JPH01291990A - Dyestuff fixing material - Google Patents

Abstract

PURPOSE:To attain the light-resistance and preservation stability of a dyestuff image, by providing a specific oxygen barrier layer on a paper substrate, by adding further an oxidation inhibitor thereto, and by providing a dyestuff fixing layer accepting subliming dye, hot-melt ink or a dyestuff solution. CONSTITUTION:An oxygen barrier layer whose oxygen permeability at 20 deg.C and in relative humidity of 40% is 2ml/m<2>.hr.atm or below is provided on a paper substrate. Moreover, an oxidation inhibitor is added thereto. A polyolefin layer is provided on one side of the paper, while the oxygen barrier layer, a polyolefin layer and a dyestuff fixing layer are provided in this sequence on the other side thereof. It is also possible to provide the polyolefin layer on one side of the paper and to provide the polyolefin layer, the oxygen barrier layer and the dyestuff fixing layer in this sequence on the other side thereof. As to a polymer as a binder constituting the oxygen barrier layer, a homopolymer and a copolymer of vinyl alcohol are preferable, in particular. The oxidation inhibitor may be added to any layer in a dyestuff fixing material, such as a protective layer, the dyestuff fixing layer or a substrate layer. It is preferable, in particular, to add it to the dyestuff fixing layer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a dye fixing material used as a thermal transfer sheet for thermal transfer recording or an ink recording sheet for inkjet or bronter. The present invention relates to a thermal transfer sheet or an ink recording sheet that has a dye image with excellent light fastness and storage stability.

(Background Art) In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices for each information processing system have also been developed and adopted. As one of these recording methods, thermal recording method and inkjet recording method use devices that are lightweight, compact, noiseless, and have excellent operability and maintainability.
Colorization is also easy and has been widely used recently.

Thermal transfer recording methods can be roughly divided into 2fl'l methods.The first method is to apply heat to a heat-melting ink coated on a support from the support side, melting it in the form of a heat-applied pattern and recording. This is a method to obtain a hard copy by transferring it to a medium.The second method is to heat-print a heat-sensitive recording material made of a resin with a high softening point and a sublimable dye on a support from the support side in the same way as the former. In this method, a sublimable dye is sublimated in a patterned pattern and transferred to a recording medium to obtain a hard copy.

Various inkjet recording methods have been developed, but in terms of physical properties, they can be broadly divided into dye solutions containing water-soluble dyes (
There are two methods: a method using a water-based ink) and a method using a dye solution containing an oil-soluble dye (oil-based ink). The former is a method of forming an image by ejecting fine droplets of ink onto an oil-absorbing ink recording sheet and absorbing them.

Furthermore, there is also known an apparatus for drawing images on an ink recording sheet using a plotter or the like using water-soluble or oil-soluble dye inks such as those described above.

(Problems to be Solved by the Invention) However, the thermal transfer sheet or ink recording sheet on which an image is formed in this manner has sufficient hue, saturation, and brightness of the resulting image; The resulting image has insufficient light resistance and storage stability.

As described above, a dye image fixed on a layer (dye fixing layer) on which an image is formed by thermal transfer, inkjet, plotter, etc. deteriorates when exposed to light in the presence of oxygen, and is subject to photochange and discoloration.

In order to prevent photofading, an antioxidant can be included in the dye fixing element, thereby improving light fastness.

However, when paper is used as a support, the improvement effect is small and the light fastness is insufficient.

(Structure of the Invention) An object of the present invention is to provide a dye-fixing material comprising a dye-fixing layer on a paper support that receives a sublimable dye, a heat-fusible ink, or a dye solution. Oxygen transmission rate at 20°C and 40% relative humidity is 2ad/rrr-hr-
This was achieved by a dye fixing material characterized by having an oxygen barrier layer below ATM and further containing an antioxidant.

Hereinafter, a specific configuration of the present invention will be explained in detail.

The oxygen permeability in the present invention is 2d/rd-hr・at
m (20°C, 40% RH) or less (hereinafter referred to as "oxygen blocking layer") is present on the paper support side of the dye fixing layer,
They do not necessarily have to be adjacent, and can be provided in the following manner.

(1) A polyolefin (eg, polyethylene, polypropylene) N is provided on one side of the paper, and an oxygen barrier layer, a polyolefin layer, and a dye fixing layer are provided in this order on the other side.

(2) A polyolefin layer is provided on one side of the paper, and a polyolefin layer, an oxygen barrier layer (if necessary, a further polyolefin layer on the oxygen barrier layer), and a dye fixing layer are provided in this order on the other side.

(3) Polyolefin layer on one side of the paper, on the other side,
An oxygen barrier layer, a polyolefin layer, and an oxygen barrier dye fixing layer are provided in this order.

(4) An oxygen barrier layer 1 and a dye fixing layer are provided in this order on one side of the paper, and a polyolefin layer is provided on the other side in this order.

(5) Each type B includes providing an oxygen barrier layer on one or both sides of the paper, and providing a dye fixing layer on the side with the oxygen barrier layer.

In each of the above H types, one or two layers of a hydrophilic organic colloid layer such as a gelatin undercoat layer, a polymer undercoat layer, etc. are provided between the dye fixing layer and the polyolefin layer or oxygen barrier layer.
It may have more than one layer, and the polymer layer may have a West German patent 1.
, 921.641 may be applied.

A surface protective layer or the like may be provided on the dye fixing layer.

A polymer other than polyolefin may be used on the side opposite to the side with the dye fixing layer of the paper support, or it may not have a polymer layer, but the polymer used is one that forms a waterproof film. For example, olefin, vinyl chloride, vinylidene chloride, acrylonitrile,
Homopolymers and copolymers with monomers such as acrylic esters, methacrylic esters, acrylic amide, methacrylic amide, vinyl alcohol, styrene, fluorinated vinyl, ethylene terephthalate, vinyl acetate, etc., cellulose acetate, polyamide, polycarbonate, cellophane, etc. . Also, these polymers are 1
Although it may be used in layers, it may also be used in a stack of two or more layers.

There is no particular limit to the thickness of the oxygen barrier layer of the present invention, and the oxygen permeability is 2 m/r+(-hr ・at m (20℃4
The thickness may be set to 0% RH) or less, but it is preferably 1 to 100 μm, particularly 2 to 50 μm.

When the thickness is 1 μm or less, pinholes are likely to be formed to block oxygen, and there is a risk that oxygen will eventually be allowed to permeate. However, the polymer forming the oxygen barrier layer may partially penetrate into the paper support, and in this case, the oxygen impermeable layer has a thickness of 1 μm.
The desired oxygen permeability can be obtained even below.

On the other hand, if it exceeds 100 μm, it will affect the overall thickness of the dye fixing material, which is not preferable.

In addition to the polymer as a binder, the oxygen barrier layer of the present invention may optionally contain fillers such as titanium oxide and barium sulfate, optical brighteners, antistatic agents, and ultraviolet absorbers.

Polymers as binders constituting the oxygen barrier layer of the present invention include acrylonitrile, alkyl acrylates (for example, methyl acrylate, ethyl alkrylate, butyl acrylate, etc.), alkyl methacrylates (
(e.g. methyl methacrylate, ethyl methacrylate, etc.)
, methacrylonitrile, alkyl vinyl esters (e.g. vinyl acetate, vinyl propionate, vinyl ethyl butyrate, vinyl phenylacetate, etc.), alkyl vinyl ethers (e.g. methyl vinyl ether,
butyl vinyl ether, chloroethyl vinyl ether, etc.), homopolymers and copolymers such as vinyl alcohol, vinyl chloride, vinylidene chloride, vinyl fluoride, styrene, vinyl acetate (in addition to the above, examples of comonomers include ethylene, propylene, etc.), cellulose acetate ( e.g. diacetylcellulose, triacetylcellulose)
, polyester (e.g. polyethylene terephthalate)
, fluororesin, polyamide (nylon), polycarbonate, polysaccharide, pullulan, cellophane, etc., but are not limited to these.

Among these polymers, vinyl alcohol homopolymers and copolymers are particularly preferably used in the present invention.

Particularly preferred is a vinyl alcohol content of 20 to 80.
It is a copolymer with a mole % ethylene content of 80 to 20%, for example, EVAL (registered trademark is EVAL O1 and below) E from Kuraray Co., Ltd. (softening point: 155°C, melt viscosity at 210°C: 0.7 x 10' poise).

(CHl-CH) Polymer containing about 60 mol% of 0H) and EVAL F (polymer containing about 60 mol%
Softening point: 175°C, melt viscosity at 210°C: 1.3 XIO
'poise -, (CHt CH)-OH about 7
It is commercially available under the trade name of Polymer containing 0 mol%. The above-mentioned compound is a known compound described in "Eval ■" published by Kuraray Co., Ltd.'s Poval Sales Department.

Furthermore, homopolymers and copolymers of vinylidene chloride or acetonitrile are preferably used.

In the present invention, there are no particular limitations on the method of providing the oxygen barrier layer on the paper support, and any method normally used for forming a polymer film can be used.

Examples include melt extrusion methods, coating methods, and lamination methods.

As the melt extrusion method, an advantageous method is to extrude the dissolved polymer into a film through a die (T-Gui) having a linear slit at the tip of the extruder, thereby forming an oxygen barrier layer on the paper support. be. Coating methods include a method in which a polymer is dissolved in water or an organic solvent, the solution is uniformly applied onto a paper support, and dried with hot air, and a method in which a polymer emulsion is applied and dried.

In the present invention, two or more oxygen barrier layers and polyolefin layers can be simultaneously provided on a paper support by coextrusion. Further, when using a lamination method, in addition to the method of laminating the oxygen barrier layer and the polyolefin layer one by one, it is also possible to form a composite film consisting of a plurality of layers and then laminate the composite film.

Note that these oxygen-blocking layers can also be further applied to the dye-fixing layer side surface of the dye-fixing material after image formation, for example, by laminating, coating, spraying, or the like.

As the paper support for the dye-fixing material of the present invention, mixed paper made from synthetic resin bulbs such as polyethylene or polypropylene and natural bulbs, Yankee paper, baryta paper, coachite paper (especially cast coated paper), etc. are used. However, synthetic paper (eg, made of polypropylene or the like) may also be used.

As the antioxidant used in the present invention, compounds represented by the following (1) to (V) are suitable for use. These compounds will be detailed below.

General formula (1) where R1 represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or a trialkylsilyl group,
A represents a nonmetallic atom necessary to complete a 5- or 6-membered ring together with -C=C-0-.

R1, R3 and R4 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an acylamino group, a halogen atom, an alkylthio group , diacylamino group, arylthio group, alkoxycarbonyl group, acyloxy group, acyl group or sulfonamide group, which may be the same or different from each other.

Further - the compound represented by maximum (1) contains 5
or 6-membered ring bisspiro compounds.

Useful bisspiro compounds included in the present invention include those represented by the following general formula (I').

General formula (■゛) R1, R2, R3, R4, R1 in general formula (■゛)
', R2', R3', and R4' have the same meanings as R', R'', R3, and R4 in maximum (1). 5-hydroxycoumarans and 6-hydroxychromans in which the total number of atoms is up to about 40 and in which one of R8 and R3 in the bottom port → is a hydrogen atom, and -maximum (1') 6,6'-dihydroxybis-2,2'-spirochromans are particularly useful.More preferably R1, R3, R4, R2', R3' of the general formula (+) and -maximum (1') , and R4' are each an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an alkylthio group.

General formula (n) In the formula, R' is the same as defined in maximum (1), and R5 is an alkyl group, an alkoxy group, an alkoxycarbonyl group, a ruthio group, an arylsulfinyl group,
Arylsulfonyl group, aralkyl group, halogen atom,
represents an aryl group or an acyl group, Rh is a hydrogen atom,
Alkyl group, alkoxy group, (however, R'0- and R6 are not the same substituent), aralkyloxy group, alkylthio group, aralkylthio group, acylamino group, acyl group, alkylamino group, -represents an amino group or a heterocyclic amino group. R7 represents a hydrogen atom, a halogen atom, an alkyl group, an arylthio group, an alkylthio group, an arylsulfonyl group, an arylsulfinyl group, an aralkyl group, an aryl group, an aryldithio group, or an aryloxy group.

Among the compounds represented by the general formula (II), compounds represented by the general formula (■') are preferred from the viewpoint of the effects of the present invention.

General formula (■゛) Here, G is -S-1-S-S-1-〇-1-CH, -
3-CH,-1-SO,-1-SO-1(CHz)ll
G O(CHx)-S (CHx)-CO-(CHz
), 1-1- (CHI), COt (CHI), -3
-(CH Ri.-COz (CHz)-1, CHz O
CHz−1 −N−1Rzi R” +0 sho.

R2fu, or (C)It)aCOi+CH*), -Z-(CIlri)
, -COl-(CHz)@-C-(CIri, COt
CCH2), l-amount (CL)-COz(CL), and Z.

R11, RRl, R23, R''4!, better < halogen atom or alkyl group having 1 to 20 carbon atoms, aryl group,
Aralkyl group, alkylthio group, halogen atom, alkoxy group, arylthio group, aralkoxy group, allyloxy group, -COOR", -NHCOR", NH30z
R"Sow R19, -C1-COR", (CH,), represents A, R25 represents a hydrogen atom, an alkyl group, or an aryl group, and Rzi and RRl each represent a hydrogen atom, an alkyl group, or an aryl group. Or these are bonded to each other to represent a substituted 5- or 6-membered ring.

Rza represents a hydrogen atom or a methyl group, Rtq represents an alkyl group or an aryl group, R30 and R31 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Represents an aralkyl group or a 5- or 6-membered heterocycle bonded to each other and having any of the above-mentioned substituents, Z is CH A is an ester group or general formula (III), where R1 is general formula (1) is the same as defined,
R8 represents a hydrogen atom, a linear or branched alkyl group or an alkenyl group, R9 represents a linear or branched alkyl group or an alkenyl group, and Rfl and R9 may be the same or different from each other.

Further, the above substituents R8 and R9 may have an -NHCO- bond within the substituent.

- Bottom (IV) In the formula, RIG is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, or R"Co, R"so
n or R" represents a group represented by NHCO. Here, RII, R'9 and R10 each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, R
11 and RI2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group; represent.

General formula (Vn Rh.

L+ In the formula, E represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring together with C and N.

R50 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group, or a hydroxyl group. R51, B5R
1R53 and R34 may be the same or different and each represents a hydrogen atom or an alkyl group.

Examples of the 5- to 7-membered ring formed by this include a pyrrolidine ring, a piperazine ring, a morpholine ring, and a piperidine ring.

Among these, it is preferable that the ring formed by I is a piperidine ring, and more preferably, the ring formed by I is a veridine ring, or -ZIR"SR",
This is the case where at least two or more of R53, Oyo and Rh4 are methyl groups.

Specific examples of compounds represented by -bottom (0 to (V)) are listed below, but the compounds are not limited thereto.

−Bottom (■゛) ■'-1 1゛-2 ■'-3 ShiH, CH.

General formula (II) 1[-1 0■Ut12LiUUL;121! S H General formula (■') ■'-1 ■゛-2 ■ '-3 ■゛-4 ■ '-5 ■'-6 General formula (I) III -1 n[-2 H V-2 ShiII , L; 113 V-3 -I V-4 Also - chroman compounds or coumaran compounds represented by maximum (+), - phenolic derivatives represented by maximum (n), - represented by maximum (II[) Hydroquinone derivatives, spiroindane derivatives represented by -maximum (TV), and hindered amine ffli derivatives represented by -maximum (V) may be used alone or in combination of two or more. Furthermore - maximum (i')
, (■') may be used in combination with antioxidants other than the compounds represented by formulas (1) to (V).

Furthermore, U.S. Patent Nos. 2,360,290 and 2,4
No. 18,613, same No. 2. 675. 314, No. 2.701,197, No. 2,704.713, No. 2,728,639, No. 2.732,300,
2,735,765, 2,710.801, 2.816°028, British Patent No. 1,363,
Hydroquinone derivatives described in US Pat. No. 3,457.079, gallic acid derivatives described in US Pat. No. 3,069,262, etc., US Pat.
．． No. 765, Dotai No. 3,698,909, Special Publication No. 1973-
p-alkoxyphenols described in No. 20977 and No. 52-6623, U.S. Patent No. 3,432,300
No. 3,573,050, No. 3,574,62
No. 7, No. 3,764.337, JP-A-52-356
No. 33, No. 52-14743, No. 52-152225
It is also possible to use p-oxyphenol derivatives described in No. 1, etc.

The above antioxidant may be added to any layer in the dye-fixing material, such as the protective layer, dye-fixing layer, undercoat layer, etc. It is particularly preferable to add it to the dye-fixing layer, but not to the adjacent layer. Good too.

The antioxidant only needs to be present in the dye fixing material at least after image formation. Therefore, after the image forming process, a coating solution containing an antioxidant may be applied or sprayed onto the uppermost layer (for example, a protective layer) of the dye-fixing material, and may also be incorporated into the thermal transfer sheet or ink to form the dye-fixing element. It may be transferred to

The content of antioxidant in the dye fixing material is 0.01
-10 g/rd, preferably 0.1-2 g/rr+.

In the present invention, an ultraviolet absorber can be further added to the dye fixing material to further improve light fastness.

Examples of ultraviolet absorbers that can be used in the present invention include aryl group-substituted hensitriazole compounds (e.g., those described in U.S. Pat. No. 3,533.794), 4-thiazolidone compounds (e.g., U.S. Pat. ,3
14,794 and 3,352,681), benzophenone compounds (e.g., JP-A-46-27
84), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805, U.S. Pat. No. 3,707.
No. 375) butadiene compounds (such as those described in U.S. Pat. No. 4,045,229), or benzoxazole compounds (such as those described in U.S. Pat. No. 3,7
00,455) can be used.

Furthermore, U.S. Patent No. 3,499,762, JP-A-54
-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used.

Ultraviolet absorbers suitable for use in the present invention are compounds represented by the following maximum (Vl) to (IX).

General formula (Vl) +111 h+3 -Bottom (■) General formula (■) General formula (IX) In the above -bottom (Vl) to (IX), R11 to R1
may be the same or different and represent a hydrogen atom, a halogen atom, an acyloxy group, an aliphatic group, an aromatic group, R1, o- or RtySOz-, and R16 to R19 may be the same or different, a hydrogen atom, a halogen atom, hydroxy group, aliphatic group, aromatic group, carbonamide group, sulfonamide group, sulfo group, carboxy group, or RtvO
-, Rla and R21 may be the same or different, and represent a hydrogen atom, an aliphatic group, a halogen atom, or Rgto-, Rxzs R2% and R1 may be the same or different, and represent a hydrogen atom, an aliphatic group, R13 and R24 may be the same or different and may represent a cyano group, a carbamoyl group, a sulfamoyl group, a formyl group, a C0R1? , -5O
R2,, -8OtRt? , S Ot ORZ? , or -COORzq.

Here, the aliphatic group refers to a substituted or unsubstituted linear, branched, or cyclic alkyl group, and the aromatic group refers to a substituted or unsubstituted monocyclic or condensed benzene ring. Indicates the group.

- Examples of compounds represented by bottoms (Vl) to (IX) are shown below, but are not limited to these.

V-I V-2 V-3 V-4 V-5 C113C1h fCI! -Cto1-1-beC1l□-CtoTCyoOC0
0Ctli H2 V-6 0■ V-7 il U V -5 UV-9 C113(J13 (CHz -CHT--HCHz -CH←TC=O
COOCH3 Layers are preferred.

Alternatively, it may be included in the oxygen barrier layer.

Furthermore, after the image forming process, a coating solution containing an ultraviolet absorber is applied to the top layer (for example, a protective layer) of the dye-fixing material.
It may be sprayed or transferred from a thermal transfer sheet or ink to the dye fixing material. Polyethylene terephthalate (PET) containing ultraviolet absorbers
An ffi composite film or an oxygen barrier layer material such as the above may be laminated or coated or sprayed onto the dye fixing material. Alternatively, after laminating, a coating liquid containing an ultraviolet absorber may be applied or sprayed.

The content of ultraviolet absorber in the dye fixing material is 0.0
2-20 g/nf, preferably 0.1-5 g/n
(Suppose.

When the binder forming the dye fixing layer is hydrophilic, these antioxidants and ultraviolet absorbers can be introduced into Fuchu by any known method.

That is, if it is water-soluble, it may be dissolved as is.

If it is water-insoluble, an oil protection method can be used. In this method, a high boiling point solvent and, if necessary, a low boiling point solvent having a boiling point of 50° C. to 160° C. may be used in combination for dispersion.

The high boiling point solvent used in this case is JP-A-59-8
No. 3154, No. 59-178451, No. 51-178
No. 452, No. 59-178453, No. 59-1784
No. 54, No. 59-178455, No. 59-17845
Those described in No. 7 etc. can be used.

Alternatively, fine particles may be dispersed in solid form (solid dispersion method).
.

Others: Special Publication No. 51-39853, Japanese Patent Publication No. 51-59
The polymer dispersion method described in No. 943 can also be used.

When the binder forming the dye fixed layer is hydrophobic (oil-soluble), a hydrophobic (oil-soluble) antioxidant or ultraviolet absorber may be dissolved in a common solvent.

In addition, in order to laminate various films, a patent application of 1983 is required.
It may be carried out according to a known method, such as using the adhesive or hot melt adhesive described in Japanese Patent No. 234559.

A known method may be used to incorporate the antioxidant or ultraviolet absorber into the polymer film or layer.

In addition, the antioxidant and the ultraviolet absorber may be added to the same layer or may be added to separate layers. For example, the ultraviolet absorber may be contained in the protective layer and the antioxidant may be contained in the dye fixing layer, or they may be dispersed in the oil droplets using the oil protection method as described above.

The thermal transfer sheet of the present invention has a dye fixing layer, that is, a receiving layer, which receives the sublimable dye transferred from the thermal transfer sheet during printing and has a function of dyeing the sublimable dye. Generally, the thickness is 3~ including the following synthetic resins.
A 50 μm coating is preferred.

(a) Polyester resins having ester bonds, polyacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, vinyl toluene acrylate resins, etc. (rl) Polyurethane resins having urethane bonds.

(c) Those containing an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(Reference) Other materials having highly specific bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof may also be used.

Further, the receptor layer can also be formed from two types of resins having different properties.

Further, the receptor layer can be formed by adding fine silica powder to the above-mentioned resin.

Here, silica refers to silicon dioxide or a substance containing silicon dioxide as a main component. The fine powder silica to be contained in the receptor layer has an average particle size of 10 to 100I and a specific surface area of 25.
Those with an average particle size of less than 0rd/g, more preferably an average particle size of 10~
Cocoons with a 50μ cocoon and a specific surface area of 20 to 200 rrr/g are used.

Further, the content of fine powder silica is in the range of 5 to 20% by weight, more preferably 5 to 10% by weight, based on the weight of the receiving layer.

These finely powdered silicas are added in advance to the resin forming the receptor layer, and the resulting resin mixture solution is applied onto a substrate and dried to form the receptor layer.

The thermal transfer sheet of the present invention may contain a release agent in the receptor layer in order to improve the releasability from the thermal transfer sheet. As a mold release agent, solid waxes such as polyethylene wax, amide wax, and Teflon powder;
Examples include fluorine-based and phosphoric acid ester-based surfactants; silicone oil and the like, but silicone oil is preferred.

Although any oily silicone oil can be used as the silicone oil, a hardened type is preferred.

The thickness of the release agent layer is 0.01 to 5 μm, especially 0.05 to 2 μm.
μ-sho is preferred.

Note that if silicone oil is added when forming the receptor layer, the silicone oil bleeds onto the surface after coating, so a release agent layer can be formed even if it is cured after bleeding.

In the thermal transfer sheet of the present invention, an undercoat layer may be formed between the paper support and the receptor layer, and the undercoat layer is either a cushioning layer or a porous layer depending on the constituent material.
Or, in some cases, it also serves as an adhesive.

Examples of resins that meet the above conditions include the following.

Polyurethane resin Polyester resin Polybutadiene resin Polyacrylate ester resin Epoxy resin Polyamide resin Rosin modified phenol resin Terpene phenol resin Ethylene/vinyl acetate copolymer resin The above resins can be used alone or in combination of two or more.

The porous layer consists of: 1) a layer obtained by coating a base sheet with a liquid made by mechanically stirring a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene and drying it, and 2) the above synthetic resin emulsion. , a layer in which a liquid mixture of the above synthetic rubber latex and a blowing agent is applied onto a base sheet and dried; 3) a layer in which a blowing agent is mixed with a synthetic resin such as PVC blastisol, polyurethane, or a synthetic rubber such as styrene-butadiene system. 4) A layer formed by applying a liquid onto a base sheet and foaming it by heating; A mixture of a non-solvent (including those mainly composed of water) that has no solubility in thermoplastic resins or synthetic rubbers is applied onto a base sheet and dried to form micro-agglomerates. A microporous layer formed by forming a film formed by the above method is used.

The above-mentioned intermediate layer may be provided on both sides of the thermal transfer sheet when the receiving layer is provided on both sides, or may be provided on only one side. Further, the thickness of the intermediate layer is preferably 0.5 to 50 μm, particularly preferably 2 to 20 μm.

The receptor layer of the present invention has improved sliding properties, improved adhesion resistance,
Oil droplets may be present for the purpose of improving releasability and further improving curl balance.

In the present invention, an oil droplet is an independent system of oil canes finely dispersed in a hydrophilic colloid, and refers to a liquid particle that is substantially insoluble in water.The smaller the size of the oil droplet, the better; Preferably the average particle size is 3 μm or less, especially 1. It is preferably less than 0.5 microns, more preferably less than 0.5 microns.

The oil droplets in the present invention include, for example, esters (e.g., phthalate esters, phosphate esters, fatty acid esters, etc.), amides (e.g., fatty acid amides, sulfamides, etc.), ethers, alcohols, paraffins, Does it have a high boiling point, such as silicone oil, which is liquid at room temperature and does not evaporate at heat treatment temperatures? 8 medium is preferred.

The thermal transfer sheet of the present invention is used in combination with a thermal transfer sheet.

The first embodiment of the heat-sensitive transfer sheet is such that the heat-sensitive transfer layer provided on the base sheet is a heat-sensitive sublimation transfer layer comprising a heat-transferable dye and a binder resin. The heat-sensitive transfer sheet of this embodiment is prepared by preparing a coating solution by dissolving or dispersing a conventionally known heat-transferable dye, that is, a sublimation-transferable dye, and a binder resin in an appropriate solvent.
The coating liquid is applied to one surface of a conventionally known base material sheet for a thermal transfer sheet, for example, about 0.2 to 5.0μ, preferably 0.
．． It is obtained by coating in an amount that gives a dry film thickness of 4 to 2.0 μm and drying to form a heat-sensitive sublimation transfer layer.

As the dye useful for forming such a heat-sensitive sublimation transfer layer, any sublimable dye conventionally used in heat-sensitive sublimation transfer sheets can be used, but in the present invention, dyes of approximately 150 to 600% are particularly preferred. It has a relatively low molecular weight and is selected in consideration of sublimation temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc. Specifically, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. are used, and in particular, Sumikalon Yellow E4GL, Dianix Yellow H2G-FS,
Miketon Polyester Yellow 3GSL.

Kaya Set Yellow 937, Sumikaron Red EFBL
, Dianicus Red ACE, Miketon Polyester Red FB, Kayaset Red 126, Miketon Fast Prillian Blue B, Kayaset Blue 136, etc. are preferably used.

Also, JP-A-51-78.895, JP-A No. 60-28.45
No. 1, No. 60-28,453, No. 60-53,564
No. 61-148,096, No. 60-239,29
No. 0, No. 60-31,565, No. 60-30,393
No. 6 (No. 1-53゜565, No. 60-27,594)
No. 61-262.191, No. 60-152,56
No. 3, No. 61-244, 595, and No. 62-19
Sublimable yellow dye described in No. 6゜186, No. 60-2
No. 23,862, No. 60-28,452, No. 60-3
No. 1,563, No. 59-78.896, No. 60-31
．． No. 564, No. 60-30, 391, No. 61-227
, No. 092, No. 61-227゜091, No. 60-30
, No. 392, No. 6o-30, 394, No. 60-131
, No. 293, No. 61-227,093, No. 60-15
No. 9,091, No. 61-262,190, U.S. Patent No. 4
．． No. 698.651 and patent application No. 62-220,793
In the above formula, RI and Rz are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, a cyan group, an acylamino group, a sulfonylamino group, R3, R4 represent a raid group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an amino group;
represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. R1 and R4 may be combined with each other to form a sum, or R1 and R1 or R2 and R1 may be combined to form a ring. n represents an integer from 0 to S3. X, Y and Z represent -C- or a nitrogen atom (R% is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group,
(represents an aryloxy group or an amino group).

Rs Rs When X and Y are -C- or when Y and Z are -C-,
They may be bonded to each other to form a saturated or unsaturated carbon ring.

Each of the above substituents may be further substituted with other substituents. ) Sublimable Mazenk dye described in JP-A-59-7
No. 8,894, No. 59-227゜490, No. 60-1
No. 51.098, No. 59-227.493, No. 61-
No. 244,594, same 5! J-227,948, 6
No. 0-131.292, No. 60-172,591, No. 60-151.097, No. 60-131,294,
No. 60-217,266, No. 60-31,559,
No. 60-53,563, No. 61-255゜897,
No. 60-239,289, No. 61-22.993,
6m-19,396, 61-268,493,
61-35,994, 61-31,467, 61-148,269, IF-49,893,
61-57゜651, 60-239,291,
No. 60-239.292, No. 61-284,489, No. 62-191,191 and Patent Application No. 1983-176
．． Uses dye represented by No. 625. In the formula, Ql represents an atomic group containing at least one nitrogen atom and necessary to form a 5-membered or more nitrogen-containing heterocycle with the bonding carbon atom,
R' represents an acyl group or a sulfonyl group, R2 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, and R3
represents a hydrogen atom, a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, R4 represents a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, and n is O
Represents an integer from ~4. R3 is R1 or Rt or R
R5 and R& may be combined with 4 to form a ring. R5 and R& represent a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. R5 and R6 may be bonded to each other to form a ring, and R8 and/or R6 may be bonded to R4 to form a ring. ) is also suitably used.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. For example, polyamide resin, polyester resin,
Vinyl resins, including epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), polyvinylpyrrolidone, etc., polyvinyl chloride resins (e.g. vinyl chloride-2-acrylonitrile), etc. (vinyl acetate copolymer, etc.), polycarbonate resin, polysulfone, polyphenylene oxide, cellulose resin (e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate,
Cellulose acetate butyrate, cellulose triacetate, etc.), polyvinyl alcohol resins (e.g. polyvinyl alcohol, partially saponified polyvinyl alcohols such as polyvinyl butyral, etc.), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, novolac phenols resin, polystyrene resin, polyolefin resin (eg, polyethylene, polypropylene), etc. are used.

Such a binder resin is preferably used, for example, in a proportion of about 10 to 65 parts by weight per 101 parts by weight of dye.

In the present invention, as the ink solvent for dissolving or dispersing the above-mentioned dye and binder resin, conventionally known ink solvents can be freely used. Specifically, alcohol-based ink solvents include methanol, ethanol, isopropyl alcohol, butanol, Butanol, etc. Ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Aromatics include toluene, xylene, etc.
Dichloromethane, trichloroethane, etc. as halogens,
Mention may be made of dioxane, tetrahydrofuran, etc., as well as mixtures of the abovementioned solvents. It is important to select and use these solvents so that the dye used has a predetermined concentration or higher and the binder resin is sufficiently dissolved or dispersed. For example, it is preferable to use the solvent in an amount of about 9 to 20 times the total weight of the dye and binder resin.

The heat-sensitive transfer sheet of the embodiment obtained as described above is superimposed on the heat-sensitive transfer sheet of the present invention, and from either side,
Preferably, by heating the surface of the heat-sensitive transfer sheet according to the image signal using a heating means such as a thermal head, the dye in the heat-sensitive transfer layer can be easily transferred to the receiving layer of the heat-sensitive transfer sheet with relatively low energy. The image is transferred according to the size of the image, making it possible to form a gradated color image with excellent clarity and resolution.

A second embodiment of the heat-sensitive transfer sheet is an embodiment in which the heat-sensitive transfer layer of the heat-sensitive transfer sheet is a heat-sensitive melting transfer layer comprising a dye or pigment and wax. In the leisurely transfer sheet of this embodiment, an ink for forming a heat-sensitive transfer layer made of wax containing a coloring agent such as a dye or a pigment is prepared on one surface of a conventionally known base sheet for a heat-transfer sheet, and a heat-sensitive transfer layer-forming ink made of wax containing a coloring agent such as a dye or a pigment is prepared from the ink. It is obtained by forming a transfer layer. The ink is made by blending and dispersing coloring agents such as carbon black and various dyes and pigments, using waxes with appropriate melting points, such as paraffin wax, microcrystalline wax, carnauba wax, urethane wax, etc., as a binder. That's what happens. The ratio of the dye or pigment to the wax used is preferably in the range of about 10 to 65% by weight of the dye or pigment in the heat-sensitive melt transfer layer to be formed, and the thickness of the layer to be formed is about 1.5 to 6.5% by weight. A range of 0 μm is preferred. Their manufacture and application onto a substrate film can be carried out according to known techniques.

As the base sheet for the thermal transfer sheet used in the first and second embodiments of the thermal transfer sheet, any conventionally known substrate sheet can be used.For example, polyester, such as poly(ethylene terephthalate); polyamide; polycarbonate: glassine. Condenser paper; Cellulose ester; Fluorine polymer; Polyether; Polyacetal; Polyolefin; and polyimide, polyphenylene sulfide, polypropylene, polysulfone,
Examples include allophane and polyimide.

The base sheet for thermal transfer sheets generally has a thickness of 2 to 30 μm.
It is. It may also be coated with a subbing layer if necessary.

A dye-barrier layer consisting of a hydrophilic polymer may also be used in the dye-donor member between the support and the dye layer to improve dye transfer.

Dye - The dye in the donor member is
It may be coated with a slipping layer that prevents it from sticking to the donor member. Such slipping layers consist of lubricating substances, such as surfactants, liquid lubricants, solid lubricants or mixtures thereof, with or without a polymeric binder layer.

On the other hand, the dye fixing layer, that is, the ink absorbing layer of the ink recording sheet of the present invention preferably contains a mordant, and in this case, it preferably has at least one layer containing a mordant and a binder.

As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500°626 No. 5.
8-59L JP-A No. 61-88256 (32)-(41
) pages and JP-A-62-253160 (40)-(48)
Mordant as described in page 60-118834, 6
Examples include those described in Japanese Patent Application No. 0-119557, Japanese Patent Application No. 60-235134, Japanese Patent Application No. 61-87180, and Japanese Patent Application No. 61-87181.

Among such mordants, imidazole compounds are preferred. Specific examples of such compounds include polymers having a tertiary imidazole group or a quaternary imidazole salt.

Examples of polymers having such a tertiary imidazole group include homopolymers and copolymers containing vinyl monomer units having this group.

Specific examples of this include U.S. Patent No. 4,282.305, U.S. Pat.
It is described in JP-A-60-118834 and JP-A-60-122941.

Furthermore, examples of polymers having quaternary imidazolium salts include homopolymers and copolymers containing units of vinyl monomers having quaternary imidazolium salts, and preferred specific examples thereof include British Patent No. 2,056,101. , No. 2,093°041, No. 1,594,961
No. 4.124.386, No. 4,115,
No. 124, No. 4,273,853, No. 4,450
Examples include those described in No. 224, JP-A No. 4111-28225, and the like.

Among these, polymers having tertiary imidazole groups are preferred from the viewpoint of light fastness.

In the ink recording sheet of the present invention, the following water-soluble polymers can be used together as a binder in the water-based ink absorbing layer.

For example, vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium halide, cationic modified polyvinyl alcohol, and derivatives thereof (JP-A-60-145879, JP-A-60-22075)
No. 0, No. 61-143177, No. 61-235182
No. 61-235183, No. 61-237681, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polysodium acrylate, acrylic acid meccrylic acid copolymer salt, polymethacrylic Acrylic group-containing polymers such as acid soda and acrylic acid vinyl alcohol copolymer salts (JP-A-60-168651
No. 62-9988), starch, oxidized starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin,
Natural polymers or their derivatives such as sodium alginate, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroquinepropylcellulose (JP-A-59-1743'82
No. 60-262685, No. 61-143177, No. 61-181679, No. 61-193879,
61-287782), alkali-treated or acid-treated gelatin, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether maleate copolymer, N-vinylpyrrole maleate copolymer, polyethylene imine, and other synthetic polymers (
JP-A-61-32787, JP-A No. 61-237080,
61-277483) and water-soluble polymers described in JP-A-56-58869.

Further, in the ink recording sheet of the present invention, the oil droplets may be present in order to improve slipperiness, adhesion resistance, curl balance, and the like.

In the present invention, fillers such as silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobon, and satin white are added to the aqueous ink absorbing layer. It can also be dispersed in the ink absorbing layer.

Furthermore, various known additives such as a dispersant, a fluorescent dye, a pH adjuster, an antifoaming agent, a lubricant, a preservative, and a gelatin hardening agent may be added to the aqueous ink absorbing layer or its adjacent layer. .

In the present invention, the ink layer may have a single layer structure or a multilayer structure. An example of a multilayer structure is Japanese Patent Application Laid-Open No. 57-89954.
No. 60-224578 and No. 61-12388.

For example, the ink permeable layer described in JP-A-61-12388 may be further provided on the aqueous ink absorbing layer of the present invention.

An antistatic agent can also be contained in the receptor layer on at least one side of the dye fixing material of the present invention or on the surface of the receptor layer. Antistatic agents include surfactants such as cationic surfactants (for example, quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (for example, alkyl phosphates, etc.), amphoteric surfactants or nonionic surfactants. type surfactants.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these Examples.

Example 1 A coating solution having the following formulation was applied onto the paper support shown in Table 1 after drying. Dye fixing materials 101 to 124 were obtained by coating by a bar coater method so that the J thickness was approximately 5 μm.

(Formulation A-1) Coated rotic acid-treated gelatin (isoelectric point 9.0) 1 g/rd hydroxyethyl cellulose 1 Silica fine particles* (1)
8 Surfactant umbrella (1)
0.2 Hardening agent Takashi (1)
0.08 (Formulation A-2) Acid-treated gelatin (isoelectric point 9.0) 1 g/nf hydroxymethylcellulose l Silica fine particles *
(1) 8 〃Tricresyl phosphini) 1.5〃 Antioxidant■-10,8〃 Surfactant (1) 0.2 〃Hardener (1) 0.08 〃(Formulation B- 1) Polyvinyl alcohol silica fine particle book (1) 8〃 Surfactant *(1) 0.05 〃(
Formulation B-2) Polyvinyl alcohol - (1) 2g/Isilica fine particle ratio (1) 8 Tricresyl phosphate 1.5 Antioxidant 1-3 0
．． 8 〃Ultraviolet absorber rate (1) 0.
4 Surfactant Book (1) 0.1
(Formulation C-1) Polyethylene oxide book (1) l g/rr
f Phthalated gelatin IN (degree of phthalation 98%) Silica fine particle rate (1) Ill 〃
Surfactant *(1) 0.1 〃Hardening agent *(1) 0.08 〃(Formulation C-2) Polyethylene oxide *(1) 1 g/n(
Phthalated gelatin l // (degree of phthalation 98%) Silica fine particle ratio (1) 8 Surfactant * (1) 0.1 Rheophos 95 (manufactured by Ajinomoto ■) 1.5 V before oxidation
-4 0.8 〃Ultraviolet absorber rate (1
) 0.4 Hardener book (1)
0.08 [Note] Silica fine particles 1 (1): Thyroid 244: Fuji Davison Chemical ■ Surfactant 1 (1) Sodium nidodecylbenzenesulfonate\1 Ultraviolet absorber, (1): Exemplary compound (Ul-1゜2
．． Polyvinyl alcohol *(1): PUA 117 (manufactured by Kuraray ■) Method of incorporating antioxidant and ultraviolet absorber: High boiling point organic solvent (tricresyl phosphate or Rheoforce@-95 (Ajinomoto Co., Ltd.) (Made in Japan)) and 30 cc of ethyl acetate as an auxiliary solvent, dissolve an antioxidant or an ultraviolet absorber, and add this to Prescriptions A-2 and C-2: 10% gelatin soluble in water? In the case of formulation C-2, 100 g of fL was emulsified and dispersed in a 10% polyvinyl alcohol aqueous solution using a homogenizer. At this time, 5% of the surfactant ratio (1) as an emulsifier
20 cc of the aqueous solution was added to the above aqueous phase and emulsified and dispersed. Antioxidants (and UV absorbers) thus obtained
The dispersion was incorporated into the coating solution.

Supports A to F used in this example were produced as follows.

Support A: A 2% aqueous solution of polyvinyl alcohol was coated on one side (the side on which the dye fixing layer was provided) of a base paper with a pot weight of 105 g/% to a solid content of 4 g/rd and dried. Both sides of this base paper were laminated with TiO□-containing polyethylene using an extrusion method so that each layer had a thickness of 30μ steel.

Oxygen permeability lId/I・hr・atm or less (20℃,
40% RH) Support B: Support B was produced in the same manner as Support A except that the amount of polyvinyl alcohol applied was 1 g/rrl.

Oxygen permeability 12m1/11f・hr-atllll(2
0'C, 40% RH) Support C: Support C was prepared in the same manner as Support A except that polyvinyl alcohol was not applied.

Oxygen permeability 800a+1/td-hr-a Lm(2
0'C140%R [() Support D; Pot N 105 g/td Polyvinylidene chloride latex was applied to one side (the side on which the dye fixing layer was applied) at a solid content of 4 g/td. After drying, each side of this base paper is coated with 30 μm of Tie-containing polyethylene.
It was produced by laminating using the extrusion method so that the following was obtained.

In this case, the polyvinylidene chloride film is 130° when laminated.
Since it is heated above C, it becomes a uniform film without pinholes.

Support E: Instead of the polyethylene laminate on one side of the dye fixing layer in Support C, EVAL tD (manufactured by Toshi ■: polyethylene-bolivinyl alcohol copolymer) was used.
A support E was produced by laminating in the same manner using the extrusion method so that the solid content was 20 g/nI.

Support F: One side of support C (the side on which the dye fixing layer is provided) is coated with EVAL's n-propatool? Yong? (l is fixed layer and 5
A support F was prepared by coating and drying so as to give g/rd.

In addition, when the oxygen permeability of supports E and F was measured, all of them were l rrdl/nf -hr -at+s
(20''C, 40%RH).

In addition, the measurement of oxygen permeability in the above is based on ASTM D-1.
This was carried out based on the method of No. 434.

Using the dye fixing materials 101 to 124 thus produced, an inkjet printer (manufactured by Sharp ■, 1
Cyan, yellow, magenta,
A uniform image was drawn. This sample was irradiated with a fluorescent lamp fading test i (15,000 lux) for 4 weeks to perform a decolorization test. Status 8 reflection density was measured before and after irradiation, and the fastness was evaluated based on the ratio (%). The results are shown in Table 1 for magenta, which has the worst light fastness. A similar tendency was observed for cyan and yellow.

From the results in Table 1, oxygen permeability 1 ml/nI-h
It can be seen that a dye fixing material having a dye fixing layer containing an antioxidant imaged on a paper support below r.atm has significantly improved lightfastness.

Table 1 Table 1 (Continued) Example 2 (Preparation of thermal transfer sheet (A)) A polyethylene terephthalate film with a thickness of 6 μm (manufactured by Toyobo Co., Ltd., 5-μm) and corona treated on one side was used as a support.
Using wire bar coating, a coating composition for thermal transfer layer (A) having the following composition was coated on the corona-treated surface of the film to a dry thickness of 1 μm, and then coated on the back side of the member. to polyvinyl butyral (Monsanto in Butvar) (0,45g/nf)
Poly(vinyl stearate) inside (0.3g/nf
) was coated from a tetrahydrofuran solvent.

Orbital, 28 Disperse dye = (a) 4 g Polyvinyl butyral resin 4 g (electrification character missing Denka Butyral 5000-A) Toluene 40d Methyl ethyl ketone 40d Polyisocyanate
0.2d (Takene manufactured by Takeda Pharmaceutical) DI
ION) Disperse dye - (a) (Preparation of dye-fixing material) Using supports A-F, coat the surface with a paint composition for dye-fixing layer having the following composition by wire bar coating so that the dry thickness is 10 μm. Apply and dye fixing material 201
~206 were formed. Drying was performed for 30 minutes in an oven at a temperature of 100°C after temporary drying with a hair dryer.

color, ! G Polyester resin 20g (Toyobo Byron 290) Amino-modified silicone oil 0.5g (Shin-Etsu Silicone K F-857) Epoxy-modified silicone oil 0.5g (Shin-Etsu Silicone K F
-100? ) Antioxidant 11-12g Ultraviolet absorber* (2) 3g Methyl ethyl ketone 85sf! Toluene 85III cyclohexanone 30) Ultraviolet absorber * (
2) Among the UV-1 dye fixing materials 201 to 203, except for the ultraviolet absorber umbrella (2), the dye fixing material 20
7 to 209 were produced. Furthermore, dye fixing materials 201-20
In 3, antioxidant ll-1 and ultraviolet absorber I(2)
Dye-fixing materials 210 to 212 were prepared by excluding both.

Further, dye fixing materials 213 to 215 were prepared in the same manner as in dye fixing material 201, except that antioxidants 1-3, v-4, and -1 were used instead of antioxidant 1-1.

The thermal transfer sheet and the dye fixing material obtained as described above are superimposed so that the thermal transfer layer and the dye fixing layer are in contact with each other, and a thermal head is used from the support side of the thermal transfer sheet to output IW/ Dot, pulse width 0.3 to 0.45 m5ec, dot density 6 dots/y
Printing was performed under RTM conditions to dye the dye fixing layer of the dye fixing material with magenta dye in the form of an image.

The resulting recorded dye fixing material was stored at 15,000 ml for 18 days
The light fastness of the color image was examined by irradiating it with a lux fluorescent lamp. Status A reflection density was measured before and after irradiation, and the light fastness was evaluated based on the ratio. The results are shown in Table 2.

From the results in Table 2, Table 2 shows that the dye fixing material containing an antioxidant and having a layer with an oxygen permeability of 2 tttl/r+f・hr・at− or less has significantly improved light fastness. I understand.

Example 3 (Preparation of thermal transfer sheet (B)) Materials having the following composition were thoroughly mixed and dispersed to prepare a coating liquid for a slippery heat-resistant protective layer.

Methyl methacrylate 10gn-butyl acrylate 2g benzoyl peroxide 0.1g silica
2.5g toluene
35g isopropyl alcohol (rPA) 15
g A suitable mixture of toluene and IPA was added to this coating solution, diluted, and coated on a 6μ-thick polyethylene terephthalate film (hereinafter abbreviated as PET) as a substrate using a wire bar, and heated at 100°C. Dry for 1 minute to a thickness of about 1.5 cm.
A slippery heat-resistant protective layer of gra was formed.

Then, a heat-melting ink having the following composition was applied to the surface opposite to the heat-resistant protective layer.

'. g ink j Neozapon Blue 807 (coloring dye) (manufactured by BASF) 10g lanolin aliphatic barium salt 30g carnauba wax
20g paraffin wax
20g dispersant 0.
5g Liquid paraffin 5g Antioxidant U-17g Ultraviolet absorber* (2) (Same as Example-2) 3g ink of the above composition was heated to 68°C with 100% methyl ethyl ketone.
d and 130 d of toluene in a ball mill.
Distribute the quantum at 8 o'clock.

Next, a 20% by weight vinyl chloride vinyl acetate copolymer resin solution (10 parts resin, 20 parts toluene, 20 parts methyl ethyl ketone)
300 g was added to the above ink dispersion and dispersed in a ball mill for about 1 hour to form a coating of a thermal transfer composition.

This coating material was applied to the surface of the polyester film provided with the aforementioned slippery heat-resistant layer using a wire bar, and the dry humidity was 10%.
It was dried at 0° C. for 1 minute to form a heat-melting ink layer with a thickness of about 5 μm, thereby producing a thermal transfer sheet (B).

In the melt-type thermal transfer sheet (B), antioxidant 11-
A melt-type thermal transfer sheet (C) was produced in the same manner except for Example 1.

In addition, antioxidant 11 in the melt-type thermal transfer sheet (B)
Melt type thermal transfer sheet (D), (E
) and (F) were produced.

Using the obtained melt-type thermal transfer sheet) (B) and (C) and supports A, B, and C prepared in Example-1,
Transfer recording was performed using the methods described in No. 1, Ul, and I, and the light fastness was examined in the same manner. The results are shown in Table 3.

From the results in Table 3, the oxygen permeability is 1 at! /rrl・h
It has been proven that a dye fixing material using a support of r.atm or less and having a dye fixing layer (melt heat transferred ink layer) containing an antioxidant has extremely high light fastness.

Table 3

Claims (1)

[Claims] A dye-fixing material comprising a dye-fixing layer for receiving a sublimable dye, a heat-melting ink, or a dye solution on a paper support, wherein oxygen permeation is performed on the paper support at 20° C. and a relative humidity of 40%. A dye fixing material characterized in that it has an oxygen barrier layer with a rate of 2 ml/m^2.hr.atm or less, and further contains an antioxidant.