JP2017042948A - Inkjet recording material for illumination and method of manufacturing inkjet recording material for illumination, method of forming image for illumination, and illumination signboard - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recording material for illumination, on which an ink image having an excellent surface state of a white layer and excellent granularity is formed, a method of manufacturing the inkjet recording material for illumination, a method of forming an image for illumination having excellent granularity, and an illumination signboard in which an image for illumination is formed.SOLUTION: There is provided an inkjet recording material for illumination including: a white layer containing white particles, a resin and a fluorine-based surfactant on a resin substrate; and an ink reception layer that contains a resin and the fluorine-based surfactant and in which a fluorine concentration on a surface on a side opposite to a side where the white layer is disposed exceeds 0.00% and 5.00% or less by number with respect to the number of all atoms observed on the surface in order from the resin substrate side. There are also provided a method of manufacturing the inkjet recording material for illumination, a method of forming an image for illumination, and an illumination signboard.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an inkjet recording material for electrical decoration, a method for producing an inkjet recording material for electrical decoration, a method for forming an image for electrical decoration, and an electrical signboard.

  Inkjet systems that eject ink compositions in droplet form from an ink ejection port have been widely put into practical use in recent years because they are small and inexpensive, and can form images without contact with recording materials. Yes. Among inkjet methods, a piezo inkjet method in which an ink composition is ejected using deformation of a piezoelectric element, and a thermal ink jet method in which an ink composition is ejected by utilizing a boiling phenomenon of ink due to thermal energy are used for high-resolution images. It is characterized in that it is obtained and excellent in high-speed printability.

  Recently, not only home or office photo printing and document printing, but also large-format advertisements to be pasted on walls such as electrical signs, show windows, station corridors, buildings, etc. have been produced using inkjet printers. It has been broken. For example, recording materials for electrical decoration produced using an ink jet printer are provided in various places.

  In such a recording material for electrical decoration, for example, at night, light from a light source disposed inside the electrical signboard enters the recording material, and an image recorded on the recording material is visually recognized as a transmission image. In addition, in the daytime, the reflected image recorded on the recording material is visually recognized because light (for example, sunlight) incident on the recording material from the outside of the electric signboard is reflected and diffused by components such as pigments in the recording material. The

As a technique related to the above, for example, an inkjet recording sheet having a support and an ink receiving layer containing a specific resin and a crosslinking agent on at least one surface of the support has been proposed (for example, Patent Document 1).
Further, an ink jet recording sheet having an ink receiving layer containing a white pigment and a surfactant and substantially free of a cationic resin on at least one surface on a support has been proposed (for example, Patent Document 2). reference).

JP 2014-144578 A JP 2010-221688 A

The electric signboard is required to have good visibility of images (transmission image and reflection image) both at night and in the daytime, and the background on which the image is formed is white because the visibility of the image is improved. It is preferable that However, for example, when a white layer is formed using a composition including white particles, it is preferable to use a coating method, but the surface shape of the formed white layer is likely to deteriorate, and compared to a transparent layer. The part where the surface condition has deteriorated tends to stand out. Therefore, a fluorosurfactant is used as a component of the composition containing white particles. In the white layer formed by the composition containing the white particles and the fluorosurfactant, a good surface shape can be obtained. The fluorosurfactant migrates to Therefore, the fluorine-type surfactant exists in the surface of the white layer after drying a coating layer and forming a white layer. In an electric signboard, a layer adjacent to the white layer may be formed on the white layer. When an adjacent layer is formed on the white layer, the fluorosurfactant may not only stay in the white layer but also pass through the adjacent layer and migrate to the outermost surface. As a result, a phenomenon in which the ink composition does not spread to a desired size on the outermost surface on which an image is formed occurs, and graininess is deteriorated in the formed ink image, and a desired ink image may not be obtained. . As described above, it is possible to obtain a good planar white layer by using a fluorosurfactant and that the granularity of the ink image deteriorates due to the fluorosurfactant moving to the outermost surface. There is a contradictory relationship, and it is said that the improvement of the surface shape and the improvement of the graininess are not compatible.
“Granularity” means a state of spreading of ink droplets in a formed ink image, and “granularity deteriorates” means that ink droplets in an image spread to a desired size. In other words, it indicates a state in which the white background is visible and a part of the image is missing.

  An object of the present invention is to provide an inkjet recording material for electrical decoration on which an ink image having an excellent white surface layer and good graininess is formed, a method for producing an inkjet recording material for electrical decoration, and electrical decoration with good graininess An object of the present invention is to provide an image forming method and an electric signboard on which an image for electric decoration is formed.

Specific embodiments of the present invention that solve the above problems include the following embodiments.
<1> On the resin base material, a white layer containing white particles, a resin, and a fluorosurfactant, and a surface opposite to the side containing the resin and the fluorosurfactant, where the white layer is disposed An ink-jet recording material for electrical decoration, having an ink receiving layer in which the fluorine concentration in the layer is more than 0.00% by number and less than 5.00% by number with respect to the number of all atoms observed on the surface, in order from the resin substrate side .

<2> The ink jet recording material for electrical decoration according to <1>, wherein the fluorine concentration is 0.10% by number to 4.00% by number.
<3> The inkjet recording material for electrical decoration according to <1> or <2>, wherein the fluorine-containing surfactant contained in the white layer is a nonionic fluorine-containing surfactant.
<4> The total content of the fluorosurfactant contained in the white layer and the ink receiving layer is 0.100% by mass to 0.400% by mass with respect to the total mass of the white layer and the ink receiving layer <1. The inkjet recording material for electrical decoration according to any one of> to <3>.
<5> The inkjet recording material for electrical decoration according to any one of <1> to <4>, wherein the molecular weight of the fluorosurfactant contained in the white layer is 1,000 or less.

<6> The inkjet recording material for electrical decoration according to any one of <1> to <5>, wherein the white layer has a thickness of 0.5 μm or more and 10 μm or less.
<7> The ink-jet recording material for electrical decoration according to any one of <1> to <6>, wherein the thickness of the ink receiving layer is from 0.01 μm to 5 μm.
<8> The ink receiving layer according to any one of <1> to <7>, wherein the ink contact angle on the surface opposite to the side on which the white layer is disposed is 29 ° to 41 °. Inkjet recording material for decoration.

<9> The resin substrate according to any one of <1> to <8>, having a white layer on one side of the resin substrate and having at least one of an antistatic layer and a protective layer on the other side of the resin substrate. Inkjet recording material for electrical decoration.

<10> A step of forming a white layer by applying a white layer forming composition containing white particles, a resin, and a fluorosurfactant on a resin substrate; and a composition for forming an ink receiving layer containing a resin Ink acceptance in which the fluorine concentration is more than 0.00% by number and less than 5.00% by number with respect to the number of all atoms observed on the surface opposite to the side where the white layer is disposed. Forming a layer, and a method for producing an inkjet recording material for electrical decoration.
<11> The content of the fluorosurfactant in the composition for forming a white layer is 0.100% by mass to 0.400% by mass with respect to the total solid content mass of the composition. A method for producing an inkjet recording material for electrical decoration.
<12> The method for producing an inkjet recording material for electrical decoration according to <10> or <11>, wherein the fluorine-based surfactant in the white layer forming composition is a nonionic fluorine-based surfactant.

<13> An image for electrical decoration including an ink ejection process for ejecting an ink composition by an inkjet method on the ink receiving layer of the inkjet recording material for electrical decoration according to any one of <1> to <9>. Forming method.
<14> The ink composition is a radiation curable ink composition,
The method for forming an image for electrical decoration according to <13>, further comprising a curing step of irradiating the radiation curable ink composition ejected in the ink ejection step with radiation to cure the radiation curable ink composition.

The electrical decoration signboard which has the image arrange | positioned on the inkjet recording material for electrical decoration as described in any one of <15> <1>-<9>, the inkjet recording material for electrical decoration, and a light source.

  INDUSTRIAL APPLICABILITY According to the present invention, an ink-jet recording material for electric decoration on which an ink image having an excellent white layer surface shape and good graininess is formed, a method for producing an ink-jet recording material for electric decoration, and electric decoration with good graininess An image forming method and an electric signboard on which an image for electric decoration is formed are provided.

It is sectional drawing which shows typically the preferable embodiment of the inkjet recording material for electrical decoration. It is sectional drawing which shows typically the other preferable embodiment of the inkjet recording material for electrical decoration.

Hereinafter, the inkjet recording material for electrical decoration of the present invention, the method for producing the inkjet recording material for electrical decoration, the method for forming the image for electrical decoration, and the electrical signboard will be described in detail.
In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

<Inkjet recording material for electrical decoration>
The ink-jet recording material for electrical decoration according to the present invention includes a white layer containing white particles, a resin, and a fluorosurfactant, and a white layer disposed on the resin base material, the resin and the fluorosurfactant. An ink receiving layer having a fluorine concentration on the surface opposite to the surface on the surface opposite to the number of all atoms observed on the surface of more than 0.00% and not more than 5.00% by number from the resin substrate side. Have in order.
The form of the inkjet recording material for electrical decoration of the present invention is not particularly limited as long as inkjet recording is possible, and forms such as an inkjet recording sheet for electrical decoration and an inkjet recording film for electrical decoration are preferable.

The reason why the effect of the present invention appears is not clear, but is estimated as follows.
As described above, the white layer formed using the composition containing the white particles and the fluorosurfactant can obtain a good surface shape, but the fluorosurfactant is adjacent after the white layer is formed. It may move to the surface of the layer, and graininess may deteriorate in the ink image. Thus, in the past, when a fluorosurfactant was used, there was a two-way conflict between obtaining a good planar white layer and deteriorating the granularity of the ink image. It is said that the improvement of the particle size and the improvement of the graininess are not compatible.
In the ink-jet recording material for electrical decoration of the present invention, a white layer and an ink receiving layer are sequentially arranged on a resin base material from the resin base material side. The surfactant used for forming the white layer is a fluorosurfactant, and the number of all atoms in which the fluorine concentration on the surface of the ink receiving layer opposite to the side where the white layer is disposed is observed on the surface. And more than 0.00% by number and 5.00% by number or less. The fluorosurfactant can easily obtain a high surfactant effect in a small amount as compared with a surfactant other than the fluorosurfactant. In other words, when a fluorosurfactant is used, the surface shape of the white layer can be improved, and when the fluorine concentration on the surface of the ink receiving layer falls within a specific range, the granularity of the formed ink image can be reduced. It is thought that it can be improved.

  Hereinafter, the ink-jet recording material for electrical decoration of the present invention will be described in detail.

[White layer]
The inkjet recording material for electrical decoration of the present invention has a white layer containing white particles, a resin, and a fluorosurfactant on a resin substrate.

(Fluorosurfactant)
The white layer of the inkjet recording material for electrical decoration contains at least one fluorine-based surfactant. In other words, when forming the white layer, the white layer-forming composition contains at least one fluorine-based surfactant, so that a white layer having a good surface shape is formed.
Further, even if a part of the fluorosurfactant contained in the white layer moves to the ink receiving layer described later, the fluorine concentration on the surface of the ink receiving layer is suppressed to a predetermined range. As a result, the ink-jet recording material for electrical decoration is excellent in the granularity of the ink image to be formed.

  The fluorosurfactant is not particularly limited and can be selected from known fluorosurfactants. Examples of the fluorosurfactant include nonionic fluorosurfactants, anionic fluorosurfactants, cationic fluorosurfactants, and amphoteric fluorosurfactants. Moreover, the fluorosurfactant described in "Surfactant Handbook" (Nishi-Ichiro, Imai Ichiichiro, Kasai Shozo edition, Sangyo Tosho Co., Ltd., 1960 issue) is mentioned.

  Among these, from the viewpoint of difficulty in shifting to the adjacent layer, a nonionic fluorosurfactant is preferable, a nonionic fluorosurfactant having a perfluoro group is more preferable, and a perfluoroalkylethylene oxide adduct is used. Further preferred.

  As the fluorosurfactant, commercially available ones may be used. For example, Megafac (registered trademark) F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F444 , F 475, F 479, F 482, F 554, F 780, F 781, etc. Mega-Face (registered trademark) series (above, manufactured by DIC Corporation), Footent 100, 300, 400 SW, FTX-215M, 251, 222F, 240G, 212P , FTX-218, 710FL, and the like (Neos Co., Ltd.), sodium bis (3, 3, 4, 4, 5, 5, 6, 6-nonafluoro) = 2-sulfonite oxys Kushinato (Fujifilm Fine Chemicals Co., Ltd.), Florard Fluorard series such as C430, FC431, FC171 (Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC- 381, SC-383, S393, KH-40 and other Surflon (registered trademark) series (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).

The molecular weight of the fluorosurfactant contained in the white layer is preferably 1,000 or less. If the molecular weight of the fluorosurfactant contained in the white layer is 1,000 or less, a surfactant effect can be easily obtained with a small amount, and the blending amount of the fluorosurfactant in the white layer can be reduced. A white layer having a good surface shape can be formed while suppressing the transfer of the surfactant to the surface.
As the molecular weight, a calculated value calculated from the molecular formula is used. When the molecular weight cannot be calculated from the molecular formula, such as when the molecular formula is unknown, the weight average molecular weight measured using a gel permeation chromatograph (GPC) may be used as the molecular weight of the fluorosurfactant.

  The gel permeation chromatograph (GPC) uses HLC-8020GPC (manufactured by Tosoh Corporation), and three columns of TSKgel and Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used. THF (tetrahydrofuran) is used as the eluent. The conditions are as follows: the sample concentration is 0.45 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and the suggested refractive index (RI) detector is used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It is prepared from 8 samples of “A-2500”, “A-1000”, “n-propylbenzene”.

The content of the fluorosurfactant in the white layer is preferably more than 0.000% by mass and not more than 1.000% by mass, and preferably 0.001% by mass to 0.800% by mass with respect to the total mass of the white layer. Is more preferably 0.010% by mass or more and 0.600% by mass or less, and particularly preferably 0.100% by mass or more and 0.400% by mass or less.
The content of the fluorosurfactant in the white layer is contained in the white layer by a general extraction operation using an organic solvent such as methanol after removing the ink receiving layer described later from the inkjet recording material for electrical decoration. This is a value obtained by extracting the fluorosurfactant that is obtained to determine the mass of the fluorosurfactant and dividing by the total mass of the white layer.

(White particles)
The white layer includes at least one kind of white particles.

White particles include white inorganic particles such as white pigment, white organic particles, and the like.
Examples of the white pigment include titanium oxide, silica, calcium carbonate, talc, zeolite, alumina, barium sulfate, and kaolinite.
Examples of the white organic particles include polystyrene, polystyrene-divinylbenzene copolymer, polymethyl methacrylate (hereinafter, PMMA), cross-linked polymethyl methacrylate (hereinafter, cross-linked PMMA), styrene / acrylic copolymer, melamine resin, Examples thereof include particles in which polymer particles such as benzoguanamine resin are colored white.
Among these, white inorganic particles are preferable, titanium oxide is more preferable, and rutile-type titanium oxide called titanium white is more preferable because it has excellent performance of reflecting light with a wavelength in the visible region.

Commercially available products that are commercially available may be used as the white particles. Examples of commercially available white particles include TYPEQUE (registered trademark) CR-93, CR-95, and R780-2 (all manufactured by Ishihara Sangyo Co., Ltd.), TITANIX. JR-603, TITANIX JR-805 (trade name, both manufactured by Teika), TI-PURE R706 (trade name, manufactured by DuPont), and the like.
Examples of the polymer particles include MR-2G, MX-150, MX-180, MX-80H3WT (above, cross-linked PMMA particles manufactured by Soken Chemical Co., Ltd.), Nippon UFN1008 (manufactured by Nippon Zeon Co., Ltd.), and the like. It is done.

The average primary particle diameter of the white particles is preferably in the range of 0.1 μm to 10 μm, more preferably 0.1 μm to 1 μm, and even more preferably 0.1 μm to 0.5 μm, in order to further increase the vividness of the image. .
The average primary particle diameter is obtained by observing the particles with a scanning electron microscope (SEM), obtaining the projected area of the particles from the obtained photograph, and obtaining the equivalent circle diameter from the projected area to obtain the particle diameter. The particle diameter is obtained for 50 white particles, and the value obtained by arithmetically averaging the 50 particle diameters is defined as the average primary particle diameter.

-Silica having an average primary particle size of 200 nm or less-
Silica can be preferably used because it can improve the scratch resistance of the image for electric decoration. Among them, silica having an average primary particle diameter of 200 nm or less is particularly advantageous in that an image for electric decoration that is further excellent in scratch resistance can be obtained. preferable.
Silica having an average primary particle size of 200 nm or less is commercially available as so-called “colloidal silica” and can be easily obtained.
Colloidal silica is in a state in which silica particles are stably dispersed in water with the aid of a dispersant (also referred to as a stabilizer) if necessary.
Examples of the dispersant include quaternary ammonium salts and silane coupling agents.
In the silica particles, a part of silicon atoms (Si) present on the surface of the particles may be substituted with a metal oxide such as alumina or zinc, a metal atom or the like.
Examples of silica having an average primary particle size of 200 nm or less include Snowtex (registered trademark) (average primary particle size 20 nm) commercially available from Nissan Chemical Industries, Ltd., and Aerosil (available from Nippon Aerosil Co., Ltd.). Registered trademark).
Silica having an average primary particle diameter of 200 nm or less is preferable, for example, in that it can be used in combination with titanium oxide to obtain an image for electrical decoration that is further excellent in scratch resistance.
The average primary particle diameter of silica can be determined by the method described above.

It is preferable that the white particles are contained in the white layer in a range of 1.0 g / m ² or more and 10.0 g / m ² or less because the image is excellent as an electric decoration image.

(resin)
The white layer contains at least one resin.
Examples of the resin contained in the white layer include acrylic resin, polyolefin, polyester, and polyurethane.

-Acrylic resin-
When the total mass of the acrylic resin is 100% by mass, the total mass of repeating units formed by polymerizing a monomer having at least one group selected from an acryloyl group and a methacryloyl group is 50% by mass. It is a resin exceeding.
The acrylic resin may be a homopolymer of a (meth) acryl monomer, or a copolymer obtained by polymerizing a (meth) acryl monomer and another monomer. Examples of other monomers include polymers having a carbon-carbon double bond (for example, polyester, polyurethane, etc.). Examples of the copolymer include a block copolymer and a graft copolymer.
The acrylic resin also includes a polymer (including a mixture of polymers) obtained by homopolymerizing or copolymerizing a (meth) acrylic monomer with another monomer in a polyester solution or a polyester dispersion. The acrylic resin also includes a polymer obtained by homopolymerizing or copolymerizing a (meth) acrylic monomer with another monomer in a polyurethane solution or polyurethane dispersion. Acrylic resins also include polymers obtained by homopolymerizing or copolymerizing (meth) acrylic monomers with other monomers in other polymer solutions or dispersions.
The acrylic resin may have at least one group selected from a hydroxy group and an amino group in order to further improve the adhesion between the white layer and the adjacent layer (for example, a resin substrate or an ink receiving layer).
In the present specification, a monomer having an acryloyl group is also referred to as an “acrylic monomer”, and a monomer having a methacryloyl group is also referred to as a “methacrylic monomer”. Further, when both “acrylic monomer” and “methacrylic monomer” are comprehensively included, it is referred to as “(meth) acrylic monomer”.

  Specific examples of the (meth) acrylic monomer are not particularly limited, but typical compounds include, for example, acrylic acid, methacrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; alkyls such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, etc. ) Acrylate; (meth) acrylamide; N-substituted acrylamide such as diacetone acrylamide and N-methylol acrylamide; and silicon-containing monomers such as (meth) acrylonitrile and γ-methacryloxypropyltrimethoxysilane. That.

  As the acrylic resin, a commercially available product may be used. Examples of the commercially available product include Julimer (registered trademark) ET-410 (manufactured by Toa Gosei Chemical Co., Ltd.) and AS-563A (manufactured by Daicel Finechem Co., Ltd.). Can be mentioned.

-Polyolefin-
Polyolefin is a polymer obtained by polymerizing alkenes such as ethylene, butylene, and propylene. The polyolefin may be a copolymer of an alkene and a polymerizable monomer other than the alkene, and examples thereof include the following copolymers.
A copolymer formed from ethylene or propylene and an acrylic monomer other than acrylic acid or a methacrylic monomer other than methacrylic acid.
A copolymer formed from ethylene or propylene and an unsaturated carboxylic acid (including anhydride).
A copolymer formed from ethylene or propylene, an acrylic monomer other than acrylic acid or a methacrylic monomer other than methacrylic acid, and an unsaturated carboxylic acid (including anhydride).

  Preferable specific examples of acrylic monomers other than acrylic acid and methacrylic monomers other than methacrylic acid include methyl methacrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate and the like.

Preferable examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic anhydride.
Alkenes, acrylic monomers other than acrylic acid, methacrylic monomers other than methacrylic acid, and unsaturated carboxylic acids may be used alone or in combination of two or more.

The weight average molecular weight of the polyolefin is preferably 2,000 or more and 200,000 or less. The polyolefin may have a linear structure or a branched structure.
The weight average molecular weight is a value measured using the gel permeation chromatograph (GPC) described above.

  The polyolefin is preferably used in an aqueous dispersion called so-called latex. The method for producing the aqueous polyolefin dispersion includes an emulsification method and an emulsification dispersion method, the former being preferred. For a specific method, for example, the method described in Japanese Patent No. 3699935 can be referred to.

  When the polyolefin is in the form of an aqueous dispersion, the polyolefin preferably has a water-affinity functional group such as a carboxyl group or a hydroxyl group. If the polyolefin is in the form of an aqueous dispersion, an emulsion stabilizer such as a surfactant (eg, anionic or nonionic surfactant) or polymer (eg: polyvinyl alcohol) is added to improve the stability. You may make it contain. Further, if necessary, a pH adjuster (eg, ammonia, triethylamine, sodium hydrogen carbonate, etc.), an antiseptic (eg, 1,3,5-hexahydro- (2-hydroxyethyl) -s-triazine, 2- (4 -Thiazolyl) benzimidazole, etc.), thickeners (eg, sodium polyacrylate, methylcellulose, etc.), film-forming aids (eg, butyl carbitol acetate, etc.), etc. Good.

  Aqueous dispersions of polyolefin are commercially available and can be used in the present invention. Specific examples of commercially available products include Bondine HX-8210, HX-8290, TL-8030, LX-4110 (manufactured by Sumitomo Chemical Co., Ltd.), Arrow Base (registered trademark) SA-1200, SB-1010. SE-1013N, SE-1200 (above, manufactured by Unitika Co., Ltd.), Nipol (registered trademark) UFN1008 (manufactured by Nippon Zeon Co., Ltd.), and the like.

-Polyester-
Polyester is a general term for polymers having an ester bond in the main chain, and is usually obtained by the reaction of a dicarboxylic acid and a polyol. Examples of the dicarboxylic acid include fumaric acid, itaconic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, sulfoisophthalic acid, and naphthalenedicarboxylic acid. Examples of the polyol include ethylene glycol, propylene glycol, glycerin, hexanetriol, butanediol, hexanediol, and 1,4-cyclohexanedimethanol. As the polyester and the raw material of the polyester, for example, those described in “Polyester resin handbook” (Eiichiro Takiyama, Nikkan Kogyo Shimbun, published in 1988) can be used.
Examples of the polyester include polyhydroxybutyrate (PHB), polycaprolactone (PCL), polycaprolactone butylene succinate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), Polybutylene succinate carbonate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, polytetramethylene adipate terephthalate, polybutylene adipate terephthalate, polyethylene succinate (PES), polyglycolic acid (PGA), polylactic acid (PLA) type polyester, carbonate copolymer of aliphatic polyester, and copolymer of aliphatic polyester and polyamide.
The polyesters are Finetex (registered trademark) ES650, ES2200 (manufactured by DIC Corporation), Bayronal (registered trademark) MD1245, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.), Pesresin (registered trademark) A-110, A -124GP, A-520, A-640 (manufactured by Takamatsu Yushi Co., Ltd.), Plus Coat (registered trademark) Z502, Z561, Z730, Z687, Z592 (manufactured by Kyoyo Chemical Co., Ltd.) is there.

-Polyurethane-
Polyurethane is a general term for polymers having a urethane bond in the main chain, and is usually obtained by reaction of diisocyanate and polyol. Examples of the diisocyanate include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalene diisocyanate), TODI (tolidine diisocyanate), HDI (hexamethylene diisocyanate), and IPDI (isophorone diisocyanate). Examples of the polyol include ethylene glycol, propylene glycol, glycerin, and hexanetriol. As the isocyanate, a polymer obtained by subjecting a polyurethane polymer obtained by the reaction of diisocyanate and polyol to a chain extension treatment to increase the molecular weight can also be used. For the diisocyanate, polyol, and chain extension treatment described above, for example, the description of “Polyurethane Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987) can be referred to.
Polyurethanes are Superflex (registered trademark) 470, 210, 150HS, 150HF, Elastron (registered trademark) H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran (registered trademark) AP-20, AP-40F, WLS. -210 (manufactured by DIC Corporation), Takerak (registered trademark) W-6061, Olester (registered trademark) UD-350 (manufactured by Mitsui Chemicals, Inc.) are also commercially available.

(Crosslinking agent)
The white layer may include a structure in which at least a part of the resin contained in the white layer is crosslinked with a crosslinking agent. By including the resin crosslinked by the crosslinking agent in the white layer, the adhesive force with the adjacent layer is further enhanced. As the crosslinking agent, a compound that causes a crosslinking reaction with the resin contained in the white layer is used.

  The cross-linking agent used for the white layer is preferably selected from oxazoline compounds, carbodiimide compounds, epoxy compounds, isocyanate compounds, and melamine compounds, and two or more cross-linking agents may be used in combination.

-Oxazoline compound-
An oxazoline compound is a compound having two or more oxazoline groups in the molecule.
Examples of the oxazoline compound include a polymer having an oxazoline group, for example, a polymerizable unsaturated monomer having an oxazoline group, and a polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having an oxazoline group, if necessary. Examples thereof include a polymer obtained by copolymerization with a monomer by a known method (for example, solution polymerization, emulsion polymerization, etc.). As the polymerizable unsaturated monomer having an oxazoline group, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl Examples thereof include compounds containing 2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline and the like as monomer units.
Examples of the oxazoline compound include Epocross (registered trademark) K-2020E, Epocross (registered trademark) K-2010E, Epocross (registered trademark) K-2020E, Epocross (registered trademark) K-2030E, Epocross (registered trademark) WS-300. , Epocros (registered trademark) WS-500, Epocros (registered trademark) WS-700, and other commercial products (available from Nippon Shokubai Co., Ltd.).

-Carbodiimide compound-
A carbodiimide compound is a compound having a functional group represented by -N = C = N-. Polycarbodiimide is usually synthesized by a condensation reaction of an organic diisocyanate, but the organic group of the organic diisocyanate used for the synthesis is not particularly limited, either aromatic or aliphatic, or aromatic and aliphatic Mixed systems can also be used. However, aliphatic systems are particularly preferred from the viewpoint of reactivity. As a raw material for synthesis, organic isocyanate, organic diisocyanate, organic triisocyanate, and the like are used.
Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.
The carbodiimide compound is also available as a commercial product such as Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Co., Ltd.).

-Epoxy compound-
The epoxy compound is a compound having an epoxy group in the molecule and a compound obtained as a result of reaction of the epoxy group. Examples of the compound having an epoxy group in the molecule include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and other hydroxyl groups and amino groups, such as polyepoxy compounds, diepoxy compounds, Examples include monoepoxy compounds and glycidylamine compounds.
Examples of the polyepoxy compound include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and triglyceryl ether. Examples include methylolpropane polyglycidyl ether.
Examples of the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diester. Examples thereof include glycidyl ether and polytetramethylene glycol diglycidyl ether.
Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether.
Examples of the glycidylamine compound include N, N, N ′, N ′,-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N-diglycidylamino) cyclohexane.
Specific examples of the water-soluble monomer having an epoxy group include “Denacol (registered trademark) -614B” (sorbitol polyglycidyl ether, epoxy equivalent 173, trade name, manufactured by Nagase ChemteX Corporation), “Denacol (registered trademark)”. -EX-313 "(glycerol polyglycidyl ether, epoxy equivalent 141, trade name, manufactured by Nagase ChemteX Corporation)," Denacol (registered trademark) -EX-521 "(polyglycerol polyglycidyl ether, epoxy equivalent 168, commodity Name, manufactured by Nagase ChemteX Corporation), and "Denacol (registered trademark) -EX-830" (polyethylene glycol diglycidyl ether, epoxy equivalent 268, trade name, manufactured by Nagase ChemteX Corporation) is there.

-Isocyanate compound-
The isocyanate compound is a compound having a partial structure of -N = C = O. Examples of the organic isocyanate compound include aromatic isocyanate and aliphatic isocyanate. An isocyanate compound may be used individually by 1 type, and may mix and use 2 or more types of compounds. Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Examples include diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, and the like. Examples of the organic monoisocyanate include isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.
The isocyanate compound may be, for example, Elastolon (registered trademark) H-3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), DP9C214 (manufactured by Baxenden), Takenate (registered trademark) XWD-HS30 (manufactured by Mitsui Chemicals, Inc.). It is available.

-Melamine compounds-
A melamine compound is a compound having two or more methylol groups in the molecule. An example of a melamine compound is hexamethylol melamine.
Examples of commercially available melamine compounds include becamine (registered trademark) PM-N, becamine (registered trademark) J-101, and becamine (registered trademark) M-3 (manufactured by DIC Corporation).

A crosslinking agent may be contained in the white layer in combination of two or more compounds.
The crosslinking agent is preferably contained in the range of 3% by mass to 30% by mass, and more preferably in the range of 10% by mass to 27% by mass with respect to the total mass of the resin contained in the white layer. preferable.
By containing 3% by mass or more of the crosslinking agent with respect to the resin, the adhesion between the white layer and the adjacent layer (for example, the resin base material and the ink receiving layer) is improved, and an image for electrical decoration having excellent scratch resistance is easy. Is obtained. By containing the crosslinking agent in a range of 30% by mass or less with respect to the resin, when the resin of the ink receiving layer forms a crosslinked structure by the crosslinking agent, an appropriate amount of the crosslinked structure is formed. When the resin contained in the white layer has a crosslinked structure, for example, even when exposed to a high temperature and high humidity such as a temperature of 60 ° C. or higher and a relative humidity of 90% or higher for a long time, An effect of maintaining an image having high adhesiveness with the ink receiving layer is obtained.

(Other additives)
The white layer may contain additives such as a colorant, a non-fluorinated surfactant, an antifoaming agent, a preservative, a fluorescent whitening agent, and a water-resistant agent, if necessary.

-Colorant-
The white layer may contain a colorant for the purpose of adjusting the color tone of the white layer. The colorant does not include the white particles described above.
As the colorant, a pigment is preferable. In particular, when at least one selected from a blue pigment and a violet pigment is contained, an impression of visually high whiteness is observed when the electric signboard is observed with the naked eye. This is preferable because of the background.
Suitable blue pigments include, for example, copper phthalocyanine blue (β) (for example, EP-700 Blue GA manufactured by Dainichi Seika Co., Ltd.).
Suitable violet pigments include dioxane pigments (for example, TB1548 manufactured by Dainichi Seika Co., Ltd.).

-Surfactants other than fluorosurfactants-
The white layer may contain a surfactant other than the fluorosurfactant (hereinafter also referred to as a non-fluorine surfactant) from the viewpoint of imparting production suitability.
Examples of the non-fluorinated surfactant include known anionic non-fluorinated surfactants, nonionic non-fluorinated surfactants, and cationic non-fluorinated surfactants. As for the non-fluorinated surfactant, for example, the description in “Surfactant Handbook” (Nishi Ichiro, Imai Seiichiro, Kasai Shozo Edition, Sangyo Tosho Co., Ltd., 1960) can be referred to.
Among these, anionic non-fluorine surfactants and nonionic non-fluorine surfactants are preferred because they are excellent in the effect of improving the wettability to the surface to be coated when applying the white layer forming composition. .

Examples of the anionic non-fluorinated surfactant include higher fatty acid salts such as potassium stearate and potassium behenate, and alkyl ethers such as polyoxyethylene (hereinafter abbreviated as “POE”) lauryl ether carboxylate sodium. N-acyl-L-glutamate such as carboxylate, N-stearoyl-L-glutamate monosodium salt, higher alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, POE lauryl sulfate triethanolamine, POE lauryl sulfate Alkyl ether sulfates such as sodium, N-acyl sarcosine salts such as sodium lauroyl sarcosine, higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyltaurine, and sodium stearyl phosphate Alkyl ether phosphates such as kill phosphate, sodium POE oleyl ether phosphate, sodium POE stearyl ether phosphate, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, lauryl polypropylene glycol sulfosuccinate Sulfosuccinates such as sodium acid, sodium linear dodecylbenzene sulfonate, linear dodecyl benzene, triethanolamine sulfonate, alkyl benzene sulfonates such as linear dodecyl benzene sulfonic acid, dodecyl diphenyl ether disulfonic acid, hydrogenated coconut oil fatty acid sodium glycerine sulfate, etc. Higher fatty acid ester sulfate ester salts.
Examples of commercially available anionic non-fluorine surfactants include Lapisol (registered trademark) A-90, Lapisol (registered trademark) A-80, Lapisol (registered trademark) BW-30, and Lapisol (registered trademark) B-. 90, Lapisol (registered trademark) C-70 (manufactured by NOF Corporation), NIKKOL (registered trademark) OTP-100 (manufactured by Nikko Chemicals Corporation), Kohakuur (registered trademark) ON (manufactured by Toho Chemical Industry Co., Ltd.) ), Kolacool (registered trademark) L-40 (trade name, manufactured by Toho Chemical Industry Co., Ltd.), Phosphanol (registered trademark) 702 (manufactured by Toho Chemical Industry Co., Ltd.), Beaulite (registered trademark) A-5000 , And Viewlite (registered trademark) SSS, Sanded (registered trademark) BL (manufactured by Sanyo Chemical Industries, Ltd.).

Examples of the cationic non-fluorinated surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, dialkyldimethylammonium salts such as distearyldimethylammonium chloride, and poly (N, Ndimethyl-chloride). 3,5-methylenepiperidinium), alkyl pyridinium salts such as cetyl pyridinium chloride, alkyl quaternary ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl isoquinolinium salts, dialkyl morpholinium salts, POE alkyl amines, alkyl amines Examples thereof include salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride. By using the surfactant as described above, aggregation of particles during the drying process of the coating film can be suppressed, and uniform surface irregularities can be formed.
Other commercially available cationic non-fluorine surfactants include, for example, phthalocyanine derivatives (EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (Meta) Acrylic acid (co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Examples of commercially available nonionic non-fluorinated surfactants include, for example, NAROACTY (registered trademark) CL-95, HN-100 (manufactured by Sanyo Chemical Industries), Risolex (registered trademark) BW400 (higher alcohol industry ( Co., Ltd.), EMALEX (registered trademark) ET-2020 (Nippon Emulsion Co., Ltd.), Unilube (registered trademark) 50MB-26, Nonion (registered trademark) IS-4 (NOF Corporation).

  When the white layer contains a non-fluorinated surfactant, the amount of the non-fluorinated surfactant is preferably 0.5% by mass or more and 5.0% by mass or less based on the total solid mass of the white layer, 0.5 mass% or more and 3.0 mass% or less are more preferable.

~ Thickness of white layer ~
The thickness of the white layer is preferably from 0.01 μm to 15 μm, more preferably from 0.1 μm to 11 μm, further preferably from 0.5 μm to 10 μm, further preferably from 1 μm to 8 μm, and particularly preferably from 2 μm to 6 μm. .
When the thickness of the white layer is 0.01 μm or more, an image for electrical decoration that is excellent as a white background color is obtained, and repellency failures that are likely to occur when forming the layer are suppressed, which is preferable. On the other hand, when the thickness of the white layer is 15 μm or less, the content of the fluorosurfactant in the white layer does not increase excessively, and it is easy to adjust the fluorine concentration on the surface of the ink receiving layer described later.
Here, “repellency” means that when there is a part (contamination part) having a low surface tension between the coating solution, the gas-liquid interface, or between the coating object and the coating solution interface from the application to the drying process. This refers to a dent that occurs when the coating solution is repelled around.

[Ink receiving layer]
The ink-jet recording material for electrical decoration of the present invention contains a resin and a fluorosurfactant, and the fluorine concentration on the surface opposite to the side where the white layer is disposed is the number of all atoms observed on the surface. On the other hand, the ink receiving layer is more than 0.00% by number and 5.00% by number or less.

~ Fluorine concentration ~
The fluorine concentration on the surface of the ink receiving layer is more than 0.00% by number and 5.00% by number or less with respect to the number of all atoms observed on the surface. When the fluorine concentration is 5.00% by number or less, an ink image having excellent granularity can be obtained.
From the same viewpoint as described above, the fluorine concentration is preferably 0.10% to 4.00%, more preferably 0.30% to 3.00%, and 0.50% to 2.70%. % Is more preferable.
The fluorine concentration can be adjusted by adjusting the thickness of the white layer, the thickness of the ink receiving layer, the amount of the fluorosurfactant in the white layer forming composition, and the like.

  The fluorine concentration is a value measured by X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis) using an X-ray photoelectron spectroscopy analyzer AXIS HSi (manufactured by Shimadzu Corporation). Specifically, a monochromatic Al—Kα ray (output 150 W) is applied to the surface of the ink receiving layer, and the emitted photoelectrons are guided to the analyzer by a magnetic lens at a take-off angle of 90 degrees, and the spectrum is obtained by spectroscopy. Obtained. The magnetic lens uses a Hybrid mode, and the photoelectron capturing area at this time is approximately 1 mm × 2 mm. A neutralizing gun is used for measurement. In addition, in X-ray photoelectron spectroscopy, since hydrogen atoms cannot be observed, “all atoms observed on the surface” does not include hydrogen atoms.

~ Ink contact angle ~
The ink receiving layer preferably has an ink contact angle of 29 ° to 50 °, more preferably 29 ° to 46 °, on the surface opposite to the side on which the white layer is disposed. More preferably, it is 29 ° to 41 °, and particularly preferably 29 ° to 36 °.
When the ink contact angle is within the above range, the granularity of the formed ink image is excellent.
The ink contact angle can be adjusted by adjusting the fluorine concentration on the surface of the ink receiving layer.

  The ink contact angle is KI ink (KI215 cyan, Fuji Film Co., Ltd.) using a contact angle measuring device (manufactured by Kyowa Interface Chemical Co., Ltd., DMC-MC3) in an environment of temperature 25 ° C. and humidity 50%. ) Was dropped, and the ink contact angle was measured after 100 ms (milliseconds).

(Fluorosurfactant)
The ink receiving layer contains a fluorinated surfactant.
The fluorosurfactant contained in the ink receiving layer may be transferred from the white layer or may be contained in the ink receiving layer forming composition when the ink receiving layer is formed. In other words, the ink receiving layer is formed in the composition for forming an ink receiving layer without containing the fluorine surfactant, and the fluorine surfactant is transferred from the white layer, so that the fluorine surfactant is transferred to the ink receiving layer. It may be included.
In the ink jet recording material for electrical decoration, the fluorine-containing surfactant contained in the white layer moves from the white layer through the ink receiving layer to the surface of the ink receiving layer. For this reason, even if the ink receiving layer at the time of formation does not contain a fluorosurfactant, it may contain a fluorosurfactant that has migrated from the white layer over time after formation.

  The fluorine-containing surfactant contained in the ink receiving layer is not particularly limited, and examples thereof include known fluorine-based surfactants. Examples of the fluorosurfactant contained in the ink receiving layer include the same surfactants as the fluorosurfactants that can be used in the white layer described above, and preferred embodiments are also the same.

The content of the fluorosurfactant in the ink receiving layer is preferably more than 0.000% by mass and 0.100% by mass or less, and 0.001% by mass to 0.050% by mass with respect to the total mass of the ink receiving layer. % Or less is more preferable.
The content of the fluorosurfactant in the ink receiving layer can be measured by the method described above.

  The total content of the fluorosurfactant contained in the white layer and the ink receiving layer is 0.000 with respect to the total mass of the white layer and the ink receiving layer from the viewpoint of the surface shape and graininess of the white layer. More than 1.000 mass%, more preferably 0.001 mass% or more and 0.800 mass% or less, further preferably 0.010 mass% or more and 0.600 mass% or less, more preferably 0.100 mass%. % To 0.400% by mass is particularly preferable.

(resin)
The resin contained in the ink receiving layer is not particularly limited, but preferably contains at least one resin selected from polyester, polyurethane, acrylic resin, styrene butadiene copolymer resin, and polyolefin. It is particularly preferable that the resin contained in the ink receiving layer is water-soluble or water-dispersible from the viewpoint that the load on the environment is small.
Regarding polyester, polyurethane, acrylic resin, and polyolefin, the resins described as the resin contained in the white layer described above can be used as the resin contained in the ink receiving layer, and the preferred resins are also the same.

  The ink receiving layer preferably contains polyester and polyurethane from the viewpoints of transparency and ink adhesion. The content ratio of polyester to polyurethane is preferably 0.1 / 0.9 or more and 0.9 / 0.1 or less, and 0.3 / 0.7 or more and 0.7 / 0. 3 or less is more preferable, and 0.4 / 0.6 or more and 0.6 / 0.4 or less is particularly preferable.

The ink receiving layer may contain a crosslinking agent, and preferably has a structure in which the resin contained in the ink receiving layer is crosslinked by the crosslinking agent.
It is preferable that a crosslinking agent contains at least 1 sort (s) chosen from an oxazoline compound and a carbodiimide compound from a viewpoint of transparency and film | membrane intensity | strength.
Preferred oxazoline compounds and carbodiimide compounds include the compounds described in the description relating to the white layer, and preferred compounds are also the same.

The crosslinking agent in the ink receiving layer is preferably contained in the range of 3% by mass to 30% by mass with respect to the resin contained in the ink receiving layer, and is preferably contained in the range of 3% by mass to 20% by mass. More preferred.
By containing the crosslinking agent in an amount of 3% by mass or more based on the resin, the ink composition can easily penetrate into the ink receiving layer, and fixability between the ink receiving layer and the ink composition after image formation is achieved. There is an advantage that an excellent image can be easily obtained. By containing the crosslinking agent in a range of 30% by mass or less with respect to the resin, when the resin of the ink receiving layer forms a crosslinked structure by the crosslinking agent, an appropriate amount of the crosslinked structure is formed. Since the resin of the ink receiving layer has a cross-linked structure, the ink composition and the ink receiving layer can be used even when exposed to a high temperature and high humidity such as a temperature of 60 ° C. or higher and a relative humidity of 90% or higher for a long time. The effect that the image with high adhesiveness is maintained is obtained.

(Other additives)
The ink receiving layer may contain a non-fluorinated surfactant, a lubricant, an antifoaming agent, a dye, a pigment, a fluorescent brightening agent, a preservative, a water-proofing agent, particles, and the like, if necessary.
As the non-fluorinated surfactant, the surfactant to be contained in the white layer described above can also be used in the ink receiving layer.

-Lubricant-
As the lubricant, an aliphatic wax or the like is preferably used.
Specific examples of the aliphatic wax include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax. Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax. Of these, carnauba wax, paraffin wax, and polyethylene wax are particularly preferable.
The lubricant can be used as an aqueous dispersion because it can reduce environmental burden and is easy to handle. Examples of commercially available products include Cellozol (registered trademark) 524 (manufactured by Chukyo Yushi Co., Ltd.).
Only one type of lubricant may be used, or two or more types may be combined.

-Preservative-
Examples of preservatives include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzothiazolin-3-one, sodium sorbate, sodium pentachlorophenol, etc. Can be mentioned.

~ Thickness of ink receiving layer ~
The thickness of the ink receiving layer is preferably from 0.001 μm to 10 μm, more preferably from 0.05 μm to 6 μm, and still more preferably from 0.01 μm to 5 μm.
When the thickness of the ink receiving layer is 0.001 μm or more, the adhesion with the adjacent layer can be further improved. On the other hand, when the thickness of the ink receiving layer is 10 μm or less, the thickness of the ink receiving layer can be uniformly formed with good surface shape.

[Resin substrate]
The inkjet recording material for electrical decoration of the present invention has a resin substrate.
As the resin base material, a polymer compound formed into a plate shape by a melt film forming method and a solution film forming method can be used.

Examples of resin substrates include polyesters (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), etc.), polyarylate, polyethersulfone, polycarbonate , Polyether ketone, polysulfone, polyphenylene sulfide, polyester liquid crystal polymer, triacetyl cellulose, cellulose derivatives, polyolefin (for example, polypropylene), polyamide, polyimide, polycycloolefin, and the like.
Among these, PET, PEN, triacetyl cellulose, and cellulose derivatives are more preferable, and PET or PEN is particularly preferable from the viewpoint of cost and mechanical strength.

  As the resin base material, a biaxially stretched film is preferably used. A biaxially stretched stretched film can be obtained by stretching a resin sheet formed into a long shape in two directions perpendicular to each other in the longitudinal direction and the width direction. In the present invention, biaxially stretched PET or PEN is particularly preferred from the viewpoint of elastic modulus and transparency.

  Further, it is preferable that at least one of the one surface and the other surface of the resin base material is subjected to a surface treatment such as a corona discharge treatment, a vacuum glow discharge treatment, or a flame treatment. By applying the surface treatment, the surface of the resin substrate is hydrophilized, and the wettability of various aqueous coating liquids can be improved. Furthermore, you may introduce | transduce functional groups, such as a carboxyl group and a hydroxy group. Thereby, the adhesiveness between the layers (for example, a white layer, an antistatic layer, and a protective layer) disposed in contact with the resin base material can be effectively improved.

  The thickness of the resin substrate 11 is, for example, in the range of 30 μm to 500 μm, and more preferably in the range of 50 μm to 300 μm. When the thickness of the resin substrate 11 is 30 μm or more, handling becomes easy, which is advantageous in manufacturing. On the other hand, when the thickness of the resin base material 11 is 500 μm or less, it is easy to achieve a reduction in size and weight of the display device, and it is possible to reduce the cost of manufacturing costs.

[Antistatic layer]
The ink jet recording material for electrical decoration may have an antistatic layer.
Inkjet recording materials with antistatic layers are less likely to malfunction when an image for decorating is formed by the inkjet method, and the image for decorating is installed on the frame for decorating. During production, static electricity is generated and dust is effectively prevented from adhering.
The antistatic layer may be disposed, for example, on the side opposite to the side on which the white layer of the resin substrate is disposed, or may be disposed between the resin substrate and the white layer. It may be arranged between the receiving layers.

(Metal oxide)
The antistatic layer is preferably a layer containing a metal oxide.
Examples of the metal oxide include oxides of metals such as tin, zinc, titanium, aluminum, indium, magnesium, barium, and molybdenum. Specifically, metal oxides such as SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ , and metal composite oxides including two or more metals Is included. Further, it may be a different metal composite metal oxide in which different atoms are contained in the metal oxide or metal composite oxide.
As the metal oxide, SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ or MgO is preferable, and SnO ₂ is particularly preferable. The SnO _2, SnO ₂ are preferred doped with antimony, SnO ₂ is particularly preferable antimony-doped in the range of 2.0 mol% or less than 0.2 mol%.

The metal oxide has a particle shape. The shape is not particularly limited and includes shapes such as a spherical shape, a cubic shape, an octahedral shape, a needle shape, and a spindle shape. The average primary particle diameter of the metal oxide is preferably 0.4 μm or more and 3.0 μm or less. By setting the average primary particle diameter of the metal oxide in the above range, an ink-jet recording material for electric decoration that can produce an image with little occurrence of malfunction during ink-jet recording and less dust adhesion can be easily obtained.
In the present invention, the average primary particle diameter of the metal oxide is a value calculated by the method described above.

  The amount of the metal oxide contained in the antistatic layer is suitably from 10% by mass to 80% by mass with respect to the total solid content mass of the antistatic layer. By setting it as the above range, it is possible to easily obtain an ink-jet recording material for electrical decoration that is less likely to malfunction during ink-jet recording and can provide an image with less dust adhesion. The lower limit of the amount of metal oxide contained in the antistatic layer is more preferably 30% by mass or more based on the total solid content of the antistatic layer. The upper limit of the amount of metal oxide contained in the antistatic layer is more preferably 60% by mass or less with respect to the total solid mass of the antistatic layer.

(Resin contained in the antistatic layer)
The resin contained in the antistatic layer has a function as a binder that uniformly disperses the metal oxide and adheres to the resin substrate. The resin contained in the antistatic layer may be any of water-insoluble, water-soluble, and water-dispersible resins, but a water-soluble or water-dispersible resin is preferable from the viewpoint of less environmental load.
The resin contained in the antistatic layer preferably contains at least one selected from polyester, polyurethane, and acrylic resin.
As the polyester, polyurethane, and acrylic resin, the resins described as the resin contained in the white layer described above can be used as the resin contained in the antistatic layer, and preferable resins are also the same.

The antistatic layer may contain a resin other than the above.
Examples of other resins include polystyrene, polyolefin, and polyamide.

  The amount of the resin contained in the antistatic layer is suitably from 30% by mass to 80% by mass with respect to the total solid content of the antistatic layer. By setting it as the above range, it is possible to easily obtain an ink-jet recording material for electrical decoration that is less likely to malfunction during ink-jet recording and can provide an image with less dust adhesion. The lower limit of the amount of the resin contained in the antistatic layer is more preferably 40% by mass or more based on the total solid mass of the antistatic layer. The upper limit of the amount of resin contained in the antistatic layer is more preferably 60% by mass or less with respect to the total solid content mass of the antistatic layer.

The antistatic layer may contain, for example, a surfactant in addition to the metal oxide and the resin.
Examples of the surfactant include known anionic non-fluorine surfactants, nonionic non-fluorine surfactants, cationic non-fluorine surfactants, and silicone surfactants. The surfactant is described in, for example, “Surfactant Handbook” (Nishi Ichiro, Imai Shunichiro, Kasai Shozo, Sangyo Tosho Co., Ltd., 1960).
The antistatic layer preferably contains an anionic non-fluorinated surfactant and / or a nonionic non-fluorinated surfactant.
As the anionic non-fluorinated surfactant and / or the nonionic non-fluorinated surfactant, the compounds described in the description relating to the white layer can be applied, and preferable compounds are also the same.

When the surfactant is contained in the antistatic layer, the amount of the surfactant is preferably 0.5% by mass or more and 5.0% by mass or less, and preferably 0.5% by mass with respect to the total solid mass of the antistatic layer. % To 3.0% by mass is more preferable.
The thickness of the antistatic layer is in the range of 0.05 μm or more and 5.0 μm or less. It is preferable in that it can be easily obtained. The lower limit of the thickness of the antistatic layer is more preferably 0.07 μm or more. The upper limit of the thickness of the antistatic layer is more preferably 3.0 μm or less.

The surface on the side having the antistatic layer of the ink jet recording material for electrical decoration preferably has a surface resistivity at a temperature of 23 ° C. and a relative humidity of 30% of 1.0 × 10 ¹² Ω / sq or less. By having a surface resistivity in the above range, it is possible to easily obtain an ink-jet recording material for electrical decoration that is less likely to malfunction during ink-jet recording and can provide an image with less dust adhesion. The surface resistivity on the side having the antistatic layer of the ink-jet recording material for electrical decoration is more preferably 1.0 × 10 ¹¹ Ω / sq or less.
The surface resistivity can be adjusted by the type and content of the metal oxide contained in the antistatic layer.
The “surface on the side having the antistatic layer of the ink jet recording material for electrical decoration” means the surface of the outermost layer on the side having the antistatic layer with respect to the resin substrate. For example, when it has an antistatic layer and the below-mentioned protective layer in order on the other surface of the resin base material, it means the surface of the protective layer.
The surface resistivity means a value measured according to JIS K 6911: 1995.

[Protective layer]
The ink jet recording material for electrical decoration may have a protective layer.
By providing the protective layer so as to cover the surface of the antistatic layer, physical damage to the antistatic layer is reduced.
The protective layer preferably contains particles and a resin.
The protective layer preferably further contains a surfactant. As the surfactant, the fluorine-based surfactant and the non-fluorine-based surfactant described in the above description regarding the white layer can be applied.
A protective layer is arrange | positioned on the opposite side to the side by which the white layer is arrange | positioned of the resin base material.

(particle)
The particles contained in the protective layer are preferably at least one selected from inorganic particles and resin particles.
Examples of the inorganic particles include titanium oxide, silica, calcium carbonate, talc, zeolite, alumina, barium sulfate, and kaolinite.
The resin particles are preferably crosslinked resin particles, and examples include crosslinked acrylic resin particles, crosslinked methacrylic resin particles, and crosslinked polystyrene resin particles.
The crosslinked resin particles may be an aqueous dispersion of resin particles called so-called latex.
The content of the particles contained in the protective layer is preferably 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, based on the total solid content of the protective layer.
The average primary particle diameter of the particles contained in the protective layer is preferably in the range of 0.4 μm to 3.0 μm.
Here, the average primary particle diameter is a value calculated and calculated by the method described above.

(resin)
The resin contained in the protective layer is preferably a resin that functions as a binder for the particles contained in the protective layer and that functions to adhere the protective layer to the antistatic layer. For example, the resin of the ink receiving layer, the resin contained in the antistatic layer, the resin of the white layer, etc. can be used as the resin contained in the protective layer. The resin contained in the protective layer may include a structure in which at least a part is crosslinked by a crosslinking agent.
As the resin contained in the protective layer, a silicon-containing resin is preferable because a protective layer having a pencil hardness of F or higher can be formed and the effect of protecting the antistatic layer is excellent.

(Silicon-containing resin)
As the silicon-containing resin, a resin having a structure including a three-dimensional structure in which silicon atoms (Si) and oxygen atoms (O) are alternately bonded is preferable, and alkoxysilane (also referred to as a silane coupling agent) is hydrolyzed. And a resin obtained by condensation.
The alkoxysilane is a mixture of a tetrafunctional alkoxysilane having four alkoxy groups and a bifunctional alkoxysilane having two or three alkoxy groups or a trifunctional alkoxysilane, and the mixture is hydrolyzed and condensed. The resin obtained is particularly preferable. A mixture of a bifunctional alkoxysilane, a trifunctional alkoxysilane, and a tetrafunctional alkoxysilane may be used.
The mixing ratio of the tetrafunctional alkoxysilane in the mixture to at least one alkoxysilane selected from bifunctional alkoxysilane and trifunctional alkoxysilane is the former (tetrafunctional alkoxysilane): the latter (bifunctional alkoxysilane and trifunctional alkoxysilane). The molar ratio of at least one alkoxysilane selected from silanes) is preferably in the range of 25:75 to 85:15, more preferably in the range of 30:70 to 70:30.

Specific examples of the tetrafunctional alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methoxytriethoxysilane, ethoxytrimethoxysilane, methoxytripropoxysilane, ethoxytripropoxysilane, propoxytrimethoxysilane. , Propoxytriethoxysilane, dimethoxydiethoxysilane, and the like. Of these, tetramethoxysilane and tetraethoxysilane are preferred.
The trifunctional alkoxysilane preferably has an epoxy group. Specific examples thereof include glycidyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.
Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyldiethoxysilane.

(catalyst)
When the alkoxysilane is hydrolyzed and condensed, it is preferable to contain a catalyst.
The catalyst includes an acidic compound (hereinafter also referred to as “acidic catalyst”) or a basic compound (hereinafter also referred to as “basic catalyst”). The catalyst may be used by dissolving in a solvent such as water or alcohol.
The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, if a basic catalyst with a too high concentration is used, a precipitate may be generated and appear as a defect in the conductive layer. It is preferably (mol / L) or less.

  The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the conductive layer is preferable. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and a structural formula represented by RCOOH. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, and the like. Can be mentioned.

  The catalyst is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the non-volatile component of the reaction solution for hydrolyzing and condensing alkoxysilane. A catalyst may be used independently or may be used in combination of 2 or more type.

  In addition, the reaction liquid for hydrolyzing and condensing alkoxysilane may contain a curing agent such as a metal chelate compound such as an aluminum chelate compound, a surfactant, and the like. As the surfactant, as described in the description of the antistatic layer, known anionic non-fluorine surfactants, nonionic non-fluorine surfactants, cationic non-fluorine surfactants, silicone-based interfaces An activator is mentioned.

(solvent)
The reaction liquid for hydrolyzing and condensing alkoxysilane may contain an organic solvent.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, chloroform, and methylene chloride. Chlorine solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include glycol ether solvents.
When the organic solvent is contained, a range of 50% by mass or less is preferable with respect to the total mass of the coating solution, and a range of 30% by mass or less is more preferable.

The reaction liquid for hydrolyzing and condensing alkoxysilane and the above-mentioned particles are mixed, and after application, heating and drying are performed, whereby hydrolysis and condensation reaction of alkoxysilane occurs in the coating film, and the protective layer Is formed.
The heating temperature is suitably in the range of 30 ° C. or higher and 200 ° C. or lower, and more preferably in the range of 50 ° C. or higher and 180 ° C. or lower. The heating and drying time is preferably from 10 seconds to 300 minutes, more preferably from 1 minute to 120 minutes.

  The thickness of the protective layer is preferably in the range of 0.4 μm to 3.0 μm, more preferably in the range of 0.7 μm to 2.0 μm, and particularly preferably in the range of 0.8 μm to 1.8 μm.

~ Structure of inkjet recording material for electrical decoration ~
As shown in FIG. 1, one of the preferred embodiments of the ink-jet recording material for electrical decoration is that the white layer 23 and the ink receiving layer 21 are sequentially formed on one surface of the resin base material 11 from the side close to the resin base material 11. Is placed.

The ink-jet recording material for electrical decoration preferably has a white layer on one side of the resin substrate and has at least one of an antistatic layer and a protective layer on the other side of the resin substrate.
As shown in FIG. 2, inkjet printing is an inkjet recording material for electrical decoration having an antistatic layer 31 on the other surface opposite to the one surface on which the white layer 23 of the resin substrate 11 is provided. And it is preferable from the point of an effect for dust adhesion prevention at the time of construction.
In addition, as shown in FIG. 2, when the antistatic layer 31 is disposed on the other surface opposite to the one surface on which the white layer 23 of the resin base material 11 is provided, the antistatic layer 31 is protected. It is preferable to further provide a protective layer 33.

<Method for producing inkjet recording material for electrical decoration>
The method for producing an inkjet recording material for electrical decoration according to the present invention includes a step of forming a white layer by applying a white layer forming composition containing white particles, a resin, and a fluorosurfactant on a resin base material. The composition for forming an ink-receiving layer containing a resin is applied, and the fluorine concentration is 0.00% by number with respect to the total number of atoms observed on the surface opposite to the side on which the white layer is disposed. Forming an ink receiving layer that is more than 5.00% in number.

The fluorosurfactant in the white layer forming composition is not particularly limited and can be selected from known fluorosurfactants. As the fluorinated surfactant in the white layer forming composition, the fluorinated surfactant described as the fluorinated surfactant contained in the white layer can be used.
Among these, from the viewpoint of difficulty in shifting to the adjacent layer, a nonionic fluorosurfactant is preferable, a nonionic fluorosurfactant having a perfluoro group is more preferable, and a perfluoroalkylethylene oxide adduct is used. Further preferred.

The content of the fluorosurfactant in the white layer forming composition is preferably 0.001% by mass or more and 0.800% by mass or less, and 0.010% by mass or more and 0.600% by mass with respect to the total solid mass. % Or less is more preferable, and 0.100 mass% or more and 0.400 mass% or less is more preferable.
When the content of the fluorosurfactant in the white layer forming composition is 0.001% by mass or more, a white layer having a good surface shape can be formed. On the other hand, when the content of the fluorosurfactant is 0.800% by mass or less, the fluorine concentration on the surface of the ink receiving layer can be easily adjusted within a predetermined range, and the formed ink image has excellent granularity.

The composition for forming a white layer may contain a coating solvent. As the coating solvent, an organic solvent or water, or water and an organic solvent are used. Further, the ink receiving layer forming composition may contain a coating solvent. As a coating solvent, an organic solvent or water, or water and an organic solvent are preferably used.
When the white layer forming composition and the ink receiving layer forming composition are mixed with impurities, repelling (Cissing) may occur, resulting in surface failure. The sheet-like failure is a cause of greatly reducing the production yield of the ink-jet recording material for electrical decoration.
Impurities that cause repelling include, for example, insoluble garbage, trace amounts of metal atom-containing components derived from raw materials used (for example, white particles, resins, etc.), silicone-containing components, etc. It tends to cause repellency.
Therefore, in order to suppress planar failure, it is preferable to remove impurities that tend to cause cissing from the coating solution.

For example, at least one of the step of preparing the white layer forming composition and the step of preparing the ink receiving layer forming composition (hereinafter also referred to as “coating liquid preparation process”) is generally performed in order to remove impurities. It is preferable to include a step of purifying the white layer forming composition or the ink receiving layer forming composition by a conventional method.
In order to prepare the coating solution, the step of refining the coating solution in the final step of preparing the coating solution (ie, the step of purifying the prepared coating solution) A step of purifying a pre-prepared pre-prepared solution and / or dispersion is included.
Specifically, the following 1-4 are included.
1. The process of refine | purifying the composition for white layer formation.
2. A step of purifying a pre-prepared solution and / or dispersion prepared in advance for preparing a white layer forming composition. A specific example is a pre-prepared white in which white particles to be included in the composition for forming a white layer are dispersed in advance in a solvent (wherein the solvent includes an organic solvent and / or water; the same applies hereinafter). Examples include a step of purifying the particle dispersion, a step of purifying a pre-prepared resin solution or a pre-prepared resin dispersion prepared in advance by dissolving or dispersing in advance a resin to be contained in the white layer forming composition. .
3. A step of purifying the composition for forming an ink receiving layer.
4). A step of purifying at least one of a pre-prepared solution and a dispersion prepared in advance to prepare a composition for forming an ink receiving layer. Specific examples include, for example, a step of purifying a pre-prepared resin solution or a pre-prepared resin dispersion prepared in advance from a solution in which a resin contained in the ink-receiving layer forming composition is dissolved or dispersed in advance in a solvent. Can be mentioned.

Specific methods for purification include, for example, a filtration step through which a filter or the like is passed, a washing step, and a reprecipitation step. These steps may be performed in combination of two or more. Particularly preferred as the purification method is a filtration step of passing through a filter or the like.
Although the specific method of the filtration process which passes a filter etc. is not specifically limited, The above-mentioned coating liquid is prepared beforehand by the depth filter and screen filter which consist of a polypropylene, glass fiber, Teflon (trademark), etc. Examples of the method include removing the impurities by passing the solution and / or dispersion at least once, more preferably 1 to 5 times, particularly preferably 1 to 3 times.

  Examples of the method for detecting the presence or absence of impurities include measuring means such as nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (ESCA), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). .

1 is manufactured by forming a white layer 23 and an ink receiving layer 21 on one surface of a resin base material 11 according to a preferred embodiment of the present invention.
The white layer 23 and the ink receiving layer 21 disposed on one surface of the resin base material 11 can be formed by sequential application or simultaneous multilayer application and drying.

The application method of the white layer forming composition and the ink receiving layer forming composition is not particularly limited. As an application method, coating is preferable.
The application can be performed by, for example, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a reverse coater or the like.

The applied amount of the ink receiving layer forming composition is preferably 5 g / m ² or more and 20 g / m ² or less, and more preferably 6 g / m ² or more and 12 g / m ² or less.
The amount of the white layer forming composition applied is preferably 5 g / m ² or more and 25 g / m ² or less, more preferably 10 g / m ² or more and 18 g / m ² or less.

<Method for forming image for illumination>
The method for forming an image for electrical decoration of the present invention includes an ink ejection step of ejecting an ink composition by an inkjet method onto the ink receiving layer of the inkjet recording material for electrical decoration of the present invention.
Since the image for electrical decoration is formed on the ink receiving layer of the inkjet recording material for electrical decoration of the present invention, the graininess of the formed image is excellent.

  In the method for forming an image for electrical decoration according to the present invention, the ink composition is a radiation curable ink composition, and the radiation curable ink composition ejected in the ink ejection step is irradiated with radiation to form the radiation curable ink composition. It is preferable to include a curing step for curing the product.

As the radiation curable ink composition used in the present invention, a known radiation curable ink composition can be used. A so-called solvent-free radiation-curable ink composition that does not contain a volatile organic compound (VOC) as an organic solvent and also serves as a liquid polymerizable compound as a solvent is particularly preferable.
The radiation is not particularly limited and includes α rays, γ rays, X rays, ultraviolet rays, visible rays, electron beams, and the like. Among these, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferable. Therefore, in the present invention, an ultraviolet curable ink composition is preferred.

As the radiation curable ink composition, for example, descriptions in JP 2010-47015 A and JP 5-214280 A can be referred to.
As the solventless radiation curable ink composition, for example, descriptions in JP-A Nos. 2004-131725 and 2009-299057 can be referred to.

  The method for forming an image for electrical decoration of the present invention includes the above-described steps, whereby the image for electrical decoration is formed by an ink composition cured on an inkjet recording material.

Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, a piezo-type inkjet head, a storage tank that stores ink, a supply pipe that supplies the ink from the storage tank to the inkjet head, an immediately preceding ink supply tank, and a filter. The piezo-type inkjet head preferably has a multi-size dot of 1 pl (picoliter) or more and 100 pl or less, more preferably 8 pl or more and 30 pl or less, preferably 320 dpi × 320 dpi (dot per inch) or more and 4,000 dpi × 4,000 dpi or less. More preferably, it can be driven so that ejection can be performed at a resolution of 400 dpi × 400 dpi or more and 1,600 dpi × 1,600 dpi or less, and more preferably 720 dpi × 720 dpi. In the present invention, dpi represents the number of dots per inch (2.54 cm).

Ink compositions such as radiation curable ink compositions are preferably provided with a means for stabilizing the temperature of the ink composition in the ink jet recording apparatus since it is desirable that the ejected ink composition has a constant temperature. . The part which makes the temperature constant is a discharge port of an ink jet head from a tank (an intermediate tank if there is an intermediate tank) for storing the ink composition. That is, heat insulation and heating can be performed from the ink composition supply tank to the inkjet head portion.
The method for controlling the temperature is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the ink composition flow rate and the environmental temperature. The temperature sensor can be provided near the ink composition supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of thermal energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

For discharging the ink composition, the ink composition is preferably heated to 25 ° C. or more and 80 ° C. or less, more preferably 25 ° C. or more and 50 ° C. or less, and the viscosity of the ink composition is preferably 3 mPa · s or more and 15 mPa · s or less. It is preferable to carry out after lowering to a range of 3 mPa · s to 13 mPa · s. In particular, in the present invention, it is preferable that the ink composition viscosity at 25 ° C. is 50 mPa · s or less as the ink composition, since it can be discharged satisfactorily.
A radiation curable ink composition generally has a higher viscosity than a water-based ink composition that is usually used in an ink composition for ink jet recording, and therefore has a large viscosity variation due to temperature variation during ejection. Viscosity fluctuation of the ink composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, and thus causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink composition during ejection as constant as possible. Therefore, in the present invention, the temperature control range of the ink composition is preferably set to ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably set temperature ± 1 ° C. .

Next, a curing process for curing the ink composition by irradiating the ink composition discharged on the ink jet recording material for electrical decoration with radiation will be described.
The ink composition ejected onto the ink jet recording material for electrical decoration is cured by irradiation with radiation, and a cured image is obtained.
When the ink composition is irradiated with radiation, the radical polymerization initiator contained in the ink composition is decomposed by radiation irradiation to generate radicals, and the generated radical causes a polymerization reaction of the radical polymerizable compound. Promoted. When a radical polymerization initiator and a sensitizer are present, the sensitizer in the ink composition absorbs radiation to be in an excited state, and promotes decomposition of the radical polymerization initiator by contact with the radical polymerization initiator, A more sensitive curing reaction can be achieved.

  Here, although the peak wavelength of the radiation used depends on the absorption characteristics of the sensitizer, for example, it is preferably 200 nm or more and 600 nm or less, more preferably 300 nm or more and 450 nm or less, and 350 nm or more and 420 nm or less. More preferably.

In addition, the ink composition has sufficient sensitivity even with low output radiation. Therefore, the illumination intensity on the exposed surface, preferably 10 mW / cm ² or more 4,000 mW / cm ² or less, and more preferably it is appropriate to cure at 20 mW / cm ² or more 2,500 mW / cm ² or less.

Mercury lamps, gas and solid lasers are mainly used as radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording ink compositions. ing. At present, mercury-free is strongly desired from the viewpoint of environmental protection, and GaN-based semiconductor ultraviolet light emission is very useful industrially and environmentally. Furthermore, from the viewpoints of small size, long life, high efficiency, and low cost, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are preferable.
In particular, when an ultraviolet ray source is required, UV-LED and UV-LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit radiation centered between 300 nm and 370 nm. Other UV-LEDs are also available and can radiate radiation in different ultraviolet bands. A particularly preferred radiation source in the present invention is a UV-LED, and a UV-LED having a peak wavelength of 350 nm to 420 nm is particularly preferred.
Incidentally, it is preferable that maximum illuminance of the LED illuminations for ink jet recording material on is 10 mW / cm ² or more 2,000 mW / cm ² or less, it is 20 mW / cm ² or more 1,000 mW / cm ² or less more preferably, and particularly preferably 50 mW / cm ² or more 800 mW / cm ² or less.

The ink composition is suitably irradiated with radiation, preferably 0.01 seconds or more and 120 seconds or less, more preferably 0.1 seconds or more and 90 seconds or less.
Radiation irradiation conditions and irradiation methods are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink composition discharge device, and the head unit and the light source are scanned by a so-called shuttle method. The irradiation with radiation is performed for a certain period of time after the ink composition has landed (preferably 0.01 seconds to 0.5 seconds, more preferably 0.01 seconds to 0.3 seconds, further preferably 0.01 seconds to 0 seconds). For 15 seconds or less). By controlling the time from landing of the ink composition to irradiation to an extremely short time, it is possible to prevent the ink composition that has landed on the ink-jet recording material for electrical decoration from bleeding before curing.
Further, the curing may be completed by another light source that is not driven. In International Publication No. 99/54415, a method using an optical fiber or a method of irradiating a recording unit with ultraviolet (UV) light by applying a collimated light source to a mirror surface provided on the side of the head unit is disclosed. Therefore, it can be applied to the manufacturing method of the present invention.

The inkjet recording apparatus using the inkjet system preferably uses a wide format inkjet printer system, and preferably uses a wide format UV inkjet printer system. A wide format inkjet printer system is a system that cures the ejected ink composition by irradiating the ink composition almost simultaneously with the ejection of the ink composition from the inkjet recording apparatus, and produces a large print in a short time. Is possible. Wide format printers are generally defined as printers capable of printing 24 inches (61 cm) or more in width.
Printers with a width of 44 inches (111.7 cm) or more and 64 inches (162.5 cm) or less are the mainstream, but some printers can print up to a width of 197 inches (500 cm).
Wide format UV inkjet printer systems include LuxelJet (registered trademark) UV360GTW / XTW and UV550GTW / XTW series, AcuityLED (registered trademark) 1600 (both manufactured by FUJIFILM Corporation), inca SP320 / SP320e / SP320S / SP320W (Inca (Digital Printers Limited) can be used.

An ink set containing an ink composition can be suitably used for the method for forming an image for electrical decoration. For example, a combination of yellow ink, cyan ink, magenta ink, and black composition may be used as an ink set. In order to obtain a full-color image using the ink composition, an ink set in which four dark ink compositions of yellow, cyan, magenta, and black are combined is preferable. More preferably, the ink set is a combination of a dark ink composition group of five colors consisting of yellow, cyan, magenta, black and white and a light cyan and light magenta ink composition group. The “dark ink composition” means an ink composition in which the pigment content exceeds 1% by mass of the entire ink composition.
In addition, in order to obtain a color image by the method for forming an image for electrical decoration of the present invention, each color ink composition (ink set) is used, and the ink composition having a low lightness is used in order from the ink composition having a low lightness. It is preferable to overlap. Specifically, when using an ink set composed of yellow, cyan, magenta, and black ink compositions, it is applied on the ink jet recording material for electrical decoration of the present invention in the order of yellow → cyan → magenta → black. It is preferable. Furthermore, when using an ink set including at least a total of seven colors of light cyan and light magenta color ink composition groups and cyan, magenta, black, white and yellow dark color ink composition groups, It is preferably applied on the inkjet recording material for electrical decoration of the present invention in the order of light cyan → light magenta → yellow → cyan → magenta → black.
As described above, by sequentially stacking the ink composition having a low lightness to the ink composition having a high lightness, it becomes easier for the radiation to reach the lower ink composition, resulting in good curing sensitivity, reduction of residual monomers, and adhesion. Improvement can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.

<Images for electrical decoration and electrical signs>
The image for electrical decoration of the present invention is formed by the method for forming an image for electrical decoration of the present invention.
Since the image for electrical decoration of the present invention is formed on the ink receiving layer disposed on the white layer, it can be visually recognized as a reflected image in daylight with sunlight.
Furthermore, the image for electrical decoration of this invention can be used as the electrical decoration signboard provided with a light source.
The electrical decoration signboard of the present invention has the above-described electrical recording ink-jet recording material, an image formed on the electrical decoration inkjet recording material, and a light source.
The image is preferably arranged between two types of acrylic resin plates having excellent transparency and weather resistance.
The light source is not particularly limited, and for example, a light bulb, a fluorescent lamp, a light emitting diode (LED), an electroluminescence panel (ELP), one or a plurality of cold cathode fluorescent lamps (CCFL), a hot cathode fluorescent lamp (HCFL), etc. are used. be able to.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the following description, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.

Example 1
[Production of resin base material]
Polyethylene terephthalate (hereinafter referred to as “PET”) resin polycondensed using an antimony compound as a catalyst was dried until the water content was 50 ppm or less. The dried PET resin was supplied to an extruder having a heater temperature set at 280 ° C. to 300 ° C. and melt kneaded. The melt-kneaded PET resin was discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous PET sheet. Next, the obtained amorphous PET sheet was stretched 3.1 times in the sheet running direction (MD; Machine Direction), then stretched 3.8 times in the width direction (TD; Transverse Direction), and the thickness was 180 μm. A PET support (resin substrate) was obtained.

[Formation of white layer and ink receiving layer]
One surface of the PET support was subjected to corona discharge treatment under the condition of 730 J / m ² , and then the following coating solution A-1 was applied by a bar coating method. The coating film of the coating liquid A-1 applied on one surface of the PET support was dried at 145 ° C. for 1 minute, and the thickness of 3 μm and the content of white particles was 2. on one surface of the PET support. An 8 g / m ² white layer was formed.
After the corona discharge treatment was performed on the surface of the white layer formed on one surface of the PET support under the condition of 288 J / m ² , the following coating solution B-1 was applied by the bar coating method. The coating film of the coating liquid B-1 applied to the surface of the white layer was dried at 160 ° C. for 1 minute to form an ink receiving layer having a thickness of 0.5 μm on the white layer.

[Preparation of coating liquid A-1 (composition for forming a white layer)]
(Preparation of titanium dioxide dispersion)
A mixture obtained by mixing each component of the composition of the following titanium dioxide dispersion was subjected to a dispersion treatment for 1 hour using a dynomill type disperser.
(Composition of titanium dioxide dispersion)
Titanium dioxide: 456.0 parts (white particles: Taipei (registered trademark) CR-95, manufactured by Ishihara Sangyo Co., Ltd., solid content: 100%, average primary particle size: 0.3 μm)
Polyvinyl alcohol: 233.0 parts (PVA-105, manufactured by Kuraray Co., Ltd., 10% solid content aqueous solution)
-Surfactant: 5.6 parts (Demol (registered trademark) EP, manufactured by Kao Corporation, 25% solid content aqueous solution)
・ Distilled water: the amount by which the total mass of the titanium dioxide dispersion is 1000 parts

(Composition of coating liquid A-1)
The composition of the coating liquid A-1 is as follows. In addition, content of the fluorochemical surfactant in coating liquid A-1 (composition for white layer formation) is 0.006% with respect to the total solid of a coating liquid.
-Titanium dioxide dispersion prepared above: 232.1 parts (solid content 48.1%)
-Polyolefin: 293.9 parts (Unitika Co., Ltd. Arrow Base (registered trademark) SE-1013N, solid content 20% aqueous dispersion)
Acrylic resin: 90.8 parts (Daicel Finechem Co., Ltd., AS-563A, solid content 28% aqueous dispersion, resin)
-Crosslinking agent: 84.9 parts (oxazoline compound. Nippon Shokubai Co., Ltd., Epocross (registered trademark) WS-700, solid content 25% aqueous solution)
・ Catalyst: 6.6 parts (manufactured by Nippon Chemical Industry Co., Ltd., 35% aqueous solution of dietary dibasic ammonium phosphate)
Silica with an average primary particle size of 20 nm: 113.0 parts (manufactured by Nissan Chemical Industries, Snowtex (registered trademark), aqueous dispersion with a solid content of 20%)
-Blue pigment aqueous dispersion: 6.4 parts (phthalocyanine blue (EP-700 Blue GA manufactured by Dainichi Seika Co., Ltd., 35% solids aqueous dispersion) diluted to 1% with ion-exchanged water) object)
-Aqueous dispersion of purple pigment: 9.3 parts (a dispersion obtained by diluting dioxane-based purple pigment (TB1548, manufactured by Dainichi Seika Co., Ltd., 20% solids aqueous dispersion) to 1% with ion-exchanged water)
Nonionic fluorosurfactant 1.0.1 part (manufactured by DIC Corporation, MegaFac (registered trademark) F-444 ethanol solution with a solid content of 10%)
・ Distilled water: Amount by which the total mass of coating liquid A-1 is 1000 parts

The blue pigment filter filtrate and the purple pigment filter filtrate contained in the coating liquid A-1 were prepared as follows.
[Preparation of blue pigment filter filtrate]
A blue pigment (phthalocyanine blue (EP-700 Blue GA, manufactured by Dainichi Seika Co., Ltd., 35% solid dispersion in water) was diluted with ion-exchanged water to obtain a 1% aqueous dispersion. The aqueous dispersion solution having a concentration was passed through a depth filter (1 μm, profile II) manufactured by Nippon Pole Co., Ltd. twice under the condition of a flow rate of 1 L / min, and the filter filtration was performed to obtain a target blue pigment filter filtrate. It was confirmed that the silicone compound was present in the filtrate of the blue pigment filter, or that the silicone compound was absent when measured by X-ray photoelectron spectroscopy (ESCA).

[Preparation of purple pigment filter filtrate]
A purple pigment (dioxane-based purple pigment (TB1548 manufactured by Dainichi Seika Co., Ltd., solid dispersion 20%) was diluted with ion-exchanged water to obtain a 1% concentration aqueous dispersion. The aqueous dispersion was passed through a depth filter (1 μm, profile II) manufactured by Nippon Pole Co., Ltd. twice under the condition of a flow rate of 1 L / min to perform filter filtration to obtain a target purple pigment filter filtrate. It was confirmed that the silicone compound was present in the pigment filter filtrate when it was measured by ESCA.

[Preparation of coating liquid B-1 (composition for forming an ink receiving layer)]
Each component of the composition of the following coating liquid B-1 was mixed to prepare coating liquid B-1.
The composition of the coating liquid B-1 is as follows.
Polyester: 165.1 parts (manufactured by Kyoyo Chemical Co., Ltd., Pluscoat (registered trademark) Z592, aqueous dispersion with a solid content of 25%, resin)
-Polyurethane ... 46.6 parts (Daiichi Kogyo Seiyaku Co., Ltd. Superflex (registered trademark) 150HS, solid content 38% aqueous dispersion, resin)
Crosslinking agent: 10.5 parts (manufactured by Nippon Shokubai Co., Ltd., Epocross (registered trademark) K-2020E, solid content: 20%)
Anionic non-fluorinated surfactant: 16.91 parts (1% aqueous solution of Rapisol (registered trademark) A-90 manufactured by NOF Corporation)
・ Sliding agent: 23.2 parts (Carnauba wax dispersion cellosol 524, solid content 3%, manufactured by Chukyo Yushi Co., Ltd.)
Nonionic non-fluorinated surfactant: 40.87 parts (manufactured by Sanyo Chemical Industries, 1% aqueous solution of NAROACTY (registered trademark) CL-95)
Preservative: 1.0 part (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
-Distilled water: the amount by which the total mass of the coating liquid B-1 is 1000 parts

[Formation of antistatic layer]
The other surface of the polyethylene terephthalate (PET) support (the surface of the PET support opposite to the surface on which the white layer and the ink receiving layer were formed) was subjected to corona discharge treatment under the condition of 310 J / m ² . Thereafter, the following antistatic layer composition was applied by a bar coating method. The coating amount of the antistatic layer composition was 8.4 cm ³ / m ² . The coating film of the composition for antistatic layer applied to the other surface of the PET support was dried at 145 ° C. for 1 minute to form a layer containing a metal oxide having an average thickness of about 0.1 μm.

(Composition for antistatic layer)
The composition of the antistatic layer composition is as follows.
-Self-crosslinking polyurethane-31.5 parts (Mitsui Chemicals, Takelac (registered trademark) WS-5100, solid content 30%)
-Antimony-doped tin dioxide (needle shape) aqueous dispersion 43.7 parts (Ishihara Sangyo Co., Ltd., FS-10D, solid content 20%)
-Surfactant: 2.1 parts (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of Sanded (registered trademark) BL, anionic non-fluorine surfactant)
Surfactant: 21.0 parts (manufactured by Sanyo Chemical Industries, 1% aqueous solution of NAROACTY (registered trademark) CL-95, nonionic non-fluorine surfactant)
-Distilled water: An amount that the total mass of the antistatic layer composition is 1000 parts

[Formation of protective layer]
The antistatic layer formed on the other surface of the PET support was subjected to a corona discharge treatment under the condition of 200 J / m ² , and then the following protective layer forming composition was applied by a bar coating method. The coating amount of the protective layer composition was 13.8 cm ³ / m ² . The coating film of the protective layer forming composition applied to the surface of the antistatic layer applied to the other surface of the PET support is dried at 145 ° C. for 1 minute to form a protective layer having an average thickness of about 0.85 μm. And the inkjet recording material 1 for electrical decoration of Example 1 was produced.

(Preparation of protective layer forming composition)
The following components were used for the preparation of the protective layer forming composition.
Acetic acid aqueous solution: 402.0 parts (manufactured by Daicel Corporation, 1% aqueous solution of industrial acetic acid)
・ 3-glycidoxypropyltriethoxysilane ... 110.0 parts (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403)
・ Tetraethoxysilane ・ 127.6 parts (Shin-Etsu Chemical Co., Ltd., KBE-04)
・ Hardener: 1.3 parts (Aluminum chelate A (W), manufactured by Kawasaki Fine Chemical Co., Ltd.)
Surfactant A 14.7 parts (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of Sanded (registered trademark) BL, anionic non-fluorinated surfactant)
Surfactant B: 40.9 parts (Sanyo Chemical Industry Co., Ltd., 1% aqueous solution of NAROACTY (registered trademark) CL-95, nonionic non-fluorine surfactant)
-Acrylic resin particles: 9.2 parts (manufactured by Soken Chemical Co., Ltd., MX-150 average primary particle size: 1.5 μm)
-Acrylic resin particles: 9.2 parts (manufactured by Soken Chemical Co., Ltd., MX-80H3WT average primary particle size 0.8 μm)
-Aqueous dispersion of polystyrene particles: 6.9 parts (Nipol (registered trademark) UFN1008 manufactured by Nippon Zeon Co., Ltd., 20% solid content, average primary particle size: 1.9 μm)
-Distilled water: the amount by which the total mass of the protective layer composition is 1000 parts

A composition for forming a protective layer was prepared by the following method using the above components.
3-Glycidoxypropyltriethoxysilane was added dropwise over 3 minutes while vigorously stirring the acetic acid aqueous solution in a constant temperature bath at 25 ° C. After completion of the dropwise addition, stirring was continued for 1 hour, followed by addition of tetraethoxysilane in an acetic acid aqueous solution over 5 minutes while stirring vigorously, and stirring was continued for 2 hours after completion of the addition. It was. Furthermore, it cooled to 10 degreeC over 1 hour. Let the obtained aqueous solution be the aqueous solution X.
Separately, a curing agent, surfactants A and B, distilled water, and three types of resin particles were mixed, and the mixture was ultrasonically dispersed for 5 minutes. The obtained resin particle dispersion is designated as aqueous solution Y.
The aqueous solution Y and distilled water were sequentially added to the aqueous solution X, and then cooled to 10 ° C. to obtain a protective layer forming composition.

(Example 2 to Example 8)
In Example 1, except that the content of the nonionic fluorosurfactant 1 in the white layer forming composition was changed to “Content in the composition” shown in Table 1, the same as in Example 1, An ink jet recording material for electrical decoration of each example was produced.

(Example 9 to Example 12)
Similarly, the ink-jet recording material for electrical decoration of each example was produced except that the nonionic fluorosurfactant 1 used in Example 1 was changed to the type shown in Table 1 and “content in composition”. did.

(Example 13 to Example 17)
In Example 1, except that the thickness of the white layer was changed to the thickness shown in Table 1, the inkjet recording material for electrical decoration of each example was produced in the same manner as in Example 1.

(Example 18 to Example 22)
In Example 1, the ink-jet recording material for electrical decoration of each example was produced in the same manner as in Example 1 except that the thickness of the ink receiving layer was changed to the thickness shown in Table 2.

(Example 23 to Example 25)
In Example 1, the resin of each example was changed in the same manner as in Example 1 except that the resin of the white layer, the white particles of the white layer, and the resin of the ink receiving layer were changed to the resins or white particles shown in Table 2. A decorative inkjet recording material was prepared.

(Example 26)
In Example 1, an ink-jet recording material for electrical decoration was produced in the same manner as in Example 1 except that the composition for forming an ink receiving layer was changed to the following coating liquid B-2.

(Composition of coating liquid B-2)
The composition of the coating liquid B-2 is as follows.
[Preparation of coating liquid B-2 (composition for forming an ink receiving layer)]
Each component of the composition of the following coating liquid B-2 was mixed to prepare coating liquid B-2.
The composition of the coating liquid B-2 is as follows.
Polyester: 165.1 parts (manufactured by Kyoyo Chemical Co., Ltd., plus coat (registered trademark) Z592, aqueous dispersion having a solid content of 25%)
-Polyurethane ... 46.6 parts (Daiichi Kogyo Seiyaku Co., Ltd. Superflex (registered trademark) 150HS solid content 38% aqueous dispersion)
Crosslinking agent: 10.5 parts (manufactured by Nippon Shokubai Co., Ltd., Epocross (registered trademark) K-2020E, solid content: 20%)
Nonionic fluorosurfactant 1... 0.003 parts (manufactured by DIC Corporation, MegaFac (registered trademark) F-444 in 10% solid solution in ethanol)
Anionic non-fluorinated surfactant: 16.91 parts (1% aqueous solution of Rapisol (registered trademark) A-90 manufactured by NOF Corporation)
・ Sliding agent: 23.2 parts (Carnauba wax dispersion cellosol 524, solid content 3%, manufactured by Chukyo Yushi Co., Ltd.)
Nonionic non-fluorinated surfactant: 40.87 parts (manufactured by Sanyo Chemical Industries, 1% aqueous solution of NAROACTY (registered trademark) CL-95)
Preservative: 1.0 part (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
・ Distilled water: amount that the total mass of coating liquid B-2 is 1000 parts

(Comparative Examples 1 to 4)
An ink jet recording material for electrical decoration of each comparative example was produced in the same manner except that the nonionic fluorosurfactant 1 used in Example 1 was changed to the types and blending amounts shown in Table 2.

  Each of the produced ink jet recording materials for electrical decoration was evaluated by the following method. The evaluation results are shown in Tables 1 and 2.

[Granularity]
A contact angle measuring device (manufactured by Kyowa Interface Chemical Co., Ltd., DMC-) in an environment of a temperature of 25 ° C. and a humidity of 50% on the ink receiving layer of the ink-jet recording material for electrical decoration produced in each example and comparative example. 1 μL of KI ink (KI215 cyan, manufactured by Fuji Film Co., Ltd.) was added dropwise using MC3). The ink contact angle when 100 ms (milliseconds) elapsed after dropping was measured, and the graininess was evaluated according to the following criteria.
The granularity is good when it is AA in the following evaluation criteria, and the granularity deteriorates in the order of A, B, C, and D. In the following evaluation criteria, AA to C are practically acceptable levels, and D is evaluated to be a level that cannot be practically used.

-Evaluation criteria-
AA: The ink contact angle is 29 ° to 36 °.
A: The ink contact angle is 37 ° to 41 °.
B: The ink contact angle is 42 ° to 46 °.
C: The ink contact angle is 47 ° to 50 °.
D: The ink contact angle is 51 ° or more.

[Surface]
About the inkjet recording material for electrical decoration produced in each Example and the comparative example, the white layer and the ink receiving layer were observed visually, and the surface state of the white layer and the ink receiving layer was evaluated according to the following criteria, respectively. “Failure” in the following criteria refers to a concave abnormal part (repel failure: Cissing) that occurs when the coating solution is repelled during layer formation, and a convex abnormality that is formed due to the occurrence of aggregates during layer formation. Part (pure defects), and an abnormal part (blurred image) where the coating liquid does not spread uniformly during layer formation and a part of the layer thickness is reduced.

(White layer)
-Evaluation criteria-
In the following evaluation criteria, A to C are practically acceptable levels, and D is evaluated to be a level that cannot be practically used.
A: The number of failures is less than 10/5000 m ² .
B: The number of failures is 10/5000 m ² or more and less than 30/5000 m ² .
C: The number of failures is 30/5000 m ² or more and less than 60/5000 m ² .
D: The number of failures is 60/5000 m ² or more.

(Ink receiving layer)
-Evaluation criteria-
In the following evaluation criteria, A and B were practically acceptable levels, and C was evaluated to be a level that cannot be practically used.
A: The number of failures is less than 10/5000 m ² .
B: The number of failures is 10/5000 m ² or more and less than 100/5000 m ² .
C: The number of failures is 100/5000 m ² or more.

Details of the components in Table 1 are as follows.
Nonionic fluorosurfactant 1: manufactured by DIC Corporation, MegaFac (registered trademark) F-444, solid content 10%
Nonionic fluorosurfactant 2: manufactured by Neos Co., Ltd., FTX-215M, solid content 10%
Anionic fluorosurfactant 1: manufactured by Fuji Fine Chemical Co., Ltd., sodium = bis (3, 3, 4, 4, 5, 5, 6, 6-nonafluoro) = 2-sulfonite oxysuccinate, solid content 2%
Nonionic non-fluorinated surfactant 1: manufactured by Nippon Emulsion Co., Ltd., Emarex (registered trademark) 110, solid content 10%
Nonionic non-fluorinated surfactant 2: Sanyo Chemical Industries, NAROACTY (registered trademark) CL-95, solid content 10%
Polyolefin: manufactured by Unitika Ltd., Arrow Base (registered trademark) SE-1013N
Acrylic resin: Daicel Finechem Co., Ltd., AS-563A; Resin PVC: Nissin Chemical Co., Ltd., Vinibrand 278
Polyester: manufactured by Kyoyo Chemical Co., Ltd., Plus Coat (registered trademark) Z592; resin polyurethane: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150HS; resin Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd. Registered trademark) CR-95
Zeolite: manufactured by Union Showa Co., Ltd., molecular sieve 3A

  From Table 1, it can be seen that the ink jet recording material for electrical decoration of the examples is excellent in the surface shape and graininess of the white layer.

[Production of illuminated images]
Using the ink-jet recording material for electrical decoration of Examples 1 to 26, a color image is formed on the surface of the ink receiving layer of each ink-jet recording material for electrical decoration by the ink-jet method under the following conditions. Images were made.
Solvent-free radiation curable ink (manufactured by FUJIFILM Special Ink System Limited), product numbers UVIJET KO 021 White, UVIJET KO 004 Black, UVIJET KO 215 Cyan, UVIJETK
Using a “wide format UV inkjet press LuxelJet (registered trademark) UV550GTW, manufactured by FUJIFILM Corporation” as a printing machine, printing a color image twice at (wavelength: 365 nm to 405 nm, printing speed 22 m ² / hr) Thus, an image for electrical decoration having a size of about 2 m × 1.5 m was obtained.

  As a result of visually observing the obtained image for electrical decoration, it was an electrical decoration image with good image quality.

DESCRIPTION OF SYMBOLS 1 Inkjet recording material 11 for electrical decoration Resin base material 21 Ink receiving layer 23 White layer 31 Antistatic layer 33 Protective layer

Claims (15)

On the resin substrate,
A white layer containing white particles, a resin, and a fluorosurfactant;
The fluorine concentration on the surface opposite to the side on which the white layer is disposed, including a resin and a fluorosurfactant, exceeds 0.00% by number with respect to the total number of atoms observed on the surface. An ink-receiving layer that is less than or equal to 0.00% by number;
An ink-jet recording material for electrical decoration having the above in order from the resin substrate side.   The inkjet recording material for electrical decoration according to claim 1, wherein the fluorine concentration is 0.10% by number to 4.00% by number.   The inkjet recording material for electrical decoration according to claim 1 or 2, wherein the fluorine-containing surfactant contained in the white layer is a nonionic fluorine-containing surfactant.   The total content of the fluorosurfactant contained in the white layer and the ink receiving layer is 0.100% by mass to 0.400% by mass with respect to the total mass of the white layer and the ink receiving layer. The inkjet recording material for electrical decoration according to any one of claims 1 to 3.   5. The ink-jet recording material for electrical decoration according to claim 1, wherein the fluorine-containing surfactant contained in the white layer has a molecular weight of 1,000 or less.   The thickness of the said white layer is 0.5 micrometer or more and 10 micrometers or less, The inkjet recording material for electrical decoration of any one of Claims 1-5.   The thickness of the said ink receiving layer is 0.01 micrometer or more and 5 micrometers or less, The inkjet recording material for electrical decoration of any one of Claims 1-6.   The electrical decoration according to any one of claims 1 to 7, wherein the ink receiving layer has an ink contact angle of 29 ° to 41 ° on the surface opposite to the side on which the white layer is disposed. Inkjet recording material.   9. The device according to claim 1, comprising the white layer on one side of the resin substrate, and having at least one of an antistatic layer and a protective layer on the other side of the resin substrate. Inkjet recording material for electrical decoration. Forming a white layer by applying a white layer forming composition containing white particles, a resin, and a fluorosurfactant on a resin substrate; and
A composition for forming an ink-receiving layer containing a resin is applied onto the white layer, and the fluorine concentration is relative to the number of all atoms observed on the surface on the surface opposite to the side on which the white layer is disposed. Forming an ink receiving layer that is more than 0.00% and not more than 5.00%;
The manufacturing method of the inkjet recording material for electrical decorations containing this.   The content of the fluorine-type surfactant in the said composition for white layer formation is 0.100 mass%-0.400 mass% with respect to the total solid content mass of a composition, The electrical decoration of Claim 10 For producing an inkjet recording material.   The method for producing an inkjet recording material for electrical decoration according to claim 10 or 11, wherein the fluorine-based surfactant in the white layer forming composition is a nonionic fluorine-based surfactant.   The formation method of the image for electrical decoration including the ink discharge process which discharges an ink composition by the inkjet system on the ink receiving layer of the inkjet recording material for electrical decoration of any one of Claims 1-9. The ink composition is a radiation curable ink composition;
Furthermore, the formation method of the image for electrical decoration of Claim 13 including the hardening process which irradiates a radiation curable ink composition discharged at the said ink discharge process and hardens a radiation curable ink composition.   The electrical decoration signboard which has the inkjet recording material for electrical decoration of any one of Claims 1-9, the image arrange | positioned on the said inkjet recording material for electrical decoration, and a light source.