# Patent

## Title
Stencil printing ink

## Abstract

There are disclosed a stencil printing ink having an ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s of 30 mm or longer at 23° C.; and a stencil printing ink comprising a water-based ink comprising an unsaturated straight-chain carboxylic acid-based water-soluble polymer.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a stencil printing ink and, in particular, to a stencil printing ink that is suitable for use in a rotary digital stencil printing machine.
2. Description of Related Art
The stencil printing process, unlike printing processes such as offset printing, gravure printing, and relief printing, has ease of operation and simplicity since there is no necessity for complicated operations such as washing after use and no necessity for a specialist operator. In accordance with the use of a heat sensitive plate-making method employing a thermal head as a device, in the stencil printing process, image processing is digitized, high quality printed material can be obtained simply in a short period of time, and its convenience as an information processing terminal is therefore widely acknowledged.
Rotary stencil printing machines in which plate making/plate mounting/plate ejecting operations for a stencil sheet (master), an ink supply operation, a printing operation, etc. are automated are known as digital stencil printing machines, etc. and are widely used in offices, schools, etc.
As the stencil printing ink, a water-in-oil (W/O) type emulsion ink has been generally used conventionally. W/O type emulsion inks have the function of suppressing changes in ink composition and physical properties even if the ink within the printing machine is in contact with the atmosphere when the printing machine is allowed to stand in a nonoperating state. That is, water, which is an inner phase component of the emulsion ink, is covered by oil, which is an outer phase component, and evaporation of water is therefore suppressed.
It is thought that drying of ink on a printed material printed with a W/O type emulsion ink proceeds as a result of the ink penetrating between paper fibers of printing paper, which is a substrate (print medium), and the emulsion being gradually separated into an oil phase and a water phase by contact with the paper fibers, and water, which is a main component of the ink, evaporating by contact with the atmosphere. However, since water in the ink transferred to the substrate cannot come into contact with the atmosphere for a short period of time subsequent to printing, the drying properties immediately after printing rely on drying by penetration, and since the viscosity of the W/O type emulsion ink is designed to be relatively high, the penetration speed is not high, and it cannot be said that the ink drying properties immediately after printing are adequate.
Speeding up the drying of a printed material is very important in stencil printing. Unless the printed material is dry, an operator cannot handle the printed material, and the advantage of stencil printing of ‘obtaining high quality printed material in a short period of time’ cannot be fully exploited.
Various improvements have been carried out in order to improve the drying properties on printed materials; for example, an ultraviolet curing type ink for stencil printing that is dried and fixed by irradiation with ultraviolet rays (Japanese Patent Laid-Open Publication No. 2002-30238) is known. Furthermore, a water-based ink for stencil printing has been developed from the viewpoint of environmental protection and safety, and a stencil printing method in which penetration of a water-based ink into paper is enhanced by adding a base to a printed surface immediately after printing is known (Japanese Patent Laid-Open Publication No. 2001-302955).
However, when a drying method involving a chemical reaction is used, it is necessary to employ irradiation equipment for the curing energy, coating equipment for a reaction solution, energy therefor, etc., and it is also necessary for the ink to contain expensive starting materials.
In stencil printing, the ink is transferred onto the surface of a printing paper by passing through perforations of a stencil sheet by means of printing pressure caused when the stencil sheet and the printing paper are pressed against each other, and if the viscosity of the ink is decreased in order to increase the speed of penetration of the ink into the printing paper, the ink passes easily through the perforations, the volume of ink transferred becomes excessive, fine characters, fine lines, etc. therefore spread, and as a result there are the problems that a detailed image cannot be obtained and the drying properties become poor.
It is therefore an object of the present invention to provide a stencil printing ink that enables the volume of ink transferred to a substrate to be controlled regardless of the level of viscosity of the ink, thereby enabling a detailed image to be printed, and that enables the drying properties on printed material to be improved without using special means, equipment, energy, etc. such as the application of heat, light, or a reactive material; and a stencil printing method employing the stencil printing ink.
SUMMARY OF THE INVENTION
The present inventors have found that the volume of ink transferred can be restricted by controlling the thread-forming properties rather than the viscosity of the ink.
That is, a first aspect of the present invention relates to a stencil printing ink having an ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s of 30 mm or longer at 23° C.
A second aspect of the present invention relates to a stencil printing ink comprising a water-based ink (water-based ink for stencil printing) comprising an unsaturated straight-chain carboxylic acid-based water-soluble polymer.
A third aspect of the present invention relates to a stencil printing method employing the above stencil printing ink according to the present invention.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a preferable embodiment of the stencil printing machine and is a schematic view thereof
FIG. 2 shows the preferable embodiment of the stencil printing machine and is a perspective view of a drum.
FIG. 3 shows the preferable embodiment of the stencil printing machine and is a cross-sectional view taken along the line A1-A1 in FIG. 2.
FIG. 4 shows the preferable embodiment of the stencil printing machine and is a cross-sectional view taken along the line B1-B1 in FIG. 2.
FIG. 5 shows the preferable embodiment of the stencil printing machine and is a plan view of the drum showing an ink supply unit.
FIG. 6 shows the preferable embodiment of the stencil printing machine and is a cross-sectional view taken along the line C1-C1 in FIG. 5.
FIG. 7 shows the preferable embodiment of the stencil printing machine and is a partial cross-sectional view explaining an ink diffusion mechanism.
FIG. 8 shows a diagram schematically showing an outline arrangement of an instrument used for measurement of thread-forming length.
FIGS. 9A and 9B show photographs showing ink thread-forming properties actually observed.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the stencil printing ink according to the first aspect of the present invention (hereinafter, the stencil printing ink is simply called ‘ink’), the ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s is 30 mm or longer at 23° C. This ink thread-forming length is preferably 40 mm or longer, and more preferably 50 mm or longer.
Specifically, the thread-forming length can be measured using a measuring instrument shown in FIG. 8. This measuring instrument comprises a container 201 containing an ink, a 15 mm diameter chrome steel ball 202, a stepping motor 203, and a belt 204. The chrome steel ball 202 is fixed to the belt 204, which is rotated by the stepping motor 203, so as to move up and down at a constant speed. The measurement environment is set at 23° C., the whole of the chrome steel ball 202 is immersed in the ink within the container 201 so that the upper part of the ball coincides with the line of the ink liquid surface, and the ball is pulled out vertically at a speed of 150 mm per second. Pictures of this procedure are taken and recorded using photographic equipment (not illustrated) placed in front of the measuring instrument, and the maximum length of the ink thread formed between the ink liquid surface and the steel ball immediately before the ink thread is broken (distance between the ink liquid surface and the lower part of the steel ball) is read off from a recorded image.
The reason why the volume of ink transferred to a printing paper is small when the ink has a long thread-forming length, such as the thread-forming length by the above-mentioned measurement method being 30 mm or longer, can be surmised to be as follows. That is, the ink having a long thread-forming length has the property that the ink is not easily broken up, that is, it is difficult to divide the ink. When the ink is transferred to a printing paper, it is necessary as a preliminary step for the ink to be divided and pass through each perforation of the stencil sheet, and it is thought that it is difficult for an ink having the above-mentioned physical properties to be forced through the perforations of the stencil sheet. Alternatively, since the ink is not easily broken up even by contact with the printing paper, it is difficult for the ink to be transferred to the printing paper. It is thought that because of these or other reasons, the volume of ink transferred to the printing paper is decreased.
The upper limit of the thread-forming length is not particularly restricted, but it is preferably not more than 500 mm, more preferably not more than 250 mm, and yet more preferably not more than 200 mm. When the thread-forming length exceeds 500 mm, the volume of ink transferred is suppressed excessively, fine characters and fine lines, etc. might be partially missing, and if it exceeds 250 mm, when there is a solid printed section in an image, the solid printed section might become uneven. The reason therefor is not clear either, but it is thought that, when the stencil sheet is peeled off from the printing paper, the ink that has been transferred through the perforations of the stencil sheet to the printing paper is attracted to the ink that has not been transferred, thus causing unevenness in the image formed.
With regard to the viscosity of the ink, the ink viscosity at a shear stress of 10 Pa when the shear stress is increased from 0 Pa at a speed of 1 Pa/s is preferably 500 mPa·s or less at 23° C., more preferably 300 mPa·s or less, and particularly preferably 100 mPa s or less. The ink viscosity measured in the same manner is preferably 1.5 mPa·s or greater, more preferably 3.0 mPa·s or greater, and yet more preferably 5.0 mPa·s or greater.
By decreasing the viscosity of the ink in this way, it is possible to improve the speed of penetration of the ink into the substrate, thus enabling the drying properties of the printed material to be easily improved.
When the thread-forming length and viscosity of conventional, commercial emulsion inks for stencil printing are measured in the same manner as above, ‘RISO SOY Ink RP (black)’ manufactured by Riso Kagaku Corporation has a thread-forming length of 25 mm and a viscosity of 1,000 Pa·s (1,000,000 mPa·s) or greater, and ‘Ink type 400 (black)’ manufactured by Ricoh Company, Ltd. has a thread-forming length of 20 mm and a viscosity of 1,000 Pa·s or greater. It is clear from these results that the ink according to the present invention is a novel ink having very different physical properties from those of the conventional inks.
The form of the ink is not particularly limited and can be in the form of a W/O type emulsion, etc., but it is preferably a water-based ink. Water contained in the ink easily evaporates into the atmosphere immediately after printing; furthermore, since the ink is pressed into and penetrates between fibers of the printing paper during printing, the interface between the ink and the air within the printing paper rapidly enlarges and water easily evaporates, and as a result the drying properties of the printed material can be further improved.
A water-based ink typically contains water, a coloring agent, and an agent for imparting thread-forming properties.
It is preferable for water to be contained in the ink at 50 wt % or more from the viewpoint of enhancement of the drying properties of the printed material, and control of the thread-forming length and viscosity of the ink, and more preferably for it to be contained 65 wt % or more. The upper limit of the amount of water added is not particularly restricted; it may be determined appropriately while taking into consideration the balance with other components added, and is preferably, for example, about 80 wt % or less.
With regard to the coloring agent of the ink, a pigment or a dye may be used, and two or more types thereof may be used in combination. Examples of the pigment include azo-based, phthalocyanine-based, dye-based, fused ring-based, nitro-based, and nitroso-based organic pigments (Brilliant Carmine 6B, Lake Red C, Watchung Red, Disazo Yellow, Hansa Yellow, Phthalocyanine Blue, Phthalocyanine Green, Alkali Blue, Aniline Black, etc.); inorganic pigments such as metals, metal oxides, and sulfides of cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, etc., yellow ochre, ultramarine, and Prussian blue; and carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black. Examples of the dye include water-soluble dyes and water-soluble dyes that become water-soluble by reduction, etc., selected from basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, reactive dyes, vat dyes, sulfide dyes, etc. Either of the pigment or the dye, or both thereof, may be used as the coloring agent, but it is preferable to use the pigment since ink spreading or print-through in an image is suppressed and an ink having excellent weatherability can be obtained.
The content of the coloring agent in the ink is usually 1 to 20 wt %, and preferably 3 to 15 wt %. In order to further increase the print density of the printed material, it is preferable for the content to be 5 wt % or greater.
The ink preferably contains an agent for imparting thread-forming properties that can impart appropriate thread-forming properties to the ink. Among others, an unbranched, uncrosslinked, straight-chain, unsaturated carboxylic acid-based water-soluble polymer containing a repeating unit represented by formula (I) below is preferably used since the ink thread-forming properties can be controlled appropriately.




(In the formula, R1, R2, and R3 independently denote H, CH3, or (CH2)nCOOH (n is an integer of 0 or 1).)

When there are two or more carboxyl groups, they may form an acid anhydride. In the case of a copolymer, the copolymer form may be any of random, alternating, block, graft, etc.
Examples of the unsaturated carboxylic acid-based water-soluble polymer include water-soluble polymers containing in the main chain at least one type of unsaturated carboxylic acid selected from the group consisting of acrylic acid or methacrylic acid (hereinafter, the two are together called ‘(meth)acrylic acid’), maleic anhydride, maleic acid, fumaric acid, crotonic acid, and itaconic acid; and salts thereof. This unsaturated carboxylic acid-based water-soluble polymer becomes a superpolyvalent ionic polymer having a high quantity of negative charge when dissolved in water, and it is thought that this strong ionic atmosphere generates an effect of imparting thread-forming properties.
Specific examples thereof include poly(meth)acrylic acid, an acrylic acid-methacrylic acid copolymer, a (meth)acrylic acid-maleic acid copolymer, a (meth)acrylic acid-sulfonic acid type monomer copolymer, a (meth)acrylic acid-itaconic acid copolymer, a (meth)acrylate-maleic acid copolymer, a (meth)acrylic acid-(meth)acrylamide copolymer, a (meth)acrylic acid-(meth)acrylate copolymer, a (meth)acrylic acid-vinylpyrrolidone copolymer, polymaleic acid, polyfumaric acid, polycrotonic acid, polyitaconic acid, and a maleic anhydride-alkyl vinyl ether copolymer; and salts thereof.
With regard to the salts, monovalent metal salts and amine salts are preferable and, for example, in the case of poly(meth)acrylic acid, examples of the salt thereof include poly(sodium (meth)acrylate), poly(potassium (meth)acrylate), poly(ammonium (meth)acrylate), and poly(triethanolamine (meth)acrylate). Other preferred examples thereof include poly(sodium itaconate), poly(sodium maleate), a sodium acrylate-methacrylate copolymer, a sodium acrylate-maleate copolymer, and a sodium acrylate-acrylamide copolymer.
When these unsaturated carboxylic acid-based water-soluble polymers are of an unneutralized type, the ink usually contains, in addition to the water-soluble polymer, an alkaline neutralizing agent such as sodium hydroxide, potassium hydroxide, aqueous ammonia, triethanolamine, or diisopropanolamine. When a neutral salt of an unsaturated carboxylic acid-based water-soluble polymer is used, it is unnecessary to add these alkaline neutralizing agents.
When the unsaturated carboxylic acid-based water-soluble polymer is of a straight-chain structural type, if compared with compounds having the same molecular structure, the larger the weight-average molecular weight, the longer the ink thread-forming length, and the lower the content thereof in the ink, the lower the ink viscosity.
Among the above-mentioned unsaturated carboxylic acid-based water-soluble polymers, since the thread-forming length can be increased without increasing the viscosity of the ink, polymers (homopolymer or copolymer) formed only from an unsaturated carboxylic acid monomer (acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid) and salts of these polymers are preferably used, and polyacrylic acid and salts thereof are particularly preferably used.
The unsaturated carboxylic acid-based water-soluble polymer such as polyacrylic acid and salts thereof preferably has a weight-average molecular weight of 10,000 or greater, more preferably 100,000 or greater, yet more preferably 600,000 or greater, and particularly preferably 1,200,000 or greater. When the molecular weight is less than 10,000, in order to increase the thread-forming length of the ink, it is necessary to increase the content of the unsaturated carboxylic acid-based water-soluble polymer, and as a result it becomes difficult to reduce the viscosity of the ink. Furthermore, the molecular weight is preferably not more than 10,000,000, and more preferably not more than 6,000,000. When the molecular weight exceeds 10,000,000, although it is possible to increase the thread-forming length of the ink with a low content of the unsaturated carboxylic acid-based water-soluble polymer, in order to obtain a thread-forming length that is not too large, it is necessary to make the content very low, and it becomes difficult to obtain stable physical properties for the ink.
The content of the unsaturated carboxylic acid-based water-soluble polymer in the ink depends on the type thereof; it is typically 0.01 to 5 wt %, preferably 0.05 to 3 wt %, more preferably 0.1 to 1 wt %, and yet more preferably 0.1 to 0.5 wt %. Since the ink thread-forming length might change due to the influence of other ink components, the type and the content of the agent that imparts thread-forming properties are preferably adjusted as appropriate while taking into consideration the influence of other ink components.
It is preferable for the ink to further contain a water-soluble organic solvent from the viewpoint of prevention of drying in perforations of the stencil sheet during printing.
As the water-soluble organic solvent, an organic compound that is a liquid at room temperature and can be dissolved in water is used. Examples thereof include lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, and 2-methyl-2-propanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol; glycerol; acetins (monoacetin, diacetin, triacetin); glycol derivatives such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, and sulfolane. It is also possible to use a low molecular weight polyalkylene glycol such as a polyethylene glycol having an average molecular weight in the range of 190 to 630, for example, an average molecular weight of 200, 300, 400, or 600, a diol type polypropylene glycol having an average molecular weight in the range of 200 to 600, for example, an average molecular weight of 400, or a triol type polypropylene glycol having an average molecular weight in the range of 250 to 800, for example, an average molecular weight of 300 or 700. These water-soluble organic solvents may be used singly or in a combination of two or more types.
The content of the water-soluble organic solvent in the ink, as a total content when two or more types are used, is preferably 5 wt % or more, and more preferably 10 wt % or more. The upper limit of the content is not particularly restricted, but in order to suppress print-through of the image, it is preferably about 45 wt % or less, and more preferably about 35 wt % or less. It is preferable to add to the ink 5 wt % or more of a water-soluble organic solvent having a boiling point higher than that of water, and more preferably a boiling point of 150° C. or higher, since drying in the perforations of the stencil sheet during printing can be prevented effectively.
The ink may further contain, as an ink viscosity adjusting agent, any viscosity increasing agent and may, for example, contain one or more types from a water-soluble polymer type viscosity increasing agent other than the above-mentioned unsaturated carboxylic acid-based water-soluble polymer, an unsaturated carboxylic acid type viscosity increasing agent other than a straight-chain structure type, and a clay mineral type viscosity increasing agent.
With regard to the water-soluble polymer type viscosity increasing agent, a natural polymer, a semisynthetic polymer, or a synthetic polymer may be used. Examples of the natural polymer include vegetable-based natural polymers such as gum arabic, carrageenan, guar gum, locust bean gum, pectin, tragacanth gum, corn starch, konjac mannan, and agar; microbial-based natural polymers such as pullulan, xanthan gum, and dextrin; and animal-based natural polymers such as gelatin, casein, and animal glue. Examples of the semisynthetic polymer include cellulose-based semisynthetic polymers such as ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and hydroxypropylmethyl cellulose; starch-based semisynthetic polymers such as hydroxyethylstarch, sodium carboxymethylstarch, and cyclodextrin; alginic acid-based semisynthetic polymers such as sodium alginate and propylene glycol alginate; and sodium hyaluronate. Examples of the synthetic polymer include vinyl-based synthetic polymers such as polyvinylpyrrolidone, polyvinylalcohol, poly(vinyl methyl ether), poly(N-vinylacetamide), and polyacrylamide; poly(ethylene oxide), polyethyleneimine, and polyurethane.
With regard to the unsaturated carboxylic acid-based viscosity increasing agent other than the straight-chain structure type, among the above-mentioned unsaturated carboxylic acid-based water-soluble polymers cited as examples, those not of a straight-chain structural type and having, for example, a branched, crosslinked structure by use of a crosslinking agent, can be cited as examples.
Examples of the clay mineral type viscosity increasing agent include smectite type clay minerals such as montmorillonite, hectorite, and saponite.
The water-soluble polymer cited above as an example of the viscosity increasing agent may, depending on the type and amount of the water-soluble polymer, be used as a fixing agent for fixing the coloring agent to the printing paper as well as the ink viscosity increasing agent. It can also be used as a dispersing agent for the pigment when a pigment is used as the coloring agent.
The ink may contain, in addition to the above-mentioned components, any of a pigment dispersing agent, a fixing agent, an antifoaming agent, a surface tension reducing agent, a pH adjusting agent, an antioxidant, a preservative, etc. as appropriate.
The ink may contain an alkali-soluble resin as a fixing agent for fixing the coloring agent to the substrate such as a printing paper. When a pigment is used as the coloring agent, an alkali-soluble resin may also be used as the dispersing agent for the pigment. The alkali-soluble resin referred to here means a polymer that is insoluble in water but becomes water-soluble in the presence of an alkali. Even when the compound name is the same, for example, an acrylic acid-acrylate copolymer, in the present invention it is classified as a water-soluble polymer or an alkali-soluble resin depending on the solubility.
Examples of the alkali-soluble resin include a styrene-(meth)acrylic acid copolymer, a styrene-α-methylstyrene-(meth)acrylic acid copolymer, a styrene-(meth)acrylate-(meth)acrylic acid copolymer, a styrene-maleic anhydride copolymer, a vinylnaphthalene-(meth)acrylic acid copolymer, a vinylnaphthalene-maleic acid copolymer, an isobutylene-maleic anhydride copolymer, a (meth)acrylate-(meth)acrylic acid copolymer, and an acrylate-methacrylate-(meth)acrylic acid copolymer. They may be used singly or in a combination of two or more types. These alkali-soluble resins may be neutralized with any alkali, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, aqueous ammonia, or an alkanolamine such as triethanolamine, to impart water-solubility thereto.
When a large amount of alkali-soluble resin is added, there is a possibility that the printing performance of a printing machine after a nonoperating period might be degraded, and it is therefore preferably contained at 5 wt % or less on a solids content basis, and more preferably 3 wt % or less.
The ink may contain an oil-in-water (O/W) type resin emulsion as the fixing agent for fixing the coloring agent to the substrate such as a printing paper. When a pigment is used as the coloring agent, this resin emulsion may be used as a dispersing agent for the pigment.
Examples of the oil-in-water (O/W) type resin emulsion include resin emulsions such as poly(vinyl acetate), an ethylene-vinyl acetate copolymer, a vinyl acetate-acrylate copolymer, polyacrylate, polymethacrylate, polystyrene, a styrene-acrylate copolymer, a styrene-butadiene copolymer, a vinylidene chloride-acrylate copolymer, poly(vinyl chloride), a vinyl chloride-vinyl acetate copolymer, and polyurethane. They may be used in a combination of two or more types.
When a large amount of resin emulsion is added, there is a possibility that the printing performance of a printing machine after a nonoperating period might be degraded, and it is therefore preferably contained in the ink at 5 wt % or less on a solids content basis, and more preferably 2 wt % or less.
In order to improve the image quality of printed material, the ink may contain a body pigment.
Examples of the body pigment include white earth, talc, clay, diatomaceous earth, calcium carbonate, barium carbonate, barium sulfate, alumina white, silica, kaolin, mica, and aluminum hydroxide. They may be used in a combination of two or more types.
When a large amount of body pigment is added, there is a possibility that the fixing of the coloring agent to the substrate might be hindered and the printing performance of a printing machine after a nonoperating period might be degraded, and it is therefore preferably contained in the ink at 5 wt % or less, and more preferably 2 wt % or less.
Furthermore, as the pigment dispersing agent, the antifoaming agent, the surface tension reducing agent, etc., the ink may contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant, or a polymer-based, silicone-based, or fluorine-based surfactant.
In order to adjust the viscosity or pH of the ink, the ink may contain an electrolyte. Examples of the electrolyte include sodium sulfate, potassium hydrogen phosphate, sodium citrate, potassium tartarate, and sodium borate, and they may be used in a combination of two or more types. It is also possible to use, as the ink viscosity increasing adjuvant or the pH adjusting agent, sulfuric acid, nitric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, etc.
By adding an antioxidant, oxidation of ink components can be prevented, and the storage stability of the ink can be improved. Examples of the antioxidant include L-ascorbic acid, sodium L-ascorbate, sodium isoascorbate, potassium sulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, and sodium pyrosulfite.
By adding a preservative, it is possible to prevent the ink from decomposing, thus improving the storage stability. Examples of the preservative include isothiazolone-based preservatives such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 1,2-benzoisothiazolin-3-one; triazine-based preservatives such as hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine; pyridine/quinoline-based preservatives such as sodium 2-pyridinethiol-1-oxide and 8-oxyquinoline; dithiocarbamate-based preservatives such as sodium dimethyldithiocarbamate; organobromine-based preservatives such as 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol, and 1,2-dibromo-2,4-dicyanobutane; methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, potassium sorbate, sodium dehydroacetate, and salicylic acid.
An ink according to the second aspect of the present invention is now explained. The ink according to the second aspect of the present invention is a water-based ink comprising an unsaturated straight-chain carboxylic acid-based water-soluble polymer. In the explanation below, details that would duplicate those of the ink according to the first aspect of the present invention are omitted.
Details of the unsaturated straight-chain carboxylic acid-based water-soluble polymer are the same as those described for the ink of the first aspect of the present invention. The molecular weight thereof is preferably 10,000 to 10,000,000, and the content thereof is preferably 0.01 to 5 wt %. The ink of the second aspect of the present invention further contains water and a coloring agent and may freely contain various types of components, and the details thereof are also the same as those described for the ink of the first aspect of the present invention. It is preferable for water to be contained at 50 wt % or more.
The ink of the second aspect of the present invention preferably has an ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s of 30 mm or longer at 23° C., and more preferably not greater than 500 mm.
With regard to the viscosity of the ink, the ink viscosity at a shear stress of 10 Pa when the shear stress is increased from 0 Pa at a speed of 1 Pa/s is preferably 500 mPa·s or less at 23° C.
The ink according to the first or second aspect of the present invention can be produced by mixing the components, and the details thereof are not particularly limited. For example, part of the water, a pigment, and a pigment dispersing agent may be mixed and the pigment may be dispersed using dispersing means such as a ball mill or a bead mill; separately, the rest of water, an unsaturated straight-chain carboxylic acid-based water-soluble polymer, and a water-soluble organic solvent may be mixed, and the two mixtures may be combined.
In the ink according to the first aspect of the present invention, since the ink thread-forming length thereof is at least the specified value, it is possible to control the volume of ink transferred to a substrate.
In the ink according to the second aspect of the present invention, since an unsaturated straight-chain carboxylic acid-based water-soluble polymer is contained therein, it is possible to adjust the ink thread-forming properties and control the volume of ink transferred to a substrate. In accordance with use of the stencil printing ink according to the first or second aspect of the present invention, fine characters and fine lines can be represented in a detailed manner regardless of the level of viscosity of the ink, that is, even when the ink has low viscosity, and an image having excellent drying properties can be obtained.
A stencil printing method according to the third aspect of the present invention is carried out by employing the ink according to the first or second aspect of the present invention. Specifically, the method comprises a step of preparing a stencil sheet by plate-making, and a step of transferring the ink according to the present invention to a print medium (substrate) by passing the ink through perforations of the plate-made stencil sheet by pressing the stencil sheet and the print medium against each other.
A printing machine used is not particularly limited, but is preferably a digital stencil printing machine from the viewpoint of excellent operability.
The ink according to the present invention is suitably used in a stencil printing method employing, in particular, a novel stencil printing machine according to an invention by the present inventors (Japanese Patent Application No. 2003-322419) that does not change the composition or the physical properties of the ink even when the printing machine is allowed to stand in a nonoperating state.
The stencil printing machine comprises: a drum which is rotatable and has a outer peripheral wall formed by an ink impermeable member and in which a stencil sheet is mounted on a surface of the outer peripheral wall; an ink supply device which has an ink supply unit at a printing position upstream of a maximum printing area of the outer peripheral wall of the drum and supplies ink on the surface of the outer peripheral wall from the ink supply unit; and a pressure roller which presses a fed print medium onto the outer peripheral wall.
In this stencil printing machine, when the print medium is fed while the outer peripheral wall of the drum is rotated and ink is supplied on the surface of the outer peripheral wall from the ink supply unit, the print medium is conveyed while being pressed by the pressure roller onto the stencil sheet and the outer peripheral wall of the drum. Meanwhile, the ink between the outer peripheral wall of the drum and the stencil sheet is diffused downstream of a printing direction while being squeezed by the pressing force of the pressure roller. At the same time, the diffused ink oozes from perforations of the stencil sheet and is transferred on the print medium, thus an ink image is printed on the print medium.
That is, the ink is supplied by being squeezed by the pressure roller between the surface of the drum and the stencil sheet. The ink that has been supplied to the drum is retained in a substantially sealed space between the outer peripheral wall of the drum and the stencil sheet, and contact with the atmosphere can be minimized. It is therefore possible to prevent the water contained in the ink from evaporating and the ink from deteriorating in the stencil printing machine, and as a result high quality printed material that has excellent drying properties and for which an image does not smudge even when handled immediately after printing can be provided. Moreover, after the printing machine is allowed to stand for a long period of time in a nonoperating state, printing can be resumed without requiring an operation such as washing, and the same level of printing performance as that of the printed material prior to the printing machine being left standing can be obtained for the printed material in the initial printing subsequent to the nonoperating state.
When, for example, a water-based ink having a high water content is used as the ink of the present invention, in the above-mentioned stencil printing machine, the ink within the printing machine is sealed and the water is prevented from evaporating into the atmosphere, thus enabling the same effect as above to be exhibited.
Furthermore, it is unnecessary in this machine to set the viscosity of the ink at a relatively high value in order to ensure that it matches the printing machine so that, for example, the ink is prevented from leaking from the printing machine, as in a conventional arrangement.
If the viscosity of the ink is high, it is necessary to set the pressing force of the pressure roller at a high value, and when this value is too high, there is a possibility that the volume of ink transferred might increase, or expansion or contraction of an image might occur due to elongation of the stencil sheet, but when a low viscosity ink is used as the ink of the present invention, the above-mentioned problems do not occur, an optimum supply of ink in the above-mentioned stencil printing machine can be ensured, there are no image defects at the edges of the printed surface, and the speed of penetration of the ink into the print medium can be improved, thereby enabling the drying properties of the printed material to be easily improved.
Preferable embodiments of the printing machine will be described hereinbelow referring to the drawings.
FIG. 1 shows a schematic view of the stencil printing machine; FIG. 2 shows a perspective view of a drum; FIG. 3 shows a cross-sectional view taken along the line A1-A1 in FIG. 2; FIG. 4 shows a cross-sectional view taken along the line B1-B1 in FIG. 2; FIG. 5 shows a plan view of the drum showing an ink supply unit; FIG. 6 shows a cross-sectional view taken along the line C1-C1 in FIG. 5; and FIG. 7 shows a partial cross-sectional view explaining an ink diffusion mechanism.
As shown in FIG. 1, the stencil printing machine is mainly constructed by an original reading unit 1, a stencil making unit 2, a printing unit 3, a paper feed unit 4, a paper delivery unit 5 and a stencil disposal unit 6.
The original reading unit 1 includes an original setting tray 10 on which the originals to be printed are stacked, reflective-type original sensors 11 and 12 which senses presence of the originals on the original setting tray 10, original conveyer rollers 13 and 14 which convey the original on the original setting tray 10, a stepping motor 15 which drives and rotates the original conveyer rollers 13 and 14, a contact image sensor 16 which optically reads out image data of the original conveyed by the original conveyer rollers 13 and 14 and converts the data into electrical signals, and an original discharging tray 17 on which the originals discharged from the original setting tray 10 are stacked. The original stacked on the original setting tray 10 is conveyed by the original conveyer rollers 13 and 14, and the image sensor 16 reads out the image data of the conveyed originals.
The stencil making unit 2 has a stencil sheet housing 19 which houses a long and rolled stencil sheet 18, a thermal print head 20 placed downstream of this stencil sheet housing 19 in a conveying direction, a platen roller 21 placed at a position opposite to the thermal print head 20, and a pair of stencil sheet transfer rollers 22 and 22 placed downstream of the platen roller 21 and the thermal print head 20 in the conveying direction, a write pulse motor 23 which drives and rotates the platen roller 21 and the stencil sheet transfer rollers 22, and a stencil sheet cutter 24 placed downstream of the pair of stencil sheet transfer rollers 22 and 22 in the conveying direction.
The long stencil sheet 18 is conveyed by the rotation of the platen roller 21 and the stencil sheet transfer rollers 22. Based on the image data read out by the image sensor 16, each of dot-shaped heating elements of the thermal print head 20 selectively performs heating operations, and thereby the stencil sheet 18 is perforated due to thermal sensitivity thereof to make a stencil. Then, the stencil sheet 18 thus made is cut by the stencil sheet cutter 24 to make the stencil sheet 18 with a predetermined length.
The printing unit 3 has a drum 26 which rotates in a direction of an arrow A of FIG. 1 by driving force of a main motor 25, a stencil sheet clamping portion 27 which is provided on the outer peripheral surface of the drum 26 and clamps an end of the stencil sheet 18, a stencil sheet confirming sensor 28 which senses whether or not the stencil sheet 18 is wound and mounted on the outer peripheral surface of the drum 26, a datum position detecting sensor 30 which detects the datum position of the drum 26, and a rotary encoder 31 which detects rotation of the main motor 25. Based on detection output of the datum position detecting sensor 30, an outputted pulse by the rotary encoder 31 is detected, thus enabling the rotation position of the drum 26 to be detected.
In addition, the printing unit 3 has a pressure roller 35 positioned below the drum 26. This pressure roller 35 is constructed to be movable between a press position where the pressure roller 35 presses the outer peripheral surface of the drum 26 by driving force of a solenoid device 36, and a holding position where the pressure roller 35 is spaced apart from the outer peripheral surface of the drum 26. The pressure roller 35 is always placed at the press position during a printing mode period (including trial print) and placed at the holding position during a period other than the printing mode.
Thereafter, the end of the stencil sheet 18 conveyed from the stencil making unit 2 is clamped by the stencil sheet clamping portion 27, and the drum 26 is rotated while the stencil sheet 18 is clamped so that the stencil sheet 18 is wound and mounted on the outer peripheral surface of the drum 26. Then, print paper (print medium) 37, which is fed by the paper feed unit 4 in synchronization with the rotation of the drum 26, is pressed onto the stencil sheet 18 wound and mounted on the outer peripheral surface of the drum 26 by the pressure roller 35. Therefore, ink 56 is transferred from perforations of the stencil sheet 18 onto the print paper 37, and an image is printed.
The paper feed unit 4 has a paper feed tray 38 on which the print paper 37 is stacked, first paper feed rollers 39 and 40 which convey only the print paper 37 at the uppermost position from this paper feed tray 38, and a pair of second paper feed rollers 41 and 41 which convey the print paper 37, which has been conveyed by the first paper feed rollers 39 and 40, between the drum 26 and the pressure roller 35 in synchronization with the rotation of the drum 26, and a paper feed sensor 42 which senses whether or not the print paper 37 is conveyed between the pair of second paper feed rollers 41 and 41. The first paper feed rollers 39 and 40 are constructed so that the rotation of the main motor 25 is selectively transferred thereto through a paper feed clutch 43.
The paper delivery unit 5 has a paper removal claw 44 which removes the printed print paper 37 from the drum 26, a conveying passage 45 through which the print paper 37 removed from the drum 26 by the paper removal claw 44 is conveyed, and a paper receiving tray 46 on which the print paper 37 delivered from the conveying passage 45 is stacked.
The stencil disposal unit 6 has disposed stencil conveying means 47, a stencil disposal box 48 and a disposed stencil compression member 49. The disposed stencil conveying means 47 guides the end of the used stencil sheet 18 unclamped from the outer peripheral surface of the drum 26 and conveys the used stencil sheet 18 that has been guided while peeling it off from the drum 26. The stencil disposal box 48 houses the stencil sheet 18 conveyed by the disposed stencil conveying means 47. The disposed stencil compression member 49 pushes the stencil sheet 18, which has been conveyed by the disposed stencil conveying means 47 into the stencil disposal box 48, into the bottom of the stencil disposal box 48.
As shown in FIGS. 2 to 4, the drum 26 has a support axis 50 fixed to the machine body H (shown in FIG. 1), a pair of side disks 52 and 52 rotatably supported by the support axis 50 through each of bearings 51, and a cylindrical outer peripheral wall 53 fixed between the pair of side disks 52 and 52. The outer peripheral wall 53 is driven and rotated by rotation force of the main motor 25 together with the pair of side disks 52 and 52. The outer peripheral wall 53 is also rigid so as not to deform by the pressure of the pressure roller 35 and formed by an ink impermeable member which does not allow the ink 56 to permeate therethrough. Furthermore, the outer peripheral surface of the outer peripheral wall 53 is processed with fluorine contained resin coating process such as Teflon (registered trademark) coating process and formed to have an even cylindrical surface.
The stencil sheet clamping portion 27 is provided by utilizing a concave portion for clamping 53a formed along an axis direction of the support axis 50 on the outer peripheral wall 53. One end of the stencil sheet clamping portion 27 is rotatably supported by the outer peripheral wall 53. The clamping portion 27 is provided so as to protrude from the outer peripheral wall 53 in an unclamping state as shown by a virtual line in FIG. 4 and so as not to protrude from the outer peripheral wall 53 in a clamping state shown by a solid line in FIG. 4. Therefore, the stencil sheet clamping portion 27 is capable of clamping the stencil sheet 18 without protruding from the outer peripheral wall 53.
The outer peripheral wall 53 is rotated in a direction of an arrow A of FIGS. 2 and 4, and a starting point of printing thereon is set to a position near the stencil sheet clamping portion 27, which is found after a small rotation of the outer peripheral wall 53. Hence, the rotating direction A equals to a printing direction M, and the area below the starting point of printing is set as a printing area. In this first embodiment, a maximum printing area is set to a region in which A3 size print paper can be printed. In addition, an ink supply unit 55A of an ink supply device 54 is provided at an upstream position of the maximum printing area of the outer peripheral wall 53 in the printing direction M.
As shown in FIGS. 2 to 6, the ink supply device 54 includes an ink container 57 in which the ink 56 is stored, an inking pump 58 which suctions the ink 56 within the ink container 57, a first pipe 59 which supplies the ink 56 suctioned by the inking pump 58, the support axis 50 to which the other end of the first pipe 59 is connected and in which an ink passage 60 is formed and a hole 61 is formed at a position 180 degrees opposite thereto, a rotary joint 63 which is rotatably supported on the outer peripheral side of the support axis 50 and in which a through hole 62 that communicates with the hole 61 is formed, a second pipe 64 in which one end thereof is connected to the rotary joint 63 and the other end thereof is connected to the outer peripheral wall 53, and the ink supply unit 55A to which the other end of the second pipe 64 is opened. The first pipe 59, the support axis 50 and the second axis 64 and the like constitute a conduit for supplying ink between the surface of the outer peripheral wall 53 of the drum 26 and the stencil sheet 18 without expose ink to the atmosphere.
The ink supply unit 55A includes an ink diffusion groove 65 which diffuses the ink 56 from the second pipe 64 in a printing perpendicular direction N, a plurality of through holes 66 which are opened at an interval in the ink diffusion groove 65 in the printing perpendicular direction N, and an ink supply port 55a which communicates with the plurality of through holes 66 and is opened to the surface of the outer peripheral wall 53. The ink supply unit 55A is covered and closed up by the stencil sheet 18 for supplying ink between the surface of the outer peripheral wall 53 of the drum 26 and the stencil sheet 18 without expose ink to the atmosphere.
As shown in FIGS. 5 and 6, the ink diffusion groove 65 and the plurality of through holes 66 as well as the ink supply port 55a are formed by a concave portion for ink supply 67 and an ink distribution member 68. The concave portion for ink supply 67 is formed along a perpendicular direction to the printing direction M (i.e., the printing perpendicular direction N) on the outer peripheral wall 53, and the ink distribution member 68 is formed inside of the concave portion 67. The ink supply port 55a is formed along the printing perpendicular direction N and supplies the ink 56 almost uniformly in the printing perpendicular direction N on the outer peripheral wall 53.
Next, an operation of the stencil printing machine with the above-mentioned structure will be briefly described.
First of all, when a stencil making mode is selected, in the stencil making unit 2, the stencil sheet 18 is conveyed by rotation of the platen roller 21 and the stencil sheet transfer rollers 22. Then, based on image data read out by the original reading unit 1, the multiple heating elements of the thermal printing head 20 selectively perform heating operations, and thereby the stencil sheet 18 is perforated due to its thermal sensitivity to make the stencil. The stencil sheet 18 thus made is cut at predetermined positions, and thus the stencil sheet 18 with a predetermined dimension is made.
In the printing unit 3, an end of the stencil sheet 18 made in the stencil making unit 2 is clamped by the stencil sheet clamping portion 27 of the drum 26, and the drum 26 is rotated while clamping the stencil sheet 18. The stencil sheet 18 is then wound and mounted on the outer peripheral surface of the drum 26.
Next, when the printing mode is selected, in the printing unit 3, the drum 26 is driven and rotated, and the ink supply device 54 starts driving. Then, the ink 56 is supplied to the outer peripheral wall 53 from the ink supply port 55a. Thereafter, the supplied ink 56 is held between the outer peripheral wall 53 and the stencil sheet 18, and the pressure roller 35 is moved from the holding position to the press position.
In the paper feed unit 4, the print paper 37 is fed between the drum 26 and the pressure roller 35 in synchronization with the rotation of the drum 26. The fed print paper 37 is pressed by the pressure roller 35 onto the outer peripheral wall 53 of the drum 26 and conveyed by the rotation of the outer peripheral wall 53 of the drum 26, that is, the print paper 37 is conveyed while closely contacting the stencil sheet 18.
Further, as shown in FIG. 7, as the print paper 37 is conveyed, the ink 56 held between the outer peripheral wall 53 of the drum 26 and the stencil sheet 18 is simultaneously diffused downstream in the printing direction M while being squeezed by the pressure of the pressure roller 35. Then, the diffused ink 56 oozes from perforations of the stencil sheet 18 and is transferred on the print paper 37. Accordingly, an ink image is printed on the print paper 37 in a process of passing between the outer peripheral wall 53 of the drum 26 and the pressure roller 35. The end of the print paper 37 which has passed between the outer peripheral wall 53 of the drum 26 and the pressure roller 35 is peeled off from the drum 26 by the paper removal claw 44 at its end, and the print paper 37 removed from the drum 26 is delivered to the paper receiving tray 46 through the conveying passage 45 and stacked thereon.
Once printing of a set quantity of the printing paper is completed, the rotation of the outer peripheral wall 53 of the drum 26 is stopped and the ink supply device 54 stops driving. Consequently, supply of the ink 56 to the outer peripheral wall 53 is stopped. The pressure roller 35 is returned back to the holding position from the press position and goes into a holding mode.
When a stencil disposal mode is selected for starting new stencil making or the like, the stencil sheet clamping position 27 of the drum 26 is moved to an unclamping position, and the end of the unclamped stencil sheet 18 is guided by the disposed stencil conveying means 47 as the drum 26 rotates and then housed in the stencil disposal box 48.
As described so far, in this stencil printing machine, the ink 56 is supplied to the outer peripheral wall 53 of the drum 26 and diffused on the outer peripheral wall 53 by being squeezed by pressure force of the pressure roller 35, and the diffused ink 56 is transferred onto the print paper 37 from the perforations of the stencil sheet 18 by the pressure force of the pressure roller 35. Therefore, when the printing mode is finished, the ink 56 supplied to the drum 26 is held in an approximately sealed space between the outer peripheral wall 53 of the drum 26 and the stencil sheet 18, thus contact with the atmosphere is minimized. Accordingly, the ink 56 does not deteriorate even when printing is not carried out for a long time, and the deterioration of the ink 56 can be certainly prevented. Moreover, it is not required to place various rollers for supplying ink within the drum 26 like the conventional examples. Therefore, the drum 26 can be made even smaller and light-weighted.
Moreover, since the outer peripheral wall 53 of the drum 26 is formed by the ink impermeable member, a materials therefor can be selected from a wider range of varieties. In addition, since the structure is simple, the drum 26 can be manufactured at low cost. Furthermore, since strength of the drum 26 is easily increased, a non-uniform image due to fluctuations of the printing pressure can be prevented.
Moreover, since the ink 56 is basically prevented from contacting the atmosphere to a minimum, the ink 56 is used for printing in the best condition with almost no deterioration. Furthermore, since no cares are required for preventing deterioration of the ink 56, there is a higher degree of flexibility in selecting the ink 56.
In this embodiment, the ink supply unit 55A includes ink supply port 55a formed continuously along the printing perpendicular direction N and supplies the ink 56 through the ink supply port 55a almost uniformly in the printing perpendicular direction N. Accordingly, the ink 56 can be diffused in the printing perpendicular direction N without unevenness when the ink 56 is diffused downstream in the printing direction M while being squeezed by the pressure of the pressure roller 35. Thus, non-uniform density in printing perpendicular direction N can be certainly prevented.
EXAMPLES
The present invention is explained further in detail below by way of Examples, but the present invention is not limited thereby. In the explanation below, ‘wt %’ is expressed simply as ‘%’.
Example 1
5.0% of carbon black (‘#40’ manufactured by Mitsubishi Chemical Corporation) as a coloring agent, 1.0% of polyvinylpyrrolidone (‘K17’ manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a pigment dispersing agent, and 14.0% of distilled water were mixed and dispersed thoroughly by means of a bead mill to give 20.0% of a pigment dispersion. Separately, while stirring 19.9% of distilled water, 0.1% of a straight-chain sodium polyacrylate (1) (‘Aronvis S’: molecular weight 4,000,000 to 5,000,000, manufactured by Nihon Junyaku Co., Ltd) was gradually added thereto and dissolved. 20.0% of the aqueous straight-chain sodium polyacrylate solution thus obtained, 20.0% of the pigment dispersion, 15.0% of polyethylene glycol (‘polyethylene glycol #200’ manufactured by Wako Pure Chemical Industries, Ltd.) as a water-soluble organic solvent, and the balance (45.0%) of distilled water were mixed to give an ink of Example 1.
Examples 2 to 9 and Comparative Examples 1 to 5
The procedure of Example 1 was repeated except that the compositions were changed as shown in Table 1 and Table 2 to give inks of Examples and Comparative Examples. Details of the components in the tables are as follows.
Direct dye: ‘Daiwa IJ Blue 319H’ manufactured by Daiwa Dyestuff Mfg. Co., Ltd.
Straight-chain sodium polyacrylate (2): ‘Aronvis M’ (molecular weight 2,000,000 to 3,000,000) manufactured by Nihon Junyaku Co., Ltd.
Straight-chain polyacrylic acid: ‘Jurymer AC-10H’ (molecular weight about 150,000, 20% aqueous solution; the content in Table 1 is expressed on a solids content basis) manufactured by Nihon Junyaku Co., Ltd.
Straight-chain acrylic acid-methacrylic acid copolymer: ‘Jurymer AC-20H’ (molecular weight about 50,000 to 80,000, 20% aqueous solution; the content in Table 1 is expressed on a solids content basis) manufactured by Nihon Junyaku Co., Ltd.
Crosslinked sodium polyacrylate: ‘Rheogic 250H’ manufactured by Nihon Junyaku Co., Ltd.
Crosslinked polyacrylic acid copolymer: ‘Carbopol 940’ manufactured by BF Goodrich Corporation
Sodium carboxymethylcellulose: manufactured by Kanto Kagaku
Printing was carried out on printing paper (‘Riso paper thin type’ manufactured by Riso Kagaku Corporation) using the inks prepared in the Examples and Comparative Examples above in a stencil printing machine (a prototype manufactured by Riso Kagaku Corporation) shown in FIGS. 1 to 7; and the printed materials thus obtained were evaluated in terms of image properties (sharpness of fine characters, uniformity of solid printed surface), drying properties, and printing performance at the edges of the printed surface.
The image properties were evaluated visually as the sharpness of fine characters; when fine characters (6 points) were sufficiently legible the rating was A, when reading was difficult it was B, and when fine characters were illegible it was C.
The uniformity of a solid printed surface was expressed as follows: a uniform solid printed surface was rated A, an almost uniform solid printed surface was B, and a solid printed surface that did not give the impression of being uniform was C.
The drying properties of the printed material were evaluated by means of staining of a finger when the image was touched; when there was no staining of the finger three seconds after printing it was rated A, when there was no staining of the finger five seconds after printing it was B, and when there was stain on the finger even five seconds after printing it was C.
The printing performance at the edges of the printed surface was evaluated; when an image could be printed on the left and right rear edges of a printing paper it was rated A, when printing could be carried out but there was slight fading it was B, and when printing could not be carried out it was C.
The thread-forming length of the ink was measured using a measuring instrument similar to one whose outline is shown schematically in FIG. 8. That is, in a 23° C. environment, the container 201 was filled with an ink, and the whole of the chrome steel ball 202 (diameter 15 mm) was immersed in the ink so that the upper part of the ball coincided with the line of the ink liquid surface, and the chrome steel ball was subsequently pulled out vertically at a speed of 150 mm per second, pictures of this procedure were taken and recorded using photographic equipment (3CCD color videocamera module XC-003, manufactured by Sony Corporation) (not illustrated), and the maximum length of the ink thread formed between the ink liquid surface and the steel ball immediately before the ink thread was broken (distance between the ink liquid surface and a lower part of the steel ball) was read off from a recorded image. FIG. 9 shows a part of the image recorded in Example 1, FIG. 9A shows an image when the distance between the ink liquid surface and the lower part of the steel ball was 100 mm, and FIG. 9B shows an image when the distance between the ink liquid surface and the lower part of the steel ball was 165 mm, where the thread length of the ink was the maximum.
The viscosity of the ink was measured using a stress controlled rheometer RS75 (cone angle 1°, diameter 60 mm) manufactured by Haake.
The results are given in Table 1 and Table 2.









TABLE 1









Example

















1
2
3
4
5
6
7
8
9









Amount added/wt %





















Coloring agent
Furnace carbon black
5.0
5.0
5.0
5.0
5.0
10.0
—
—
—



Direct dye
—
—
—
—
—
—
5.0
5.0
10.0


Pigment dispersing agent
Polyvinylpyrrolidone
1.0
1.0
1.0
1.0
1.0
2.0
—
—
—


Water
Distilled water
78.9
78.7
78.8
76.0
71.5
62.9
79.94
78.44
89.6


Water-soluble organic
Polyethylene glycol
15.0
15.0
15.0
15.0
15.0
25.0
15.0
15.0
—


solvent


Agent for imparting thread-
Straight-chain poly(sodium
0.1
0.3
—
—
—
0.1
0.06
0.06
—


forming properties
acrylate) (1)



Straight-chain poly(sodium
—
—
0.2
—
—
—
—
—
0.4



acrylate) (2)



Straight-chain polyacrylic acid
—
—
—
1.0
—
—
—
—
—



Straight-chain acrylic acid/
—
—
—
—
5.0
—
—
—
—



methacrylic acid copolymer


Viscosity adjusting agent
Sodium
—
—
—
—
—
—
—
1.5
—



carboxymethylcellulose


pH adjusting agent
Triethanolamine
—
—
—
2.0
—
—
—
—
—



Sodium hydroxide
—
—
—
—
2.5
—
—
—
—


Physical properties
Thread-forming length (mm)
165
270
120
45
35
165
60
60
85



Viscosity (mPa · s)
31
247
58
293
340
73
4.6
60
13


Results
Sharpness of fine characters
A
A
A
A
A
A
A
A
A



Uniformity of solid printed
A
B
A
A
A
A
A
A
A



surface



Drying properties of printed
A
A
A
B
B
B
A
A
A



material



Printing properties at edges of
A
A
A
A
B
A
A
A
A



printed surface


















TABLE 2









Comparative Example













1
2
3
4
5









Amount added/wt %

















Coloring agent
Furnace carbon black
5.0
5.0
5.0
5.0
—



Direct dye
—
—
—
—
5.0


Pigment dispersing agent
Polyvinylpyrrolidone
1.0
1.0
1.0
1.0
—


Water
Distilled water
79.0
78.8
78.53
78.82
78.5


Water-soluble organic
Polyethylene glycol
15.0
15.0
15.0
15.0
15.0


solvent


Viscosity adjusting agent
Crosslinked poly(sodium acrylate)
—
0.2
0.47
—
—



Crosslinked polyacrylic acid
—
—
—
0.06
—



copolymer



Sodium carboxymethylcellulose
—
—
—
—
1.5


pH adjusting agent
Triethanolamine
—
—
—
0.12
—


Physical properties
Thread-forming length (mm)
20
15
15
10
20



Viscosity (mPa · s)
3.3
11
1690
830
45


Results
Sharpness of fine characters
C
C
B
C
C



Uniformity of solid printed surface
A
A
A
A
A



Drying properties of printed
C
C
C
C
C



material



Printing properties at edges of
A
A
C
C
A



printed surface









As is clear from the tables above, in all of the Examples, compared with the Comparative Examples, printed materials having good sharpness of fine characters, good drying properties of the printed material, etc. were obtained.
The disclosure of the present application relates to subject matter described in Japanese Patent Application No. 2004-084528 filed on Mar. 23, 2004, the contents of the disclosures therein being incorporated herein by reference.
It should be noted that, in addition to those described above, the above-mentioned embodiments can be modified and changed in various ways without departing from the novel and advantageous features of the present invention. Therefore, all such modifications and changes are intended to be included in the appended claims.

## Claims

1. A stencil printing ink comprising a water-based ink comprising a water-soluble, straight chain polymer obtained by polymerization of at least one kind of unsaturated carboxylic acid and 50 wt % or more of water, wherein the ink has an ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s of 40 mm or longer at 23° C. and a viscosity at a shear stress of 10 Pa when the shear stress is increased from 0 Pa at a speed of 1 Pa/s of 500 mPa·s or less at 23° C., and wherein the water-soluble, straight chain polymer has a molecular weight of 100,000 to 10,000,000.

2. The stencil printing ink according to claim 1, wherein the ink thread-forming length is not greater than 500 mm.

3. The stencil printing ink according to claim 1, wherein the water-soluble, straight chain polymer has a molecular weight of 600,000 or more.

4. The stencil printing ink according to claim 1, wherein the ink comprises 0.01 to 5 wt % of the water-soluble, straight chain polymer.

5. A stencil printing method employing the stencil printing ink according to claim 1.

6. A stencil printing ink comprising 65 wt % or more of water and 0.01 to 5 wt % of a water-soluble, straight chain polymer obtained by polymerization of at least one kind of unsaturated carboxylic acid, wherein the ink has an ink thread-forming length when a 15 mm diameter chrome steel ball is pulled out of the ink at 150 mm/s of 50 mm to 250 mm at 23° C. and a viscosity at a shear stress of 10 Pa when the sheer stress is increased from 0 Pa at a speed of 1 Pa/s of 500 mPa·s or less at 23° C., and wherein the water-soluble, straight chain polymer has a molecular weight of 600,000 to 10,000,000.