WO2008032869A1 - Feuille de réception de transfert thermique - Google Patents

Feuille de réception de transfert thermique Download PDF

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Publication number
WO2008032869A1
WO2008032869A1 PCT/JP2007/068328 JP2007068328W WO2008032869A1 WO 2008032869 A1 WO2008032869 A1 WO 2008032869A1 JP 2007068328 W JP2007068328 W JP 2007068328W WO 2008032869 A1 WO2008032869 A1 WO 2008032869A1
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WO
WIPO (PCT)
Prior art keywords
acid
layer
thermal transfer
polyester resin
sheet
Prior art date
Application number
PCT/JP2007/068328
Other languages
English (en)
Japanese (ja)
Inventor
Masato Kawamura
Kyoko Uchida
Takaaki Koro
Naoki Kubo
Toshikazu Ohnishi
Yoshio Mizuhara
Original Assignee
Oji Paper Co., Ltd.
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
Priority claimed from JP2006327819A external-priority patent/JP2009285830A/ja
Priority claimed from JP2007098360A external-priority patent/JP2009285831A/ja
Application filed by Oji Paper Co., Ltd. filed Critical Oji Paper Co., Ltd.
Publication of WO2008032869A1 publication Critical patent/WO2008032869A1/fr

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Classifications

    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates

Definitions

  • the present invention relates to a thermal transfer receiving sheet (hereinafter simply referred to as “receiving layer”) having an image receiving layer (hereinafter also referred to simply as “receiving layer”) containing a dye dyeable resin as a main component.
  • the recording density is high and the light fastness of the image is good.
  • ink peelability (hereinafter also referred to as “increpon”) during high-speed printing
  • protective layer transfer layer of incripon
  • the increpone and the receiving sheet are superposed, the sublimation dye in the ink-reply dye layer is transferred onto the receiving layer of the receiving sheet by the heat supplied from the thermal head, etc., and then both are peeled off. An image is formed.
  • the dye dyeable resin used in the receiving layer include vinyl chloride resins, polyester resins, polyvinyl butyral resins, acrylic resins, and cellulose resins. Silicone release agents and fluorine resins are used as release agents. Release agents, fatty acid release agents, and the like have been proposed.
  • the “overlaminate” method in which three or four dyes on the incripon are sequentially transferred and then a protective layer is provided, has become the mainstream.
  • this method it is necessary to realize contradictory physical properties such that the receiving layer has peelability on the surface of the ink layer of the ink crypon and adhesiveness on the surface of the protective layer of the ink lipone.
  • the coexistence of peelability and adhesiveness The use of vinyl chloride resins and cellulose resins as dye-dyeing resins in the receiving layer was possible, but vinyl chloride resins have been avoided in recent years because they tend to generate dioxin during disposal and combustion. In addition, the cellulose resin has a low recording density, so it cannot cope with the recent increase in printer speed.
  • plasticizers have been proposed to increase the recording density of cellulosic resins, but when printing images are stored at high temperatures and high humidity, the images will bleed, or when stored for a long period of time, the plasticizer will pre- If you cannot record images normally
  • a polyester resin has been conventionally used as a dye dyeing resin having a high recording density (for example, JP-A-5-7-108585 (page 1)).
  • No. 5 81 page 2)
  • Japanese Patent Laid-Open No. 5-6 697 78 page 2)
  • Japanese Patent Laid-Open No. 5-2 3 8 1 6 7 page 2
  • Japanese Patent Laid-Open No. 20 0 3 — 2 0 0 6 6 8 See page 2
  • a polyester resin with a low glass transition temperature is used in order to obtain a high printing density, the heat resistance of the receptor layer will decrease.
  • Polyester resins usually have heat resistance by using a curing agent such as isocyanate, but the number of molecular structural sites that can be chemically bonded to the protective layer is reduced. Is used for crosslinking with the curing agent, the adhesion to the protective layer I can't get it. On the other hand, if the amount of the curing agent used is reduced to obtain adhesion to the protective layer, sufficient heat resistance cannot be obtained.
  • a curing agent such as isocyanate
  • polyester resin is a dye-dyeing resin that provides a high printing density, but the heat resistance of the receiving layer is low, and a part of the receiving layer is fused in high-energy printing to reduce the printing density.
  • the phenomenon occurs, the adhesiveness to the protective layer is poor, and the protective layer is difficult to transfer.
  • proposals have been made to use cellulose butyrate acetate (also called cellulose acetate butyrate, CAB).
  • CAB cellulose acetate butyrate
  • the base material of the receiving sheet when looking at the base material of the receiving sheet, it is possible to use a film made of polyethylene terephthalate, polypropylene, etc., bonded with fine paper or coated paper, or hollow particles on fine paper or coated paper. And a sheet-like support laminated by extruding a hot-melted polyethylene resin are used.
  • hollow particle-containing undercoat coated paper, polypropylene film, coating layer containing hollow particles, and polyethylene resin are preferred because they are inexpensive.
  • these materials can easily transfer the dye transferred to the receiving layer.
  • problems such as blurred images, changes in color tone, and fading tend to occur over time.
  • a barrier layer or the like is provided between the receiving layer and the sheet-like support.
  • a barrier layer mainly composed of a swellable inorganic layered compound and an adhesive resin is provided, and the adhesive layer resin includes polyvinyl alcohol, ethylene monovinyl alcohol copolymer resin, ethylene monoacrylic acid copolymer resin, etc.
  • polyester resins, nylon 6 resins, polyvinyl chloride resins, polyacrylonitrile resins, and polyurethane resins have been proposed as resins having high gas barrier properties for use in the barrier layer (for example, JP-A 2 0 0 4—3 1 4 3 7 8 (see paragraph 2)).
  • a manufacturing method in which a receiving layer is formed with a water-soluble coating instead of a paint dissolved in a solvent has been preferred.
  • Japanese Patent Application Laid-Open No. 6-2 2 7 1 59 page 2
  • Water-soluble resins described in Japanese Patent Application Laid-Open Nos. 2000-284-834 paragraph 2
  • the barrier layer using the material has insufficient water resistance, and when a water-soluble paint is applied onto the barrier layer, the barrier layer is redissolved in the water-soluble coating, and a uniform receiving layer is not formed. There is a problem that the quality is significantly impaired.
  • the conventional polyester resin has a high dyeing property, the dye diffuses into the barrier layer, and the effect of preventing bleeding of the printed image in a high temperature and high humidity environment is unsatisfactory. Disclosure of the invention
  • the object of the present invention is to improve the above-mentioned drawbacks of the prior art and to achieve high speed printing.
  • the transferability of the ink-replon protective layer to the receiving layer surface is good, the peeling performance from the ink lipon is excellent, the recording density is high, the light resistance is good, and the stability of the image is maintained even in a high-temperature, high-humidity environment. It is intended to provide a high acceptance sheet.
  • the present invention includes the following inventions.
  • a thermal transfer receiving sheet having a sheet-like support and an image receiving layer formed on at least one surface of the sheet-like support, the image receiving layer contains 75 moles of all the polyvalent carboxylic acid components.
  • Polyester resin obtained by polycondensation of a polyvalent carboxylic acid component in which at least% is isophthalic acid and a polyhydric alcohol component mainly composed of an aliphatic polyhydric alcohol and / or an alicyclic polyhydric alcohol, and a urethane resin
  • a thermal transfer receptive sheet characterized by containing '.
  • the glass transition temperature of the polyester resin is 30 to 90, and the glass transition temperature of the urethane resin is 150 to 40 ° C.
  • an overcoat layer containing a silicone graph / copolymer resin is further provided, and the coating amount of the overcoat layer is 1 to 25 mg / m 2 (1)
  • the thermal transfer receptor sheet according to any one of items (3) to (3).
  • the image-receiving layer is crosslinked with a compound having both a hydrolyzable alkoxysilyl group and an epoxy group in one molecule (1) to
  • the rear layer is mainly composed of an aqueous polyester resin obtained by polycondensation of a polyvalent carboxylic acid component and a polyhydric alcohol component and a swellable inorganic layered compound.
  • the swellable inorganic layered compound has a particle average major axis of 0.1 to l OO ⁇ m and an aspect ratio (ratio of particle average major axis / thickness of the layered compound) of 5 or more.
  • the barrier layer contains a swelling inorganic layered compound at a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the aqueous polyester resin.
  • the swellable inorganic layered compound is at least one selected from a swellable clay mineral, a swellable synthetic smectite, and a swellable synthetic my strength (6) or (7 ) Thermal transfer receiving sheet according to item
  • the swellable inorganic layered compound has a particle average major axis of 6 to 20 and an aspect ratio of 300 to 500.
  • thermo transfer receiving sheet according to any one of (6) to (10), wherein the aqueous polyester resin contained in the barrier layer contains naphthalenedicarboxylic acid as a polyvalent carboxylic acid component.
  • the receiving sheet of the present invention maintains a high printing density and good light resistance. Furthermore, it is a receptive sheet with excellent releasability from incripon, good image stability under high temperature and high humidity environment, and good transferability of protective layer of ink ribbon. This is useful for the thermal transfer system full-color printer.
  • the present invention provides a receptor sheet in which a receptor layer is formed on at least one surface of a sheet-like support, wherein the receptor layer includes a polyester resin having a specific composition in a molecule, and a urethane resin. It is what
  • the polyester resin used in the receiving layer of the present invention is synthesized by polycondensation of a polyvalent carboxylic acid component and a polyhydric alcohol component.
  • the polyester resin used in the receiving layer of the present invention is characterized in that it contains 75 mol% or more of isophthalic acid component in all the polyvalent carboxylic acid components of the polyester resin, and more preferably, the polyvalent carbon acid.
  • the boric acid component contains 85 to 100 mol% of isophthalic acid component. If the isophthalic acid component is less than 75 mol%, the light resistance of the resulting polyester resin may be lowered.
  • an alicyclic dicarboxylic acid In the polyvalent carboxylic acid component used in the present invention, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid other than isophthalic acid may be used as long as the effects of the present invention are not impaired. It is possible.
  • Alicyclic dicarboxylic acids include those having at least one alicyclic ring in the molecule as the basic skeleton of the molecular structure. Specific examples of the alicyclic ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, decalin ring, norpolnan ring. An adamantane ring and the like are preferable.
  • alicyclic dicarboxylic acids include 1,4-cyclohexane dicarboxylic acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, 2-propyl 1 , 4-Cyclohexanedicarboxylic acid, 2-butyl-1,4-monocyclohexanedicarboxylic acid, 2-t to butyl-1,4-cyclohexanedicarboxylic acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid , 2,3 monojetyl-1,4-cyclohexanedicarboxylic acid, 2,3-dipropyl-1,4-cyclohexanedicarboxylic acid, 2,3-dibutyl-1,4-cyclohexanedicarboxylic acid, 2-monomethyl-1,3- Ethyl-1,4-cyclohexan
  • 2-cyclohexanedicarboxylic acid 4-methyl-12-cyclohexanedicarboxylic acid, 12-cyclopentanedicarboxylic acid, 13-cyclopentanedicarboxylic acid, 2,3-nornornandicarboxylic acid, adamantanedicarboxylic Examples include acid, dimethyladamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, 44 'monocarboxymethyl D hexane, 4,4, -carboxyethylcyclohexane, and the like.
  • aromatic dicarboxylic acids other than isophthalic acid the basic skeleton of the molecular structure has one aromatic ring, and an independent aromatic in the form of biphenyl, diph- urene, pbenzil, stilbene, etc. Those having 2 to 3 rings in the skeleton, and those having a condensed ring of 5-membered or 6-membered carbocyclic ring on the aromatic ring such as indene and tetralin can be used. .
  • the aromatic dicarboxylic acid usually has 8 carbon atoms.
  • the range is 3 0, preferably 8 20, more preferably 8 15.
  • aromatic dicarboxylic acid examples include terephthalic acid, furic acid, P-xylylenka J-reponic acid, 1, 4 —naphthalene dicarboxylic acid 2 6 —naphthalene dicarboxylic acid, 2 7 -naphthoic acid Range carboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-diphenyl methanedicarboxylic acid, 44-diphenylpropanedicarboxylic acid 4, 4, 4-diphenyl terdicarboxylic acid, 4, 4, monobenzophenone dicarboxylic acid, and the like.
  • Examples of the derivative of the carboxylic acid used in the same manner as the polyvalent carboxylic acid include the ester compounds, acid anhydrides, and acid halides of the dicarboxylic acid.
  • ester compounds and acid anhydrides are preferable, and ester compounds including lower alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, amyl, and hexyl are particularly preferable as ester compounds. preferable.
  • an aliphatic dicarboxylic acid or the like is contained as necessary in addition to the above-described alicyclic and aromatic dicarboxylic acids as long as the effects of the present invention are not impaired. May be.
  • the aliphatic dicarboxylic acid include linear or branched aliphatic dicarboxylic acids and derivatives thereof such as ester compounds, acid halides, and acid anhydrides.
  • Aliphatic dicarboxylic acids include malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, iso sebacic acid, brassic acid, dodecanedicarboxylic acid
  • Aliphatic saturated dicarboxylic acids such as polyalkenyl succinic acid, aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and dartaconic acid, dimer acid of polymerized fatty acid, hydrogenated dimer acid, etc.
  • adipic acid, sebacic acid, succinic anhydride, and maleic anhydride are preferably used.
  • a trivalent or higher carboxylic acid can be contained for the purpose of forming a branched structure of the polyester resin and increasing the glass transition temperature, as long as the effects of the present invention are not impaired.
  • the trivalent or higher carboxylic acid component include, for example, trimellitic acid, tristralvaleric acid, camphoronic acid, trimesic acid, 2,5—Naphthalenetricarboxylic acid, 2,3,6—Naphthalenetricarboxylic acid, 1,8,4 mononaphthalenetricarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimer acid of polymerized fatty acid, etc.
  • Examples thereof include trivalent or higher carboxylic acids and ester compounds and acid anhydrides thereof.
  • the content of the compound is preferably from 0.5 to 10 mol%, more preferably from 1 to 7 mol% in the full strength rubonic acid component.
  • polyvalent carboxylic acid component used in the present invention formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, valeric acid, isooctylic acid, lauric acid, myristic acid, as long as the effects of the present invention are not impaired.
  • It may contain monovalent carboxylic acids such as palmitic acid, stearic acid, isostearic acid, araquinic acid, linoleic acid, oleic acid, elaidic acid, tall fatty acid and / or ester compounds thereof.
  • the content of these compounds is usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less in the polyvalent carboxylic acid component.
  • the polyester resin used in the receiving layer of the present invention is characterized by containing an alicyclic polyhydric alcohol and / or an aliphatic polyhydric alcohol as a main component as a polyhydric alcohol component, such as light resistance. It is better at this point.
  • the total content of the alicyclic polyhydric alcohol and / or the aliphatic polyhydric alcohol is preferably 50 to 100 mol% in all the components of the polyhydric alcohol.
  • alicyclic or aliphatic polyhydric alcohol mainly alicyclic darcols and aliphatic glycols are preferably used, and these may be used alone or in appropriate combination of two or more. May be used.
  • Specific examples of alicyclic glycols include 1,4-cyclohexane diol, 1,2-cyclohexane diol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, and tricyclodecane dimethanol.
  • BIS-A hydrogenated bisphenol A
  • 1,2-cyclopentanediol 1,4-cyclooctane diol
  • 2,5-mononorpornandiol 2,5-mononorpornandiol
  • adamanan diol 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated BIS-1A, etc. are preferably used.
  • aliphatic glycol examples include ethylene glycol, propylene glycol, 1,4 monobutanediol, 1,2-butanediol, 1,5 monopentanediol, 1,6-hexanediol, and neopentyl glycol. , 2-n-butyl-2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like. Of these, ethylene glycol, neopentyl glycol and the like are preferably used.
  • polycondensation can be carried out by adding a trihydric or higher polyhydric alcohol in addition to the above Daricol component.
  • the trihydric or higher polyhydric alcohol compounds include glycerol compounds such as glycerin, diglycerol, and polydaricerol, trimethylolethane, trimethylolpropane, trimethylolbutane, penicillary erythritol, ditrimethylolpropane, and dipentylol.
  • methylol compounds such as erythritol.
  • the content of these compounds is preferably 0.5 to 10 mol%, more preferably 1 to 7 mol%, based on the total alcohol component.
  • the resulting polyester resin Gelation due to cross-linking of fat becomes prominent and resin solubility may be poor. On the other hand, if it is less than 0.5 mol%, the resulting polyester resin has a small branched structure, and a sufficient heat resistance improvement effect may not be obtained.
  • the molecular weight of the polyester resin of the present invention synthesized from the above raw materials is not particularly limited.
  • the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC) is 300 to 500.
  • a range of 0 0 0 is preferable, and a range of 5 0 0 0 to 3 0 0 0 0 is more preferable.
  • the number average molecular weight is less than 300,000, the receptor layer and the ink ribbon may be fused.
  • the number average molecular weight exceeds 500,000, When dissolved and used, the viscosity of the polyester resin-containing coating solution is increased and the smoothness of the coated surface may be inferior.
  • the glass transition temperature of the polyester resin used in the present invention is preferably 30 to 90 ° C, more preferably 40 to 80 ° C.
  • the glass transition temperature of the polyester resin is less than 30 ° C, fusion between the receiving layer and the ink ribbon may occur.
  • the glass transition temperature exceeds 90 ° C, the receiving layer Insufficient print density may not be obtained.
  • the glass transition temperature of the polyester resin is appropriately adjusted mainly by the blending ratio of the aromatic component, alicyclic component, aliphatic component, etc. in the polyvalent carboxylic acid component and the polyhydric alcohol component.
  • the glass transition temperature (° C.) of the present invention is a value determined according to J I S K 7 1 2 1.
  • the polyester resin used in the receiving layer of the present invention can be selected from organic solvent-soluble type, emulsion, and water-soluble form, depending on the coating method and production equipment.
  • the present invention is characterized in that a urethane resin is contained in the receiving layer, and the light resistance of the printed matter can be further improved. It is.
  • the mass ratio of the polyester resin and urethane resin content (polyester resin Z urethane resin) is preferably in the range of 40 0 Z 60 to 95/5, more preferably 50 0/500 to 90/10. Is in the range.
  • the mass ratio of the content of the polyester resin and the urethane resin is less than 40/60, the storability of the printed matter in a high temperature and high humidity environment may be deteriorated.
  • the light resistance of the printed material may be insufficient.
  • the amount of the urethane resin used is more preferably 10 to 50 parts by mass, and further preferably 15 to 40 parts by mass with respect to 100 parts by mass of the total solid content of the receiving layer.
  • the urethane resin used in the receiving layer of the present invention is synthesized from polyester, polycarbonate, long-chain polyether, isocyanate, glycol component, and the like.
  • Polyacrylic, polyamide, polychlorinated It may be copolymerized with one or more kinds of prepolymers selected from vinyl, polyvinyl acetate and the like, and in particular, polyurethane resin copolymerized with polyacrylic prepolymers has excellent light resistance and is used as a material for use in the present invention. preferable.
  • the form of the urethane resin used in the receiving layer is appropriately selected from organic solvent-soluble type, emulsion, and water-soluble depending on the coating method and production equipment.
  • the glass transition temperature of the urethane resin used in the receiving layer of the present invention is preferably in the range of ⁇ 50 to 40, more preferably 40 to 30. C urethane resin is used. When the glass transition temperature of the urethane resin is less than 150 ° C, the heat resistance of the receiving layer is lowered and the peelability from the increpon may be deteriorated. Further, if the glass transition temperature of the urethane resin exceeds 40 ° C, the light resistance of the printed matter may be insufficient.
  • the glass transition temperature of the urethane resin is a synthetic material such as polyester, long-chain polyether, isocyanate, and glycol components. It adjusts suitably according to the kind and the compounding ratio.
  • an overcoat layer further containing a silicone graft copolymer resin is provided on the receiving layer.
  • the overcoat layer it is possible to obtain a receiving sheet that is excellent in releasability from the increpon and excellent in transferability of the protective layer of the ink lipon.
  • the silicone graft copolymer resin include those obtained by graft polymerization of silicone to acryl resin, urethane resin, polyester resin, polyamide resin or the like.
  • the coating amount of the overcoat layer is preferably 1 to 25 mg Zm 2 , more preferably 2 to 20 mg / m 2 , further preferably 4 to 1 O mg / m 2 .
  • the coating amount is less than 1 mgZm 2 overcoat layer, it may be insufficient peelability of improvement from Inkuripo down, whereas, if the problem in the protective layer transferring property more than 2 5 mg / m 2 is produced is is there.
  • the receptor layer contains a compound having both a hydrolyzable alkoxysilyl group and an epoxy group in the i molecule (hereinafter referred to as an alkoxysilyl group epoxy group-containing compound) as a crosslinking agent.
  • an alkoxysilyl group epoxy group-containing compound a compound having both a hydrolyzable alkoxysilyl group and an epoxy group in the i molecule
  • curing proceeds easily at room temperature, and a cured product with excellent weather resistance and heat resistance is obtained. It is known to give.
  • a hydrolyzable alkoxysilyl group is hydrolyzed to form a siloxane bond by a dehydration condensation reaction of a silanol group.
  • Siloxane bonds in which silicon and oxygen are bonded alternately, are characterized by excellent heat resistance due to their large bond energy.
  • the alkoxysilyl group epoxy group-containing compound of the present invention is blended as a crosslinking agent in the receptor layer of the receptor sheet, the dyeing resin in the receptor layer is crosslinked and a siloxane bond is formed by self-crosslinking.
  • the heat resistance of the entire receiving layer is remarkably improved, and as a result, the ink lipo It is possible to obtain a receiving sheet excellent in peelability from the adhesive.
  • alkoxysilyl group-epoxy group-containing compound of the present invention examples include vinyl polymers having both an alkoxysilyl group and an epoxy group, and silane coupling agents having an epoxy group.
  • a vinyl polymer having both an alkoxysilyl group and an epoxy group a known method can be applied.
  • it has a hydrolyzable alkoxysilyl group such as vinyltrimethoxysilane or vinyltrioxysilane.
  • vinyl monomers and epoxy group-containing vinyl monomers such as alkylglycidyl ether, methyldaricidyl (meth) acrylic acid, methyldaricidyl fumarate, and dimethyldaricidyl maleic acid, It can be obtained by a method such as solution radical copolymerization.
  • silane coupling agent containing ⁇ 3 ephedro group examples include 3-dalicydoxypropyl-trimethoxysilane, 3-glycidoxypropylmethylgexysilane, 3-gu U-sidoxypropyltriethoxysilane, and the like.
  • the alkoxysilyl group of the present invention is not particularly limited. For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentyloxy group. And an alkoxy group that is easily hydrolyzed, such as an octyloxy group, is bonded to one or more silicon atoms.
  • an alkyl group, aryl group, aralkyl group, amino group, aminooxy, phenoxy group, or the like may be bonded to the silicon atom.
  • the compounding amount of the alkoxysilyl group-epoxy group-containing compound in the receptor layer is preferably in the range of 0.1 to 10% by mass, and 0.2 to 8% by mass with respect to the total solid mass of the receptor layer. More preferred. Less than 0% quality
  • the effect of improving the peelability is small, and when it exceeds 10% by mass, the dyeing resin
  • the dyeing resin In order to improve the peelability from the incripon at a blending amount that does not impair the performance of the present invention, there may be a problem that the dye density of the ink is impaired and the printing density is lowered.
  • the releasable substance is not particularly limited.
  • epoxy-modified silicone oil epoxy-modified silicone oil, epoxy polyether-modified silicone oil, alcohol-modified silicone oil, dimethyl silicone oil, polyether-modified silicone oil, amino-modified silicone oil , Modified silicone oils such as strong l-poxyl-modified silicone oil and methacrylic acid-modified silicone oil, hydrocarbons such as non-raffin wax, polyethylene and fluorocarbon, fatty acids such as stearic acid, aliphatic amides, Examples include releasable substances such as stealth, alcohol, metal stone, and natural wax. These releasable substances are preferably blended in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the dye-dyeable resin of the receiving layer, but are not particularly limited.
  • the dye-dyeable resin can be cross-linked by a cross-linking agent such as a polyisocyanate compound, an epoxy compound, an oxazoline compound, a calpositimide compound, or an organometallic compound.
  • a cross-linking agent such as a polyisocyanate compound, an epoxy compound, an oxazoline compound, a calpositimide compound, or an organometallic compound.
  • a known dye-stainable resin may be used in combination as appropriate.
  • polyacetate resins such as cellulose butyrate acetate, polyvinyl formal, polyacetal, polybipropylyl, bisphenol Nord A (BPA) type epoxy resin, Hydrogenated BPA type epoxy resin, Polyvinyl chloride, Polyvinylidene chloride, Polyvinyl acetate, Polystyrene, Styrene-acrylonitrile copolymer, Polyethylene, Polypropylene, Ethylene monoacetate copolymer , Polymethyl methacrylate, Methyl methacrylate-styrene copolymer, Polyamide, Ethyl cellulose, Cellulose acetate, Propyl cellulose, Cellulose nitrate, Polycarbonate, Phenoxy resin, etc. It is also possible.
  • a plasticizer can be used for the purpose of controlling the dyeing property.
  • the plasticizer known ones such as fuuric acid ester type, aliphatic dibasic acid ester type, trimellitic acid ester type, phosphoric acid ester type, epoxy type, and polyester type can be used. It is also possible to use more than one species in combination.
  • the blending amount of the plasticizer is preferably about 1 to 50 parts by mass with respect to 100 parts by mass of the dye-dyeable resin of the receiving layer. A combination is more preferably used.
  • UVA ultraviolet absorber
  • HAL S hindered amine light stabilizer
  • an antioxidant may be used alone or in combination.
  • UVA ultraviolet absorber
  • HAL S hindered amine light stabilizer
  • an antioxidant may be used alone or in combination.
  • benzotriazole UVA, triazine UVA, oxalic acid UVA, and benzophenone UVA are known as UVA, but especially benzotriazol UVA has an absorption wavelength compared to other UVAs. Since it has a wide band, has a maximum absorption peak on the high wavelength side, and has a large absorbance, it is preferably used because it has a particularly excellent effect when used in combination with HAL S.
  • HALS is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in the molecule and is not particularly limited as long as it has this skeleton. HALS is blended in an amount of 1 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin of the receiving layer. It is done.
  • the solid coating amount of the receiving layer is preferably about 1 to 12 g Zm 2 , and more preferably 2 to 10 g / m 2 .
  • the solid coating amount of the receiving layer is less than 1 g Z m 2
  • the solid coating amount of the receiving layer not only has the effect exceeds 1 2 g Z m 2 is uneconomical saturated, or insufficient strength of the receiving layer, the support thickness of the receiving layer is increased The thermal insulation effect may not be fully exhibited, and the image density may decrease.
  • papers mainly composed of cellulose pulp, synthetic resin films and the like are used.
  • paper such as high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper, glass paper, and resin-laminated paper, or polyolefins such as polyethylene and polypropylene, polyethylene terephthalate Polyester, Polyamide, Polyvinyl chloride, Polystyrene, Polycarbonate, Polyvinyl alcohol, Polyvinyl chloride, etc.
  • Porous single-layer stretched film or porous multilayer stretched film for example, synthetic paper
  • a laminate or the like obtained by laminating and attaching paper or the like is appropriately used.
  • the substrate surface layer (substrate on the receiving layer side) of the support is not particularly limited, but from the viewpoint of the uniformity and gradation of the printed image, heat such as polyolefin and polyester is used.
  • a porous single-layer stretched film or a porous multilayer stretched film (for example, synthetic paper) mainly composed of a plastic resin is preferably used.
  • the present invention among the above sheet-like supports, papers mainly composed of cellulose pulp are advantageous in terms of cost, and the texture of the receiving sheet obtained is close to photographic paper for silver salt photography. Therefore, it is preferably used.
  • a paper support it is preferable to provide an intermediate layer containing hollow particles on the support.
  • the material and manufacturing method of the hollow particles used in the intermediate layer are not particularly limited. Specifically, as the material for forming the walls of the hollow particles, acrylonitrile, vinylidene chloride, styrene, acrylate esters, etc. Homopolymers, their copolymers, and mixtures of these homopolymers.
  • Examples of the method for producing these hollow particles include a method in which butane gas is encapsulated in resin particles and heated and foamed, and an emulsion polymerization method.
  • the hollow particles preferably have an average particle size of 0.3 to 20 x m and a volume hollowness of 45 to 97%.
  • an aqueous polyester resin having a glass transition temperature in a specific range;
  • the aspect ratio ratio of average particle diameter / thickness of layered compound
  • the aspect ratio is 5 or more and the average length It includes a swellable inorganic layered compound having a diameter of 0.1 to 100 m.
  • the solid content of the swellable inorganic layered compound in the barrier layer is preferably from 1 to 20 parts by weight of the swellable inorganic layered compound with respect to 100 parts by weight of the aqueous polyester resin. If the solid content of the swellable inorganic layered compound is less than 1 part by mass, image blurring may not be sufficiently prevented, while if it exceeds 20 parts by mass, the adhesive strength of the paria layer may be insufficient.
  • the polyester resin used in the barrier layer of the present invention at least one kind is appropriately selected from those having a glass transition temperature of 55 ° C. to 110 °. If the glass transition temperature is less than 55 ° C, the heat resistance is poor, and the Paria layer may peel off from the support during printing due to the heat of the thermal head. On the other hand, when the glass transition temperature exceeds 110 ° C., the film forming property of the barrier layer is inferior, and a uniform barrier layer is not formed, so that the image quality and the image stability under a high temperature and high humidity environment are remarkably lowered.
  • the glass transition temperature of the polyester resin and the like in the present invention is a value measured using D S C according to J I S K 7 1 2 1.
  • the aqueous polyester resin used in the barrier layer of the present invention is synthesized by polycondensation of a polyvalent carboxylic acid component and a polyhydric alcohol component.
  • examples of the aqueous polyester resin used in the Paria layer of the present invention include those obtained by introducing a hydrophilic group into a molecule to make it water-soluble, and emulsions dispersed in water.
  • the method of introducing a sulfone group into the molecule is an effective means for increasing the hydrophilicity of the polyester, and improves the coatability and drying properties.
  • a sulfone group can be introduced into a polyester resin using a polyvalent carboxylic acid component containing a sulfone group.
  • Polyvalent carboxylic acid component containing a sulfone group The content of is preferably 10% by mass or less, more preferably 5% by mass or less in the polyvalent carboxylic acid component.
  • the polyester resin used in the barrier layer of the present invention is characterized by containing 80 mol% or more of a terephthalic acid component in the polyvalent carboxylic acid component of the polyester resin, and more preferably 80-1
  • the terephthalic acid component in the polyvalent carboxylic acid component is preferably in the range of 85 to 100 mol%.
  • the terephthalic acid component is less than 80 mol%, the dye barrier property of the resulting polyester resin is lowered, and the image stability in a high temperature and high humidity environment is lowered.
  • an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid other than terephthalic acid may be used as long as the effects of the present invention are not impaired. It is possible.
  • naphthalenedicarboxylic acid as long as the glass transition temperature of the produced polyester resin does not exceed the range of ⁇ 5 to 110 C, increases the heat resistance of the barrier layer, and in a high temperature and high humidity environment. This is preferable because image stability can be improved.
  • the polyvalent carboxylic acid component preferably contains about 5 to 20 mol% of the naphthalenedicarboxylic acid component.
  • the alicyclic dicarboxylic acid the molecular structure has a basic skeleton with a small number of alicyclic rings in the molecule. Both have one.
  • cyclopropane ring examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a norbornane ring, and an adamantane ring.
  • alicyclic dicarboxylic acids include 1,4-cyclohexane dicarboxylic acid, 2-methyl-1,4-cyclohexane dicarboxylic acid , 2-Ethyl-1,4-cyclohexanedicarboxylic acid, 2-Propyl 1,4-cyclohexanedicarboxylic acid, 2-Petilu 1,4-cyclohexanedicarboxylic acid, 2-tert-butyl-1,4-cyclohexanedicarboxylic acid Acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid, 2,3-jetyl-1,4-cyclohexanedicarboxylic acid, 2,3-dipropyl-1,4-cyclohexanedicarboxylic acid, 2,3- Dibutyl-1,4-cyclohexanedicarboxylic acid, 2-monomethyl-1-3-ethyl-1,4-cyclohexan
  • the basic skeleton of the molecular structure has one aromatic ring, and an independent aromatic ring in the form of biphenyl, diphenylmethane, bibenzyl, stilbene, etc.
  • aromatic dicarboxylic acid usually has 8 3 carbon atoms.
  • aromatic dicarboxylic acids that are 0, preferably 8 to 20 and more preferably 8 to 15 include isofuric acid, phthalic acid
  • Examples thereof include 4-phenyl ether dicarboxylic acid, 4,4 'monobenzonon dicarboxylic acid, and the like.
  • ester compounds of the above dicarboxylic acids examples include ester compounds of the above dicarboxylic acids, acid anhydrides, acid halides, and the like.
  • ester compounds and acid anhydrides are preferable, and as the ester compounds, lower alkyl ester compounds having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, amyl, and hexyl are particularly preferable.
  • aliphatic dicarboxylic acid examples include linear or branched aliphatic dicarboxylic acids and derivatives thereof such as ester compounds, acid halides, and acid anhydrides.
  • Specific examples of aliphatic dicarboxylic acids include malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isosebacin Of aliphatic saturated dicarboxylic acids such as acid, brassylic acid, dodecanedicarboxylic acid, polyalkenyl succinic acid, aliphatic unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, and polymerized fatty acid Examples include dimer acid and hydrogenated dimer acid. Of these, adipic acid, sebacic acid, succinic anhydride, and maleic anhydride are
  • a trivalent or higher carboxylic acid may be included for the purpose of increasing the glass transition temperature of the polyester resin and forming a branched structure, as long as the effects of the present invention are not impaired. it can.
  • the trivalent or higher carboxylic acid component include, for example, trimellitic acid, tristralvaleric acid, camphoronic acid, trimesic acid, 1, 2, 5 —naphthalene tricarboxylic acid, 2, 3, 6—Naphthalene tricarboxylic acid, 1, 4, 8 —Naphthalene tricarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimer acid of polymerized fatty acid, and ester compounds of these And acid anhydrides.
  • the content of the compound is preferably from 0.5 to 10 mol%, more preferably from 1 to 7 mol% of the full strength rubonic acid component. is there.
  • polyvalent carboxylic acid component used in the present invention formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, valeric acid, isooctylic acid, lauric acid, myristic acid, as long as the effects of the present invention are not impaired.
  • It may contain monovalent carboxylic acids such as palmitic acid, stearic acid, isostearic acid, araquinic acid, linoleic acid, oleic acid, elaidic acid, tall fatty acid, and ester compounds thereof.
  • the content of the compound is usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less in the polyvalent carboxylic acid component.
  • the polyester resin used in the barrier layer of the present invention is characterized by containing 80 mol% or more of ethylene glycol in the polyhydric alcohol component of the polyester resin, and more preferably in the range of 80 to 100 mol%. It is a circle.
  • the amount of ethylene glycol component used is less than 80 mol%, depending on the other polyhydric alcohol components used together, the heat resistance of the resulting polyester resin will decrease, and image stability in high-temperature and high-humidity environments will be reduced.
  • the printability is lowered, the flexibility of the resin is lowered and cracks are generated in the barrier layer, and the print quality is lowered, or the storage stability of the image is lowered.
  • polyhydric alcohol components used in combination with ethylene glycol in the range of less than 20 mol% include alicyclic glycol, aromatic glycol, Aliphatic Daricol other than ethylene glycol can be used.
  • alicyclic glycols include 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, and lysic chloride.
  • Methanol hydrogenated BIS— A (hydrogenated bisphenol) A), 1,2-cyclopentanediol, 1,4-cyclooctanediol, 2,5-norpolnandiol, adamantanediol and the like.
  • BIS— A hydrogenated bisphenol
  • 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated BIS and A are preferably used.
  • aromatic glycol examples include bisphenol A, or ethylene oxide and Z or propylene oxide adduct of bisphenol A.
  • an ethylene oxide adduct of bisphenol A is one in which ethylene oxide is ether-bonded to the hydroxyl group of bisphenol A, and preferably 1 to 5 moles of ethylene oxide is ether-bonded to bisphenol A.
  • 4,4′-bis (2-hydroxyethyl) bisphenol A and the like are exemplified.
  • Do and Z or propylene oxide adducts are preferably used.
  • aliphatic daricols other than ethylene dalycol include propylene glycol, 1,4 monobutanediol, 1,2-butanediol, 1,5-pentanediol, 1,6- Xanthdiol, neopentyl glycol, 2 — n —butyl 2 — Examples include 1,3 propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene glycol. Of these, neopentyl alcohol is preferably used.
  • polycondensation can be performed by adding a trihydric or higher polyhydric alcohol in addition to the glycol component.
  • trihydric or higher alcohol compounds include glycerol compounds such as glycerin, diglycerol, and polyglycerose, trimethylol propane, trimethylolpropane, ⁇ -methylolbutane, pentylerythritol, ⁇ - ⁇ And methylol compounds such as methylolpropane and dipentyl erythritol.
  • the content of the compound is preferably 0.5 to 10 mol%, more preferably 1 to 7 mol% of all alcohol components.
  • the content of the trihydric or higher polyhydric alcohol component exceeds 10 mol%, gelation due to crosslinking of the resulting polyester resin becomes remarkable, and the resin solubility may be poor. On the other hand, if it is less than 0.5 mol%, the resulting polyester resin has a small branched structure, and a sufficient heat resistance improvement effect may not be obtained.
  • the molecular weight of the polyester resin of the present invention synthesized from the above raw materials is not particularly limited.
  • the polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC) is 300 to 500.
  • a range of 0 0 0 is preferable, and a range of 5 0 0 0 to 4 0 0 0 0 is more preferable.
  • the number average molecular weight is less than 300,000, the receptor layer and the ink ribbon may be fused, and if the number average molecular weight exceeds 500,000, the emulsion is When dispersed in water, the stability may decrease and aggregation may occur.
  • Graphite, phosphate derivative compounds (zirconium phosphate compounds, etc.), chalcogenides, hydrated talcite compounds, and lithium aluminum composite hydroxides have unit crystal layers stacked on top of each other.
  • a compound or substance having a layered structure, in which a surface in which atoms are strongly bonded by a covalent bond or the like and densely arranged is piled up substantially in parallel by a weak bonding force such as Juan and Del Warska. It refers to the overlapping structure.
  • a “chalcogenide” is a dichalcogenide of a group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and / or group VI (Mo, W) element. And MX 2 (M represents the above element, and X represents chalcogen (S, Se, Te)).
  • Clay-based minerals generally have a two-layer structure with an octahedral layer of aluminum or magnesium as the central metal on the upper part of the silica tetrahedral layer, and the silica tetrahedral layer is made of aluminum or magnesium. It is classified as a type with a three-layer structure in which an octahedral layer with a central metal etc. is confined from both sides. Examples of the former two-layer structure type include the Kaolinite group and the anti-gorite group. The latter three-layer structure type includes the smectite group, vermiculite group, and Myriki group depending on the number of interlayer cations. Etc.
  • clay minerals include Kaolinite, Datekite, Nakulite, Eight Roysite, Antigolite, Chrysotile, Pyrophyllite, Montmorillonite, Hectrite, Tetrasilicate Kumai power, sodium teniolite, margarite, talc, vermiculite, zanzolite, chlorite
  • swellable inorganic layered compound of the present invention among the clay-based minerals, a smectite group, a bamquilite group, a Myr group, and the like are preferably used.
  • smectite group for example, montmorillonite, high delite, nontronite, sabonite, iron saponate, hectolite, soconite, stevensite and the like are more preferably used.
  • these swellable inorganic layered compounds may be either synthetic products or processed products (for example, surface treatment products of silane coupling agents).
  • synthetic products for example, synthetic smectites .
  • Synthetic smectite and synthetic power can be produced by hydrothermal reaction method (see JP 6-3 4 5 4 19), solid phase reaction method, melting method (Japanese Patent Laid-Open No. 5-2). There are three methods of synthesis.
  • the hydrothermal reaction method uses an aqueous solution or aqueous slurry containing various raw materials such as silicates, magnesium salts, alkali metal ions, alkali metal salts, and fluorine ions in an autoclave or pipe reactor. This is a method of synthesis by reacting under high temperature and high pressure of ° C.
  • the crystal growth since the crystal growth is slow, generally large particles cannot be obtained, and most of them have a particle diameter of 10 to 100 nm.
  • large particles with a particle size of 1 m or more can be produced if they are synthesized under conditions of low concentration, low temperature, and long time. However, in this case, the manufacturing cost is extremely high. Then there is a problem.
  • the solid-phase reaction method is a method for producing synthetic strength by reacting with talc, alkali silicofluoride and other raw materials for several hours in the range of 400 to 1,00.
  • elemental movement occurs while leaving the structure of the raw material talc to generate my strength (topotaxi), so the quality of the resultant synthetic strength depends on the physical properties of the raw material talc and its impurities. Because element transfer cannot be controlled completely, the purity and crystallinity of the synthetic my power may be low.
  • the melting method consists of melting anhydrous silicic acid, magnesium oxide, aluminum oxide, silicic acid potassium fluoride, potassium carbonate, and other raw materials at a melting point of My strength (for example, 1,500 ° C) or higher, followed by slow crystallization.
  • This is a method for producing synthetic strength and synthetic smectite.
  • there are an external heating method and an internal heating method.
  • the external heating type melting method is a method in which the raw material is put into a chamber with a temperature higher than the melting point and the temperature is raised, and then moved to a chamber with a temperature lower than the melting point. Is expensive.
  • the internal heating method is a method in which a raw material is heated and melted by energization in a vessel equipped with a graphite (carbon) electrode or a metal electrode, and then cooled.
  • the internal heating method is generally used. It is.
  • the fusion synthesis method can produce a synthetic product with controlled particle size by pulverizing and classifying the cooled and crystallized lump.
  • raw materials with high purity can be used as raw materials, and since the raw materials can be mixed uniformly by melting, the synthetic strength and synthetic smectite have high crystallinity, large particle size, and high purity. There are advantages to being able to manufacture.
  • the synthetic swelling inorganic layered compound for example, fluorine phlogopite (KM g 3 A 1 S i 3 O 10 F, a fusion method or a solid phase reaction method), potassium tetrasilicic mica (KMg 2. 5 S i 4 0 1 Q F 2, a fusion method), sodium tetraborate silicon mica (N ag 2. 5 S i 4 O i 0 F 2, melting process), sodium polybutenyl Orai preparative (N a M g 2 L i S i 4 ⁇ ).
  • synthetic strength such as sodium tetrasilicon mica, sodium teniolite, lithium teniolite, synthetic smectite such as sodium hectite, lithium hectite, sabonite, and montmorillonite
  • a natural smectite such as a tomato is more preferably used.
  • sodium tetrasilicon mica is particularly preferable, and a desired particle size, aspect ratio, and crystallinity can be obtained by a fusion synthesis method.
  • clay minerals examples include natural bentonite, commonly called sodium bennite, Kunipia (: trade name, natural montmorillonite, manufactured by Kunimine Industries), smecton (: trade name, hydrothermal reaction method) Synthetic smectite, manufactured by Kunimine Kogyo Co., Ltd., Bee Gum (: product name, Panderbilt Co., Ltd.), Labonite (: product name, manufactured by Laborte Co., Ltd.), DM Clean A, DMA-3500, Na-T s ( : Brand name, all three types can be listed as melt synthetic power, sodium tetrasilicon mica, manufactured by Topy Industries, Ltd.), Bengel (: product name, manufactured by Toyoshun Yoko Co., Ltd.), etc. Two or more kinds may be mixed and used.
  • the swellable inorganic layered compound preferably used in the present invention is a swellable inorganic layered compound that easily swells, cleaves and disperses in water. Swelling
  • the degree of the “swelling / cleavage” property of the organic inorganic layered compound to the solvent can be evaluated by the “swelling / cleavage” test.
  • the swelling property of the swellable inorganic layered compound is preferably about 5 m 1 Z 2 g or more, more preferably about
  • the swelling capacity of the swellable inorganic layered compound is, for example, Kunipia (swelling capacity: 65 m 1 2 g or more), smecton (swelling power: 60 m 1 Z 2 g or more), DM Clean A, DMA— 3 50, Na-T s (swelling power: 30 ml / 2 g or more), ME—100 (: trade name, manufactured by Coop Chemical Co., swollen cap: 2 Om 1 2 3 3 g or more) and Wengel (swelling power:
  • the swelling test will be described in detail. Using 100m1 graduated cylinder as a test container, slowly add 2g of swellable inorganic layered compound to 100m1 of solvent and let stand, then 23 ° C, 24 hours The volume of the swellable inorganic layered compound dispersion layer is read from the scale of the interface between the swellable inorganic layered compound dispersion layer and the supernatant layer. The larger this numerical value (ml ZS g) is, the higher the swelling property is.
  • As the solvent water is preferably used.
  • the cleavage property of the swellable inorganic layered compound is preferably about 5 ml or more, more preferably about 2 Oml or more.
  • a solvent having a density smaller than the density of the swellable inorganic layered compound is used, and preferably water is used.
  • the swellable inorganic layered compound those having a aspect ratio of 5 or more are used, and preferably those having a ratio of 100 or more are used. More preferably, the aspect ratio of the swellable inorganic layered compound is in the range of 300 to 500, and most preferably 500 to 400. If the aspect ratio is less than 5, image blurring may occur.
  • S E M scanning electron microscope
  • T E transmission electron microscope
  • the average particle diameter of the swellable inorganic layered compound used in the present invention is generally in the range of 0.1 to 100 / im, preferably 2 to 20 m, and 6 to 20 m. Is more preferable.
  • the average particle major axis is less than 0.1 l m, the aspect ratio becomes small, and it becomes difficult to lay in parallel on the intermediate layer, so that it is not possible to completely prevent image blurring.
  • the average major axis of the particle exceeds 100 m, the swellable inorganic layered compound protrudes from the barrier layer, resulting in irregularities on the surface of the barrier layer, and the smoothness of the surface of the receiving layer is reduced, resulting in an image quality. Gets worse.
  • the running property is improved, the static electricity is prevented, the receiving layer is prevented from being damaged by rubbing between the receiving sheets, and the printed receiving sheet is stacked.
  • the back layer may be formed for the purpose of preventing dye transfer from the receiving layer to the back surface of the receiving sheet adjacent to and in contact with the receiving layer.
  • Resin as adhesive component and various conductive agents for antistatic treatment are added to the back layer You can do it.
  • a cationic polymer as the conductive agent.
  • the cationic polymer polyethyleneimine, an acrylic polymer containing a cationic monomer, a cationic modified acrylamide polymer, cationic starch, and the like can be used.
  • an overcoating layer can be provided on the receiving layer for the purpose of improving the paper feedability of the printer or for preventing sticking to the ink jet at the time of printing.
  • the resin used in the overcoat layer is not particularly limited in the present invention, but silicon graphacrylic resin, silicone resin and the like can be used.
  • the receiving sheet may be subjected to a calendering treatment, and the unevenness of the receiving layer surface can be reduced and smoothed.
  • the calendering process may be performed at any stage after coating the intermediate layer, barrier layer, or receptor layer.
  • the calender device used for force-rendering treatment the nipping pressure, the number of nippings, or the surface temperature of the metal roll, but the pressure conditions for force-rendering treatment are 0.5 5 0 M
  • P a is preferable, and more preferably l 30 M Pa.
  • the temperature condition is preferably 20 ° 150 ° C., more preferably 30 ° 30 ° C.
  • a force render device generally used in the paper industry, such as a calendar, a soft calendar, a Daros calendar, a clearance force renderer, etc. can be used as appropriate.
  • polyester resin (emulsion) was synthesized by a known method using a polyvalent carboxylic acid component and a polyhydric alcohol component shown in Table 1 below.
  • thickness 1 5 0 ⁇ m art paper (trade name: OK KINFUJI N, 1 7 4. 4 g Zm 2, Oji Paper Co., Ltd.) was used, intermediate layer of the following composition on one side Coating solution 1 was coated and dried so that the film thickness after drying was 51 m, to form an intermediate layer.
  • Pre-expanded hollow particles made of a copolymer based on acrylonitrile and methacrylonitrile (average particle size 3.2 m, volumetric hollowness 7 6%) 5 0 parts Polyvinyl alcohol (trade name: P VA 2 0 5, made by Kuraray)
  • a barrier layer coating solution 1 having the following composition was applied onto the intermediate layer so that the solid content coating amount was 2 g / m 2 and dried to form a barrier layer.
  • coating solution for receiving layer A having the following composition was coated so that the solid content coating amount was 5 g / m 2 and dried to form a receiving layer.
  • Swellable inorganic layered compound sodium 4 silicon mica, particle average major axis 6.3 mm, aspect ratio 2 7 0 0
  • polyvinyl alcohol trade name: P V A 10 5, manufactured by Kuraray
  • Polyester resin emulsion A 8 0 parts Urethane resin (Product name: Neo sticker 1 2 0 0, manufactured by Nikka Chemical, glass transition temperature: 120 ° C) 2 0 parts Polyisocyanate (Product name: NK Assist IS— 7 0 S,
  • the back layer coating solution 1 of the following composition to a solid content coating amount of 3 g / m 2 after drying.
  • coating and drying were performed to form a back layer, and then heat treatment was performed at 50 ° C. for 4 days. Further, calendering (roll surface temperature 78 ° C., nip pressure 2.5 MPa) was performed to smooth the surface of the sheet-like support on which each coating layer was formed.
  • Polyvinyl acetal resin (trade name: S-LEC KX-1; manufactured by Sekisui Chemical Co., Ltd.) 40 parts Polyacrylic acid ester resin (trade name: Julima I AT 6 1 3; manufactured by Nippon Pure Chemicals) 2 0 parts Particles (trade name: MW 3 30, manufactured by Shinto Paint) 1 0 parts Zinc stearate (trade name: Z-7-7-30, manufactured by Chukyo Yushi) 1 0 parts Cationic conductive resin (trade name: Chemistastat) 9 8 0 0,
  • an overcoat having the following composition is formed on the receiving layer of the sheet-like support.
  • the coating liquid for layer 1 was applied so that the solid content coating amount was 3 mg / m 2 and dried to form an overcoat layer, thereby preparing a receiving sheet.
  • Silicone graph acrylic resin (trade name: X 2 2-8 0 5 3, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Isopropanol 100 parts
  • Example 2 Silicone graph acrylic resin (trade name: X 2 2-8 0 5 3, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Isopropanol 100 parts
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution B was used instead of the receiving layer coating solution A.
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution C was used instead of the receiving layer coating solution A.
  • Polyester resin emulsion A 8 0 parts Urethane resin (Product name: Neo sticker 1700, manufactured by Nikka Chemical, glass transition temperature ⁇ 20 ° C) 2 0 parts Polyisocyanate (Product name: NK Assist IS— 7 0 S,
  • a receiving sheet was prepared in the same manner as in Example 1 except that polyester resin emulsion B was used instead of polyester resin emulsion A in the coating liquid A for receiving layer of Example 1.
  • Example 5
  • a receiving sheet was prepared in the same manner as in Example 1 except that polyester resin emulsion C was used instead of polyester resin emulsion A in the coating liquid A for receiving layer of Example 1.
  • Example 6
  • Example 7 In the formation of the overcoat layer in Example 1, except that the overcoat layer was formed by coating and drying so that the solid coating amount of the overcoat layer was 15 mg / m 2. A receiving sheet was prepared in the same manner as in Example 1.
  • Example 7 In the formation of the overcoat layer in Example 1, except that the overcoat layer was formed by coating and drying so that the solid coating amount of the overcoat layer was 15 mg / m 2.
  • a receiving sheet was prepared in the same manner as in Example 1.
  • Example 7 Example 7
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1D was used instead of the receiving layer coating solution 1A.
  • Polyester resin emulsion A 8 0 parts Urethane resin (Product name: Evaphanol A P C— 5 5,
  • Example 8 A receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution E was used instead of the receiving layer coating solution A.
  • Polyester resin emulsion A 80 parts Urethane resin (Product name: Neo sticker 5500, manufactured by Nikka Chemical, glass transition temperature: 40 ° C) 20 parts Polyisocyanate (Product name: NK Assist IS — 7 0 S,
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1 F was used instead of the receiving layer coating solution 1 A.
  • Polyester resin emulsion A 6 0 parts Urethane resin (Product name: Neo sticker 1 2 200, manufactured by Nikka Chemical, glass transition temperature: 120 ° C) 4 0 parts Polyisocyanate (Product name: NK Assist IS — 7 0 S,
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1 G was used instead of the receiving layer coating solution 1 A.
  • Polyester resin emulsion A 4 0 parts Urethane resin (Product name: Neo sticker 1 2 0 0, manufactured by Nikka Chemical, glass transition temperature: — 2 0 ° C) 6 0 parts Polyisocyanate (Product name ⁇ NK Assis ⁇ ⁇ IS— 7 0 S, 2)
  • Example 1 1
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1H was used instead of the receiving layer coating solution 1A.
  • Polyester resin emulsion A 9 5 parts Urethane resin (Product name: Neo sticker 1220, manufactured by Nikka Chemical, glass transition temperature: 120 ° C) 5 parts Polyisocyanate (Product name: NK Assis ⁇ IS — 7 0 S,
  • Example 1 In the formation of the overcoat layer of Example 1, applied as solid coating amount of the overcoat layer is 1 mg Z m 2, dried over - except for the formation of the coating layer, as in Example 1 A receiving sheet was prepared in the same manner.
  • Example 1 3 In the formation of the overcoat layer of Example 1, applied as solid coating amount of the overcoat layer is 1 mg Z m 2, dried over - except for the formation of the coating layer, as in Example 1 A receiving sheet was prepared in the same manner.
  • Example 1 3 Example 1 3
  • Example 1 In the formation of the overcoat layer in Example 1, except that the overcoat layer was formed by coating and drying so that the solid coating amount of the overcoat layer was 25 mg / m 2. A receiving sheet was prepared in the same manner as in 1.
  • Example 1 4 In the formation of the overcoat layer in Example 1, except that the overcoat layer was formed by coating and drying so that the solid coating amount of the overcoat layer was 25 mg / m 2.
  • a receiving sheet was prepared in the same manner as in 1.
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution I was used instead of the receiving layer coating solution I.
  • Receptive layer coating liquid I Receptive layer coating liquid
  • Polyester resin emulsion A 8 0 parts Urethane resin (Product name: Neo sticker 1 2 0 0, manufactured by Nikka Chemical, glass transition temperature: 1 2 0 ° C) 2 0 parts
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution I was used instead of the receiving layer coating solution A.
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution K was used instead of the receiving layer coating solution A.
  • Polyester resin emulsion D 6 5 parts Urethane resin (Product name: Neo sticker 1700, Nikka Chemical, glass transition temperature: 20 ° C) 4 5 parts Polyisocyanate (Product name: NK Assist IS — 7 0 S,
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1 L was used instead of the receiving layer coating solution 1 A.
  • Polyester resin emulsion E 6 5 parts Urethane resin (Product name: Neo sticker 1700, Nikka Chemical, glass transition temperature: 20 ° C) 4 5 parts Polyisocyanate (Product name: NK Assist IS — 7 0 S,
  • a receiving sheet was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1 M was used instead of the receiving layer coating solution 1 A.
  • a receiving sheet was prepared in the same manner as in Comparative Example 1 except that the formation of the overcoat layer (Example 1) was omitted.
  • the printed matter was processed until the accumulated illuminance was 10 0, 0 00 kJ / m 2 in the Xe feed domain. Based on JISZ 8 7 2 1, it was measured using a color difference meter (Daretag). The measured value is JISZ
  • a commercially available thermal transfer video printer (product name: UP—50, manufactured by Sony Corporation) equipped with a sublimation thermal transfer ink clip (product name: UP—540, manufactured by Sony Corporation) on the obtained receiving sheet. It was used to print 10 images of black evening images under 50 ° C environment. At that time, the fusing state between the receiving sheet surface and the ink replies as the printability, and the paper discharge performance of the receiving sheet from the printer, etc. were evaluated according to the following criteria, and the repon peelability is shown in Table 2. .
  • Impossible Some of the receiving sheet surface and the ink lip are fused and may not be ejected normally, making them unsuitable for practical use.
  • the thermal transfer tester product name: TH — PMI 2, manufactured by Okura Electric Co., Ltd.
  • the applied energy was varied to obtain a sublimation thermal transfer ink reply (product name: UP-5540 (manufactured by Sony Corporation) was transferred, and the minimum energy that the protective layer could transfer was determined.
  • UP-5540 manufactured by Sony Corporation
  • each polyester resin (A to D) was synthesized by a known method, and an aqueous polyester emulsion (solid content 25%) ) was used to prepare the coating solution.
  • art paper product name: ⁇ K Kanafuji N, 17.4. 4 g / m 2 , made by Oji Paper Co., Ltd.
  • An intermediate layer was formed by coating and drying the intermediate layer coating solution 1 having the composition of 1 so that the film thickness after drying was 51 m.
  • a barrier layer coating solution having the following composition on the intermediate layer was coated and dried so that the solid content coating amount was 2 g / m 2 , and a barrier layer was formed. Apply the coating solution for receiving layer 1 N of the following composition to the solid content. It was coated dried as E amount is 5 g Zm 2, to form a receiving layer.
  • Swellable inorganic layered compound sodium 4 silicon mica
  • Polyester resin emulsion A 8 0 parts Urethane resin (Product name: Neo sticker 1 2 0 0, manufactured by Nikka Chemical)
  • the back layer coating solution 1 having the composition described in Example 1 is applied, and the solid content coating amount after drying is 3 gZm.
  • the back layer was formed by coating and drying to 2 and then heat-treated at 50 ° C. for 4 days. Further, in order to smooth the surface of the receiving sheet, a calendar process (roll surface temperature 78 ° C., nip pressure 2.5 MPa) was performed to prepare a receiving sheet.
  • an overcoat layer was formed by coating the coating solution for overcoat layer 12 having the following composition on the receptor layer and drying it so that the solid content was 3 mg / m 2 .
  • Silicone graph acrylic resin (trade name: X 2 4— 7 9 8 A, Manufactured by Shin-Etsu Chemical Co., Ltd.) Isopropanol 0 0 parts
  • a receiving sheet was prepared in the same manner as in Example 16 except that the barrier layer coating solution 1 was used in place of the NORIA layer coating solution 1-2.
  • Swellable inorganic layered compound sodium 4 silicon mica
  • Receiving layer coating solution A receiving sheet was prepared in the same manner as in Example 16 except that the receiving layer coating solution 1 O was used instead of N.
  • a receiving sheet was prepared in the same manner as in Example 16 except that the receiving layer coating solution-P was used instead of the receiving layer coating solution-N.
  • Coating solution for barrier layer Use 4 coating solution for barrier layer instead of 2, and further apply coating solution for receiving layer K instead of N coating solution for receiving layer (prepared in Comparative Example 1).
  • a receiving sheet was prepared in the same manner as in Example 16 except that was used.
  • Swellable inorganic layered compound sodium 4 silicon mica
  • barrier layer coating solution 1 instead of barrier layer coating solution 1 2 and receptive layer coating solution 1 N instead of receiving layer coating solution N (prepared in Comparative Example 1).
  • a receiving sheet was prepared in the same manner as in Example 16 except that was used.
  • Swellable inorganic layered compound sodium 4 silicon mica, (Average particle length 6.3 u rn, aspect ratio 1 0 0 0)
  • barrier layer coating solution 1 instead of barrier layer coating solution 1 2 and receptive layer coating solution 1 N instead of receiving layer coating solution 1 K (prepared in Comparative Example 1).
  • a receiving sheet was prepared in the same manner as in Example 16 except that was used.
  • Swellable inorganic layered compound sodium 4 silicon mica
  • a commercially available thermal transfer video pudding (product name: UP-5 50, manufactured by Sony Corporation) equipped with a sublimation type thermal transfer lipon (product name: UP-540, manufactured by Sony Corporation) was used on the obtained receiving sheet.
  • the printed matter was treated in an environment of 60 ° C. and 85% RH for 2 weeks. Using a color difference meter (Daretag), the color difference before and after processing was measured. The color difference is measured by the method specified in JISZ 8 7 2 2 using a color difference meter (manufactured by Daretag), and the reflection characteristics before and after processing of the printed material are measured and specified in JISZ 8 7 30. The color difference ⁇ E * before and after processing of the printed matter was calculated by the method described above. If the color difference is 13 or less, there is no practical problem.
  • Daretag color difference meter
  • a commercially available thermal transfer video printer (trade name: UP-5 50, manufactured by Sony Corporation) equipped with a sublimation thermal transfer ribbon (trade name: UP—540, manufactured by Sony Corporation) on the obtained receiving sheet. Then, a fine line image was printed at 20 ° C., and the width of the fine line was measured using a microscale under an optical microscope. The measured thin line image was processed for 2 weeks in an environment of 60 ° C. and 85% RH, and then the width of the thin line was measured again using a microscale under an optical microscope. The ratio of the width of the thin wire after the treatment to the width of the thin wire before the treatment was determined and used as the bleeding rate. If the bleed rate is less than 120%, it is at a level where there is no practical problem.
  • a commercially available thermal transfer video printer (trade name: UP-50, manufactured by Sony Corporation) equipped with a sublimation thermal transfer lipon (trade name: UP-540, manufactured by Sony Corporation) was used on the obtained receiving sheet.
  • UP-50 thermal transfer video printer
  • UP-540 sublimation thermal transfer lipon
  • Impossible Some sheets may not be properly ejected due to fusion between the receiving sheet and the repon, which is not suitable for practical use.
  • the receptive sheet of the present invention is excellent in transferability of the protective layer and peelability from the ink-reply, has a high printing density, is excellent in light resistance of the image, and is storable in an environment of high temperature and humidity. It is useful for full power labeling of various thermal transfer systems, including the sublimation thermal transfer system, and contributes greatly to the industry.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

L'invention concerne une feuille de réception de transfert thermique qui comprend un substrat de type feuille et une couche de réception d'image formée sur au moins une surface du substrat de type feuille, où la couche de réception d'image comprend : une résine polyester produite par la polycondensation d'un composant d'acide carboxylique polyhydrique et d'un composant d'alcool polyhydrique, où l'acide isophthalique comprend 75% en moles ou plus du montant total du composant d'acide carboxylique polyhydrique et l'alcool polyhydrique comprend principalement un alcool polyhydroxyle aliphatique et/ou un alcool polyhydrique alicyclique ; une résine uréthanique ; et un composé ayant un groupe alcoxysilyle hydrolysable et un groupe époxy dans la molécule.
PCT/JP2007/068328 2006-09-15 2007-09-13 Feuille de réception de transfert thermique WO2008032869A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2006250901 2006-09-15
JP2006-250901 2006-09-15
JP2006-327819 2006-12-05
JP2006327819A JP2009285830A (ja) 2006-09-15 2006-12-05 熱転写受容シート
JP2007-098360 2007-04-04
JP2007098360A JP2009285831A (ja) 2007-04-04 2007-04-04 熱転写受容シート

Publications (1)

Publication Number Publication Date
WO2008032869A1 true WO2008032869A1 (fr) 2008-03-20

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WO (1) WO2008032869A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017217844A (ja) * 2016-06-08 2017-12-14 凸版印刷株式会社 昇華転写用受像シート
CN114728530A (zh) * 2019-11-20 2022-07-08 大日本印刷株式会社 热转印图像接受片、印相物的制造方法和印相物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0564978A (ja) * 1991-03-28 1993-03-19 Dainippon Printing Co Ltd 熱転写受像シート
JPH0648056A (ja) * 1984-07-17 1994-02-22 Dainippon Printing Co Ltd 被熱転写シート

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0648056A (ja) * 1984-07-17 1994-02-22 Dainippon Printing Co Ltd 被熱転写シート
JPH0564978A (ja) * 1991-03-28 1993-03-19 Dainippon Printing Co Ltd 熱転写受像シート

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017217844A (ja) * 2016-06-08 2017-12-14 凸版印刷株式会社 昇華転写用受像シート
CN114728530A (zh) * 2019-11-20 2022-07-08 大日本印刷株式会社 热转印图像接受片、印相物的制造方法和印相物
CN114728530B (zh) * 2019-11-20 2023-10-20 大日本印刷株式会社 热转印图像接受片、印相物的制造方法和印相物

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