JPH10166565A - Image recorded matter forming method and image recorded matter - Google Patents

Abstract

(57) [Summary] [Problem] To prevent the occurrence of nozzle clogging, suppress the migration phenomenon, maintain good image quality, and coat even when a resin coating layer is provided on the surface of the ink receiving layer after image formation. Without swelling, peeling, turbidity, etc.
An object of the present invention is to provide a method for forming an image recorded matter capable of simultaneously satisfying various properties such as durability, such as water resistance, light resistance, and scratch resistance, of the obtained image recorded matter in a well-balanced manner. SOLUTION: After forming an image on a recording medium by discharging a liquid ink containing a pigment as a coloring material into droplets according to predetermined information and forming an image on the recording medium, at least a part of the recording medium is substantially formed. An image-recorded material forming method for forming a resin-coated layer by coating a transparent resin to obtain an image-recorded material, wherein the recording medium is washed with water after the image is formed, and the image-recorded material is obtained by the method. Image record.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image recording by ink jet and an image recording.

[0002]

2. Description of the Related Art Hitherto, as a recording medium used for ink jet recording, many recording media provided with an ink receiving layer on the surface in order to obtain good image quality are known. However, in a recording medium provided with an ink receiving layer,
Because the ink receiving layer requires ink absorption as a property,
When an image is formed by an ink jet recording method using an aqueous ink, there is a problem that the formed image has inferior water resistance.

Various proposals have been made to solve this problem. Examples of the ink receiving layer itself provided with water resistance include, for example, JP-A-63-221077,
JP-A-5-221112, JP-A-5-26202
No. 8, JP-A No. 7-1828, etc., a recording sheet provided with an ink receiving layer made of acetal-modified polyvinyl alcohol;
There is a recording sheet composed of polyvinyl alcohol and polyvinyl butyral as described in JP-A-02391. Further, a recording sheet characterized by crosslinking a water-soluble resin described in JP-A-58-89391 and a crosslinked polyvinyl alcohol described in JP-A-2-67177 are provided on a receptor layer. Or a cured product of a monomer having a radical polymerizable double bond described in JP-A-7-40649, or a photopolymerizable double bond described in JP-A-8-18455. It is known to use a cured product of a resin composition containing a cationic synthetic resin having the following.

In order to improve the image durability of the obtained image recorded matter such as water resistance, light resistance and scratch resistance, a protective layer is provided on the surface of the recording material after image formation. It is disclosed. For example, a method of laminating various plastic films on an image recorded matter is disclosed in
2-56184, JP-A-62-59076, JP-A-62-60683, JP-A-62-20
2794, JP-A-62-273889, JP-A-62-273890, JP-A-62-2800
No. 85, JP-A-62-280086 and the like.

Also, JP-A-53-50744, JP-A-59-196285, and JP-A-59-201.
No. 891 discloses a method in which a thermoplastic organic polymer fine particle is contained in an ink receiving layer, and printing is performed in a state where the ink absorbing property is maintained. Then, the fine particle is melted by heat or a solvent.
A method of forming a protective film by dissolving a resin film on the surface to form a protective film is described. JP-A-1-141772 and JP-A-2-194958 disclose a polyisocyanate compound and an acrylic resin after printing. It is described that a protective layer is provided by applying a urethane resin. afterwards,
Covering with a film is also disclosed. Japanese Patent Application Laid-Open No. Hei 7-72325 discloses a method for manufacturing a color filter, in which a transparent protective film is provided on a recording medium after ink jet recording. It is disclosed that durability is improved.

[0006]

In recent years, the ink jet recording system has been rapidly spread because it has low noise, can print multicolor images at a high speed, and can obtain a large area image. Water-based inks are widely used in view of safety, odor, and printing characteristics. As the recording material at that time, a material obtained by coating a material such as an ink absorbing layer on a plain paper, a coated paper, or a plastic film is generally used.

[0007] With the widespread use of the ink jet recording method, higher and wider characteristics have been required for the image recorded matter produced by this method. That is, properties such as high water resistance, moisture resistance, light resistance, and scratch resistance are required. Conventionally, several methods have been tried to satisfy these requirements. One of them is a method of forming the ink receiving layer itself from a water-resistant material. However, since the primary purpose of the ink receiving layer is to obtain good image quality, it is required to have a high ink absorption rate, that is, a property of high water absorption rate. Therefore, such a conventional ink receiving layer cannot satisfy the contradictory requirements of an image forming ability for achieving good image quality and a water-resistant high-strength film.

There is also a method in which thermoplastic organic polymer fine particles are contained in an ink receiving layer and a transparent resin film is formed on the surface by applying heat or a solvent after printing.
Here, there is a problem that the print quality is degraded when the film is formed. Furthermore, it is also difficult to completely cover the ink receiving layer by this method, and complete water resistance has not been obtained.
As another method, there is a method of laminating a film after printing, but this method causes a problem of peeling between the recording medium and the film.

In the case of ink jet recording using an aqueous ink, a water-soluble high-boiling solvent is added to the ink for the main purpose of preventing drying at the nozzle tip of the ink jet recording head. When recording is performed using such an aqueous dye ink, the water-soluble high-boiling solvent contained in the ink remains in the receiving layer, and the dye molecules move during storage, that is, migration. Phenomenon cannot be completely suppressed.

Also, the method of coating the ink receiving layer after forming an image with a polyisocyanate compound or an acrylic urethane resin, or laminating a film after the treatment, can completely suppress the migration of the dye. Can not. In addition, when an ink receiving layer is provided on the surface of a non-ink-absorbing recording medium and such a coating treatment is performed after printing, the high boiling point contained in the ink is particularly high in a portion where the amount of ink discharged is large. It was also found that the action of the solvent caused swelling, peeling, and turbidity of the coating layer. On the other hand, if the coating layer is made thicker to suppress the swelling, the cost is increased and the recording medium may be deformed, which is not a good idea.

On the other hand, in ink jet recording performed in the case of manufacturing a color filter, the use is limited, there is no need to superimpose and print multiple colors, and the ink ejection amount can be reduced. Without adding a high boiling point solvent, these solvent components do not remain in the printed matter. However, when such an ink is used, a special recovery mechanism for maintaining stable ejection of the ink jet recording head is required, but it is costly to apply this to an inexpensive recorded material. Difficult from.

Accordingly, an object of the present invention is to provide a case where a resin coating layer is provided on the surface of an ink receiving layer after image formation, while suppressing the migration phenomenon and maintaining good image quality without causing nozzle clogging. Swelling and peeling of the coating layer,
An object of the present invention is to provide a method for forming an image recorded matter which does not cause turbidity or the like, and which can simultaneously satisfy various properties such as durability such as water resistance, light resistance and scratch resistance of the obtained image recorded matter in a well-balanced manner. .

[0013]

The above object is achieved by the present invention described below. That is, the present invention provides a method for forming an image on a recording medium by discharging a liquid ink containing a pigment as a coloring material into droplets according to predetermined information, and then forming an image on at least a part of the recording medium. A method for forming an image recording material, comprising forming a resin coating layer by covering a transparent resin to obtain an image recording material, wherein the recording medium is washed with water after image formation, and the method. Is an image recorded matter obtained by the above method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The recording medium used in the image recording material forming method of the present invention is preferably used when the image forming surface is non-ink-absorbing. However, the recording medium surface is not particularly provided with an ink receiving layer. Or a recording medium provided with an ink receiving layer. In the present invention, a recording medium having a water-resistant ink-receiving layer provided on the surface of a water-resistant substrate is particularly preferably used. Hereinafter, the recording material used in the present invention will be specifically described.

In the method for forming an image recorded matter according to the present invention,
As the base material of the recording medium, for example, metal, glass, ceramics, polyester, polysulfone, polyvinyl chloride, polycarbonate, polystyrene, polymethacrylate,
A non-ink-absorbing water-resistant substrate such as cellulose acetate, polyethylene, and polypropylene is used.

When printing is directly performed on these substrates without providing an ink receiving layer, it is preferable that the printing density of an image to be formed is not relatively high. In this case, it is necessary to quickly remove the volatile solvent in the ink by heating the base material when printing, and to suppress the movement of the printed ink droplet.

On the other hand, when a recording medium in which an ink receiving layer is provided on a substrate as described above is used, it is necessary to have a water resistance that does not cause problems such as dissolution and peeling in a subsequent washing step. It is preferable to provide it to the ink receiving layer.
As such an ink-receiving layer, any of the above-described conventionally known ink-receiving layers themselves provided with water resistance can be applied, and in particular, high-duty printing is possible.
The following having good resistance to the washing step is preferable. That is, an ink receiving layer which is a modified polyvinyl alcohol and contains at least a polyvinyl acetal resin component having an acetalized portion and an acetyl group and a hydroxyl group in its molecular structure is particularly preferable in the present invention.

As a method for forming an ink receiving layer on a substrate using these resin components, when the resin component is a thermoplastic resin, it may be applied directly in a molten state at a high temperature. Specifically, the raw material (unreacted material) of the resin to be applied, or its solvent diluted solution, emulsion or colloidal state, is spray-coated, curtain-coated, dipped, wire-bar coated, applicator-coated, spin-coated, or rolled After application by a method such as coating, electrodeposition coating, or brush coating, the solvent is removed by drying, and if necessary, a curing reaction is performed to form an ink receiving layer.

In the method for forming an image recorded matter according to the present invention,
A liquid ink containing a pigment is used as a coloring material, but an aqueous liquid ink is preferably used. The reason for using a pigment as a coloring material is that, first, the pigment has better light fastness than the dye, and second, it is a water-insoluble coloring material. That is, the pigment is insoluble in water, and is dispersed in a liquid medium by a dispersant in an ink state. However, on a recording medium after printing, evaporation of the liquid medium and insolubilization of the dispersant are performed. For the reason, the dispersion is destroyed, and in the state where the dispersion is destroyed, the pigment becomes water-insoluble in its original state. Therefore, in the present invention, the recording medium can be washed with water after image formation.

As the pigment which can be used in the present invention, all conventionally known organic pigments and inorganic pigments can be used. For example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments, and polycyclics such as phthalocyanine pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. Formula pigments, dye lakes such as basic dye lakes and acid dye lakes, organic pigments such as nitro pigments, aniline black, daylight fluorescent pigments, and inorganic pigments such as titanium oxide, iron oxide and carbon black. Can be

In the present invention, it is desirable that the content of these pigments is usually in the range of 1 to 30% by weight based on the total ink amount. If it is less than 1% by weight, the density of the image becomes insufficient, and if it exceeds 30% by weight, the viscosity becomes too high and the ejection becomes unstable, which is not preferable. The content of the pigment in the ink is more preferably 2 to 15% by weight, and more preferably 3 to 10% by weight. In this range, good image density and dischargeability can be obtained.

As the dispersant used for dispersing the above-mentioned pigment in a liquid medium for ink, the following resins or water-soluble surfactants can be used. As the resin that can be used in the present invention,
A resin soluble in an aqueous solution in which an amine or a base is dissolved is preferably a resin having a molecular weight of 3,000 to 30,000, and more preferably a resin having a molecular weight of 5,000 to 15,000. As such a resin, specifically, for example, styrene-acrylic acid copolymer, styrene-acrylic acid-alkyl acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid-acrylic acid Alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid-alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene- A maleic acid copolymer, a styrene-maleic anhydride-maleic acid half ester copolymer, a salt thereof, or the like can be used.

Specific examples of the water-soluble surfactant used in the present invention include, for example, anionic surfactants include higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, and alkyl allyls. Sulfate, alkyl allyl ether sulfate, alkyl naphthalene sulfonate, sulfosuccinate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, alkyl allyl ether phosphate and the like.

Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, tetraalkylammonium salts, benzalkonium salts, alkylpyridium salts, imidazolinium salts, and the like. For example, betaine type, aminocarboxylic acid and the like, as nonionic surfactants, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, Sugar ester, polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyethylene ether of sorbitol ester, fatty acid alkanolamide, polyoxyethylene fat Amides, amine oxides, and the like.

When a resin is used as the dispersant, the amount of the dispersant is preferably in the range of usually 5 to 60% by weight based on the weight of the pigment. That is, when the amount of resin is 5
If the content is less than 60% by weight, a stable dispersion state of the pigment cannot be maintained. If the content exceeds 60% by weight, the viscosity increases, and it becomes difficult to obtain a stable discharge. More preferably, it is used in the range of 10 to 40% by weight. When a water-soluble surfactant is used as the dispersant, the amount of the water-soluble surfactant is preferably in the range of usually 1 to 40% by weight based on the pigment. When the amount of the surfactant is less than 1% by weight, the pigment cannot maintain a stable dispersion state, and when the amount exceeds 40% by weight, the surface tension of the ink decreases, and when the inkjet recording method is applied in the present invention, This causes an undesired situation such as printing distortion due to the wetting of the nozzle tip (shift of the landing point of the ink droplet). In the present invention, 5 to 20% by weight
It is more preferable to be within the range.

In the present invention, as the liquid medium for dispersing the pigment as described above, any of those used in the conventional liquid medium for ink jet recording ink can be used. For example, water and / or a water-soluble organic solvent are preferable, and examples of the organic solvent include, for example,
C1-C4 alkyl alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol; dimethylformamide, dimethylacetamide and the like Amides; ketones such as acetone and diacetone alcohol, or keto alcohols; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, and triethylene glycol , 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc. Alkylene glycols containing 6 carbon atoms; glycerin; lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone and the like.

A particularly preferred liquid medium composition constituting the ink used in the present invention is water and at least one water-soluble organic solvent. It contains a water-soluble high-boiling organic solvent having the above boiling point. For example, such water-soluble high-boiling organic solvents include polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. The amount of the liquid medium in the ink used in the present invention is such that when the ink composition is adjusted, the content of the above-mentioned pigment in the ink is in the range of about 0.1 to 20% by weight. preferable.

In the method for forming an image recorded matter according to the present invention,
An image is formed by ejecting ink into droplets corresponding to predetermined information on a recording medium to form an image. It is preferable to use an inkjet recording method as an image forming method. As a method for producing an ink jet recording ink having the above composition, a component such as a pigment is mixed, and a conventionally known grinding means, for example, a ball mill, a sand mill, a mixing and grinding treatment by a speed line mill, and the like, It is general to adjust the concentration with a liquid medium as needed and finally obtain a pH of 4 to 10. At this time, if the particle size of the pigment in the ink is too large, problems such as clogging of nozzles during ink jet recording may occur. Therefore, the particle size is usually about 3 μm or less, preferably about 2 μm or less.

In the present invention, in addition to the ink jet recording method, a method of forming an image by ejecting ink in droplets corresponding to predetermined information can be applied. However, if an ink jet recording method is used, an expensive printing apparatus is used. This eliminates the need for a printing plate and eliminates the need for a printing plate, so that an inexpensive image recorded matter can be provided, and further, there is an advantage that the product delivery time can be extremely short.

As an ink jet recording method which can be used in the image recording material forming method of the present invention, an image is formed on a recording medium by discharging the ink having the above-described structure into droplets corresponding to predetermined information. Any method may be used as long as it can be formed. As a typical example of those methods, for example, IEEE Transactions on Indu
stry Applicactions Vol.IA-13 No.1 (197
January and February 1995, Nikkei Electronics 305 (1
All of the methods described in these publications are suitable for the present invention. Some of them are described below.

First, there is an electrostatic suction method. In this method, a strong electric field is applied between a nozzle and an accelerating electrode placed several mm ahead of the nozzle to form ink particles from the nozzle and draw it out one after another. There are a method in which an information signal is applied to the deflection electrode while the drawn ink flies between the deflection electrodes and recording is performed, and a method in which the ink particles are ejected in response to the information signal without deflecting the ink particles. All of them are effectively applied to the image recorded matter forming method of the present invention.

A second method is to apply high pressure to the ink with a small pump and mechanically vibrate the nozzle with a quartz oscillator or the like to forcibly eject fine ink particles. The particles are charged in response to the information signal simultaneously with the ejection. The charged ink particles are deflected according to the charge amount when passing between the deflection electrode plates. As another method utilizing this method, there is a method called a micro dot ink jet method. In this method, ink pressure and excitation conditions are kept at appropriate values within a certain range, two types of ink droplets are generated from the nozzle tip, and only the small droplets among these are used for recording. The feature of this method is that a group of fine droplets can be obtained even with a nozzle diameter as large as the conventional one.

As a third method, there is a piezo element method. In this method, a piezo element is used as a pressure means for applying ink instead of a mechanical means such as a pump as in other methods. That is, in this method, pressure is applied to the ink by applying an electrical signal to the piezo element to cause mechanical displacement, and the ink is ejected from the nozzle.

As an ink jet recording method preferably used in the present invention, a rapid change in volume of ink subjected to the action of thermal energy, such as the method described in JP-A-54-51837, is proposed. Then, an ink jet method is used in which ink is ejected from a nozzle by the action force caused by the state change.

In the present invention, preferably, characters and images are printed and recorded on a non-ink-absorbing recording medium using the aqueous pigment ink described above by the above-described various ink jet recording methods. . In this case, the pigment on the recording medium is removed by drying the formed image on the recording medium with hot air or the like, thereby removing water and volatile solvents in the image and destroying the dispersion of the pigment. To be established. In this state, the high-boiling solvent in the ink is difficult to remove by heating or drying under reduced pressure, so that the high-boiling solvent remains in the ink dry component (image), and the recording is performed as it is. When at least a part of the image and the recording medium is covered with the resin, problems such as peeling and swelling of the resin coating layer occur.

Therefore, in the present invention, the recording medium is washed with water after image formation. By introducing this washing step, the water-soluble high-boiling organic solvent contained in the ink constituting the image formed on the recording medium is easily removed by water. On the other hand, since the pigment added as a coloring material of the ink is originally water-insoluble, it does not flow out in the water washing step in a state where the dispersion state is broken due to evaporation of a solvent generated by drying or the like. Further, in the present invention, preferably, a water-resistant substrate is used as a recording medium, so that the recording medium can be easily washed with water. Furthermore, when a recording medium provided with an ink receiving layer is used, since the water-resistant ink receiving layer is provided, the ink receiving layer is not removed by the above-mentioned washing step.

In the step of washing the recording medium after image formation used in the present invention, any method may be used, as long as the high boiling organic solvent in the ink forming the image is removed by water. Although it does not matter, specifically, for example, a method of washing the surface of the recording medium on which an image is formed with running water,
Alternatively, it is preferable to perform the method by immersing a recording medium on which an image is formed in stirring water put in a washing tank or the like. By these washing steps, only the water-soluble high-boiling organic solvent in the ink forming the image is removed from the recording medium. The recording medium after washing with water may be dried by an ordinary drying method.

In the present invention, after the recording medium is washed with water, at least a part of the recording medium is coated with a substantially transparent resin to form a resin coating layer. At this time, it is preferable to provide a resin coating layer having water resistance, light resistance, and scratch resistance. The term "waterfastness" as used herein means a higher level than the waterfastness described above for the ink receiving layer. That is, in the case of the ink receiving layer, the ink absorbing layer is necessary because of its properties, and is formed of a material having a water absorbing property. However, in the case of the above-mentioned resin coating layer, since water absorption is unnecessary, it is possible to select a more durable material.

As a material constituting such a resin coating layer, first, an image of a formed image (hereinafter, referred to as a recorded matter intermediate) before the surface is coated with the resin is not damaged. The color tone is preferably colorless and transparent. Specifically, it is preferable that the increase in the reflection density of the image before and after the application is within a range of 0.5 or less in the application thickness of the resin coating layer described later. The required transparency changes depending on the pattern of the intermediate of the recorded matter, but the increase in the reflection density is 0.5%.
In the case where it exceeds, coloring or opacity may occur, so that a feeling of deterioration in image quality cannot be avoided unless there is a special intention.

Examples of the material for forming such a resin coating layer include, for example, azelaic acid, chloresic acid, succinic acid, trimellitic acid, orthophthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, Adipic acid, polybasic acids such as sebacic acid, and polyhydric alcohols such as α-methylglucoside, dipentaerythritol, glycerol, glycols, trimethylolmethane, trimethylolpropane, tripentaerythritol, sorbitol, and fatty acids. Alkyd resin obtained; copolymerized alkyd resin and silicone intermediate such as siloxane; silicone alkyd; amino resin such as urea formaldehyde and melamine formaldehyde hydride resin obtained by reaction of formaldehyde with urea and melamine; , Phenolic resins, amines, polyamides, epoxy resins crosslinked by an isocyanate, and the like; polyester resins, unsaturated polyester resins, silicone resins, urethane resins, polyamide resins, polyimide resins, fluorocarbon resins and the like can also be used. In addition, acrylic resins and the like obtained by polymerization or copolymerization of acrylic acid or methacrylic acid esters can also be used. Also, a mixture or reaction of these resins can be used.

As a method of applying the above-mentioned resin on the base material of the recording medium, for example, generally, an unreacted material (reaction raw material) of the applied resin, a solvent diluent thereof, an emulsion Or what is in colloidal state,
Examples of the method include spray coating, curtain coating, dipping, wire bar coating, applicator coating, spin coating, roll coating, electrodeposition coating, and brush coating.
After applying the resin composition by these methods, the solvent is dried and removed, and if necessary, a curing reaction is performed to form a resin coating layer. Examples of the curing method at this time include methods such as thermal curing and irradiation with active energy rays.

In the present invention, the thickness of the resin coating layer formed on the recording medium is adjusted to be 0.1 to 50 μm after drying or curing. And more preferably 1 to 30
μm range. If the thickness of the resin coating layer is less than 0.1 μm, the required mechanical strength cannot be obtained, and an image having excellent durability such as scratch resistance cannot be obtained. Further, in the case of a recording medium provided with an ink receiving layer, it is difficult to completely cover a necessary portion of the ink receiving layer due to the flatness of the ink receiving layer and the influence of foreign matter during coating. The occurrence rate of coating failure increases, and an image with excellent durability cannot be obtained.
Further, when an ultraviolet absorber or a fungicide, which will be described later, is internally added to the resin coating layer, if the thickness of the resin coating layer is smaller than 0.1 μm, in order to exhibit these effects, each of the internal addition rates is required. Needs to be increased, so that it becomes more difficult to obtain the characteristics of the resin coating layer. On the other hand, the thickness of the resin coating layer is 50 μm.
If it exceeds, there is almost no merit in characteristics and it is uneconomical, and in some cases, due to shrinkage that occurs during curing when forming the resin coating layer, deformation, peeling, cracking, etc. may occur, and it is preferable. Absent.

When the resin coating layer is formed on at least a part of the recording medium, when the resin is coated, cissing may occur depending on the compatibility with the underlying ink receiving layer and the like. In the image recorded matter forming method of the present invention, in order to prevent this, it is also effective to treat the surface of the ink receiving layer or the like before coating the resin to eliminate cissing. As a specific method of the treatment performed at this time, for example, treatment with oxygen plasma, treatment with ozone generated by performing ultraviolet irradiation in an oxygen-containing gas, or the like is particularly suitable.

In a preferred embodiment of the present invention, the resin coating layer preferably contains an ultraviolet absorber and / or an ultraviolet ray blocking agent. As a result, the light fastness of the pigment used for image formation can be further improved, and the yellowing deterioration of the ink receiving layer or the resin coating layer itself is suppressed, and further long-term stability of the image recorded matter is obtained. . The ultraviolet absorber used in the present invention refers to light (3) having a wavelength in the ultraviolet region having a high energy level.
(450-450 nm) and emits this as heat energy, and has a function of suppressing discoloration of a recorded image due to ultraviolet rays in sunlight or illumination light.

In the present invention, when such an ultraviolet absorber is added to the resin coating layer, the amount of the ultraviolet absorber is 0.1 to 10% based on the weight of the material forming the resin coating layer. It is preferred to use That is, if the amount of the ultraviolet absorbent used is less than 0.1%, the effect of improving the light resistance of the image is not sufficient, while if the amount used exceeds 10%,
In addition to not being able to obtain the effect of being excessively added, the film-forming properties and properties of the resin coating layer may be adversely affected, which is not preferable.

Examples of the ultraviolet absorber usable in the present invention include salicylates, benzophenones and the like.
Conventionally known ones such as benzotriazole, acrylonitrile, hindered amine and metal complex salts can be used. Preferred are, for example, phenyl salicylate, pt-butylphenyl salicylate, p-octyl salicylate, 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4
-Octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-dodecyloxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, sodium-2,2'-dihydroxy-4,4'
-Dimethoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl- 5 '
-Methylphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-3'-t-butyl-5'-octylphenylpropionate) -5-chlorobenzotriazole, 5'-octylphenylpropionate-5-
Chlorobenzotriazole, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2- (2 '
-Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5-di-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3',
5-di-t-amylphenyl), 2- [2-hydroxy-
3,5-di (2,2-dimethylbenzine) -phenyl] -2
H-benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2
-Cyano-3,3'-diphenyl acrylate, nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-t-octylphenolate)]-n-butylamine nickel, 3- [3-
(2H-benzotriazole) -2-yl-5-t-butyl-4-hydroxyphenyl] propionic acid mono- and diesters, nickel complex-3,5-di-t-
Butyl-4-hydroxybenzyl-phosphate monoethylate, nickel dibutyldithiocarbamate, resorcinol monobenzoate, hexamethylphosphoryltriamide, 2,4,5-trihydroxybutylphenone, di-
p-octylphenyl terephthalate, di-pn-norylphenyl isophthalate, and 2- (3,5-di-t
-Butyl-4-hydroxybenzyl) -2-n-butylmalonic acid, hindered amines such as bis (1,2,2,6-pentamethyl-4-piperidine), and other monomers and introduced into the copolymer Is 2-oxy-
4- (2-oxy-3-methacryloxy) propoxybenzophenone, ethyl diphenylmethylene cyanate, and the like.

The ultraviolet blocking agent used in the present invention refers to an agent that blocks light having a wavelength in the ultraviolet region, and has an action of suppressing discoloration and fading of a recorded image formed by ultraviolet light. Examples of the ultraviolet blocking agent that can be used in the present invention include silica, talc, mica, cerium oxide and the like. When such an ultraviolet ray blocking agent is contained in the resin coating layer, it is preferable that the ultraviolet ray blocking agent be contained in the range of 0.1 to 30% by weight of the material forming the resin coating layer. If the amount of the ultraviolet ray blocking agent is less than 0.1%, the effect of improving the light fastness of the image is not sufficient, while if the amount exceeds 30%, not only the effect of excessive addition is not obtained but also In addition, the opacity of the resin coating layer may increase, which may hinder image appreciation. or,
In some cases, the film forming property of the resin coating layer and its properties are adversely affected.

In the present invention, it is also a preferred embodiment to include a fungicide in the resin coating layer. As the fungicide that can be used in the present invention, any of the conventionally known fungicides listed below can be used,
The amount of the fungicide used in the resin coating layer is preferably from 0.01 to 10% by weight based on the weight of the material for forming the resin coating layer. That is, if the amount used is less than 0.01% by weight, the effect of the fungicide is insufficient, while if the amount exceeds 10% by weight, the fungicidal property is improved according to the amount used. Absent.

The effect of the fungicide differs depending on the type of fungi to be treated. Therefore, it is also effective to use two or more kinds of different fungicides in a total amount not exceeding the above range. It is. Preferred examples of the fungicide that can be used in the present invention include, for example, benzoic acid, sorbic acid and salts thereof, p-hydroxybenzoic acid ester, dihydroxyacetic acid, propionic acid, salts thereof, and diphenyl, o
-Phenylphenol, copper-8-quinolylate, PC
P, PCP-Na, p-chloro-m-xylenol, dihydroethylamine pentachlorophenol, 4-chloro-2-phenylphenol, N- (trichloromethylthio) phthalamide, N, N-dimethyl-N'-phenyl
(N'-fluorodichloromethylthio) sulfamide, N
-(Trichloromethylthio) -4-cyclohexene-1,
2-dicarboximide, 2,4,5,6-tetrachloro-
Examples include iso-phthalonitrile, bis (tri-n-butyltin) oxide, tributyltin laurate, 10,10'-oxybisphenoxyarsine, and thiabendazole.

The use of the image recorded matter of the present invention is as follows.
For example, notices such as advertisements and billboards, exhibits, CD-RO
M, CD-R, CD-E, DVD, etc., in which scratch resistance is particularly required, and printing on building material exterior parts. In addition, printing by an ink jet method can be applied to printing on irregularities and surfaces since printing can be performed on a recording material in a non-contact manner. Specific examples include golf balls, soccer balls, cans, bottles, and the like.

[0051]

The present invention will be described more specifically below with reference to examples and comparative examples. In the following description, “parts” or “%” is based on weight unless otherwise specified. An ink jet recording method was used as a recording method on the recording medium. That is, Canon's bubble jet color printer BJC
An image was formed by using a paper feed portion of -600 modified so as to be able to carry horizontally by a belt. The printing was performed in the OHP sheet mode.

The inks mounted on the above-mentioned printer include:
A liquid pigment ink using a pigment prepared as described below as a coloring material was used. First, an aqueous pigment dispersion in which the pigments of each color listed below were dispersed in a water-soluble resin and water, respectively, was prepared. At this time, a styrene-acrylic acid copolymer (weight average molecular weight 7,000) was used as the water-soluble resin, and the mixing ratio of the pigment, the water-soluble resin, and water was expressed in a weight ratio of pigment /
The water-soluble resin / water was set to be 10/3/87. Each color pigment used: cyan (pigment name: CI Pigment Blue 15: 1) magenta (pigment name: CI Pigment Red 122) yellow (pigment name: CI Pigment Yellow 74) black (pigment name) :Carbon black)

Using the aqueous pigment dispersion obtained above, liquid pigment inks of each color having the following compositions were prepared. The viscosity of the obtained ink was about 3 to 5 cps. -60% of the aqueous pigment dispersion prepared above-5% of glycerin-10% of diethylene glycol-10% of isopropyl alcohol-15% of water

Examples 1 to 3 First, as a substrate of a recording medium, in Example 1, 100
μm thick white PET (Melinex 33 manufactured by ICI)
9), a methacryl plate (como glass made by Kuraray) having a thickness of 1 mm was prepared in Example 2, and an aluminum plate (5052 material) was prepared in Example 3 respectively. These were all commercially available, and no ink receiving layer was provided on the surface of the substrate. Next, while printing these base materials with black ink using the above-described printer while heating the base materials to about 80 ° C. with a dryer, the printed recording medium is heated at 80 ° C. for 30 minutes.
And dried. Next, the recording medium was immersed in pure water being stirred by a stirrer and washed for 5 minutes. The recording medium was pulled up, water adhered was removed by air blow, and then dried at 80 ° C. for 30 minutes to obtain a recorded material intermediate.
Next, the surface of the recording material intermediate was subjected to ultraviolet / ozone cleaning for 5 minutes. As the washing machine, an eye ozone washing machine (model: OC-253) manufactured by Iwasaki Electric was used.

Further, a coating material having the following composition was applied by spraying to the surface of the recording medium after washing on which the image was formed, to form a resin coating layer. -ZPP-N-1000 (phosphazene-based methacrylate: manufactured by Kyoeisha Chemical) 70 parts-NK ester A-9530 (dipentaerythritol polyacrylate: manufactured by Shin-Nakamura Chemical Industry) 30 parts-Irgacure 184 (ultraviolet curing agent: manufactured by Nippon Ciba Geigy) 5 parts-Tinuvin 400 (ultraviolet absorber: manufactured by Nippon Ciba-Geigy) 3 parts-Tinuvin 123 (hindamine: manufactured by Nippon Ciba-Geigy) 2 parts-Cellosolve acetate (diluting solvent: manufactured by Kishida Chemical) 200 parts-Calcium propionate (prevention) Fungicide: Ueno Pharmaceutical) 0.3 parts

After the application, the recording medium was heated at 80 ° C. for 30 minutes and dried, and then irradiated with ³ J / cm ^{2 using} an ultra-high pressure mercury lamp to form a cured film. The thickness of the formed resin coating layer was 10 μm. When the resin coating layer was observed, no defect of the resin coating layer was recognized, and the image was clear and beautiful. Table 1 shows the evaluation results of each image.

Examples 4 to 6 In Example 4, the same recording medium as in Example 1 was used, and in Example 5, the same as in Example 2 was used. In this example, the same components as in Example 3 were used. A colorless and transparent resin having the following composition was applied to the surface of each of these substrates, and dried at 80 ° C. for 20 minutes to form ink receiving layers. The coating thickness after drying was 10 μm. -100 parts of polyvinyl acetal resin-20 parts of alumina hydrate (AS-100 manufactured by Nissan Chemical)-20 parts of cationic resin (PAA-HCL-1L (1000) manufactured by Nitto Boseki) As the polyvinyl acetal resin used above, The polyvinyl acetal was synthesized from polyvinyl alcohol using a known acetalization technique, that is, polyvinyl alcohol (Kuraray's PVA220) was acetalized with benzaldehyde, and the polyvinyl acetal resin had an acetalization degree of 12 mol%. 4 hydroxyl groups
What contained 0 mol% was used.

The above-described printer was used for each of the recording media on which the ink receiving layer was formed, using the printer described above.
Full color inkjet printing was performed. Thereafter, in the same manner as in Examples 1 to 3, the recording medium after printing was washed with water, and then an image recorded matter subjected to a resin coating treatment was obtained. As a result, similarly to Examples 1 to 3, no failure of the resin coating layer was recognized. The image was clear and beautiful. Table 1 shows the evaluation results of each image.

Comparative Example 1 A methacryl plate was used as a substrate of a recording medium, and the recording medium was used without an ink receiving layer provided on the surface of the substrate. In addition, as for the image forming method, an image recorded matter subjected to a resin coating treatment was obtained in the same manner as in Examples 1 to 3 except that the washing treatment was not performed after the image formation. As a result, swelling of the resin coating layer occurred in a portion where printing duty was high. Table 1 shows the evaluation results.

Comparative Example 2 A methacrylic plate was used as a base material of a recording medium, on which an ink receiving layer similar to that of Examples 4 to 6 was provided, and a water washing treatment was performed after image formation. Except for the absence, resin-coated image recordings were obtained in the same manner as in Examples 4 to 6. As a result, swelling of the resin coating layer occurred in a portion where printing duty was high. Table 1 shows the evaluation results.

Comparative Example 3 A methacryl plate was used as a base material of a recording medium, and was used without an ink receiving layer as in Examples 1 to 3.
Further, an image recorded matter was obtained without performing a water washing treatment and a resin coating treatment after image formation. Table 1 shows the evaluation results of the obtained images.

Comparative Example 4 A methacrylic plate was used as a base material of a recording medium.
The same ink receiving layer as that of No. 6 to No. 6 was provided on the substrate surface. Further, an image recorded matter was obtained without performing a water washing treatment and a resin coating treatment after image formation. Table 1 shows the evaluation results of the obtained images.

Comparative Example 5 A methacrylic plate was used as a base material of a recording medium, and an ink receiving layer similar to that of Examples 4 to 6 was provided thereon. Was used to form an image. When the washing process was performed after the image formation, a slight outflow of the dye was recognized, and thus the washing process was not performed. Subsequent resin coating steps are described in Examples 4 to
In the same manner as in Example 6, a resin-coated image recorded matter was obtained.

The evaluation of the obtained image recorded matter was performed by the following method. Table 1 shows the evaluation results. Evaluation item (1) Abnormality of resin coating layer The resin coating layer was visually observed, and a defect in which defects such as swelling, peeling, and turbidity were recognized was evaluated as x. If no abnormality was observed, it was marked as “○”. (2) Scratch resistance The surface of the recorded material was rubbed 10 times with an eraser,
X indicates that a defect such as surface scratching occurred, and o indicates that no defect was observed. (3) Storage of image recorded matter Each image recorded matter was stored in an environment of 35 ° C./RH 95% for 20 minutes.
After storage for days, the images were compared and evaluated before storage. As compared to the image before storage, ink overflow, bleeding and thickening of the character occurred, and the image quality was poor, and the image quality was inferior.

[0065]

[Table 1] Table 1

[0066]

As described above, according to the present invention,
It is possible to suppress the occurrence of swelling, peeling, turbidity, and the like that occur when a resin coating layer is provided on a recorded matter formed by inkjet recording. Further, according to the present invention, since the pigment ink is used, it is possible to obtain an image recorded matter excellent in storability without deterioration of an image after storage. Further, according to the present invention, there is no possibility that the color material is removed or the surface is not scratched by the external force such as rubbing of the formed image recorded matter. or,
According to the present invention, a water-soluble organic solvent having a high boiling point can be used in the ink composition to be used.Therefore, even when an ink jet recording method is used, there is little fear of nozzle clogging, and in order to prevent nozzle clogging. There is no need to prepare a special ink jet recording apparatus provided with a mechanism, and an inexpensive image recorded matter can be provided.

Claims (12)

[Claims] 1. An image is formed on a recording medium by discharging a liquid ink containing a pigment as a coloring material into droplets corresponding to predetermined information to form an image on the recording medium. In a method for forming an image-recorded material to obtain an image-recorded material by forming a resin-coated layer by coating a transparent resin on the substrate, an ink containing at least a water-soluble high-boiling organic solvent is used, and the image-recorded material is formed after image formation. An image recorded matter forming method, comprising washing a medium with water. 2. The method according to claim 1, wherein the image forming surface of the recording medium is non-ink-absorbing. 3. The image forming method according to claim 1, wherein the recording medium has a water-resistant ink-receiving layer provided on the surface of a water-resistant substrate. 4. An ink receiving layer comprising a modified polyvinyl alcohol having an acetalized portion in its molecular structure;
The image forming method according to claim 3, further comprising a polyvinyl acetal resin component having an acetyl group and a hydroxyl group. 5. The method according to claim 1, wherein the means for discharging the liquid ink into droplets corresponding to predetermined information is an ink jet recording method. 6. The method according to claim 5, wherein the ink jet recording method is a method in which thermal energy is applied to the ink to eject the ink as droplets. 7. The method according to claim 1, wherein the water-soluble high-boiling organic solvent has a boiling point of 180 ° C. or more at 1 atm. 8. The method according to claim 1, wherein the coating treatment comprises irradiating the substantially transparent resin with active energy rays to cure the resin. 9. The method according to claim 1, wherein the resin coating layer contains an ultraviolet absorbent. 10. The method according to claim 1, wherein the resin coating layer contains an ultraviolet blocking agent. 11. The method according to claim 1, wherein a fungicide is contained in the resin coating layer. 12. An image recorded matter obtained by the image recorded matter forming method according to any one of claims 1 to 11.