JPS62260152A - Image receiving element of heat transfer material having excellent fastness of dye image to light - Google Patents

Abstract

PURPOSE:To obtain an image receiving element of a heat transfer material which decreases the color fading of a dye image and can be stably preserved even after exposure to UV rays for a long period of time by incorporating a polymer from which a specific monomer is derived into the image receiving element. CONSTITUTION:This image receiving element which is put into the relation of superposition in at least the stage of heating transfer with the heat transfer element having the layer contg. a dye donative material capable of releasing or forming a dye which can be transferred by heat or the dye which can be transferred by heat as a function of heat development on a substrate. Such image receiving element contains the polymer derived from the monomer expressed by formula I. In formula I, Q is preferably expressed by formula II. A is exemplified by preferably the residual compd. residue expressed by formulas III-VI. The polymer derived from the monomer expressed by formula I may be a homopolymer or copolymer and may be a copolymer consisting of >=1 kinds of comonomers having other copolymerizable ethylenic unsatd. groups.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an image-receiving element in a thermal transfer material, and more particularly, the present invention relates to an image-receiving element in a thermal transfer material. This invention relates to an image receiving element in a thermal transfer material having excellent robustness. [Background of the Invention] Image forming methods using dry heat treatment are known, in which dyes are transferred using heat to form an image in order to obtain a dye image.
There are two main types of this. One is a technique using a diffusion transfer type heat-developable photosensitive material, and the other is a technique using a heat-sensitive transfer material. Diffusion transfer type heat-developable light-sensitive materials basically consist of a light-sensitive element and an image-receiving element. may also serve as a reducing agent) and a binder, and organic silver salts and various additives are added as necessary. The image-receiving element transfers a transferable dye released from or formed as a function of thermal development from a dye-providing substance contained in the photosensitive element to an image-receiving layer, thereby forming a dye image on the image-receiving layer. If necessary, the image receiving element has a support. On the other hand, a heat-sensitive transfer material basically consists of a heat-sensitive element and an image-receiving element.The heat-sensitive element is basically formed by coating a heat-sensitive ink layer containing a heat-transferable dye on a support, is formed by coating on a support an image-receiving layer capable of forming a dye image by thermal transfer of the heat-transferable dye. The relationship between the thermal transfer element and the image receiving element in the thermal transfer material by these thermal diffusion transfer methods is at least a stacking relationship at the time of thermal transfer, and there are cases where they are configured in advance as an integral type and a stacking relationship at the time of thermal transfer. There are cases where the configuration is
There are also types in which both elements are peeled off after thermal transfer, and types in which both elements are integrated, and each type can be used depending on the purpose. In the technology described above that uses thermal diffusion to obtain a color image on an image-receiving element, the pigment that forms the image is exposed to light,
In particular, it has the disadvantage that it fades significantly when exposed to ultraviolet light. An image receiving element containing a specific ultraviolet absorber for the purpose of improving the above-mentioned drawbacks is disclosed, for example, in JP-A-59-158289. Even if the amount was increased, a sufficient effect could not be obtained. This seems to be because during thermal transfer at high temperatures, the ultraviolet absorber is transferred from the image-receiving element side to the heat-sensitive element side or to the photosensitive element side (opposite to the dye transfer direction), reducing the concentration of the ultraviolet absorber in the image-receiving element. . Further, when a certain amount of ultraviolet absorber was added, precipitation of the ultraviolet absorber occurred. Therefore, there has been a strong desire for an image-receiving element made of a thermal transfer material that has sufficient UV protection ability and does not cause precipitation of UV absorbers. [Object of the Invention] The first object of the present invention is to provide an image-receiving element in a thermal transfer material that can be stably stored with little fading of the dye image even if the dye image formed by a thermal transfer method is exposed to ultraviolet rays for a long time. Our goal is to provide the following. A second object of the present invention is to provide stable transfer of the ultraviolet absorbent from the image receiving element side to the photosensitive element side or the heat sensitive element side during thermal transfer, and no precipitation of the ultraviolet absorbent on the image receiving element. An object of the present invention is to provide an image receiving element in a thermal transfer material that can contain [Structure of the Invention] The object of the present invention is to provide a thermally transferable dye on a support,
or for a thermal transfer element having a layer containing a dye-providing substance capable of releasing or forming a thermally transferable dye as a function of thermal development, at least in an image receiving element placed in stacked relationship during thermal transfer. This was achieved by incorporating a polymer derived from a monomer represented by the following general formula [11] into the image-receiving element. General formula [I] -A [wherein Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and A represents a residue of a compound having ultraviolet absorbing ability. ] [Specific Structure of the Invention 1 The polymer derived from the monomer represented by the general formula [I] will be explained. In the general formula [I], Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is preferably represented by the following general formula [I]. General formula [1] In the formula, R1 and R'+ each represent a hydrogen atom, a carboxy group, an alkyl group (e.g. methyl group, ethyl group, etc.) or a halogen atom (e.g. chlorine atom, bromine atom, etc.), and this alkyl group may have a substituent, for example, a halogen atom and a carboxy group of the substituent form a salt. Jl and J2 each represent a divalent bonding group, and examples of the divalent bonding group include -N HC〇-1-CO
NH-1-COO-1-OCO-1-C-1-SCO-
1-COS-1-0-1-S-1-8O-1-8O2-
1-NH-isotheal. xl and x2 each represent a divalent hydrocarbon group; examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group; examples of the alkylene group include: Examples include methylene group, ethylene group, propylene group, etc., examples of arylene groups include phenylene groups, etc., examples of aralkylene groups include phenylmethylene groups, and examples of alkylenearylene groups include methylenephenylene groups. , Examples of the arylene alkylene group include a phenylene methylene group. , 21, Ill, and 12.12 each represent O or 1. A represents the residue of a compound having ultraviolet absorbing ability, and is preferably represented by general formula [1], [IV], [V] or [VI
] can be mentioned. General formula [■] General formula (IV) General formula [■] l'L General formula (VI) In the general formula [1[] to [VI], R1 is a hydrogen atom, -0R3mat; -L; t-G OOR4e table was. R3 represents a hydrogen atom, an alkyl group or an aryl group, and R4 represents an argyl group, an aryl group or a heterocyclic residue. Specific examples of the alkyl group represented by R3 and R4 include methyl group, ethyl group, propyl group, i-propyl group, butyl group, t-butyl group, and hexyl group. Specific examples of the aryl group represented by R3 and R4 include phenyl group and naphthyl group. Specific examples of the heterocyclic residue represented by R4 include furyl group and pyrazolyl group. m is 1.2 or 3. Further, when l is 2 or 3, R2 may be the same or different groups. R5 and R6 are each a hydrogen atom, a halogen atom,
Represents an alkyl group, alkoxy group, acyl group, acyloxy group, hydroxy group or amine group. R5 and R
Specific examples of the halogen atom represented by 6 include a chlorine atom and a bromine atom. Specific examples of the alkyl group represented by R5 and R6 include the same groups as the specific examples of the alkyl group represented by R3. Specific examples of the alkoxy group represented by R5 and R6 include methoxy, ethoxy, propoxy, and butoxy groups. Specific examples of the acyl group represented by R5 and R6 include formyl group, acetyl group, propionyl group, and benzoyl group. R5 and R6
Specific examples of the acyloxy group represented by include an acetoxy group and a benzoyloxy group. n is 1
Or 2. When n is 2, R6 may be the same or different groups. R7 and R8 each represent a hydrogen atom, an alkyl group, or an aryl group, and R7 and R8 may be bonded to each other to form a nitrogen-containing heterocyclic residue. However, Ra and R9 are not both hydrogen atoms. Specific examples of the alkyl group and aryl group represented by R7 and R8 include those similar to the specific examples of the alkyl group and aryl group represented by R3. Specific examples of the nitrogen-containing heterocyclic residue include a pyridyl group and an oxazoyl group. R9 and Rlo are each a cyano group, -COORt
+ , -CONHR++ , -COR++ or -8O
Represents 2R11. Rat represents an alkyl group or an aryl group. Specific examples of the alkyl group and aryl group represented by R++ include the same groups as the specific examples of the alkyl group and aryl group represented by R3. Also R
At least one of 7, R8, R9 and R+o is bonded to Q. Specific examples of the monomer represented by the general formula [I] of the present invention are described below. The following margins C=0 C=0 C=O C=O CH7=C C;O Fee [8] OH OH [13]. H3 [18] Hs [19] [20] [21] [22] C4H9(L) C+Hoft) [24] [26] [28] [29] Cl-1゜[30] [31] [32] CH. ■ [33] [34] [35] [36] The polymer having repeating units derived from the monomer represented by the general formula [I] of the present invention is a polymer having a repeating unit derived from the monomer represented by the general formula [I].
Even if it is a so-called homopolymer of repeating units consisting of only one type of monomer represented by the general formula [I],
It may be a copolymer made of a combination of two or more monomers represented by the above formula, or it may be a copolymer made of one or more other copolymerizable comonomers having an ethylenically unsaturated group. Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula [E] of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, and styrenes. , crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional Examples include monomers and various unsaturated acids. More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, ter
t-Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate , dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3 -Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxynibutyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2
-methoxyethoxy)ethyl acrylate, 2-(2-
butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n=
9), 1-bromo 2-methoxyethyl acrylate,
Examples include 1,1-dichloro-2-ethoxyethyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate,
amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate,
Naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxyethyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2
-acetoxyethyl methacrylate, 2-aceI~acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-
methoxyethoxy)ethyl methacrylate, 2-(2-
1-xyethoxy)ethyl methacrylate, 2-(2
-butoxyethoxy)ethyl methacrylate, ω-me I
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butylene Examples of olefins include dicyclopentadiene, ethylene , propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isobrobyl subrene, chloromethylstyrene,
Examples include methoxystyrene, acetoxystyrene, chlorobrene, dichlorostyrene, bromustyrene, and methyl ethyl vinylbenzoate. . Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the maleic acid diesters include diethyl maleate, dimethyl maleate, and dibutyl maleate. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other konitsuma include the following: Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylamineethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide , β-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl) acrylamide, etc.: Methacrylamides, such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert
-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide,
Dimethylaminoethylmethacrylamide, phenylmethacrylamide, diethylacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N
-(2-acetoacetoxyethyl)methacrylamide etc.; Allyl compounds such as allyl acetate, allyl caproate,
Allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.: Unsaturated nitriles,
For example, acrylonitrile, methacrylate trile, etc.; polyfunctional monomers, such as divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, itacon g'c-noethyl, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, etc. Monobutyl maleate, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2-acrylamido-2-methylbutanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid , 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, e.g. 2-
methacrylamide-2-methylethanesulfonic acid, 2-
methacrylamide-2-methylpropanesulfonic acid, 2
- methacrylamide-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxybrosulfate; Biru-2-phosphate etc.: Examples include sodium 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (such as N8%) or ammonium ions. Furthermore, other comonomers include U.S. Pat. Nos. 3,459,790 and 3,438.
, No. 708, No. 3.554.987, No. 4.21
No. 5.195, No. 4.247.673, JP-A-57
Crosslinkable monomers described in the specification of Japanese Patent No. 205735 and the like can be used. Specific examples of such crosslinking materials include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and the like. Further, when forming a copolymer with the monomer represented by the general formula [I] of the present invention and the comonomer, preferably the repeating unit consisting of the monomer represented by the general formula [I] is 10-90% by weight of the total polymer
It is a case where it is contained, and more preferably a case where it is contained in an amount of 30 to 70% by weight. Generally, the polymer ultraviolet absorber is polymerized by an emulsion polymerization method or a solution polymerization method, and the above general formula [I] according to the present invention
The polymer ultraviolet absorber of the present invention having a repeating unit derived from the monomer represented by can also be polymerized in a similar manner. Regarding the emulsion polymerization method, U.S. Pat.
No. 080,211, No. 3,370,952, and U.S. Pat.
The method described in No. 0 can be used. These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the commoner may be a liquid comonomer, which in the case of emulsion polymerization normally also acts as a solvent for the immobilized monomers. . Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art. Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene turgortan monolaurate, polyoxyethylene-polyoxybrobylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. The types of these activators and their effects are described in Bergische Ch.
emische industry), 28.16
-2o (1963). In order to disperse a lipophilic polymer UV absorber synthesized by a solution polymerization method etc. in the form of latex in an aqueous gelatin solution, first the lipophilic polymer UV absorber is prepared! After dissolving in a solvent, this is dispersed into a latex form in an aqueous gelatin solution using an ultrasonic wave, a colloid mill, etc. with the help of a dispersant. A method for dispersing a lipophilic polymeric UV absorber in the form of a latex in an aqueous gelatin solution is described in U.S. Pat.
The method described in No. 451,820 can be referred to. As the organic solvent for dissolving the lipophilic polymer ultraviolet absorber, esters such as methyl acetate, ethyl acetate, propyl acetate, alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used. Further, these organic solvents can be used alone or in combination of two or more. In producing the polymer ultraviolet absorber according to the present invention, the solvent used for polymerization is preferably a solvent that is a good solvent for the monomer and the resulting polymer ultraviolet absorber and has low reactivity with the polymerization initiator. Specific examples include water, toluene, alcohol (e.g. methanol, ethanol, 1SO-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc. These solvents may be used alone or in combination of two or more. Although it is necessary to consider the type of polymerization initiator, the type of solvent used, etc., the polymerization temperature is usually in the range of 30 to 120°C. Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the polymer ultraviolet absorber of the present invention include those shown below. Examples of water-soluble polymerization initiators include perrjA salts such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis(2-amidino). Water-soluble azo compounds such as (propane) hydrochloride and hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-(2,4-dimethylvaleronitrile),
'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexanone-1-carbonitrile), 2,2'-azobisisocyanobutyric acid, 2゜2'- Dimethyl azobisisobutyrate, 1.1
Azo compounds such as '-azobis(cyclohexanone-1-carbonitrile), 4,4'-azobis-4-cyanovaleric acid, benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisopropyl peroxydyl carbonate - etc. Among these, preferred are benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like. These polymerization initiators can be contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the monomers in emulsion polymerization and solution polymerization. Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization and bulk polymerization, can also be applied. That is,
In the present invention, a homopolymer of the monomer represented by the general formula [I] of the present invention, a copolymer formed by combining two or more of the monomers, or a copolymer of the monomer and at least one other monomer is used.
It includes all copolymers consisting of a species of polymerizable comonomer as a copolymerization component, and is not limited by the synthesis process. Specific representative examples of the polymer ultraviolet absorber of the present invention will be listed below, but the invention is not limited thereto. Margin below P-1 CH. "CH. X: Y: Z=60:25:15P-5CH.! x:y=50:50 The above-mentioned polymer ultraviolet absorber of the present invention is disclosed in, for example,
It is synthesized according to the synthesis method described in No. 3-107835 and JP-A-58-178351. The polymer UV absorber of the present invention has an average molecular weight of 32.000
~200,000 is preferred. The polymer ultraviolet absorbers of the present invention may be used alone or in combination of two or more. The amount used is not limited, but one unit of IJV absorber monomer of the polymer is 0.1 to 100 per unit of the image receiving element.
It is preferable to use 111 mol/12, preferably 1 to 10+e mol/V. The method of incorporating the polymer ultraviolet absorber of the present invention into an image-receiving element is not particularly limited. In the case of an image-receiving element integrated with the thermal transfer element, there is a method of coating or dipping the surface of the thermal transfer element as an image-receiving layer, or [B] When forming a support, the polymer ultraviolet absorber of the present invention may be added in advance. There are ways to keep it. In the former case [A], the polymer ultraviolet absorber of the present invention is dissolved in a suitable organic solvent (e.g., acetone, methanol, ethanol, ethyl acetate, dimethylformamide, dibutyl phthalate, tricresyl phosphate, ethylene chloride, tetrahydrofuran, etc.).
The image-receiving element can be added by dipping the image-receiving element in a solution in which the image-receiving element is dissolved, or by applying these solutions to the support or image-receiving layer. Alternatively, it can be added without a solvent or by dispersing it using a suitable organic solvent when producing the image-receiving layer. On the other hand, in the case of the latter [B], there is a method of making paper using a paper machine using a hot mixed solution (slurry) in which the polymer ultraviolet absorber of the present invention is added to a natural or synthetic valve together with a paper strength agent, a sizing agent, a filler, etc. There is a method in which the polymer ultraviolet absorber of the present invention is added to a synthetic polymer dope and formed into a film to form the image receiving element of the present invention. Image receiving elements that can be used in the present invention include paper and synthetic polymers (films). Examples of synthetic polymers (films) include polyacrylates (e.g. polymethyl acrylate, polyethyl acrylate), polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer,
Polyacetal, polyether chloride, polynylidene chloride, polyvinyl chloride, polyvinyl carbazole, polystyrene, styrene-butadiene copolymer, polyacetate cellulose, polyacetals (e.g. polyvinyl butyral, polyvinyl formal), polytetrafluoroethylene, polychloro Trifluoroethylene, polyethylene, chlorinated polyethylene, polycarbonate, polyvinyl acetate, polyvinyl alcohol, polypropylene, polyvinylpyrrolidone, polyacrylates (e.g. polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, poly-

[-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glyconyl dimethacrylate, poly-2-cyano-ethyl dimethacrylate, etc.], polyesters (for example, polyethylene terephthalate, etc.), polyamide, polyimide, polysulfone, etc. These synthetic polymers may be used alone or as a mixture, or as a copolymer. Particularly preferred image receiving elements include polyvinylidene chloride,
From polyvinyl chloride, polycarbonate, polyethylene terephthalate, triacetate, polyacetate cellulose such as diacetate, heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid. Examples include polyamides synthesized, polyesters synthesized from diethylene glycol and diphenylcarboxylic acid, and ethylene glycol and bis-p-carboxyphenoxybutane. When the image-receiving element of the present invention is used as an image-receiving element for a heat-developable color photosensitive material, the image-receiving layer of the image-receiving element has a function of receiving the dye in the thermal image-sensitive layer released or formed by heat development. For example, a polymer containing a tertiary amine or a quaternary ammonium salt, as described in U.S. Pat. No. 3.70
Those described in No. 9.690 are preferably used. For example, as a polymer containing an ammonium salt, polystyrene-N,N,N-tri-hexyl-N
-The ratio of vinyl-benzylammonium chloride is 1
=4 to 4:1, preferably 1:1. Examples of polymers containing tertiary amines include polyvinylpyridine. A typical image-receiving layer for diffusion transfer is obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. Another useful dye-receiving material is JP-A-57-2072.
The glass transition temperature described in No. 50 is 40°C or higher, 25
Examples include those formed of heat-resistant organic polymer substances of 0° C. or lower. These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support. Examples of the heat-resistant organic polymer substances include polystyrene, polystyrene derivatives having substituents having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarbazolevinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluoroethylene, polyacrylonitrile, polyN,N-dimethylacrylamide, p-cyanophenyl group , pentachlorophenyl group and 2. Polyacrylate with 4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-
Polyesters such as ethyl methacrylate and polyethylene terephthalate, polysulfone, bisphenol A
Examples include polycarbonates such as polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook 2nd Edition (edited by G.I. Brandrup and E.H. Inmargat), John Wiley & Sons (Polymer Handbook 2nd Edition)
ed. (J. 3randrup, E. H.Immer
gut l) John Wiley & Sons
) Synthetic polymers with glass transition temperatures below 40° C. that are described in publications are also useful. Generally, the molecule m of the polymer substance is 2,00
0 to 200,000 are useful. These polymeric substances may be used alone or in a blend of two or more,
Moreover, two or more types may be combined and used as a copolymer. Useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as heptamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, and diethylene glycol. and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyester, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4-benzenesulfonic acid, etc. as a modifier is also effective. A particularly preferable image-receiving layer is JP-A-59-22342
Layer made of polyvinyl chloride described in No. 5 and JP-A No. 6
0-19138, a layer consisting of polycarbonate and a plasticizer. These polymers can also be used as a support and an image-receiving layer, in which case the support may be formed from a single layer or from multiple layers. As the support for the image-receiving element, any material such as a transparent support or an opaque support may be used. Supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and curcum, baryta paper, RC paper laminated with thermoplastic resin containing pigments on paper, cloth, glass, and metals such as aluminum. etc., supports on which an electron beam curable resin composition containing a pigment is coated and cured, and supports on which a coating layer containing a pigment is provided. can be mentioned. In particular, a support that is coated with an electron beam curable resin composition containing a pigment on paper and cured, or a support that has a pigment coating layer directly on the paper or an electron beam curable resin composition on the pigment coating layer. The resin layer of the support coated with the composition and cured can itself be used as an image-receiving layer, so it can be used as it is as an image-receiving element. When the present invention is applied to a heat-developable color light-sensitive material, the above-mentioned various polymers can be used as a mordant for a dye image and as an image-receiving layer. It may be an image-receiving element or the image-receiving layer may be a single layer that is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, which layer transmits the desired amount of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. It is used for reflection. Opaque FJ! The (reflective layer) can contain various reagents to provide the necessary reflection, such as titanium dioxide. The image-receiving layer of the image-receiving element can also be formed in a mold that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. Further, after imagewise exposure and uniform heat development of the heat-developable color photosensitive element, an image-receiving layer can be placed thereon and heated at a temperature lower than the development temperature to transfer the dye image released or formed from the dye-providing substance. The image-receiving element of the present invention can efficiently exhibit the effects of the present invention when applied to an image-receiving element used in combination with the above heat-developable color photosensitive material. Heat-developable color photosensitive materials basically consist of photosensitive silver halide, a dye-providing substance, and a binder on a support, and organic silver salts, reducing agents, and other additives are added as necessary. Ru. Any of the above constituent components and structural aspects can be used, for example, JP-A-59-1
No. 24338, No. 59-159159, No. 59-1
No. 81345, No. 59-124327, No. 59-1
No. 66954, No. 60-2950, No. 59-22
No. 9556, No. 57-179 & 40, No. 57-186
No. 744, No. 59-168440, No. 59-1748
No. 32, No. 59-174833, No. 59-17483
No. 4, No. 59-180550, patent application No. 59-18
No. 2507, No. 59-182506, No. 59-272
Examples include those described in various specifications such as No. 335. The dye-providing substance in the heat-developable color photosensitive material participates in the reduction reaction of the photosensitive silver halide and/or Akebono silver salt used as necessary, and forms or releases a diffusible dye as a function of the reaction. Depending on the reaction mode, a negative dye-donor that acts on a positive function (i.e., forms a negative dye image when negative-working silver halide is used) and a negative It can be classified as a positive-working dye-providing substance that acts on the function of (i.e., forms a positive dye image when negative-working silver halide is used). Negative dye-donor substances are further divided into reducible dye-releasing compounds that release diffusible dyes upon oxidation, and compounds that form diffusible dyes upon coupling reaction with reducing agents; They can be classified in detail into compounds that release dyes and compounds that form dyes. The dye-providing substance used in the heat-developable color photosensitive material applicable to the present invention may be any of the above types,
The dye formed or released from the dye-donor material is transferred to the image-receiving element of the invention. Further, the image receiving element of the present invention is disclosed in Japanese Patent Application Laid-open No. 59-106997.
No. 59-109394, No. 59-109395, No. 59-124890, No. 51-154446, No. 54-68253, No. 57-160691, etc. It can be used as an image receiving element for thermal transfer used in recording methods. That is, for example, an ink sheet for thermal transfer and an image receiving element of the present invention may be superimposed, and the image may be transferred onto the image receiving element of the present invention in response to thermal information from a thermal head, a laser, a Gisenon lamp, or the like. The general art regarding heat sensitive elements is known and the image receiving element of the present invention may be used in combination with any of these types of heat sensitive elements. In the present invention, thermal transfer refers to sublimation of the dye by heat (not limited to those that vaporize from solid to liquid without passing through, but also includes those that vaporize with melting) or diffusion by a solvent,
It means to be transcribed. Furthermore, when the image receiving element of the present invention is used as a heat-sensitive transfer material, (1) the heat-sensitive element is colored by a thermal head composed of a printed resistor, a thin film resistor, a semiconductor resistor, etc., or by a heat source such as a laser or a xenon lamp; In addition to the method of recording images in equal parts, (2) 1V depending on image information from another system.
As a method of obtaining an image or the like on an image receiving element using a heat source, it is of course applicable to a thermal transfer method in which a dye is transferred from a heat sensitive element to an image receiving element using a heat source. The constituent members of the image receiving element in the above thermal transfer material applicable to the present invention include the above-mentioned paper and various polymeric compounds as main constituent members, and the following binders, thermal transfer aids such as wax, and other additives. may be used. Various additives can be added to the image receiving element of the present invention. For example, titanium white, silica, talc, clay, talc,
Inorganic additives such as liIiIM barium, calcium carbonate, glass powder, kaolin, zinc oxide, etc. may be added. It may also contain an antioxidant, a quenching substance, etc. for the purpose of improving the fastness of the image or for other purposes. The image-receiving element of the present invention is capable of dye transfer, and comprises:
At least during transfer, the thermal transfer element is placed in a stacked relationship with the thermal transfer element and can be used in combination with any type of thermal transfer element containing a thermal transferable dye-providing substance. The element may be of a so-called integral type or a so-called peelable type. The dye used here may be any of azo dyes, anthraquinone dyes, azomethine dyes, indoaniline dyes, naphthoquinone dyes, nitro dyes, styryl dyes, phthalocyanine dyes, quinophthalone triphenylmethane dyes, cyanine dyes, etc. , azomethine dyes, and indoaniline dyes. [Effects of the Invention] By incorporating the polymer ultraviolet absorber used in the present invention into an image-receiving element for thermal transfer, the dye image obtained on the image-receiving element was able to obtain sufficient light resistance. Further, no precipitation of ultraviolet absorber occurs. The image-receiving element includes an image-receiving element of a transfer-type heat-developable color photosensitive material and an image-receiving element of a heat-sensitive transfer material, and the effects of the present invention are particularly remarkable in the former case. [Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments. Example-1 Preparation of image-receiving element-1> Polyvinyl chloride (n=1,100
Polyvinyl chloride
20/12, one monomer unit of the ultraviolet absorber in the polymer ultraviolet absorber was adjusted to 4 mmol/12. <Preparation of image-receiving element-2> Polycarbonate (Teijin Kasei Panlite L-1,250) and polymer ultraviolet absorber (P
The ethylene chloride solution of -1) was applied so that the polycarbonate was 15CI/w'' and the ultraviolet absorber unit of the polymer ultraviolet absorber was 41I1 mol/f.Preparation of image-receiving element-3> Polyethylene terephthalate 100 (1, 2 mmol of polymer ultraviolet absorber (P-1), dibutyl phthalate o,
SOG is heated and melted at 300°C and biaxially stretched to 100
It was formed into a μm film. Preparation of Image-Receiving Element-4> The following layers were sequentially coated on a transparent polyethylene terephthalate film having a thickness of 100 μm to prepare an image-receiving element. (1) Layer made of polyacrylic acid (7,0(+/i'
) (2) Layer consisting of cellulose acetate (4,01 J/v'
)(3) A layer consisting of a 1:1 copolymer of styrene and N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride and gelatin.
(Copolymer 3.oQ/v2) (Gelatin 3.oQ/v2)
h/v2) (4) Urea and polyvinyl alcohol (saponification degree 98%
) layer consisting of (urea 4.OQ/12) (polyvinyl alcohol 3.00/v2) Example-2 Preparation of organic silver salt dispersion> Reaction of 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent The obtained 5-methylbenzotriazole 28.8Q and poly(N-vinylpyrrolidone) 16.0 () were dispersed in an alumina ball mill, and
)85.5 and finished it at 200112. [Preparation of dye-providing substance dispersion] The following dye-providing substance (1) was mixed with 35.5 (1) of the following hydroquinone compound s, oog and the following development inhibitor 0.7 (1).
was dissolved in 200 vn of acetic acid nibble, and alkanol XC (
DuPont) 5% aqueous solution 12411, phenylcarbamoylated gelatin (Rouslow, type 17819)
P C) Mix with 720 d of gelatin aqueous solution containing 30.5 g, disperse by ultrasonic homogenization, distill off ethyl acetate, and adjust to pH 5.5 to obtain γ95112.
lko. Dye-donor substance (1) CH. y: 60% by weight Hydroquinone compound H Development inhibitor [Preparation of photosensitized silver iodobromide emulsion] Preparation of silver iodobromide emulsion At 50°C, special #i! No. 57-92523, No. 5
No. 7-92524 Using the mixing and stirring shown in each si+s, 11.6 g of potassium iodide was added to solution A in which 20 g of ossein gelatin, 1000 nN of distilled water and ammonia were dissolved.
(L) and potassium bromide 130 (L) and nitrate P.
1 mol of IL silver and Solution C, a 500% aqueous solution containing ammonia, were simultaneously added while keeping the pAg and pH constant. By roughly controlling the addition speed of liquid B and liquid C,
Silver iodide content 7 mol%, regular hexahedron, average grain size 0.25μ
A core emulsion of m was prepared. Next, in the same manner as described above, by coating a silver halide shell with a silver iodide content of 1 mol %, regular hexahedral grains with an average diameter of 0.3 μm (shell thickness 0.05 μff1) were formed. A core/shell type silver halide (monodisperse 8%) emulsion was prepared by vA. The above emulsion was washed with water and desalted to obtain a yield of 7001 g. Preparation of green-sensitive silver iodobromide emulsion The above silver halide 7001Q4- Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.49 Gelatin 32 Q Sodium thiosulfate 10mg Sensitizing dye below 1% methanol solution 80t12 Distilled water
1200112 Sensitizing dye (b) Preparation of reducing agent solution] The following reducing agent 22.2Q, poly(4-vinylvinylidene) 14.6 (1, the following fluorosurfactant 0.50Q)
was dissolved in water and adjusted to DH5.5 to 2501N. Surfactant (m, n=2 or 3) Reducing agent [Preparation of heat-developable photosensitive element-1] Organic silver salt dispersion 12.5d, photosensitive silver iodobromide emulsion 6.0
0 reduction, dye-donor dispersion 39.8.1! , 12.5 parts of the reducing agent solution were mixed, and then a hardening agent solution (tetra(vinylsulfonylmethyl)methane and taurine were reacted in a ratio of 1:1 (weight ratio)) to 1 part of the phenylcarbamoylated gelatin.
% aqueous solution so that the amount of tetra(vinylsulfonylmethyl)methane is 3% by weight) is 2.5%.
g, polyethylene glycol 300 as a heat solvent; 3.
Thickness after adding 80iJ and subbing: 180μ
m photographic polyethylene terephthalate film,
It was coated so that the silver amount was 1.76Q/f, and then the phenylcarbamoylated geladine and poly(N-
A protective layer consisting of a mixture of (vinylpyrrolidone) was provided. The heat-developable photosensitive element ~1 was exposed to 1,6000 M5 through a step wedge, and the image receiving element ~1
1 or the image receiving element-2 in a heat developing machine (Developer Module 277, 3M Company) at 150°C.
After thermal development was carried out for 20 seconds, the photosensitive element and image receiving element were peeled off to obtain a magenta transferred image on Receptor II. At this time, it was visually determined whether or not the ultraviolet absorber was deposited on the surface of the image receiving element. × for those with precipitation;
A sample with a slight amount of precipitation was graded △, and a sample with no precipitation was graded ○. In addition, the maximum density ([)max) and minimum density (fog □m1n) of the obtained transferred image were measured, and the obtained transferred image was irradiated with a 6000W xenon lamp for 48 hours (illuminance on the image surface was 6000 lux). The optical density of the maximum density portion before and after irradiation (irradiation #Do, post-irradiation D+) was measured, DH/QoxtOO (%) was taken as the residual rate, and the light resistance was tested. Table 1 shows these results.
Shown below. Example-3 The polymer ultraviolet absorbers of the image-receiving elements-1 and 2 are shown below.
Polymer UV absorber shown in 1 or comparative UV absorber (
The same image receiving elements (Samples No. 3 to 16) were prepared except that the amount of the comparative ultraviolet absorber added was changed (as shown in Table 1). After exposure of 1,600 CMS through the step wedge 8, the same heat development as in Example-2 was performed with each image-receiving element, and the density of the obtained image was measured. A similar lightfastness test was conducted. These results are shown in Table-1. The following margin is compared to the purple Tato line absorber AI: l The following margin is Example-4 Preparation of dye-donor dispersion tricresyl 30.01;1
and ethyl acetate 90.01N, mixed with gelatin aqueous solution 4601ρ containing the surfactant used in Example-2, dispersed with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to obtain 5oo16. did. Preparation of heat-developable photosensitive element-2 using dye-providing substance> Photosensitive silver iodobromide emulsion 40 obtained in Example-2. . vQs Akebono silver salt dispersion 251N, the above dye-providing substance dispersion 50. Od was mixed, and polyethylene glycol 300 (1111 manufactured by Tokagaku) 4.20 (+,
3.01 g of the hardening agent solution used in Example-2 and a 10% water-alcohol solution of guanidine trichloroacetic acid 2
0. A photosensitive element was prepared by adding OIR and coating it on a photographic polyethylene terephthalate film having a thickness of 180 μm and undercoating so that the amount of silver was 2.50 L't'. The photothermographic element-2 was subjected to the same exposure as in Example-2, and combined with the image-receiving element-4 described in Example-1,
After carrying out the same thermal development as in Example 2, the photosensitive element and the image receiving element were peeled off to obtain a magenta transferred image on the image receiving element. The maximum density (Dmax) and minimum density (fog Qmin) of the obtained transferred image were measured, and the obtained transferred image was irradiated with a 6000 W xenon lamp for 48 hours (the illumination intensity on the image surface was 6000 lux), and before and after irradiation. Optical density of the maximum density part after irradiation (DO1 before irradiation, D+ after irradiation
) was measured, D+/DoX100 (%) was taken as the residual rate, and the light resistance was tested. These results are shown in Table-2. Example 5 The same pedestal element was produced except that the polymer ultraviolet absorber of image receiving element 4 described in Example 1 was changed to the polymer ultraviolet absorber and comparative ultraviolet absorber shown in Table 2, and −
The heat-developable photosensitive element-2 used in Example 4 was exposed to 1,600 CMS through a step wedge, and then heat-developed in the same manner as in Example-4 with each image-receiving element. In addition to measuring, Example-2
I did the same lightfastness test. These results are shown in Table-2. Margin Example 6: Preparation of heat-sensitive transfer element> The following composition was applied using a wire bar to a wet film thickness of 60 μm on a polyethylene terephthalate film base with a thickness of 6 μm, and dried to form an ink layer. Formed. Cellulose diacetate 0.6g 2-phenylazo-4-methoxy-1-naphthol 0.31J Acetone 201g Subsequently, the following composition was applied on the ink layer to a wet film thickness of 27.4μ.
The mixture was coated and dried to form a heat-fusible layer to obtain a heat-sensitive transfer element. Vermarine PN (manufactured by Sanyo Chemical) 10 Daisui

101N2% anionic activator 0.3
d The ink layer of the obtained thermal transfer element and the image receiving element-2 or 3 described in Example-1 are stacked facing each other, and the dye is heated from the support side of the thermal transfer element through a heating element with a thermal head. It was thermally transferred. The obtained transferred image was subjected to the same light fastness test as in Example-2. Further, the same thermal transfer was carried out using the same image receiving elements except that the ultraviolet absorbers of Image Receiving Elements 2 and 4 were changed as shown in Table 3, and a light resistance test was conducted. J6 season 14 Table-3 and the following margin table-3 When an image receiving element containing a comparative ultraviolet absorber is used in combination with a heat-developable color light-sensitive element as shown in Examples 2 to 5 above, the dye image It can be seen that the stability against light is insufficient, and that precipitation occurs when the amount of ultraviolet absorber added to improve stability is increased. In contrast, it can be seen that when the image receiving element of the present invention is used, the stability of the dye image against light is sufficiently improved without precipitation. This seems to be because in the case of the comparative ultraviolet absorber, the ultraviolet absorbing effect is impaired mainly because it is transferred to the photosensitive element side during thermal transfer. Furthermore, as shown in Example 6, it can be seen that the stability of images against light is improved even when used in combination with a heat-sensitive transfer element. When the image receiving element of the present invention is used in combination with a heat-developable photosensitive element, the effects of the present invention are large, and this is a preferred embodiment. Margin below

Claims (1)

Claims: For a thermal transfer element having a layer containing a thermally transferable dye on a support, or a dye-donor substance capable of releasing or forming a thermally transferable dye as a function of thermal development, An image receiving element in a thermal transfer material, wherein the image receiving element is placed in a stacked relationship during thermal transfer, and the image receiving element contains a polymer derived from a monomer represented by the following general formula [I]. . General formula [I] Q-A [wherein Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and A represents a residue of a compound having ultraviolet absorbing ability. ]