JP2002003749A - Record, method for recording and recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a record having a part developing a color by light interference and stably fixed to a desired position on a recording medium and water resistance, a method for recording thereof and a recording device. SOLUTION: This record is characterized by jetting an emulsion ink of a polymer having >=-10 and <=70 deg.C glass transition temperature onto a surface layer part of a fine particle aggregate 1 and making a transparent resin layer 9 present in the ink jet type record obtained by printing an ink containing fine particles dispersed therein on the recording medium 2, aggregating and orienting solid fine particles, forming a regular periodic structure, sticking the formed regular periodic structure thereto and making the regular periodic structure present in at least a part on the recording medium 2. An oxide, a compound oxide, etc., for example silica, alumina or SiO2.Al2O3 can be utilized as the solid fine particles.

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 water-resistant recorded material in which a portion colored by 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 provides a recorded material 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. -10 ° C or higher 7
A recorded matter provided with a transparent resin layer having a temperature of 0 ° C. or lower. 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, after the fine particles have formed an ordered structure, the glass transition temperature is -10 ° C or more and 7 or more.
Provided is a recording method, which comprises applying a polymer emulsion having a temperature of 0 ° C. or lower and drying the same to form a transparent resin layer on the surface of the regular structure of the fine particles. Further, the present invention relates to 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 the glass transition temperature is from −10 ° C. to 70 ° C. Provided is a recording apparatus having means for applying a polymer emulsion as droplets.

[0013]

Next, the present invention will be described in more detail with reference to preferred embodiments. The recorded matter of 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. Is -1
A transparent resin layer having a temperature of 0 ° C. or more and 70 ° C. or less exists.

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 glass transition temperature is-
The transparent resin layer having a temperature of from 10 ° C. to 70 ° C. is formed by drying the aqueous polymer emulsion. The resins used as such aqueous emulsions are the same as those used for ordinary aqueous emulsion paint applications. Specific examples include (meth) acrylic resins, vinyl acetate resins, and styrene resins. Examples of the polymer include a polymer having any one selected from the above as a main component. In addition, the (meth) acrylic resin means both a methacrylic resin and an acrylic resin (the same applies hereinafter). When the glass transition temperature of the above resin is less than -10 ° C, the resin layer is too soft at room temperature or the surface layer of the resin layer becomes sticky, so that it does not function sufficiently as a protective layer for aggregates of the fine particles. . On the other hand, when the glass transition temperature exceeds 70 ° C., the resin does not sufficiently fuse when the emulsion is applied and dried at room temperature, and the aggregation of the fine particles is protected in terms of transparency, liquid permeability, and toughness. It becomes unsuitable as a layer. The above resin may contain a conventionally known plasticizer component for the purpose of lowering its glass transition temperature.

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. The recording method of the present invention is 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. Then, after forming the ordered structure of the fine particles, a polymer emulsion having a glass transition temperature of −10 ° C. or more and 70 ° C. or less is applied, and dried to form a transparent resin layer on the surface portion of the ordered structure of the fine particles. It is characterized by doing.

The recording medium, solid fine particles and the resin constituting the transparent resin layer 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 dyne / cm 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.

In the polymer emulsion, the transparent resin having a glass transition temperature of -10 ° C. or more and 70 ° C. or less is suspended in an aqueous liquid. As this liquid, the same liquid as that used for suspending the fine particles can be used. The polymer emulsion is usually prepared by emulsion polymerization or suspension polymerization. In many cases, an emulsion stabilizer or a surfactant is used at the time of preparation, but it can be used for the purpose of the present invention without sufficiently removing them. The polymer concentration of the emulsion is preferably in the range of 0.05 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, but the optimum range is determined depending on the substance used. There is a need to.

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, but any method can be used as long as the above-mentioned 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.

It is convenient to use the same ink jet system as described above as a method for attaching the polymer emulsion 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. 7 (C) and 7 (D), the droplet 7 of the polymer emulsion is discharged toward the fine particle aggregate 1 by the second droplet discharging means. There is no particular problem even if the polymer emulsion droplets 7 are ejected to a wider area than the place where the aggregates 1 exist, and the polymer emulsion droplets 7 may be ejected to the entire surface of the recording medium 2.
The polymer fine particles of the polymer emulsion are fine particle aggregate 1
, Does not penetrate into the inside, covers the surface of the fine particle aggregate 1, and is dried to form the transparent resin layer 9.
Is formed (FIG. 7D). Since the surface layer of the fine particle aggregate 1 is covered with the transparent resin layer 9 and is not easily collapsed by an external force, the recorded matter thus formed is solid. Further, since the polymer of the polymer emulsion is not water-soluble, the formation of this transparent resin layer results in a water-resistant recorded material. The drying step includes:
It is usually sufficient to leave the mixture for about 5 seconds to 5 minutes, but when the glass transition temperature of the polymer of the emulsion used is 30 ° C. or higher, drying by slight heating is performed.
A more robust recorded matter can be obtained.

[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 milky white silica fine particles was dropped and dried on an aluminum plate, the dried film of the silica fine 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 1 part by weight of ethylene glycol were added to 1 part by weight of the suspension of silica fine particles to prepare a fine particle ink.

In a container having a nitrogen atmosphere, 250 ml of water was heated to 72 ° C., and 0.09 g of sodium dodecyl sulfate and 0.7 g of potassium persulfate were dissolved with stirring. A mixed solution of 1.4 g of styrene, 1.4 g of methyl methacrylate and 0.7 g of hydroxyethyl methacrylate was added to the solution, and the mixture was stirred for 15 minutes. Further, a mixed solution of 8 g of n-butyl acrylate, 12 g of methyl methacrylate and 1.5 g of hydroxyethyl methacrylate was added to the above-mentioned container while stirring little by little. The resulting emulsion was allowed to cool and then filtered through a nylon cloth. A solution obtained by diluting this emulsion 100 times with water was evaluated by a laser scattering method.
The polymer emulsion was found to have a particle size of 0 nm. Further, the emulsion was dried in an aluminum pan, and subjected to differential scanning calorimetry.
The glass transition temperature was found to be around 20 ° C. To 1 part by weight of the polymer emulsion, 3 parts by weight of water, 0.2 parts by weight of isopropyl alcohol and 0.04 parts by weight of ethylene glycol were added to obtain a polymer emulsion ink.

The above-mentioned fine particle ink and polymer emulsion ink 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 transparent polyester film (Lumilar 100T-60) as a recording medium
(Manufactured by Panac Co., Ltd.), and 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 position where the fine particle ink is first discharged from the head filled with the polymer emulsion ink of the above-described apparatus. The polymer emulsion ink was ejected. When the discharged polymer emulsion ink was observed after drying, orange colored reflected light based on the arrangement of the fine particles could be confirmed.

For comparison, only the same two-dimensional pattern of fine particle ink was ejected onto the same recording medium surface,
A printed portion in which ejection of the polymer emulsion ink was omitted was also prepared. After drying the print sample surface on which the orange-colored pattern was formed on the surface for 3 hours, water droplets were allowed to adhere to a part of the color-developed print sample, and the polymer emulsion ink was discharged. The coloring did not disappear in the formed recording portion of the present invention, but the orange portion was lost in the recording portion where the ejection of the polymer emulsion ink was omitted. The printed sample surface was rubbed against a 25 cm ² flannel cloth with a load of 20 g. 98% or more of the printed pattern having the orange colored reflection at the portion where the polymer emulsion ink was discharged later remained. Only 32% of the printed pattern having colored reflection in the portion where the polymer emulsion ink was not ejected remained.

<Comparative Example 2> For the sake of comparison, the same two-dimensional pattern of fine particle ink as in Example 1 was ejected onto a recording medium. The polymer emulsion ink was ejected from the head filled with the molecular emulsion ink. After drying,
Colored reflected light was hardly visible on the recording medium.

<Example 2> Water 1 was placed in a container in a nitrogen atmosphere.
25 ml and 0.7 g of sodium polyoxyethylene (20) nonylphenyl ether sulfate were added, and the mixture was kept at 80 ° C. and stirred while stirring 9 g of styrene and 0.4 g of methacrylic acid.
g and emulsified, and further ammonium persulfate 0.4 g
Was dissolved and stirred for 50 minutes. Next, 1 g of ammonium persulfate was added to the reactor, and styrene 110 was added to 60 ml of water.
g, ethyl acrylate 14.5 g, methacrylic acid 1.7
g, 3 g of N-methylolacrylamide and 0.8 g of sodium polyoxyethylene (20) nonylphenyl ether sulfate were gradually added while stirring. After completion of the addition, the mixture was heated and stirred for 2 hours, and the obtained emulsion was allowed to cool and then filtered through a nylon cloth.

A solution obtained by diluting the above emulsion 100 times with water was evaluated by a laser scattering method.
It was found to be a polymer emulsion having a particle size of m. The emulsion was dried by placing it in an aluminum pan and subjected to differential scanning calorimetry. As a result, it was found that the glass transition temperature was about 55 ° C. 20 parts by weight of water, 1 part by weight of isopropyl alcohol, and 0.1 part by weight of ethylene glycol were added to 1 part by weight of the polymer emulsion, and this was used as a polymer emulsion ink.

The fine particle ink was discharged in a predetermined two-dimensional pattern in the same manner as in Example 1 except that the above-mentioned emulsion ink was used. The printed sample surface was dried for 3 hours and then placed on a 25 cm ² flannel cloth.
When rubbed with a load of g, 98% or more of the printed pattern having orange colored reflected light 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 fine particles of about 260 nm on average.

A print sample of a two-dimensional pattern was prepared in the same manner as in Example 1 except that the above-mentioned fine particle ink was used.
A 25 cm ² flannel cloth was rubbed under a load of 20 g. 97% or more of the printed pattern having green colored reflection in the portion where the polymer emulsion was discharged later remained.

[0060]

As described above, the recorded matter of the present invention has a vivid color utilizing color development by light interference, and is a hard recorded matter which is hardly worn. 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 plane, a plurality of different interference colors can be seen even when viewed from a certain direction, and the recorded matter becomes gorgeous. The display / exhibition effect is high in combination with the features. or,
According to the recording method of the present invention, a recorded matter utilizing light interference can be manufactured 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 of applying droplets of fine particle suspension, (B) is a state of aggregation of fine particle arrangement, (C) is a state of applying droplets of polymer emulsion, and (D) is a state of drying polymer emulsion.

[Explanation of symbols]

 1: Aggregate of fine particles 2: Recording medium 3: Fine particles 4: Droplet 5: Droplet discharging means 6: Liquid pool 7: Polymer emulsion 8: Second droplet discharging means 9: Transparent resin layer 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 : Ejection recovery unit 65: recording head 66: carriage 67: guide shaft 68: motor 69: belt 70: inkjet cartridge 71: Head portion 72: air vent

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // G03F 7/11 501 G03F 7/11 501 F term (Reference) 2H025 AA11 AA13 AB20 BH05 CB06 CB07 CB14 CB16 CB60 CC20 DA29 DA39 FA25 2H086 BA15 BA33 BA34 BA41 BA45 4J038 CC021 CF021 CG141 MA10 MA13 NA01 PA18 PC01 PC03 PC08 4J039 AD03 AD10 BA13 BA15 BA21 BA24 BA32 BA35 BA39 BC10 BE12 BE22 BE28 CA06 GA24

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 glass transition temperature of a surface layer portion of the fine particle aggregate is − A recorded matter comprising a transparent resin layer having a temperature of 10 ° C. or more and 70 ° C. or less. 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 recorded matter according to claim 1, wherein the transparent resin layer mainly comprises any one selected from a (meth) acrylic resin, a vinyl acetate resin, and a styrene resin. 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. A method of forming a transparent resin layer by applying a polymer emulsion having a glass transition temperature of −10 ° C. to 70 ° C. and drying after forming the ordered structure of the fine particles. 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 recording method according to claim 10, wherein the polymer comprises, as a main component, any one selected from a (meth) acrylic resin, a vinyl acetate resin, and a styrene resin. 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 lyophobic surface, and the glass transition temperature is -10 ° C. or more and 70 ° C. or less. A recording apparatus comprising means for applying a molecular emulsion as droplets. 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 recording apparatus according to claim 19, wherein the polymer comprises, as a main component, any one selected from a (meth) acrylic resin, a vinyl acetate resin, and a styrene resin.