JP2003063153A - Thermal transfer image receiving sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer image receiving sheet, which is excellent in antistatic properties and water resistance, has no dependence on humidity and is excellent in reliability such as recording characteristics or the like. SOLUTION: This thermal transfer image receiving sheet, which is formed by providing a dye receiving layer at least on one side of a support, has a crosslinkable electric conductive layer employing a crosslinkable electric conductive composition containing a water-soluble electric conductive polymer having a sulfonic acid group and/or a carboxyl group, a solvent, a silane coupling agent and, when necessary, a polymer compound and/or a colloidal silica in at least one selected from the group consisting of between the support on the receiving layer, within the receiving layer, on the receiving layer and on the rear surface of the support.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermal transfer image-receiving sheet, more specifically, a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group on a support, a solvent and a silane coupling agent. The present invention relates to a thermal transfer image-receiving sheet having a crosslinkable conductive layer formed from a crosslinkable conductive composition containing as essential components.

[0002]

2. Description of the Related Art The thermal transfer system uses a sublimation type dye as a recording material and a thermal head capable of controlling the amount of heat generation, and the dyes corresponding to the amount of heat generation transfer multicolored colors from a thermal transfer sheet to an image receiving sheet in a short time. Then, by fixing, a full-color hard copy is formed. In such a dye thermal transfer printer, the thermal transfer sheet is usually supplied in a roll state, but the thermal transfer image receiving sheet is generally supplied as an individual sheet.

In the above-mentioned thermal transfer image receiving sheet used in the sublimation type thermal transfer system, it is an important technical problem how to efficiently use the heat generation amount of the thermal head for forming an image. Therefore, in order to reduce heat loss on the base material of the thermal transfer image-receiving sheet, a plastic sheet having smoothness, good cushioning and adhesiveness, and high heat insulation, a laminated sheet of plastic sheet and paper, synthetic paper, coated Paper (art paper), cast coated paper, PPC paper, etc. are used. Further, since a resin is also used for the receiving layer for forming an image, the charging property is high, and static electricity is easily generated by feeding and discharging paper in the printer. Therefore, double feed, paper jam, etc. may occur, or the printer may malfunction due to static electricity generated when the thermal transfer sheet and thermal transfer image receiving sheet are separated during printing, or dust or dust may be sucked in, causing partial recording. There is a problem that troubles such as not being generated occur.

In order to prevent the above problems due to charging,
It is known to form an antistatic layer on the surface of the thermal transfer image receiving sheet with a surfactant or the like, but the surfactant has hygroscopicity, so that the thermal transfer image receiving sheet may become sticky or the antistatic effect may be deteriorated over time. However, there is a problem that the effect is not sufficiently exhibited under the condition of low humidity. Also,
There is also a method of forming a conductive layer using conductive carbon black or a metal oxide such as tin oxide or indium-tin oxide (ITO). This method has the problems that the conductivity is excellent, but the transparency is low, and the method for forming the conductive layer is complicated, so that the cost is high.

As the conductive material used for providing the conductive layer, a cation-based or anion-based ionic polymer conductive material and an inorganic conductive agent such as carbon, metal or metal oxide are known. However, when an ionic polymer conductive material is used as the conductive layer, the conductivity changes depending on the humidity, and when an inorganic conductive material is used, there is no humidity dependency, but the conductivity is controlled. However, there is a problem that stable image characteristics cannot be obtained.

For this reason, JP-A-10-217623 and JP-A-2000-43430 propose to use a water-soluble conductive polymer having no humidity dependency as a conductive material. However, since it is a water-soluble polymer, its water resistance is insufficient, which has been a serious problem in actual use.

Further, Japanese Patent Laid-Open No. 2000-296680 proposes reacting an epoxy resin to a layer containing a polyanilinesulfonic acid compound and curing it to impart water resistance. The weather resistance is still insufficient, which is a practical problem.

[0008]

The present invention has been made to solve the above-mentioned various problems, and is excellent in antistatic property and film-forming property, and can be applied and coated by a simple method. We provide a thermal transfer image-receiving sheet with excellent water resistance, hardness, and weather resistance, which prevents the effect of electrification by the substrate, makes the thermal transfer image-receiving sheet run smoothly, and has excellent reliability in recording characteristics. To provide an image receiving sheet.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group, a solvent, a silane coupling agent. A thermal transfer image-receiving sheet using a crosslinkable conductive composition containing a crosslinkable conductive layer is suitable for this purpose, and by using this crosslinkable conductive composition, water resistance, film-forming property, transparency, conductivity In addition to water resistance by adding a polymer compound and colloidal silica to it, it is possible to form a crosslinkable conductive layer having excellent properties, hardness, weather resistance, etc. The present invention has been accomplished by finding that an extremely excellent crosslinkable conductive layer having improved strength and weather resistance can be formed.

That is, the present invention provides a thermal transfer image-receiving sheet having a dye receiving layer provided on at least one surface of a support, between the support and the receiving layer, in the receiving layer, on the receiving layer and on the support. A water-soluble conductive polymer (a) having at least one sulfonic acid group and / or carboxyl group selected from the back surface, a solvent (b), a silane coupling agent (c) represented by the general formula (1),

[Chemical 7] (In the above formula, R ₁ , R ₂ , and R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms.
6 is a straight-chain or branched alkoxy group, an amino group, an acetyl group, a phenyl group, and a halogen group. X is

[Chemical 8] And n and m are numbers from 1 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group and an epoxycyclohexyl group. The present invention relates to a thermal transfer image-receiving sheet having a crosslinkable conductive layer formed by coating and / or impregnating a crosslinkable conductive composition containing a). The crosslinkable conductive composition further comprises at least one polymer compound (d) selected from a water-soluble polymer compound and a polymer compound forming an emulsion in an aqueous system, and / or colloidal silica (e). Can be improved.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermal transfer image-receiving sheet of the present invention will be described in more detail below.

The water-soluble conductive polymer (a) used in the present invention is not particularly limited as long as it is a water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group, and specifically, it is unsubstituted or substituted. On the skeleton of a π-conjugated polymer containing iminophenylene as a repeating unit or on the nitrogen atom in the polymer, a sulfonic acid group and / or a carboxyl group, or an alkyl group substituted with a sulfonic acid group and / or a carboxyl group, or Examples thereof include water-soluble conductive polymers having an alkyl group containing an ether bond.

A preferred water-soluble conductive polymer has the general formula (2):

[Chemical 9] (In the formula, R _{4 to} R ₈ are each independently H, —S.
^{_{O 3 -, -SO 3 H,}} -R 29 SO 3 -, -R 29 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
_{l, -Br, -I, -N (} R 29) 2, -NHCOR
^{_{29, -OH, -O -, -SR}} 29, -OR 29, -O
COR ₂₉ , -NO ₂ , -COOH, -R ₂₉ COO
H, -COOR ₂₉ , -COR ₂₉ , -CHO and -C.
N is selected from the group consisting of N, wherein R ₂₉ has 1 to 1 carbon atoms.
24 alkyl, aryl or aralkyl groups or alkylene, arylene or aralkylene groups,
And at least one of R _{4 to} R ₈ is —SO ₃ ⁻ , −
^{_{SO 3 H, -R 29 SO 3}} -, -R 29 SO 3 H, -C
It is a group selected from the group consisting of OOH and —R ₂₉ COOH. Is a water-soluble conductive polymer containing 20 to 100% of the repeating unit consisting of (4) in the total number of repeating units of the entire polymer.

Among these water-soluble conductive polymers, the water-soluble conductive polymers represented by the following general formula (3) are more preferably used.

[Chemical 10] (In the above formula, y represents an arbitrary number of 0 <y <1, and R₉~
R₂₆Are each independently H, -SO_Three ⁻, -SO_ThreeH,-
R₂₉SO_Three ⁻, -R₂₉SO_ThreeH, -OCH_Three, -C
H_Three, -C_TwoH₅, -F, -Cl, -Br, -I, -N
(R₂₉)_Two, -NHCOR₂₉, -OH, -O⁻,-
SR₂₉, -OR₂₉, -OCOR₂₉, -NO_Two,-
COOH, -R₂₉COOH, -COOR₂₉, -CO
R₂₉, -CHO and -CN,
Here, R₂₉Is an alkyl or aryl group having 1 to 24 carbon atoms.
Or aralkyl group or alkylene, arylene or
Is an aralkylene group, and R₉~ R₂₆At least
One is -SO_Three ⁻, -SO _ThreeH, -R₂₉SO_Three ⁻,
-R₂₉SO_ThreeH, -COOH and -R₂₉COOH
It is a group selected from the group consisting of ) Repetition
20 to 20 units in the total number of repeating units of the entire polymer.
It is a water-soluble conductive polymer containing 100%. Where poly
Sulfonic acid groups and / or the total number of repeating units of mer
Or the content of the repeating unit having a carboxyl group
50% or more soluble conductive polymer has very high solubility
Since it is good, it is preferably used, and more preferably 70%.
Or more, more preferably 90% or more, particularly preferably 10%
0% polymer is used.

Further, the substituent added to the aromatic ring is preferably an electron-donating group from the viewpoint of conductivity and solubility, specifically, an alkyl group, an alkoxy group, a halogen group or the like is preferable, and an alkoxy group is particularly preferable. Most preferred are water-soluble conductive polymers. Among these combinations, the most preferable general formula (4) of the water-soluble conductive polymer is shown below.

[Chemical 11] (In the above formula, R ₂₇ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and their alkali metal salts, ammonium salts and substituted ammonium salts, and R ₂₈ is a methyl group, an ethyl group. , N-propyl group,
iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group Group, a tert-butoxy group, a heptoxy group, a hexoxy group, an octoxy group, a dodecoxy group, a tetracosoxy group, a fluoro group, a group selected from the group consisting of a chloro group and a bromo group, X is 0 <X <1 Is an arbitrary number, and n is a degree of polymerization and is 3 or more. Here, it is preferable that at least a part of R ₂₇ is a free acid type sulfonic acid group and / or a carboxyl group from the viewpoint of improving conductivity.

As the water-soluble conductive polymer used in the present invention, a polymer obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used. For example, JP-A-7-196791 proposed by the present inventors, JP-A-7-
The synthesis method described in Japanese Patent No. 324132 is applied. That is, the following general formula (5),

[Chemical 12] (In the above formula, R_Thirty~ R₃₅Are each independently H, -SO
_Three ⁻, -SO_ThreeH, -R ₂₉SO_Three ⁻, -R₂₉SO_Three
H, -OCH_Three, -CH_Three, -C_TwoH₅, -F, -C
l, -Br, -I, -N (R₂₉)_Two, -NHCOR
₂₉, -OH, -O⁻, -SR₂₉, -OR₂₉, -O
COR₂₉, -NO_Two, -COOH, -R₂₉COO
H, -COOR₂₉, -COR₂₉, -CHO and -C
Selected from the group consisting of N, where R₂₉Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
An alkylene, arylene or aralkylene group,
R_Thirty~ R ₃₅At least one is -SO_Three-,-
SO_ThreeH, -R₂₉SO_Three-, -R ₂₉SO_ThreeH, -C
OOH and -R₂₉A group selected from the group consisting of COOH
Is. ) Acidic group-substituted aniline represented by
Limetal salt, ammonium salt and / or substituted ammonium
Polymerized with an oxidizing agent in a solution containing a basic compound.
The water-soluble conductive polymer obtained by
Be done.

As a particularly preferred water-soluble conductive polymer, an alkoxy group-substituted aminobenzenesulfonic acid, its alkali metal salt, ammonium salt and / or substituted ammonium salt is polymerized with a oxidizing agent in a solution containing a basic compound. The obtained water-soluble conductive polymer is used.

From the viewpoint of improving conductivity, it is desirable that at least a part of the acidic group contained in the water-soluble conductive polymer used in the present invention is a free acid type. The mass average molecular weight of the water-soluble conductive polymer used in the present invention is G
2000 or more in terms of PC polyethylene glycol
Those having a weight average molecular weight of 3,000,000 or less and 1,000,000 or less are more preferable, and those having a weight average molecular weight of 5,000 or more and 500,000 or less are most preferable.

As the silane coupling agent (c) which is an essential constituent of the present invention, one having a hydroxyl group, a thiol group, an amino group, an epoxy group or an epoxycyclohexyl group represented by the above general formula (1) is used. Specifically, those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, and γ-glycidyloxypropyltriethoxysilane, and those having an amino group include γ-aminopropyl. Triethoxysilane, β-aminoethyltrimethoxysilane, γ-aminopropoxypropyltrimethoxysilane, and the like having thiol groups include γ-mercaptopropyltrimethoxysilane, β
-Mercaptoethylmethyldimethoxysilane, etc. having a hydroxyl group, β-hydroxyethoxyethyltriethoxysilane, γ-hydroxypropyltrimethoxysilane, etc., having an epoxycyclohexyl group, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane and the like can be mentioned.

The solvent (b) which is another essential constituent of the present invention dissolves or disperses the water-soluble conductive polymer (a), the silane coupling agent (c) and the polymer compound (d). If it is one, it is not particularly limited, but water,
Alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, acetone, methyl ethyl ketone, ethyl isobutyl ketone,
Ketones such as methyl isobutyl ketone, ethylene glycols such as ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl Propylene glycols such as ethers, amides such as dimethylformamide and dimethylacetamide, pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone, methyl lactate, ethyl lactate, β-
Hydroxyesters such as methyl methoxyisobutyrate and methyl α-hydroxyisobutyrate are preferably used.

Further, in the present invention, the use of the polymer compound (d) further improves the adhesion and strength of the crosslinkable conductive layer to the substrate. The polymer compound (d) used in the present invention is not particularly limited as long as it can be dissolved or dispersed in the solvent (b) used in the present invention. Specifically, it is a water-soluble polymer compound or an aqueous system. A polymer compound forming an emulsion is used, and a polymer compound having an anion group is particularly preferably used.

Specific examples of the water-soluble polymer compound include polyvinyl alcohols such as polyvinyl alcohol and polyvinyl formal, polyacrylamides such as polyacrylamide and polyacrylamidemethylpropanesulfonic acid, polyvinylpyrrolidones, water-soluble alkyd resins, and water-soluble polymers. -Soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, water-soluble acrylic resin, water-soluble urethane resin, water-soluble acrylic / styrene resin, water-soluble vinyl acetate / acrylic copolymer resin , A water-soluble polyester resin, a water-soluble styrene / maleic acid copolymer resin, a water-soluble fluororesin and a copolymer thereof.

Specific examples of the polymer compound that forms an emulsion in an aqueous system include an aqueous alkyd resin, an aqueous melamine resin, an aqueous urea resin, an aqueous phenolic resin, an aqueous epoxy resin, an aqueous polybutadiene resin, an aqueous acrylic resin, an aqueous urethane resin, Water-based acrylic / styrene resin,
Examples thereof include water-based vinyl acetate / acrylic copolymer resin, water-based polyester resin, water-based styrene / maleic acid copolymer resin, water-based fluororesin, water-based chlorinated polyolefin resin, and copolymers thereof. Particularly, it is preferable to use one kind or a mixture of two or more kinds of water-based acrylic resin, water-based polyester resin, water-based urethane resin and water-based chlorinated polyolefin resin.

In the present invention, a crosslinkable conductive composition containing a water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group, a solvent (b) and an essential component of a silane coupling agent (c) is provided. Further colloidal silica (e)
Can be used together. The surface hardness of the crosslinkable conductive layer obtained from the crosslinkable conductive composition in which colloidal silica (e) is used in combination is remarkably improved. The colloidal silica (e) used in the present invention is not particularly limited, but those dispersed in water, an organic solvent or a mixed solvent of water and an organic solvent are preferably used. Here, as the organic solvent,
Although not particularly limited, for example, methanol, ethanol,
Alcohols such as isopropyl alcohol, propyl alcohol, butanol and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone and methyl isobutyl ketone; ethylene such as ethylene glycol, ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether. Glycols,
Propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether are preferably used.

The particle size of colloidal silica used is 1 nm to 300 nm, preferably 1 nm to 150 nm, more preferably 1 nm to 50 nm.
Those in the range of are used. Here, if the particle size is too large, the hardness becomes insufficient, and the solution stability of the colloidal silica itself also deteriorates.

The ratio of the component (a) to the solvent (b) used is such that the component (a) is 0.
The amount is 01 to 20 parts by mass, preferably 0.1 to 15 parts by mass. If the amount of component (a) is less than 0.01 parts by mass, the conductivity may be poor, while if it exceeds 20 parts by mass, the conductivity almost reaches the peak and does not increase further.

The ratio of the component (c) to the component (b) used is 0.001 to 20 parts by mass, preferably 0.01 to 100 parts by mass of the component (b). ~
15 parts by mass. When the amount of the component (a) is less than 0.001 part by mass, the improvement in water resistance is relatively small, while when it exceeds 20 parts by mass, the solubility, flatness, transparency, and conductivity may deteriorate.

The ratio of the component (d) to the component (b) used is 0.1 to 400 parts by mass of the component (d) per 100 parts by mass of the component (b), preferably 0.5. ~ 30
It is 0 part by mass. If it is less than 0.1, the film-forming property, formation and strength may be inferior, while if it exceeds 400 parts by mass, the solubility or conductivity of the water-soluble conductive polymer (a) may be lowered.

The ratio of the component (e) to the component (b) used is 0.001 to 100 parts by mass, preferably 0.01 to 100 parts by mass of the component (b).
˜50 parts by mass. When the amount of the component (a) is less than 0.001 part by mass, the water resistance and the degree of improvement in hardness may be small, while when it exceeds 100 parts by mass, the solubility, flatness, transparency,
Also, the conductivity may deteriorate.

The crosslinkable conductive composition of the present invention can form a film having good performance only with the components (a), (b), (c), (d) and (e). However, if a surfactant is added, the flatness, coatability and conductivity are further improved. Surfactants include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, N-
Methyl-N-oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil and fat, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl Anionic surfactants such as phenyl ether phosphoric acid, naphthalene sulfonic acid formaldehyde condensate and salts thereof, primary to tertiary fatty amines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium alkylpyridinium, 2-alkyl- 1-alkyl-1-hydroxyethylimidazolinium, N, N
-Cationic surfactants such as dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea polycondensate of polyethylene polyamine fatty acid amide, quaternary ammonium of urea polycondensate of polyethylene polyamine fatty acid amide and salts thereof, N, N-dimethyl -N-alkyl-N-carboxymethyl ammonium betaine, N,
N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate ester betaine, 2
Betaines such as -alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N,
Amphoteric surfactants such as aminocarboxylic acids such as N-dialkylaminoalkylene carboxylates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene-polyoxypropylene glycols, Polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, poly Nonionic surfactants such as oxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine oxide and Le Oro alkyl carboxylic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group preferably has 1 to 24 carbon atoms,
More preferably, it has 3 to 18 carbon atoms. It should be noted that two or more kinds of surfactants may be used without any problem.

The ratio of the surfactant used is that of component (b) 10
It is 0 to 10 parts by weight, preferably 0 to 5 parts by weight, relative to 0 parts by weight. When the proportion of the surfactant exceeds 10 parts by weight, the coating property is improved, but the flatness is lowered, or the flatness is improved but the conductivity is deteriorated.

Further, in the crosslinkable conductive composition used in the present invention, if necessary, a pigment, a dye, a plasticizer, a dispersant, a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, an antioxidant. Various known substances such as a storage stabilizer, an adhesion aid, and a thickener can be added and used.

When mixing these constituents, a spiral mixer, a planetary mixer, a disperser,
A blade type stirring and kneading device such as a hybrid mixer is preferably used. After this, it is desirable to further thoroughly disperse and dissolve by using a ball-type kneading device such as a ball mill, a vibration mill, a sand mill or a roll mill.

The crosslinkable conductive composition used to form the crosslinkable conductive layer on one side of the support of the present invention is
The surface of the support is processed by a method used for general coating to form a crosslinkable conductive layer. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fan ten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. coating method, air A spraying method such as spray coating such as spraying and airless spraying, and a dipping method such as dipping are used.

The treatment after applying the crosslinkable conductive composition to form the crosslinkable conductive layer may be performed at room temperature, or may be performed by heat treatment. The heat treatment further promotes the crosslinking reaction between the component (c), the component (d), the component (e) and the component (a), and imparts water resistance in a shorter time, and the amount of the remaining component (b). Is more preferable and the conductivity is further improved, which is preferable. The heat treatment temperature is
Heating at 250 ° C. or lower, preferably 40 ° C. to 200 ° C. is preferable. If the temperature is higher than 250 ° C, the water-soluble conductive polymer (a) itself is decomposed and the conductivity is remarkably lowered.

The coating thickness of the crosslinkable conductive layer is 0.01 to.
The range is preferably 100 μm, more preferably 0.1 to
Applied in the range of 50 μm.

The crosslinkable conductive layer in the thermal transfer image receiving sheet of the present invention has a low humidity condition (for example, temperature 2) from the viewpoint of running property, antistatic property and recording property of the thermal transfer image receiving sheet.
Surface resistance at 5 ° C, relative humidity 15%) 10 ⁵ to 1
It is preferably 0 ¹² Ω, further 10 ⁵ to 10 ¹⁰
It is preferable to have a performance of Ω.

The crosslinkable conductive layer in the thermal transfer image-receiving sheet of the present invention is required to have excellent water resistance under high humidity or when water is attached after printing. For that purpose, it is necessary to impart water resistance so that performances such as conductivity are not deteriorated by immersion in water. As for the water resistance, the surface resistance value before immersion (SR0 in the examples) was compared with the surface resistance value after immersion in pure water at 40 ° C. for 1 hour (S in the examples).
The change rate (SR1 / SR0) of R1) is preferably 5 or less, and more preferably 3 or less.

Further, in the crosslinkable conductive composition of the present invention, since the water-soluble conductive polymer which is one component of the composition exhibits good conductivity at a very low concentration, the characteristics of the binder polymer which is another component are The conductive performance can be sufficiently exhibited without lowering.

The crosslinkable conductive composition of the present invention also comprises
A conductive substance may be contained in order to further improve the conductivity. Examples of the conductive substance include conductive carbon black, carbon-based substances such as graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel and copper.

The support used for forming the thermal transfer image-receiving sheet of the present invention is not particularly limited, but various plastic films and sheets, fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, Various papers such as synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin internal-added paper, paperboard and the like are suitable, and the thickness of these supports is not particularly limited, but in general, The thickness is about 50 to 200 μm. Since the crosslinkable conductive layer is formed on at least one surface of these polymer films, the surface of the film is preferably subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the conductive layer.

A foamed resin sheet, for example, a foamed polypropylene sheet, a foamed polyethylene, a foamed polystyrene, or a synthetic paper made of a foamed resin sheet, which is laminated on both surfaces of the support, can be used as the support. In consideration of various strengths and cushioning properties, foamed polypropylene is preferable. The preferable thickness of these cushion layers is 30 μm to 80 μm.

The dye receiving layer of the present invention is for receiving the sublimable dye transferred from the thermal transfer image receiving sheet and maintaining the formed image. As the binder resin for forming the dye receiving layer, for example, polyolefin resin such as polypropylene, polyvinyl chloride, vinyl halide resin such as polyvinylidene chloride, polyvinyl acetate, vinyl resin such as polyacrylic ester, Polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, polycarbonates. And the like, and particularly preferable ones are vinyl resins and polyester resins.

The dye receiving layer preferably contains a releasing agent in order to impart good releasing property to the thermal transfer sheet. Preferred releasing agents include silicone oils, phosphate ester type surfactants, fluorine type surfactants and the like, but silicone oils are preferable. Examples of the silicone oil include epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified,
Modified silicone oils such as alkyl aralkyl polyether modified, epoxy / polyether modified, and polyether modified are desirable.

The structure of the thermal transfer image-receiving sheet of the present invention is a thermal transfer receiving sheet having a dye receiving layer formed on one surface of a support, between the support and the receiving layer, in the receiving layer, on the receiving layer and on the support. At least one of which is provided with a crosslinkable conductive layer. Particularly, those having a crosslinkable conductive layer between the support and the receiving layer are preferable.

EXAMPLES The present invention will be described in more detail with reference to examples, but the following examples do not limit the scope of the present invention.

Production of Conductive Polymer (Production Example 1, Conductive Polymer (A-1)) Synthesis of Poly (2-sulfo-5-methoxy-1,4-iminophenylene) 2-Aminoanisole-4- Sulfonic acid 100 mmol
Was dissolved in a 4 mol / L ammonia aqueous solution with stirring at 25 ° C., and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 15 g of polymer powder. The volume resistance value of this polymer is 9.0 Ω · c.
It was m.

(Production Example 2, Conductive Polymer (A-2)) Synthesis of Poly (2-sulfo-1,4-iminophenylene) 100 mmol of m-aminobenzenesulfonic acid was added at 25 ° C.
Was dissolved in a 4 mol / liter trimethylamine aqueous solution with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 10 g of a polymer powder. The volume resistance of this product is 12.0Ω ・
It was cm.

Preparation of Conductive Composition Conductive Composition 1 2 parts by mass of the conductive polymer (A-1) of Production Example 1 above, γ-
Glycidyloxypropylmethyldiethoxysilane 0.
5 parts by mass was dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 2 1 part by mass of the conductive polymer (A-2) of Production Example 2 above, γ-
0.5 parts by mass of aminopropyltriethoxysilane, an aqueous emulsion polyester resin "Bylonal M"
D-1100 "(manufactured by Toyobo Co., Ltd.) 20 parts by mass of water 100
It melt | dissolved in room temperature at room temperature, and prepared the crosslinkable electroconductive composition.

Conductive composition 3 1 part by mass of the conductive polymer (A-1) prepared in the above Production Example 1, γ-
1 part by mass of glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle diameter: 20 nm), an acrylic resin "Dianal MX-1" which is an aqueous emulsion.
845 "(manufactured by Mitsubishi Rayon Co., Ltd.)
It melt | dissolved in room temperature at room temperature, and prepared the crosslinkable electroconductive composition.

Conductive composition 4 1.5 parts by mass of the conductive polymer (A-2) of Production Example 2 above.
0.5 parts by mass of γ-glycidyloxypropylmethyldiethoxysilane, a urethane resin “Adekapon Titer UX-232” (Asahi Denka Co., Ltd.) that is an aqueous emulsion 1
0 part by mass was dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 5 1.0 part by mass of the conductive polymer (A-1) of the above Production Example 1,
0.5 parts by mass of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, chlorinated polypropylene resin “Hurdane EH-202” which is an aqueous emulsion.
5 parts by mass (manufactured by Toyo Kasei Co., Ltd.) was dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 6 2 parts by weight of the conductive polymer (A-1) prepared in the above Production Example 1 was added to 1 part of water.
It was dissolved in 100 parts by mass at room temperature to prepare a conductive composition.

Conductive Composition 7 1 part by mass of the conductive polymer (A-2) prepared in the above Production Example 2 and a polyester resin "Vylonal M" which is an aqueous emulsion.
D-1100 "(manufactured by Toyobo Co., Ltd.) 20 parts by mass of water 100
A part by mass was dissolved at room temperature to prepare a conductive composition.

Conductive composition 8 5 parts by mass of conductive carbon "Ketchin black" (manufactured by Kao Corporation), 20 parts by mass of acrylic resin "Dianal MX-1845" (manufactured by Mitsubishi Rayon Co., Ltd.), which is an aqueous emulsion, and 100 parts by mass of water. Was dissolved and dispersed at room temperature to prepare a conductive composition.

Conductive Composition 9 Sodium Polystyrene Sulfonate "Chemistat SA-
9 parts (manufactured by Sanyo Chemical Co., Ltd.) and 20 parts by mass of an acrylic resin “DIANAL MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.), which is an aqueous emulsion, are dissolved and dispersed in 100 parts by mass of water at room temperature to be conductive. A composition was prepared.

Preparation of Receptor Layer Composition Polyester Resin "Byron 200" (Toyobo Co., Ltd.) 8
0 parts by mass, 3 parts by mass of silicone oil “KF105” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 parts by mass of isocyanate “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) are dissolved / dispersed in 400 parts by mass of toluene at room temperature to form a receiving layer. A composition was prepared.

Preparation of Thermal Transfer Image-Receiving Sheet Examples 1-2 (between support and receiving layer) A conductive composition coating liquid was dried on one surface of the support during drying.
It was applied so as to be 5 g / m ² and dried to form a crosslinkable conductive layer. Further, the composition for a receiving layer was applied onto this layer so as to be 1.5 g / m ² when dried, and dried to form a receiving layer. Thus, a thermal transfer image receiving sheet was produced.

Example 3 (in receiving layer) 1. On one surface of a support, a conductive composition coating solution was dried at the time of 2.
It was coated at 5 g / m ² and dried to form a receptive layer / crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Example 4 (on Receptor Layer) On one side of a support, 1.5 g of the composition for a receptor layer was dried.
It was applied so as to be / m ² and dried to form a receiving layer. Further, a conductive composition coating liquid was applied onto this layer so as to be 2.5 g / m ² when dried and dried to form a crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Example 5 (Back Side of Support) On one side of the support, 1.5 g of the composition for a receiving layer when dried was used.
It was applied so as to be / m ² and dried to form a receiving layer. Further, a conductive composition coating liquid was applied onto the back surface of the support so as to be 2.5 g / m ² when dried, and dried to form a crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Comparative Example 1 (between a support and a receiving layer) A conductive composition coating solution was dried on one surface of the support during drying.
It was applied so as to be 5 g / m ² and dried to form a crosslinkable conductive layer. Further, the composition for a receiving layer was applied onto this layer so as to be 1.5 g / m ² when dried, and dried to form a receiving layer. Thus, a thermal transfer image receiving sheet was produced.

Comparative Example 2 (In Receiving Layer) A conductive composition coating liquid was applied to one side of a support at the time of drying.
It was coated at 5 g / m ² and dried to form a receptive layer / crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Comparative Example 3 (on Receptor Layer) On one surface of the support, 1.5 g of the composition for a receptor layer was dried.
It was applied so as to be / m ² and dried to form a receiving layer. Further, a conductive composition coating liquid was applied onto this layer so as to be 2.5 g / m ² when dried and dried to form a crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Comparative Example 4 (Back Side of Support) One side of the support was coated with 1.5 g of the composition for a receiving layer when dried.
It was applied so as to be / m ² and dried to form a receiving layer. Further, a conductive composition coating liquid was applied onto the back surface of the support so as to be 2.5 g / m ² when dried, and dried to form a crosslinkable conductive layer. Thus, a thermal transfer image receiving sheet was produced.

Evaluation Method The thermal transfer image-receiving sheets prepared in Examples and Comparative Examples were evaluated for the following items. The results are shown in Table 1.・ 2 for measuring surface resistance under the condition of surface resistance of 25 ℃ and 15% RH.
The terminal method (distance between electrodes: 20 mm) was used. -Water resistance evaluation Surface resistance value (S after forming a crosslinkable conductive layer on a support)
R0) was measured. This support was immersed in pure water at 40 ° C. for 1 hour, and the appearance was observed and the surface resistance value (SR1) was measured.
SR1 / SR0 was calculated. -Appearance of coated surface After immersing in hot water at 40 ° C, the appearance was visually observed to observe the state of the coating film. ◯: No change from before immersion (gloss and transparency) ×: Component elution and image uniformity evaluation Yellow, magenta, which was provided with an ink layer containing a sublimable dye together with a binder on a polyester film having a thickness of 6 μm, By contacting the ink sheet of each of the three colors of cyan with the surface of the receiving layer and using a commercially available thermal transfer video printer to heat stepwise with a thermal head, a predetermined image is thermally transferred to the surface of the receiving layer, and a halftone image of each color is obtained. Single-color and overlaid images were printed. With respect to the recorded image transferred on this receiving layer, the reflection density was measured for each applied energy using a Macbeth reflection densitometer, and the uniformity of the recorded image in the gradation portion where the optical density (black) was 1.0. Regarding (1), the presence or absence of unevenness in light and shade, and (2) the presence or absence of white spots were visually observed. ○: Good ×: Poor (not practically usable)

[0067]

[Table 1] Substrate Synthetic paper: 10 μm polypropylene film containing inorganic pigment PET: 100 μm polyester film

[0068]

INDUSTRIAL APPLICABILITY The present invention has excellent transparency, conductivity (especially conductivity at low humidity) and film formability without impairing the characteristics of the conductive polymer itself having a sulfonic acid group or a carboxyl group in the conductive layer. In addition, since the coating film is a crosslinkable conductive layer having excellent water resistance and warm water resistance, the influence of electrification by the support is prevented, and a plurality of image receiving sheets are simultaneously fed by static electricity ( It is possible to obtain a thermal transfer image receiving sheet having excellent reliability such as recording characteristics and the like, preventing double feeding), smooth running of the thermal transfer image receiving sheet, preventing malfunction of the printer due to static electricity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 175/04 C09J 179/02 179/02 201/02 201/02 B41M 5/26 101H F term (reference) 2H111 AA01 AA27 CA01 CA02 CA04 CA05 CA30 CA31 CA33 CA41 4J004 AA05 AA07 AA08 AA09 AA10 AA11 AA12 AA14 AA15 AB03 CB02 CB04 CD08 FA05 FA10 4J040 CA041 GA0807 GA11B11H11B11B01B11B011DH011DH011DH071DH011DH011DH011DH031 HD32 JB02 KA16 KA23 KA42 LA09 MB03

Claims (12)

[Claims] 1. A thermal transfer image-receiving sheet having a dye receiving layer on at least one surface of a support, which is selected from between the support and the receiving layer, in the receiving layer, on the receiving layer and on the back surface of the support. A water-soluble conductive polymer (a) having at least one of which has a sulfonic acid group and / or a carboxyl group, a solvent (b), a silane coupling agent (c) represented by the general formula (1), and (In the above formula, R ₁ , R ₂ , and R ₃ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms.
6 is a straight-chain or branched alkoxy group, an amino group, an acetyl group, a phenyl group, and a halogen group. X is [Chemical 2] And n and m are numbers from 1 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group and an epoxycyclohexyl group. A heat transfer image-receiving sheet having a crosslinkable conductive layer formed by coating and / or impregnating a crosslinkable conductive composition containing 2. The crosslinkable conductive composition contains at least one polymer compound (d) selected from a water-soluble polymer compound and a polymer compound which forms an emulsion in an aqueous system. The thermal transfer image-receiving sheet described above. 3. At least one polymer compound (d) selected from a water-soluble polymer compound and a polymer compound forming an emulsion in a water system, wherein the water-based acrylic resin, water-based polyester resin, water-based urethane resin and / or water-based chlorine. The thermal transfer image-receiving sheet according to claim 2, which is a modified polyolefin resin. 4. The crosslinkable conductive composition contains colloidal silica (e), according to any one of claims 1 to 3.
A thermal transfer image-receiving sheet as described in the item. 5. The particle size of colloidal silica (e) is 1 n.
The thermal transfer image-receiving sheet according to claim 4, having a thickness of m to 300 nm. 6. A water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group is represented by: (In the formula, R _{4 to} R ₈ are each independently H, —S.
^{_{O 3 -, -SO 3 H,}} -R 29 SO 3 -, -R 29 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
_{l, -Br, -I, -N (} R 29) 2, -NHCOR
^{_{29, -OH, -O -, -SR}} 29, -OR 29, -O
COR ₂₉ , -NO ₂ , -COOH, -R ₂₉ COO
H, -COOR ₂₉ , -COR ₂₉ , -CHO and -C.
N is selected from the group consisting of N, wherein R ₂₉ has 1 to 1 carbon atoms.
24 alkyl, aryl or aralkyl groups or alkylene, arylene or aralkylene groups,
And at least one of R _{4 to} R ₈ is —SO ₃ ⁻ , −
^{_{SO 3 H, -R 29 SO 3}} -, -R 29 SO 3 H, -C
It is a group selected from the group consisting of OOH and —R ₂₉ COOH. The thermal transfer image-receiving sheet according to any one of claims 1 to 5, which is a water-soluble conductive polymer containing 20 to 100% of the repeating unit consisting of 4) in the total number of repeating units of the whole polymer. . 7. Sulfonic acid group and / or carboxyl
The water-soluble conductive polymer (a) having a group is [Chemical 4] (In the above formula, y represents an arbitrary number of 0 <y <1, and R₉~
R₂₆Are each independently H, -SO_Three ⁻, -SO_ThreeH,-
R₂₉SO_Three ⁻, -R₂₉SO_ThreeH, -OCH_Three, -C
H_Three, -C_TwoH₅, -F, -Cl, -Br, -I, -N
(R₂₉)_Two, -NHCOR₂₉, -OH, -O⁻,-
SR₂₉, -OR₂₉, -OCOR₂₉, -NO_Two,-
COOH, -R₂₉COOH, -COOR₂₉, -CO
R₂₉, -CHO and -CN,
Here, R₂₉Is an alkyl or aryl group having 1 to 24 carbon atoms.
Or aralkyl group or alkylene, arylene or
Is an aralkylene group, and R₉~ R₂₆At least
One is -SO_Three ⁻, -SO _ThreeH, -R₂₉SO_Three ⁻,
-R₂₉SO_ThreeH, -COOH and -R₂₉COOH
It is a group selected from the group consisting of ) Repetition
20 to 20 units in the total number of repeating units of the entire polymer.
It contains 100%, Any one of Claims 1-5 characterized by the above-mentioned.
A thermal transfer image-receiving sheet as described in the item. 8. A water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group is represented by: (In the above formula, R ₂₇ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and their alkali metal salts, ammonium salts and substituted ammonium salts, and R ₂₈ is a methyl group, an ethyl group. , N-propyl group,
iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group Group, a tert-butoxy group, a heptoxy group, a hexoxy group, an octoxy group, a dodecoxy group, a tetracosoxy group, a fluoro group, a group selected from the group consisting of a chloro group and a bromo group, X is 0 <X <1 Is an arbitrary number, and n is a degree of polymerization and is 3 or more. ) Is a thermal transfer image-receiving sheet according to any one of claims 1 to 5. 9. Sulfonic acid group and / or carboxyl
The water-soluble conductive polymer (a) having a group is [Chemical 6] (In the above formula, R_Thirty~ R₃₅Are each independently H, -SO
_Three ⁻, -SO_ThreeH, -R ₂₉SO_Three ⁻, -R₂₉SO_Three
H, -OCH_Three, -CH_Three, -C_TwoH₅, -F, -C
l, -Br, -I, -N (R₂₉)_Two, -NHCOR
₂₉, -OH, -O⁻, -SR₂₉, -OR₂₉, -O
COR₂₉, -NO_Two, -COOH, -R₂₉COO
H, -COOR₂₉, -COR₂₉, -CHO and -C
Selected from the group consisting of N, where R₂₉Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
An alkylene, arylene or aralkylene group,
R_Thirty~ R ₃₅At least one is -SO_Three-,-
SO_ThreeH, -R₂₉SO_Three-, -R ₂₉SO_ThreeH, -C
OOH and -R₂₉A group selected from the group consisting of COOH
Is. ) Acidic group-substituted aniline represented by
Limetal salt, ammonium salt and / or substituted ammonium
Polymerized with an oxidizing agent in a solution containing a basic compound.
It is a water-soluble conductive polymer obtained by
The heat transfer according to any one of claims 1 to 5, characterized in that
Image receiving sheet. 10. A water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group is a basic compound which is an alkoxy group-substituted aminobenzene sulfonic acid, its alkali metal salt, ammonium salt and / or substituted ammonium salt. The thermal transfer image-receiving sheet according to any one of claims 1 to 5, which is a water-soluble conductive polymer obtained by polymerizing with a oxidant in a solution containing. 11. The surface resistance value of at least one layer of the crosslinkable conductive layer at a temperature of 25 ° C. and a relative humidity of 15% is 10 ⁵ to 10 ¹² Ω. 10. The thermal transfer image-receiving sheet according to any one of 10. 12. The rate of change in surface resistance value after at least one layer of the crosslinkable conductive layer is immersed in pure water at a temperature of 40 ° C. for 1 hour (SR1 (1 hour in pure water at 40 ° C. The surface resistance value after the immersion) / SR0 (the surface resistance value before the immersion)) is 5 or less.
The thermal transfer image-receiving sheet according to any one of 1.