WO2017169844A1 - Feuille translucide et verre décoratif - Google Patents

Feuille translucide et verre décoratif Download PDF

Info

Publication number
WO2017169844A1
WO2017169844A1 PCT/JP2017/010649 JP2017010649W WO2017169844A1 WO 2017169844 A1 WO2017169844 A1 WO 2017169844A1 JP 2017010649 W JP2017010649 W JP 2017010649W WO 2017169844 A1 WO2017169844 A1 WO 2017169844A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
translucent sheet
receiving layer
mass
transparent support
Prior art date
Application number
PCT/JP2017/010649
Other languages
English (en)
Japanese (ja)
Inventor
隆志 清水
隆浩 中澤
池田　貴美
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2018509018A priority Critical patent/JP6655168B2/ja
Publication of WO2017169844A1 publication Critical patent/WO2017169844A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

Definitions

  • the present invention relates to a translucent sheet and decorative glass.
  • a decoration is provided in part, or a blindfold is provided in part to block the line of sight.
  • a method of providing decoration or blindfold on a part of window glass etc. there is a method of pasting a decoration sheet on the part where decoration or blindfold is to be provided, or a boundary part between the part where the decoration sheet is pasted and the part where it is not pasted.
  • a method in which a decorative sheet is attached to almost the entire surface of a window glass or the like see Patent Documents 1 and 2).
  • Patent Document 1 includes a decorative portion and a non-decorative portion of the same color as the base layer on one surface of a base layer made of a thermoplastic resin film having a haze value of 20% or more measured according to JIS K 7105. A light-shielding decorative sheet formed with a design layer is described. JIS is an abbreviation for Japan Industrial Standards.
  • Patent Document 2 describes that the scratch resistance of a printed matter is improved by using an active energy ray-curable ink that is cured with an active energy ray such as ultraviolet rays.
  • the portion provided with the blindfold was low in translucency because the decorative portion having the same color as that of the base layer was formed using the ink having the same color as that of the base layer.
  • Patent Document 1 does not describe image formation with clear ink, and there is no suggestion of blinding using clear ink.
  • Patent Document 2 did not suggest that both translucency and blindness are compatible. In particular, Patent Document 2 does not describe image formation with clear ink, and there is no suggestion of blinding using clear ink.
  • the problem to be solved by the present invention is to provide a translucent sheet having good scratch resistance, translucency and blinding.
  • the problem to be solved by the present invention is to provide a decorative glass having a translucent sheet having good scratch resistance, translucency and blinding.
  • the present inventors have a transparent support having a low haze value, an ink receiving layer having a high pencil hardness, and an ink image portion having a haze value higher than that of the transparent support and an active energy ray curable type. It has been found that the above problem can be solved by using a light-sensitive sheet in which the ink image portion contains clear ink and the surface of the ink image portion has irregularities, and the present invention has been completed.
  • a transparent support which is a thermoplastic resin film having a haze value measured in accordance with JIS K 7136 of 10% or less, An ink receiving layer located on one side of the transparent support and having a pencil hardness of H or more measured according to JIS K 5600-5-4; An haze value measured in accordance with JIS K 7136 is larger than that of the transparent support, and has an ink image portion that is an active energy ray curable type, The ink image part contains clear ink, A translucent sheet in which the surface of the ink image portion has irregularities.
  • the ink image portion is located on at least a part of one surface of the ink receiving layer, The translucent sheet according to [1] or [2], wherein the ink receiving layer and the ink image portion are in direct contact with each other.
  • the polymerizable compound contains a trifunctional or higher functional (meth) acrylate monomer and an ester monomer of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid.
  • the decorative glass which has a translucent sheet
  • the contents of the present invention will be described in detail.
  • the description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to the embodiments.
  • “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • “transparent” means that the transmittance at a wavelength of 550 nm is 80% or more.
  • “translucency” refers to a property in a state where the opposite shape or the like cannot be clearly recognized through the material because the transmitted light is diffused or the transmittance is low.
  • “clear ink” refers to an ink having an average transmittance of 80% or more at a wavelength of 380 to 780 nm when a film having a thickness of 8 ⁇ m is formed on a transparent substrate.
  • the clear ink may have wavelength dispersion or a colored clear ink.
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • the translucent sheet of the present invention is located on one surface side of a transparent support, which is a thermoplastic resin film having a haze value measured in accordance with JIS K 7136 of 10% or less, and JIS K 7136.
  • An ink receiving layer having a pencil hardness measured in accordance with K 5600-5-4 of H or higher, and a haze value measured in accordance with JIS K 7136 is larger than that of a transparent support, and is an active energy ray curable type.
  • an ink image portion In the translucent sheet of the present invention, the ink image portion contains clear ink, and the surface of the ink image portion has irregularities.
  • the translucent sheet of the present invention having this configuration has good scratch resistance, translucency and blinding.
  • the translucent sheet of the present invention has an ink receiving layer having a pencil hardness of H or higher and an ink image portion of an active energy ray curable type, the scratch resistance is good.
  • the translucent sheet of the present invention has good translucency because the transparent support has a low haze value, the ink image portion contains clear ink, and the surface of the ink image portion has irregularities.
  • the ink image portion contains clear ink, and the surface of the ink image portion has irregularities, so that the blinding property is good.
  • the transparent support and the ink image portion containing clear ink in this way, it has a high-class feeling that achieves both translucency and blindness compared to the ink image portion containing non-clear ink (for example, white ink).
  • a pattern for example, gradation
  • a transparent material such as clear ink can improve gradation fineness (discrimination), and it is easy to give a high-class feeling.
  • seat of this invention is demonstrated below.
  • the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet is preferably 3% or more, more preferably 8% or more, and particularly preferably 15% or more from the viewpoint of blinding.
  • the difference between the maximum value and the minimum value of the haze value in the surface of the translucent sheet is 3% or more, details such as the outer edge and characters of the object are blurred over the glass with the translucent sheet, or Blindness such as inability to recognize contours and shapes can be preferably confirmed.
  • the larger the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet the better the blinding property, so that it is preferable. Since clear ink is used, the upper limit of the difference between the maximum value and the minimum value of the haze value in the surface of the translucent sheet is about 80%.
  • the maximum value of the in-plane haze value of the translucent sheet is preferably the maximum in-plane haze value of the ink image portion containing clear ink (hereinafter also referred to as the haze value of the ink image portion).
  • the maximum value of the in-plane haze value of the translucent sheet is preferably 80% or less, more preferably 70% or less, and particularly preferably 60% or less.
  • the lower limit value of the in-plane haze value of the translucent sheet is at least the haze value of the transparent support.
  • FIG. 4 is a schematic view showing a cross section of an example of the translucent sheet of the present invention.
  • the translucent sheet 20 shown in FIG. 4 has at least the transparent support 1, the ink receiving layer 2 positioned on one surface side of the transparent support 1, and the ink image portion 11.
  • the ink image portion 11 is positioned at least in a part of one surface of the ink receiving layer 2, and the ink receiving layer 2 and the ink image portion 11 are in direct contact with each other. It is preferable from the viewpoint.
  • the portion of the translucent sheet 20 excluding the ink image portion 11 is referred to as a recording sheet 10.
  • the translucent sheet 20 has an ink image portion 11 formed on the recording sheet 10 and has an embodiment shown in FIG.
  • the translucent sheet of the present invention has good scratch resistance of the ink image portion 11 and the ink receiving layer 2 in the non-image portion.
  • the non-image portion refers to a portion of the ink receiving layer 2 other than the ink image portion 11 (that is, the portion of the ink receiving layer 2 where ink is not fixed).
  • the width of the translucent sheet is not particularly limited, but is preferably recorded by a wide format inkjet printer system, preferably 0.3 to 5 m, more preferably 0.5 to 4 m, and particularly preferably 1 to 3 m. .
  • the preferable width of the recording sheet is the same as the preferable width of the above-described translucent sheet of the present invention.
  • the recording sheet 10 includes at least a transparent support 1 and an ink receiving layer 2 positioned on one surface side of the transparent support 1.
  • the ink receiving layer 2 may be positioned on at least one surface side of the transparent support 1 and may be positioned on both sides, but it is preferable that the ink receiving layer 2 is positioned only on one side from the viewpoint of providing an adhesive layer described later.
  • the recording sheet 10 preferably has an adhesive layer 5 on the surface of the transparent support 1 opposite to the surface having the ink receiving layer 2.
  • the recording sheet 10 preferably has a release film 6 on the adhesive layer 5. As shown in FIG.
  • the recording sheet 10 is composed of a single layer or two or more layers between at least one of the ink receiving layer 2 and the transparent support 1 and between the adhesive layer 5 and the transparent support 1. It is also preferable to have at least one of the intermediate layers 3A, 3B, 3C, 3D, 3E and 3F.
  • FIG. 3 there are three layers of intermediate layers 3A, 3B and 3C in this order from the transparent support 1 side between the ink receiving layer 2 and the transparent support 1, and the transparent layer 1 is transparent between the adhesive layer 5 and the transparent support 1.
  • An embodiment is described in which three layers of intermediate layers 3D, 3E, and 3F are provided in this order from the support 1 side.
  • the present invention is not limited to this aspect, and the number and arrangement order of the intermediate layers are not particularly limited. Hereinafter, each member will be described.
  • the transparent support is a thermoplastic resin film having a haze value measured in accordance with JIS K 7136 of 10% or less.
  • the haze value of the transparent support is preferably 0.01 to 5.0%, more preferably 0.05 to 2.0%, and particularly preferably 0.1 to 1.0%. preferable.
  • the single haze value of the transparent support in the translucent sheet can be measured by peeling the transparent support from the translucent sheet.
  • the transparent support preferably has a transmittance at a wavelength of 550 nm of 80% or more, more preferably 85% or more, and particularly preferably 89% or more.
  • thermoplastic resin film can be used for the transparent support.
  • thermoplastic resin film used for the transparent support include films containing cellulose ester such as polyester, polyethylene, polypropylene, polystyrene, cyclic olefin resin, polyvinyl alcohol, polycarbonate, and triacetyl cellulose.
  • a transparent support body is a film containing polyester as a component contained 50 mass% or more of a transparent support body, and additives, such as a plasticizer, may be contained.
  • the polyester is not particularly limited, and for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and the like are used. Among these, polyethylene terephthalate is particularly preferable from the viewpoint of cost and mechanical strength.
  • the draw ratio is not particularly limited, but is preferably in the range of 1.5 to 7 times. If the draw ratio is less than 1.5 times, the mechanical strength may be insufficient. Conversely, if it exceeds 7 times, the thickness may not be uniform.
  • the draw ratio is more preferably in the range of 2 to 5 times. Particularly preferable stretching directions and magnifications are in the range of 2 to 5 times in two directions orthogonal to each other.
  • the thickness of the transparent support is, for example, preferably from 30 ⁇ m to 500 ⁇ m, more preferably from 50 ⁇ m to 300 ⁇ m, and particularly preferably from 50 ⁇ m to 120 ⁇ m. It is easy to handle when the thickness of the transparent support is 30 ⁇ m or more. On the other hand, when the thickness of the transparent support is not more than the upper limit of the preferred range, it is easy to reduce the size and weight of the display device, which is advantageous in terms of cost.
  • the thickness of the transparent support is not more than the upper limit of the preferred range, it becomes easy to reduce the minimum value of the in-plane haze value of the translucent sheet, and the maximum in-plane haze value of the translucent sheet And the difference between the minimum values can be easily increased, and the blinding property can be improved.
  • a transparent support that has been subjected to a surface treatment such as a corona discharge treatment, a vacuum glow discharge treatment, or a flame treatment on at least one of the one surface and the other surface.
  • a surface treatment such as a corona discharge treatment, a vacuum glow discharge treatment, or a flame treatment
  • At least one of the one surface and the other surface of the transparent support is hydrophilized by surface treatment, and the wettability of each type of aqueous coating liquid can be improved.
  • functional groups such as carboxyl groups and hydroxy groups can be introduced. Thereby, the adhesive force between one surface of the transparent support and the ink receiving layer or the intermediate layer can be further increased.
  • the ink receiving layer is located on one surface side of the transparent support, and the pencil hardness measured according to JIS K 5600-5-4 is H or more.
  • the pencil hardness of the ink receiving layer is preferably 2H or more.
  • the ink receiving layer is preferably a cured layer of a composition containing a polymerizable compound, a polymerization initiator and a surfactant. Moreover, you may have another component as needed.
  • Polymerizable compound there is no restriction
  • the polymerizable compound in the present invention is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and from a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. More preferably, it is selected.
  • This compound is widely known in the same technical field as the present invention, and these can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers (ie, dimers, trimers and oligomers), or mixtures thereof and copolymers thereof.
  • the polymerizable compound those described in [0116] to [0126] of JP2011-127096A can be used, and the contents of the above publication are incorporated in the present invention.
  • monomers and copolymers thereof include unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid), esters thereof and amides thereof.
  • esters of aliphatic polyhydric alcohols and unsaturated carboxylic acids, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds are used.
  • unsaturated carboxylic acid esters or unsaturated carboxylic acid amides having a nucleophilic substituent such as a hydroxy group, an amino group and a mercapto group, and a monofunctional or polyfunctional isocyanate or monofunctional or polyfunctional epoxy An addition reaction product of the above; and a dehydration condensation reaction product of the above unsaturated carboxylic acid ester or unsaturated carboxylic acid amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group and an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also possible.
  • the monomer of an ester of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • Acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • EO is an abbreviation for ethylene oxide) Acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diaquo 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate Examples include acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, and isocyanuric acid EO-modified triacrylate.
  • the details of usage methods can be arbitrarily set according to the final performance design of a composition.
  • the polymerizable compound preferably has a structure having a high unsaturated group content per molecule, and in many cases, bifunctional or higher. In order to increase the strength of the cured layer, a trifunctional or higher functional layer is preferable.
  • the selection of the polymerizable compound is also required for the compatibility and / or dispersibility with other components contained in the composition (for example, a polymerization initiator and a light shielding material (pigment or dye) such as titanium dioxide).
  • the compatibility may be improved by using a low-purity compound or using two or more kinds of other components in combination.
  • a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.
  • the polymerizable compound is preferably an ester monomer of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid, more preferably an acrylic ester or a methacrylic ester, and an acrylic ester. It is particularly preferred. Two or more kinds of polymerizable compounds are preferably used from the viewpoint of controlling physical properties such as the elastic modulus of the film.
  • a combination of a tri- or higher functional (meth) acrylate monomer and an ester monomer of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid is preferable from the viewpoint of ink adhesion and scratch resistance.
  • the trifunctional or higher functional (meth) acrylate monomer is preferably an ester monomer of an aliphatic polyhydric alcohol and a trifunctional or higher functional (meth) acrylic acid.
  • An ester monomer of polyhydric alcohol and (meth) acrylic acid not containing a tri- or higher functional alkylene oxide chain is more preferable.
  • Examples of commercially available products of tri- or higher functional (meth) acrylate monomers when two or more polymerizable compounds are used in combination include KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
  • the monomer of an ester of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid is an ester of an aliphatic polyhydric alcohol and a bifunctional or higher functional (meth) acrylic acid.
  • Monomers are preferable, monomers of aliphatic polyhydric alcohols and esters of bifunctional or higher functional (meth) acrylic acid having an alkylene oxide chain are more preferable, and aliphatic polyhydric alcohols and bifunctional or higher functional EO-modified (meth) acrylates are more preferable. Particularly preferred.
  • Examples of commercially available monomers of an ester of an aliphatic polyhydric alcohol and an unsaturated carboxylic acid when two or more kinds of polymerizable compounds are used in combination include Biscoat V360 manufactured by Osaka Organic Chemical Industry Co., Ltd. it can.
  • the polymerizable compound in the ink receiving layer may not have any polymerizable groups remaining as a result of completely curing to form the ink receiving layer, and may be polymerized as a result of forming the ink receiving layer by lowering the curing rate.
  • the sex group may remain. From the viewpoint of improving ink adhesion and yellowness, it is preferable to form an ink receiving layer with a reduced curing rate and leave a polymerizable group (ethylenically unsaturated bond) in the polymerizable compound in the ink receiving layer. preferable.
  • the method for leaving a polymerizable group in the polymerizable compound in the ink-receiving layer is not particularly limited, and examples thereof include a method for leaving an ethylenically unsaturated bond by reducing the amount of UV exposure. This method will be described in a recording sheet manufacturing method described later.
  • the content of the polymerizable compound in the ink receiving layer or in the total solid content of the composition for forming the ink receiving layer is preferably in the range of 50% by mass to 99% by mass, and 80% by mass to 98% by mass. % Is more preferable, and the range of 90% by mass to 97% by mass is even more preferable. Within this range, the ink adhesion is good and preferable.
  • Polymerization initiator There is no restriction
  • the polymerization initiator those known as polymerization initiators described below can be used.
  • the polymerization initiator those described in [0128] to [0177] of JP2011-127096A can be used.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity to light in the ultraviolet band to the visible band are preferable. Further, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of monomer.
  • hydroxyacetophenone compounds As the polymerization initiator, hydroxyacetophenone compounds, aminoalkylphenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names: all manufactured by BASF) can be used as the aminoalkylphenone initiator.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
  • acylphosphine-based initiator commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • IRGACURE-819 and DAROCUR-TPO trade names: both manufactured by BASF
  • examples of other polymerizable compounds the description of [0040] to [0046] in JP-A-2015-163457 can be referred to. The contents of this publication are incorporated herein.
  • the polymerization initiator used in the present invention may be used in combination of two or more as required.
  • the content of the polymerization initiator contained in the ink receiving layer (the total content in the case of two or more types) is 0.1% by mass or more and 50% by mass or less with respect to the total solid content contained in the ink receiving layer. More preferably, it is 0.5 mass% or more and 30 mass% or less, More preferably, it is 0.5 mass% or more and 20 mass% or less. In this range, good sensitivity can be obtained.
  • the content of the polymerization initiator contained in the ink receiving layer is particularly preferably 2% by mass or more and 10% by mass or less from the viewpoint of appropriate scratch resistance, ink adhesion, and yellowness. Yellowness can be suppressed by making content of a polymerization initiator into below the upper limit of the said preferable range. By setting the content of the polymerization initiator to be equal to or higher than the lower limit value of the above preferred range, the ink receiving layer can be easily cured, and scratch resistance and ink adhesion can be improved.
  • surfactant There is no restriction
  • the surfactant By having the surfactant, the clear ink can be sufficiently cured even when the ink density set in the printer is lowered and the clear ink is ejected in a frosted manner. If the clear ink is difficult to spread, it is possible to suppress the influence of polymerization inhibition of the ejected clear ink by oxygen or the like, the clear ink can be easily cured, and the ink adhesion can be improved.
  • surfactant examples include known anionic, nonionic, cationic, fluorine and silicone surfactants.
  • the surfactant is described in, for example, “Surfactant Handbook” (Nishi Ichiro, Ichiro Imai, Shozo Kasai, Sangyo Tosho Co., Ltd., 1960).
  • Fluorosurfactants include fluoroaliphatic group-containing copolymers (sometimes abbreviated as “fluorine polymer”).
  • the fluoropolymer preferably has a structural unit derived from a fluorine-containing vinyl monomer and a structural unit for imparting crosslinkability.
  • Preferable examples of the structural unit of the fluorine-based polymer include, for example, compounds described in paragraph numbers 0095 to 0102 of JP2011-75942A.
  • Examples of the fluorine-based polymer include random copolymers of perfluoroolefin and vinyl ethers or vinyl esters.
  • These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%.
  • Preferred polymers are disclosed in JP 2002-243907, JP 2002-372601, JP 2003-26732, JP 2003-222702, JP 2003-294911, JP 2003-329804, JP 2004. And those described in JP-A No. 4444 and JP-A No. 2004-45462.
  • a polysiloxane structure may be introduced into the fluoropolymer for the purpose of imparting antifouling properties.
  • the method for introducing the polysiloxane structure is not limited, but as described in, for example, JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, silicone macroazo Method of introducing polysiloxane block copolymer component using initiator; Method of introducing polysiloxane graft copolymer component using silicone macromer as described in JP-A-2-251555 and JP-A-2-308806 Is preferred.
  • Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and copolymers A-2 and A-3 of JP-A-2-251555.
  • anionic surfactants examples include Lapisol A-90, Lapisol A-80, Lapisol BW-30, Lapisol B-90, Lapisol C-70 (trade name: manufactured by NOF Corporation), NIKKOL OTP -100 (trade name: manufactured by Nikko Chemicals Co., Ltd.), Kohakuur ON, Kolacool L-40, Phosphanol 702 (Toho Chemical Co., Ltd.), Viewlight A-5000 and Viewlight SSS (Sanyo Chemical Industries, Ltd.) )) And the like.
  • nonionic surfactants examples include, for example, NAROACTY CL-95, HN-100 (trade name: manufactured by Sanyo Chemical Industries, Ltd.), Risolex BW400 (manufactured by Higher Alcohol Industry Co., Ltd.), EMALEX ET-2020. (Nippon Emulsion Co., Ltd.), Unilube 50MB-26 and Nonion IS-4 (Nippon Oil Co., Ltd.).
  • fluorosurfactants include MegaFuck F171, F172, F173, F176, F177, F141, F141, F142, F143, F144, R30, F437, F475, and the like.
  • F479, F482, F554, F554, F780, F781, F781 (above DIC Corporation), Florad FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) Examples thereof include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
  • cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid. (Co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • silicone surfactants examples include, for example, Tore Silicone DC3PA, Tore Silicone SH7PA, Tole Silicone DC11PA, Tole Silicone SH21PA, Tole Silicone SH28PA, Tole Silicone SH29PA, Tore Silicone SH30PA, Tore Silicone SH8400 (above, Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) )), BYK307, BYK323 and BYK330 (above, manufactured by BYK Chemie).
  • the surfactant is preferably a surfactant represented by the following formula C-1.
  • a fluorine-based surfactant having a hydrogenated terminal represented by the formula C-1 is preferable from the viewpoint of adhesion between the ink receiving layer and the ink image portion.
  • R 11 and R 12 each independently represent a hydrogen atom or a methyl group
  • X 11 and X 12 each independently represent an oxygen atom, a sulfur atom or NR 14
  • m1 is 1 or more and 6 or less.
  • N1 represents an integer of 2 or more and 20 or less
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X is 20 or more.
  • R 11 and R 12 each independently represents a hydrogen atom or a methyl group.
  • X 11 and X 12 each independently represent an oxygen atom, a sulfur atom, or NR 14
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group represented by R 14 may be linear, branched or cyclic.
  • the alkyl group represented by R 14 preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • R 14 is particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • X 11 and X 12 are preferably an oxygen atom or NR 14 , and more preferably an oxygen atom.
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • a part of the carbon chain is an ether bond (—O—), an ester bond (—C ( ⁇ O) —O—), a carbonyl group (—C ( ⁇ O) —).
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples include an alkyleneoxyalkyl group and a poly (alkyleneoxy) alkyl group. R 13 may further have a substituent, and examples of the substituent include a hydroxy group.
  • n1 represents an integer of 2 or more and 20 or less, preferably 2 to 16, more preferably 3 to 12, and still more preferably 4 to 8.
  • X represents a molar ratio (mol%) of each monomer unit, and X is 20 or more. X is preferably 40 to 100, more preferably 60 to 100, still more preferably 80 to 99, and particularly preferably 90 to 99.
  • the monomer unit contained in X mol% may be one kind alone, or two or more kinds may be contained.
  • it may be a polymer composed of a plurality of monomer units different from at least one of m1 and n1.
  • the monomer unit contained in (100-X) mol% may be one kind alone, or two or more kinds may be contained.
  • the monomer unit derived from acrylic acid and acrylic acid ester may be included.
  • fluorine-based surfactant having a hydrogenated terminal represented by the formula C-1 examples include the fluorine-based surfactants GF-1, GF-2, and GF-3 used in Examples described later. be able to.
  • the weight average molecular weight of the surfactant is preferably 1,000 to 1,000,000, more preferably 2,500 to 300,000, and further preferably 5,000 to 100,000. preferable.
  • the glass transition temperature (Tg) of the surfactant can be, for example, ⁇ 45 ° C. to ⁇ 10 ° C.
  • the glass transition temperature of the surfactant is preferably ⁇ 40 ° C. to ⁇ 10 ° C., more preferably ⁇ 35 ° C. to ⁇ 20 ° C., and preferably ⁇ 35 ° C. to ⁇ 31 ° C. Further preferred.
  • the glass transition temperature of the surfactant is equal to or higher than the lower limit of the preferred range, the ink adhesion becomes good.
  • the glass transition temperature of the surfactant is not more than the upper limit of the preferred range, the coating property of the ink receiving layer is good.
  • the glass transition temperature is measured by the following method. Specifically, using a differential scanning calorimeter (for example, X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.), 5.0 mg of a sample is placed in a simple sealed container, and the heating rate is 10 ° C./min in a nitrogen atmosphere. The temperature at which the base line of the obtained DSC (Differential scanning calorimetry) curve and the tangent at the inflection point intersect is read.
  • a differential scanning calorimeter for example, X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.
  • the solid content of the surfactant contained in the ink receiving layer can be, for example, 0.0001 to 0.0100 g / m 2 .
  • the solid content of the surfactant contained in the ink receiving layer is preferably 0.0004 to 0.0050 g / m 2 , more preferably 0.0008 to 0.0032 g / m 2. Of 0.0008 to 0.0024 g / m 2 , more preferably 0.0008 to 0.0016 g / m 2 .
  • the ink receiving layer may be a resin, a crosslinking agent, a slip agent, an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, an antiseptic, if necessary.
  • other components such as a water resistant agent, particles, an organic solvent, and distilled water may be contained.
  • the ink receiving layer may contain a resin.
  • the function of the resin contained in the ink receiving layer is not particularly limited.
  • the resin include a polyester-based resin that functions as a binder, a polyurethane-based resin, an acrylic resin, and the like, and a cellulose acylate resin that functions as a viscosity modifier.
  • the resin contained in the ink receiving layer is preferably a cellulose acylate resin and may contain two or more kinds.
  • Examples of commercially available products include cellulose acetate butyrate (CAB, manufactured by Eastman Chemical Japan).
  • the resin contained in the ink receiving layer is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, and more preferably 1 to 5% by weight with respect to the total solid content contained in the ink receiving layer. % Is particularly preferred. When two or more kinds of resins are contained in the ink receiving layer, the total amount of the resins may be within the above range.
  • the thickness of the ink receiving layer is, for example, preferably 0.1 to 50 ⁇ m, more preferably 1 to 40 ⁇ m, and particularly preferably 3 to 30 ⁇ m. It is preferable from the viewpoint of facilitating curing that the thickness of the ink receiving layer is not more than the upper limit of the preferred range. When the thickness of the ink receiving layer is at least the lower limit of the preferred range, scratch resistance and ink adhesion can be improved.
  • the translucent sheet of the present invention has an ink image portion that has a haze value measured in accordance with JIS K 7136 that is larger than that of a transparent support and is an active energy ray curable type, and the ink image portion includes clear ink.
  • the surface of the ink image portion has irregularities.
  • the ink image portion has a haze value measured according to JIS K 7136, which is larger than that of the transparent support, and is preferably 1 to 80%, and more preferably 3 to 60%.
  • the ink image portion is an active energy ray curable type. That the ink image portion is of the active energy ray curable type means that the ink image portion is a cured layer cured with the active energy ray.
  • the ink image portion includes clear ink.
  • clear ink There is no restriction
  • product names manufactured by Fujifilm Corporation: LL391, product names manufactured by Fujifilm Corporation: UVIJET ACUITY KN391, product names manufactured by Dai Nippon Printing Co., Ltd .: Truepress Ink HardLED Clear, and Mimaki Corporation A product name manufactured by Engineering: Uwin Clear Liquid SPC-0371CL, and the like.
  • the surface of the ink image portion has irregularities.
  • the surface of the ink image portion is included in the shape having unevenness.
  • the surface of the ink image portion preferably has irregularities having a difference between the maximum height of the surface of the ink image portion and the minimum height of the surface of the ink image portion of 0.01 to 2000 ⁇ m. It is more preferable that the difference in the minimum height of the surface of the ink image portion is unevenness of 0.1 to 1800 ⁇ m, and the difference between the maximum height of the surface of the ink image portion and the minimum height of the surface of the ink image portion is 1.0.
  • the haze value of the ink image portion is affected by the unevenness of the surface of the ink image portion. For example, to increase the glossiness, it is conceivable to make the surface of the ink image portion flatter. In this case, the glossiness increases, but the haze value of the ink image portion tends to decrease. Further, in order to emphasize the frost tone and enhance the matte feeling, it is conceivable to increase the unevenness of the surface of the ink image portion. Depending on the unevenness of the surface of the ink image portion, even when the printer setting ink density of the clear ink used for forming the ink image portion is increased, the haze value of the ink image portion does not necessarily increase.
  • the increase in the haze value of the ink image portion is considered to be caused by light scattering on the surface of the image portion, and it is presumed that light scattering is likely to occur when the surface of the ink image portion has an uneven shape.
  • the shape of the surface of the ink image portion can be controlled by, for example, a droplet ejection shape of clear ink described later. Even when the clear ink density in the ink image area is increased, if the unevenness on the surface of the image area becomes uniform and becomes nearly flat, there will be no difference from the shape of the surface of the ink image area formed by the bar coating method. It becomes a state close to a general clear coat.
  • the haze value of the ink image portion may be lowered. Even when the same clear ink is used, the haze value of the ink image portion can be controlled by changing the unevenness of the surface of the ink image portion. That is, by changing the unevenness of the surface of the ink image portion, it is possible to control the blinding property associated with the difference between the maximum value and the minimum value of the in-plane haze value.
  • the ink image portion includes ink jet droplets.
  • the shape of the surface of the ink image portion can be controlled by the droplet ejection shape of the clear ink. Therefore, the haze value of the ink image portion is affected by the droplet ejection shape of the clear ink.
  • the clear ink that has been ejected is made more flat (from granular).
  • the frost tone and enhance the matte feeling it is conceivable to make the ejected clear ink more granular, and to reduce the droplet ejection size to increase the number of droplet ejection.
  • the droplet ejection shape of the clear ink can be changed by adjusting or changing the specifications and settings of the ink jet printer to be used.
  • FIG. 6 is a graph showing the relationship between the printer set ink density and the haze value.
  • a printer setting ink density of C% (C represents 0 to 100) is synonymous with an ink droplet ejection amount, and the value is C% based on a standard amount that is standardly set in an ink jet printer. means.
  • the printer set ink density can be freely selected within a range that satisfies the desired blindness and designability.
  • the setting of the ink jet printer is not particularly limited, but a general printer print setting can be used. From the viewpoint of design and blindness, it is preferable to use them when there are specific settings such as “matte”, “frost”, “gloss”, “fine” and “high definition”. From the viewpoint, “mat” and “frost” are more preferable.
  • the setting “matte 1” means a setting for printing an image that is not glossy and cloudy compared to the standard printer setting.
  • the setting “mat 2” means a setting for image printing that is more glossy and cloudy when there are a plurality of “mat” settings.
  • the setting “glossy” means a setting for glossy image printing as compared with the standard printer setting.
  • the thickness of the ink image portion is preferably 1 ⁇ m to 2 mm, more preferably 1 to 800 ⁇ m.
  • the translucent sheet of the present invention may further have an intermediate layer between the ink receiving layer and the transparent support.
  • seat of this invention may have an intermediate
  • middle layer contains resin at least.
  • middle layer A well-known resin can be used.
  • the intermediate layer preferably contains at least one of a polyester resin, a polyurethane resin, an acrylic resin, and a polyolefin resin.
  • the intermediate layer may be composed of a single layer or may be composed of two or more layers.
  • the intermediate layer between the ink receiving layer and the transparent support will be described, but the preferred range of the intermediate layer between the adhesive layer and the transparent support is also the same.
  • the preferred range is the same.
  • the preferable range of the below-mentioned intermediate layer B preferable as an intermediate layer between the ink receiving layer and the transparent support and the preferable range of the below-described intermediate layer E preferable as an intermediate layer between the adhesive layer and the transparent support are the same.
  • the preferable range of the below-mentioned intermediate layer C preferable as an intermediate layer between the ink receiving layer and the transparent support and the preferable range of the below-described intermediate layer F preferable as an intermediate layer between the adhesive layer and the transparent support are the same. is there.
  • the intermediate layer A having a thickness of less than 0.1 ⁇ m from the viewpoint of improving both ink adhesion and scratch resistance.
  • the intermediate layer between the ink receiving layer and the transparent support is composed of a single layer, it is preferable to include this intermediate layer A from the viewpoint of improving both ink adhesion and scratch resistance.
  • the intermediate layer is composed of two or more layers, the intermediate layer A is preferably included from the viewpoint of improving both the ink adhesion and the scratch resistance.
  • the recording sheet preferably has a transparent support, the intermediate layer A, and the intermediate layer B in this order from the viewpoint of improving ink adhesion.
  • the composition of the intermediate layer A is not particularly limited.
  • the intermediate layer A comprises a polyester resin, polyurethane resin (preferably an isocyanate compound-containing self-crosslinking polyurethane resin containing an isocyanate group), a crosslinking agent catalyst, and a surfactant (preferably an anionic interface). Activator) and fine particles.
  • At least one of the intermediate layers is preferably an intermediate layer B having a thickness of 0.1 ⁇ m or more and having a polyolefin-based resin of 10% or more from the viewpoint of improving ink adhesion.
  • the elastic modulus of the intermediate layer B is preferably at most 500 MPa, that is, 500 MPa or less.
  • the elastic modulus of the intermediate layer B is more preferably in the range of 10 MPa to 500 MPa, and still more preferably in the range of 50 MPa to 500 MPa.
  • the conventional intermediate layer has an elastic modulus of 600 MPa or more, whereas the intermediate layer B has such a very low elastic modulus.
  • the intermediate layer B when the transparent support or the ink receiving layer is elastically deformed, the intermediate layer B also expands and contracts at a very micro level so as to follow the change in the shape of the transparent support or the ink receiving layer. For example, when the ink receiving layer is deformed so as to be pressed against the transparent support, the intermediate layer B shrinks so that the thickness becomes small. Further, when the deformed ink receiving layer returns to its original shape, the intermediate layer B returns to its original thickness and shape. Thus, the intermediate layer B has a property of changing the thickness and restoring the shape. By providing the intermediate layer B with elasticity, even if the shape of the ink receiving layer is changed, the ink receiving layer is maintained in an adhesive state without being peeled off from the transparent support and remains in close contact.
  • the ink receiving layer and the transparent support are peeled off means that the ink receiving layer is peeled off from the intermediate layer B, the intermediate layer B is destroyed from the inside, or the intermediate layer is peeled off from the transparent support.
  • the intermediate layer B preferably contains at least 10% by mass of a polyolefin resin. By including 10 mass% or more of the polyolefin resin, the intermediate layer B comes to have the above elastic modulus.
  • the intermediate layer B preferably contains a polyolefin-based resin in a range of 10% by mass to 90% by mass, and more preferably in a range of 20% by mass to 80% by mass.
  • the composition of the intermediate layer B is not particularly limited except that it has 10% or more of the polyolefin resin, but the intermediate layer B further contains an acrylic resin, and the intermediate layer B is combined with the polyolefin resin to increase the elongation at break of the intermediate layer. It is preferable from the viewpoint of enlargement. Examples of commercially available products include AS-563A (manufactured by Daicel Finechem). Moreover, it is preferable that the intermediate
  • the intermediate layer may be composed of two or more layers, and at least one of the intermediate layers is preferably an intermediate layer C containing at least one of a polyester resin and a polyurethane resin.
  • the intermediate layer C can improve the ink adhesion by facilitating the diffusion of the polymerization initiator and the polymerizable compound contained in the ink receiving layer. Further, the intermediate layer C can be used by being laminated with the intermediate layer B, whereby the ink adhesion can be further improved, and the recording sheet may have the transparent support, the intermediate layer B, and the intermediate layer C in this order. This is preferable from the viewpoint of improving ink adhesion.
  • the composition of the intermediate layer C is not particularly limited except that it contains at least one of a polyester-based resin and a polyurethane-based resin, but preferably contains a crosslinking agent, a surfactant, a slip agent, and a preservative.
  • resins that can be preferably used for the intermediate layer will be described.
  • resins that can be preferably used for the intermediate layer reference can be made to the descriptions of [0066] to [0078] in JP-A-2015-163457. The contents of this publication are incorporated herein.
  • the intermediate layer may contain a polyester resin.
  • Polyester resins are Finetex ES650, ES2200 (manufactured by DIC Corporation), Vironal MD1245, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.), Pesresin A-110, A-124GP, A-520, A-640 (Takamatsu) (Available from Yushi Co., Ltd.), plus coat Z561, Z730, Z687 and Z592 (manufactured by Kyogo Chemical Co., Ltd.).
  • Polyurethane resin- Polyurethane resins are Superflex 470, 210, 150HS, Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-20, AP-40F, WLS-210 (DIC Corporation), Takelac W It is also available as a commercial product of -6061 and Olester UD-350 (Mitsui Chemicals).
  • middle layer contains acrylic resin.
  • the acrylic resin can increase the elongation at break of the intermediate layer by using it in combination with the same intermediate layer as the polyolefin.
  • Acrylic ester copolymers such as Jurimer ET-410 (manufactured by Toagosei Chemical Co., Ltd.) and EM-48D (manufactured by Daicel Corporation) are preferably used as commercial products.
  • Polyolefin resin- Polyolefin resins are generally known to have low adhesion to polyester, and conventionally, they have not been used as a main component in an intermediate layer that bonds an ink receiving layer made of polyester and a transparent support. Further, the use of polyolefin resin for the intermediate layer is limited to the case where polyolefin is used for the transparent support or the ink receiving layer. In the present invention, it is preferable to use polyolefin in the intermediate layer B between the transparent support and the ink receiving layer. Thus, when polyolefin is used as the main component of the intermediate layer B, the thickness T of the intermediate layer B is preferably 0.1 ⁇ m or more in order to prevent the ink receiving layer and the transparent support from peeling off.
  • the thickness of the intermediate layer is 0.1 ⁇ m or more, the ink receiving layer and the support are difficult to peel off, and particularly difficult to peel off at high density printing portions where the ink discharge amount is large. Furthermore, by setting it as said thickness, the stress applied as a load by the crosscut etc. to the ink receiving layer or the transparent support in the crosscut test is relieved by the intermediate layer B, for example.
  • the thickness T of the intermediate layer B is preferably in the range of greater than 0.1 ⁇ m and not greater than 5.0 ⁇ m, more preferably in the range of greater than 0.3 ⁇ m and not greater than 5.0 ⁇ m, and not less than 0.2 ⁇ m and not greater than 4 ⁇ m. More preferably, it is in the range.
  • the thickness T of the intermediate layer B is preferably constant.
  • the stress is dispersed by having the intermediate layer B, the ink adhesion can be improved even if the ink receiving layer does not sufficiently soak the ink composition.
  • the above-mentioned elasticity can be obtained even in a state of wet heat aging (for example, drying at 85 ° C. or passage of 100 to 500 hours at 65 ° C. and 95% relative humidity).
  • the rate and elongation at break are maintained.
  • the polyolefin-based resin is a resin that hardly deteriorates under high temperature and high humidity, the above-described elastic modulus and elongation at break are maintained by using the polyolefin-based resin even in a state of wet heat aging.
  • the intermediate layer preferably contains a crosslinking agent.
  • the cross-linking agent is used to further increase the adhesion between the ink receiving layer and the support.
  • the cross-linking agent is not particularly limited as long as it causes a cross-linking reaction when forming the intermediate layer, and does not need to remain as a cross-linking agent in the formed intermediate layer.
  • the cross-linking agent increases the number of molecules in the intermediate layer and the number of cross-linking points in the molecule, thereby improving the property of restoring the shape of the intermediate layer, and improving the adhesion of the intermediate layer to the ink receiving layer and the support. Or improve it.
  • an oxazoline compound, a carbodiimide compound, an epoxy compound, an isocyanate compound and a melamine compound are preferable. It may be included.
  • oxazoline compounds and carbodiimide compounds are particularly preferable. Examples of commercially available products include Carbodilite V-02-L2 (Nisshinbo Co., Ltd.) and Epocross K-2020E (Nippon Shokubai Co., Ltd.).
  • the carbodiimide compound and the oxazoline compound the same crosslinking agents as those contained in the ink receiving layer can be used, and preferred ranges thereof are also the same.
  • the addition amount of the crosslinking agent is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 25% by mass. If the addition amount of the cross-linking agent is less than 1% by mass, it may be insufficient to cross-link the polyolefin-based resin. Too much.
  • water-soluble monomers having an epoxy group examples include “Denacol-614B” (sorbitol polyglycidyl ether, epoxy equivalent 173, trade name, manufactured by Nagase ChemteX), “Denacol-EX-313” (glycerol polyglycidyl ether, epoxy Equivalent 141, trade name, manufactured by Nagase ChemteX), “Denacol-EX-521” (polyglycerol polyglycidyl ether, epoxy equivalent 168, trade name, manufactured by Nagase ChemteX), and “Denacol-EX-830” ( Polyethylene glycol diglycidyl ether, epoxy equivalent 268, trade name, manufactured by Nagase ChemteX Corporation).
  • Isocyanate compounds are available, for example, as Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), DP9C214 (Baxenden Co.) and Takenate XWD-HS30 (Mitsui Chemicals Co., Ltd.).
  • melamine compounds examples include becamine PM-N, becamine J-101, and becamine M-3 (manufactured by DIC Corporation).
  • the intermediate layer comprises a surfactant, an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, a water-resistant agent, an antistatic agent, and a crosslinking agent as necessary. Etc. may be included.
  • the catalyst for the crosslinking agent include elastrone catalyst (Daiichi Kogyo Seiyaku Co., Ltd .: trade name Cat64).
  • surfactant those listed as the surfactant for the ink receiving layer can be used, and the preferred range is also the same.
  • an aliphatic wax or the like is preferably used as the slip agent.
  • 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
  • synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax.
  • carnauba wax, paraffin wax and polyethylene wax are particularly preferable.
  • These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle. Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.). Only one type of slipping agent may be used, or two or more types may be combined.
  • organic or inorganic fine particles can be used.
  • polymer fine particles such as polystyrene, polymethyl methacrylate (PMMA), silicone resin and benzoguanamine resin
  • inorganic fine particles such as silica, calcium carbonate, magnesium oxide and magnesium carbonate can be used.
  • preservatives include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, parahydroxybenzoic acid ethyl ester, 1,2-benzothiazolin-3-one, sodium sorbate and sodium pentachlorophenol. It is done.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited as long as it can bond two objects by their pressure-sensitive adhesive action.
  • the adhesive layer those described in JP-A 2010-115818 [0069] to [0074] can be used.
  • the pressure-sensitive adhesive a rubber system, a vinyl polymerization system, a condensation polymerization system, a thermosetting resin system, a silicone system, and the like can be used.
  • rubber-based adhesives include butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), chloroprene polymer and isobutylene-isoprene copolymer. Examples thereof include a polymer system (butyl rubber).
  • Examples of the vinyl polymerization pressure sensitive adhesive include acrylic, styrene, vinyl acetate-ethylene copolymer system, and vinyl chloride-vinyl acetate copolymer system.
  • Examples of the condensation polymerization pressure-sensitive adhesive include polyester.
  • examples of the thermosetting resin-based pressure-sensitive adhesive include epoxy resin-based, urethane resin-based and formalin resin-based adhesives.
  • an acrylic pressure-sensitive adhesive is suitably used in consideration of translucency, weather resistance, heat resistance, wet heat resistance, substrate adhesion, and the like.
  • acrylic pressure-sensitive adhesives include SK Dyne (registered trademark) 1310, 1435, SK Dyne 1811L, SK Dyne 1888, SK Dyne 2094, SK Dyne 2096, SK Dyne 2137, SK Dyne 3096, manufactured by Soken Chemical Co., Ltd.
  • Suitable examples include SK Dyne 1852, manufactured by Toyochem Co., Ltd., BPS5961, BPS4622, BPS4849-40, BPS6130TF, BPS6078TF, EG354J, BPS5296, and BPS5963.
  • the acrylic pressure-sensitive adhesive alone has a low cohesive force, it is preferably crosslinked with a crosslinking agent.
  • a crosslinking agent an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, or the like is preferably used.
  • acrylic pressure-sensitive adhesive examples include a curing accelerator (for example, BXX3778-10, BXX4805, etc., manufactured by Toyochem Co., Ltd.), a curing retarder (for example, BXX5638, manufactured by Toyochem Co., Ltd.), and a curing agent (for example, BXX6269, manufactured by Toyochem Co., Ltd.). ) And other additives (Toyochem Co., Ltd., BXX6342 etc.) are preferably used.
  • the acrylic pressure-sensitive adhesive suitably contains an antioxidant, an ultraviolet absorber, a silane coupling agent, a metal deactivator, etc., in addition to the coloring pigment or coloring dye. It is also preferable to use it.
  • the thickness of the adhesive layer after drying is preferably 1 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m.
  • the recording sheet preferably has a release film on the adhesive layer in consideration of workability.
  • the release film can be peeled from the adhesive layer, and the adhesive layer and glass can be bonded to form a decorative glass.
  • a film in which a release agent such as silicone is coated on a film substrate such as polyester is preferably used.
  • Specific examples of such a release film include “Therapel (registered trademark) WZ, BKE, BX8A” manufactured by Toray Film Processing Co., Ltd.
  • a method for producing a translucent sheet includes a step of discharging an ink composition onto a recording sheet by an ink jet recording apparatus, and a step of irradiating the discharged ink composition with ultraviolet rays to cure the ink composition. It is preferable to include.
  • the method for producing a recording sheet has a step of forming an ink receiving layer on one surface of a transparent support, and the step of forming an ink receiving layer cures a composition containing at least a polymerization initiator and a polymerizable compound.
  • the step is preferably a step of curing a composition containing a polymerizable compound, a polymerization initiator and a surfactant.
  • the step of forming the ink receiving layer will be described.
  • the ink-receiving layer-forming composition is applied on one surface of the transparent support or on the surface of the intermediate layer disposed on one surface of the transparent support, and dried as necessary.
  • the composition can be cured to form an ink receiving layer. If necessary, other processes may be included.
  • Coating can be performed with a blade coater, air knife coater, roll coater, bar coater, gravure coater, reverse coater, or the like. Further, when using a simultaneous multilayer coating method in which a plurality of coating liquids are applied simultaneously without providing a drying step, for example, a slide bead coater, a slide curtain coater, a curtain flow coater, and an extrusion die coater can be used. . Further, for example, the “Wet-On-Wet method” (WOW method) described in paragraph numbers 0016 to 0037 of JP-A-2005-14593 may be used.
  • the coating amount of the composition used for forming the ink receiving layer is preferably 5 to 20 g / m 2 and more preferably 7 to 10 g / m 2 .
  • At least the step of curing the composition is not particularly limited, and may be curing using photopolymerization, curing using thermal polymerization, or curing combining photopolymerization and thermal polymerization. From the viewpoint of achieving both scratch resistance and ink adhesion, curing using photopolymerization is preferred.
  • the polymerization initiator is preferably a photopolymerization initiator
  • the step of curing the composition is preferably a photosensitive curing step of irradiating the composition with ultraviolet rays.
  • the ultraviolet irradiation amount is 10 to 200 mJ / cm 2 , and the curing rate is lowered, leaving a polymerizable group in the polymerizable compound in the ink receiving layer, It is preferable from the viewpoint of good adhesion.
  • more preferably ultraviolet irradiation amount is 30 ⁇ 150mJ / cm 2, particularly preferably 50 ⁇ 100mJ / cm 2.
  • the method for producing the recording sheet is not particularly limited as the step of forming the intermediate layer, and a known method can be used.
  • the step of forming one or two or more intermediate layers by sequentially applying or simultaneously applying one or two or more intermediate layer forming coating solutions on at least one surface of the transparent support and drying. It can produce suitably with the provided manufacturing method, and another process may be provided as needed.
  • an intermediate layer formed between the ink receiving layer and the transparent support and an intermediate layer formed between the adhesive layer and the transparent support may be formed simultaneously. Specifically, it is preferable that a coating solution for forming an intermediate layer is simultaneously coated on both surfaces of the transparent support and dried.
  • the manufacturing method of a recording sheet includes the 1st extending
  • the recording sheet manufacturing method preferably includes a step of applying an intermediate layer forming coating solution on at least one surface of the transparent support film after the first stretching step.
  • a method for producing a recording sheet is obtained by stretching a film for a transparent support after applying a coating solution for forming an intermediate layer in a direction orthogonal to the stretching direction in the first stretching step, and a thickness of 0.1 ⁇ m with the transparent support. It is preferable to include the 2nd extending process which forms less than intermediate
  • the first stretching step is preferably stretching in the film transport direction
  • the second stretching step is preferably stretching in the direction orthogonal to the film transport direction.
  • the stretch ratio in the first stretching step and the second stretching step when forming the intermediate layer A is not particularly limited, and the preferred range of each stretch ratio is the preferred range of the stretch ratio of the transparent support described above. It is the same as the described range.
  • the coating amount of the coating solution used for forming the intermediate layer is preferably 5 to 20 g / m 2 and more preferably 7 to 10 g / m 2 .
  • Step of forming the adhesive layer There is no restriction
  • the method for preparing the coating solution for forming the adhesive layer is not particularly limited, but it may be prepared by mixing the adhesive main agent, solvent, additive, curing accelerator and curing retarder, and then mixing the curing agent. it can.
  • the solid content concentration of the coating solution for forming the adhesive layer is preferably 5 to 40% by mass, and more preferably 10 to 20% by mass.
  • the coating amount of the coating liquid for adhesive layer formation is preferably 5 ⁇ 500g / m 2, more preferably 50 ⁇ 250g / m 2.
  • the pressure-sensitive adhesive layer is preferably applied directly on the transparent support or via another layer and then held in a heated oven to dry the solvent.
  • the drying time is preferably 1 to 10 minutes, for example.
  • the oven temperature is preferably 80 to 140 ° C. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of the adhesive layer start to volatilize.
  • Step of forming a release film There is no restriction
  • the ink composition used in the present invention is not particularly limited as long as it can form an active energy ray-curable ink image portion.
  • the ink composition is preferably an active energy ray curable ink composition.
  • the ink composition is particularly preferably a solventless active energy ray-curable ink composition that does not contain a solvent.
  • the ink includes a non-aqueous ink containing an organic solvent and a solventless ink containing no organic solvent. Since the organic solvent dissolves the resin that forms the ink receiving layer on the recording sheet, the ink easily permeates and ink adhesion is easily obtained. On the other hand, from the viewpoint of eliminating the step of volatilizing the organic solvent and reducing the working environment for handling the organic solvent (volatile organic compounds; VOC), it is preferable to use a solventless active energy ray curable ink. Solventless active energy ray-curable inks do not dissolve the ink-receiving layer, so that the ink is less likely to penetrate. Furthermore, there is a demand for improved adhesion between the active energy ray-curable ink and the recording sheet.
  • the active energy ray is not particularly limited as long as it can impart energy capable of generating a starting species in the ink composition by irradiation, and is widely ⁇ -ray, ⁇ -ray, X-ray, ultraviolet ray, visible. It includes light rays and electron beams. Of these, ultraviolet rays and electron beams are preferred from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferred. Therefore, in the present invention, an ultraviolet curable ink composition is preferred.
  • active energy ray-curable ink composition for example, descriptions in JP 2010-47015 A and JP 5-214280 A can be referred to, and the contents of these gazettes are incorporated in this specification.
  • solventless active energy ray-curable ink composition for example, descriptions in JP-A-2004-131725 and JP-A-2009-299057 can be referred to, and the contents of these publications are incorporated in this specification. It is.
  • the method for producing a translucent sheet of the present invention includes the above-described steps, whereby an ink image portion is formed by the ink composition cured on the recording sheet, and the translucent sheet is formed as shown in FIG. Is done.
  • the ink jet system that discharges an ink composition in droplets from an ink discharge port is used in many printers because it is small and inexpensive, and can form an image without contact with a recording sheet.
  • a piezoelectric ink jet method that ejects ink using deformation of a piezoelectric element, and a thermal ink jet method that ejects droplets of an ink composition using a boiling phenomenon of an ink composition that uses thermal energy are: Excellent high resolution and high speed printability.
  • 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 active energy ray source.
  • an apparatus including an ink supply system, a temperature sensor, and an active energy ray source for examples of the ink jet recording apparatus and ink discharge conditions, the descriptions in [0110] to [0112] of JP-A-2015-163457 can be referred to. The contents of this publication are incorporated herein.
  • the ink composition discharged onto the recording sheet is cured by irradiating with active energy rays. This is because the radical polymerization initiator contained in the ink composition is decomposed by irradiation with active energy rays to generate radicals, and the polymerization reaction of the radical polymerizable compound is caused and accelerated by the radicals.
  • the sensitizer in the system absorbs the active energy ray to be in an excited state and comes into contact with the radical polymerization initiator, thereby causing the radical polymerization initiator.
  • Decomposition can be promoted, and a more sensitive curing reaction can be achieved.
  • the peak wavelength of the active energy ray used depends on the absorption characteristics of the polymerization initiator or sensitizer, but is preferably, for example, 200 to 600 nm, more preferably 300 to 450 nm, More preferably, it is 350 to 420 nm.
  • the ink composition has sufficient sensitivity even with a low output active energy ray. Therefore, it is appropriate that the exposure surface illuminance is preferably 10 to 4,000 mW / cm 2 , more preferably 20 to 2,500 mW / cm 2 .
  • the curing condition is not particularly limited as long as it is an exposure amount for curing the ink.
  • it is preferably 10 to 500 mJ / cm 2 , more preferably 20 to 400 mJ / cm 2 , and 50 to 200 mJ / cm 2. It is particularly preferred that By setting the curing condition to be equal to or lower than the upper limit value of the above preferable range, yellowness can be suppressed.
  • the curing condition By setting the curing condition to be equal to or higher than the lower limit of the above-mentioned preferable range, the ink receiving layer can be easily cured, and scratch resistance and ink adhesion can be improved.
  • mercury lamps, gas or solid lasers are mainly used, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording inks. ing.
  • mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally.
  • LEDs (particularly UV-LEDs) and LDs (particularly UV-LDs) are small, have a long life, have high efficiency and are low in cost, and are expected as light sources for photocurable ink jet recording.
  • a light emitting diode (LED) and a laser diode (LD) can be used as an active energy ray source.
  • an ultraviolet LED and an ultraviolet LD can be used.
  • Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm.
  • US Pat. No. 6,084,250 discloses an LED that can emit active energy rays centered between 300 nm and 370 nm.
  • Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands.
  • a particularly preferred active energy ray source in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength in the range of 350 to 420 nm.
  • maximum illumination intensity of the LED is 10 ⁇ 2,000mW / cm 2, more preferably 20 ⁇ 1,000mW / cm 2, particularly preferably 50 ⁇ 800mW / cm 2.
  • this active energy ray preferably for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds.
  • the irradiation conditions of active energy rays and the basic irradiation method are disclosed in JP-A-60-132767.
  • the light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method.
  • the active energy ray is irradiated for a certain period of time after ink landing (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, still more preferably 0.01 to 0.15 seconds). Will be done.
  • the ink jet recording apparatus using the ink jet recording apparatus preferably uses a wide format ink jet printer system, and preferably uses a wide format UV ink jet printer system that performs UV irradiation immediately after ink landing.
  • the wide format ink jet printer system is suitable for printing large-format advertisements such as decorative glass in which printed matter obtained by printing characters and patterns on a window decoration recording sheet is attached to glass such as a show window and an automatic door.
  • the wide format inkjet printer system is a system that cures the ejected ink composition by irradiating active energy rays almost simultaneously with the ejection of the ink composition from the inkjet recording apparatus. Can be produced.
  • Wide format printers are generally defined as printers capable of printing 24 inches (61 cm; 1 inch is 2.54 cm) wide or larger. Printers with a width of 44 inches (111.7 cm) to 64 inches (162.5 cm) are the mainstream, but some can print up to a width of 197 inches (500 cm).
  • Wide format UV inkjet printer systems include LuxJet UV360GTW / XTW and UV550GTW / XTW series, Accuity LED 1600 (both manufactured by Fujifilm Corporation), and inca SP320 / SP320e / SP320S / SP320W (manufactured by Inca Digital Printers). Can be used.
  • an ink set containing an ink composition of clear ink can be suitably used.
  • seat of this invention may have the ink image part containing the ink of another color other than the ink image part containing clear ink.
  • an ink image portion containing inks of other colors reference can be made to the description in [0119] of JP-A-2015-163457. The contents of this publication are incorporated herein.
  • the translucent sheet of the present invention is preferably used for glass decoration, and more preferably used for blinding decoration of indoor glass.
  • Decorative glass has glass and the translucent sheet
  • the configuration of the decorative glass will be described based on the drawings.
  • the decorative glass 30 is formed with the glass 21 and the translucent sheet 20 of the present invention located on the glass 21, and has an example shown in FIG. 5.
  • the decorative glass is excellent in ink adhesion, has good scratch resistance of the ink receiving layer 2 in the ink image portion 11 and the non-image portion, and becomes a high-quality decorative glass.
  • the image part is made into the opposite side to glass, and an adhesion layer and glass are bonded together.
  • an adhesion layer and glass are bonded together.
  • dirt cannot be removed it is preferable to wipe off with an alcohol sanitary wiper.
  • the image area is vented with a cleaning roller or a cleaning wiper. Examples of how the decorative glass is used include a show window, an automatic door, and a glass shade.
  • Example 1 ⁇ Transparent support> As a transparent support, Toyobo Co., Ltd. Cosmo Shine A4300-50 (described as A4300 in the following table, having an easy-adhesion layer as an intermediate layer on both sides) was used.
  • the transmittance at a wavelength of 550 nm of the transparent support used in each example was measured by the following method. As a result, the transmittance at a wavelength of 550 nm of the transparent support used in each Example was 80% or more and was transparent.
  • the transmittance at a wavelength of 550 nm of the transparent support is a value measured according to the method described in JIS A5759 using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
  • the haze value of the transparent support used in each example was measured by the following method in accordance with JIS K 7136. The results obtained are listed in the table below.
  • the total light transmittance and the diffuse transmittance were measured for the test pieces of each Example and Comparative Example according to the method for obtaining haze specified by JIS K 7136, and the haze value was calculated.
  • the composition G-1 prepared with the following composition was coated on one easy-adhesion layer of the transparent support with a bar coater and dried at 90 ° C. for 20 seconds. Thereafter, using a 160 W / cm air-cooled metal halide lamp (manufactured by Igrafx Co., Ltd.) under a nitrogen purge, the coating layer is cured by irradiating 77 mJ / cm 2 of ultraviolet rays to form an ink receiving layer. A laminate in which an intermediate layer, a transparent support, an intermediate layer, and an ink receiving layer were provided in this order was formed. In this case, the ink receiving layer after drying was applied so that the thickness thereof was 5 ⁇ m.
  • composition of Composition G-1 Polymerizable compound: acrylic monomer 299.62 parts by mass (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) Polymerizable compound: Acrylic monomer 179.73 parts by mass (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 1 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant (GF-1) 0.121 parts by mass Solvent 347.29 parts by mass (Mitsui Chemical Co., Ltd., methyl isobutyl ketone) tyl ketone (MIBK) solvent) 148.85 parts by mass of solvent (manufactured by Tonen Petroleum, methyl e
  • the above-described first polymerizable compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) and the above-described second polymerizable compound (Osaka Organic Chemical Industry) used in Composition G-1
  • a combination of KK Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) is described in the table below as “acrylic monomer system 1”.
  • the fluorosurfactant GF-1 used and the fluorosurfactants GF-2 and GF-3 described later are fluorosurfactants shown in the following table.
  • the subscript of each monomer unit represents the molar ratio (%) of the monomer unit.
  • the glass transition temperature of the surfactant was measured by using X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd. as a differential scanning calorimeter, putting 5.0 mg of the sample in a simple sealed container, and heating rate of 10 ° C. in a nitrogen atmosphere. This is a value obtained by reading the temperature at which the base line of the obtained DSC curve intersects with the tangent at the inflection point.
  • the weight average molecular weight (Mw) of the surfactant is a value measured by the following method. It is the value measured as a polymethylmethacrylate (PMMA) conversion value using gel permeation chromatography (GPC).
  • the calibration curves are “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500”, “A-1000” and “n-propyl”. It was prepared from 8 samples of “benzene”.
  • the measurement conditions are as follows. ⁇ Conditions> ⁇ GPC: HLC-8220 GPC [manufactured by Tosoh Corporation] Column: TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL SuperHZ2000 (all manufactured by Tosoh Corporation) ⁇ Mobile phase solvent: Hexafluoroisopropanol ⁇ Standard sample: Polymethyl methacrylate (PMMA) Sample concentration: 0.45% by mass ⁇ Flow rate: 0.35 ml / min ⁇ Column temperature: 40 ° C. Sample injection volume: 10 ⁇ l ⁇ Uses a differential refractometer (RI) detector
  • the coating liquid H-1 for forming the adhesive layer was applied on the intermediate layer opposite to the ink receiving layer by the wire bar coating method, and dried in an oven at 100 ° C. for 2 minutes to form an adhesive layer.
  • the following coating solution H-1 having a solid content concentration of about 15% is applied by selecting an appropriate bar coater so that the thickness after drying is about 25 ⁇ m, and the adhesive layer, intermediate layer, transparent support, intermediate layer and ink A laminate provided in the order of the receiving layer was formed.
  • Coating solution H-1 was prepared by the following method.
  • Main agent (Toyochem Co., Ltd., BPS6078TF) 100.0 parts by mass, solvent (ethyl acetate) 200.0 parts by mass, curing accelerator (Toyochem Co., Ltd., BXX3778-10) 0.1 parts by mass and curing retarder (Toyochem) Co., Ltd., BXX5638) 1.0 part by mass was mixed for 30 minutes. Thereafter, 5.0 parts by mass of a curing agent (BXX6269, manufactured by Toyochem Co., Ltd.) was further added and mixed for 30 minutes to obtain a coating solution H-1.
  • a curing agent (BXX6269, manufactured by Toyochem Co., Ltd.) was further added and mixed for 30 minutes to obtain a coating solution H-1.
  • a 38 ⁇ m-thick release film (Toray Film Processing Co., Ltd., Therapy BKE) was laminated on the adhesive layer. As a lamination method, it bonded together by crimping
  • ⁇ Ink-receiving layer thickness> In the recording sheet before printing the ink image portion, a microtome (Leica RM2255) was used to perform cross-section cutting. The thickness of the ink receiving layer of each sample was measured by observing the obtained cross section with a scanning electron microscope (S-4700, manufactured by HITACHI).
  • a solventless active energy ray-curable clear ink manufactured by Fuji Film Co., Ltd., product name: LL391, described as clear ink A in the following table
  • As a printing machine “wide format UV inkjet press LuxelJet UV550GTW, manufactured by FUJIFILM Corporation” was used.
  • a roll-to-roll fine art mode wavelength 365 to 405 nm, printing speed 22 m 2 / hour
  • an ink image portion is formed by printing a clear ink image on the ink receiving layer, and approximately 1.5 m width ⁇ 1
  • a translucent sheet of Example 1 having a size of 5 m was obtained.
  • the thickness of the ink image portion after drying was 3 ⁇ m.
  • the obtained translucent sheet had an ink image part in a part of the surface and a non-image part (a part where the ink receiving layer was exposed) in the other part of the surface.
  • the obtained ink image portion contained irregularities due to ink jet droplets on the surface.
  • the presence or absence of irregularities on the surface of the ink image portion due to ink jet droplets was evaluated according to the following criteria. Existence: The surface of the ink image portion has irregularities where the difference between the maximum height of the surface of the ink image portion and the minimum height of the surface of the ink image portion is 0.01 ⁇ m or more.
  • the surface of the ink image part has a difference between the maximum height of the surface of the ink image part and the minimum height of the surface of the ink image part of less than 0.01 ⁇ m.
  • Inkjet droplets were set to a printer-set ink density of 70% and the setting was “Mat 1”.
  • the haze value at various points in the plane of the ink image portion was measured by the following method in accordance with JIS K 7136. Based on JIS K 7136, the haze value was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The maximum value of the haze value in the surface of the ink image portion formed in each example was used as the haze value of the ink image portion. The results obtained are listed in the table below.
  • Example 2 In Example 1, instead of Cosmoshine A4300-50, PET1 produced by the following method was used, except that the ink receiving layer and the adhesive layer were directly provided on the transparent support without an intermediate layer. 1 was obtained in the same manner as in Example 1.
  • a polyethylene terephthalate (hereinafter referred to as PET) resin having an intrinsic viscosity of 0.64 polycondensed using a Ti compound as a catalyst is dried to a moisture content of 50 ppm (parts per million) or less, and a heater temperature of 270 to 300 ° C. is set. It was melted in the extruder. The melted PET was extruded from a die part onto a chill roll electrostatically applied to obtain a band-shaped amorphous base. The obtained amorphous base was stretched 3.3 times in the longitudinal direction, and then stretched 3.8 times in the width direction to obtain a transparent support having a thickness of 50 ⁇ m. The obtained transparent support was designated as PET1.
  • Example 3 A translucent sheet of Example 3 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-2 in forming the ink receiving layer G of Example 2. .
  • the composition of the composition G-2 is as follows. (Composition G-2) 299.62 parts by mass of polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 177.73 parts by mass of polymerizable compound monomer (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.181 parts by mass Solvent 347.29 parts by mass (Mitsui Chemical
  • Example 4 A translucent sheet of Example 4 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-4 in forming the ink receiving layer G of Example 2. .
  • the composition of the composition G-4 is as follows. (Composition of Composition G-4) Polymerizable compound: acrylic monomer 299.62 parts by mass (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) Polymerizable compound: Acrylic monomer 179.73 parts by mass (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.060 parts by mass Solvent 347.29 parts by mass (
  • Example 5 A translucent sheet of Example 5 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-9 in forming the ink-receiving layer G of Example 2. .
  • the composition of the composition G-9 is as follows.
  • composition of Composition G-9) Polymerizable compound: acrylic monomer 299.62 parts by mass (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) Polymerizable compound: Acrylic monomer 179.73 parts by mass (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.030 parts by mass Solvent 347.29 parts by mass (Mitsui Chemicals, Inc., methyl isobutyl ketone (MIBK) solvent) Solvent 147.45 parts by mass (made by Tonen Petroleum, methyl ethyl ketone (MEK))
  • Example 6 A translucent sheet of Example 6 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-12 in the formation of the ink receiving layer G of Example 2. .
  • the composition of the composition G-12 is as follows.
  • Polymerizable compound acrylic monomer 299.62 parts by mass (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate)
  • Polymerizable compound Acrylic monomer 179.73 parts by mass (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB)
  • Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.242 parts by mass Solvent 347.29 parts by mass
  • Example 7 A translucent sheet of Example 7 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-5 in the formation of the ink receiving layer G of Example 2. .
  • the composition of the composition G-5 is as follows. (Composition G-5) 299.62 parts by mass of polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 177.73 parts by mass of polymerizable compound monomer (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-2 0.069 parts by mass Solvent 347.29 parts by mass (Mitsui
  • Example 8 A translucent sheet of Example 8 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-6 in forming the ink-receiving layer G of Example 2. .
  • the composition of the composition G-6 is as follows.
  • composition G-6 299.62 parts by mass of polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 177.73 parts by mass of polymerizable compound monomer (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-3 0.069 parts by mass Solvent 347.29 parts by mass (Mitsui Chemicals, Inc., methyl isobutyl ketone (MIBK) solvent) 148.85 parts by mass of solvent (manufactured by Tonen Petroleum, methyl ethyl ketone (MEK))
  • Example 9 A translucent sheet of Example 9 was obtained in the same manner as in Example 2 except that the thickness of the ink receiving layer after drying was changed from 5 ⁇ m to 3 ⁇ m in the formation of the ink receiving layer G of Example 2.
  • Example 10 A translucent sheet of Example 10 was obtained in the same manner as in Example 2 except that the amount of ultraviolet irradiation was changed from 77 mJ / cm 2 to 148 mJ / cm 2 in the formation of the ink receiving layer of Example 2.
  • Example 11 A translucent sheet of Example 11 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-8 in the formation of the ink receiving layer G of Example 2. .
  • the composition of the composition G-8 is as follows. (Composition G-8) 299.62 parts by mass of polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 177.73 parts by mass of polymerizable compound monomer (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) 0.403 parts by mass of a fluorosurfactant (manufactured by DIC Corporation, MegaFuck
  • Example 12 A translucent sheet of Example 12 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-10 in forming the ink receiving layer G of Example 2. .
  • the composition of the composition G-10 is as follows. (Composition G-10) 299.62 parts by mass of polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 177.73 parts by mass of polymerizable compound monomer (Osaka Organic Chemical Industry Co., Ltd., Biscoat V360, trimethylolpropane EO-modified triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 3.2 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.121 parts by mass Solvent 347.29 parts by mass (Mitsui Chemicals
  • Example 13 In the formation of the transparent support PET1 of Example 2, a transparent support PET2 formed so that the thickness after stretching was 150 ⁇ m was formed. A translucent sheet of Example 13 was obtained in the same manner as Example 2 except that the transparent support was changed from PET1 to PET2.
  • PET resin having an inherent viscosity of 0.64 polycondensed using a Ti compound as a catalyst is dried to a moisture content of 50 ppm or less and melted in an extruder with a heater temperature of 270 to 300 ° C. It was. The melted PET was extruded from a die part onto a chill roll electrostatically applied to obtain a band-shaped amorphous base. The obtained amorphous base was stretched 3.3 times in the longitudinal direction, and then subjected to corona discharge treatment in air, and the following coating solution A-1 was applied to both surfaces by the bar coating method.
  • PET polyethylene terephthalate
  • the coated uniaxially stretched film is guided to a preheating zone while being gripped with a clip, dried at 90 ° C., continuously stretched 3.8 times in the width direction in a heating zone at 100 ° C., and further 215 ° C. Heat treatment was applied in the heating zone.
  • a transparent support PET1 having a thickness of 50 ⁇ m and a laminate in which the intermediate layers A and D were disposed on both sides of the PET1 were obtained.
  • the coating thickness after drying of the intermediate layers A and D formed by drying the coating solution A-1 was 0.04 ⁇ m.
  • Coating fluid A-1 used in this example was prepared according to the following method. 95 parts of dimethyl terephthalate, 95 parts of dimethyl isophthalate, 35 parts of ethylene glycol, 145 parts of neopentyl glycol, 0.1 part of zinc acetate and 0.1 part of antimony trioxide are charged into a reaction vessel, and the ester is added at 180 ° C. over 3 hours. An exchange reaction was performed. Next, 6.0 parts of 5-sodium sulfoisophthalic acid was added and the esterification reaction was carried out at 240 ° C. over 1 hour, followed by heavy polymerization over 2 hours at 250 ° C. under reduced pressure (10 to 0.2 mmHg).
  • a condensation reaction was performed to obtain a copolyester resin having a molecular weight of 19,500 and a softening point of 60 ° C. 67 parts of a 30% by mass aqueous dispersion of the obtained copolyester resin (A), a 20% by mass aqueous solution of a self-crosslinking polyurethane resin (B) containing an isocyanate group blocked with sodium bisulfite (first) Kogyo Seiyaku Co., Ltd .: Trade name Elastron H-3) 40 parts, Elastron catalyst (Daiichi Kogyo Seiyaku Co., Ltd .: trade name Cat 64) 0.5 parts, water 478 parts and isopropyl alcohol 5 parts mixed.
  • both surfaces were subjected to corona discharge treatment under the condition of 955 J / m 2 .
  • the following coating solution B-5 was applied on both sides by the bar coating method. And this was dried at 145 degreeC for 1 minute, and the laminated body by which the intermediate
  • the coating thickness after drying of the intermediate layer B and the intermediate layer E was 0.5 ⁇ m.
  • the composition of the coating liquid B-5 is as follows.
  • An ink receiving layer G was formed on the obtained intermediate layer B in the same manner as in Example 1, and an adhesive layer H was formed on the obtained intermediate layer E in the same manner as in Example 1 to obtain A release film was formed on the adhesive layer H in the same manner as in Example 1 to obtain a recording sheet.
  • the obtained recording sheet comprises a release film, an adhesive layer H, an intermediate layer E (formed from coating solution B-5), an intermediate layer D (formed from coating solution A-1), a transparent support, and an intermediate layer A (coated solution).
  • the laminate was formed in the order of the intermediate layer B (formed from the coating liquid B-5) and the ink receiving layer G. Then, the translucent sheet
  • Example 15 The transparent support PET-1 formed in Example 2 was conveyed at a conveyance speed of 105 m / min, and both surfaces were subjected to corona discharge treatment under the condition of 955 J / m 2. To both sides. And this was dried at 145 degreeC for 1 minute, and also the corona discharge process was further performed on both surfaces on the conditions of 288 J / m ⁇ 2 >. Thereafter, the coating liquid C-1 was applied to both surfaces by a bar coating method. Then, this is dried at 145 ° C. for 1 minute, and is formed by drying the intermediate layers B and E formed by drying the coating liquid B-1 and the coating liquid C-1 on both surfaces of the transparent support.
  • a laminated body was obtained in which the intermediate layers C and F were provided in the order of the intermediate layer F, the intermediate layer E, the transparent support, the intermediate layer B, and the intermediate layer C.
  • the coating thicknesses after drying of the intermediate layers B and E and the intermediate layers C and F were each 0.3 ⁇ m.
  • composition of the coating liquid B-1 is as follows.
  • (Coating fluid B-1) Acrylic acid ester copolymer 31.1 parts by mass (manufactured by Toagosei Chemical Co., Ltd. Jurimer ET-410 solid content 30% by mass) 108.8 parts by mass of polyolefin (produced by Unitika Ltd.
  • the composition of the coating liquid C-1 is as follows.
  • (Coating liquid C-1) Polyester resin aqueous solution 51.2 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z687 solid content 25% by mass) 33.7 parts by mass of polyurethane resin aqueous dispersion (Orestar UD350, solid content 38% by mass, manufactured by Mitsui Chemicals, Inc.)
  • Cross-linking agent (carbodiimide compound) 13.9 parts by mass (Nisshinbo Co., Ltd.
  • An ink receiving layer G was formed on the obtained intermediate layer C in the same manner as in Example 1, and an adhesive layer H was formed on the obtained intermediate layer F in the same manner as in Example 1 to obtain.
  • a release film was formed on the adhesive layer H in the same manner as in Example 1 to obtain a recording sheet.
  • the obtained recording sheet comprises a release film, an adhesive layer H, an intermediate layer F (formed from the coating liquid C-1), an intermediate layer E (formed from the coating liquid B-1), a transparent support, and an intermediate layer B (coated liquid).
  • B-1), intermediate layer C (formed from coating liquid C-1) and ink receiving layer G were provided in this order. Then, the translucent sheet
  • Example 16 A light-transmitting sheet of Example 16 was obtained in the same manner as in Example 14 except that the composition G-1 used in the formation of the ink-receiving layer G of Example 14 was changed to the above-described composition G-5. .
  • Example 17 A light-transmitting sheet of Example 17 was obtained in the same manner as in Example 15 except that the composition G-1 used in the formation of the ink receiving layer G of Example 15 was changed to the above-described composition G-5. .
  • Example 18 A translucent sheet of Example 18 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-11 in forming the ink receiving layer G of Example 2. .
  • the composition of the composition G-11 is as follows. (Composition G-11) 479.35 parts by mass of a polymerizable compound monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD PET-30, pentaerythritol triacrylate) 7.35 parts by mass of cellulose acetate butyrate (manufactured by Eastman Chemical Japan, CAB) Photopolymerization initiator 16.60 parts by mass (manufactured by BASF, IRGACURE-127) Fluorosurfactant GF-1 0.121 parts by mass Solvent 347.29 parts by mass (Mitsui Chemicals, Inc., methyl isobutyl ketone (MIBK) solvent) 148.85 parts by mass of solvent (manufactured by Tonen Petroleum, methyl eth
  • Example 19 In the printing of the ink image portion of Example 2, the light-transmitting sheet of Example 19 is the same as Example 2 except that the ink jet droplets are changed from the printer setting ink density of 70% to the printer setting ink density of 30%. Got.
  • Example 20 In the printing of the ink image portion of Example 2, the light-transmitting sheet of Example 20 is the same as Example 2 except that the ink jet droplets are changed from the printer setting ink density of 70% to the printer setting ink density of 100%. Got.
  • Example 21 In printing the ink image part of Example 2, from clear ink A to solvent-free active energy ray-curable clear ink (manufactured by Fuji Film Co., Ltd., product name: UVIJET ACUITY KN391, described in the table below as clear ink B) A translucent sheet of Example 21 was obtained in the same manner as in Example 2 except that the change was made.
  • Example 22 In printing the ink image part of Example 2, from clear ink A to solventless active energy ray-curable clear ink (Dai Nippon Printing Co., Ltd., product name: Truepress Ink HardLED Clear, the following table shows clear ink C and A translucent sheet of Example 22 was obtained in the same manner as in Example 2 except that the description was changed to “Description”.
  • Example 23 In printing the ink image portion of Example 2, from clear ink A to solvent-free active energy ray-curable clear ink (Mimaki Engineering Co., Ltd., product name: Uwin Clear Liquid SPC-0371CL, the following table shows clear ink D
  • the light-transmitting sheet of Example 23 was obtained in the same manner as in Example 2 except that it was changed to
  • Example 24 In the printing of the ink image portion of Example 2, the translucent sheet of Example 24 was obtained in the same manner as Example 2 except that the ink jet droplets were changed from the setting “Matte 1” to the setting “Matte 2”. It was.
  • Example 25 In the printing of the ink image portion of Example 24, the light-transmitting sheet of Example 25 was obtained in the same manner as in Example 24 except that the ink jet droplets were changed from the printer ink density 70% to the printer ink density 100%. Got.
  • Example 26 In the printing of the ink image portion of Example 2, the light-transmitting sheet of Example 24 was obtained in the same manner as in Example 2 except that the ink jet droplet was changed from the setting “Matte 1” to the setting “Glossy”. .
  • Example 27 In the printing of the ink image portion of Example 26, the translucent sheet of Example 27 was used in the same manner as in Example 26 except that the ink jet droplets were changed from the printer ink density 70% to the printer ink density 100%. Got.
  • Example 1 The transparent support PET-1 formed in Example 2 was conveyed at a conveyance speed of 105 m / min, and both surfaces were subjected to corona discharge treatment under the condition of 955 J / m 2 , and then the coating liquid B-1 described above was applied to the bar coating method. To both sides. Then, this was dried at 145 ° C. for 1 minute, and the intermediate layers B and E formed by drying the coating liquid B-1 on both surfaces of the transparent support were formed from the intermediate layer E (coating liquid B-1). ), A transparent support, and an intermediate layer B (formed from coating solution B-1) were provided in this order. The coating thicknesses after drying of the intermediate layers B and E were each 0.3 ⁇ m.
  • Comparative Example 2 A translucent sheet of Comparative Example 2 was obtained in the same manner as in Example 2 except that the composition G-1 was changed to the following composition G-18 in forming the ink receiving layer G of Example 2. .
  • the translucent sheet of Comparative Example 2 did not have an ink image area because the ink image area was not fixed on the ink receiving layer G, and did not form a translucent sheet body.
  • the composition of the composition G-18 is as follows.
  • composition G-18 Acetic acid aqueous solution: 402.0 parts by mass (1% by mass aqueous solution of industrial acetic acid, manufactured by Daicel Corporation) 3-glycidoxypropyltriethoxysilane: 110.0 parts by mass (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) Tetraethoxysilane: 127.6 parts by mass (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.) Curing agent: 1.3 parts by mass (aluminum chelate A (W), manufactured by Kawasaki Fine Chemical Co., Ltd.) Surfactant C: 14.7 parts by mass (10% by mass aqueous solution, anionic) of Sanded BL (manufactured by Sanyo Chemical Industries, Ltd.) Surfactant A: 40.9 parts by mass (Naroacty CL-95 (Sanyo Chemical Industries Co., Ltd.
  • composition G-18 1% by weight aqueous solution, nonionic) Distilled water: ⁇ part by mass ( ⁇ : the amount was adjusted so that the whole composition G-18 was 1,000 parts by mass)
  • the polymerizable compound monomers used in Composition G-18 are listed in the table below as “silanol monomers”.
  • Surfactants A and C used in Composition G-18 were 1% by weight aqueous solution of Naroacty CL-95 (Sanyo Chemical Industries, Ltd.) and 10% by weight of Sanded BL (manufactured by Sanyo Chemical Industries, Ltd.), respectively. It is an aqueous solution. Since Tg is a non-fluorinated surfactant, both surfactants A and C were omitted from the measurement.
  • Example 3 In Example 2, the transparent support was changed from PET1 to Lincool Co., Ltd., Lumicool 1301 (described as Lumicool in the table below), and the ink image portion was printed on Lumicool 1301 instead of on the ink receiving layer.
  • a translucent sheet of Comparative Example 3 was obtained in the same manner as in Example 2 except that this was performed. However, the translucent sheet of Comparative Example 3 did not have an ink image portion because the ink image portion was not fixed, and thus did not have a body of the translucent sheet.
  • Comparative Example 4 A translucent sheet of Comparative Example 4 was obtained in the same manner as in Comparative Example 3, except that the clear ink A was changed to the above-described clear ink B in printing the ink image portion of Comparative Example 3. However, the translucent sheet of Comparative Example 4 did not have an ink image area because the ink image area was not fixed, and thus did not have a body of translucent sheet.
  • Comparative Example 5 In printing the ink image portion of Example 2, from clear ink A, solvent-free active energy ray-curable white ink (manufactured by Fujifilm Corporation, product name: UVIJET KO 021 / White, The light-transmitting sheet of Comparative Example 5 was obtained in the same manner as in Example 2 except that the description was changed to “Description”.
  • Comparative Example 6 In the printing of the ink image portion of Comparative Example 5, the light-transmitting sheet of Comparative Example 6 was the same as Comparative Example 5 except that the ink jet droplets were changed from the printer set ink density of 70% to the printer set ink density of 40%. Got.
  • the surface of the ink receiving layer (non-image portion) of the translucent sheet of each Example and Comparative Example and the surface of the ink image portion was 500 g.
  • scratching was repeated five times with a pencil of each hardness to obtain the hardest pencil scale without any scars.
  • the surface of the ink image portion and the surface of the ink receiving layer (non-image portion) are both pencil hardness H or higher. Is preferable, and 2H or more is more preferable.
  • the pencil hardness of the surface of the ink receiving layer is determined by removing the ink image portion from the translucent sheet. Find the pencil hardness.
  • ⁇ Translucency> Using a spectrophotometer V-560 (manufactured by JASCO Corporation) with an integrating sphere attachment device ARV-474 attached, the transmissivity of the translucent sheet with respect to 550 nm light was measured. The measurement was performed under conditions where light was incident from the side opposite to the side having the white layer of the resin base material. As measurement conditions, the measurement was performed in the transmittance measurement mode in the spectrophotometer described above, and air was used as a blank measurement (baseline). The measurement was performed at a measurement wavelength of 550 nm, a bandwidth of 5 nm, and a response medium.
  • the transmittance a simple average value obtained by measuring the transmittance data obtained in the target wavelength band five times and dividing by the number of data is adopted. The following five steps were evaluated as follows.
  • D The transmittance at 550 nm is 60% or more and less than 75%.
  • E Transmittance at 550 nm is less than 60%.
  • the A, B, and C evaluations are acceptable levels on the product, and the D and E evaluations are unacceptable levels.
  • a or B evaluation is preferable, and A evaluation is more preferable.
  • the blinding property of the translucent sheet of each example and comparative example was evaluated as a difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet.
  • the haze value of each part in the surface of a non-image part (place where an ink image part does not exist) in the surface of the translucent sheet was measured by the following method.
  • the total light transmittance and the diffuse transmittance were measured for the test pieces of each Example and Comparative Example according to the method for obtaining haze specified by JIS K 7136, and the haze value was calculated.
  • the minimum value of the haze value in the surface of the non-image part of the translucent sheet of each example was defined as the minimum value of the haze value of the translucent sheet.
  • the haze value of the ink image portion measured in each example was set as the maximum value of the haze value of the translucent sheet.
  • the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet was calculated. The results were evaluated as follows in the following five stages. A: When the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet is 15% or more.
  • B When the difference between the maximum value and the minimum value of the haze value in the surface of the translucent sheet is 8% or more and less than 15%.
  • C When the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet is 3% or more and less than 8%.
  • D When the difference between the maximum value and the minimum value of the in-plane haze value of the translucent sheet is less than 3%.
  • E Ink image area is not fixed and measurement is not possible. The A, B, and C evaluations are acceptable levels on the product, and the D and E evaluations are unacceptable levels. A or B evaluation is preferable, and A evaluation is more preferable.
  • Ink adhesion was evaluated in the following five stages as follows. A: When the number of peeled lattices is zero. B: When the number of peeled lattices is 1 or more and less than 5. C: When the number of peeled lattices is 5 or more and less than 15. D: When the number of peeled lattices is 15 or more. E: Ink image area is not fixed and measurement is not possible. The A, B, and C evaluations are acceptable levels on the product, and the D and E evaluations are unacceptable levels. A or B evaluation is preferable, and A evaluation is more preferable.
  • yellowishness was calculated
  • seat obtained by each Example and the comparative example was set
  • the translucent sheet of the present invention had good scratch resistance, translucency and blinding.
  • ink adhesiveness and yellowishness were also made favorable. It was found that the translucent sheets of Comparative Examples 1 and 2 in which the ink image portion was not fixed and the translucent sheet was not formed were poor in blinding.
  • ⁇ Formation of decorative glass> As an example, commercially available glass (Corning Eagle XG glass, thickness 1.1 mm) was prepared, and dust and dirt on the surface were removed with a cleaning roller or a cleaning wiper. If the dirt could not be removed, it was wiped with an alcohol sanitary wiper. The dust and dirt on the opposite side of the ink image portion of the translucent sheets of Examples 1 to 27 were removed with a cleaning roller or a cleaning wiper. The release film was peeled from the translucent sheets of Examples 1 to 27, and then the adhesive layer and the glass were bonded together with the ink image portion on the side opposite to the glass, and an 18 mm width tape was applied. The ink image part was deaerated with a cleaning roller or a cleaning wiper to obtain a decorative glass. The obtained decorative glass had good scratch resistance, translucency and blinding.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille translucide comprenant : un support transparent qui est un film de résine thermoplastique ayant une valeur de trouble de 10 % ou moins telle que mesurée conformément à la norme JIS K 7136 ; une couche de réception d'encre qui est disposée dans un côté de surface du support transparent et présente une dureté au crayon de H ou plus telle que mesurée conformément à la norme JIS K 5600-5-4 ; et une partie d'image d'encre qui présente une valeur de trouble, telle que mesurée conformément à la norme JIS K 7136, supérieure à la valeur de trouble du support transparent et qui est durcissable par rayonnement d'énergie active, la partie d'image d'encre comprenant une encre claire et des saillies et des évidements étant formés sur la surface de la partie d'image d'encre. La feuille translucide selon l'invention est fortement résistante aux rayures, présente une translucidité élevée et un excellent effet de bandeau. L'invention concerne également un verre décoratif.
PCT/JP2017/010649 2016-03-31 2017-03-16 Feuille translucide et verre décoratif WO2017169844A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018509018A JP6655168B2 (ja) 2016-03-31 2017-03-16 透光性シートおよび装飾ガラス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-071228 2016-03-31
JP2016071228 2016-03-31

Publications (1)

Publication Number Publication Date
WO2017169844A1 true WO2017169844A1 (fr) 2017-10-05

Family

ID=59964387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/010649 WO2017169844A1 (fr) 2016-03-31 2017-03-16 Feuille translucide et verre décoratif

Country Status (2)

Country Link
JP (1) JP6655168B2 (fr)
WO (1) WO2017169844A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020015846A (ja) * 2018-07-26 2020-01-30 株式会社リコー 印刷物、貼付け用印刷物、及び印刷物の製造方法
WO2020218270A1 (fr) * 2019-04-26 2020-10-29 花王株式会社 Liquide de traitement
WO2022149242A1 (fr) * 2021-01-07 2022-07-14 リンテック株式会社 Feuille pour impression à jet d'encre

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030016280A1 (en) * 2001-06-14 2003-01-23 Xing-Ya Li Ink-receptive composition
JP2011505283A (ja) * 2007-12-04 2011-02-24 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 印刷方法
WO2011122123A1 (fr) * 2010-03-31 2011-10-06 大日本スクリーン製造株式会社 Imprimante à jet d'encre et support imprimé
JP2012232470A (ja) * 2011-04-28 2012-11-29 Seiko Epson Corp 液体噴出装置及び液体噴出方法
JP2014071354A (ja) * 2012-09-28 2014-04-21 Nippon Steel & Sumikin Chemical Co Ltd 受容層を用いたカラーフィルターの製造方法
JP2015163457A (ja) * 2013-08-21 2015-09-10 富士フイルム株式会社 インクジェット用記録シート、インクジェット用記録シートの製造方法、印刷物、印刷物の製造方法および装飾ガラス

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016007737A (ja) * 2014-06-23 2016-01-18 株式会社ミマキエンジニアリング 画像形成方法
JPWO2016017721A1 (ja) * 2014-07-31 2017-04-27 富士フイルム株式会社 電飾用インクジェット記録材料、電飾用画像及びその形成方法、並びに電飾看板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030016280A1 (en) * 2001-06-14 2003-01-23 Xing-Ya Li Ink-receptive composition
JP2011505283A (ja) * 2007-12-04 2011-02-24 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 印刷方法
WO2011122123A1 (fr) * 2010-03-31 2011-10-06 大日本スクリーン製造株式会社 Imprimante à jet d'encre et support imprimé
JP2012232470A (ja) * 2011-04-28 2012-11-29 Seiko Epson Corp 液体噴出装置及び液体噴出方法
JP2014071354A (ja) * 2012-09-28 2014-04-21 Nippon Steel & Sumikin Chemical Co Ltd 受容層を用いたカラーフィルターの製造方法
JP2015163457A (ja) * 2013-08-21 2015-09-10 富士フイルム株式会社 インクジェット用記録シート、インクジェット用記録シートの製造方法、印刷物、印刷物の製造方法および装飾ガラス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020015846A (ja) * 2018-07-26 2020-01-30 株式会社リコー 印刷物、貼付け用印刷物、及び印刷物の製造方法
JP7143663B2 (ja) 2018-07-26 2022-09-29 株式会社リコー 印刷物、貼付け用印刷物、及び印刷物の製造方法
WO2020218270A1 (fr) * 2019-04-26 2020-10-29 花王株式会社 Liquide de traitement
WO2022149242A1 (fr) * 2021-01-07 2022-07-14 リンテック株式会社 Feuille pour impression à jet d'encre

Also Published As

Publication number Publication date
JP6655168B2 (ja) 2020-02-26
JPWO2017169844A1 (ja) 2019-02-14

Similar Documents

Publication Publication Date Title
US9776447B2 (en) Inkjet recording sheet, method for manufacturing inkjet recording sheet, printed article, method for manufacturing printed article, and ornamental glass
JP5914395B2 (ja) 積層フィルムおよび表示装置
KR101931399B1 (ko) 적층 필름 및 성형체
JP6655168B2 (ja) 透光性シートおよび装飾ガラス
US9931879B2 (en) Ink jet recording medium, method for manufacturing same, printed material, method for manufacturing same, ornamental glass, and roll
KR20050107495A (ko) 표면보호용 점착시트 및 그 제조방법
JP6196450B2 (ja) 電飾用シート、電飾用印刷物およびその製造方法ならびに電飾看板
JP5997621B2 (ja) インクジェット用記録シート、印刷物、および印刷物の製造方法
WO2015198762A1 (fr) Film de réflexion optique ainsi que procédé de fabrication de celui-ci, et corps de réflexion optique mettant en œuvre celui-ci
TW201512334A (zh) 輻射硬化性塗料組成物
WO2018168284A1 (fr) Film optique
JP6288666B2 (ja) ハードコート転写媒体
KR101758295B1 (ko) 자외선 차단기능을 갖는 비산방지필름
WO2005097496A1 (fr) Feuille de protection de surface
WO2016017721A1 (fr) Matériau d'impression à jet d'encre pour éclairage décoratif, image pour éclairage décoratif et son procédé de formation et enseigne éclairée
JP6568294B2 (ja) 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、及びその製造方法、物品、並びに防曇方法
JP2017042948A (ja) 電飾用インクジェット記録材料及び電飾用インクジェット記録材料の製造方法、電飾用画像の形成方法、並びに電飾看板
WO2016017779A1 (fr) Matériau d'enregistrement par jet d'encre pour éclairage décoratif, image pour éclairage décoratif et procédé de formation associé, et panneau de signalisation éclairé
WO2019163638A1 (fr) Composition de résine durcissable par rayonnement d'énergie active, stratifié antisalissure antibuée, et procédé de fabrication, article et procédé antibuée de celui-ci
JP2021081493A (ja) 剥離フィルム付き蛍光体保護フィルム、およびそれを使用した波長変換シートとその製造方法
JP5641306B2 (ja) 加飾成形体の製造方法
JP2012000781A (ja) 表面に凹凸を有する化粧シートの製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2018509018

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17774388

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17774388

Country of ref document: EP

Kind code of ref document: A1