JP2001239661A - Recording and method for recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording having a clear color at an arbitrary position on a plane generated through interference of light in which the coloring light generated through interference provides fresh feeling at all times when viewed with eyes from any direction thus providing a vivid impression unattainable from a recording employing an ordinary dye, and a method for producing a recording having such excellent characteristics without forming any special plate. SOLUTION: In a recording having a part where fine solid particles adhere while aggregating to form a regular periodic structure on the liquid repellent face of a recording material, color of the liquid repellent face is black or dark having standard color chart brightness of 6 or below and chroma of 8 or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a recorded matter having a color developed by light interference on its surface, and a recording method thereof.

[0002]

2. Description of the Related Art Ordinary printed matter has a dye attached to a surface to be printed, and the printed surface emits light in a certain wavelength range depending on the dye by light absorption of the attached dye. It appears colored by reflection or transmission. There are many kinds of the above-mentioned dyes that can be used for printed matter, and in particular, synthetic organic dyes can be made of various kinds and can produce various colors. However, since the coloring by the dye is due to absorption of light energy, the dye may cause a chemical change by the absorbed light energy. The photo-fading phenomenon that causes fading when a printed matter using a dye is exposed to light is known as "burn". Therefore, in particular, printed matter to be exhibited outdoors is exposed to direct sunlight, and in this case, it is essential to use a dye having light resistance.

[0003] Some dyes have the property of emitting absorbed light energy as light of another wavelength, and are known as so-called fluorescent dyes. When such a fluorescent dye is used for a printed material, not only light in a specific wavelength region depending on the dye is absorbed, but also light of another specific wavelength depending on the dye is emitted. A printed matter with a strong emphasized impression is obtained. In particular, when a fluorescent dye whose emission energy is concentrated in a narrow wavelength region is used for printing,
Since light with high color purity is visually recognized, a printed matter with a vivid impression can be obtained.

[0004] On the other hand, as a technique for obtaining coloring without using a dye as described above, a technique utilizing light interference is known. In color development using light interference, in addition to visually recognizing light with high color purity as in the case of using fluorescent dyes, interference conditions change depending on the angle between the object and the illumination or line of sight, and brightness and Changes in color appear. Therefore, a more impressive visual recognition effect can be obtained compared to printing using a fluorescent dye. Coloring without using these dyes has the advantage that there is no light fading phenomenon seen in the dyes and no fading occurs.

The hologram is a technique in which interference fringes of light are recorded on a film, and when a reproduction light is applied to the film, interference occurs in transmitted light or reflected light to display a colored three-dimensional image or the like. / Holograms requiring development are not suitable for simple mass production of printed matter. Embossed holograms, on the other hand, form irregularities that cause optical interference on the surface and enable reproduction and display of the image as described above. Since the irregularities can be formed by stamping using a mold, mass production is possible. Suitable for However, since it is necessary to form concavities and convexities with a precision close to the wavelength of light, a high-precision mold is required for printing. Further, the shape and material of the substrate for forming the unevenness cannot be freely selected.

Therefore, as a method of printing an embossed hologram on an arbitrary substrate, first, a transfer foil on which an embossed hologram is formed is formed, and the hologram is printed on the substrate by transferring the transfer foil to the substrate. ing. However, in this case, since a predetermined interference pattern is recorded on the transfer foil in advance, it is difficult to change this pattern at the time of transfer to the substrate. To erase the part, for example, as proposed in JP-A-5-11676,
Special ingenuity is required. Therefore, printing using this transfer foil has not been a simple method of forming a portion having optical interference in any predetermined region of the substrate.

[0007] Some cholesteric liquid crystal materials develop a color when the helical pitch of the liquid crystal layer interferes with visible light. It is also known to control the helical pitch with temperature. For example, Nobuyuki Tamaki et al., ADVANCED MAT
In ERIALS, 1997 Vol. 9, No. 14, page 1102, a material having a diacetylene portion and a cholesteryl portion exhibits a cholesteric liquid crystal phase at around 100 ° C., and develops a color in the visible region according to the temperature, and a coloration state. It was found that the color development state was fixed when the material was quenched, and it was reported that color recording could be performed by performing heat writing and quenching and fixing operations on the material sandwiched between two glass plates. are doing. Tamaki et al.'S method is excellent as a color display device in that it can be repeatedly rewritten by heating and cooling.However, in that a glass medium holding a special liquid crystal material is used, a recording medium is not used. It has the disadvantage of being limited.

It is known that when fine particles made of a transparent material having a uniform particle size are regularly arranged, light interference occurs due to the fine particle arrangement, and colored reflected light is obtained. For example, ADVANCED MA by MAYORAL et al.
As described in TERIALS, 1997, Vol. 9, No. 3, page 257, a monodisperse particle of silica is precipitated from a suspension and heat-treated to obtain a sintered body showing colored reflected light. I have.

[0009] It is also known that coloring of plastic fine particles occurs similarly. For example, JORN
AL of the OPTICAL SOCIETY
of AMERICA, 1954, 44, 8 No. 603
On the page, VANDERHOFF et al. Report that a uniform particle-based latex of a vinyl polymer yielded a material exhibiting coloration due to strong light interference.

On the other hand, with respect to suspending fine particles of a transparent material in ink, see, for example, Japanese Patent Application Laid-Open No. 62-9157.
Japanese Patent Application Laid-open No. 4 (1994) discloses that silica fine particles are used for the purpose of improving the dispersion stability of the pigment of the ink.
JP-A-63-145381 proposes to add resin particles to ink for the same purpose. Further, Japanese Patent Application Laid-Open No. 6-287492 proposes that fine particles of titania or alumina are added to ink for inkjet recording to improve print density and bleeding. Furthermore, Japanese Patent Application Laid-Open No. 7-196965 proposes using polyester monodispersed fine particles having a particle size of 0.2 to 1 μm as ink for an ink jet printer. In order to obtain a good recorded image, the fine particles are used in a state of being colored with a dye or a pigment.

However, none of the above-mentioned inks in which the fine particles are dispersed are inks used for the purpose of the present invention, which are prepared for the purpose of obtaining light interference by an arrangement of fine particles having a strictly aligned particle diameter. Was. As mentioned above,
Various recordings and recording methods are known, but it is not possible to obtain a printed matter having bright reflected light colored by light interference with a printing machine having an arbitrary pattern such as a dot matrix type without using a plate. Not yet realized. Of course, even in various states such as the direction of the visual observation, a printed matter made of a light interference coloring material in which colored light is clearly felt stably has not been obtained.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a vivid color at an arbitrary position on a surface by utilizing the color generated by light interference, and furthermore, even when viewed from various directions with the naked eye. It is an object of the present invention to provide a recorded matter which gives a strong impression that the colored light due to the interference is always felt vividly and which cannot be obtained by a recorded matter using ordinary dyes, and a recording method and a recording apparatus therefor. It is a further object of the present invention to provide a recording method capable of producing a recorded matter having the above-described excellent characteristics utilizing light interference without producing a special plate.

[0013]

The above object is achieved by the present invention described below. That is, the present invention relates to a recorded material having an attached portion in which solid fine particles are aggregated and arranged on a part of the liquid-repellent surface of a recording material to form a regular periodic structure and adhere. A recorded matter and a recording method, characterized in that the color of the surface is a black or dark color having a standard color chart lightness of 6 or less and a saturation of 8 or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to preferred embodiments of the present invention. As described above, it has been conventionally known that fine particles are dispersed in ink and that a structure in which light interference occurs when fine particles are arranged can be formed, but printing using ink in which particles are dispersed has been known. It is known that a recorded matter causing light interference can be obtained, and further, a printed matter made of a light interference coloring material in which colored light is clearly and stably sensed even in various states such as the direction of visual observation. Did not.

On the other hand, the present inventor has conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, using solid fine particles having transparency, Monodisperse fine particles are adhered to form a regular periodic structure in which the particles are aggregated and arranged, and the color of the liquid-repellent surface is black or dark with a standard color chart lightness of 6 or less and a saturation of 8 or less. If
The present invention has been found that it is possible to easily obtain a recorded material in which colored light due to light interference can be clearly and stably sensed even in various states such as the direction of the visual observation. In the present invention, a particle arrangement is formed using a suspension in which solid fine particles are dispersed. Unlike the ordinary ink, the suspension does not contain a coloring material. The same applies to the liquid in that a recorded matter is formed by light interference, and therefore, a recording liquid containing the same is also called an ink.

The material used as the solid fine particles used in the present invention must have a property of transmitting light. For visible light, for example, silica, alumina, titania, an inorganic oxide such as zirconia, SiO ₂ ·
Al ₂ O ₃ , SiO ₂ · B ₂ O ₃ , TiO ₂ · CeO ₂ , Sn
O ₂ · Sb ₂ O ₅ , SiO ₂ · Al ₂ O ₃ · TiO ₂ , or T
Ceramics such as complex inorganic oxides such as iO ₂ · CeO ₂ · SiO ₂ , oxyacid salts such as metal titanates, and methacrylic resins, acrylic resins, styrene resins, olefin resins, vinyl ester resins, etc. Synthetic resins and the like can be used.

Such a light transmitting material is prepared into fine particles having a uniform particle diameter by a method suitable for each. In the case of an inorganic oxide such as the silica described above,
For example, fine particles having a uniform particle size can be prepared by utilizing a so-called sol-gel method in which hydrolysis and polycondensation reactions are performed from a solution of a corresponding metal alkoxide. In the case of an addition polymer such as an acrylic resin, fine particles having a uniform particle size can be prepared by using a method such as suspension polymerization or soap-free polymerization. During preparation, for the purpose of stabilizing the shape of the particles of the addition polymer, as part of the polymerizable monomer,
It is preferable to carry out polymerization by mixing bifunctional crosslinking monomers. The bifunctional cross-linking monomer referred to here is a monomer having a plurality of polymerizable sites in a molecule, such as divinylbenzene, ethylene glycol dimethacrylate and the like.

In the recorded matter of the present invention, the solid fine particles as described above are adhered in a state of being densely arranged on a part of the liquid-repellent surface of the recording material, and the resulting solid fine particles are ordered. The light is caused to interfere by the periodic structure to form a colored portion on the substrate. Therefore, the fine particles are required to be monodispersed. The ideal monodispersion is a state in which the particle diameters are completely uniform, but in the present invention, the coefficient of variation of the particle diameter distribution (the ratio of the standard deviation to the average particle diameter) is used in the present invention. , The value is 5% or less,
Preferably, the case of 3% or less is defined as monodispersion. The state of the particle size distribution can be confirmed by direct observation with an electron microscope, light scattering of a liquid in which fine particles are suspended, or measurement by a Coulter counter method. In the recorded matter of the present invention, as the particle size distribution of the solid fine particles used approaches the ideal monodispersion, the coloring of the obtained recorded matter due to light interference becomes more vivid. Conversely, the particle size distribution broadens,
When the distance from the ideal monodispersion is deviated, coloring of the obtained recorded matter due to light interference becomes weak, and it becomes difficult to obtain a bright recorded matter.

The solid fine particles which can be suitably used in the present invention have an average particle diameter of about 100 to 1000 nm. The particle size of the solid fine particles used in the present invention may be determined from the conditions under which interference with visible light occurs and the conditions under which the fine particles are stably dispersed in a liquid. However, 1
When fine particles smaller than 00 nm are used, optical interference of visible light due to the arrangement is unlikely to be expected.
When fine particles larger than 0 nm are used, optical interference of visible light due to higher-order diffraction can be expected, but the stability of the suspension in which the fine particles used in the ink are dispersed is deteriorated.
Not practical.

It is considered that the relationship between the particle size of the solid fine particles and the light interference phenomenon requires Bragg's condition in crystal X-ray diffraction. When the monodisperse fine particles are densely arranged to form an ordered structure, the particles form a lattice plane. The reflection of visible light by this lattice plane is represented by Bragg's conditional expression 2n
It is considered that Dcos θ = mλ (1) is satisfied. (1)
In the formula, m is a natural number representing the order of diffraction, θ is the angle between incident light and the normal to the lattice plane, D is the lattice plane interval, and n is the average refractive index of the particle array structure.

The lattice spacing D in the formula (1) exists innumerably for one lattice system. For example, the shortest hexagonal or cubic close-packed lattice has a particle diameter d. In this case, it can be estimated that D = d (√2 / √3). or,
The average refractive index n is represented by the refractive index n ′ of the particles and the volume fraction φ of the particles.
From this, it can be estimated that n = n′φ. However, it is difficult to accurately measure the refractive index of fine particles of the order of the wavelength of light, and the refractive index of the bulk of the same material is not necessarily the same as the refractive index of the fine particles. The accuracy of estimating the visible light interference wavelength is not very high. Rather, it is better to obtain the apparent average refractive index from the observed particle size and interference light and use it for designing the particle size with the same material system.

The recorded matter of the present invention is constituted by attaching solid fine particles to a part of the liquid-repellent surface of the recording material as described above. The liquid-repellent surface for providing a surface energy of 45 m
N / m or less, or a surface having a contact angle with water at room temperature of 70 degrees or more is preferable. Such liquid-repellent surfaces include, for example, polyvinyl resins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride; acrylic resins such as polyisobutyl methacrylate; polyamide resins such as 11-nylon; polyester resins such as polyethylene terephthalate; A surface formed of a water-resistant synthetic resin material such as a fluorine resin such as hydrogenated ethylene, a polycarbonate resin, a polyurethane resin, a polysulfone resin, an epoxy resin, a phenol resin, and a urea resin can be used. In this case, the molded article made of the synthetic resin as described above is used as the recording material, and the surface thereof may be used, or, for example, on the surface of a substrate made of another material such as paper, as described above. It is also possible to coat a suitable synthetic resin layer and use the coated surface.

The liquid-repellent surface for providing a regular arrangement of monodisperse fine particles that can be used in the present invention includes:
In addition, a liquid-repellent surface obtained by physically adsorbing or chemically bonding an organic component to the surface of an inorganic material such as glass, ceramics, or metal can be used. In this case, examples of the organic component to be physically adsorbed include hydrocarbons such as mineral oil, lipids such as fats, fatty acids, fatty acid salts, and phospholipids. Examples of organic components to be chemically bonded include alkylating agents such as octyltriethoxysilane and hexamethyldisilazane, and fluoroalkylating agents. With this configuration, a component having a C—H bond or a C—F bond is present on the surface of an inorganic material such as glass, and the surface becomes lyophobic.

Further, in the recorded matter of the present invention, the color of the liquid-repellent surface made of the above-mentioned material has a standard color chart lightness of 6
And a black or dark color having a saturation of 8 or less. That is, in order to achieve the requirement of clarity of the recorded matter composed of the light interference coloring matter, it is necessary that the scattered reflected light from the base is sufficiently weaker than the interference light reflected from the fine particle array aggregate. Become. Generally, when a printed matter is viewed by the naked eye, the illumination light is white light, while the interference light is observed as monochromatic light. Therefore,
In order for the interference light to be visually felt stronger than the scattered reflected light of the base of the printed record, it is completely impossible to make the interference light intensity larger than the intensity of the scattered reflected light of the base at the center wavelength of the interference light. It is enough.

On the other hand, the present inventor has made various studies on the conditions under which light coherent particle aggregates in which transparent particles are regularly arranged are formed on a plastic film, and colored light due to interference looks vivid under illumination light. As a result, it was found that when the film itself forming the particle aggregates was darkened or the background of the film was darkened, colored light due to interference in the particle aggregates formed on the film surface was clearly visible. . Specifically, when the color of the liquid-repellent surface was a color having a brightness of 6 or less and a chroma of 8 or less in the standard color solid, the interference light was clearly perceived by the eyes.

As the liquid-repellent surface satisfying such conditions, a colored material is used as the constituent material of the liquid-repellent surface described above, or when a transparent liquid-repellent surface material is used,
It can be obtained by painting or sticking a black or dark material on the back surface. Specific examples of the colored liquid-repellent coating material include various oil-based paints, oil-based printing inks, emulsion-based paints, and the like. From these, the color after application to the substrate surface and the liquid wettability May be selected in consideration of the above. Further, when the recording material has a liquid-repellent surface, the recording material itself may be formed from a colored material. In that case, various resin materials that can be molded and colored, specifically, As easily available,
For example, a colored sheet or a colored plate of a vinyl chloride resin, an acrylic resin, a propylene resin, a styrene resin, or the like can be used.

The interference light generated from the fine particle array aggregates is clearly felt on the black or dark surface as described above because the illumination light from the front of the printing surface and the external light from the back surface are the black or the dark. It is considered that light other than interference light from the fine particle array aggregates is hardly perceived by being absorbed or shielded by the dark background, and the color contrast is increased. Further, even when the interference light is viewed from a weak observation angle, it is considered that light other than the interference light hardly enters the eyes, so that the direction in which the interference light can be perceived is widened.

Next, the recording method of the present invention for obtaining the recorded matter of the present invention as described above will be described. In the recording method of the present invention, solid fine particles are attached to desired positions on the liquid-repellent surface of a recording material to form a regular periodic structure by aggregation and arrangement. A suspension in which light-transmitting monodisperse solid fine particles are suspended is attached as droplets to a black or dark liquid-repellent surface having a lightness of 6 or less and a saturation of 8 or less, and the suspension is applied. It is characterized by forming a regular periodic structure in which monodispersed solid fine particles are aggregated and arranged by drying.

The liquid used for obtaining the fine particle suspension in which the monodispersed solid fine particles are suspended is preferably a liquid that does not practically dissolve the fine particles and has a volatility. Used for These liquids can be used alone or as a mixture of two or more. When two or more types of liquids are mixed and used, it is preferable to use a combination in which the liquids to be mixed are uniformly mixed.

An example of such a liquid that can be commonly used is water or a mixture of water and an organic liquid soluble in water. By using an organic liquid, an ink containing a fine particle suspension in which solid fine particles are suspended is ejected in the form of droplets by inkjet means to stably eject the fine particles on the liquid-repellent surface. And the aggregation and arrangement of the suspended particles after the droplets adhere to the liquid repellent surface. Examples of the organic liquid that can be used at this time include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, and 2-methyl-2.
-Lower alcohols such as butanol, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, thiodiglycol and triethylene glycol, 1,3-butanediol, 2-methoxyethanol, 2-ethoxyethanol and 1-methoxy- Lower alkyl ethers of polyhydric alcohols such as 2-propanol and 1-ethoxy-2-propanol; ketones such as acetone and butanone; keto alcohols such as diacetone alcohol; ethers such as dioxane and tetrahydropyran; dimethylformamide , Amides such as dimethylacetamide, N-methyl-2-pyrrolidone, 2
-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like.

Of course, instead of using these organic liquids, water alone may be used as the liquid for preparing the fine particle suspension. However, as described above, the ejection stability is improved when an ink jet unit described later is used for forming a recorded matter, and the fine particle suspension is ejected to the liquid-repellent surface and dried. For the purpose of improving the alignment of the adhered fine particles, it is preferable to use a mixture obtained by adding the above-mentioned organic liquid to water.

When the ink jet means is used, the ratio of the above-mentioned organic liquid component effective for stabilizing the discharge is in the range of 3 to 50% by weight of the weight of the particle suspension (ink). It is preferable that the content be in the range of 3 to 40% by weight. The amount of water used is 1% of the total weight of the ink.
It is in the range of 0 to 90% by weight, preferably 30 to 80% by weight. The content of the monodispersed fine particles in the suspension (ink) is 1 to 20% by weight, preferably 2 to 15% by weight. If the content of fine particles in the ink is low,
The amount of fine particles discharged to the liquid-repellent surface is reduced, and the color is weakened. On the other hand, when the content of the fine particles is high, ejection becomes difficult when an ink jet method described later is used as a means for attaching the fine particles.

In order to make the ink used in the present invention an ink having desired physical properties, in addition to the above-mentioned fine particle suspension component, if necessary, a surfactant, a defoaming material, a preservative, etc.
A water-soluble dye or the like can be added. For example, the surfactant may be any as long as it does not adversely affect the storage stability or the like of the suspension. Examples thereof include fatty acid salts, higher alcohol sulfate salts, and liquid fatty oil sulfate salts. Nonionic surfactants such as anionic surfactants such as alkyl allyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohol and acetylene glycol. Can be These can be used alone or by appropriately selecting two or more kinds.

The use amount of these surfactants is desirably 0.01 to 1% by weight based on the ink. However, it is preferable to determine the amount of the surfactant to be added so that the surface tension of the ink is 55 dm / m or more. In the case of using an ink having a surface tension smaller than this, in an ink jet recording method, undesired situations such as printing distortion due to wetting of the nozzle tip may occur, and in the lyophobic recording surface as described above. During drying, the formation of the array structure of the suspended monodisperse fine particles is disturbed, which may adversely affect the coloring of the recorded matter, which is not preferable.

In the recording method of the present invention, the ink having the suspension of the monodispersed fine particles as described above is applied in the form of droplets to the liquid-repellent surface of the recording material. An ink jet method is convenient as a means used in this step. However, as long as the printing means can form a liquid pool of ink on a desired portion of the liquid-repellent surface of the recording material as described above, the ink jet method is not necessarily used. It is not limited to the method. However, as described above, since the surface tension of the ink used is large and the surface energy of the liquid-repellent surface is low, it is difficult to attach the ink to the liquid-repellent surface by the contact transfer method.

In the ink jet system, a thermal energy corresponding to a recording signal is applied to a recording liquid in a chamber of a recording head to generate a droplet by the energy, or a voltage is applied to an electrostrictive material to deform the material. There is a piezo method or the like for discharging droplets, and any method can be used as long as the monodispersed fine particle suspension having the above-described configuration used as ink can be discharged.

It is known that an ink-jet type image forming apparatus can form a two-dimensional image in accordance with a recording signal as an output device of a computer. If such an apparatus is used, a liquid (ink) in which the above-mentioned monodispersed fine particles are suspended can be discharged in an arbitrary two-dimensional pattern on the above-mentioned liquid-repellent surface.

FIGS. 1 to 3 show examples of the structure of a head which is a main part of the above-described thermal energy type ink jet apparatus.
FIG. 1 is a cross-sectional view illustrating a configuration example of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view illustrating a cross section taken along line AB in FIG. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head.

In FIG. 1, a head 13 is obtained by bonding a glass, ceramic or plastic plate having a groove 14 through which ink passes to a heating head 15 used for thermal recording. The heating head 15 includes a protective film 16 made of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome or the like,
It is composed of a heat storage layer 19 and a substrate 20 having good heat dissipation such as alumina. The ink 21 has a discharge orifice (fine hole) 2
2, and the meniscus 23 is formed by the pressure P.

When an electric signal is applied to the electrodes 17-1 and 17-2, the area of the heating head 15 indicated by n rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area, and the pressure is increased. As a result, the meniscus 23 protrudes, the ink 21 is discharged, and becomes a recording droplet 24 from the orifice 22 and flies toward the recording medium 25 having a liquid-repellent surface.

The multi-head shown in FIG.
And a heating head 28 similar to that described with reference to FIG.

In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is disposed at a position adjacent to a recording area of the recording head, and in this example, is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the moving direction of the recording head to come into contact with the ejection surface to perform capping. The cap 62 has the same shape in association with a head 65 described later. Further, 63 is an ink absorber provided adjacent to the blade 61, similar to the blade 61.
It is held in a form protruding into the movement path of the recording head.
The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 6
3 removes moisture, dust and dirt from the ink ejection port surface.

In FIG. 4, reference numeral 65 denotes a recording head having ejection energy generating means for performing recording by discharging ink onto a recording material facing a discharge port surface provided with discharge ports.
Is a carriage on which the recording head 65 is mounted to move the recording head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). Accordingly, the carriage 66 can move along the guide shaft 67, and the recording head 65
Can move the recording area and its adjacent area.

Reference numeral 51 denotes a paper feed unit for inserting a recording material having a liquid-repellent surface, and 52 denotes a paper feed roller driven by a motor (not shown). With such a configuration, the recording material is fed to a position facing the ejection port surface of the recording head, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the carriage 62 of the head ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 is moved by the moving path. Protruding inside. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62
Moves so as to protrude into the movement path of the recording head.
When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result,
Also in this movement, the ejection port surface of the recording head 65 is wiped.

The above-described movement of the print head to the home position is performed not only at the end of printing and at the time of ejection recovery, but also at a predetermined interval while the printing head moves through the printing area for printing. Position, and the wiping is performed along with the movement.

FIG. 5 shows an ink cartridge 4 containing ink supplied to the head via an ink supply tube.
FIG. 5 is a diagram showing an example of a fifth example. Here, reference numeral 40 denotes an ink bag containing the supply ink, and a rubber stopper 4 is provided at the tip thereof.
2 are provided. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. 44 is an ink absorber for receiving the waste ink.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, and the one in which they are integrated as shown in FIG. Can be FIG. 6 is a perspective view of an embodiment of an ink jet recording apparatus in which a head and an ink cartridge are integrated. In FIG. 6, 70
Is an ink jet cartridge, in which an ink absorber impregnated with ink is stored, and the ink in the ink absorber is ejected as ink droplets from a head unit 71 having a plurality of orifices. Has become. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The ink jet cartridge 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

When a droplet of a liquid (ink) in which monodispersed fine particles are suspended is applied to the liquid-repellent surface of a recording material by the ink jet recording apparatus having the above-described configuration, and then dried, Aggregates of fine particles are formed on the liquid-repellent surface. Since the formed monodispersed fine particle aggregate has densely arranged particles having a uniform particle size, coloring by interference is observed when light is applied. Further, as shown in FIG. 7, the surface shape of the aggregate is usually a part of a sphere as shown in FIG. 7A, or a concave caldera at the center as shown in FIG. 7B. It is. As described above, the monodispersed fine particle aggregate formed on the liquid-repellent surface of the recording material has a non-planar surface,
Colored light can be reflected by interfering with light from various directions.

The process of forming a fine particle array in which light interference occurs by the recording method of the present invention will be described with reference to FIG.
In the example shown in FIG. 8, an agglomeration array of monodisperse fine particles was formed on the liquid-repellent surface of the recording material by the ink jet method. As shown in FIG. 8A, a liquid (ink) droplet 4 in which monodisperse fine particles 3 are suspended is ejected from a recording head 5 of an ink jet apparatus, and a black or dark liquid-repellent surface is formed. If the droplets 2 adhere to the surface, the surface energy of the liquid-repellent surface is low, so that the droplets 4 cannot spread on the surface, and form a liquid pool 6 on the spot. As shown in FIG. 8B, the liquid pool 6 contracts as the liquid dries. At the time of the contraction of the liquid pool, the fine particles 3 inside are concentrated, and finally, about the center of the position where the liquid pool 6 was located,
An aggregate 1 of fine particles remains. When the fine particles are monodispersed, particles of the same size are densely packed inside the agglomerate to form a face-centered cubic lattice, a hexagonal close-packed lattice, or a particle arrangement close thereto. The repetition period of the regular arrangement depends on the size of the monodispersed fine particles. Therefore, in order to obtain a desired periodic structure, one having an appropriate size for the fine particles may be selected and used.

Further, if one or both of the recording head 5 and the liquid repellent surface 2 or both moving means (not shown) are used,
It is also possible to produce a desired two-dimensional recording. That is, with this configuration, after the droplets 4 are adhered to the liquid repellent surface 2 as described above, the relative position between the recording head 5 and the liquid repellent surface 2 is changed by the moving means, The droplet 4 is ejected again to the liquid-repellent surface 2 to form a liquid pool 6 at an arbitrary position on the liquid-repellent surface 2, and is further dried to form an arbitrary liquid on the liquid-repellent surface 2. The aggregate 1 having a two-dimensional pattern shape can be formed. By controlling the moving means and the droplet discharge at a predetermined timing, it is possible to manufacture a desired two-dimensional recording material composed of aggregates.

In the recording method of the present invention described above, if the surface tension of the ink containing the fine particles to be used is insufficient, or if the base for forming the particle arrangement is a surface that is easily wetted by the liquid, the fine particles may be removed. No aggregation occurs, and a regular structure sufficient for light interference cannot be obtained. In order to form a regular array of fine particles where light interference can be seen, it is necessary that contraction force due to surface tension acts strongly when the ink reservoir is dried, and that the base of the reservoir becomes wet. It is important that the surface be very lyophobic.

The size of the aggregate formed as described above is determined by increasing the amount of fine particles in the suspension (ink) discharged by the ink jet apparatus having the above-described structure, Can be increased by either or both. Further, by discharging a plurality of droplets to the same position on the liquid-repellent surface of the recording material, the same effect as increasing the discharge amount of the suspension can be obtained. In general, when a droplet is ejected to a sufficiently close position on the liquid-repellent surface, the droplets are coalesced on the liquid-repellent surface, and a large liquid pool is formed almost at the center of the fused portion. The size of the aggregate can also be increased by a method of densely discharging droplets sufficiently close to a predetermined range.

[0054]

The present invention will now be described more specifically with reference to examples and comparative examples of the present invention. Note that the present invention is not limited to this embodiment. Parts are based on weight. First, inks 1 to 3 to be used were prepared as described below. (Preparation of First Ink) 9 parts of tetraethoxysilane, 28 parts of ethanol and 6 parts of water were mixed, and while stirring, 8 parts of 28% aqueous ammonia and 8 parts of ethanol were added to this mixed solution.
Parts, a mixed solution consisting of 8 parts of water was dropped over about 1 hour,
Hydrolysis and polycondensation. When a part of the obtained suspension of milky white silica particles was dropped on an aluminum plate and dried, a dried film exhibiting a light reddish purple color was obtained. When the dried film was observed with a scanning electron microscope, it had a diameter of about 280 nm, and the ratio of the standard deviation of the particle size to the average particle size (= coefficient of variation, hereinafter referred to as particle size variation) was 4.8%.
It was found to be composed of aggregated silica fine particles having a uniform particle size. 1 part of water and 0.02 part of ethylene glycol were added to 1 part of the suspension having silica fine particles having a diameter of about 280 nm obtained above to obtain a first ink.

(Preparation of Second Ink) While mixing and stirring 7 parts of tetraethoxysilane, 28 parts of ethanol and 6 parts of water, 8 parts of 28% ammonia water, 8 parts of ethanol and 8 parts of water were added to this solution. The resulting mixture was added dropwise over about 1 hour to effect hydrolysis and polycondensation. When a part of the obtained suspension of silica particles was dropped on an aluminum plate and dried, a dried film having a pale green color was obtained. When the dried film was observed with a scanning electron microscope, it was found that the dried film was composed of aggregated silica fine particles having a diameter of about 250 nm and a uniform particle diameter of 2.6%. To 1 part of the silica particle suspension obtained above, 1 part of water and 0.02 part of ethylene glycol were added to prepare a second ink.

(Preparation of Third Ink) 6.3 parts of tetraethoxysilane, 28 parts of ethanol and 6 parts of water were mixed and stirred, and while stirring, 8 parts of 28% ammonia water, 8 parts of ethanol and 8 parts of water were added to this solution. Part of the mixture was dropped over about 1 hour to effect hydrolysis and polycondensation. When a part of the obtained suspension of silica particles was dropped on an aluminum plate and dried, a dried film having a pale green color was obtained. When the dried film was observed with a scanning electron microscope, it was found that the film was composed of aggregated silica fine particles having a diameter of about 205 nm and a uniform particle diameter of 2.4%. To 1 part of the silica particle suspension obtained above, 1 part of water and 0.02 part of ethylene glycol were added to obtain a third ink.

<Examples 1 to 3> Using the first, second, and third inks obtained as described above, light was applied to a part of the liquid-repellent surface of a transparent recording material by the following method. Monodisperse solid fine particles colored by interference formed a regular periodic structure in which they were aggregated and arranged. Then, various JIS standard color chips having different saturation and lightness are brought into close contact with one side of the transparent recording material, thereby changing the color of the liquid-repellent surface, which is the base, in various ways, and causing interference while changing the angle of light. The light was visually observed, and a sensory evaluation was performed on the vividness of the colored light felt from the aggregates.

First, each of the first, second, and third inks obtained above was charged into a BC-02 bubble jet head manufactured by Canon Inc., and the carriage of a recording apparatus as shown in FIG. Fixed to. As a recording material having a liquid-repellent surface, a transparent polyester film (Lumirror 100
T-60 (manufactured by Panac Corporation)) was used. On this occasion,
Various JIS standard color patches were adhered to one side of the film. Then, ink was discharged onto these films in a predetermined two-dimensional pattern using the above-described recording apparatus.
In the ink jet recorded matter obtained by drying and drying the ejected ink, the portions where the first, second, and third inks are ejected have red, green, and blue interference reflected light, respectively. The visible area appeared.

Next, for each of the recorded materials obtained above,
Simulated solar lamp (KXW-75 manufactured by Wacom Denso Co., Ltd.)
Mold, color temperature 5400K, average color rendering index 97) to 0.
Under lighting 7m away, while changing the viewing angle in various ways,
The appearance of the interference reflected light was visually observed. By using the hues 5P, 5G, 5Y, and 5R as the standard color chips, the color of the liquid-repellent surface, which is the base on which the aggregates of the solid fine particles are attached, is changed, and the saturation N and the lightness V are changed. , Table 1, Table 2, Table 3, and Table 4 can be sequentially changed. In these tables, saturation N is arranged in columns and lightness V in rows.

Tables 1, 2, 3 and 4 show the results of the sensory evaluation on the vividness of the colored light felt from the aggregates. The symbols 記号 and △△△ in the table represent the vividness of the colored light felt from the aggregates formed by the above three types of inks when the aggregates appear at a viewing angle of 0.1 degree. Was subjected to a sensory evaluation. ○ indicates vivid, and Δ indicates not vivid. In addition, three symbols represent the results of the aggregates composed of the first, second, and third inks in order from the front. The symbol... In the table indicates that there is no corresponding color data.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

As described above, it was shown that the vividness of colored light due to the light interference of the fine particle aggregates was visually observed by the color of the liquid-repellent surface as the base. As shown in Tables 1 to 4, it was found that a color having a brightness of 6 or less and a saturation of 8 or less should be used for the base in order to make the interference light look vivid.

[0066]

As described above, according to the present invention,
A recorded matter having a vivid color utilizing color development due to light interference. That is, since there is little unnecessary light from the base, colored light due to interference was clearly felt even when viewed from various directions with the naked eye. Further, according to the present invention, it is possible to manufacture a recorded material utilizing light interference without producing a special plate. Further, according to the present invention, it is possible to manufacture a recorded matter having an arbitrary pattern utilizing interference of light according to an electric signal.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a head constituting a recording apparatus of the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a head constituting the recording apparatus of the present invention. It is sectional drawing in the AB line of FIG.

FIG. 3 is an external view illustrating a multi-head in which a number of recording heads shown in FIG. 1 are arranged.

FIG. 4 is a perspective view for explaining an ink jet recording apparatus incorporating the recording head shown in FIG.

5 is a cross-sectional view illustrating an example of an ink cartridge that stores ink supplied to the recording head illustrated in FIG. 1 via an ink supply tube.

FIG. 6 is a perspective view for explaining an example of an ink cartridge recording apparatus in which a head and an ink cartridge are integrated.

FIG. 7 is a conceptual diagram for explaining the shape of a fine particle aggregate formed on a liquid-repellent surface. (A) is spherical, (B)
Indicates a concave shape at the center.

FIG. 8 is a conceptual diagram for explaining a process of forming fine particle aggregates on a liquid repellent surface. (A) is a state where a droplet is applied, and (B) is a state where a droplet is dried.

[Explanation of symbols]

 1: Aggregate of fine particles 2: Liquid-repellent surface 3: Fine particles 4: Droplet 5: Droplet discharging means 6: Liquid pool 13: Head 14: Groove 15: Heating head 16: Protective film 17: Aluminum electrode 18: Heating resistance Body layer 19: Thermal storage layer 20: Substrate 21: Ink 22: Discharge orifice 23: Meniscus 24: Recording droplet 25: Recording medium 26: Multi-groove 27: Top plate 28: Heating head 40: Ink bag 42: Plug 44: Ink absorber 45: ink cartridge 51: paper feed unit 52: paper feed roller 53: paper discharge roller 61: blade 62: cap 63: ink absorber 64: discharge recovery unit 65: recording head 66: carriage 67: guide shaft 68 : Motor 69: Belt 70: Inkjet cartridge 71: Head 72: Atmospheric communication port

Claims (25)

[Claims] 1. A printed material having an attached portion in which solid fine particles are aggregated and arranged on a part of a liquid-repellent surface of a recording material to form a regular periodic structure and adhere to the liquid-repellent surface. A recorded matter characterized in that the color of the surface is black or dark with a standard color chart lightness of 6 or less and a saturation of 8 or less. 2. The recorded matter according to claim 1, wherein the particle size distribution of the fine particles at the position where the solid fine particles adhere is monodispersed. 3. The method according to claim 1, wherein the solid fine particles are ceramics.
Or the recorded matter according to 2. 4. The solid fine particle is an inorganic oxide.
The recorded matter described in. 5. The inorganic oxide is silica, alumina, titania, zirconia, SiO ₂ .Al ₂ O ₃ , SiO ₂ .B ₂
O ₃ , TiO ₂ · CeO ₂ , SnO ₂ · Sb ₂ O ₅ , SiO ₂
・ Al ₂ O ₃ .TiO ₂ or TiO ₂ .CeO ₂ .SiO ₂
The recorded matter according to claim 4, which is any one of the following. 6. The recorded matter according to claim 1, wherein the solid fine particles are a synthetic resin. 7. The recorded matter according to claim 6, wherein the synthetic resin is an addition polymer. 8. The recorded matter according to claim 6, wherein the synthetic resin is any one of a methacrylic resin, an acrylic resin, a styrene resin, an olefin resin, and a vinyl ester resin. 9. The solid fine particles having a number average particle size of 100 to 10
The recorded matter according to any one of claims 1 to 8, which is in a range of 00 nm. 10. The recorded matter according to claim 1, wherein the liquid-repellent surface has a CH bond or a CF bond. 11. The liquid repellent surface is made of a synthetic resin.
0 recorded matter. 12. The liquid repellent surface has a surface energy of 45 mN.
/ M or less, the recorded matter according to any one of claims 1 to 11. 13. The recorded matter according to claim 1, wherein a contact angle of water with respect to the liquid-repellent surface is 70 degrees or more. 14. A recording method in which solid fine particles are adhered to a desired position on a liquid-repellent surface of a recording material to form a regular periodic structure by agglomeration and arrangement, and a standard color chart having a lightness of 6 or less and a chroma of 8 or less. On the following black or dark liquid-repellent surface, a suspension in which light-transmitting monodisperse solid fine particles are suspended is attached as droplets, and the suspension is dried to obtain monodisperse solid fine particles. A recording method characterized by forming a regular periodic structure in which aggregation is arranged. 15. The recording method according to claim 14, wherein the solid fine particles are ceramics. 16. The recording method according to claim 14, wherein the solid fine particles are an inorganic oxide. 17. The inorganic oxide is silica, alumina, titania, zirconia, SiO ₂ .Al ₂ O ₃ , SiO ₂ .B
₂ O ₃ , TiO ₂ · CeO ₂ , SnO ₂ · Sb ₂ O ₅ , SiO ₂
・ Al ₂ O ₃ .TiO ₂ or TiO ₂ .CeO ₂ .SiO ₂
The recording method according to claim 16, wherein the recording method is any one of the following. 18. The solid fine particle is a synthetic resin.
4. The recording method according to item 4. 19. The method according to claim 1, wherein the synthetic resin is an addition polymer.
8. The recording method according to item 8. 20. The recording method according to claim 19, wherein the synthetic resin is a methacrylic resin, an acrylic resin, a styrene resin, an olefin resin, or a vinyl ester resin. 21. The number average particle diameter of the solid fine particles is 100 nm.
The recording method according to any one of claims 14 to 20, which is in a range from 1 to 1000 nm. 22. The recording method according to claim 14, wherein the liquid-repellent surface has a CH bond or a CF bond. 23. The liquid-repellent surface is made of a synthetic resin.
3. The recording method according to 2. 24. The liquid repellent surface has a surface energy of 45 mN.
The recording method according to any one of claims 14 to 23, wherein the recording method is not more than / m. 25. The recording method according to claim 14, wherein a contact angle of water with respect to the liquid-repellent surface is 70 degrees or more.