JP5810571B2 - Inkjet recording method - Google Patents

Description

  The present invention relates to an inkjet recording method and a recorded matter.

  In recent years, there has been an increasing demand for recorded matter in which an image having glitter is formed on a recording surface. As a method for forming an image having glitter, conventionally, for example, a recording medium having a recording surface with high flatness is prepared, and a foil-pressing recording method in which a metal foil is pressed against the recording medium, and the recording surface is smooth. A method of vacuum-depositing metal or the like on a plastic film, a method of applying a glittering pigment ink to a recording medium, and further press working are known. Further, a method for recording by ejecting ink having a glitter pigment (hereinafter referred to as glitter pigment ink) by an ink jet method is known (for example, see Patent Document 1).

JP 2008-174712 A

  However, in the case of non-absorptive materials such as metal and glass, or materials with extremely low absorptivity, if the ink receiving layer is not provided, the smoothness of the surface of the glittering pigment will be caused by convection of the solvent before the ink dries. As a result, the problem of gloss deterioration has occurred. In addition, in a non-absorbing material or a recording medium having extremely low absorbency, the adhesion of the glitter pigment to the recording medium is not sufficient, and good scuff resistance (durability against friction) cannot be obtained. was there. Further, when recording on a recording medium having a rough surface, the glitter pigments are not arranged smoothly, and there is a problem that good glossiness (brightness) cannot be obtained. Furthermore, when recording a white color material on a recording medium using white ink, the white color material has a larger average particle diameter than a normal pigment, and the surface of the white color material region is a very rough region. As a result, there is a problem that the glitter pigment is not well arranged on the region.

  As a result of investigation, the present inventors applied a resin ink contained in a resin in advance, and after the resin ink was dried, the glittering pigment was discharged to the area where the resin ink was applied, thereby obtaining good gloss. I found out that an image to show off can be obtained. However, when drying the resin ink, even if a heating process such as a heater is used, it takes a lot of time to dry, and the conventional serial method that scans and records only in one direction provides good drying. There was a problem that the glittering ink could not be discharged until it proceeded, and the recording work was stagnant. In addition, in order to save time until the drying proceeds well, when the recording medium is once discharged, the recording medium is fed again and another image is formed using color ink other than the glitter ink. However, due to the difficulty in controlling the conveyance of the recording medium, there was a problem that the glitter ink landed outside the region formed by the resin ink. In addition, many roller scratches remain on the recording medium during a plurality of times of conveyance, causing deterioration in image quality.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

  Application Example 1 An ink jet recording method according to this application example is an ink jet recording method in which a glitter pigment ink in which a glitter pigment is dispersed is recorded on a recording medium by an ink jet method, and the recording medium is placed at a predetermined position. In the state where the recording medium is held, the resin layer containing the resin component is applied to the recording medium to form a base layer, and in the state where the recording medium is held at a predetermined position, A glittering layer is formed by applying the glittering pigment ink to the underlayer using a recording head that is provided in a carriage that moves in a second direction that intersects the first direction and that ejects the glittering pigment ink. And a glittering layer forming step.

  According to this configuration, when the glitter pigment ink is applied to the underlayer formed on the recording medium, the solvent or the like contained in the glitter pigment ink penetrates into the underlayer, and the glitter layer The pigment is oriented flat. As a result, the glitter layer is smoothed and can exhibit excellent gloss (brightness). Further, by forming the underlayer on the recording medium, the adhesion between the recording medium and the underlayer is ensured, and the rub resistance (durability due to friction) of the recorded matter can be improved. Further, the base layer and the glitter layer are formed in a state where the holding position of the recording medium is kept constant. That is, since the recording medium does not move in the underlayer forming process and the glitter layer forming process, the recording medium is not passed through when moving from the underlayer forming process to the glittering layer forming process. It is possible to prevent the occurrence of scratches on the image surface due to errors and the like, and to suppress the landing position deviation of the ink, so that the glittering layer can be reliably formed on the underlayer. Thereby, a high-quality glitter image can be formed.

  Application Example 2 In the ink jet recording method according to the application example, the recording medium is a non-ink-absorbing or low-absorbing recording medium.

  According to this configuration, even in the case of a non-ink-absorbing or low-absorbing recording medium, since the underlayer has a function as an ink receiving layer, an image with excellent glitter can be formed.

  Application Example 3 In the ink jet recording method according to the application example, the recording medium is a kind selected from the group consisting of a recording medium having a surface roughness of arithmetic average roughness of 20 μm or more, a fabric, and plain paper. It is characterized by.

  According to this configuration, even for a recording medium or the like having a surface roughness of 20 μm or more in arithmetic average roughness, the surface is flattened by the formation of the underlayer, and an image with excellent glitter can be formed.

  Application Example 4 In the ink jet recording method according to the application example, the base layer forming step includes a drying step of heating and drying the applied resin ink.

  According to this configuration, the base layer can be formed efficiently.

  Application Example 5 In the undercoat layer forming step of the ink jet recording method according to the above application example, a plurality of the undercoat layers are stacked.

  According to this configuration, the surface shape (for example, uneven shape) of the recording medium can be relaxed by forming the underlayer, and the interface between the underlayer and the glittering layer can be flattened. Thereby, glitter can be improved.

  Application Example 6 In the ink jet recording method according to the application example, the recording medium is long.

  According to this configuration, even when the recording medium is long, a high-quality image without landing position deviation can be formed.

  Application Example 7 In the ink jet recording method according to the application example, chromatic ink is applied to the glitter layer in a state where the holding position of the recording medium is maintained in the glitter layer forming step. And a chromatic color layer forming step of forming a chromatic layer.

  According to this configuration, a high-quality image having a good colored glitter image can be formed.

  Application Example 8 A recorded matter according to this application example is recorded by the above-described inkjet recording method.

  According to this configuration, it is possible to provide a recorded matter on which a high-quality image is recorded.

  [Application Example 9] An ink jet recording method according to this application example is an ink jet recording method in which a glitter pigment ink in which a glitter pigment is dispersed is recorded on a recording medium by an ink jet method, and the recording medium is placed at a predetermined position. In this state, a resin layer containing a resin component is applied to the white color material region formed on the recording medium to form a base layer, and the recording medium is placed at a predetermined position. In the held state, the glitter pigment ink is applied to the base layer using a recording head that is provided in a carriage that moves in a first direction and a second direction that intersects the first direction and that ejects the glitter pigment ink. And a glittering layer forming step of forming a glittering layer.

  According to this configuration, the white color material is formed on the recording medium, and the base layer is formed on the white color material. When the glitter pigment ink is applied on the underlayer, the solvent or the like contained in the glitter pigment ink penetrates into the underlayer, and the glitter pigment is oriented flat in the glitter layer. Thereby, even if it is on a white color material, a glittering layer is smooth | blunted and can exhibit the outstanding glossiness (brightness). Further, by forming the underlayer on the recording medium, the adhesion between the recording medium and the underlayer is ensured, and the rub resistance (durability due to friction) of the recorded matter can be improved. Further, the base layer and the glitter layer are formed in a state where the holding position of the recording medium is kept constant. That is, since the recording medium does not move in the underlayer forming process and the glitter layer forming process, the recording medium is not passed through when moving from the underlayer forming process to the glittering layer forming process. It is possible to prevent the occurrence of scratches on the image surface due to errors and the like, and to suppress the landing position deviation of the ink, so that the glittering layer can be reliably formed on the underlayer. Thereby, a high-quality glitter image can be formed.

Sectional drawing which shows the structure of a recorded matter. Schematic which shows the structure of an inkjet recording device. Process drawing which shows the inkjet recording method. Sectional drawing which shows the structure of the recorded matter concerning a modification.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, the scale of each layer and each member is made different from the actual scale so that each layer and each member can be recognized.

[Composition of recorded material]
First, the configuration of the recorded material will be described. FIG. 1 is a cross-sectional view showing a configuration of a recorded matter. As shown in FIG. 1, the recorded matter 1 includes a recording medium 2, a base layer 3 formed on the recording medium, and a glitter layer 4 formed on the base layer 3.

The recording medium 2 is not particularly limited. For example, the recording medium 2 is a recording medium that does not have an ink receiving layer. Alternatively, the recording medium has a poor ink receiving layer. That is, it is a non-ink-absorbing or low-absorbing recording medium. More quantitatively, a non-ink-absorbing and low-absorbing recording medium is such that the recording surface has a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method. A recording medium is shown. This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Examples of the non-ink-absorbing recording medium include a plastic film coated on a base material such as a plastic film or paper that is not surface-treated for ink jet recording (that is, has no ink receiving layer). And those having a plastic film adhered thereto. Examples of the plastic here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. In addition, it may be cloth or plain paper.

  Examples of the low ink-absorbing recording medium include coated paper, and recording paper (printing paper) such as finely coated paper, art paper, coated paper, matte paper, and cast paper. Coated paper is a paper whose surface is coated with paint to enhance aesthetics and smoothness. The paint is made by mixing a pigment such as talc, pyrophyllite, clay (kaolin), titanium oxide, magnesium carbonate, calcium carbonate and an adhesive such as starch. The paint is applied using a machine called a coater in the paper manufacturing process. There are two types of coater: an on-machine type in which papermaking and coating are performed as a single step by being directly connected to a paper machine, and an off-machine type in which the papermaking and coating are performed separately. It is mainly used for recording and is classified as coated paper for printing in the “Production Dynamic Statistics Classification” of the Ministry of Economy, Trade and Industry.

The finely coated paper refers to a recording paper having a coating amount of 12 g / m ² or less. Art paper refers to recording paper obtained by coating a high-grade recording paper (quality paper, paper with a chemical pulp usage rate of 100%) with a coating amount of about 40 g / m ² . The coated paper refers to a recording paper coated with a paint having a coating amount of about 20 g / m ² or more and 40 g / m ² or less. The cast paper refers to a recording paper obtained by finishing art paper or coated paper by applying pressure to the surface with a machine called a cast drum so that the gloss and the recording effect are further enhanced. In the present specification, the coating amount is the total value of the coating values on both sides of the recording paper.

  In addition, the recording medium 2 in the present embodiment may be a recording medium having a surface roughness of arithmetic average roughness (Ra) of 20 μm or more. The arithmetic average roughness (Ra) can be measured using, for example, a surface roughness meter or an optical interference microscope, and a specific surface roughness measuring device includes a step and surface roughness. A fine shape measuring device P-15 (manufactured by KLA-Tencor) is available. Examples of the recording medium 2 having the rough surface include high-quality paper “55PW8R”, XeroxP (manufactured by Fuji Xerox; arithmetic average roughness Ra = 29.2 μm), plain design paper, black paper (manufactured by Tochiman Corporation). Arithmetic mean roughness Ra = 30.2 μm), super fine paper (manufactured by Seiko Epson; Ra = 36.6 μm), B flute cardboard sheet (manufactured by Rengo; arithmetic mean roughness Ra = 39.9 μm), etc. Can be mentioned. In addition, cloth, plain paper, and the like are also examples of the transfer medium having a rough surface. Plain paper is paper mainly composed of cellulose fibers and widely used for recording such as inkjet printers, laser printers, copiers, etc., for example, paper displayed as `` plain paper '' as a trade name, Paper recognized under the name of “plain paper”, etc., and paper that does not substantially have a “swelling layer” made of a resin such as urethane resin or a “void layer” made of inorganic particles such as silica or alumina. It is. Typical examples of plain paper include double-sided high-quality plain paper <Recycled Paper> (manufactured by Seiko Epson Corporation), XeroxP (manufactured by Fuji Xerox Corporation), Canon plain paper / white (manufactured by Canon Inc.), and plain plain paper finish ( FUJIFILM Co., Ltd.), BROTHER exclusive A4 fine plain paper (Brother Co., Ltd.), KOKUYO KB paper (co-paper) (Kokuyo Co., Ltd.), etc.

  The underlayer 3 is formed by applying resin ink to the recording medium 2. The average film thickness of the underlayer 3 is preferably 0.1 μm or more and 30 μm or less, and more preferably 1 μm or more and 15 μm or less. As a result, an image having more excellent glitter can be formed. The resin ink according to the present embodiment preferably contains a water-soluble resin solvent (dispersion medium) and a resin component that is compatible with the water-soluble resin solvent, but is used as a pigment dispersant. Resin may be used. The term “compatible” refers to a combination that dissolves or swells particles when a resin is mixed in the water-soluble resin solvent. In the present invention, the resin ink may be either water-based ink (water content is 50% or more) or non-aqueous ink (water content is less than 50%). Hereinafter, each component will be described by taking a case of water-based ink as a specific example. It is preferable that the resin ink does not substantially contain a color material. “Substantially free” means, for example, that the coloring material is less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. .

(1) Water Water is the main medium of water-based ink, and preferred water is ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, etc. for the purpose of reducing ionic impurities as much as possible. Pure water or ultrapure water can be used. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, it is preferable because the generation of mold and bacteria can be prevented when the pigment dispersion and the aqueous ink using the pigment dispersion are stored for a long period of time. .

(2) Water-soluble resin solvent The present invention is preferably selected from water-soluble solvents that contain a water-soluble resin solvent and are compatible with the resin that is simultaneously added to the resin ink. There are optimum combinations depending on the resin to be used. For example, water-soluble heterocyclic compounds, water-soluble alkylene glycol alkyl ethers and the like are preferable. N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl Pyrrolidones such as 2-pyrrolidone and 2-pyrrolidone, lactones such as γ-butyrolactone, sulfoxides such as dimethyl sulfoxide, lactams such as ε-caprolactam, methyl lactate, ethyl lactate, isopropyl lactate, and butyl lactate Esters of ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl Oxyalkylene glycol ethers such as ether, diethylene glycol diethyl ether, diethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol monopropyl ether, 1,4-dioxane And the like are preferred. In particular, alkylene glycols such as pyrrolidones, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether and the like in terms of storage stability of resin ink, sufficient drying speed, and promotion of film formation of underlayer 3 Monoalkyl ethers are particularly preferred.

  The addition amount of the water-soluble resin solvent is preferably 1.0% by mass or more and 20.0% by mass or less, and more preferably 2.0% by mass or more and 15.0% by mass or less with respect to the total amount of the resin ink. More preferred. If the amount of the water-soluble resin solvent added is less than the lower limit, depending on the type of the resin component, there will be an obstacle to the film formation of the resin in the resin ink and the base forming wax, resulting in solidification / fixing of the resin ink. It may be insufficient. On the other hand, when the addition amount of the water-soluble resin solvent exceeds the upper limit, the storage stability of the resin ink may be lowered.

(3) Resin (resin component)
It is preferable that the resin is compatible with a water-soluble resin solvent to form a strong resin film (underlayer) after the resin ink is dried. When used in an inkjet device, by using a resin that can be dispersed in water, it is possible to keep the viscosity of each ink low while adding a sufficient amount of the resin component to the resin ink. It is preferable because the property can be secured. The resin component may be used as a dispersion resin for dispersing a pigment.

  Specific examples of such water-dispersible resins include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer. , Chloroprene copolymer, fluororesin, vinylidene fluoride, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, Cellulose resins such as polyvinyl acetate, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose acetate butyrate, vinyl acetate resin, ethylene-vinyl acetate Polymers, vinyl acetate - acrylic copolymer, vinyl chloride resin, polyurethane, and rosin esters, and the like is not limited thereto.

  Among the above, it is preferable to use at least one selected from the group consisting of a styrene-acrylic resin and polyurethane as the resin component. Since these components are excellent in film formability, a smoother underlayer 3 can be formed, and as a result, the brightness of the formed image can be further improved. Further, the adhesion of the image to the recording medium 2 can be made higher, and the abrasion resistance can be made more excellent.

  The resin may be dissolved in the dispersion medium or dispersed as fine particles, but is preferably contained in the ink in the form of a resin emulsion. The reason for this is that an emulsion form is preferable from the viewpoint of dispersibility because the resin particles may be insufficiently dispersed even if they are added to the ink as resin particles. The emulsion is preferably an acrylic emulsion and more preferably a styrene-acrylic acid copolymer emulsion from the viewpoint of the storage stability of the resin ink.

  In the present specification, “resin particles” are those in which pigments are dispersed in a water-soluble or emulsion form, those in which a water-insoluble resin is dispersed in a particle form in a dispersion medium mainly composed of water, or It means a resin in which a water-insoluble resin is dispersed in the form of particles in a dispersion medium mainly composed of water, and further includes a dried product thereof. In addition, the term “emulsion” is intended to include a solid / liquid dispersion called dispersion, latex, or suspension.

  If the resin is obtained in the form of an emulsion, it can be prepared by mixing the resin particles in water, optionally with a surfactant. For example, an emulsion of an acrylic resin or a styrene-acrylic acid copolymer resin may be used as an interface between a (meth) acrylic ester resin or a styrene- (meth) acrylic ester resin, and optionally a (meth) acrylic resin. It can be obtained by mixing the active agent with water. The mixing ratio of the resin component and the surfactant is usually preferably about 50: 1 to 5: 1. When the amount of the surfactant used is less than the above range, it is difficult to form an emulsion, and when it exceeds the above range, the water resistance of the ink may be lowered or the adhesion may be deteriorated. Absent.

  Commercially available resin emulsions can also be used as the resin emulsion. For example, Microgel E-1002, E-5002 (styrene-acrylic resin emulsion; manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin emulsion; Dai Nippon Ink Chemical Co., Ltd.), Boncoat 5454 (styrene-acrylic resin emulsion; Dainippon Ink and Chemicals Co., Ltd.), SAE1014 (styrene-acrylic resin emulsion; Nippon Zeon Co., Ltd.), Resamine D-1060 (Urethane resin emulsion; manufactured by Dainichi Seika Kogyo Co., Ltd.) or Cybinol SK-200 (acrylic resin emulsion; manufactured by Seiden Chemical Co., Ltd.).

  The resin component is preferably contained in the resin ink in a range of 1% by mass to 50% by mass in terms of solid content, and more preferably 3% by mass to 25% by mass. More preferably, it is 20% by mass or less. The preferred range of the content of these resins defines the upper limit value from the viewpoints of the appropriate ink jet physical properties and reliability (clogging, ejection stability, etc.) of the resin ink, and the effects of the present invention (such as abrasion resistance) are more enhanced. The lower limit is defined from the viewpoint of obtaining effectively.

(4) Wax The resin ink may further contain a wax. Thereby, it has the characteristic which reduces the frictional resistance of the ink film surface after drying. Examples of components constituting such a wax include plant and animal waxes such as carnauba wax, candeli wax, beeswax, rice wax, and lanolin; paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, petrolatum, and the like. Petroleum waxes; mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, stearamide, and natural / synthetic wax emulsions such as α-olefin / maleic anhydride copolymer The compounding wax or the like can be used singly or as a mixture of plural kinds. Among these, preferred types of wax are polyolefin wax, particularly polyethylene wax and polypropylene wax, and polyethylene wax is more preferable from the viewpoint of abrasion resistance with respect to non-ink-absorbing or low-absorbing recording medium 2. . As the wax, commercially available products can be used as they are, for example, Nopcoat PEM17 (trade name, manufactured by San Nopco), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals), AQUACER 515 (trade name, Big Chemie Japan Co., Ltd.). Manufactured) and the like.

  The wax content of the resin ink is preferably 0.5% by mass to 6% by mass and more preferably 1% by mass to 3% by mass in terms of solid content in the resin ink. The preferred range of the content of these waxes defines the upper limit value from the viewpoint of the appropriate ink jet physical properties and reliability (clogging, ejection stability, etc.) of the resin ink, and the effects of the present invention (rubbing resistance, etc.) are more enhanced. The lower limit is defined from the viewpoint of obtaining effectively.

  In the recorded matter 1 in which a layer is formed with the above-described resin ink and the layer of the glitter pigment is recorded thereon, the glitter pigment can be smoothly arranged on the surface layer, and the gloss is increased. In addition, this makes it possible to exhibit the glitter even on the recording medium 2 that could not exhibit the glitter. Further, the abrasion resistance as the recorded material 1 becomes good, and the formation of a strong underlayer 3 becomes possible. The reason why the abrasion resistance is good is not yet clear, but is presumed as follows. The present invention is not particularly limited to the following functions. The resin has the property of fixing on the recording medium and hardening the film after drying. On the other hand, the wax has a characteristic of reducing the frictional resistance on the surface of the film. Accordingly, it is presumed that the rub resistance of the recorded matter 1 is improved because a resin film that is hard to be scraped off from the outside and hardly peeled off from the recording medium 2 can be formed. In addition, when the layer is formed with resin ink, the resin ink also functions as an ink demand layer, and has an effect of suppressing bleeding of the glitter pigment on the recording medium, and can perform good recording. It becomes possible. In addition, even if it becomes possible to dramatically improve the fixability and drying property of the glitter pigment ink itself, it is necessary to increase the average particle diameter of the pigment particles in order to ensure glossiness. When recording from the head, the recording reliability is lowered, and there is a possibility of further clogging or recording failure. Therefore, it is advantageous to form a resin ink layer even in consideration of such problems. It is.

(5) Other components As other components, the resin ink contains a water-soluble solvent and a surfactant as necessary. These addition amounts can be appropriately adjusted according to the recording medium 2 and the type of ink. Further, as necessary, moisturizers, preservatives / fungicides, pH adjusters, dissolution aids, antioxidants / ultraviolet absorbers, metal trapping agents and the like can be mentioned.

(5-1) Water-soluble solvent The water-soluble solvent has a function of increasing the wettability of the resin ink with respect to the recording medium 2 and wetting it uniformly in synergy with the surfactant described later. Therefore, it is preferable to add a water-soluble solvent to the resin ink from the viewpoint that the base layer 3 can be formed uniformly. Examples of such water-soluble solvents include monohydric alcohols or polyhydric alcohols and derivatives thereof. As the monohydric alcohol, a monohydric alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, or n-butanol can be used.

  As polyhydric alcohols and derivatives thereof, divalent to pentavalent alcohols having 2 to 6 carbon atoms and complete or partial ethers of them with lower alcohols having 1 to 4 carbon atoms can be used. Here, the polyhydric alcohol derivative is an alcohol derivative in which at least one hydroxyl group is etherified, and does not mean a polyhydric alcohol itself that does not contain an etherified hydroxyl group.

  Specific examples of these polyhydric alcohols and their lower alkyl ethers include 1,2-hexanediol, 1,3-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,2-octane. Diols, diols such as 1,3-octanediol, 1,2-pentanediol, mono-, di- or triethylene glycol-mono or di-alkyl ether, mono-, di- or tripropylene glycol-mono or di-alkyl ether Preferably, 1,2-hexanediol, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, or propylene glycol monobutyl , And the like ether. The content of the water-soluble solvent is, for example, 0.5% by mass or more and 15.0% by mass or less, and preferably 1.0% by mass or more and 8.0% by mass or less with respect to the total amount of ink of each color.

(5-2) Surfactant The surfactant has a function of increasing the wettability of the color ink with respect to the recording medium 2 and wetting it uniformly in synergy with the above-described water-soluble solvent. As the surfactant, a silicon-based surfactant and an acetylene glycol-based surfactant are preferable. The silicon-based surfactant has an action of spreading uniformly so as not to cause ink recording unevenness and bleeding on the recording medium.

  As the silicon-based surfactant, a polysiloxane compound or the like is preferably used, and examples thereof include polyether-modified organosiloxane. For example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348 (above trade name, manufactured by Big Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned, and BYK-348 is preferable.

  The content of the silicon-based surfactant is preferably 0.1% by mass or more and 1.5% by mass or less with respect to the total amount of ink of each color. When the content of the silicon-based surfactant is less than 0.1% by mass, the ink is difficult to uniformly spread on the recording medium, so that ink recording unevenness and bleeding are likely to occur. On the other hand, when the content of the silicon surfactant exceeds 1.5% by mass, the storage stability and ejection stability of the water-based ink may not be ensured.

  The acetylene glycol-based surfactant is superior to other surfactants in that it has an excellent ability to maintain surface tension and interfacial tension, and has almost no foaming property. As a result, the color ink containing the acetylene glycol surfactant can appropriately maintain the surface tension and the interface tension with the printer member in contact with the ink such as the head nozzle surface, and this is applied to the ink jet recording method. In this case, the discharge stability can be improved. In addition, since the color ink containing the acetylene glycol surfactant exhibits good wettability / penetration with respect to the recording medium 2, a high-definition image with less ink recording unevenness and bleeding can be obtained.

  Examples of acetylene glycol surfactants include Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61. , 82, DF37, DF110D, CT111, CT121, CT131, CT136, TG, GA (all trade names, manufactured by Air Products and Chemicals Inc.), Olphin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.) and the like, and Surfynol 104PG-50 and DF110D are preferable.

  The content of the acetylene glycol surfactant is preferably 0.05% by mass to 1.0% by mass with respect to the total amount of each color ink. When the content of the acetylene glycol surfactant is less than 0.05% by mass, the ink is difficult to spread uniformly on the recording medium, and therefore, ink recording unevenness and bleeding are likely to occur. On the other hand, when the content of the acetylene glycol surfactant exceeds 1.0% by mass, the storage stability and ejection stability of the color ink may not be ensured.

  Particularly preferred is a combination comprising a silicon surfactant and an acetylene glycol surfactant having an HLB value of 6 or less at the same time. It is preferable that the surface tension of the water-based ink is used in the range of 23.0 mN / m to 40.0 mN / m, more preferably 25.0 mN / m to 35.0 mN by combining the above water-soluble solvent and the surfactant. / M range.

(5-3) Moisturizer As the moisturizer, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, hexylene glycol, 2,3-butanediol, etc. Examples thereof include polyhydric alcohols, sugars and sugar alcohols.

(5-4) Preservatives and fungicides Examples of preservatives and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1 , 2-dibenzisothiazolin-3-one (Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN from ICI) and the like.

(5-5) pH adjuster As the pH adjuster, amines such as diethanolamine, triethanolamine, propanolamine, morpholine and their modified products, inorganic salts such as potassium hydroxide, sodium hydroxide, lithium hydroxide, Examples thereof include ammonium hydroxide, quaternary ammonium hydroxide (such as tetramethylammonium), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates.

(5-6) Dissolution aid Examples of the dissolution aid include urea, thiourea, dimethylurea, and tetraethylurea.

(5-7) Antioxidants and UV absorbers Antioxidants and UV absorbers include allophanates such as allophanate and methyl allophanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, and L-ascorbine. Acids and salts thereof, Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, etc. manufactured by Ciba Geigy, or lanthanide oxides, etc. can give.

(5-8) Metal trapping agent Examples of the metal trapping agent include chelating agents such as ethylenediaminetetraacetic acid disodium.

(5-9) Polymerizable compound The resin ink may contain a polymerizable compound. By containing such a compound, the ink is cured by an activation energy ray typified by ultraviolet rays. The polymerizable product used is not particularly limited as long as it is a compound that polymerizes and solidifies upon irradiation with light such as ultraviolet rays by the action of a polymerization initiator described later, but it is a monofunctional group, a bifunctional group, and a trifunctional group. Various monomers and oligomers having the above polyfunctional groups can be used.

  Examples of the monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid and salts or esters thereof, urethane, amide and anhydride thereof, acrylonitrile, styrene, various types Unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Examples of the oligomer include oligomers formed from the above monomers such as linear acrylic oligomers, epoxy (meth) acrylate, aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, and polyester (meta). ) Acrylates. Moreover, an N-vinyl compound may be included as another monofunctional monomer or polyfunctional monomer. Examples of the N-vinyl compound include N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, and derivatives thereof.

  The glitter layer 4 is formed by applying glitter pigment ink to the underlayer 3. The film thickness of the image is preferably 0.02 to 10 μm, more preferably 0.05 to 5 μm. If the thickness of the glitter layer 4 is less than 0.02 μm, glitter may not be obtained on the recording surface. The glitter pigment ink according to this embodiment contains a glitter pigment. As the glitter pigment contained in the glitter pigment ink, any pigment can be used as long as the ink droplets can be ejected by the ink jet recording method. The glitter pigment has a function of imparting glitter when the glitter pigment ink is deposited on the resin ink layer, and can also impart glitter to the deposit. Examples of such bright pigments include pearl pigments and metal particles. Representative examples of pearl pigments include pigments having pearly luster and interference gloss such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. On the other hand, examples of the metal particles include particles of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, copper, etc., and are selected from these simple substances or alloys thereof and mixtures thereof. At least one kind can be used. The glitter pigment used in the present embodiment is preferably silver particles from the viewpoint of high glossiness (brightness). Hereinafter, a silver ink will be described as a specific example of the glitter pigment ink.

(1) Silver particle As mentioned above, the silver ink which concerns on this embodiment contains a silver particle. As described above, when the silver ink contains silver particles (particularly, when it contains a wax that satisfies a predetermined condition), an image having excellent metallic luster can be formed. Moreover, since silver is a metal having high whiteness among various metals, various metal colors such as gold and copper can be expressed by overlapping with other color inks.

  The average particle diameter of the silver particles is preferably 5 nm or more and 100 nm or less, and more preferably 20 nm or more and 65 nm or less. Thereby, the glossiness (brightness) and abrasion resistance of the image formed using the silver ink can be made particularly excellent. Further, ink ejection stability (landing position accuracy, ejection amount stability, etc.) by the ink jet method can be made particularly excellent, and an image with a desired image quality can be more reliably formed over a long period of time. . In the present specification, the “average particle size” means a volume-based average particle size unless otherwise specified. The average particle diameter can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the laser diffraction type particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrack UPA” manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle can be used.

  The silver particle content in the silver ink is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 5.0% by mass or more and 15% by mass or less. Thereby, the discharge stability by the ink jet system of ink and the storage stability of ink can be made particularly excellent. Also, good image quality and abrasion resistance are realized in a wide range of density from low to high density of silver particles (content per unit area) on the recording medium when the recording material 1 is obtained. can do. The silver particles may be prepared by any method. For example, the silver particles can be suitably formed by preparing a solution containing silver ions and reducing the silver ions.

(2) Resin The silver ink according to the present invention may contain a resin, and by containing this, fixability and abrasion resistance are improved. Resins include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, fluororesin, fluoride resin Vinylidene, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyamide, rosin Resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin such as cellulose acetate butyrate, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer Coalescence, vinyl chloride resin, polyurethane, and rosin esters, and the like is not limited thereto.

(3) Water The ink according to the present invention preferably contains water. In the ink, water mainly functions as a dispersion medium for dispersing silver particles and wax particles. When the ink contains water, the dispersion stability of the silver particles and the like can be improved, and the ink is unintentionally dried (dispersion medium) in the vicinity of the nozzle of the droplet discharge device as described later. The evaporation on the recording medium to which the ink is applied can be quickly performed, and thus desired high-speed recording of a desired image can be suitably performed over a long period of time. The content of water in the ink is not particularly limited, but is preferably 20% by mass or more and 80% by mass or less, and more preferably 25% by mass or more and 70% by mass or less.

(4) Polyhydric alcohol The ink according to the present invention preferably contains a polyhydric alcohol. When the ink according to the present embodiment is applied to an ink jet recording apparatus, the polyhydric alcohol can suppress drying of the ink and prevent clogging by the ink in the ink jet recording head portion.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, and trimethylolethane. , Trimethylolpropane, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol and the like. Especially, a C4-C8 alkanediol is preferable and a C6-C8 alkanediol is more preferable. Thereby, the permeability to the recording medium 2 can be made particularly high. The content of polyhydric alcohol in the ink is not particularly limited, but is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. Among the above polyhydric alcohols, the ink preferably contains 1,2-hexanediol and trimethylolpropane. As a result, the dispersion stability of the silver particles in the ink can be made particularly excellent, the storage stability of the ink can be made particularly excellent, and the ink ejection stability is particularly excellent It can be.

(5) Glycol ether The ink according to the present invention preferably contains a glycol ether. By containing glycol ether, the wettability of the recording medium 2 or the like to the recording surface can be increased and the ink permeability can be increased. As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Mention may be made of lower alkyl ethers of polyhydric alcohols such as monomethyl ether, triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether. Among these, when triethylene glycol monobutyl ether is used, good recording quality can be obtained. The content of glycol ether in the ink is not particularly limited, but is preferably 0.2% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 10% by mass or less.

(6) Surfactant The ink according to the present invention preferably contains an acetylene glycol surfactant or a polysiloxane surfactant. The acetylene glycol surfactant or the polysiloxane surfactant can increase the wettability of the recording surface such as the recording medium 2 and increase the ink permeability.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol and the like can be mentioned. Moreover, a commercial item can also be utilized for acetylene glycol type-surfactant, for example, Orphine E1010, STG, Y (above, Nissin Chemical Co., Ltd.), Surfinol 104, 82, 465, 485, TG (above , Air Products and Chemicals Inc.).

  Commercially available products can be used as the polysiloxane surfactant, and examples thereof include BYK-347, BYK-348 (manufactured by BYK Japan). Furthermore, the ink according to the present invention can also contain other surfactants such as an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. The content of the surfactant in the ink is not particularly limited, but is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. Is more preferable.

(7) Other components The ink according to the present invention may contain components other than the above (other components). Examples of such components include pH regulators, penetrants, organic binders, urea compounds, drying inhibitors such as alkanolamines (such as triethanolamine), and thiourea.

(1) White color material The white ink can contain a white color material having an average particle diameter d50 of 280 nm to 700 nm as a white color material. Examples of the white color material include metal oxide particles such as titanium dioxide, zinc oxide, silica, alumina, magnesium oxide, and zirconium oxide, and particles having a hollow structure. Among these, from the viewpoint of excellent whiteness, it is preferable to use titanium dioxide particles in which titanium dioxide is powdered.

  Moreover, when using a metal oxide particle, the average particle diameter d50 (volume basis) is 280 nm or more and 440 nm or less. Thus, the ink jet recording apparatus can perform good ejection from the head 9, and a white ink layer having good whiteness can be recorded. On the other hand, even when the particle size is increased, it is possible to record a layer having high glitter (glossiness) by sandwiching the resin ink in the middle.

  As the titanium dioxide particles, commercially available ones can be used. For example, ultrafine titanium oxide TTO series (manufactured by Ishihara Sangyo Co., Ltd.), fine particle titanium oxide (manufactured by Teika Co., Ltd.), NanoTek (R) Slurry ( CAI Kasei Co., Ltd.).

  The average particle diameter d50 is measured using, for example, a particle diameter accumulation curve. The particle size accumulation curve is a curve obtained by statistically processing the results of measurements that can determine the particle diameter and the number of particles present in particles such as ink. It is a kind. The particle size accumulation curve takes the diameter of the particle on the horizontal axis, and the particle mass (the product of volume, particle density, and number of particles when the particle is regarded as a sphere), the particle from the small diameter to the large particle The value (integrated value) integrated toward the vertical axis is taken on the vertical axis. And, the particle size d50 is 50% (0.50) when the vertical axis is normalized (the total mass of the measured particles is 1) in the particle size accumulation curve. The value on the horizontal axis, that is, the particle diameter. The average particle diameter of the metal oxide particles can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. As the particle size distribution measuring device, for example, a particle size distribution meter (for example, “Microtrac UPA-EX150” manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle can be used.

  The white ink can contain particles having a hollow structure as a white color material. The particles having a hollow structure are not particularly limited, and known particles can be used. For example, particles described in specifications such as US Pat. No. 4,880,465 can be preferably used. Commercially available particles can be used as the particles having a hollow structure and made of an organic compound. Commercially available products include the sx866 series (manufactured by JSR Corporation).

  The particles having a hollow structure have a core-shell structure and have an outer diameter and an inner diameter. The average particle diameter (outer diameter) (d50) is 280 nm or more and 700 nm or less. If the outer diameter of the particles having a hollow structure is within the above range, the dispersion in the white ink can be kept good, and an image with good whiteness can be obtained when attached to the recording medium. it can. On the other hand, when the outer diameter exceeds 600 nm, the particles may settle and the dispersion stability may be impaired, and the head may be clogged when applied to an ink jet recording apparatus. The average particle diameter d50 of the particles having a hollow structure can be measured by the same method as the average particle diameter d50 of the metal oxide particles.

(2) Others The solvent used in the white ink is not particularly limited. For example, the solvents (2) to (7) described in the description of the silver particles can be used.

[Inkjet recording method]
Next, the ink jet recording method will be described. Here, prior to the description of the inkjet recording method, an inkjet recording apparatus (droplet discharge apparatus) applied to the inkjet recording method will be described.

  2A and 2B show the configuration of the ink jet recording apparatus, where FIG. 2A is a schematic side view, and FIG. 2B is a plan view.

  As shown in FIG. 2A, the ink jet recording apparatus 20 is held at a predetermined position, a transport unit 30 that transports the recording medium 2, a platen 40 that holds the transported recording medium 2 at a predetermined position, and the like. In addition, a recording head 50 for applying the functional liquid to the recording medium 2 and a control unit (not shown) for controlling these members are provided. The recording medium 2 of the present embodiment is long and is a long continuous recording medium as shown in FIG. In the case of a long recording medium, unlike a cut sheet, it is difficult to perform a paper feeding operation after the paper is discharged and then record, so that the present invention is more effective.

  The conveyance unit 30 includes a supply roller 31 that supplies the recording medium 2 to the platen 40 side, a material removal roller 32 that winds up and removes the recording medium 2 on which an image is formed, and an auxiliary that assists conveyance of the recording medium 2. It has a roller 33 and the like.

  The platen 40 is provided with an adsorbing device that adsorbs the conveyed recording medium 2 by negative pressure, and can adsorb the recording medium 2 and hold it at a predetermined position. Further, the platen 40 includes a heating device and can dry the functional liquid applied to the recording medium 2.

  The recording head 50 performs recording by discharging functional liquid as droplets to the recording medium 2. For example, an ink jet head can be applied to the recording head 50. The recording head 50 is mounted on the carriage 51. The carriage 51 is connected to a drive mechanism (not shown) that reciprocates in the X-axis direction and a drive mechanism (not shown) that reciprocates in the Y-axis direction. Then, by driving the drive mechanism, the carriage 51 can be moved along the X-axis direction and the Y-axis direction. The recording head 50 moves with the movement of the carriage 51, ejects the functional liquid as droplets to a predetermined position of the recording medium 2, and can apply the functional liquid onto the recording medium 2.

  Next, a method for controlling the ink jet recording apparatus 20 will be described. Here, a control method related to image formation for the predetermined image region 60 will be described. First, the suction device of the platen 40 is driven to hold the recording medium 2 at a predetermined position (predetermined holding position 70). As shown in FIG. 2B, when the recording head 50 starts to form an image from a predetermined position P1, the carriage 51 is moved (scanned) in the X1 direction of the X axis, and the liquid is discharged from the recording head 50. Let the drops be ejected. As a result, an image for the first scan is formed on the recording medium 2.

  Next, the carriage 51 is moved in the Y2 direction of the Y axis. Thereafter, the carriage 51 is moved (scanned) in the X2 direction of the X axis, and droplets are ejected from the recording head 50. As a result, an image for the second scan is formed on the recording medium 2.

  Next, the carriage 51 is moved in the Y2 direction of the Y axis. Thereafter, the above operation is repeated until the recording head 50 reaches the predetermined position P2. In this way, an image is formed in the predetermined image area 60.

  When the image formation is completed, a predetermined image area 60 minutes on which the image is formed is conveyed in the X1 direction (the material removal roller 32 side) of the X axis. The recording medium 2 newly conveyed from the supply roller 31 side is held at a predetermined holding position 70 on the platen 40. Then, with the recording medium 2 held at the predetermined holding position 70, an image is formed in the predetermined image area 60 as described above. In this way, image formation in units of 60 image areas and conveyance of the recording medium 2 are performed alternately (lateral method). Thereby, images can be continuously formed on the long recording medium 2.

  Next, the ink jet recording method will be described. FIG. 3 is a process diagram showing the ink jet recording method. The ink jet recording method according to this embodiment is an ink jet recording method in which a glitter pigment ink in which a glitter pigment is dispersed is recorded on a recording medium or a white color material region by an inkjet method, and the recording medium is placed at a predetermined position. In the held state, a resin ink containing a resin component is applied to the recording medium to form an underlayer, and in the state where the recording medium is held at a predetermined position, the first direction and the first Formation of a glittering layer that forms a glittering layer by applying the glittering pigment ink to the underlayer using a head that is provided in a carriage that moves in a second direction that intersects the first direction and that ejects the glittering pigment ink. A process. Furthermore, the undercoat layer forming step of the ink jet recording method according to this embodiment preferably includes a drying step of heating and drying the applied resin ink. The “white color material region” is a region formed by applying white ink on the recording medium. Further, the “predetermined positions” in the underlayer forming process and the glittering layer forming process need not be completely the same. Furthermore, the recording medium on which the white color material region is formed is not necessarily an ink non-absorbing or low-absorbing recording medium, a recording medium having an arithmetic average roughness of 20 μm or more, a cloth, plain paper, or the like. There is no. Details will be described below.

  In the underlayer forming step, first, as shown in FIG. 3A, a resin ink 3a is applied onto the recording medium 2. Specifically, in the inkjet recording apparatus 20 (see FIG. 2), the recording medium 2 is held at a predetermined position (predetermined holding position 70). In this state, the resin ink 3a is ejected as droplets onto the recording medium 2 or a predetermined image area 60 in the white color material area, and the resin ink 3a is applied onto the recording medium 2.

  Next, in the drying step, the applied resin ink 3a is dried. In the drying step, the resin ink 3a applied on the recording medium 2 is heated by a heating means and dried. Thereby, as shown in FIG.3 (b), the base layer 3 is formed. The underlayer 3 can have a more excellent function as an ink receiving layer, and can further improve the adhesion of the formed image to the recording medium 2. As a result, it is possible to form a recorded material 1 having better abrasion resistance. Further, by improving the function of the underlayer 3 as an ink receiving layer, the glitter pigment can be arranged more smoothly, and higher gloss (brightness) can be exhibited. In addition, the drying process in a base layer formation process is the case where the drying process is performed in accordance with the formation of the base layer 3 (including the case where the drying process is performed during the glittering layer formation process), or A case where the drying process is performed after the formation of the formation 3 is finished. That is, in this case, an integrated process including a drying process is a base layer forming process.

  As a drying method, the resin ink 3a can be dried using a heating device provided in the platen 40 of the inkjet recording apparatus 20. The drying temperature (heating temperature) can be appropriately determined according to the heat resistance and the like of the recording medium 2, but is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 80 ° C. or lower. . Thereby, the drying speed of the resin ink 3a can be increased. As a result, the recorded matter 1 having excellent abrasion resistance can be efficiently formed. Further, the deformation of the recording medium due to heat can be suppressed. In addition, as a drying method, you may dry by the means which sends warm air. Further, other known drying means and heating means may be used.

  In the present embodiment, the application of the resin ink 3a is performed using the ink jet recording apparatus 20 as described above. Thereby, the foundation layer 3 can be formed at an arbitrary location. In addition, the base layer 3 can be selectively formed at the site where the glitter layer 4 is formed, the amount of the resin ink 3a used can be reduced, and this is economically superior.

  In the present embodiment, the application using the inkjet recording apparatus 20 has been described as the means for applying the resin ink 3a. However, the present invention is not limited to this, and a known technique can be selected. For example, it may be applied by a conventionally used analog coater such as a bar coater, a blade coater, a roll coater, a spray coater, or a slit coater. In the case of an analog coater, the resin ink 3a has a wide viscosity limit range, and is excellent in that it can be applied at a high speed. As a commercially available analog coater, for example, K hand coater (manufactured by Matsuo Sangyo Co., Ltd.), bar coater (manufactured by Daiichi Rika Co., Ltd.), Capillary Coater small substrate & small capacity type (manufactured by Hirano Techseed Co., Ltd.), No579 bar coater (stock Company Yasuda Seiki Seisakusho).

  Next, the glitter layer forming step will be described. In the glitter layer forming step, the ink jet recording apparatus 20 is used to eject droplets of the glitter pigment ink 4 a onto the foundation layer 3 and apply the glitter pigment ink 4 a onto the foundation layer 3. At this time, the glitter pigment ink 4a is applied onto the underlayer 3 in a state where the holding position 70 of the recording medium 2 is maintained in the underlayer forming step. That is, the predetermined holding position 70 of the recording medium 2 is in the same state in the underlayer forming process and the glittering layer forming process.

  This step can be performed at room temperature, for example, and may be performed at a higher temperature. When carried out at a high temperature, the drying rate when the solvent is contained in the glitter pigment ink 4a can be increased. The temperature at a high temperature is preferably 30 ° C. or higher and 120 ° C. or lower, and more preferably 40 ° C. or higher and 80 ° C. or lower. The temperature is the temperature of the surface area in contact with the resin ink of the recording medium. In addition, when the recorded matter 1 having an area having high gloss and an area slightly suppressed in gloss is desired, a drying process in which heating is performed partially (for example, a part of the platen 40 that is partially heated by hot air is applied). Recording material 1 having a target gloss can be obtained. Further, recording is performed with the bright pigment ink 4a in an area where gloss is desired to be suppressed a little, followed by a drying step, and recording is performed again in the area where high gloss is desired with the bright pigment ink, thereby achieving the target gloss. Can be obtained. In this way, the glitter pigment ink 4a is dried, and the glitter layer 4 is formed as shown in FIG.

  By performing the above steps, the recorded matter 1 (FIG. 3D) is formed.

  As described above, according to the present embodiment, the following effects can be obtained.

  When the glitter pigment ink 4a is applied on the base layer 3 formed on the recording medium 2, the solvent or the like contained in the glitter pigment ink 4a penetrates into the base layer 3, and the glitter layer 4 The pigment is oriented flat. Thereby, the glitter layer 4 is smoothed and can exhibit excellent gloss (brightness). Further, by forming the underlayer 3 on the recording medium 2, the adhesion between the recording medium 2 and the underlayer 3 is ensured, and the rub resistance (durability due to friction) of the recorded matter 1 can be improved. . Further, the base layer 3 and the glitter layer 4 are formed in a state where the holding position of the recording medium 2 is kept constant. That is, since the recording medium 2 does not move in the underlayer forming process and the glitter layer forming process, the recording medium 2 is not passed through (conveyed) when moving from the underlayer forming process to the glitter layer forming process. In addition, it is possible to prevent the occurrence of scratches on the image surface due to the conveyance error of the recording medium 2 and the like, and to prevent the landing position deviation of the ink, so that the glitter layer 4 can be reliably formed on the underlayer 3. Thereby, a high-quality glitter image can be formed.

  Note that the present invention is not limited to the above-described embodiment, and various modifications and improvements can be added to the above-described embodiment. A modification will be described below.

  (Modification 1) In the above embodiment, the ink jet recording method using the long recording medium 2 has been described. However, the present invention is not limited to this. For example, the recording medium 2 may be in the form of a sheet such as a sheet (flat size). Even in such a form of the recording medium 2, the same effect as described above can be obtained by holding the recording medium 2 at the same position in the underlayer forming process and the glittering layer forming process.

  (Modification 2) Although the single underlayer 3 is formed in the underlayer forming step in the ink jet recording method of the above embodiment, the present invention is not limited to this configuration. For example, in the underlayer forming step, the underlayer 3 composed of a plurality of layers may be formed. That is, a plurality of base layers 3 may be stacked. In this way, the surface shape (for example, uneven shape) of the recording medium 2 can be relaxed by forming the underlayer 3, and the interface between the underlayer 3 and the glitter layer 4 can be flattened. As a result, the glitter can be further enhanced, and in this embodiment, it is possible to satisfactorily suppress the landing deviation of the glitter ink and the image quality deterioration due to the conveyance of the roller.

  (Modification 3) A chromatic color layer may be provided on the recorded matter 1 in the above embodiment. FIG. 4 is a cross-sectional view illustrating a configuration of a recorded matter according to a modification. As shown in FIG. 4, the recorded material 10 includes a base layer 3 formed on the recording medium 2, a glitter layer 4 formed on the base layer 3, and a chromatic color formed on the glitter layer 4. Layer 5 is provided. In this case, in the ink jet recording method, the chromatic color that forms the chromatic layer 5 by applying chromatic ink to the glitter layer 4 while maintaining the holding position 70 of the recording medium 2 in the glitter layer forming step. And a layer forming step. Examples of the chromatic color ink include cyan, magenta, yellow, light cyan, light magenta, dark yellow, red, green, blue, orange, violet and other color inks. As the pigment used in the color ink, a known pigment can be used. In this way, a high-quality image having a colored glitter image can be formed. In the case of this modification, the structure is a three-layer structure including a base layer, a glitter layer, and a chromatic color layer. However, according to the present invention, ink is ejected in an arbitrary order, and an image is formed at an arbitrary position. Can be formed freely, and exhibits a higher effect.

[Example]
Next, specific examples of the present invention will be described.

[1] Preparation of resin ink The resin ink was prepared by adjusting a styrene-acrylic acid copolymer (thermoplastic resin particles, average particle diameter 50 nm, molecular weight 55000, glass transition temperature 80 ° C., acid value 130) to 20% by mass. , 2-Hexanediol 2 5% by mass, 2-Pyrrolidone 4% by mass, Silicone surfactant (BIC Chemie Japan Co., Ltd., trade name “BYK-348”, polyether-modified siloxane) 0.5% %, 0.2% by mass of acetylene glycol surfactant (manufactured by Nissin Chemical Industry Co., Ltd., trade name “Surfinol 104PG-50”), 6% by mass of propylene glycol, and the remainder added as ion-exchanged water. did. Then, the mixture was stirred at room temperature for 1 hour.

[2] Preparation of glitter pigment ink Polyvinylpyrrolidone (PVP, polymerization average molecular weight 10,000) was heated at 70 ° C. for 15 hours, and then cooled at room temperature. The PVP 1000g was added to the ethylene glycol solution 500ml, and the PVP solution was adjusted. In another container, 500 ml of ethylene glycol was added, 128 g of silver nitrate was added, and the mixture was sufficiently stirred with a magnetic stirrer to prepare a silver nitrate solution. While stirring the PVP solution using an overhead mixer at 120 ° C., the silver nitrate solution was added and the reaction was allowed to proceed by heating for about 80 minutes. And it was made to cool at room temperature after that. The obtained solution was centrifuged for 10 minutes with a centrifuge at 2200 rpm. Thereafter, the separated silver particles were taken out and added to 500 ml of an ethanol solution in order to remove excess PVP. Then, further centrifugation was performed to take out silver particles. Furthermore, the taken-out silver particle was dried on 35 degreeC and 1.3 Pa conditions with the vacuum dryer.

[3] Adjustment of white ink The white ink is made of 10% by mass of titanium dioxide (NanoTek (R) _Slurry: manufactured by CI Kasei Co., Ltd.), 2% by mass of a styrene-acrylic acid copolymer, and 1,2-hexanediol. 5% by mass, 10% by mass of glycerin, 0.9% by mass of triethanolamine, 0.5% by mass of BYK-348 (Bic Chemie Japan Co., Ltd.), and ion-exchanged water were used as the balance.

[4] Formation of recorded matter (Examples 1 to 10)
First, PX-G930 (manufactured by Seiko Epson Corporation) was used as an ink jet printer, and the above-described white ink (volume average diameter 330 nm) was recorded on the recording medium shown in Table 1 with a predetermined pattern of 100% duty. Then, a resin ink layer was recorded at 100% duty on the white ink layer.

  10% by mass of silver particles produced as described above, 10% by mass of propylene glycol, 5% by mass of 1,2-hexanediol, 5% by mass of 2-pyrrolidone, and 1 of silicon surfactant (BYK-348) By adding mass% and further ion-exchanged water as a residue, a bright pigment ink was obtained.

[4] Recording medium (1) 55PW8R (Lintech Co., Ltd. fine paper label)
(2) Yupo80 (film synthetic paper label manufactured by Yupo Corporation)

[5] Formation of recorded matter (Example 1)
A recorded product was formed by a lateral ink jet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was conveyed onto the platen (the number of times of paper passing was 1), and the recording medium was held at a predetermined position. The resin ink was drawn once with a 100% duty on the predetermined image forming area of the recording medium. At this time, the amount of resin ink per unit area was 1.25 mg / inch ² . Then, the applied resin ink was dried to form a base layer on the recording medium. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, 80% duty of bright pigment ink was applied on the underlayer. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

Here, “duty” is a value calculated by the following equation.
duty (%) = actual recording dot number / (vertical resolution × horizontal resolution) × 100 (where “actual recording dot number” is the actual recording dot number per unit area, “vertical resolution” and “horizontal resolution”.
Is the resolution per unit area. )

  In addition, the “lateral method” in the ink jet recording method is a recording method in which image formation in a predetermined image forming area unit and conveyance of a recording medium are alternately performed as shown in FIG. That is, the recording medium is not conveyed until an image of a predetermined image forming area unit is formed. Therefore, in this embodiment, as shown in FIG. 3, the underlayer is formed in a state where the recording medium is held at a predetermined holding position, and the glitter layer is formed on the underlayer.

(Example 2)
A recorded product was formed by a lateral ink jet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was conveyed onto the platen (the number of times of paper passing was 1), and the recording medium was held at a predetermined position. Then, the resin ink was repeatedly drawn four times at 100% duty on the predetermined image forming area of the recording medium. At this time, the amount of resin ink per unit area was 5.00 mg / inch ² . Then, the applied resin ink was dried to form a base layer on the recording medium. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, 80% duty of bright pigment ink was applied on the underlayer. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

(Example 3)
A recorded product was formed by a lateral ink jet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was conveyed onto the platen (the number of times of paper passing was 1), and the recording medium was held at a predetermined position. A white color material area was recorded on the predetermined image forming area of the recording medium using the above-described white ink (volume average diameter d50 is 330 nm) with a predetermined pattern of 100% duty. Resin ink was drawn once at 100% duty on the white color material region. At this time, the amount of resin ink per unit area was 1.25 mg / inch ² . Then, the applied resin ink was dried to form a base layer on the recording medium. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, 80% duty of bright pigment ink was applied on the underlayer. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

(Comparative Example 1)
A recorded product was formed by a serial inkjet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was conveyed onto the platen (the number of times of paper passing), and 80% duty of pigment ink was applied to the recording medium. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

  Here, the “serial method” in the ink jet recording method is a method of drawing while relatively moving the recording head and the recording medium in units of rows. Therefore, in the serial method of this embodiment, the recording medium is drawn while being conveyed each time.

(Comparative Example 2)
A recorded product was formed by a serial inkjet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was transported onto the platen (first pass of paper), and the recording medium was held at a predetermined position. Then, the resin ink was drawn once with 100% duty on the recording medium. At this time, the amount of resin ink per unit area was 1.25 mg / inch ² . Then, the applied resin ink was dried to form a base layer on the recording medium. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, the recording medium on which the underlayer was formed was conveyed again onto the platen (the number of times of paper passing was the second time), and 80% duty of the glitter pigment ink was applied to the underlayer. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

(Comparative Example 3)
A recorded product was formed by a serial inkjet recording method. Specifically, using an ink jet recording apparatus, first, the recording medium was transported onto the platen (first pass of paper), and the recording medium was held at a predetermined position. Then, the resin ink was drawn once with 100% duty on the recording medium. Then, the applied resin ink was dried to form a first underlayer on the recording medium. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, the recording medium on which the first underlayer was formed was conveyed again onto the platen (the number of times of paper passing was second), and the resin ink was drawn once on the first underlayer at 100% duty. Then, the applied resin ink was dried to form a second underlayer on the first underlayer. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, the recording medium on which the second underlayer was formed was conveyed again onto the platen (the number of times of paper passing was 3rd), and the resin ink was drawn once with 100% duty on the second underlayer. Then, the applied resin ink was dried to form a third underlayer on the second underlayer. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Next, the recording medium on which the third underlayer was formed was conveyed again onto the platen (fourth paper passing), and the resin ink was drawn once with 100% duty on the third underlayer. Then, the applied resin ink was dried to form a fourth underlayer on the third underlayer. The drying was performed by setting the temperature of the platen to 45 ° C. and adjusting the temperature of the recording medium to 45 ° C. Thus, an underlayer consisting of four layers (first to fourth underlayers) was formed on the recording medium. Next, the recording medium on which the underlayer was formed was conveyed again onto the platen (the number of times of paper passing was 5), and 80% duty of the glitter pigment ink was applied to the underlayer. At this time, the amount of the glitter pigment ink per unit area was 7 mg / inch ² . The applied glitter pigment ink was dried to form a glitter layer, thereby forming a recorded matter.

(Comparative Example 4)
A recorded matter was prepared in the same manner as in Example 3 except that the above resin ink was not drawn.

  In the above examples and comparative examples, the glossiness, the degree of scratches on the surface of the recorded material, and the image displacement (landing position accuracy) were evaluated. The evaluation results are as shown in Tables 1 and 2.

  [5] Evaluation content

(5.1) Glossiness The glossiness at a turning angle of 60 ° was measured using a glossiness meter (MINOLTA MULTI GLOSS 268) on the recording surface of the recorded matter of each Example and each Comparative Example, and in accordance with the following criteria: evaluated.
A: Glossiness is 330 or more.
B: Glossiness is 230 or more and less than 330.
C: Glossiness is 130 or more and less than 230.
D: Glossiness is less than 130.

(5.2) Degree of scratches on the surface of the recorded material The recorded surfaces of the recorded materials of each Example and each Comparative Example were visually observed and evaluated according to the following criteria.
○: Scratches due to transport rollers are hardly seen.
X: Many scratches due to the conveyance roller or the like are observed.

(5.3) Image displacement (landing accuracy)
The dots recorded in the recorded matter of each Example and each Comparative Example were observed with a microscope and evaluated according to the following criteria.
A: Adjacent dots overlap to form a substantially circular dot.
B: Although the shape is not circular, adjacent dots overlap to form a continuous dot.
C: A gap is formed between adjacent dots.

  As shown in Tables 1 and 2, the ink jet recording method according to the present invention was excellent for all evaluation contents of glossiness, the degree of scratches on the surface of the recorded material, and image displacement. On the other hand, in the comparative example, a satisfactory result was not obtained.

  DESCRIPTION OF SYMBOLS 1,10 ... Recorded matter, 2 ... Recording medium, 3 ... Underlayer, 3a ... Resin ink, 4 ... Glossy layer, 4a ... Glossy pigment ink, 5 ... Chromatic color layer, 20 ... Inkjet recording device, 30 ... Conveyance Part 31, supply roller 32, material removal roller 33, auxiliary roller 40, platen 50, recording head 51, carriage 60, predetermined image area 70, predetermined holding position

Claims (6)

A resin ink containing a resin component is applied to a recording medium to form a base layer, and a glitter pigment ink in which a glitter pigment is dispersed using a recording head mounted on a carriage is applied to the base layer by an inkjet method. An ink jet recording method for recording an image on the recording medium by applying the image on the recording medium ,
In the Bristow method, the recording medium has a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 , the recording medium can be transported in the first direction, and the carriage can move in the first direction and the Movable in a second direction intersecting the first direction,
While holding the recording medium in a predetermined position, an underlayer forming step of drying and heating the resin ink of the underlying layer with the resin ink application to the on the recording medium to form the underlying layer ,
While holding the recording medium in the same position as the predetermined position, the carriage is moved in the first direction and the second direction, the underlying layer of the bright pigment ink from the recording head in the moving region grant above, the bright layer forming step of forming a photoluminescent layer,
A recording medium conveying step of conveying the recording medium in the first direction;
Have
By alternately performing the base forming step and the glitter layer forming step performed in a state where the recording medium is held at the predetermined position, and a recording medium conveying step of conveying the recording medium in the first direction. An ink jet recording method comprising forming an image on the recording medium . The inkjet recording method according to claim 1 ,
An ink jet recording method, wherein the recording medium has a surface roughness of an arithmetic average roughness of 20 μm or more. The inkjet recording method according to claim 1 ,
The ink jet recording method, wherein the underlayer forming step is a step of forming a plurality of the underlayers. The inkjet recording method according to claim 1 ,
An inkjet recording method comprising using a continuous continuous recording medium as the recording medium . The inkjet recording method according to claim 1 ,
The glittering layer formation step, thereby forming the recording medium the glittering layer while holding the same position as the predetermined position, the chromatic layer Grant chromatic ink onto the glittering layer An ink jet recording method characterized by being formed. A resin ink containing a resin component is applied to a recording medium to form a base layer, and a glitter pigment ink in which a glitter pigment is dispersed using a recording head mounted on a carriage is applied to the base layer by an inkjet method. An ink jet recording method for recording an image on the recording medium by applying the image on the recording medium ,
In the Bristow method, the recording medium has a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 , the recording medium can be transported in the first direction, and the carriage can move in the first direction and the Movable in a second direction intersecting the first direction,
In a state where the recording medium is held at a predetermined position, a white ink containing a white color material is applied on the recording medium to form a white color material region, and the resin ink is applied on the white color material region. A base layer forming step of forming a base layer and heating and drying the resin ink of the base layer;
While holding the recording medium in the same position as the predetermined position, the carriage is moved in the first direction and the second direction, the underlying layer of the bright pigment ink from the recording head in the moving region grant above, the bright layer forming step of forming a photoluminescent layer,
A recording medium conveying step of conveying the recording medium in the first direction;
Have
By alternately performing the base forming step and the glitter layer forming step performed in a state where the recording medium is held at the predetermined position, and a recording medium conveying step of conveying the recording medium in the first direction. An ink jet recording method comprising forming an image on the recording medium .

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