JP2002002103A - Recorded matter, recording method and recording apparatus - Google Patents

Abstract

(57) [Abstract] (with correction) [PROBLEMS] To provide a water-resistant recorded material in which a portion that develops color by light interference stably adheres to a desired position on a recording medium;
To provide a recording method and a recording device. SOLUTION: In a recorded matter in which solid fine particles are aggregated and arranged on at least a part of a recording medium 2 to form a regular periodic structure and adhere thereto, a water-soluble polymer is present in a particle gap of the fine particle aggregate 1. 9. A recorded matter characterized in that 9 is present.

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, a recording method thereof, and a recording apparatus.

[0002]

2. Description of the Related Art Ordinary printed matter has a dye attached to a surface to be printed. The printing surface is due to the light absorption of the dye,
It appears colored by reflecting or transmitting light in a certain wavelength range depending on the dye. A wide variety of dyes are available, and in particular, synthetic organic dyes are available in a wide variety of colors. However, coloring by a dye is due to absorption of light energy, and thus the dye may have a chemical change due to the absorbed light energy. The photobleaching phenomenon of fading when light is applied to a printed material using such a dye is known as "burn". In particular, printed matter to be displayed outdoors is exposed to direct sunlight, and therefore, the dye used for coloring the light must have light resistance.

Some dyes have a property of emitting absorbed light energy as light of another wavelength, and the dye is known as a fluorescent dye. The use of fluorescent dyes in prints not only absorbs light in a specific wavelength range depending on the dye, but also emits light of another specific wavelength depending on the dye, which is visually emphasized. A print with a strong impression can be obtained. When a fluorescent dye whose emission energy is concentrated in a narrow wavelength region is used for printing, light with high color purity is visually recognized, so that a printed matter with a vivid impression can be obtained.

[0004] Techniques for obtaining coloring without using a dye include:
A device 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 than printing using a fluorescent dye. Coloring without the use of a dye also has the advantage that there is no light fading phenomenon seen in the dye and no fading occurs.

The hologram is a technique in which interference fringes of light are recorded on a film, and when reproduced 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 exposure / development are not suitable for simple mass production of printed matter. However, embossed holograms have irregularities that cause optical interference on the surface to enable reproduction and display of images as described above. Since the irregularities can be formed by stamping using a mold, they are suitable for mass production. I have.
However, since it is necessary to form concavities and convexities with a size close to the wavelength of light, a high-precision mold is required for replication. Further, the shape and material of the substrate on which the irregularities are formed cannot be freely selected.

Therefore, as a method of forming an embossed hologram on an arbitrary substrate, first, a transfer foil on which an embossed hologram is formed is prepared, and the transfer foil is transferred to the substrate to form a hologram on the substrate. Have been done. Since a predetermined interference pattern is recorded on such a transfer foil in advance, it is difficult to change this pattern when transferring to a substrate. In order to erase a part of the interference pattern when transferring the transfer foil to the substrate, a special device such as that proposed in, for example, Japanese Patent Application Laid-Open No. Hei 5-11676 is required. Therefore, the method using the transfer foil is not very simple as a method for forming a portion having optical interference in an arbitrary predetermined region of the base.

[0007] Some cholesteric liquid crystal materials develop a color by the helical pitch of the liquid crystal layer interfering with visible light. It is also known to control the helical pitch with temperature.
For example, Nobuyuki Tamaki et al., ADVANCED MATERIALS, 1997
In Vol. 9, No. 14, p. 1102, a material having a diacetylene portion and a cholesteryl portion shows a cholesteric liquid crystal phase at around 100 ° C. and develops a color in the visible region depending on the temperature, and quenches the material in a color-developed state to produce color. They found that the state was fixed, and reported that color recording could be performed by thermally writing the above-mentioned material between two glass plates and performing a quenching and fixing operation. Tamaki et al.'S method is excellent as a color display device in that it can be repeatedly rewritten by heating and cooling.However, the recording medium is limited in that a glass plate holding a special liquid crystal material is used. There is a disadvantage.

When fine particles of a transparent material having a uniform particle size are regularly arranged, light interference occurs due to the arrangement of the fine particles, and colored reflected light is obtained. By precipitating silica monodisperse particles from the suspension and heat-treating, a sintered body showing colored reflected light has been obtained (for example, ADVANCED MATERIALS by MAYORAL et al., 1997, Vol. 9, No. 3, page 257). ). It is known that color development occurs similarly for fine particles of plastic (for example, JORNAL of the OPTICAL SOCI
In ETY of AMERICA, 1954, Vol. 8, No. 8, p. 603, VANDERHOFF et al. Reported that a material exhibiting strong color interference due to light interference was obtained from a uniform latex of a vinyl polymer. ).

It is disclosed in Japanese Patent Publication No. Sho 45-3 that an opal-like glossy object can be obtained by enclosing the resin emulsion in a wet state in a container or forming a dry body and coating the resin emulsion with a resin.
No. 2046 discloses it by Watanabe et al. After dispersing uniform fine particles of a synthetic polymer using a polymerizable monomer as a solvent and forming a three-dimensional array of particles, by polymerizing the polymerizable monomer solvent, a stable color-forming object is obtained, and a plate, It can be used for decoration, display as sticks, balls and containers, and can be painted on the surface of objects.
It has been disclosed by Gisou et al. In JP-A-3-31173. Research on these fine particle aggregates focuses on a phenomenon in which the fine particle aggregates themselves are colored by light interference, and relates to a method of manufacturing a colored object.

On the other hand, with respect to suspending fine particles made of a transparent material in ink, see, for example, JP-A-62-91.
No. 574 discloses the use of silica fine particles for the purpose of improving the dispersion stability and the like of a pigment in an ink. JP-A-63-145381 proposes to add resin particles to ink for the same purpose. 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.
Further, JP-A-7-196965 discloses that the particle size is 0.2
It has been proposed to use polyester monodisperse fine particles of about 1 μm as an ink for an ink jet printer. However, in order to obtain a good recorded image having a high image density without bleeding, the fine particles are used by coloring with a dye or a pigment. Have been. None of the fine particle-dispersed inks described above was prepared for the purpose of obtaining optical interference by an arrangement of fine particles having strictly aligned particle diameters.

[0011]

It has not yet been realized to obtain a printed matter having bright reflected light colored by light interference by an arbitrary pattern printer such as a dot matrix type printer which does not use a plate. It has been conventionally known that fine particles are dispersed in ink and that a structure in which light interference occurs when the fine particles are arranged can be formed.However, printed matter that causes light interference by printing using ink in which fine particles are dispersed is known. There is no known example of obtaining. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a recorded material in which a portion that develops color due to light interference is stably fixed at a desired position on a recording medium, a recording method thereof, and a recording apparatus.

[0012]

The above object is achieved by the present invention described below. That is, the present invention relates to a recorded matter in which solid fine particles are aggregated and arranged on at least a part of a recording medium to form a regular periodic structure and adhere thereto. Is provided. Also, the present invention provides a recording method in which solid fine particles are aggregated and arranged at a desired position on a recording surface to form a regular periodic structure, wherein a liquid in which monodisperse fine particles are suspended is attached to a recording medium as droplets. At least, there is provided a recording method characterized in that after the fine particles form an ordered structure, a solution of a water-soluble polymer is applied and dried. The present invention also provides a recording apparatus in which a liquid in which solid fine particles having a monodisperse particle size distribution are suspended is attached as droplets to a lyophobic surface, and a solution of a water-soluble polymer is applied as droplets. There is provided a recording device having means.

[0013]

Next, the present invention will be described in more detail with reference to preferred embodiments. The recorded matter according to the present invention is a recorded matter in which solid fine particles are aggregated and arranged on at least a part of a recording medium to form a regular periodic structure and adhere to the recording medium. Characterized by the presence of a molecule.

The recording medium used in the present invention is, for example,
Solid such as paper, plastic, glass, metal, etc., may be transparent or opaque, and may be colorless or colored. These are usually used in the form of a flat plate or a flat film, but may be in the form of a curved surface. A recording medium used in a recording method and a recording apparatus according to the present invention described later needs to have a liquid-repellent surface. The liquid-repellent surface in the present invention means a surface having a surface energy of 45 mN / m or less or a contact angle with water at room temperature of 70 degrees or more.

As the liquid repellent surface as described above, for example,
Polyethylene, polypropylene, polystyrene, polyvinyl resin such as polyvinyl chloride, acrylic resin such as polyisobutyl methacrylate, polyamide resin such as 11-nylon, polyester resin such as polyethylene terephthalate, fluorine resin such as polyfluorinated ethylene, polycarbonate resin, Polyurethane resin, polysulfone resin,
A surface of a synthetic resin having water resistance such as an epoxy resin, a phenol resin, and a urea resin can be used. The surface of the molded product of the resin may be used, or a surface of a molded product made of another material such as paper coated with the synthetic resin layer may be used.

Further, as the liquid-repellent surface of the present invention, a surface which is made liquid-repellent by an organic component physically adsorbed or chemically bonded to the surface of an inorganic material such as glass, ceramics or metal can be used. Examples of the organic components that physically adsorb include hydrocarbons such as mineral oil, lipids such as fats, fatty acids, fatty acid salts, and phospholipids. Examples of the organic component chemically bonded include an alkylating agent such as octyltriethoxysilane and hexamethyldisilazane, or a fluoroalkylating agent. These surfaces become liquid-repellent surfaces due to the presence of a component having a C—H bond or a C—F bond on the surface of the inorganic material.

The solid fine particles constituting the recorded matter of the present invention
The material used as a material has the property of transmitting light
Must. As a material that transmits visible light,
For example, silica, alumina, titania, zirconia and the like
Inorganic oxide, SiO_Two・ Al_TwoO_Three, SiO_Two・ B_TwoO_Three, T
iO_Two・ CeO_Two, SnO_Two・ Sb_TwoO_Five, SiO_Two・ Al _Two
O_Three・ TiO_Two, TiO_Two・ CeO_Two・ SiO_TwoNo compound such as
Ceramics such as oxides and oxyacid salts such as metal titanates
Box, (meth) acrylic resin, styrene resin,
Addition weight of refining resin or vinyl ester resin
Combination etc. 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 using a process called a sol-gel method in which a hydrolysis reaction is performed from a corresponding alkoxide solution. In the case of an addition polymer such as the (meth) acrylic resin, fine particles having a uniform particle size can be prepared by using a method such as suspension polymerization or soap-free polymerization. For the purpose of stabilizing the shape of the particles of the addition polymer, a bifunctional crosslinking monomer may be mixed as a part of the polymerized monomer. The bifunctional cross-linking monomer is a monomer having a plurality of polymerizable sites in a molecule, such as divinylbenzene and ethylene glycol dimethacrylate.

According to the present invention, such fine particles are densely arranged on at least a part of a recording medium, and light is interfered by the regular arrangement structure to form a colored portion on the recording medium. Therefore, the fine particles need to be monodispersed. The ideal monodispersion means that the particle diameters are uniform, but in the present invention, the standard deviation of the particle diameter distribution of the particles is at most 5%, preferably 3%, relative to the average particle diameter. The following cases will be referred to as monodispersion. 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. As the particle size distribution of the fine particles approaches the ideal monodispersion, coloring of the obtained recorded matter by light interference becomes more vivid. Conversely, if the particle size distribution widens and departs from the ideal monodispersion, coloring of the obtained recorded matter due to light interference becomes weak.

The particle size of the fine particles usable in the present invention is in the range of about 100 nm to 1000 nm. This is determined by the condition of interference with visible light and the condition of stable dispersion in liquid. In the case of fine particles having a particle size of less than 100 nm, optical interference of visible light due to their arrangement cannot be expected, and a particle size of 10
Fine particles exceeding 00 nm can be expected to interfere with visible light due to higher-order diffraction, but are not practical because the stability of the suspension-dispersed liquid deteriorates.

It is considered that the relationship between the particle size 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. It is considered that the reflection of visible light by the lattice plane satisfies the Bragg condition 2nDcosθ = mλ. In the above equation, 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. Although the lattice spacing D exists innumerably for one lattice system, for example, the shortest of hexagonal or cubic close-packed lattices is
When the particle diameter is d, it is considered that D = d (√2 / √3).

In addition to the above conditions, considering that light is incident on the layer having the average refractive index n from the air layer to cause refraction, the equation of the interference wavelength is mλ = 2 (√2 / √3) d ( n ² −sin ² θ) ^1/2 . The average refractive index n can be estimated as n = n′φ from the refractive index n ′ of the particles and the volume fraction φ of the particles. However, it is difficult to accurately measure the refractive index of fine particles of a size on the order of the wavelength of light, and the refractive index of the bulk of the same material and the refractive index of the fine particles do not always match. The accuracy of estimating the visible light interference wavelength is not very high. Rather, the apparent average refractive index may be obtained from the observed particle diameter and the interference light, and used for designing the particle size using the same material system.

In the present invention, the water-soluble polymer is
A material that can be dissolved in water or a homogeneous solvent composed of water and an organic solvent to form a polymer solution. Specific examples of such a polymer include ethyleneimine, allylamine,
As an example, a polymer containing any one selected from vinyl alcohol, vinylpyrrolidone, acrylamide, dimethylacrylamide and the like as a main component can be mentioned. The polymer may contain a hydrophobic monomer component, for example, an alkyl ester of (meth) acrylic acid, styrene or a derivative thereof, vinyl naphthalene or a derivative thereof as a copolymer monomer component within a range not losing water solubility. Good. The weight-average molecular weight of these water-soluble polymers is from 1,000 to 30,000, preferably from 3,000 to 1,000.
The range is 5000. The presence of the polymer material in the interparticle gaps of the fine particle aggregates enhances the binding between the particles of the fine particle aggregates, resulting in a solid aggregate.
Further, the presence of the polymer material in the gap between the fine particles and the recording medium enhances the binding between the fine particle aggregates and the recording medium.

Next, a method for recording a recorded matter of the present invention and a recording apparatus for performing recording by the method will be described. According to the recording method of the present invention, in a recording method in which solid fine particles are aggregated and arranged at a desired position on a recording surface to form a regular periodic structure, a liquid in which monodisperse fine particles are suspended is attached to a recording medium as droplets. After the fine particles form an ordered structure, a solution of a water-soluble polymer is applied and dried.

The recording medium, solid fine particles and water-soluble polymer used in the method of the present invention are as described above. The liquid in which the solid fine particles are suspended is a liquid that does not practically dissolve the fine particles and has volatility. One type of liquid can be used alone, but two or more types can be used in combination. When two or more kinds of liquids are mixed and used, the liquids to be mixed should be uniformly mixed. Examples of commonly available liquids include water or a mixture of water and an organic liquid soluble in water. The organic liquid improves the stability of ejection of the droplets by the ink jet means and the aggregation and arrangement of the suspended particles after the droplets adhere to the recording medium.

Examples of the organic liquid include methanol,
Ethanol, 1-propanol, 2-propanol, 1
-Butanol, 2-butanol, 2-methyl-2-propanol, lower alcohols such as 2-methyl-2-butanol, ethylene glycol, propylene glycol,
Alkylene glycols such as diethylene glycol, thiodiglycol, triethylene glycol, etc .; 1,3-butanediol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, etc. Lower alkyl ethers of polyhydric alcohols, ketones such as acetone and butanone,
Keto alcohols such as diacetone alcohol; ethers such as dioxane and tetrahydrofuran; amides such as dimethylformamide and dimethylacetamide; N-methyl-2-pyrrolidone, 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone And the like.

Instead of using the organic liquid, only water may be used as the liquid for suspending the fine particles. However, for the purpose of improving the ejection stability when used in an ink jet unit described later, and for the purpose of improving the arrangement of the fine particles after the fine particle suspension is discharged to a recording medium, the organic liquid is added to water. Is preferably added. The proportion of the organic liquid component effective for stabilizing the ejection of the inkjet means is in the range of 3 to 50% by weight of the weight of the fine particle suspension,
It is preferably in the range of 3 to 40% by weight, and the water used is 10 to 90% by weight, preferably 30 to 8% by weight of the total weight of the ink.
The range is 0% by weight.

The content of the monodispersed fine particles in the suspension is 1 to 20% by weight, preferably 2 to 15% by weight. When the content of the fine particles is low, the amount of the fine particles discharged to the liquid-repellent surface is reduced, and the coloring is weakened. When the content of the fine particles is high, it becomes difficult to perform ejection by an ink jet method described later. In addition to the above-mentioned components, a surfactant, an antifoaming agent, a preservative, a water-soluble dye, and the like can be added to the suspension, if necessary, to obtain an ink having desired physical properties. .

For example, the surfactant may be any one which does not adversely affect the storage stability or the like of the suspension. Examples thereof include fatty acid salts, higher alcohol sulfates, and liquid fatty oil sulfates. Nonionic surfactants such as salts, anionic surfactants such as alkyl allyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohol and acetylene glycol There is. These one
The species or two or more species can be appropriately selected and used.

The amount of the activator used is preferably 0.01 to 1% by weight based on the fine particle suspension. However, it is preferable to determine the amount of the activator to be added so that the surface tension of the fine particle suspension is 22 mN / m or more. Showing a surface tension smaller than this may cause undesired situations such as printing distortion due to wetting of the nozzle tip in the ink jet recording method, and the arrangement of the suspended fine particles during drying on the recording medium surface. In some cases, the formation of the structure is disturbed, which adversely affects the color development of the recorded matter.

The solution of the water-soluble polymer is obtained by dissolving the water-soluble polymer in a liquid. As this liquid, the same liquid as that used for suspending the fine particles can be used. The polymer concentration of the solution of the water-soluble polymer is preferably in the range of 0.05 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, depending on the substance used. Need to determine the optimal range.

The ink composed of the suspension of the monodispersed fine particles is attached to the recording medium as droplets. As a means used in this step, an ink jet system is convenient. In the ink jet method, thermal energy corresponding to a recording signal is applied to ink in a chamber of a recording head, and a droplet is generated by applying a voltage to an electrostrictive material by applying a voltage to an electrostrictive material. There is a piezo method or the like for discharging, and any method can be used as long as the monodispersed fine particle suspension can be discharged.

It is known that an ink-jet type image forming apparatus can form a two-dimensional image according to a recording signal as an output device of a computer. If such an apparatus is used, the liquid in which the monodispersed fine particles are suspended can be discharged onto the recording medium in an arbitrary two-dimensional pattern.

For the above-mentioned water-soluble polymer solution, it is convenient to use the same ink-jet method as described above as a method of attaching it to the recording medium. FIGS. 1A, 1B and 2 show examples of the configuration of a head which is a main part of the above-described thermal energy type ink jet apparatus. Figure 1
1A is a cross-sectional view illustrating a configuration example of a head 13 along an ink flow path, and FIG. 1B is a cross-sectional view taken along line A-A of FIG.
It is sectional drawing explaining the cut surface in the B line. FIG. 2 shows FIG.
An external view of a multi-head in which a number of heads shown in FIG. FIG. 3 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 and a heating head 15 used for thermal recording. The heating head 15 includes a protective film 16 made of silicon oxide or the like, and aluminum electrodes 17-1 and 17.
-2, a heating resistor layer 18 made of nichrome or the like, 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. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 generates heat rapidly, and bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 is generated by the pressure. Ejects the ink 21, and becomes an ink droplet 24 from the orifice 22, and flies toward the recording medium 25.

The multi-head shown in FIG. 2 is formed by bonding a top plate 27 having a multi-groove 26 and a heating head 28 similar to that described with reference to FIG. In FIG. 3, reference numeral 61 denotes a blade serving as a wiping member, one end of which is held by a blade holding member and serves as a fixed end in the form of 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 abut on the ejection surface to perform capping. A plurality of caps having the same shape are interlocked in correspondence with the number of heads 65 described later. Further 63
Is an ink absorber provided adjacent to the blade 61, and is held in a form protruding into the movement path of the recording head, similarly to the blade 61. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery section 64,
The blade 61 and the absorber 63 remove moisture, dust, dirt, and the like on the ink ejection port surface.

Reference numeral 65 denotes a recording head which has discharge energy generating means and discharges ink to a recording medium facing a discharge port surface having discharge ports to perform recording, and 66 denotes a recording head on which a recording head 65 is mounted. Is a carriage for performing the movement. In FIG. 3, the recording head 65 is
Although an example in which three print heads are mounted is shown, three or more print heads may be mounted on a larger carriage. The plurality of recording heads 65 are filled with ink in which fine particles having different particle sizes are dispersed. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is
It is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 moves the guide shaft 6
7, the recording area by the recording head 65 and the area adjacent thereto can be moved.

In FIG. 3, the recording head 65 is shown as a set of two independent and equivalent heads. However, as shown in FIG. 2, a plurality of ejection nozzles are provided for one head, and a plurality of ink tanks (not shown) ) Is a device that can execute the recording method of the present invention even if only one head is apparently used. Further, the plurality of recording heads 65 may be moved by different carriages 66 and carriage driving systems.

Reference numeral 51 denotes a paper feed unit for inserting a recording medium, and reference numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the discharge 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 head recovery section 64
The carriage 62 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. 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, even 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 or at the time of ejection recovery, but also at a predetermined interval while the print head moves through the printing area for printing to the home position adjacent to the printing area. Then, the wiping is performed along with this movement.

FIG. 4 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 42 is provided at the tip of the ink bag.
Is provided. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives 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. 5 is also suitably used.

FIG. 5 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. 5, reference numeral 70 denotes an ink-jet cartridge, in which an ink absorber impregnated with ink is stored, and the ink in the ink absorber is supplied as ink droplets from a head unit 71 having a plurality of orifices. It is configured to be ejected. 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. 3, and is detachable from the carriage 66.

When droplets of the liquid in which the fine particles are suspended are applied to the recording medium by the ink jet apparatus, aggregates of the fine particles are formed on the recording medium. In the fine particle aggregate, fine particles are densely arranged, and when irradiated with light, coloring due to interference is observed. As shown in FIG. 6, the surface shape of the agglomerate is usually a shield type (FIG. 6 (A)) or a caldera with a concave center (FIG. 6 (B)). As described above, since the surface of the aggregate is not planar, the aggregate can interfere with light from various directions and reflect colored light. When the reflection and scattering of light on the recording medium surface are suppressed, the colored light due to the fine particle aggregates can be easily recognized, and a recorded matter having a higher display effect can be obtained. In order to suppress the reflection and scattering of light on the recording medium surface, for example, the recording medium surface itself or its base may be made transparent or dark.

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. When the droplets 4 of the liquid in which the fine particles 3 are suspended are discharged from the droplet discharge means 5 to the recording medium 2, a liquid pool 6 is formed on the spot (FIG. 7A). The liquid pool shrinks as the liquid dries. When the liquid pool shrinks, the internal fine particles 3
Is concentrated, and an aggregate 1 of fine particles remains (FIG. 7 (B)).
If the fine particles are monodispersed, fine particles of the same size are densely packed inside the aggregate to form a face-centered cubic lattice, a hexagonal close-packed lattice, or a particle arrangement close to the lattice. At this point, the aggregate 1 reflects incident light of a specific wavelength due to light interference based on its regular arrangement. Since the repetition period of the regular arrangement depends on the size of the monodispersed fine particles, a desired periodic structure may be obtained by selecting and using an appropriate size for the fine particles.

After the relative position between the recording head 5 and the recording medium 2 is changed by using one or both of the recording head 5 and the recording medium 2 (not shown), the droplets 4 By discharging the liquid again, the liquid pool 6 can be formed at an arbitrary position on the recording medium 2. By drying this, the aggregate 1 can be formed at an arbitrary position on the recording medium 2. By controlling the moving means and the droplet discharge at a predetermined timing, a desired two-dimensional pattern shape composed of aggregates can be drawn.

The size of the agglomerates can be determined by either or both of increasing the amount of fine particles in the suspension discharged by the ink jet device and / or increasing the discharge amount of the suspension.
Can be bigger. Performing a plurality of droplet ejections at the same position on the recording medium has the same effect as increasing the ejection amount of the suspension. In addition, when the droplets are ejected to a position sufficiently close to the general recording medium, the droplets are merged on the recording medium, and a large liquid pool is formed almost at the center of the merged place. Therefore, even if the droplets are densely ejected sufficiently close to a predetermined range, the size of the aggregate can be increased.

Next, as shown in FIGS. 7C and 7D, the droplet 7 of the water-soluble polymer solution is discharged to the fine particle aggregate 1 by the second droplet discharging means. The discharged solution permeates into the aggregate 1. In FIG. 7 (C), aggregate 1
The droplet 7 is ejected right above the surface of the recording medium 2 because the water-soluble polymer solution only needs to penetrate into the aggregate 1. If it is on the top, it is not always necessary to discharge it directly above the aggregate 1.
In addition, there is no particular problem even if the droplet 7 of the water-soluble polymer solution is ejected to a wider area than the place where the aggregate 1 exists, and the droplet 7 of the water-soluble polymer solution is ejected to the entire surface of the recording medium 2. It does not matter. When the water-soluble polymer solution that has permeated the fine particle aggregates is dried, the water-soluble polymer remains in the particle gaps of the aggregates and binds the particles to each other or to the recording medium. Therefore, in order to prevent the particle aggregate on the recording medium from being broken by an external force, the recording material becomes solid.

[0050]

The present invention will be specifically described below with reference to examples. The present invention is not limited to this embodiment. <Example 1 and Comparative Example 1> 9 parts by weight of tetraethylsilane, 28 parts by weight of ethanol and 6 parts by weight of water were mixed and stirred, and while stirring, 8 parts by weight of 28% by weight aqueous ammonia, 8 parts by weight of ethanol and 8 parts by weight of water were added. About 1 part by weight of the mixture
It was dropped over time. When a part of the obtained suspension of the milky white silica particles was dropped and dried on an aluminum plate, the dried film of the silica particles exhibited a light red-purple color. When the dried film is observed with a scanning electron microscope, it may be composed of fine particles having a diameter of about 280 nm and a ratio of the standard deviation of the particle diameter to the average particle diameter (hereinafter referred to as particle diameter variation) of 4.8%. understood.
1 part by weight of water and 0.02 part by weight of ethylene glycol were added to 1 part by weight of the silica particle suspension to prepare a fine particle ink.

To 1 part by weight of a 30% by weight aqueous solution of polyethyleneimine (average molecular weight: 70,000, manufactured by Tokyo Chemical Industry Co., Ltd.)
15 parts by weight of water, 2 parts by weight of ethanol and 0.2 parts by weight of ethylene glycol were added to obtain a water-soluble polymer solution. The fine particle ink and the above water-soluble polymer solution were filled in a BC-02 bubble jet head manufactured by Canon Inc., respectively, and fixed to a carriage of a recording apparatus as shown in FIG. A4 size "Lapiro"# 30 as a recording medium
Using a 0W type (manufactured by Kimoto Co., Ltd.), the above-described recording apparatus was used to eject the fine particle ink in a predetermined two-dimensional pattern.

After the ejected fine particle ink is almost dried and orange colored reflection based on the arrangement of the particles is recognized, the fine particle ink is first passed through the head filled with the water-soluble polymer solution of the above apparatus. The water-soluble polymer solution was discharged to the position where the was discharged. When the discharged water-soluble polymer solution was observed after drying, orange colored reflected light based on the arrangement of the fine particles could be confirmed. For comparison, only the fine particle ink having the same two-dimensional pattern as described above was ejected on the same recording medium surface, and a printed portion in which the ejection of the water-soluble polymer solution was omitted was also prepared.

After the above-mentioned printed sample surface on which the orange-colored pattern was formed was dried for 3 hours, 25 c
It was rubbed under a load of 20g in flannel land of cloth of m ^2. 95% or more of the printed pattern having the orange colored reflection at the portion where the water-soluble polymer solution was discharged later remained. Only 30% of the print pattern having colored reflection in the portion where the water-soluble polymer solution was not discharged remained.

<Example 2> 7 parts by weight of tetraethylsilane, 28 parts by weight of ethanol and 6 parts by weight of water were mixed and stirred, and 8 parts by weight of 28% by weight aqueous ammonia, 8 parts by weight of ethanol and 8 parts by weight of water were added to this solution. About 1 part of the mixture
It was dropped over time. When a part of the obtained suspension of the silica particles was dropped and dried on an aluminum plate, the dried film of the silica particles turned pale green. Observation of the dried film by a scanning electron microscope revealed that the film was composed of fine particles having a diameter of about 250 nm and a particle size variation of 2.6%. 1.5 parts by weight of water and 0.01 parts by weight of ethylene glycol were added to 1 part by weight of the above suspension of silica particles to obtain a fine particle ink.
Polyvinyl alcohol (average degree of polymerization 500, degree of saponification 95
%, 2% by weight of Kuraray Co., Ltd.) and 15% by weight of 2-propanol were prepared as a water-soluble polymer solution.

The fine particle ink and the water-soluble polymer solution were charged into a BC-02 bubble jet head manufactured by Canon Inc. in the same manner as in Example 1, and fixed to a carriage of a recording apparatus as shown in FIG. did. A4 as a recording medium
Size transparent polyester film (Lumirror 100T
-60 (manufactured by Panac Co., Ltd.), the fine particle ink was discharged in a predetermined two-dimensional pattern using the above recording apparatus. After the ejected fine particle ink is almost dried and green colored reflected light based on the arrangement of the particles can be recognized, the recording medium is substantially moved from the head filled with the water-soluble polymer solution of the device. A water-soluble polymer solution was discharged to the whole.

For comparison, the same two-dimensional pattern of fine particle ink was discharged onto the surface of the recording medium, and before the fine particle ink dried and color formation was observed, the water-soluble polymer solution of the above-described apparatus was discharged. From the filled head, a water-soluble polymer solution was ejected to almost the entire recording medium. In this sample, near white scattered light due to the fine particles was observed in the portion where the fine particle ink was discharged, but almost no colored reflected light was visible. After drying the print sample surface for 3 hours, 25c
When a load of 20 g was rubbed on a flannel cloth of m ² with a load of 20 g, 98 of a printed pattern having green colored reflected light was obtained.
% Or more remained.

<Embodiment 3> In a container in a nitrogen atmosphere, 17
5 ml of water was warmed to 72 ° C. and 0.5 g of potassium persulfate was dissolved with stirring. A mixed solution of 1 g of styrene, 1 g of methyl methacrylate, and 0.5 g of hydroxyethyl methacrylate was added to the solution and stirred for 15 minutes. Further, a mixed solution of 18.8 g of styrene, 4 g of methyl methacrylate, and 1.3 g of hydroxyethyl methacrylate was added little by little to the container while stirring. The resulting emulsion was allowed to cool and then filtered through a nylon cloth. When this solution was applied on recycled paper for copying machines with a brush, the applied portion became a light green glossy surface after drying. Observation of this glossy surface with a scanning electron microscope revealed that the glossy surface was composed of particles having an average of about 260 nm.

To a mixture of 9 parts by weight of water, 1 part by weight of ethanol and 0.1 part by weight of ethylene glycol, 1 part by weight of the above-mentioned poly (styrene-methyl methacrylate-hydroxyethyl methacrylate) particle suspension was added. Average pore size 10
The particles were filtered through a μm membrane filter (JC type manufactured by Japan Millipore Co., Ltd.) to obtain fine particle ink. The fine particle ink and the water-soluble polymer solution were filled in a BC-02 bubble jet head manufactured by Canon Inc. in the same manner as in Example 2, and fixed to a carriage of a recording apparatus as shown in FIG. . Using the transparent polyester film (Lumirror 100T-60) as a recording medium, the fine particle ink was discharged to a predetermined two-dimensional pattern position by the above recording apparatus.

After the discharged fine particle ink was almost dried and green colored reflection based on the arrangement of particles was recognized, a polyvinyl alcohol solution was discharged thereon in the same manner as in Example 2. 20g on 25cm ² flannel cloth
And rubbed. The printing pattern having a green colored reflection at the portion where the water-soluble polymer solution is discharged later is 95
% Or more remained.

[0060]

As described above, the recorded matter of the present invention is:
It has a vivid color utilizing color development due to light interference, and is a hard recorded material that is hard to wear. Further, when the illumination direction or the angle of observation is changed, the interference condition changes, so that the color tone slightly changes. Such a recorded matter can give a viewer a strong impression that cannot be obtained with a recorded matter using a normal dye.

In the recorded matter of the present invention, since a plurality of types of light interference portions coexist on the same surface, a plurality of different interference colors can be seen even when viewed from a certain direction, and the recorded matter becomes a gorgeous recorded matter. The display / exhibition effect is high. Further, the recording method of the present invention can produce a recorded material utilizing light interference without preparing a special plate. The recording apparatus of the present invention can produce a recorded matter having an arbitrary pattern using light interference according to an electric signal.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a head. FIG. 3A is a cross-sectional view illustrating a configuration example of a head. FIG. 2B is a cross-sectional view illustrating a cross section taken along line AB in FIG.

FIG. 2 is an external view illustrating a multi-head in which a number of heads shown in FIG. 1- (A) are arranged.

FIG. 3 is a perspective view illustrating an ink jet recording apparatus incorporating a head.

FIG. 4 is a cross-sectional view illustrating an example of an ink cartridge containing ink supplied to a head via an ink supply tube.

FIG. 5 is a perspective view illustrating an example of an ink cartridge recording apparatus in which a head and an ink cartridge are integrated.

FIG. 6 is a shape diagram of a fine particle aggregate formed on a recording medium. (A) is a shield-like face down, (B) is a concave shape at the center.

FIG. 7 is an explanatory diagram of a process in which fine particle aggregates are formed on a recording medium. (A) is a state in which droplets of fine particle suspension are applied, (B) is a state in which fine particles are aggregated, (C) is a state in which droplets of a water-soluble polymer solution are applied, and (D) is a state in which a water-soluble polymer solution is dried.

[Explanation of symbols]

 1: Aggregate of fine particles 2: Recording medium 3: Fine particles 4: Droplet 5: Droplet discharge means 6: Liquid pool 7: Water-soluble polymer solution 8: Second droplet discharge means 9: Water-soluble polymer 13: Head 14: Groove 15: Heating head 16: Protective film 17: Aluminum electrode 18: Heating resistor layer 19: Heat storage layer 20: Substrate 21: Ink 22: Discharge orifice 23: Meniscus 24: Ink 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: 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: Ink jet cartridge 71: Head portion 72: air vent

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09D 11/00 C09D 11/00

Claims (27)

[Claims] In a recorded matter in which solid fine particles are aggregated and arranged on at least a part of a recording medium to form a regular periodic structure and adhere thereto, a water-soluble polymer is present in a particle gap of the fine particle aggregate. A record characterized by being present. 2. The recorded matter according to claim 1, wherein at least one type of particle size distribution of the fine particles at the attachment location is monodisperse. 3. The recorded matter according to claim 1, wherein at least one of the fine particles is made of ceramics. 4. The recorded matter according to claim 1, wherein at least one of the fine particles is made of an inorganic oxide. 5. The method according to claim 1, wherein at least one of the fine particles 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.
The recorded matter according to claim 1, wherein the recorded matter is CeO ₂ · SiO ₂ . 6. The recorded matter according to claim 1, wherein at least one of the fine particles is made of a synthetic resin. 7. The recorded matter according to claim 1, wherein at least one of the fine particles is made of an addition polymer. 8. The recorded matter according to claim 1, wherein at least one of the fine particles is a (meth) acrylic resin, a styrene resin, an olefin resin, or a vinyl ester resin. 9. The method according to claim 9, wherein the water-soluble polymer is ethylene imine,
Allylamine, vinyl alcohol, vinylpyrrolidone,
The recorded matter according to claim 1, wherein any one selected from acrylamide and dimethylacrylamide is used as a main component. 10. A recording method in which solid fine particles are aggregated and arranged at a desired position on a recording surface to form a regular periodic structure, wherein a liquid in which monodisperse fine particles are suspended is attached as droplets to a recording medium. And a method of applying a solution of a water-soluble polymer and drying after the fine particles form an ordered structure. 11. The recording method according to claim 10, wherein at least one of the fine particles is made of ceramics. 12. The recording method according to claim 10, wherein at least one of the fine particles is made of an inorganic oxide. 13. The method according to claim 1, wherein at least one of the fine particles 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.
The recording method according to claim 10 is a CeO ₂ · SiO _2. 14. The recording method according to claim 10, wherein at least one of the fine particles is made of a synthetic resin. 15. The recording method according to claim 10, wherein at least one of the fine particles is made of an addition polymer. 16. The recording method according to claim 10, wherein at least one of the fine particles is a (meth) acrylic resin, a styrene resin, an olefin resin, or a vinyl ester resin. 17. The method according to claim 1, wherein at least one of the fine particles has a particle size in a range of 100 nm to 1000 nm.
0. The recording method according to item 0. 18. The water-soluble polymer according to claim 10, wherein the main monomer component is any one selected from ethyleneimine, allylamine, vinyl alcohol, vinylpyrrolidone, acrylamide and dimethylacrylamide.
Recording method described in 1. 19. A recording apparatus in which a liquid in which solid fine particles having a monodispersed particle size distribution are suspended is attached as droplets to a liquid-repellent surface, means for applying a solution of a water-soluble polymer as droplets. A recording device comprising: 20. The recording apparatus according to claim 19, wherein at least one of the fine particles is made of ceramics. 21. The recording apparatus according to claim 19, wherein at least one of the fine particles is made of an inorganic oxide. 22. At least one of the fine particles 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.
The recording apparatus according to claim 19 which is a CeO ₂ · SiO _2. 23. The recording apparatus according to claim 19, wherein at least one of the fine particles is made of a synthetic resin. 24. The recording apparatus according to claim 19, wherein at least one of the fine particles is made of an addition polymer. 25. The recording apparatus according to claim 19, wherein at least one of the fine particles is a (meth) acrylic resin, a styrene resin, an olefin resin, or a vinyl ester resin. 26. The particle according to claim 1, wherein at least one particle diameter of the fine particles is in a range of 100 nm to 1000 nm.
10. The recording device according to 9. 27. The main monomer component of the water-soluble polymer, which is selected from ethyleneimine, allylamine, vinyl alcohol, vinylpyrrolidone, acrylamide and dimethylacrylamide.
The recording device according to claim 1.