pigment in an aq. liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet printing method for an ink jet bulletin board printed matter using a water-based ink, in which a base material and a coating layer are strong and have water resistance and light resistance, and further, storage stability of a recording medium. The present invention relates to a jet printing method capable of obtaining a bulletin board excellent in blocking resistance.

[0002]

2. Description of the Related Art There has been a remarkable progress in the technology of an ink jet color printer which uses an ink jet recording system to produce a color hard copy at a high speed. Inkjet is common in that an ink droplet flies from an ink head and the droplet directly reaches the printing medium to form an image, but it is necessary for the continuous type that the ink always circulates. It is roughly classified into a drop-on-demand type in which droplets are landed only on the part. In any of the methods, in order to obtain a high-quality image, there is a remarkable development of a recording medium in which the ink that has landed on the recording medium does not bleed and the ink is quickly absorbed in the thickness direction of the recording medium. .

Conventional inkjet recording liquids have been disclosed in JP-A-53-61412 and JP-A-54-89.
As disclosed in JP-A-811 and JP-A-55-65269, water-soluble dyes such as acid dyes, direct dyes and basic dyes dissolved in a glycol solvent and water are often used. However, as the water-soluble dye, those having high solubility in water are generally used in order to obtain stability of the recording liquid. Therefore, the ink jet recorded matter generally has poor water resistance, and when water is spilled, there is a problem in that dye bleeding easily occurs in a recorded portion. In order to improve such poor water resistance, it has been attempted to change the structure of the dye or prepare a recording liquid having a strong basicity, as disclosed in JP-A-56-57862. Further, JP-A-50-49004 and JP-A-57-36692 are also available.
JP, JP-A-59-20696, JP-A-59-
As disclosed in Japanese Patent No. 146889, attempts have been made to improve the water resistance by making good use of the reaction between a recording paper and a recording liquid. Although these methods have a remarkable effect on a specific recording paper, they lack versatility in that they are restricted by the recording paper, and when a non-specific recording paper is used, a water-soluble dye is used. In many cases, the recording liquid used cannot obtain sufficient water resistance of the recorded matter. Further, as a recording liquid having good water resistance, there are those in which an oil-soluble dye is dispersed or dissolved in a high-boiling point solvent, and those in which an oil-soluble dye is dissolved in a volatile solvent, but the odor of the solvent or the discharge of the solvent On the other hand, it may be environmentally disliked, and the necessity of solvent recovery may become a problem when recording a large amount of data or depending on the installation location of the device.

Therefore, in order to improve the water resistance of the recorded matter, a recording solution in which a pigment is dispersed in an aqueous medium has been developed. Although these methods have a remarkable effect on a specific recording paper, they lack versatility in that they are restricted by the recording paper, and when a non-specific recording paper is used, a water-soluble dye is used. In many cases, the recording liquid used cannot obtain sufficient water resistance of the recorded matter.

Japanese Examined Patent Publication No. 55-34173 proposes that a recording medium coated with an emulsion specified for metal, glass, wood, etc. has good printability of a non-permeable material.

Further, JP-A-55-51583 discloses a coating layer comprising non-colloidal silica (particle size: 0.1 to 10 μm) and a polymer binder, and JP-A-56-145856 discloses a fine particle silicic acid. And a non-aqueous solvent-soluble resin, or it is disclosed that a receptive layer consisting of fine particle silicic acid and other inorganic pigment particles and a non-aqueous solvent-soluble resin is provided on the substrate, respectively. In this respect, it is easily conceivable that the ink redissolves in water in this method.

Japanese Unexamined Patent Publication No. 59-178288 discloses an example in which a recording medium is heat-treated to make the ink receiving layer transparent and consequently improve water resistance. It is difficult to say that it is practical because it requires heat treatment. In addition, as an example of a coating agent for overhead projector (OHP) film, Japanese Patent Laid-Open No.
Japanese Patent Application Laid-Open No. 9-207277 discloses that a water-soluble substance and a polyhydric alcohol are contained in the ink absorption layer, but since a water-soluble substance is used, there is still a problem in terms of water resistance after the ink has landed. For the same purpose, JP-A-60-145879 discloses a combination of polyvinyl alcohol and polyvinylpyrrolidone having a high saponification degree in the coating layer, and JP-A-60-171143 discloses an ionic hydrophilic surface. A recording medium coated with a water-soluble polymer having a group is exemplified, but both have poor water resistance after ink landing, and when the printed matter is soaked in water and rubbed, the ink and receiving layer itself easily peel off. There is a problem that ends up.

Regarding the method of improving the water resistance after the ink has landed, for example, JP-A-61-277481 discloses that an ink receiving layer contains a cationic and amphoteric pigment, and further contains a cationic silica or aluminum oxide and a cationic polymer. Japanese Patent Publication No. 61-59239 discloses an example in which a polycationic polymer electrolyte is contained, and further Japanese Patent Publication No. 62-797 discloses that a recording medium coated with a water-soluble polymer is prepared by using an aqueous ink. There has been proposed a method of increasing the water resistance of a recording medium by applying a water-proofing agent that insolubilizes the water-soluble polymer to the recording medium after inkjet recording. Further, as a recording liquid having good water resistance, it is said that an oil-soluble dye dispersed or dissolved in a high boiling point solvent is preferable, but it may be environmentally disliked for the discharge of odor and solvent, The necessity of solvent recovery may be a problem when recording a large amount of data or depending on the installation location of the device. Therefore, in order to improve the water resistance of the recorded matter, a recording solution in which a pigment is dispersed in an aqueous medium is being developed.

As described above, various methods have been proposed for making the ink jet receiver water resistant and the ink itself water resistant, but all of them are weak against humidity and the recording medium is coated, dried and wound up. At that time, blocking occurs and it cannot be wound up as it is. Further, as an example of physically improving the ink absorption, as shown in Japanese Patent Application Laid-Open No. 2-76775, in the case where there is an ink absorption layer in which a spherical polymer is adhered with a binder resin on a sheet-shaped substrate, Although it can provide good water resistance, it has a defect that the abrasion resistance as a printed material is not good and the ink receiving layer is peeled off from the substrate.

[0010]

In order to solve the above problems, there is provided an ink jet printing method for bulletin printing, which has good blocking property, winding property, is strong, is water resistant, has high printability, and has excellent print quality characteristics. The purpose is to provide.

[0011]

The first invention is an ink jet receiver having an aqueous ink receiving layer provided on at least one surface of a support made of a plastic film, and the aqueous ink receiving layer. An adhesive layer is formed on the surface opposite to the inkjet receiving layer whose resin composition is a poly (meth) acrylic acid ester copolymer whose main component is a radically polymerizable monomer having methyl methacrylate, ethyl acrylate and a carboxyl group. A jet for a printed matter, characterized in that an ink is prepared by dispersing colored particles, in which resin particles having an average particle size of 50 to 300 nm are covered with an organic pigment, in an aqueous liquid, to an inkjet receiver having the particles. The printing method.

A second aspect of the invention is a resin composition of an aqueous ink receiving layer comprising a poly (meth) acrylic acid ester copolymer mainly composed of methyl methacrylate, ethyl acrylate and a radically polymerizable monomer having a carboxyl group. The jet printing method for a bulletin board according to the first invention is characterized in that the acid value is in the range of 50 to 80. The third invention is
The jet printing method for printed matter of the first invention is characterized in that the average particle diameter of the organic pigment in the water-based ink is 10 to 70 nm.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic film of the present invention is a polyethylene terephthalate film, triacetyl cellulose film, polycarbonate film, polyamide film, polyetherimide film, polysulfone film, polyethylene film, polypropylene film, soft polyvinyl chloride film, Examples of the film include ethylene-vinyl acetate copolymer films. When using the above film as a support for use as an outer wall or a building material, a polyethylene film having a small tensile elastic modulus of the support, polypropylene A film, a soft vinyl chloride film or a film made of an ethylene-vinyl acetate copolymer is suitable.
Further, in the case of OHP use, a polyester type, that is, a polyethylene terephthalate film has its optical characteristics,
It is preferable in terms of mechanical properties and workability. Polyethylene terephthalate film, if necessary, various surface treatment,
That is, if the ink is subjected to corona discharge treatment (in air, nitrogen, carbon dioxide, etc.) or easy adhesion treatment, it is expected to improve the adhesion of the ink receiving layer to the substrate and the water resistance. it can. Further, the optical characteristics of the substrate for OHP use are preferably such that the total light transmittance is 80% or more.

The support film can be selected from transparent and white films depending on the application. To make the support white, silica, titanium, zirconium,
A filler of a metal oxide such as aluminum or a metal carbonate such as calcium carbonate may be mixed, and the support may be a foam, and the filler is not limited thereto. In the case of soft vinyl chloride film, heat stabilizer,
A plasticizer, an ultraviolet absorber, an antistatic agent and the like may be blended as necessary. Further, various additives may be added in order to enhance the product value, and the additives are not limited as long as they do not impair the object of the present invention.

Examples of the plasticizer include basic carboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid and oleic acid, and a monovalent compound. Alternatively, a low molecular weight ester plasticizer with a polyhydric alcohol compound, a polyester plasticizer, an alkyd plasticizer, an epoxy plasticizer, etc. can be freely selected, but weather resistance,
From the viewpoint of flexibility retention, a polyester plasticizer, an alkyd plasticizer, or an epoxy plasticizer is preferable.

Examples of the heat stabilizer include calcium stearate, barium stearate, lead stearate, lead sulfite, lead phosphite, dibutyltin malate, dibutyltin laurate, dibutyltin mercaptide, dioctyltin malate stabilizer, dioctyl. Examples include tin laurate stabilizers, dioctyl tin mercaptide stabilizers, tin diol derivatives, and composites thereof. As the ultraviolet absorber, 290 to 400n
Examples of compounds that absorb m-wavelength light include benzophenone compounds, benzotriazole compounds, salicylic acid phenyl ester compounds, hindered amine compounds, cyanoacrylate compounds, cinnamic acid compounds, and aminobutadiene compounds.
You may use these materials 1 type or in mixture of 2 or more types. Further, as the antistatic agent, polyoxyethylene alkylamine, polyoxyalkyl amide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate alkyl phosphate, quaternary ammonium sulfate, etc. However, the present invention is not limited to these.

To achieve the object of the present invention, the weight ratio of methyl methacrylate to ethyl acrylate is 9/1.
˜2 / 8, preferably 7/3 to 6/4. If the amount of ethyl acrylate is more than this, blocking tends to occur, and if it is less than this, the coating film of the ink receiving layer is broken. In this case, the acid value is an important factor of the ink receiving layer.
The acid value is generally measured by titration with potassium hydroxide. When the acid value is high, the amount of carboxylic acid contained in the resin is high, and the water-based ink receptivity is improved.
Water resistance deteriorates. On the other hand, when the acid value is low, the water-based ink receptivity is poor, but the water resistance of the receptive layer itself is good. Therefore, according to the present invention, when the weight ratio of methyl methacrylate to ethyl acrylate is 7/3 to 6/4, the acid value is 50 to 80.
It is preferable because the ink receptivity is good and the water resistance after printing is good only when it is. The above monomers can be copolymerized and various additives can be added.

As the radically polymerizable monomer having a carboxyl group, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or the like is used. In addition, examples of the monomer copolymerized as necessary include 2-hydroxyethyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the like. (Meth) acrylic amide, N-methyl (meth) acrylic amide, N-ethyl (meth) acrylic amide, N-methylol (meth) acrylic amide, N-diethyl (meth) acrylic amide, 2-dimethylaminoethyl (meth) Acrylate, 7-amino-
3,7-Dimethyloctyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, glycidyl (meth) acrylate, allylglycidyldi Examples thereof include ethers, vinyl sulfonates and monomers containing those salts, vinyl isocyanates, vinyl methyl ethers, alkyl maleic acid monoesters, vinyl chloride and vinylidene chloride. These are copolymerized by a conventional method.

As a method of forming the prepared resin solution on a target support, a known method can be applied. For example, a method such as wire bar coating, rod coating, gravure direct coating, gravure reverse roll coating, die coating, curtain coating, and kiss touch gravure reverse roll coating is preferable, but the method is not limited to this as long as it can be applied uniformly. Not a thing. If necessary, the coated surface may be smoothed by a machine calendar, gloss calendar, super calendar or the like after drying.

In the ink receiving layer on the support, the glass transition point of the resin layer is preferably in the range of 50 to 70 ° C, preferably 60 to 70 ° C. If the formed glass transition point is lower than this, it can be expected that the dried coating film will maintain the viscosity, and thus dust will be easily adsorbed and blocking will easily occur. On the other hand, if the glass transition point is higher than this, cracking of the coating film of the ink receiving layer will occur.

To form the ink receiving layer on the support,
It is desirable to form it on the recording medium using the coater or the like. If an adhesive layer has already been formed on the surface opposite to the ink receiving layer formed on the support, it can be used by pasting it on the adherend after printing by inkjet, that is, the signboard application mark. It can be used as a thing. In this case, when the support is made of soft vinyl chloride, it is useful as an outdoor signboard.

Specific examples of the organic pigment in the ink used in the present invention include insoluble azo pigments such as toluidine red, toluidine maroon, hansa yellow, benzidine yellow and pyrazolone red, litol red, heliobordeaux and pigment scarlet. , Soluble azo pigments such as Permanent Red 2B, derivatives from vat dyes such as alizarin, indanthrone and thioindigo maroon, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, quinacridone pigments such as quinacridone magenta, and perylene. Red, perylene scarlet and other perylene pigments,
Isoindolinone yellow, isoindolinone orange and other isoindolinone pigments, benzimidazolone yellow, benzimidazolone orange, benzimidazolone red and other imidazolone pigments, pyranthrone red,
Pyranthrone pigments such as pyranthrone orange, thioindigo pigments, condensed azo pigments, thioindigo pigments, flavanthrone yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthron orange, dianthra Other pigments such as quinonyl red and dioxazine violet can be exemplified.

In addition, the organic pigment is referred to as a color index (C.
I.) number, CI Pigment Yellow 12,
13, 14, 17, 20, 24, 74, 83, 86, 9
3, 109, 110, 117, 120, 125, 13
7, 138, 147, 148, 151, 153, 15
4, 166, 168, CI Pigment Orange 16, 3
6, 43, 51, 55, 59, 61, CI Pigment Red 9, 48, 49, 52, 53, 57, 97, 12
2,123,149,168,175,176,17
7, 180, 192, 215, 216, 217, 22
0,223,224,226,227,228,23
8, 240, CI Pigment Violet 19, 23,
29, 30, 37, 40, 50, CI Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 6
4, CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26 and the like.

The ink jet recording liquid of the present invention comprises an organic pigment dispersion liquid obtained by finely dispersing an organic pigment in water together with a dispersant and a compound of the following general formula, and an average particle diameter of 50 to 300 nm. It is produced by mixing and stirring a dispersion liquid of resin particles. Formula P- [X-Y-Z-N ( R 1) R 2 ] n (In the formula, P is an organic pigment residue, a heterocyclic residue or an aromatic polycyclic compound residue, X is, S , C, N, O, H, a divalent linking group consisting of a chemically rational combination composed of 2 to 15 atoms, Y is a direct bond, -NR-
(However, R is H or an alkyl group having 1 to 18 carbon atoms),
A divalent linking group selected from —O—, Z is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, or R ¹
And R ² may form a heterocycle, which may have a substituent, and n represents an integer of 1 to 3. )

As the dispersant, various surfactants, low molecular weight dispersants, resin-based dispersants having a hydrophilic functional group and a hydrophobic functional group, and the like are used. As the surfactant, anionic, nonionic, cationic or amphoteric surfactant can be used.

Examples of the anionic activator include fatty acid salt, alkyl sulfate ester salt, alkyl aryl sulfonate, alkyl naphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl diaryl ether disulfonate and alkyl phosphate. Salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, etc. It can be illustrated.

As the nonionic activator, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Examples thereof include glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based and silicon-based nonionic activators.

Examples of the cationic activator include alkylamine salts, quaternary ammonium salts, alkylpyridinium salts and alkylimidazolium salts. Examples of the zwitterionic activator include alkyl betaine, alkyl amine oxide, phosphadyl choline and the like. Fine dispersion of organic pigments in water is performed by sand mill, ball mill,
It can be carried out by a method using a disperser such as an attritor, a paint shaker, a pearl mill, and an ultrasonic disperser.

In order to further miniaturize the organic pigment, the organic pigment is kneaded with a water-soluble inorganic salt, a water-soluble solvent and, if necessary, a compound of the general formula and dispersed in water. The organic solvent is preferably removed to produce an organic pigment dispersion. In this method, the water-soluble inorganic salt is used as a crushing aid, and the primary particles of the organic pigment are mechanically finely divided. Specifically, a small amount of a water-soluble solvent as a wetting agent is added to a mixture of an organic pigment, a water-soluble inorganic salt, and the following general formula compound, and after kneading with a kneader or the like, the mixture is put into water at a high speed. Stir with a mixer to make a slurry. Next, the slurry is repeatedly filtered and washed with water to remove the water-soluble inorganic salt and the water-soluble solvent.

More specifically, X in the general formula is -S.
_{O 2 -, -CO -, -} CH 2 -, - CH 2 S -, - C
_{H 2 O -, - O -} , - COO -, - NH -, - CH 2 N
HCOCH-, or a combination thereof,
Of these, —SO ₂ —, —CO—, and —CH ₂ — are preferable. The constituent elements other than carbon in the heterocycle formed by R ¹ and R ² include N, O and S. It should be noted that the organic pigment and P in the above general formula compound, that is, the organic dye residue, the heterocyclic residue or the aromatic polycyclic compound residue, are combined in the same system from the viewpoint of a normal hue, and particularly a blue pigment. It is preferable to combine a phthalocyanine-based residue with a red pigment, a quinacridone-based residue with a red pigment, and a benzimidazole-based residue with a yellow pigment, but they do not necessarily match.

The above general formula compound is preferably partially soluble in a water-soluble solvent used as a wetting agent at the time of kneading. When it is not soluble, a dilute acid is added to the general formula compound for neutralization treatment. It is preferable to carry out the above process to make it soluble. As the acid, acetic acid, hydrochloric acid, sulfuric acid or the like can be used. Further, in the present invention, two or more kinds of the compounds represented by the above general formula can be used in combination.

As the water-soluble inorganic salt, sodium chloride,
Examples thereof include potassium chloride.

The water-soluble solvent is not particularly limited, but a solvent having a high boiling point is preferable from the viewpoint of safety, since the temperature rises during the kneading process and the solvent is easily evaporated. For example, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol and the like are used.

When the organic pigment is kneaded with the water-soluble inorganic salt, the water-soluble solvent and, if necessary, the compound of the general formula, additives such as a dispersant and a plasticizer may be used together. Further, two or more kinds of organic pigments may be mixed and finely dispersed. Obtained dispersion of organic pigment and average particle size 50 to 300
The dispersion liquid of the resin particles having a particle diameter of 10 nm is mixed and stirred with water, an aqueous solvent and a dispersant as necessary to disperse the colored particles in which the resin particles are covered with the organic pigment in the aqueous liquid. An ink jet recording liquid is obtained. The mixing and stirring can be performed by a mixing stirrer such as a high speed disperser or an emulsifier, in addition to a normal stirrer using a blade.

A water-soluble resin may be used in the ink jet recording liquid of the present invention in order to firmly fix the colored particles. Examples of the water-soluble resin include acrylic, styrene-acrylic, polyester, polyamide, and polyurethane resins that are soluble in water. The water-soluble resin is preferably used in the recording liquid in an amount of 5% by weight or less. If it exceeds 5% by weight, the ejection stability of the recording liquid may be deteriorated.

The ink jet recording liquid of the present invention uses water and an aqueous liquid containing an aqueous solvent as the medium. As water, deionized water or distilled water from which metal ions and the like have been removed is used. In order to prevent the recording liquid from drying at the nozzle portion and to solidify the recording liquid, and to prevent stable ejection of the recording liquid and drying of the nozzle over time, the aqueous solvent may be used alone or in a mixture of 0 to 0% of the recording liquid. It can be used in the range of 50% by weight.

As the aqueous solvent, ethylene glycol,
Diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether,
Examples include ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. .

Alcohols such as methanol, ethanol and isopropyl alcohol can also be used for the purpose of speeding up the drying of the recording liquid on paper. When the material to be printed with the recording liquid is a permeable material such as paper, a penetrant can be added in order to stop the permeation of the recording liquid into the paper and accelerate the apparent drying property. As the penetrant, glycol ether such as diethylene glycol monobutyl ether exemplified as an aqueous solvent, alkylene glycol, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium dioctylsulfosuccinate and the like can be used. it can. These are sufficiently effective when used in an amount of 5% by weight or less of the recording liquid, and if the amount is more than this amount, bleeding of printing occurs, which is not preferable.

A fungicide may be added to the recording liquid of the present invention in the range of 0.05 to 1.0% by weight based on the recording liquid in order to prevent the generation of mold. Antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1.
-Oxide, 1,2-benzisothiazolin-3-one, amine salt of 1-benzisothiazolin-3-one and the like are used.

A chelating agent may be used in the range of 0 to 0.5% by weight of the recording liquid in order to prevent metal deposition at the nozzle portion and insoluble substances in the recording liquid. . The chelating agent sequesters metal ions in the recording liquid, and specifically, ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid. Examples thereof include tetraammonium salt of acid.

In order to adjust the pH of the recording liquid and stabilize the recording liquid or the stability of the recording liquid in the recording apparatus, a pH adjusting agent such as amine, inorganic salt or ammonia, or a buffer such as phosphoric acid is used. A liquid can be used. Further, an antifoaming agent may be added in order to prevent the circulation and movement of the recording liquid or the generation of bubbles during the production of the recording liquid. Further, for the purpose of adjusting the hue and imparting the density, the dye can be used in such a form that there is no problem in water resistance and light resistance.
Since the dispersion stability of the pigment may be deteriorated by using the dye, the amount used is 40% by weight or less of the pigment, and further 2
It is preferable that the amount is 5% by weight or less. As a dye,
Water-insoluble dyes such as disperse dyes and oil-soluble dyes, direct dyes, acid dyes, dyes obtained by insolubilizing basic dyes by lake formation, reactive dyes, metal-containing dyes and the like are used. The dye is
Purified dyes free of inorganic salts are preferred.

Other additives such as urea and dimethylurea may be added. The recording liquid is preferably prepared as a liquid having a viscosity of 0.8 to 15 cps (25 ° C.), though it depends on the type of recording device. Surface tension is 25-6
0 dyn / cm is preferable. The pH is not particularly limited, but is in the range of 4 to 12, preferably 7 to 10 neutral to weakly alkaline.

[0043]

The present invention will be described below in more detail with reference to examples. Example 1 "Production of magenta ink" Quinacridone red pigment 100
Parts, 500 parts of sodium chloride as a dispersion aid, and 100 parts of polyethylene glycol 300 were placed in a kneader and kneaded for 6 hours. Next, the mixture was stirred with a high speed mixer for about 1 hour to form a slurry. Filtration and washing with water were repeated 8 times to obtain an aqueous red pigment slurry I having an average particle diameter of 80 nm.

The following raw materials were placed in a sand mill and dispersed for 2 hours to prepare a concentrated recording liquid for inkjet. Aqueous red pigment slurry I (solid content 50%) 50.0 parts Acrylic resin aqueous solution (average particle size 300 nm, acid value 60) 3.0 parts pH adjuster 0.1 part Nonionic activator 1.0 part Purified water 50.0 parts Glycerin 6.0 parts

"Production of cyan ink" 100 parts of copper phthalocyanine pigment, 500 parts of sodium chloride, blue pigment dispersant (P- [CH ₂ NH (CH ₂ ) ₄ N (C
H ₃ ) ₂ ] ₃ , P is 50 parts of copper phthalocyanine residue) and 100 parts of polyethylene glycol (“Polyethylene glycol 300” manufactured by Tokyo Kasei Co., Ltd.) are charged into a stainless steel 1-gallon kneader and kneaded for 3 hours, and then mixed with a high speed mixer. Stir to form a slurry. Filtration and washing with water were repeated 5 times to remove sodium chloride and polyethylene glycol to obtain an aqueous blue pigment slurry II having a solid content of 50% and an average particle diameter of 70 nm.

The following raw materials were placed in a sand mill and dispersed for 3 hours to prepare a concentrated recording liquid for inkjet. Aqueous blue pigment slurry II (solid content 50%) 30.0 parts Acrylic resin aqueous solution (average particle size 250 nm, acid value 80) 3.0 parts Nonionic activator 1.0 part Purified water 50.0 parts Glycerin 6. 0 parts Concentrated recording liquid for inkjet 13.7 parts Nonionic activator 0.2 parts Acrylic resin emulsion 2.5 parts Ethylene glycol 10.0 parts Antifungal agent 0.15 parts pH adjuster 0.02 parts Purified water 63.53 copies

"Production of Yellow Ink" 100 parts of benzimidazolone pigment, 500 parts of sodium chloride, yellow pigment dispersant (P- [CH ₂ NH (CH ₂ ) ₄ N (C
H _{3) 2] 3,} P benzimidazole residue) 50 parts of polyethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd. "polyethylene glycol 300") were charged 100 parts of a one-gallon stainless steel kneader, kneaded for 3 hours, at a high speed mixer Stir to form a slurry. Filtration and washing with water were repeated 5 times to remove sodium chloride and polyethylene glycol to obtain an aqueous yellow pigment slurry III having a solid content of 50% and an average particle diameter of 50 nm. The following materials were placed in a sand mill and dispersed for 3 hours to prepare a concentrated recording liquid for inkjet. Aqueous yellow pigment slurry III (solid content 50%) 30.0 parts Acrylic resin aqueous solution (average particle size 100 nm, acid value 50) 3.0 parts Nonionic activator 1.0 part Purified water 50.0 parts Glycerin 6. 0 parts The following raw materials were mixed, filtered with a 1 μm membrane filter, and further filtered with a 0.45 μm membrane filter to prepare a recording liquid. Concentrated recording liquid for ink jet 13.5 parts Nonionic activator 0.2 parts Acrylic resin emulsion 2.2 parts Ethylene glycol 10.0 parts Antifungal agent 0.15 parts pH adjuster 0.02 parts Purified water 63. 53 parts 10 parts each of the yellow recording liquid, the magenta recording liquid and the cyan recording liquid were sampled, and were collected by Epson MJ700V.
It was set in a 2C color ink cartridge.

“Production of Black Ink” MICROJET M-800 (Orient Chemical Industry) Aqueous dispersion of carbon black (average particle diameter 60 nm, solid content 20%) 13.5 parts Nonionic activator 0.2 parts Acrylic resin Emulsion (average particle size 50 nm, acid value 60) 2.2 parts Ethylene glycol 10.0 parts Antifungal agent 0.15 parts pH adjusting agent 0.02 parts Purified water 63.53 parts Collect 10 parts of this black recording liquid Then, it was set in an Epson MJ700V2C black ink cartridge.

Preparation of Receptor Layer Coating Liquid Methylmethacrylate 54.7 parts Ethylacrylate 25.8 parts Acrylic acid 8.6 parts 2-Hydroxyethylmethacrylate 10.9 parts These are 1-liter round bottom flasks. Polymerization initiator solution prepared by dissolving benzoyl peroxide in 0.1 part of isopropyl alcohol 69.9 parts in the presence of 66.2 parts of isopropyl alcohol in a nitrogen gas atmosphere with uniform stirring at a reaction temperature of 80 ° C. Was added dropwise over 3 hours to polymerize, and 9.6 parts of ammonia and 24.2 parts of water were further added to obtain a coating resin solution. The physical properties of the synthesized resin were as follows. Acid value 67, glass transition point 62 degrees, pH of solution 10.5,
The solid content was 37.0% and the viscosity was 1230 cps. Further, the following dispersion liquid of crystalline cellulose was prepared. Asahi Kasei Corp. "Ceorus SC-701" 10.0 parts Purified water 90.0 parts These were stirred with an ace homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 10,000 rpm for 5 minutes to prepare a crystalline cellulose dispersion liquid.

40 parts of the synthesized resin solution, 20 parts of purified water,
To 2.0 parts of dimethylethanolamine and 20 parts of diacetone alcohol, 24 parts of the crystalline cellulose dispersion liquid were added, dispersed again with a homogenizer at 10,000 rpm for 1 minute, and allowed to stand for a day and night to obtain an inkjet ink receiving layer coating liquid.

This resin solution was coated on a soft vinyl chloride sheet: Dynacal DC1001 (manufactured by Toyo Ink Mfg. Co., Ltd.) with a gravure coater to give a dry film thickness of 25 .mu.m to obtain an ink jet recording medium.

When the above ink jet ink was printed on this ink jet recording medium with MJ700V2C manufactured by Epson Corporation, a full color printed matter in which the boundary of the ink did not bleed could be obtained. Further, although this printed matter was immersed in water and rubbed in water, it was possible to obtain a printed matter having good water resistance with no scratch on the printed surface. Furthermore, when a Okinawa exposure test was conducted for half a year to examine the light resistance test of the printed matter, no yellowing of the base material was observed before and after the exposure. It could be confirmed.

Example 2 A test was conducted in the same manner as in Example 1 except that the support was changed from a soft vinyl chloride sheet to a low density polyethylene film (GF-1 made by Tama Poly). In the abrasion test, the coating film did not peel off, the water resistance was good, and the printed matter without yellowing in the Okinawa exposure test could be obtained.

Example 3 Crystalline cellulose was prepared from Theolus SC-701 and Avicel R.
A test similar to that of Example 1 was carried out except that C-591 (manufactured by Asahi Kasei Co., Ltd.) was used, and the boundary of the ink was vivid and the coating film did not peel off even in the rubbing test in water, and the water resistance was also high. It was possible to obtain a printed matter that was good and did not yellow even in the Okinawa exposure test.

Comparative Example 1 The following resin was synthesized. Methyl methacrylate 62.0 parts 2-Ethylhexyl acrylate 23.0 parts Methacrylic acid 15.0 parts These were put in a 1-liter round bottom flask and the reaction temperature was 80 ° C. in the presence of 66.2 parts of isopropyl alcohol under a nitrogen gas atmosphere. While uniformly stirring with 0.1 parts of benzoyl peroxide, a polymerization initiator solution prepared by dissolving 0.1 parts of benzoyl peroxide and 69.9 parts of isopropyl alcohol was added dropwise over 3 hours to polymerize.
Further, 8.5 parts of dimethylaminoethanol and 25.3 parts of water were added to obtain a coating resin solution. The physical properties of the synthesized resin were as follows. The acid value was 98, the glass transition temperature was 53 degrees, the pH of the solution was 8.5, the solid content was 36.5%, and the viscosity was 560 cps. After that, a cellulose dispersion was prepared, a coating liquid for an inkjet receiving layer was prepared, an inkjet receiving layer was prepared by the same method as in Example 1, and a two-color printing test was carried out. The ink did not dry well, and in a rubbing test in water, the coating film was easily peeled off from the polyvinyl chloride as a support and could not be put to practical use.

Comparative Example 2 The following resin was synthesized. Styrene 70.0 parts 2-Ethylhexyl acrylate 17.0 parts Acrylic acid 13.0 parts These are put into a 1-liter round bottom flask and isopropyl alcohol 66.2 parts Reaction temperature 80 under nitrogen gas atmosphere
0.1% benzoyl peroxide with uniform stirring.
Part, and a polymerization initiator solution dissolved in 69.9 parts of isopropyl alcohol were added dropwise over 3 hours for polymerization, and 12.1 parts of ammonia and 21.7 parts of water were further added to obtain a coating resin solution. The physical properties of the synthesized resin were as follows. The acid value was 100, the glass transition temperature was 60 degrees, the pH of the solution was 8.5, the solid content was 37.2%, and the viscosity was 1000 cps. After that, a cellulose dispersion was prepared, a coating liquid for an inkjet receiving layer was prepared, an inkjet receiving layer was prepared by the same method as in Example 1, and a two-color printing test was carried out. The ink did not dry well, and in a rubbing test in water, the coating film was easily peeled off from the polyvinyl chloride as a support and could not be put to practical use.

As for the printing condition, the recording liquid was changed to an ink jet printer (“MJ700V” manufactured by Seiko Epson Corporation).
2C) was placed in the cartridge for recording, and the printed state of the recorded matter was visually evaluated. Good: Missing dots and no ink bleeding. Defective: missing dots and no ink bleeding. The water resistance was evaluated visually by performing a so-called rubbing test in which the recorded matter was dried and then bleeding of the ink when immersed in water for 24 hours and squeezing with a finger pad in water were checked for the presence or absence of flow.

Good: No ink bleeding and no bleeding. And there is no film peeling on the coating surface. Defective: There is ink bleeding and bleeding. Also, there is film peeling on the coating surface. Adhesion of the coating film to the substrate is 100% per 1 cm2 by cross-cutting with a cross cut before printing with ink.
Pieces were cut into individual pieces, and a 180 ° peel test was performed using cellophane tape manufactured by Nichiban to determine the quality. Good: No peeling. Poor: There was front peeling including partial peeling. The light resistance was measured in Okinawa by a Minolta color difference meter CR-100 for the recording material only and the full-color solid printing test piece before and after the exposure test in Okinawa for half a year.

Good: Color difference ΔE does not exceed 6. Bad: Color difference ΔE exceeds 6.

[0060]

[Table 1]

[0061]

EFFECTS OF THE INVENTION According to the present invention, a print obtained by jetting an ink jet ink using water as a medium has good printability, good adhesion to a substrate, and excellent water resistance immediately after printing. By being able to obtain a recording medium and by combining it with a water resistant pigment ink with good light resistance, it is water resistant and can be used practically as an outdoor signboard application other than office applications and as a marking material without post-treatment such as lamination. I was able to create a bulletin board.

Claims (3)

[Claims] 1. An inkjet receiver having an aqueous ink receiving layer provided on at least one surface of a support made of a plastic film, wherein the resin composition of the aqueous ink receiving layer is methyl methacrylate and ethyl acrylate. The average particle size of the ink jet receptor having an adhesive layer on the opposite side of the ink jet receptor layer made of a poly (meth) acrylic acid ester copolymer containing a carboxyl group-containing radically polymerizable monomer as a main component is 50 ~ 3
A jet printing method for a bulletin board, which comprises ejecting an ink in which colored particles in which resin particles of 00 nm are covered with an organic pigment are dispersed in an aqueous liquid. 2. The resin composition of the aqueous ink receiving layer has a poly (meth) acrylic acid ester copolymer mainly composed of methyl methacrylate, ethyl acrylate, and a radically polymerizable monomer having a carboxyl group as an acid value of 50. The jet printing method for a bulletin board according to claim 1, wherein the jet printing method is in the range of 80 to 80. 3. The average particle size of the organic pigment in the water-based ink is 10
It is -70 nm, The jet printing method for bulletin boards of Claim 1 characterized by the above-mentioned.