JPH0354270A - Image-recording ink and recording method - Google Patents

Abstract

PURPOSE:To obtain an image-recording ink improved in adhesion to a transfer medium in a rocess for performing printing by changing the adhesiveness of an ink by the application of a voltage, by compounding a colloidal sol containing a liquid dispersing medium with a polymerizable precursor. CONSTITUTION:1 pt. wt. inorganic or organic particles (A) of a mean particle diameter <= 100 mum is mixed with 40-95 pts. wt. liquid dispersing medium (B), 10-1000 pts. wt. polymerizable precursor (C) which is a compound which can be cured by a polymerization reaction such as addition polymerization or polycondensation when light and/or thermal energy is applied thereto and optionally 1-90 pts. wt. component B-soluble polymer, swellable particles, 0.1-40 pts. wt. colorant, etc., to form a colloidal sol to form 100 pts. wt. title ink which adheres to one electrode but does not adhere to the other electrode when a voltage is applied between a pair of a cathode and an anode in contact with the ink and has a viscosity (at 25 deg.C and a shear rate of 10 rad/s) of 1-10<12> P and a volume resistivity <= 10<5>OMEGA.cm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ink used in an image forming method using an ink whose adhesion changes with the application of a voltage.

[Prior Art] Printers using various recording methods, such as laser beam and
Printers, inkjet printers, thermal transfer printers 77: Printers, wire dot printers and daisy-foil printers are known.

wood! 1; 19jlIn Japanese Patent Application Laid-open No. 6, we wanted to be the first to propose a recording method in which pattern-shaped adhesiveness is chemically imparted to ink and the difference between adhesiveness and non-adhesiveness of this ink is utilized for recording.
3-302 No. 79). However, the recording method described in item 12 is not suitable for large-volume printing in terms of cost and the like.

As a new printing method that solves the above problems and connects various devices such as computers, the present applicant proposes a printing method (patent application No. 6111 -12617).

[Problems to be Solved by the Invention] Incidentally, the ink used in the method of printing by changing the adhesion of the ink by applying a -1 voltage has a problem in its fixability to the transfer medium, and the back side of the ink does not adhere after printing is completed. I sometimes suffered from bruising, and when I touched the printed surface, I sometimes got ink on my hands.

The present invention aims to improve the above-mentioned ink, and in particular, it is an object of the present invention to provide an image recording ink that has good fixability to a transfer medium.

[A Thousand Steps to Solve the Problem] The present invention provides an image recording ink that adheres only to one electrode and does not adhere to the other ZFfi by applying a voltage from a pair of Yin and Yang electrodes in contact with the ink. According to the present invention, the image recording ink is composed of a colloidal sol containing at least a liquid dispersion medium and an associative precursor. a step of supplying ink whose adhesion changes depending on the nature of the ink, a step of applying a voltage between the pair of electrodes and causing the ink to adhere to one of the electrodes to form an image, and a step of covering the adhered ink. In an image recording method that includes a step of transferring an image to a recording medium, the image is transferred to the recording medium by applying light and/or thermal energy to the recording medium using an ink containing a merging precursor. It is possible to achieve strong and stable adhesion to the film and to obtain sharp images.

That is, since the ink contains a polymerizable precursor that polymerizes and hardens by applying energy of either light or heat or both light and heat, , light or heat] Or, by applying both light and heat energy to the transferred image, the polymerizable i precursor is cured by kametsu and is firmly attached to the transfer medium. It becomes possible to achieve fixation.

Hereinafter, the principle of the image format discipline method according to the present invention will be explained with reference to the drawings. "%" and "parts" are based on weight unless otherwise specified.

i1'lA shows the -l aspect of an apparatus for forming an image using the ink of the present invention. In the figure, an ink carrying roll 1 is a member that has a cylindrical shape and rotates in the direction of the arrow ^. The roll 1 is made of a conductive material such as aluminum, copper, or stainless steel. On the surface (on the cylindrical surface) of the ink carrying roll 1, a coating roll 9 rotating in the direction of arrow E forms ink 2, which is a recording material, to a uniform thickness.

The ink carrying roll 1 is connected to one end of a DC power supply 103. The ink 2 on the surface 12 of the ink carrying roll 1 is wrapped around the plate roll 3! Version 4 is touching. The plate roll 3 is rotating in the direction of arrow B in the opposite direction to the roll 1.

For example, as shown in FIG. 2, the plate 4 has a desired pattern 4b made of an insulating material on a base material 4a made of a conductive material such as metal.

As the material of the base material 4a, aluminum, copper, stainless steel, platinum, gold, chromium, nickel, steel copper, carbon, etc., or conductive polymers or polymers with metal fillers dispersed therein are used. Materials for pattern 4b include thermal transfer recording materials (mainly wax and resin),
Electrophotographic toners, vinyl polymers and natural or synthetic polymers are used.

In this way, by applying a voltage between the plate 4 and the ink carrying roll 1 by the power supply 103, the adhesion of the ink 2 that comes into contact with the conductive portion of the plate 4 changes, and the difference in adhesion causes the ink 2 to be applied onto the plate. It is deposited in a pattern to form an ink image.

The voltage of the power supply 103 is practically 3 to 100V, and even 5V.
A DC voltage of ~80v is preferred, and a high frequency (10H7.~
By further applying an AC bias voltage of 100 kHz, the image quality can be made even sharper. In FIG. 1, the plate 4 side is the cathode, and the ink carrying roll 1 side is the
! Although it is $4, depending on the properties of the ink used, the plate 4 side may be used as the anode and the roll L side may be used as the cathode.

Specifically, the voltage from the power source 103 is preferably applied between the respective rotation axes of the printing roll 3 and the ink carrying roll 1.

The thickness of the ink layer 2 formed on the surface of the ink carrying roll 1 is determined by (the size of the gap between the ink carrying roll 1 and the coating roll 9, the fluidity or viscosity of the ink 2, and the thickness of the surface of the ink carrying roll 1). Although it varies depending on the material, surface roughness, rotational speed of the roll 1, etc.), the ink transfer position where the roll 1 faces the pattern 4 on the printing roll 3 is approximately 0.001 to 100 mm. preferable. If the thickness of the ink layer 2 is less than 0.001 mm, it will be difficult to form a uniform ink layer on the ink carrying roll 1. On the other hand, if the ink layer thickness exceeds 100 mm, it becomes difficult to convey the ink counterfeit 2 while keeping the surface layer of the ink layer (the layer in contact with the conductive pattern plate roll 4) at a uniform circumferential speed. It is also difficult to energize the support roll 1 and the plate 4.

Next, the ink image on the plate 4 is transferred to the plan cylinder 5, which rotates in the direction of arrow C while being in pressure contact with the plate 4, and the ink image on the plate cylinder 5 is further rotated in the direction of arrow D, while being in pressure contact with the plan rj45. A recording medium 7 (paper, cloth,
(metal sheet, etc.) to form an image 8 corresponding to the above-mentioned ink image on the recording medium 7.

In some cases, the ink image on the plate 4 may be directly transferred onto the recording medium 7 without providing the plan cylinder 5, but if the plan cylinder 5 is provided, the material of the plan cylinder 5 will prevent wear and deterioration of the plate. In addition, it is possible to obtain an image (positive image) with the same pattern as the plate on the recording medium.

In the present invention, in the image transferred onto the recording medium,
By applying light and/or thermal energy to cause a polymerization reaction of the polymerizable precursor contained in the ink constituting the image and curing it, the ink on the recording medium-L is firmly fixed. .

As a means of imparting this energy, any means that causes an electrolytic reaction to occur in the polymerizable precursor may be used.
For example, it can be carried out by known means such as irradiating the surface of the ink being transferred with ultraviolet light, heating with an electric heater or the like, or heating with an infrared lamp.

In addition to the above, a plate having an insulating film on which an image-like conductive pattern is formed by discharge breakdown on a base material made of a conductive material can also be used. Furthermore, it is also possible to use a plate having a photographic image on which a conductive pattern of a silver image is formed by depositing silver particles on a substrate made of a conductive material. Further, the shape of the plate is not limited to a flat surface, and may be a roll shape, a curved shape, or a square shape.

Image forming methods to which the ink of the present invention can be preferably applied include:
As explained above, the electrode (
version) and the opposing TI. By supplying a specific ink between the electrodes and applying a voltage between the pair of electrodes, the IE8
This method takes advantage of the fact that the adhesion of ink changes depending on the pattern of i.

The image forming method of the present invention basically uses ink that is sticky when no voltage is applied, and the stickiness is eliminated by applying a voltage, so that the ink adheres to the insulated portion of the plate, A desired recorded image is formed.

The ink of the present invention has the basic structure described below and further contains a polymerizable precursor described below.The basic structure of the ink will be explained below.

The following reasons can be considered for the mechanism by which the ink changes from adhesive to non-adhesive due to voltage application.

In other words, the mechanism is that when electricity is applied, the ink electrolyzes and generates gas, changing its tackiness. The ink generates gas nearby, and this gas prevents the ink from adhering to the electrode. In order for the ink to electrolyze and generate gas, the ink may contain a solvent such as water, alcohol, or glycol, or a solvent in which an electrolyte is dissolved. The lower the electrical resistance of the ink, the better, and the volume resistivity should be 10'
It is preferable to set it to Ω・clI+ or less. Volume resistance is 1
If it exceeds 0'Ω・clI1, the amount of current will decrease, or a high voltage will be required to prevent the amount of current from decreasing. The mechanism of the image forming method of the present invention is considered to be based on the above. In addition, with the ink of the present invention, the transfer of ink from the plate changes from adhesion to non-adhesion by applying a voltage.
Almost the entire portion of the ink layer to which the voltage is applied moves in the thickness direction (hereinafter referred to as bulk movement).

Regarding inks that adopt the above-mentioned mechanism, which will be further described below, if the content of a liquid such as water or alcohol is large, the cohesive force will be weak and suitable adhesiveness will not be obtained. The adhesion should be such that, for example, when the ink is applied to a vertically oriented platinum-plated stainless steel plate at a thickness of 2 ms+, the ink is substantially retained on the platinum-plated stainless steel plate. is preferred. In addition, ink was sandwiched between two platinum-plated stainless steel plates to make the ink thickness 2 m, and when the two platinum-plated stainless steel plates were separated from each other without applying any voltage, the ink appeared on both plates. It is preferable that the particles adhere to the same degree. The ink of the present invention, which adopts the above mechanism, is an amorphous solid in the form of a colloidal sol, which is basically composed of inorganic or organic fine particles and a liquid dispersion medium, and is a non-Newtonian fluid in terms of fluidity. Fine particles in ink tend to make the ink run better and improve image resolution. The viscosity is preferably 1-10" poise at 25° C. 1 orad/s, preferably 10'-to" poise. Fine particles can be produced in a dispersed form by kneading them in a liquid dispersion medium described below, for example, in a homogenizer, a colloid mill, or an ultrasonic disperser. Cu, etc.) particles, silicate (zinc sulfide ZnS, antimony sulfide Sb*Ss
．． Potassium VIA κ,S Calcium sulfide CaS
．． Germanium sulfide GeS, cobalt i-ide CoS
．． Tin sulfide SnS. Iron sulfide FeS %Copper sulfide Cul
S, manganese sulfide MnS. Molybdenum sulfide MOISs
) particles, silicic acid (orthosilicic acid LSiL, metasilicic acid H1SiOs, mesonicic acid H.Si.0, , fi
') Trisilicate H4SisOs, Me') Tetrasilicic acid H6
Si4o+ r, etc.) particles, polyamide resin particles, polyamideimide resin particles, etc. can be used, and iron hydroxide particles, aluminum hydroxide particles, fluorinated mica particles,
Polyethylene particles, montmorillonite particles, fluororesins, etc. can be used.6Also, polymer particles containing various particles used as electrophotographic toners can also be used.

The above-mentioned fine particles have an average particle diameter of 100 μm or less,
Preferably, particles of 0.1 to 20 μ can be used, preferably 10 μ or less, and such particles can be present in the ink in an amount of not less than 1 part or more per 100 to 119 parts of ink.
Preferably, it can be contained in an amount of 3 parts to 9 parts, more preferably 5 parts to 6 parts.

The liquid dispersion medium used in the ink includes ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (ffi weight average molecular weight, about 100
~+000), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl rubitol,
Ethyl rubitol, butyl carbitol, ethyl rubitol acetate, diethyl rubitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, glycerin, tonoethanolamine,
Formamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidene, 1,3-dimethylimidazolidinone, N-methylacetamide, ethylene carbonate, acetamide, succinonitrile, dimethylsulfoxide, sulfolane, furfuryl alcohol ,
N,N-dimethylformamide, 2-ethoxyethanol, hexamethylphosphoric triamide (hexamethylphosphoric triamide), 2-nitropropane, nitroethane, γ-butyrolactone, propylene carbonate,
One or a mixture of two or more of 1,2,6-hexanetriol, dipropylene glycol, hexylene glycol, and the like can be used. The liquid dispersion medium is Ink 100! It is preferable to contain 40 to 95 fILlt parts, more preferably 60 to 85 fILlt parts, based on the weight part. In a preferred embodiment of the present invention, in order to control the viscosity of the ink, the above-mentioned polymer soluble in the liquid partitioning medium is added to the ink in an amount of 1 to 90 parts by weight, more preferably 1 to 90 parts by weight, per 100 parts by weight of the ink. It can be contained in a proportion of 50 parts by weight, particularly 1 to 20 parts by weight. Examples of such polymers include plant-based polymers such as guar gum, locust bean gum, gum arabic, taragant, carrageenan, vectin, mannan, and starch; microbial polymers such as xanthan gum, dextrin, succinoglucan, and curdlan; gelatin, and casein. Animal-based polymers such as , albumin, and collagen; Cellulose-based polymers such as methylcellulose, ethylcellulose, and hydroxyethylcellulose, or starch-based polymers such as soluble starch, carboxymethyl starch, and methyl starch; and alginic acid-based polymers such as brobylene glycol alginate and alginates. Polymers and other semi-synthetic polymers such as polysaccharide derivatives: Vinyl polymers such as vorivinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymers, sodium polyacrylate; Other polyethylene glycol, ethylene oxide, oxidized Synthetic polymers such as brobylene block copolymers, alkyd resins, phenolic resins, epoxy resins, aminoalkyd reticulate resins, polyester resins, polyurethane resins, acrylic resins, polyamide resins, polyamideimide resins, polyesterimide resins, silicone resins, etc., alone or Two or more can be used in combination. It is also possible to use greases such as silicone grease and liquid polymers such as polybdenum.

If the change in the viscosity of the ink is caused by the generation of gas due to electrolysis, the liquid dispersion medium may be water, methanol, ethanol, glycerin, ethylene glycol, propylene glycol, or a solvent in which an electrolyte is dissolved. Preferably used. The contents of the liquid dispersion medium and fine particles are the same as those described above. In particular, it is preferable to use water or a liquid containing water as the liquid dispersion medium because hydrogen gas is likely to be generated on the negative electrode side. When water and another liquid dispersion medium are mixed, the content of water is preferably 1 part by weight or more, more preferably 1 part by weight or more, per 100 parts by weight of the ink.

In addition to those listed above, the m particles contained in the ink include silica, fluorocarbon, titanium oxide, etc. Carbon black, fluorinated carbon, etc. can be used.

In a preferred embodiment of the ink, considering the viscoelastic properties of the ink, the fine particles are preferably swellable fine particles that can retain the liquid dispersion medium in the particles. Examples of such swellable fine particles include Na-montmorillonite, Ca
-Montmorillonite, 3-octahedral synthetic smectite, N
Examples include fufluoride mica, synthetic mica, silica, etc., such as a-hectolite, L[-hectolite, Na-teniolite, Na-tetrasilicic mica, and Li-teniolite.

The above-mentioned fluorinated mica can be represented by the following general formula (+).

General formula (1): Stomach, +z3(X.Y)z. s 3(
Z40+a) In the Ft formula, W is Na or Li, X and Y are Mg", Fe"°Ni" Mn2 (1.^l".F
e".6-coordinate ion such as Lf+, Z is AI", Si'
°． Ge”.Fe”, B” or a combination thereof (AI”
/St" ) ft (D-coordinate rji.4) cation. The average particle diameter of the swellable fine particles is preferably 75 μm or less in a dry state, more preferably 0.815 μm or less, especially 8 μm or less.

Furthermore, the ink can contain colorants such as carbon black and other dyes and pigments that are generally used in the fields of printing and recording, if necessary. When the ink contains a colorant, the content fκ of the colorant is 0.1 to 4 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the ink.
0 −1 parts by weight is preferred. Also, instead of coloring material,
Alternatively, a color-forming compound that develops color upon application of voltage may be included together with the colorant. In addition, the ink may contain an electrolyte, a binder, and a thinning agent that impart conductivity. Furthermore, it is also possible to make the above-mentioned fine particles themselves function as a coloring agent. In the present invention, the viscosity of the ink is 25°C, 10 rad/
1 to 1012 Boaz in s, preferably 103 to]
09 poise is preferable, and the effect of changing from adhesion to non-adhesion due to gas generation can be enhanced.

Next, in addition to the basic structure explained above, the polymerizable precursor contained in the ink of the present invention will be explained.

In the present invention, a polymerizable precursor refers to a compound that undergoes a polymerization reaction such as addition polymerization or condensation upon application of light or thermal energy, or both, and is polymerized and cured. can be reliably fixed on the transfer medium. Typical compounds that cause addition polymerization that can be used in the present invention are ethylenically unsaturated polymerizable compounds, such as acrylic esters, acrylamides, methacrylic esters, methacrylamides, These include allyl compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes, and crotonic acid esters, all of which have one or more addition-polymerizable unsaturated bonds in their molecules.

Specific examples of compounds having one addition-polymerizable unsaturated bond include esdel acrylates, such as acrylic acid, alkyl acrylates (such as probyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate). ), methacrylic esters, such as methacrylic acid, alkyl methacrylates (such as methyl methacrylate, ethyl methacrylate, proyl methacrylate, isobrobyl methacrylate), acrylamides, such as acrylamide, N-alkylacrylamide, ( Examples of the alkyl group include methyl group, ethyl group, butyl group, isoprobyl group, t-butyl group, and ethylhexyl group. Examples include methyl group, ethyl group, isobrobyl group, t-
These include butyl and ethylhexyl groups. ), allyl compounds such as allyl esters (e.g. allyl acetate, allyl cabroate, allyl cabrylate, allyl laurate, allyl balmitate), vinyl ethers such as alkyl vinyl ethers (e.g. hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether) ), vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethylacedate, vinyl ethyl acetate, vinyl valerate, vinyl cabroate, and the like. Other examples include styrenes such as styrene, methylstyrene, chloromethylstyrene, alkoxystyrene, halogenated styrene, and benzoic styrene.

Examples of crotonate esters include methyl crotonate, ethyl crotonate, butyl crotonate, hexyl crotonate, and isobrobyl crotonate.

Next, specific examples of compounds having two or more addition-polymerizable unsaturated bonds will be illustrated. First, as acrylic esters and methacrylic esters, polyacrylates and polymethacrylates of polyhydric alcohols (herein "
"Poly" refers to diacrylate or more. ) or there is.

The above-mentioned polyhydric alcohols include polyethylene glycol, polybrohylene oxide, polybutylene oxyside, (β・- and dorothyethoxy)henzene, glycerin, diglyseson, neo-ethyl glycol, trimethylolbroban, l- soetylol blobane,
bentaerythritol, diventaerythritol,
sorbitan, sorbitol, l,4-butanediol,
I. ．． 2.4-butanetriol, 2-butene-1.4
1-diol, 2-butyl-2-ethyl-propanesiol, 2-butene-1,4-diol, 1,3-propanediol, triethanolamine, decalindiol,
Examples include 3-chloro-1,2-propanediol.

Furthermore, acrylates and methacrylates, which are commercially available under the names of oligoester acrylate, oligoester methacrylate, epoxy acrylate, urethane acrylate, etc., can be suitably used.

In the present invention, it is also possible to use two or more of the above-mentioned addition-polymerizable unsaturated bonds in combination.
Against the mt department! It may be used in an amount of 1000 parts by weight, preferably 15 to 900 parts by weight.

In addition, the compound having at least one 4J' addition fused unsaturated bond described in E does not necessarily need to be dissolved in the solvent C contained in the ink, but may be evenly divided or present in an emulsion state. I don't mind. In addition, the energy used for combination can be either light, heat, or a combination of both light and heat, which is the energy necessary to activate the unsaturated bonds contained in the ink and cause the aggregation reaction. It doesn't matter if it is supplied.

12. The means for dissolving, dispersing, or emulsifying the polymerizable precursor in the ink may be any method as long as it can achieve uniformity. This can be carried out by mixing and using a roll mill or the like.

Furthermore, in the present invention, it is preferable to use a polymerization initiator for the purpose of starting the polymerization reaction of the polymerizable precursor. The nine polymerization initiators include carbonyl compounds, ffi sulfur compounds,
Examples of carbonyl compounds include peroxides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. inisobutyl ether, benzyl dimethyl ketal, penzophenone, anthraquinone,
2-methylanthraquinone, 2-t-butylanthraquinone, 9,IO-phenanthrenequinone, diacetyl,
Benzyl etc. Examples of organic sulfur compounds include dibutyl disulfide, dioctyl disulfide, dibenzyl disulfide, and diphenyl disulfide. ．． These include dibenzoyl disulfide and diacetyl disulfide.

Examples of the peroxide include hydrogen peroxide, di-t-butyl peroxide, benzoyl amide, and methyl ethyl ketone peroxide. Moreover, the k-redox compound consists of a combination of a peroxide and a reducing agent,
There are ferrous ions and hydrogen peroxide, ferrous ions and A sulfate ions, ferric ions and A oxides, etc.

As azo and diazo compounds, α. αazobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azobis-cyclohexanecarbonitrile,
Examples include diazonium salts of P-aminocyphenylamine. Examples of halogen compounds include chloromethylnaphthyl chloride, phenacyl chloride, and chloroacetone. β−
Examples include naphthalenesulfonyl chloride and xylenesulfonyl chloride. Examples of photoreducible pigments include rose bengal, erythrosin, kosaishin, acriflavin, riboflavin, and thionin.

The photopolymerization initiators mentioned above may be used alone or in combination of two or more. The amount used is preferably in the range of 0.1 to 20 parts by weight per 1 part by weight of the polymerizable precursor used. You don't have to.

Next, substances that can be used in the present invention to cause polycondensation and increase the molecular weight include phenol and formaldehyde that produce phenol resin, melamine and formaldehyde that produce melamine resin, unsaturated polyester resin, diallyl phthalate, etc. There are various compounds that produce resins, furan resins, epoxy resins, silicone resins, esterimide resins, polyamide resins, amide-imide resins, urethane resins, etc., and polyamide acids that produce polyimide, and these compounds cause the above-mentioned addition polymerization. It can be used in the same formulation as the compound. [Examples] The present invention will be explained below with reference to Examples. Example 1 (Ink formulation) Glycerin 28g Colloidal hydrous silicate (swellable fine particles) 12g (Kunimine Kogyo ■
Product name: Smecton) Organite
23 g (Montmorillonite and organic compound ■manufactured by Toyojun Yoko) LiBF43 g Cyan pigment 7 g (Product name of West German Bayer Co., Ltd. Supranol Cyanine)
7BF) Triethylene glycol methacrylate 30
g Penzoin isobrobyl ether 0.6g Of the above formulation, first mix glycerin, LiBF4, and pigment in an autohomogen mixer, then mix smectone and organite. Further, triethylene glycol methacrylate and penzoin isobrobyl ether were mixed in a roll mill to obtain the ink of the present invention based on the mechanism (2). After applying the above ink to a thickness of about 2 mm on a platinum-plated stainless steel plate of 1 cm x 1 am, place the platinum-plated stainless steel plate of the same size on top of the ink, and then apply the two plates under no voltage. When the 22 platinum-plated stainless steel plates were separated by gradually widening the interval between the platinum-plated stainless steel plates, ink was adhered to almost the entire area on both platinum-plated plates.

Next, a voltage of +10■ was applied to both platinum-plated stainless steel plates with an ink layer of 2III1 thickness sandwiched between them, one of which was used as a cathode (earth) and the other as an anode, and while this voltage was applied, the two plates were When the two platinum-plated stainless steel plates were separated by gradually widening the interval between the platinum-plated stainless steel plates, all of the ink adhered to the anode side electrode, and no ink adhered to the # electrode side.

Next, image formation was performed using the printing machine shown in FIG.

As the ink carrying roll, a platinum-plated stainless steel cylindrical roll (surface roughness IS) was used, and as the plate roll 3, a diameter 3 roll with hard chrome plating on the surface was used.
A 0ml iron cylindrical roll was used. Further, as the plate roll 3, an iron cylindrical roll with a diameter of 30 a+m and whose surface was plated with hard chrome was used. A plate 4 made of an aluminum plate patterned with a vinyl resin was wound around the plate roll 3, and the above-described ink material was introduced between the ink carrying roll 1 and the coating roll 9. The ink carrying roll 1 is rotated in eight directions of arrows at a peripheral speed of 5 mmlsec,
By controlling the gap between the coating roll 9, which is a cylindrical roll made of surface Teflon rubber and rotating in the direction of arrow E, and rotating the coating roll 9 at 5 mm/sec, the thickness of the ink layer on the ink carrying roll 1 is reduced to 0. ．．
The thickness was controlled to 2 mm. Plate roll 3 moves 5 am in the direction of arrow C.
It was rotated at a circumferential speed of /sec.

When we printed with no voltage applied from the DC power supply 103 of this printing machine, no image-like printed matter was obtained, but when we printed with a DC voltage of IOV applied from the DC power supply 103, Many prints with sharp image quality were obtained. (At this time, the plate roll 3 was used as a cathode and the ink carrying roll 1 was used as an anode.)

Next, the obtained printed matter was exposed to light from a distance of 3 cm for 5 minutes using a 30 W ultraviolet lamp under heating at 70° C. from the side on which the image recording ink had been transferred to complete the addition polymerization reaction. The image thus obtained was firmly fixed on the recording medium and did not bleed through or leave ink on the fingers. Example 2 (Ink formulation) Glycerin 39g Smectone 20g (same product as used in Example 1) LiBFn 4g
Cyan pigment 4g (same product as used in Example 1) Ultraviolet curing ink IIVII-8500 IIG
3 3 g (manufactured by Asahi Chemical Research Institute) The above formulation was mixed in the same manner as in Example 1 to obtain the ink of the present invention. Next, a large number of prints with sharp image quality were obtained using the same printing machine (Figure 1) as in Example 1 and using the same method conditions. Next, the obtained printed matter was exposed to light from a distance of 70c+a for 3 minutes under heating at 80° C. from a distance of 70c+a using a 500W mercury lamp under heating at 80° C. to complete the addition polymerization reaction.

As in Example 1, the thus obtained image did not bleed through or the ink adhered to the fingers, and the ink was reliably adhered to the recording medium.

Example 3 (Ink formulation) Glycerin 39g Smectone (same product as Example 1) ZOgLiBF.
6 g cyan pigment (same product as in Example 1) 3 g pentaerythritol triacrylate 12 g epoxy acrylate (Viscoat 8 g #540 manufactured by Osaka Organic Chemical Industry ■) Penzoyl isobrobyl ether 3 g The ink of the present invention was obtained by mixing according to the procedure.

Next, using the same printing machine (FIG. 1) as in Example 1 and using the same method conditions, a large number of printed matter with sharp image quality were obtained.

Next, the obtained printed matter was exposed to light from a distance of 70 cm for 3 minutes using a 500 W mercury lamp under heating at 80° C. from the side on which the image recording ink had been transferred to complete the addition polymerization reaction.

As with Example 1, the image thus obtained did not bleed through or cause ink to adhere to the fingers.

Comparative Example 1 An ink was prepared according to the following formulation except for triethylene glycol methacrylate and penzoin isobrobyl ether in the formulation of Example 1.

Glycerin 58gLiBF43
g Smectone 12 g Organite 23 g Next, using the same printing machine as in Example 1 (FIG. 1) and under the same process conditions, many printed matter with sharp image quality were obtained.

The images thus obtained were smeared or had ink attached to the fingers, and the ink was not sufficiently fixed.

As a matter of course, even when this product was heated and irradiated with ultraviolet rays in the same manner as in Example 1, almost no improvement in adhesion was observed. Comparative Example 2 An ink was prepared using the formulation of Example 2 except for LIVR-8500 RG.

Next, using the same printing machine (FIG. 1) as in Example 1 and using the same process conditions, a large number of prints with sharp image quality were obtained.

The image thus obtained was smeared or had ink attached to the fingers, and as in Example 2, almost no improvement was observed even after heating and irradiation with ultraviolet rays.

[Effects of the Invention] As explained above, an ink whose adhesion changes depending on the polarity of the applied voltage contains a compound having an addition-polymerizable unsaturated bond or a polymerization initiator, and is transferred to a recording medium. By applying light and/or thermal energy to an image, it is possible to provide a sharp image without smearing or adhering printed ink to hands or fingers.

[Brief explanation of drawings]

FIG. 1 is a schematic side view showing an example of an apparatus for forming an image using the ink of the present invention, and FIG. 2 is a schematic perspective view showing an example of a plate that can be used in the image forming apparatus using the ink. be. 1... Ink carrying roll 2... Ink 3... Plate roll 4... Plate 4a, one conductive part 4b... Insulating part 5... Plan cylinder 6... Impression cylinder 7... Recorded object 8... Ink image 9... Coating roll 10... Ink reservoir 11... Light source (ultraviolet sensor) 12-... Heat fi (electric heater) 1 0 3 -... Power supply

Claims (1)

[Scope of Claims] 1. An image recording ink that adheres only to one electrode and does not adhere to the other electrode by applying a voltage from a pair of Yin and Yang electrodes in contact with the ink, which comprises at least:
An image recording ink comprising a colloidal sol containing a liquid dispersion medium and a polymerizable precursor. 2. The image recording ink according to claim 1, wherein the liquid dispersion medium generates gas upon application of a voltage. 3. The image recording ink according to claim 1, wherein the liquid dispersion medium contains water. 4. Claims 1 to 3, wherein the polymerizable precursor is a compound having at least one addition polymerizable unsaturated bond and a polymerization initiator.
The described image recording ink. 5. The image recording ink according to any one of claims 1 to 3, wherein the polymerizable precursor is a compound that initiates a polycondensation reaction. 6. Supplying ink whose adhesion changes depending on the polarity of the voltage applied between a pair of electrodes, applying a voltage between the pair of electrodes and causing the ink to adhere to one of the electrodes to form an image. and a step of transferring the adhered ink to a recording medium, wherein the ink contains a polymerizable precursor as a liquid dispersion medium, and after the image is transferred to the recording medium. An image recording method comprising the steps of applying light and/or thermal energy to the medium to fix the transferred image on the recording medium.