JP2008105397A - Thermal transfer image-receiving sheet and coating composition for producing thermal transfer image-receiving sheet - Google Patents

Abstract

（一般式［１］において、Ｒ¹は水素原子、ハロゲン原子またはメチル基を表し、Ｌ¹は２価の連結基を表し、Ｒ²は炭素数１〜５のアルキレン基を表す。ｎは１〜４０の整数を表す。Ｚ¹は水素原子、または炭素数１〜３０の直鎖、分岐もしくは環状の脂肪族炭化水素基を表す。ここで、Ｒ²におけるアルキレン基、Ｚ¹における脂肪族炭化水素基は置換基を有してもよく、ｎが２以上のとき、複数のＲ²は互いに同じでも異なってもよい。）
【選択図】なしA thermal transfer image-receiving sheet having high sensitivity and good image storage stability and a coating composition for producing the thermal transfer image-receiving sheet are provided.
A thermal transfer image-receiving sheet having at least one receptor layer on a support, the receptor layer containing a polymer containing a repeating unit derived from a monomer represented by the following general formula [1] Thermal transfer image receiving sheet.

(In General Formula [1], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, R ² represents an alkylene group having 1 to 5 carbon atoms, and n is 1. Represents an integer of ˜40, Z ¹ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkylene group in R ^{2 and} aliphatic carbonization in Z ¹ The hydrogen group may have a substituent, and when n is 2 or more, the plurality of R ² may be the same as or different from each other.
[Selection figure] None

Description

  The present invention relates to a heat-sensitive transfer image-receiving sheet and a coating composition for producing a heat-sensitive transfer image-receiving sheet, and more specifically, a heat-sensitive transfer image-receiving sheet having high sensitivity and good image storage stability, and a heat-sensitive transfer image-receiving sheet and a coating composition for producing a heat-sensitive transfer image-receiving sheet. About.

  Conventionally, various thermal transfer recording methods are known, and among them, the dye diffusion transfer recording method is attracting attention as a process capable of producing a color hard copy closest to the image quality of a silver salt photograph (for example, Non-Patent Document 1 and 2). In addition, it has the advantages of being dry, being able to visualize directly from digital data, and being easy to duplicate, compared to silver salt photography.

  In this dye diffusion transfer recording system, a thermal transfer sheet containing a pigment (hereinafter also referred to as an ink sheet) and a thermal transfer image receiving sheet (hereinafter also referred to as an image receiving sheet) are superposed, and then heat is generated by an electrical signal. By heating the ink sheet with a controlled thermal head, the dye in the ink sheet is transferred to the image receiving sheet to record image information. By recording three colors of cyan, magenta, and yellow in an overlapping manner, A color image having a continuous change in color shading can be transferred and recorded.

Conventionally, a polyester resin, a polycarbonate resin, a vinyl chloride resin, and the like have been used as a polymer for a receiving layer that plays a role of receiving a dye in the outermost layer of a thermal transfer image-receiving sheet. In recent years, the speed of printing has been remarkably increased. However, it has become difficult for these resins to cope with the high speed of transfer and to achieve both photographic performance such as transfer sensitivity and image storability.
Although a polymer having a specific structure has been proposed (see Patent Document 1 or 2), it has not been sufficient yet, and further improvement has been desired.

JP-A-2-265789 JP-A-8-224967 “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 “Development of Printer Materials”, issued by CMC Co., Ltd., 1995, p. 180

  An object of the present invention is to provide a heat-sensitive transfer image-receiving sheet having high sensitivity and good image storability and a coating composition for producing the heat-sensitive transfer image-receiving sheet.

  As a result of intensive studies in order to solve the problems of the prior art, the present inventor has found that if a coating composition containing a specific polymer is used, an image-receiving sheet having high sensitivity and high image storage stability can be formed. It was. The present invention has been provided based on such findings.

The above problems have been achieved by the following means.
(1) A thermal transfer image-receiving sheet having at least one receiving layer on a support, the receiving layer containing a polymer containing a repeating unit derived from a monomer represented by the following general formula [1] A heat-sensitive transfer image-receiving sheet.

(In General Formula [1], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, R ² represents an alkylene group having 1 to 5 carbon atoms, and n is 1. Represents an integer of ˜40, Z ¹ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkylene group in R ^{2 and} aliphatic carbonization in Z ¹ The hydrogen group may have a substituent, and when n is 2 or more, the plurality of R ² may be the same as or different from each other.
(2) The thermal transfer image-receiving sheet according to item (1), wherein the monomer represented by the general formula [1] is a monomer represented by the following general formula [2].

(In General Formula [2], R ³ represents a hydrogen atom, a halogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (Rc) —, where Rc is a hydrogen atom or a substituent. R ⁴ represents an alkylene group having 1 to 5 carbon atoms, m represents an integer of 1 to 40, and Z ² represents hydrogen. Represents an atom, or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkyl group in Rc, a cycloalkyl group, an alkylene group in R ⁴ , and an aliphatic hydrocarbon group in Z ² May have a substituent, and when m is 2 or more, a plurality of R ⁴ may be the same or different from each other.
(3) The sensation according to item (1) or (2), wherein the monomer represented by the general formula [1] or [2] is a monomer represented by the following general formula [3] Thermal transfer image receiving sheet.

(In General Formula [3], R ⁵ represents a hydrogen atom, a halogen atom or a methyl group, R ⁶ represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 40, and Z ³ represents hydrogen. Represents an atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, wherein the alkylene group in R ^{6 and} the aliphatic hydrocarbon group in Z ³ may have a substituent. , L is 2 or more, the plurality of R ⁴ may be the same or different from each other.)
(4) The polymer is a copolymer and has a nitrile monomer, an aromatic vinyl monomer, and a meth (a) acrylic acid ester as essential copolymerization components (1) to (3) The thermal transfer image-receiving sheet according to any one of the above.
(5) The heat-sensitive transfer image-receiving sheet according to any one of (1) to (4), wherein a heat insulating layer containing hollow particles is provided between the support and the receiving layer.
(6) A coating composition for producing a thermal transfer image-receiving sheet having at least one receptor layer on a support, the coating composition being derived from the monomer represented by the general formula [1] A coating composition for producing a thermal transfer image-receiving sheet, comprising a polymer containing a repeating unit.

  The heat-sensitive transfer image-receiving sheet of the present invention has high sensitivity and excellent image storage stability. In addition, the coating composition of the present invention can easily provide such a thermal transfer image-receiving sheet.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present invention, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Layer structure of thermal transfer image-receiving sheet)
In the heat-sensitive transfer image-receiving sheet of the present invention, a dye-receiving layer (receiving layer) is formed on a support. A base layer is preferably formed between the receptor layer and the support. For example, a white background adjustment layer, a charge adjustment layer, an adhesive layer, and a primer layer are formed. Moreover, it is preferable that the heat insulation layer is formed between the base layer and the support body. In the present invention, each layer between the support and the receiving layer is simply referred to as an “intermediate layer” and includes the above-described underlayer and heat insulating layer. The heat-sensitive transfer image-receiving sheet of the present invention contains at least one receiving layer and at least one intermediate layer. It is preferable that a curl adjusting layer, a writing layer, and a charge adjusting layer are formed on the back side of the support.

(Polymer contained in receiving layer)
The receiving layer of the present invention contains a polymer containing a repeating unit derived from the monomer represented by the general formula [1]. The coating composition for producing a thermal transfer image-receiving sheet of the present invention contains a polymer containing a repeating unit derived from the monomer represented by the general formula [1], and is used particularly for forming a receiving layer.

Hereinafter, a polymer containing a repeating unit derived from a monomer represented by the following general formula [1] according to the present invention (hereinafter referred to as an alkylene oxide chain-containing polymer or a polymer used in the present invention) will be described. . In addition, the polymer used for this invention does not mean a polymer latex, Therefore, this is not included.
The polymer used in the present invention contains a repeating unit derived from a monomer represented by the following general formula [1].

In the general formula [1], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, and R ² represents an alkylene group having 1 to 5 carbon atoms. n represents an integer of 1 to 40. Z ¹ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. Here, the alkylene group in R ^{2 and} the aliphatic hydrocarbon group in Z ¹ may have a substituent, and when n is 2 or more, the plurality of R ² may be the same as or different from each other.

When R ¹ represents a halogen atom, it is preferably a chlorine atom or a fluorine atom.
The divalent linking group in L ¹ may be any linking group, but is preferably a single bond, —O—, —C (═O) —, —NR ¹¹ — [where R ¹¹ is hydrogen. An atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is represented. _{], -S -, - SO 2 -} , - P (= O) (OR 12) - [wherein, R ¹² represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,. ], An alkylene group, an arylene group, or a divalent linking group formed by combining two or more thereof is preferable, and may have a group or a substituent represented by -C (= O) -X-. A good phenylene group is more preferable, and a group represented by -C (= O) -X- is more preferable. Here, X represents an oxygen atom, a sulfur atom or —N (R ⁰ ) —, and R ⁰ represents a hydrogen atom or a substituent (preferably the alkyl group, cycloalkyl group, aryl group, or hetero group as the substituent). A cyclic group, and more preferably Rc described later). L ¹ is most preferably —C (═O) —O—.

The alkylene group for R ² may be chained or branched, but is preferably chained. Moreover, 2-4 are preferable.
n is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and most preferably an integer of 1 to 10.
Examples of the aliphatic hydrocarbon group for Z ¹ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group, and an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group include Preferably, an alkyl group and a cycloalkyl group are more preferable, and an alkyl group is more preferable.
The alkenyl group and alkynyl group have 2 to 30 carbon atoms (preferably 2 to 20), the cycloalkyl group has 3 to 30 carbon atoms (preferably 5 to 20), and the cycloalkynyl group has 6 to 30 carbon atoms (preferably 6 to 6 carbon atoms). 20) is preferred respectively. On the other hand, the alkyl group preferably has 1 to 20 carbon atoms.
Z ¹ is preferably a hydrogen atom or an aliphatic group in the above preferred range, more preferably a hydrogen atom or an alkyl group.

Here, in the present invention, a substituent or a substituent in “optionally substituted” used in each general formula including the general formula [1] will be described.
In the present invention, any substituent may be used, but a substituent selected from the following substituent group is preferred.

(Substituent group)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. A substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms. Group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group), acyloxy A group (preferably an acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms. A silamino group, for example, an acetylamino group, a benzoylamino group, and the like, an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms). An alkoxycarbonylamino group, for example, a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Aryloxycarbonylamino group, for example, phenyloxycarbonylamino group and the like, sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 sulfonylamino groups such as methanesulfonyl And sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group). Group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably carbon number). 1 to 12 carbamoyl groups, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group).
These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

  The monomer represented by the general formula [1] is preferably a monomer represented by the following general formula [2].

In the general formula [2], R ³ represents a hydrogen atom, a halogen atom or a methyl group, and X represents an oxygen atom, a sulfur atom or —N (Rc) —. Here, Rc represents a hydrogen atom or an alkyl or cycloalkyl group having 1 to 8 carbon atoms which may have a substituent. R ⁴ represents an alkylene group having 1 to 5 carbon atoms. m represents an integer of 1 to 40. Z ² represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. Here, the alkyl group in Rc, the cycloalkyl group, the alkylene group in R ⁴ , and the aliphatic hydrocarbon group in Z ² may have a substituent, and when m is 2 or more, the plurality of R ⁴ are the same as each other But it may be different.
R ³ , R ⁴ , m and Z ² have the same meanings as R ¹ , R ² , n and Z ^{1 in the} corresponding general formula [1], and preferred ranges are also the same.
X is preferably an oxygen atom. The alkyl group represented by Rc preferably has 3 to 8 carbon atoms, and the cycloalkyl group represented by Rc preferably has 3 to 8 carbon atoms.

  The monomer represented by the general formula [1] or [2] is more preferably a monomer represented by the following general formula [3].

In the general formula [3], R ⁵ represents a hydrogen atom, a halogen atom or a methyl group, and R ⁶ represents an alkylene group having 2 to 4 carbon atoms. l represents an integer of 1 to 40. Z ³ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, the alkylene group in R ^{6 and} the aliphatic hydrocarbon group in Z ³ may have a substituent, and when l is 2 or more, the plurality of R ⁴ may be the same as or different from each other.
R ⁵ , R ⁶ and l have the same meanings as R ¹ , R ² and n in the corresponding general formula [1], and preferred ranges are also the same. Z ³ is the same as the preferable range in the range included in Z ¹ in the general formula [1].

  Specific examples of the monomer represented by any one of the general formulas [1] to [3] used in the present invention are shown below, but the present invention is not limited to these.

As a monomer represented by any one of the above general formulas [1] to [3], Nippon Oil & Fats Blemmer Series and Toagosei Co., Ltd. Aronix Series can be used (both are trade names).
The polymer used in the present invention may be a copolymer of the monomer represented by any one of the general formulas [1] to [3] with another type of monomer copolymerizable with the monomer.
There is no restriction | limiting in particular as such a monomer, The monomer group (a)-(j) shown below can be used suitably if what can superpose | polymerize by normal radical polymerization or an ionic polymerization method. These monomers can be freely selected and selected to synthesize a polymer.

-Monomer group (a)-(j)-
(A) Conjugated dienes: 1,3-pentadiene, isoprene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, cyclo Pentadiene and the like.
(B) Olefin: ethylene, propylene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, 4-pentenoic acid, methyl 8-nonenoate, vinylsulfonic acid, trimethylvinylsilane, trimethoxyvinylsilane, 1,4- Divinylcyclohexane, 1,2,5-trivinylcyclohexane, etc.

  (C) α, β-unsaturated carboxylic acid esters: alkyl acrylate (for example, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylate (for example, benzyl acrylate, 2-cyanoethyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, etc.), substituted alkyl methacrylate (eg, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxy) Ethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate Tacrylate, polypropylene glycol monomethacrylate (polyoxypropylene added mole number = 2 to 100), 3-N, N-dimethylaminopropyl methacrylate, 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl Methacrylates, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc.), derivatives of unsaturated dicarboxylic acids (eg monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate), many Functional esters (eg ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra Methacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2,4-cyclohexane tetramethacrylate, etc.).

(D) Amides of α, β-unsaturated carboxylic acids: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert-butylacrylamide N-tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetone acrylamide, itaconic acid diamide, N-methylmaleimide, 2 -Acrylamide-methylpropane sulfonic acid, methylene bisacrylamide, dimethacryloyl piperazine and the like.
(E) Unsaturated nitriles: acrylonitrile, methacrylonitrile and the like.
(F) Styrene and derivatives thereof: styrene, vinyl toluene, p-tert-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, α-methyl styrene, vinyl naphthalene, p-hydroxymethyl styrene, p-styrene sulfonic acid sodium salt P-styrene sulfinic acid potassium salt, p-aminomethylstyrene, 1,4-divinylbenzene and the like.
(G) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether and the like.
(H) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate and the like.
(I) Other polymerizable monomers: N-vinylimidazole, 4-vinylpyridine, N-vinylpyrrolidone, 2-vinyloxazoline, 2-isopropenyloxazoline, divinylsulfone, and the like.

In the polymer of the present invention, the above-mentioned monomer (c) α, β-unsaturated carboxylic acid ester, (e) unsaturated nitrile, (f) quaternary or higher copolymer comprising styrene and its derivatives as essential components It is preferable that The copolymer is preferred in that it lowers the crystallinity of the polymer.
Although the example of the specific structure of the polymer used for this invention below is shown, it is not this limitation. In addition, the number in a formula shows the mass ratio of each monomer component. Mw represents a mass average molecular weight. Moreover, the following specific examples may be a random copolymer or a block copolymer, and are not limited to the block copolymer by the following notation.

The polymer used in the present invention can be produced by a known and commonly used method, and can be easily obtained by a solution polymerization method, a suspension polymerization method, a dispersion polymerization method, an anionic polymerization method, a cationic polymerization or the like.
For example, the monomer represented by the general formula [1] can be produced by adding a general-purpose radical polymerization initiator in an organic solvent and polymerizing the monomer. Alternatively, other addition-polymerizable unsaturated compounds can be added in some cases and produced in the same manner as described above. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition.
In addition, when a polymer is obtained from a monomer having low polymerizability, or when a polymer having a uniform composition is obtained from a plurality of monomers having different polymerization properties, an emulsion polymerization method is preferably used.
As the polymerization initiator, it is sufficient that it has radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, peroxides described in “Natural peroxide catalog” of Nippon Oil & Fats, and Wako Pure Chemicals. The azo compounds described in Kogyo Co., Ltd. “Azo polymerization initiator catalog” can be used.
The polymers mentioned above can be coated on the support by dissolving them appropriately using an organic solvent (such as methyl ethyl ketone, ethyl acetate, benzene, toluene, xylene). In addition, when a polymer is synthesized by emulsion polymerization, it can be applied on a support as a polymer latex in addition to an aqueous coating solution, or after removing the polymer by distilling off water, It can also be appropriately dissolved and coated on a support.

In the present invention, the receptor layer may be used in combination with a polymer or polymer latex in addition to the polymer used in the present invention.
When used in combination, a polymer is preferable. Examples of the polymer include halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, ethylene vinyl acetate copolymers, vinyl vinyl acetate copolymers, poly Vinyl polymers such as acrylic ester, polystyrene, and polystyrene acrylic, acetal polymers such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal, polyethylene terephthalate, polypropylene terephthalate, polycaprolactone (Placcel H-5, trade name, Daicel Chemical Industries) Polyester polymers, polycarbonate polymers, cellulose polymers described in JP-A-4-296595 and JP-A-2002-264543, and cellulose acetate butyrate (CAB551-). .2, CAB321-0.1, all of which are trade names, manufactured by Eastman Chemical Co., Ltd.), polyolefin polymers such as polypropylene, and polyamide polymers such as urea resin, melamine resin, and benzoguanamine resin, Furthermore, water-soluble polymers such as gelatin and polyvinyl alcohol are listed.

  The emulsion polymerization method can be generally performed according to the following literature. Tadashi Okuda, Hiroshi Inagaki, "Synthetic Resin Emulsion", published by Polymer Publishing Association (1978), Takaaki Sugimura, Akio Kataoka, Junichi Suzuki, Keiji Kasahara, "Application of Synthetic Latex", Published by Polymer Publishing Society (1993) 1), Soichi Muroi, “Chemistry of Synthetic Latex”, published by Kobunshi Shuppankai (1970). In the emulsion polymerization method for synthesizing the polymer latex used in the present invention, a batch polymerization method, a monomer (continuous / divided) addition method, an emulsion addition method, a seed polymerization method, etc. can be selected from the viewpoint of latex productivity. A batch polymerization method, a monomer (continuous / divided) addition method, and an emulsion addition method are preferred.

  The polymerization initiator only needs to have a radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, and peroxides described in Nippon Oil & Fats Co., Ltd. “Organic Peroxide Catalog”, etc. The azo compounds described in Yaku Kogyo Co., Ltd. “Azo Polymerization Initiator Catalog” can be used. Among them, water-soluble peroxides such as persulfate and water-soluble azo compounds described in Wako Pure Chemical Industries, Ltd., `` Azo polymerization initiator catalog '' and the like are preferable, ammonium persulfate, sodium persulfate, potassium persulfate, Azobis (2-methylpropionamidine) hydrochloride, azobis (2-methyl-N- (2-hydroxyethyl) propionamide), azobiscyanovaleric acid is more preferable, and in particular, ammonium persulfate, sodium persulfate, potassium persulfate, etc. Peroxides are preferred from the viewpoints of image storage stability, solubility, and cost.

  As the addition amount of the polymerization initiator, the polymerization initiator is preferably 0.3% by mass to 2.0% by mass, and 0.4% by mass to 1.75% by mass with respect to the total amount of monomers. Is more preferable, and 0.5% by mass to 1.5% by mass is particularly preferable.

  As the polymerization emulsifier, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but the anionic surfactant has dispersibility and image storability. From the viewpoint, it is preferable to use a sulfonic acid type anionic surfactant because polymerization stability can be secured in a small amount and resistance to hydrolysis, and a long chain represented by Perex SS-H (trade name, Kao Corp.). Alkyl diphenyl ether disulfonate is more preferable, and a low electrolyte type such as Pionine A-43-S (trade name, Takemoto Yushi Co., Ltd.) is particularly preferable.

  As the polymerization emulsifier, a sulfonic acid type anionic surfactant is preferably used in an amount of 0.1% by mass to 10.0% by mass with respect to the total amount of monomers, and 0.2% by mass to 7.5% by mass is used. It is more preferable that 0.3% by mass to 5.0% by mass is used.

  In the synthesis of the polymer latex used in the present invention, it is preferable to use a chelating agent. A chelating agent is a compound capable of coordinating (chelating) multivalent ions such as metal ions such as iron ions and alkaline earth metal ions such as calcium ions. Japanese Patent Publication No. 6-8956, US Pat. 4-73645, JP-A-4-127145, JP-A-4-47073, JP-A-4-305572, JP-A-6-11805, JP-A-5-1773312, JP-A-5-66527, JP-A-5 -158195, JP-A-6-118580, JP-A-6-110168, JP-A-6-161054, JP-A-6-175299, JP-A-6-214352, JP-A-7-114161, JP-A-7- 114154, JP 7-120894, JP 7-199433, JP 7-306504, JP 9-43792, JP 8-314090, JP 10-182571, JP 10-182570 And compounds described in JP-A-11-190892 and the specification can be used.

  Examples of the chelating agent include inorganic chelate compounds (sodium tripolyphosphate, sodium hexametaphosphate, sodium tetrapolyphosphate, etc.), aminopolycarboxylic acid chelate compounds (nitrilotritriacetic acid, ethylenediaminetetraacetic acid, etc.), organic phosphonic acid chelate compounds ( Research Disclosure 18170, JP-A-52-102726, 53-42730, 56-97347, 54-121127, 55-4024, 55-4025, 55-29883, 55 -126241, 55-65955, 55-65956, 57-179443, 54-61125, and German Patent No. 1045373, and the like, and polyphenol-based chelating agents , Polyamine chelate Preferably such compounds, with aminopolycarboxylic acid derivatives being particularly preferred.

  Preferable examples of the aminopolycarboxylic acid derivatives include the compounds listed in the appendix of “EDTA (-Complexane Chemistry)” (Nanedo, 1977), and some of the carboxyl groups of these compounds are sodium or potassium. Alkali metal salts and ammonium salts such as may be substituted. Particularly preferred aminocarboxylic acid derivatives include iminodiacetic acid, N-methyliminodiacetic acid, N- (2-aminoethyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, nitrilotriacetic acid, ethylenediamine-N, N '-Diacetic acid, ethylenediamine-N, N'-di-α-propionic acid, ethylenediamine-N, N'-di-β-propionic acid, N, N'-ethylene-bis (α-o-hydroxyphenyl) glycine N, N'-di (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, ethylenediamine-N, N'-diacetic acid-N, N'-diacethydroxamic acid, N-hydroxyethylethylenediamine-N , N ′, N′-triacetic acid, ethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,2-propylenediamine-N, N, N ′, N′-tetraacetic acid, d, l-2 , 3-Diaminobutane-N, N, N ′, N′-tetraacetic acid, meso-2,3-diaminobuta -N, N, N ', N'-tetraacetic acid, 1-phenylethylenediamine-N, N, N', N'-tetraacetic acid, d, l-1,2-diphenylethylenediamine-N, N, N ' , N′-tetraacetic acid, 1,4-diaminobutane-N, N, N ′, N′-tetraacetic acid, trans-cyclobutane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, trans-cyclopentane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, trans-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cis-cyclohexane -1,2-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,3-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,4-diamine-N , N, N ′, N′-tetraacetic acid, o-phenylenediamine-N, N, N ′, N′-tetraacetic acid, cis-1,4-diaminobutene-N, N, N ′, N′-tetra Acetic acid, trans-1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, α, α′-diamino-o-xylene-N, N, N ′, N′-tetraacetic acid, 2- Hydroxy-1,3-p Lopandiamine-N, N, N ′, N′-tetraacetic acid, 2,2′-oxy-bis (ethyliminodiacetic acid), 2,2′-ethylenedioxy-bis (ethyliminodiacetic acid), ethylenediamine-N, N '-Diacetic acid-N, N'-di-α-propionic acid, ethylenediamine-N, N'-diacetic acid-N, N'-di-β-propionic acid, ethylenediamine-N, N, N', N ' -Tetrapropionic acid, diethylenetriamine-N, N, N ', N' ', N' '-pentaacetic acid, triethylenetetramine-N, N, N', N '', N '' ', N' ''- Hexaacetic acid, 1,2,3-triaminopropane-N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, and some of the carboxyl groups of these compounds are Examples include substituted alkali metal salts such as sodium and potassium, and ammonium salts.

  The addition amount of the chelating agent is preferably 0.01% by mass to 0.4% by mass, more preferably 0.02% by mass to 0.3% by mass with respect to the total amount of monomers. It is especially preferable that it is 03 mass%-0.15 mass%. When the amount of the chelating agent is less than 0.01% by mass, capture of metal ions mixed in the production process of the polymer latex becomes insufficient, stability against aggregation of the latex is lowered, and applicability is deteriorated. Moreover, when it exceeds 0.4 mass%, the viscosity of latex will rise and coatability will fall.

  A chain transfer agent is preferably used for the synthesis of the polymer latex. As the chain transfer agent, those described in “Polymer Handbook, 3rd edition” (Wiley-Interscience, 1989) are preferable. Sulfur compounds are more preferred because they have high chain transfer ability and can be used in small amounts. Hydrophobic mercaptan-based chain transfer agents such as tert-dodecyl mercaptan and n-dodecyl mercaptan are particularly preferred.

  The amount of the chain transfer agent is preferably 0.2% by mass to 2.0% by mass, more preferably 0.3% by mass to 1.8% by mass, and 0.4% by mass to 1.6% by mass with respect to the total amount of monomers. Mass% is particularly preferred.

  In emulsion polymerization, in addition to the above compounds, electrolytes, stabilizers, thickeners, antifoaming agents, antioxidants, vulcanizing agents, antifreezing agents, gelling agents, vulcanization accelerators, etc. are described in synthetic rubber handbooks, etc. These additives may be used.

  The polymer latex may be a so-called core / shell type latex in addition to a normal uniform polymer latex. In this case, it may be preferable to change the glass transition temperature between the core and the shell. The glass transition temperature of the polymer latex that can be used in the present invention is preferably −30 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., further preferably 10 ° C. to 70 ° C., and particularly preferably 15 ° C. to 60 ° C. .

  Preferred embodiments of the polymer latex may be a linear polymer, a branched polymer, a crosslinked polymer, a so-called homopolymer obtained by polymerizing a single monomer, or a copolymer obtained by polymerizing two or more types of monomers. Good. In the case of a copolymer, it may be a random copolymer or a block copolymer. These polymers have a number average molecular weight of 5,000 to 100,000, preferably 10,000 to 500,000. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

The minimum film-forming temperature (MFT) of the polymer latex is preferably −30 ° C. to 90 ° C., more preferably about 0 ° C. to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. Film-forming aids, also called temporary plasticizers, are organic compounds (usually organic solvents) that lower the minimum film-forming temperature of polymer latex. For example, Soichi Muroi, “Synthetic Latex Chemistry”, published by Kobunshi Publishing Co. (1970) )It is described in. Preferred film-forming aids are the following compounds, but the compounds that can be used in the present invention are not limited to the following specific examples.
Z-1: benzyl alcohol Z-2: 2,2,4-trimethylpentanediol-1,3-monoisobutyrate Z-3: 2-dimethylaminoethanol Z-4: diethylene glycol

  The polymer latex preferably has a polymer concentration of 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass with respect to the latex liquid. In addition, the polymer latex in the image receiving sheet of the present invention includes a gel or a dried film state formed by drying a part of the solvent after coating.

  As the polymer latex that may be used in combination with the polymer used in the present invention, the following polymers can be used. Examples of acrylic polymers include Sebian A-4635, 4718, 4601 manufactured by Daicel Chemical Industries, Ltd., Nipol Lx811, 814, 821, 820, 855, 857x2 manufactured by Nippon Zeon Co., Ltd., Dainippon Ink Chemical Co., Ltd. Voncoat R3370, 4280, Jurimer ET-410, JSR Corporation AE116, AE119, AE121, AE125, AE134, AE137, AE140, AE173, Toagosei Co., Ltd. Aron A-104, NS-600X, NS-620X manufactured by Takamatsu Oils & Fats Co., Ltd., Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, 2706 manufactured by Nissin Chemical Industry Co., Ltd. (all are trade names) .

  Examples of polyesters that may be used in combination include FINETEX ES650, 611, 675, 850 manufactured by Dainippon Ink Chemical Co., Ltd., WD-size, WMS manufactured by Eastman Chemical, A-110, A manufactured by Takamatsu Yushi Co., Ltd. -115GE, A-120, A-121, A-124GP, A-124S, A-160P, A-210, A-215GE, A-510, A-513E, A-515GE, A-520, A-610 , A-613, A-615GE, A-620, WAC-10, WAC-15, WAC-17XC, WAC-20, S-110, S-110EA, S-111SL, S-120, S-140, S -140A, S-250, S-252G, S-250S, S-320, S-680, DNS-63P, NS-122L, NS-122LX, NS-244LX, NS-140L, NS-141LX, NS-282LX , Aronmelt PES-1000 series, PES-2000 series, Toyobo Co., Ltd., Bailonal MD-1100, MD-1200, MD-1220, MD-1245, MD-1250, MD-1335, MD- Examples include 1400, MD-1480, MD-1500, MD-1930, MD-1985, and Sepoljon ES manufactured by Sumitomo Seika Co., Ltd. (all trade names).

  Examples of polyurethanes that may be used in combination include HYDRAN AP10, AP20, AP30, AP40, 101H, Vondic 1320NS, 1610NS, manufactured by Dainippon Ink and Chemicals, Inc., D-1000, D-2000 , D-6000, D-4000, D-9000, Takamatsu Yushi Co., Ltd. NS-155X, NS-310A, NS-310X, NS-311X, Daiichi Kogyo Seiyaku Co., Ltd. Also product name).

  Examples of rubbers that may be used in combination include LACSTAR 7310K, 3307B, 4700H, 7132C (above, Dainippon Ink and Chemicals), Nipol Lx416, LX410, LX430, LX435, LX110, LX415A, LX438C, 2507H, Examples include LX303A, LX407BP series, V1004, MH5055 (all manufactured by Nippon Zeon Co., Ltd.) and the like.

  Examples of polyvinyl chlorides that may be used in combination include: Z351, G351, G576, Nissin Chemical Industries, Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602 , 630, 660, 671, 683, 680, 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. Also product name). Examples of polyvinylidene chlorides include L502 and L513 manufactured by Asahi Kasei Kogyo Co., Ltd., and D-5071 manufactured by Dainippon Ink & Chemicals, Inc. (all are trade names). Examples of polyolefins include Chemipearl S120, SA100, V300 (P-40: Tg80 ° C) manufactured by Mitsui Petrochemical Co., Ltd., Voncoat 2830, 2210, 2960 manufactured by Dainippon Ink Chemical Co., Ltd., Sumitomo Seika Co., Ltd. Examples of Zyxen, Sepoljon G, and copolymerized nylons include Sepoljon PA manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of polyvinyl acetates that may be used in combination include Vinibrand 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138 manufactured by Nissin Chemical Industry Co., Ltd. , A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N, 1086A, 1086, 1086D, 1108S, 1187, 1241LT, 1580N, 1083, 1571, 1572, 1581, 4465, 4466, 4468W, 4468S, 4470, 4485LL, 4495LL, 1024 1042, 1060, 1060S, 1080M, 1084W, 1084S, 1096, 1570K, 1050, 1050S, 3290, 1017AD, 1002, 1006, 1008, 1107L, 1225, 1245L, GV-6170, GV-6181, 4468W, 4468S, etc. (All are trade names).

  Other polymers that can be used in combination with the polymer used in the present invention are preferably transparent or translucent and colorless, and form natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other films. Medium such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinylchloride, polymethacrylic acid Styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyester S, polyurethanes, phenoxy resins, polyvinylidene chlorides, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, and polyamides.

  The polymer used in the present invention is preferably used as a binder for the receiving layer. In this case, the binder of the receiving layer used has a glass transition temperature (Tg) in terms of processing brittleness and image storage stability. The thing of the range of -30 degreeC-70 degreeC is preferable, More preferably, it is the range of -10 degreeC-50 degreeC, More preferably, it is the range of 0 degreeC-40 degreeC. It is also possible to use a blend of two or more polymers as the binder, and in this case, it is preferable that the weighted average Tg in consideration of the composition falls within the above range. Moreover, when phase-separating or having a core-shell structure, the weighted average Tg is preferably within the above range.

This glass transition temperature (Tg) can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

Next, the coating composition of the present invention will be described.
(Coating composition)
The coating composition of the present invention is particularly preferably used in the receiving layer. The receiving layer serves to receive the dye transferred from the ink sheet and maintain the formed image. Therefore, a resin (dyeable receiving polymer) that is easily dyed is used for the receiving layer.
The coating composition of the present invention contains a polymer containing a repeating unit derived from the monomer represented by the aforementioned general formula [1], and preferably functions as the dyeing polymer. Therefore, it is preferable to apply the coating composition for a receiving layer of the present invention to form a receiving layer.

In the present invention, the receiving layer is coated with an organic solvent (for example, methyl ethyl ketone, toluene, etc.) (the content of water of the solvent in the coating solution is less than 60% by mass, preferably less than 50% by mass, more preferably less than 40% by mass, Further preferably, it may be less than 20% by mass), or may be applied with an aqueous coating solution containing an aqueous solvent. Furthermore, it is preferable to prepare by drying after coating.
In the present invention, “aqueous” means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water, and components other than water of the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, Water-miscible organic solvents such as alcohols such as diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether and oxyethyl phenyl ether, cellosolvs such as methyl cellosolve and ethyl cellosolve, dimethylformamide and ethyl acetate Can be used. In this case, the amount of the water-miscible organic solvent added is preferably 50% by mass or less, more preferably 30% by mass or less of the solvent.
The polymer used in the present invention may be formed by coating from water, an organic solvent or an emulsion.

The degree of dyeing property of the pigment is defined as follows.
Four colors of yellow, magenta, cyan, and black are output on the image receiving sheet so as to form a solid image with 256 gradations, and the reflection density of the obtained image is measured. Defined as receiving polymer. Note that the dyeing property of the receiving polymer may differ depending on the printer and the ink sheet.
Specifically, it is preferable to use a coating composition containing the polymer used in the present invention.

<Ultraviolet absorber>
Moreover, in this invention, in order to improve light resistance, the receiving layer may contain the ultraviolet absorber. At this time, the UV absorber can be fixed to the receiving layer by increasing the molecular weight, and can be prevented from being diffused into the ink sheet or sublimation / transpiration due to heating.
As the ultraviolet absorber, compounds having various ultraviolet absorber skeletons widely known in the field of information recording can be used. Specific examples include 2-hydroxybenzotriazole type ultraviolet absorbers, 2-hydroxybenzotriazine type ultraviolet absorbers, and compounds having a 2-hydroxybenzophenone type ultraviolet absorber skeleton. A compound having a benzotriazole type or triazine skeleton is preferable from the viewpoint of ultraviolet absorption ability (absorption coefficient) / stability, and a compound having a benzotriazole type or benzophenone type skeleton is preferable from the viewpoint of increasing the molecular weight or forming a latex. Specifically, an ultraviolet absorber described in JP 2004-361936 A can be used.

  The ultraviolet absorber preferably has absorption in the ultraviolet region and does not have an absorption edge in the visible region. Specifically, when added to the receiving layer to form a thermal transfer image-receiving sheet, the reflection density at 370 nm is preferably Abs 0.5 or more, and the reflection density at 380 nm is more preferably Abs 0.5 or more. . The reflection density at 400 nm is preferably Abs 0.1 or less. A high reflection density in the range exceeding 400 nm is not preferable because the image is yellowed.

  In the present invention, the ultraviolet absorber has a high molecular weight and preferably has a mass average molecular weight of 10,000 or more, more preferably a mass average molecular weight of 100,000 or more. As a means for increasing the molecular weight, it is preferable to graft an ultraviolet absorber onto the polymer. The polymer that becomes the main chain preferably has a polymer skeleton that is inferior in dyeability to the dye used in combination. Moreover, it is preferable to have sufficient film strength when the film is formed. The graft ratio of the ultraviolet absorber to the polymer main chain is preferably 5 to 20% by mass, and more preferably 8 to 15% by mass.

Moreover, it is more preferable that the polymer grafted with the ultraviolet absorber is made into a latex. The receptor layer can be formed by forming an aqueous dispersion type coating solution into a latex to form a latex, and the manufacturing cost can be reduced. For example, the method described in Japanese Patent No. 3450339 can be used as a method for forming a latex. Examples of the latex-made ultraviolet absorber include ULS-700, ULS-1700, ULS-1383MA, ULS-1635MH, XL-7016, ULS-933LP, ULS-935LH, Shin-Nakamura Chemical Co., Ltd. Commercially available ultraviolet absorbers such as New Coat UVA-1025W, New Coat UVA-204W, and New Coat UVA-4512M (both are trade names) can also be used.
When the polymer to which the ultraviolet absorber is grafted is made into a latex, it is possible to form a receiving layer in which the ultraviolet absorber is uniformly dispersed by mixing with the latex of the above-mentioned dyeable receiving polymer and applying it.

  The added amount of the polymer grafted with the ultraviolet absorber or the latex thereof is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to the dyeable accepting polymer latex forming the receptor layer.

<Release agent>
The receiving layer can also contain a release agent in order to prevent thermal fusion with the thermal transfer sheet during image formation. As the release agent, silicone oil and phosphoric ester plasticizer fluorine compound can be used, and silicone oil is particularly preferably used. As the silicone oil, modified silicone oils such as epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are preferably used. A reaction product of vinyl-modified silicone oil and hydrogen-modified silicone oil is preferable. The addition amount of the release agent is preferably 0.2 to 30 parts by mass with respect to the receiving polymer.

Furthermore, the receiving layer preferably contains an antioxidant and other materials. Therefore, these and the above-mentioned compounds may be contained in the coating composition of the present invention.
The coating amount of the receiving layer is preferably 0.5 to 10 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified). The thickness of the receiving layer is preferably 1 to 20 μm.

(Intermediate layer <underlayer>)
A base layer is preferably formed between the receptor layer and the support. For example, a white background adjustment layer, a charge adjustment layer, an adhesive layer, and a primer layer are formed. These layers can be formed in the same manner as described in, for example, Japanese Patent No. 3585599 and Japanese Patent No. 2925244.

(Intermediate layer <insulation layer>)
The heat insulating layer (foamed layer) plays a role of protecting the support from heat during heat transfer using a thermal head. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the substrate.

The heat insulating layer is preferably formed from a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle. For example, 1) Water is contained inside a partition formed by polystyrene, acrylic resin, styrene-acrylic resin, etc., and after coating and drying Non-foamed hollow particles in which the water inside the particles evaporates outside the particles and the inside of the particles becomes hollow. 2) Low boiling point liquids such as butane and pentane, polyvinylidene chloride, polyacrylonitrile, polyacrylic acid, polyacrylic A foamed microballoon covered with a resin comprising any of acid esters, a mixture or a polymer thereof, and after coating, the low-boiling liquid inside the particles expands by heating, and the inside becomes hollow 3) above The microballoon etc. which carried out the superheating foaming of 2) beforehand, and was used as the hollow polymer are mentioned.

  These hollow polymers preferably have a hollow ratio of about 20 to 70%, and can be used by mixing two or more kinds as necessary. Specific examples of 1) include Low and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nipol MH5055 (all trade names), and the like. . Specific examples of 2) include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of 3) include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSEL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd.

  The intermediate layer containing the hollow polymer contains a water-dispersed resin or a water-soluble resin as a binder resin as a binder resin. Examples of the binder resin used in the present invention include acrylic resin, styrene-acrylic copolymer, polystyrene resin, polyvinyl alcohol resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl chloride vinyl acetate copolymer, styrene- Known resins such as butadiene copolymers, polyvinylidene chloride resins, cellulose derivatives, casein, starch, and gelatin can be used. These resins can be used alone or in combination.

The solid content of the hollow polymer in the intermediate layer is preferably between 5 and 2000 parts by mass when the solids content of the binder resin is 100 parts by mass. Moreover, 1-70 mass% is preferable, and, as for the mass ratio which occupies with respect to the coating liquid of the solid content of a hollow polymer, 10-40 mass% is more preferable. If the ratio of the hollow polymer is too small, sufficient heat insulation cannot be obtained, and if the ratio of the hollow polymer is too large, the binding force between the hollow polymers decreases, causing problems such as powder falling off during processing or film peeling. Arise.
The particle size of the hollow polymer is preferably from 0.1 to 20 μm, more preferably from 0.1 to 2 μm, particularly preferably from 0.1 to 1 μm. Further, the glass transition temperature (Tg) of the hollow polymer is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher.

  Moreover, the heat insulation layer may be formed from resin and a foaming agent. As the resin for the heat insulating layer, a known resin such as urethane resin, acrylic resin, methacrylic resin, modified olefin resin, or a blend thereof can be used. A heat insulating layer is formed by coating a resin obtained by dissolving and / or dispersing these resins in an organic solvent or water. The heat insulating layer coating liquid is an aqueous coating liquid that does not affect the foaming agent. For example, water-soluble, water-dispersible, or SBR latex, urethane emulsion, polyester emulsion, emulsion of vinyl acetate and its copolymer, emulsion of acrylic copolymer such as acrylic and acrylic styrene, vinyl chloride Emulsions such as emulsions, or dispersions thereof can be used. However, in the case where microspheres described later are used as the foaming agent, an emulsion of vinyl acetate and its copolymer, acrylic and Emulsion of acrylic copolymer such as acrylic styrene It is preferable to use.

  Since these resins can easily control the glass transition point, flexibility, and film-forming property by changing the type of monomer to be copolymerized and their blending ratio, plasticizers and film-forming aids are added. Even if it is not, it is suitable in that the desired physical properties can be obtained, the color change is small during storage in various environments after film formation, and the physical properties change little over time. Of the above-mentioned resins, SBR latex is not preferred because it generally has a low glass transition point and is likely to cause blocking, and yellowing is likely to occur after film formation or during storage. Many urethane-based emulsions contain solvents such as NMP and DMF, and are not preferable because they easily affect the foaming agent. Polyester emulsions, dispersions, and vinyl chloride emulsions are generally not preferred because of their high glass transition points and poor microsphere foaming properties. Although some of them are soft, they are preferably not used because they are given flexibility by adding a plasticizer.

  The foaming performance of the foaming agent is greatly influenced by the hardness of the resin. In order for the foaming agent to expand to a desirable expansion ratio, a glass transition point of −30 to 20 ° C. or a film forming temperature of 20 ° C. or lower is desirable. When the glass transition point is 20 ° C. or higher, the flexibility is insufficient and the foaming performance of the foaming agent is reduced. In addition, those having a glass transition point of −30 ° C. or lower may cause blocking (generated at the foam layer and the back surface of the base material when the base material after the foam layer is wound) or thermal transfer. When the image receiving sheet is cut, a defect (such as when the image receiving sheet is cut, the resin of the foam layer is stuck to the blade of the cutter, the appearance is deteriorated, and the size of the cutting is caused, for example) occurs. Sometimes. Moreover, when the minimum film-forming temperature is 20 ° C. or higher, film-forming defects occur during coating and drying, and defects such as surface cracks occur.

  Defoaming agents such as dinitropentamethylenetetramene, diazoaminobenzene, azobisisobutyronitrile, azodicarboxamide, etc. that decompose when heated to generate gases such as oxygen, carbon dioxide, and nitrogen Examples thereof include known foaming agents such as microspheres in which a low boiling point liquid such as butane or pentane is covered with a resin such as polyvinylidene chloride or polyacrylonitrile to form microcapsules. Among these, microspheres in which a low-boiling liquid such as butane and pentane is covered with a resin such as polyvinylidene chloride and polyacrylonitrile to form microcapsules are preferably used. These foaming agents are foamed by heating after forming the foamed layer, and have high cushioning properties and heat insulation properties after foaming. The amount of the foaming agent used is preferably in the range of 0.5 to 100 parts by mass per 100 parts by mass of the resin forming the foamed layer. If it is 0.5 parts by mass or less, the cushioning property of the foam layer is low, and the effect of forming the foam layer cannot be obtained. If it is 100 parts by mass or more, the hollow ratio after foaming becomes too large, the mechanical strength of the foamed layer is lowered, and it becomes impossible to withstand normal handling. In addition, the foam layer surface loses smoothness and adversely affects the appearance and print quality. The total thickness of the foam layer is preferably 30 to 100 μm. When it is 30 μm or less, cushioning properties and heat insulation are insufficient, and when it is 100 μm or more, the effect of the foamed layer is not improved and the strength is lowered. Moreover, as a particle size of a foaming agent, that whose volume average particle diameter before foaming is about 5-15 micrometers and whose particle diameter after foaming is 20-50 micrometers is preferable. When the volume average particle size before foaming is 5 μm or less and the particle size after foaming is 20 μm or less, the cushion effect is low, the volume average particle size before foaming is 15 μm or more, and the particle size after foaming is 20 to 50 μm or more. In this case, the surface of the foam layer is made uneven, which adversely affects the image quality of the formed image.

  Particularly preferred among the foaming agents are low-temperature foaming type microspheres having a partition wall softening temperature and foaming start temperature of 100 ° C. or lower and an optimal foaming temperature (the temperature at which the foaming ratio becomes the highest with a heating time of 1 minute) of 140 ° C. or lower. It is preferable that the heating conditions during foaming be as low as possible. By using microspheres having a low foaming temperature, thermal wrinkles and curling of the base material during foaming can be prevented. The microsphere having a low foaming temperature can be obtained by adjusting the content of a thermoplastic resin such as polyvinylidene chloride or polyacrylonitrile that forms the partition walls. The volume average particle diameter is 5 to 15 μm. In the foamed layer using this microsphere, the bubbles obtained by foaming are closed cells, foamed by a simple process of heating alone, the thickness of the foamed layer can be easily controlled by the microsphere content, etc. There are advantages.

  However, this microsphere is weak against an organic solvent, and when a coating solution using an organic solvent is used as the foam layer, the partition walls of the microsphere are eroded and the foamability is lowered. Therefore, when microspheres such as those described above are used, organic solvents that attack the partition walls, for example, ketones such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, and organic solvents such as lower alcohols such as methanol and ethanol It is better to use a water-based coating solution that does not contain water. Accordingly, an aqueous coating solution, specifically, a water-soluble or water-dispersible resin, or a resin emulsion, preferably an acrylic styrene emulsion or a modified vinyl acetate emulsion may be used. In addition, even if the foamed layer is formed with an aqueous coating solution, the addition of high-boiling and highly polar solvents such as NMP, DMF, and cellosolve as co-solvents, film-forming aids, and plasticizers will affect the microspheres. Therefore, it is necessary to pay attention to the composition of the aqueous resin to be used, the amount of the high-boiling solvent added, and to confirm whether the microcapsules are adversely affected.

The intermediate layer (including the base layer and the heat insulating layer) preferably contains gelatin. The amount of the intermediate layer in the gelatin coating solution is preferably 0.5 to 14% by mass, particularly preferably 1 to 6% by mass. The coating amount of the hollow polymer in the intermediate layer is preferably ^{1~100g / m 2, 5~20g / m} 2 is more preferable.
The thickness of the intermediate layer containing the hollow polymer is preferably 5 to 50 μm, and more preferably 5 to 40 μm.

(Support)
As the support, coated paper, WP paper (double-sided laminated paper), or the like can be used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex, or polymer material on one side or both sides of a sheet such as a base paper, and the coating amount varies depending on the application. Examples of such coated paper include art paper, cast coated paper, Yankee paper, and the like.

  As the resin applied to the surface of the base paper or the like, it is appropriate to use a thermoplastic resin. Examples of such a thermoplastic resin include the following thermoplastic resins (a) to (h).

(A) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
(B) A thermoplastic resin having an ester bond. For example, dicarboxylic acid components (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.) and alcohol components (these alcohol components may be substituted with hydroxyl groups, etc.) Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate and other polyacrylate resin or polymethacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene -Methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, etc. are mentioned.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. it can.
Commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd. Polyester TP-220, R manufactured by Nippon Synthetic Chemical Co., Ltd. -188; various types of thermoplastic resins of the Hiros series manufactured by Seiko Chemical Industry Co., Ltd. (all trade names).

(C) Polyurethane resin etc. are mentioned.
(D) Polyamide resin, urea resin, etc. are mentioned.
(E) Polysulfone resin and the like.
(F) Polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
(G) Cellulose resins, such as polyol resin, ethyl cellulose resin, cellulose acetate resin, etc., such as polyvinyl butyral.
(H) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  Further, the thermoplastic resin may contain pigments or dyes such as brighteners, conductive agents, fillers, titanium oxide, ultramarine blue, and carbon black as required.

-Laminated paper-
The laminated paper is a paper obtained by laminating various resins, rubber or polymer sheets or films on a sheet such as a base paper. Examples of the laminate material include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. These resins may be used alone or in combination of two or more.

  In general, the polyolefin is often formed using low density polyethylene, but in order to improve the heat resistance of the support, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, high density polyethylene and low density polyethylene, It is preferable to use a blend of In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of cost, suitability for lamination, and the like.

The blend of the high density polyethylene and the low density polyethylene is used, for example, in a blend ratio (mass ratio) of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When forming a thermoplastic resin layer on both surfaces of the support, the back surface of the support is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. The molecular weight of polyethylene is not particularly limited, but the melt index is 1.0 to 40 g / 10 min for both high-density polyethylene and low-density polyethylene and has extrudability. preferable.
In addition, you may perform the process which gives white reflectivity to these sheets or films. Examples of such a treatment method include a method in which a pigment such as titanium oxide is contained in these sheets or films.

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose, and the support for a photographic image receiving sheet for electrophotography is close to a support for color silver halide photography. Those are preferred.

(Curl adjustment layer)
If the support is exposed as it is, the heat-sensitive transfer image-receiving sheet may be curled due to the humidity and temperature in the environment. Therefore, it is preferable to form a curl adjusting layer on the back side of the support. The curl adjusting layer not only prevents the image receiving sheet from curling but also serves as a waterproof. For the curl adjusting layer, polyethylene laminate, polypropylene laminate, or the like is used. Specifically, it can be formed in the same manner as described in, for example, JP-A-61-110135 and JP-A-6-202295.

(Writing layer / Charge adjustment layer)
An inorganic oxide colloid, an ionic polymer, or the like can be used for the writing layer and the charge adjusting layer. As the antistatic agent, for example, a cationic antistatic agent such as a quaternary ammonium salt or a polyamine derivative, an anionic antistatic agent such as an alkyl phosphate, or a nonionic antistatic agent such as a fatty acid ester can be used. . Specifically, for example, it can be formed in the same manner as described in Japanese Patent No. 3585585.

The heat-sensitive transfer image-receiving sheet of the present invention is preferably formed by simultaneously applying at least one intermediate layer and a receiving layer on a support. In the case of producing an image receiving sheet having a multilayer structure comprising a plurality of layers having different functions (such as a bubble layer, a heat insulating layer, an intermediate layer, and a receiving layer) on a support, JP-A Nos. 2004-106283 and 2004-181888 are disclosed. In addition, it is known that each layer is sequentially coated as disclosed in each publication such as JP-A 2004-345267, or the layers are previously applied on a support and bonded together.
On the other hand, it is known in the photographic industry that productivity is greatly improved, for example, by applying a plurality of layers simultaneously. For example, U.S. Pat. Nos. 2,761,791, 2,681,234, 3,508,947, 4,457,256, 3,993,019, JP 63-54975, JP-A-61-278848, 55-86557, 52-31727, 55-142565, 50-43140, 63-80872, 54-54020, Special Publications and specifications of Kaihei 5-104061, 5-127305, JP-B 49-7050, and Edgar B. Gutoff et al., "Coating and Drying Defects: Troubleshooting Operating Problems", John Wiley & Sons, 1995, 101. There are known so-called slide coating (slide coating method) and curtain coating (curtain coating method) described on pages ~ 103.

In the present invention, the plurality of layers are composed mainly of a resin. The coating solution for forming each layer is preferably water-dispersed latex. The solid content mass of the latex resin in the coating solution of each layer is preferably in the range of 5 to 80%, particularly preferably in the range of 20 to 60%. The average particle size of the resin contained in the water-dispersed latex is 5 μm or less and particularly preferably 1 μm or less. The water-dispersed latex may contain a known additive such as a surfactant, a dispersant, and a binder resin as necessary.
In the present invention, it is preferable to form a laminate of a plurality of layers on a support by the method described in US Pat. No. 2,761,791 and then solidify immediately. As an example, in the case of a multilayer structure solidified by a resin, it is preferable to quickly raise the temperature after forming a plurality of layers on the support. When a binder that gels at a low temperature such as gelatin is included, it may be preferable to quickly lower the temperature after forming a plurality of layers on the support.
The coating amount of a coating solution per one layer constituting the multilayer in the present invention in the range of 1g / m ² ~500g / m ² is preferred. The number of layers in the multilayer configuration can be arbitrarily selected as 2 or more. The receiving layer is preferably provided as the layer furthest away from the support.

The thermal transfer sheet (ink sheet) used in combination with the above-described thermal transfer image-receiving sheet of the present invention at the time of thermal transfer image formation is provided with a dye layer containing a diffusion transfer dye on a support. Ink sheets can be used. As the means for applying thermal energy at the time of thermal transfer, any conventionally known means for applying can be used. For example, recording is performed by a recording device such as a thermal printer (for example, product name, video printer VY-100, manufactured by Hitachi, Ltd.). By controlling the time, the intended purpose can be sufficiently achieved by applying thermal energy of about 5 to 100 mJ / mm ² .
The heat-sensitive transfer image-receiving sheet of the present invention can be applied to various uses such as a sheet- or roll-shaped heat-sensitive transfer image-receiving sheet, cards, and transmission-type manuscript preparation sheets capable of thermal transfer recording by appropriately selecting a support. You can also

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Reference example (preparation of ink sheet)
A polyester film having a thickness of 6.0 μm (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film. A heat-resistant slip layer (thickness 1 μm) was formed on the back side of the film, and yellow, magenta and cyan compositions having the following compositions were applied to the surface side in a single color (coating amount 1 g / m ² during dry film formation).
Yellow composition Dye (Macrolex Yellow 6G, trade name, manufactured by Bayer) 5.5 parts by weight Polyvinyl butyral resin 4.5 parts by weight (ESREC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Magenta composition Magenta dye (Disperse Red 60) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) Made by Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Cyan composition Cyan dye (Solvent Blue 63) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) ) Made)
90 parts by mass of methyl ethyl ketone / toluene (mass ratio 1/1)

Example 1
(Preparation of polymer)
(1-1) Preparation of Exemplified Polymer P-1 500 g of distilled water, 180 g of styrene, 120 g of Exemplified Monomer A-35, Pionein A-43-S (trade name, Takemoto Yushi) in a reactor equipped with a stirrer and a reflux condenser Co., Ltd.) 12 g, APS (ammonium peroxodisulfate: Wako Pure Chemical Industries, Ltd.) 2.25 g was added and heated to 70 ° C. for 6 hours under a nitrogen atmosphere to complete the reaction. The solvent was removed by lyophilization. The obtained powder was thoroughly washed with distilled water and dried to obtain an exemplary polymer P-1. The weight average molecular weight was 0.95 × 10 ⁵ .

(1-2) Preparation of Exemplified Polymer P-3 In a reactor equipped with a stirrer and a reflux condenser, 500 g of distilled water, 115 g of styrene, 60 g of acrylonitrile, 135 g of Exemplified Monomer A-30, Pionein A-43-S (trade name) , Takemoto Yushi Co., Ltd.) 12 g and APS 2.25 g were added and heated to 70 ° C. for 6 hours under a nitrogen atmosphere to complete the reaction. The solvent was removed by lyophilization. The obtained powder was thoroughly washed with distilled water and dried to obtain an exemplary polymer P-3. The mass average molecular weight was 0.55 × 10 ⁵ .

(1-3) Preparation of Exemplified Polymer P-7 In a reactor equipped with a stirrer and a reflux condenser, 500 g of distilled water, 54 g of styrene, 60 g of acrylonitrile, 150 g of 2-ethylhexyl acrylate, 30 g of Exemplified monomer A-35, 6 g of acrylic acid And 12 g of Pionein A-43-S (trade name, Takemoto Yushi Co., Ltd.) and 2.25 g of APS were added and heated to 70 ° C. for 6 hours under a nitrogen atmosphere to complete the reaction. The solvent was removed by lyophilization. The obtained powder was thoroughly washed with distilled water and dried to obtain an exemplary polymer P-7. The mass average molecular weight was 2.65 × 10 ⁵ .

(1-4) Preparation of Exemplified Polymer P-9 In a reactor equipped with a stirrer and a reflux condenser, distilled water 500 g, styrene 54 g, methyl methacrylate 60 g, dodecyl acrylate 165 g, exemplary monomer A-23 15 g, acrylic acid 6 g, 12 g of Piionin A-43-S (trade name, Takemoto Yushi Co., Ltd.) and 2.25 g of APS were added and heated to 70 ° C. for 6 hours under a nitrogen atmosphere to complete the reaction. The solvent was removed by lyophilization. The obtained powder was thoroughly washed with distilled water and dried to obtain an exemplary polymer P-9. The mass average molecular weight was 2.2 × 10 ⁵ .
(1-5) Preparation of Exemplified Polymer P-26 First, a monomer solution consisting of 200 g of methyl ethyl ketone (MEK), 50 g of styrene, 30 g of acrylonitrile, 60 g of benzyl methacrylate, 20 g of 2-ethylhexyl acrylate, and 40 g of Exemplified monomer A-29 is prepared. 60 g of the monomer solution is added to a reactor equipped with a stirrer reflux condenser and heated to 75 ° C. under a nitrogen atmosphere. 2.4 g of 2,2′-azobis (2,4′-dimethylvaleronitrile) (V65: manufactured by Wako Pure Chemical Industries, Ltd.) was added to the remaining monomer solution, and this was added dropwise to the reaction vessel over 1 hour. After 2 hours from the end of dropping, a solution of V65, 2.4 g dissolved in 24 g of MEK was dropped over 3 hours, and further aged at 75 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a copolymer solution. The obtained reaction solution was reprecipitated twice in a large excess amount of n-hexane, and the precipitated polymer was dried to obtain Exemplified Polymer P-26. The obtained polymer had a mass average molecular weight of 0.65 × 10 ⁵ .
(1-6) Preparation of Exemplified Polymer P-28 First, a monomer solution consisting of 200 g of methyl ethyl ketone (MEK), 60 g of styrene, 30 g of acrylonitrile, 40 g of methyl methacrylate, and 70 g of Exemplified monomer A-29 is prepared. 60 g of the monomer solution is added to a reactor equipped with a stirrer reflux condenser and heated to 75 ° C. under a nitrogen atmosphere. 2.4 g of 2,2′-azobis (2,4′-dimethylvaleronitrile) (V65: manufactured by Wako Pure Chemical Industries, Ltd.) was added to the remaining monomer solution, and this was added dropwise to the reaction vessel over 1 hour. After 2 hours from the end of dropping, a solution of V65, 2.4 g dissolved in 24 g of MEK was added dropwise over 3 hours, and further aged at 75 ° C. for 2 hours and 80 ° C. for 2 hours to obtain a copolymer solution. The obtained reaction solution was reprecipitated twice in a large excess amount of n-hexane, and the precipitated polymer was dried to obtain an exemplified polymer P-28. The obtained polymer had a mass average molecular weight of 0.31 × 10 ⁵ .

(Preparation of layer-receiving sheet)
(2-1) Preparation of Sample 101 (Comparative Example) A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, an intermediate layer A having the following composition was applied by a bar coater and dried, and subsequently, a receiving layer A1 having the following composition was applied by a bar coater and dried. Bar coater coating was performed at 40 ° C., and drying was performed at 50 ° C. for 16 hours for each layer. Coating was performed such that the coating amount at the time of drying was intermediate layer A: 1.0 g / m ² and receiving layer A 1: 3.0 g / m ² .
Intermediate layer A
Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight Optical brightener 1 part by weight (Uvitex OB, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Titanium oxide 30 parts by mass Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Receiving layer A1
100 parts by mass of polyester resin (Resin described in Example 1 of JP-A-2-265789)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-1) Preparation of Sample 102 (Comparative Example) A corona discharge treatment was performed on the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, an intermediate layer A having the following composition was applied by a bar coater and dried, and subsequently, a receiving layer A2 having the following composition was applied by a bar coater and dried. Bar coater coating was performed at 40 ° C., and drying was performed at 50 ° C. for 16 hours for each layer. Coating was performed such that the coating amount at the time of drying was intermediate layer A: 1.0 g / m ² and receiving layer A2: 3.0 g / m ² .
Intermediate layer A
Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight Optical brightener 1 part by weight (Uvitex OB, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Titanium oxide 30 parts by weight Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by weight Receiving layer A2
100 parts by mass of phenoxyethyl methacrylate / styrene = 95/5 copolymer (resin described in Example 1 of Japanese Patent No. 3604187)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-2) Preparation of Sample 103 (Comparative Example) A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. On top of this, an intermediate layer B and a receiving layer B having the above composition are laminated in this order from the support side by the method illustrated in FIG. 9 described in US Pat. No. 2,761,791. Application was performed. Immediately after application, the film was dried at 50 ° C. for 16 hours. Each of the coating amounts at the time of drying was applied such that the intermediate layer B was 15 g / m ² and the receiving layer B was 3.0 g / m ² .
Middle layer B
Hollow polymer latex 563 parts by mass (MH5055, trade name, manufactured by Nippon Zeon Co., Ltd.)
Gelatin 120 parts by mass Here, the hollow polymer latex is an aqueous dispersion of a hollow structure polymer having an outer diameter of 0.5 μm.
Receptive layer B
100 parts by weight of vinyl chloride resin (Viniblanc 609, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-3) Preparation of Sample 104 (Invention) Multilayer coating was performed in the same manner as Sample 103 except that the receiving layer B was replaced with a receiving layer C having the following composition. Immediately after application, the film was dried at 50 ° C. for 16 hours. Each of the coating amounts at the time of drying was applied such that the intermediate layer B was 15 g / m ² and the receiving layer C was 3.0 g / m ² .
Receptive layer C
Polymer P-1 100 parts by weight Amino-modified silicone 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-4) Preparation of Sample 105 (Invention) Multilayer coating was performed in the same manner as Sample 103 except that the receiving layer B was replaced with a receiving layer D having the following composition. Immediately after application, the film was dried at 50 ° C. for 16 hours. Each of the coating amounts at the time of drying was applied such that the intermediate layer B was 15 g / m ² and the receiving layer D was 3.0 g / m ² .
Receptive layer D
Polymer P-3 100 parts by weight Amino-modified silicone 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-5) Preparation of Sample 106 (Invention) Multilayer coating was performed in the same manner as Sample 103 except that the receiving layer B was replaced with a receiving layer E having the following composition. Immediately after application, the film was dried at 50 ° C. for 16 hours. Each of the coating amounts at the time of drying was applied such that the intermediate layer B was 15 g / m ² and the receiving layer E was 3.0 g / m ² .
Receptive layer E
Polymer P-7 100 parts by weight Amino-modified silicone 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(2-6) Preparation of Sample 107 (Invention) Multilayer coating was performed in the same manner as Sample 103 except that the receiving layer B was replaced with a receiving layer F having the following composition. Immediately after application, the film was dried at 50 ° C. for 16 hours. Each of the coating amounts at the time of drying was applied such that the intermediate layer B was 15 g / m ² and the receiving layer F was 3.0 g / m ² .
Receptive layer F
Polymer P-9 100 parts by weight Amino-modified silicone 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X-22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass (2-7) Preparation of sample 108 (present invention) Polymer P-9 in the receiving layer of sample 107 was changed to equal parts by mass and polymer P-26 A sample 108 was produced in the same manner as the sample 107 except that.
(2-8) Preparation of Sample 108 (Invention) Sample 109 was prepared in the same manner as Sample 107, except that polymer P-9 in the receiving layer of Sample 107 was changed to an equal mass part and polymer P-28. did.
(Image formation)
The ink sheet of the reference example and the image receiving sheets of the samples 101 to 109 are processed so that they can be loaded into a sublimation printer DPB1500 (trade name) manufactured by Nidec Copal, and the maximum density can be obtained in the high-speed print mode. A black solid image was output.

(Relative transfer density evaluation)
The Visual density of the black image obtained under the above conditions was measured with a Photographic Densitometer (trade name, manufactured by X-Rite Incorporated). Table 1 shows relative values when the transfer density of the sample 101 is 100.
(Smudge evaluation)
The image-receiving sheet after image output was stored in an incubator at 60 ° C. for one month, and color image bleeding was evaluated. The case where no blur was observed was evaluated as ◯, the case where the degree of blur was small was evaluated as Δ, and the case where blur was large was evaluated as X.
(Light fastness evaluation)
The image-receiving sheet after image output was evaluated by the dye residual ratio of 1.0 part of reflection density (OD) of an image stored for 2 weeks under irradiation of a fluorescent light tester of 20000 lx.
○: Dye remaining ratio ≧ 90%
Δ: 90> Dye remaining ratio ≧ 75%
×: 75%> Dye remaining rate

As is clear from the results in Table 1, the relative transfer density of the samples 101 and 102 coated with the organic solvent-based sample is low, and in the sample 103, although the relative transfer density is improved, the light fastness is lowered. It was.
On the other hand, all of the samples 104 to 109 of the present invention had high relative transfer density and high sensitivity. It was also found to be excellent in bleeding and light fastness. Thus, the heat-sensitive transfer receiving sheet of the present invention containing a polymer latex containing a repeating unit derived from the monomer represented by the general formula [1] could be obtained.

Claims (6)

A heat-sensitive transfer image-receiving sheet having at least one receptor layer on a support, wherein the receptor layer contains a polymer containing a repeating unit derived from a monomer represented by the following general formula [1] Thermal transfer image receiving sheet.

(In General Formula [1], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, R ² represents an alkylene group having 1 to 5 carbon atoms, and n is 1. Represents an integer of ˜40, Z ¹ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkylene group in R ^{2 and} aliphatic carbonization in Z ¹ The hydrogen group may have a substituent, and when n is 2 or more, the plurality of R ² may be the same as or different from each other. The thermal transfer image-receiving sheet according to claim 1, wherein the monomer represented by the general formula [1] is a monomer represented by the following general formula [2].

(In General Formula [2], R ³ represents a hydrogen atom, a halogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (Rc) —, where Rc is a hydrogen atom or a substituent. R ⁴ represents an alkylene group having 1 to 5 carbon atoms, m represents an integer of 1 to 40, and Z ² represents hydrogen. Represents an atom, or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkyl group in Rc, a cycloalkyl group, an alkylene group in R ⁴ , and an aliphatic hydrocarbon group in Z ² May have a substituent, and when m is 2 or more, a plurality of R ⁴ may be the same or different from each other. The thermal transfer image-receiving sheet according to claim 1 or 2, wherein the monomer represented by the general formula [1] or [2] is a monomer represented by the following general formula [3].

(In General Formula [3], R ⁵ represents a hydrogen atom, a halogen atom or a methyl group, R ⁶ represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 40, and Z ³ represents hydrogen. Represents an atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, wherein the alkylene group in R ^{6 and} the aliphatic hydrocarbon group in Z ³ may have a substituent. , L is 2 or more, the plurality of R ⁴ may be the same or different from each other.)   4. The polymer according to claim 1, wherein the polymer is a copolymer and has a nitrile monomer, an aromatic vinyl monomer, and a meth (a) acrylic acid ester as essential copolymerization components. The thermal transfer image-receiving sheet described in 1.   The thermal transfer image-receiving sheet according to any one of claims 1 to 4, further comprising a heat insulating layer containing hollow particles between the support and the receiving layer. A coating composition for producing a thermal transfer image-receiving sheet having at least one receptor layer on a support, wherein the coating composition is derived from a monomer represented by the following general formula [1] A coating composition for producing a thermal transfer image-receiving sheet, comprising a polymer comprising

(In General Formula [1], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, R ² represents an alkylene group having 1 to 5 carbon atoms, and n is 1. Represents an integer of ˜40, Z ¹ represents a hydrogen atom or a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, wherein an alkylene group in R ^{2 and} aliphatic carbonization in Z ¹ The hydrogen group may have a substituent, and when n is 2 or more, the plurality of R ² may be the same as or different from each other.