JPH05286261A - Image receiving sheet for thermal transfer recording and production thereof - Google Patents

Abstract

PURPOSE:To produce an image receiving sheet for thermal transfer recording capable of forming an image with high sensitivity and high transfer density, generating no curl at the time of the formation of an image and improving the preservability of a formed image. CONSTITUTION:An image receiving sheet for thermal transfer recording has a support wherein a laminate layer with a thickness of 5-50mum based on polypropylene containing white fine particles is provided on the surface of a base material on a side where an image receiving layer is laminated and is produced by forming the laminate layer on the base material directly or after primer treatment by a melt extrusion method and laminating the image receiving layer containing a basic compd. and/or a mordant on the laminate layer directly or after surface treatment by a coating method and/or a lamination method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-receiving sheet for heat-sensitive transfer recording and a method for producing the same, and more specifically, it can form an image with high sensitivity and high transfer density, and does not cause curling during image formation. Further, the present invention relates to an image-receiving sheet for thermal transfer recording in which the formed image has good storability, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a color hard copy, a color recording technology such as an ink jet method, an electrophotographic method, a heat-sensitive transfer method and the like has been studied. Is
It has advantages such as ease of operation and maintenance, downsizing of the device, cost reduction, and low running cost.

In this heat-sensitive transfer system, a transfer sheet having a heat-meltable ink layer on a support is heated by a heat-sensitive head to melt-transfer the ink from the heat-meltable ink layer onto a heat-sensitive transfer recording image-receiving sheet. And a thermal transfer recording ink sheet having an ink layer containing a thermal diffusible dye (sublimable dye) on a support is heated by a thermal head to transfer the thermal diffusible dye from the ink layer to a thermal transfer recording image receiving sheet. There are two types: thermal diffusion transfer method (sublimation transfer method). The thermal diffusion transfer method controls the gradation of the image by changing the transfer amount of the dye according to the change in thermal energy of the thermal head. Therefore, it is advantageous for full-color recording.

By the way, in the thermal transfer recording of the thermal diffusion transfer system, the dye used in the thermal transfer recording material is important, and the image storability (for example, fixability, heat resistance, light resistance) of conventional dyes is not good. It has the drawback.

In order to improve those drawbacks, various dyes for heat-sensitive transfer materials have been proposed. For example, Japanese Patent Laid-Open No. 3-8368
No. 5, No. 3-83687, No. 3-83688, No. 3-83689, No. 3-90
No. 387, No. 3-92385, No. 3-92386, No. 3-114890, No. 1
-228601, 1-229755, 1-229756, using a dye having a phenolic hydroxyl group, an image by a dye formed by the reaction of the mordant contained in the image-receiving layer and the dye, A method of forming has been proposed.

The image formed by the dye described in the above patent has a good hue and is excellent in heat resistance and fixing property when the dye and the mordant are completely reacted. It has excellent properties that ameliorates some of the problems of thermal transfer. However, since the image formation by heating of the thermal head is performed in a very short time, sufficient sensitivity and transfer density cannot be obtained, or the reaction is not completed sufficiently and dichroism due to residual unreacted dye remains. This may cause problems such as the presence of undesirable irregular absorption and poor fixability.

Further, the migration of the dye in the ink layer and
To improve the storability of the formed image, Japanese Patent Application No. 3-2580
No. 05 proposes an image forming method using an image receiving layer containing a mordant, which uses a dye formed by forming a salt with a nitrogen-containing organic base as the dye. Also in this case, the sensitivity and the transfer density may not be sufficiently obtained, probably because the dye salt is used.

By the way, in order to obtain sufficient sensitivity and transfer density, the dye diffusion property or dyeing property of the image receiving layer in the dye image receiving material is important. This is the case when an ink layer containing a dye having a phenolic hydroxyl group as described above or a dye salt formed by forming a salt with a nitrogen-containing organic base, and a heat-sensitive transfer material containing a basic compound and / or a mordant are used. In addition, although it can be improved to some extent by the resin or the additive forming the image receiving layer, it is still not sufficient.

The present invention has been made based on the above circumstances. That is, an object of the present invention is to provide a heat-sensitive transfer recording image-receiving sheet having high sensitivity and high transfer density, which is excellent in image storability without curling after image formation, and a suitable manufacturing method thereof. is there.

[0010]

The present invention for solving the above problems provides an ink containing, on a support, a dye having at least a phenolic hydroxyl group and / or a dye salt comprising at least a dye and a nitrogen-containing organic base. The ink layer of the heat-sensitive transfer recording ink sheet having a layer and the image-receiving layer of the heat-sensitive transfer recording image-receiving sheet containing at least a basic compound and / or a mordant in the image-receiving layer are faced to each other and heated according to image information. In the heat-sensitive transfer image forming method of forming a dye image according to the image information on the image-receiving layer, as the image-receiving sheet for heat-sensitive transfer recording, on the surface of the substrate on which the image-receiving layer is laminated, a thickness of 5 to 50 μm. An image-receiving sheet for heat-sensitive transfer recording, which comprises a support provided with a laminate layer containing polypropylene containing white fine particles as a main component.

Alternatively, it is an image-receiving sheet for heat-sensitive transfer recording in which an intermediate layer is further provided between a laminate layer containing polypropylene as a main component containing the above-mentioned white fine particles and an image-receiving layer, or the above-mentioned. An image-receiving sheet for heat-sensitive transfer recording using a support having a laminate layer having a thickness of 5 to 50 μm and containing white fine particles, which is further provided on the surface of the base material opposite to the surface on which the image-receiving layer is laminated.

In the present invention, a resin composition containing polypropylene as a main component containing white fine particles is melt-extruded at 5 to 50 μm by direct or primer treatment on a substrate.
To form a laminate layer by hot melt extrusion lamination with the thickness of
Alternatively, a method for producing an image-receiving sheet for heat-sensitive transfer recording, which comprises laminating an image-receiving layer containing a basic compound and / or a mordant by a laminating method, or directly or directly on the laminating layer described above. After the surface treatment, an intermediate layer is formed by a coating method and / or a laminating method, and a basic compound and / or a mordant is contained on the intermediate layer directly or after the surface treatment, by a coating method and / or a laminating method. A method for producing an image-receiving sheet for heat-sensitive transfer recording in which an image-receiving layer is laminated, or a surface opposite to the surface on which the image-receiving layer is laminated, which is directly or after a primer treatment, is white by a melt extrusion method. A laminating layer is formed by hot-melt extrusion laminating a resin composition containing fine particles to a thickness of 5 to 50 μm. A thermal transfer recording image receiving sheet method of manufacturing.

The image-receiving sheet for heat-sensitive transfer recording of the present invention, the method for producing the same, and the ink sheet for heat-sensitive transfer recording used in the present invention will be described in detail.

(1) Thermal transfer recording image-receiving sheet and manufacturing method The thermal transfer recording image-receiving sheet of the present invention basically has a thickness of 5 to 50 μm on the surface of the substrate on which the image-receiving layer is laminated.
It is composed of a laminate layer containing polypropylene as a main component containing white fine particles, and an image receiving layer further laminated thereon and containing at least a basic compound and / or a mordant.

-Substrate-As the substrate, paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, and further a plastic film formed by laminating two or more layers of the resin. Further, a sheet or a sheet, or a film or sheet obtained by laminating the above resin layer on a paper made of various polymer materials, metal, ceramics or wood pulp, cellulose pulp, sulfite pulp, or the like can be given.

As such resin or resin layer, acrylic resins such as acrylic acid esters and methacrylic acid esters, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate and polyarylate, Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyolefin resins such as polyethylene, polypropylene and polystyrene, polyamide resins such as nylon and aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide , Polyparabanic acid, phenoxy resin, epoxy resin, urethane resin, melamine resin, alkyd resin, phenol resin, fluororesin, silicone resin, etc. It is below.

In the present invention, the resin base material is preferably stretched into a sheet or film and heat-set from the viewpoint of dimensional stability. The base material may be microvoid-free or have microvoids. However, it can be appropriately selected depending on the application.

The paper used in the present invention is preferably pulp paper made from natural pulp, synthetic pulp, or a mixture thereof, and among these, natural pulp paper containing wood pulp as a main component is preferable. The paper is preferably made using a Fourdrinier paper machine and the like, and for the purpose of improving the smoothness, it is preferable to carry out calendering using a machine calendar, a super calender, a thermal calender or the like after the paper making. A base paper coated with a resin layer containing a pigment for improving smoothness can also be preferably used in the present invention. Examples of the paper in the present invention include high-quality paper, art paper, coated paper, single-glossy paper, impregnated paper, paperboard and the like.

The paper preferably has a Bekk smoothness of 50 seconds or more, and preferably 100 seconds or more, in order to provide smoothness when a polypropylene and polyolefin laminate layer containing white fine particles to be described later is provided. Is 200
It is preferable to have a smoothness of 2 seconds or more. The thickness of the paper is not particularly limited, but is preferably 30 to 800 μm, 50 to 50
0 μm is more preferable.

In the above base paper, if necessary, a sizing agent,
Fixing agent, paper strengthening agent, filler, antistatic agent, dye, pigment,
Additives such as a fluorescent whitening agent, an antioxidant and a lubricant may be contained.

The base material is preferably one having high transparency when transparency is required such as a transparent original such as OHP or a sticker to be adhered to glass, and is formed in the case of a reflection image. White pigments such as titanium oxide, zinc oxide, silica, barium sulfate, magnesium carbonate, calcium carbonate, talc, and clay may be added to the layer constituting the substrate in order to enhance the sharpness of the image.

The thickness of the substrate is usually 20 to 1,000 μm, preferably 50 to 500 μm, and is appropriately selected from such a range.

-Laminate Layer-In the present invention, on the side of the substrate on which the image receiving layer is laminated,
A laminating layer containing polypropylene as a main component containing white fine particles having a specific thickness is laminated. This laminate layer can be formed by dry lamination or the like, but in the present invention, it is preferably formed by the hot melt extrusion lamination method.

Polypropylene is particularly preferable in terms of curl prevention, transfer sensitivity or transfer density because it has heat resistance and low thermal conductivity as compared with polyolefin resins used for ordinary lamination, for example, generally used polyethylene. ..

The polypropylene preferably has a melt flow rate (test method: ASTM D1238g / 10 min) of 0.5 to 15, more preferably 1 to 10. As long as the drawdown property is good, either a homopolymer or a copolymer may be used, and one kind or two or more kinds of polypropylene may be used in combination.

The thickness of the laminate layer in the present invention is usually 5 to 50 μm, preferably 10 to 40 μm, and is appropriately selected from such a range.

Lamination by the hot melt extrusion lamination method is disclosed in JP-A 1-263081 and 1-
271289, 2-106397, 2-111586, 2-305688
No. 3-49991 and the like.

In addition, the whiteness of the laminate layer is increased,
In order to improve heat resistance, white fine particles are further contained in the composition containing polypropylene as a main component.

As the white fine particles, both inorganic fine particles and organic fine particles can be used as long as they have excellent thermal stability during lamination.

Examples of the inorganic fine particles include metal oxides such as silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide and aluminum borate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum hydroxide and water. Metal salts such as magnesium oxide and boron nitride, kaolin, clay, talc, zinc white, lead white, sikhlite, quartz, diatomaceous earth,
Examples include pearlite, bentonite, mica, and synthetic mica.

Examples of the organic fine particles include melamine resin particles, guanamine resin particles, styrene-acrylic copolymer resin particles, silicone resin particles and fluororesin particles.

Among the white fine particles, hollow resin fine particles are preferable in order to increase the transfer sensitivity or the transfer density, and the hollow fine particles include, for example, crosslinked styrene-acrylic hollow resin particles.

When the white fine particles are added, the content in the laminate layer is usually selected in the range of 0.1 to 30% by weight, preferably 1 to 20% by weight.

The average particle size of the white fine particles is usually 0.01 to
It is 2 μm, preferably 0.02 to 1 μm.

In the laminate layer, in addition to the white fine particles, an antistatic agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent whitening agent which does not decompose at the temperature during lamination. You may mix | blend additives, such as.

In this case, it is preferable that the compounding amount is usually 30% by weight or less, especially 20% by weight or less in the laminate layer forming composition.

In the present invention, when the adhesive strength between the support and the laminating layer is insufficient, the surface of the substrate is treated with a primer before laminating the composition containing polypropylene as a main component on the support. Is preferably applied.

Examples of the primer include metal alkoxides such as titanium alkoxide and zirconium alkoxide, ethylene-vinyl acetate copolymers, olefin resins such as vinylidene chloride and polybutadiene resins, urethane resins, epoxy resins and polyester resins. Resins, acrylic resins, epoxy resins, polyethyleneimine resins, and the like. Further, these resins are heat-cured using a curing agent such as an isocyanate compound, an amine compound, or an acid anhydride, or UV rays. It may be cured using an electron beam such as. Furthermore, the materials described in Chapter 33 to 36, "New Laminating Handbook", edited by Processing Technology Association, can be used in the present invention at appropriate times.

As the method for providing the primer layer, a coating method in which the primer layer is directly or dissolved in an appropriate solvent and applied and dried,
It can be provided by a melt coating method of melting and coating the layer forming component.

Examples of the solvent used in the above coating method include water, alcohols, cellosolves, aromatics, ketones, ester solvents, ethers, chlorine solvents and the like.

For the coating, conventionally known gravure roll coating methods, extrusion coating methods, wire bar coating methods, roll coating methods and the like can be adopted.

The thickness of the primer layer described above is
Usually, it is preferably provided so as to have a range of 0.001 to 2.0 μm, preferably 0.01 to 1.0 μm.

The support on which the laminate layer is laminated by the above-mentioned method may be heat set under dimensional restraint to improve the dimensional stability, or the surface of the laminate layer may be subjected to calendering treatment if necessary. Smoothing may be performed.

In the present invention, for the purpose of preventing curling and improving texture, it is preferable to provide a laminate layer made of polyolefin containing white fine particles on the surface opposite to the laminate layer of the substrate, either directly or after a primer treatment. .. The primer treatment here is the same as the case of the laminate layer described above.

This laminate layer may have the same composition as the above-mentioned laminate layer provided on the image receiving layer side or a different composition.

The resin for forming the laminate layer may be any resin as long as it has a small neck-in and a good drawdown property, for example, high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, polypentene. ,polystyrene,
Examples thereof include polyolefin resins such as ethylene-vinyl acetate copolymer, polyester resins such as polyethylene terephthalate, ionomer resins, nylon and polyurethane.

Of these, polyolefin resins are preferable, and high density polyethylene, medium density polyethylene,
It is preferable to use low-density polyethylene, polypropylene, polybutene, polypentene, ethylene-polypropylene copolymer or the like alone or in combination of two or more kinds of resins.

When polyolefin is used among these resins, the resin layer has a thickness of usually 5 to 50 μm, preferably 10 to 40 μm, and is appropriately selected from such a range.

Further, white fine particles contained in the laminate layer on the image receiving layer side are added to the resin layer containing polyolefin as a main component. Furthermore, within the range that does not impair the purpose,
Additives that can be added to the laminate layer on the image receiving layer side may be added, and their contents are the same as those of the laminate layer on the image receiving layer side.

This laminate layer can be formed on the base material by the hot melt extrusion lamination method as in the case of forming the laminate layer on the image receiving layer side. Heat set below,
Dimensional stability may be improved, and the surface of the laminate layer may be subjected to calendering treatment or embossing treatment for matting, if necessary.

-Image Receiving Layer- In the present invention, the image receiving layer is laminated on the laminate layer containing polypropylene as a main component containing the white fine particles as described above.

The image-receiving layer can be formed with a basic compound and / or a mordant, a binder for the image-receiving layer and various additives.

The binder for the image-receiving layer is not particularly limited as long as it has dyeability to the dye having a phenolic hydroxyl group and / or the dye salt consisting of a dye and a nitrogen-containing organic base used in the present invention. Further, by adding an additive, high image storability can be exhibited. In order to exert such effects, it is possible to appropriately select materials from the binder resin and basic compound and / or mordant, additives, etc. described later, and adjust the compounding amount of these and the thickness of the image receiving layer. Good.

1. Basic compound and / or mordant The dye used in the present invention described below is fixed by forming a dye image in the presence of the basic compound and / or mordant. Specifically, the dye is a basic compound. To form a salt, or to be adsorbed and fixed by a mordant, or to form and fix a dye image in the presence of a basic compound and a mordant.

The basic compound and / or mordant used in the present invention is not particularly limited, but an inorganic or organic basic compound is used. For example, the inorganic compound is
Examples thereof include calcium carbonate, sodium carbonate, sodium acetate, and the like. Examples of organic compounds include compounds having an amino group, such as alkylamines (decanoylamine, octylamine, dioctylamine, trioctylamine, etc.), arylamines (aniline and Its derivatives etc.),
There are compounds having a nitrogen-containing heterocyclic group (eg, pyridine, imidazole ring, etc.). In addition, the following general formula (1)
And a quaternary ammonium salt compound thereof, a Group 5B onium salt compound such as a phosphonium salt (including the above-mentioned ammonium salt), a sulfonium salt, a selenonium salt, a telluronium salt or the like Group 6B onium Examples thereof include salt compounds.

[0056]

[Chemical 1]

In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, an amino group (including an alkyl-substituted amino group) or a guanidine group. .. R ₁ and R ₂ and / or R ₃ and R ₄ may be bonded to each other to form a ring. X represents a vinyl group, and n represents 0 or 1.

The mordant described above may be a polymer. Examples of such a polymer mordant include JP-A-48-28325, JP-A-54-74430, and JP-A-54-124726.
No. 55, No. 55-22766, No. 55-23850, No. 55-142339, No. 6
0-23851, 60-23852, 60-23853, 60-57836
No. 60, No. 60-60643, No. 60-118834, No. 60-122940, No.
60-122941, 60-122942, 60-235134, U.S. Patents 2,484,430, 2,548,564, 3,148,061, and 3,1
48,161, 3,309,690, 3,756,814, 3,898,08
No. 8, No. 3,958,995, No. 4,115,124, No. 4,124,386,
4,193,800, 4,273,853, 4,282,305, 4,4
50,224, British Patents 1,594,961, 2,056,101, 2,
Examples include those described in No. 093,041.

The amount of the basic compound and / or the mordant in the image-receiving layer forming composition is usually 0.1 to 90% by weight, more preferably 1 to 50% by weight.

2. Binder Resin for Image Receiving Layer As the binder resin for the image receiving layer used in the present invention, known resins conventionally used in the image receiving layer of the image receiving sheet for thermal transfer recording can be used.

Examples of the binder resin described above include polyester resins, polyvinyl acetal resins, urethane resins, amide resins, cellulose resins, olefin resins, vinyl chloride resins, acrylic resins, styrene resins, Polycarbonate, polyvinyl alcohol,
Polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin and the like,
These resins may be used alone or in combination of two or more.

The binder resin described above is usually contained in the image-receiving layer forming composition in an amount of usually 20 to 99% by weight, preferably 50 to 95% by weight.

3. Additives A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), a pigment and an antistatic agent may be added to the image receiving layer. As a sensitizer, a plasticizer,
A hot solvent or the like may be added.

The layer in contact with the heat-sensitive transfer recording dye image-receiving material and the dye-donor material preferably contains a releasing agent in order to prevent fusion during the formation of an image to be described later. Examples of such a release agent include silicone oils, silicone resins; solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants. Among them, silicone oils,
Alternatively, a silicone resin is preferable.

This silicone oil and / or silicone resin is of a type that is simply added (simple addition type),
There is a type of curing or reacting (curing reaction type).

In any case, it is preferable to use a modified silicone oil and / or a modified silicone resin in order to improve the compatibility with the binder. Among them, for example, polyester modified silicone resin (or silicone modified polyester), urethane modified silicone resin (or silicone modified urethane resin), acrylic modified silicone resin (or silicone modified acrylic resin), polyimide modified silicone resin (or silicone modified polyimide resin) Etc. are preferably used.

The addition amount of these silicone oils and / or silicone resins cannot be uniformly determined because it may vary depending on the type, but generally speaking, in general, the image receiving layer is formed. 0.01 in composition
It is 30% by weight, preferably 0.1 to 20% by weight.

A release agent layer may be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the release agent in an appropriate solvent and applying the solution, followed by drying.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds and the like, and JP-A-59-182785. Issue 60-130735, Issue 61-159644
No. 1, JP-A-1-127387, "Chemical products of 11290" Kagaku Kogyo Daily, compounds described in p.862 to 868, etc., and compounds known to improve image durability in photographs and other image recording materials. Can be mentioned.

Examples of UV absorbers and light stabilizers are JP-A Nos. 59-158287, 63-74686, 63-145089 and 59-1.
96292, 62-229594, 63-122596, 61-283595
No. 1, JP-A 1-204788, “Chemical products of 11290”, Chemical Industry Daily, p.869-875, and the like. Examples of the fluorescent whitening agent include JP-A 61-237693, 63-122596 and 63-1.
Examples thereof include compounds described in JP-A-47166, and other compounds known to improve the image durability of other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, and the like, and organic particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. And so on.

Examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

Antistatic agents include cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles, and the like, as well as "11290 chemical products", Chemical Industry Daily , P.875 to p.876 and the like can also be preferably used. Examples of plasticizers include phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, and epoxy stearic acid epoxies. In addition to orthophosphoric acid esters, phosphonous acid esters, glycol esters, etc., "11290 chemical products", Chemical Daily Co., Ltd., compounds described in p.843 to p.857 and the like can also be preferably used. ..

As the heat-melting substance, terpineol, menthol, 1,4-cyclohexanediol,
Alcohols such as phenol, amides such as acetamide and benzamide, esters such as coumarin and benzyl cinnamate, ethers such as diphenyl ether and crown ether, camphor, ketones such as p-methylacetophenone, vanillin and dimethoxybenzaldehyde. Aldehydes, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide,
Monomolecular compounds represented by higher amines such as behenylamine, carnauba wax, beeswax, paraffin wax,
Waxes such as ester wax, montan wax, amide wax, ester gum, rosin maleic acid resin,
Rosin derivatives such as rosin phenol resin, phenol resin, ketone resin, diallyl phthalate resin, terpene resin, aliphatic hydrocarbon resin, cyclopentadiene resin,
Examples thereof include polymer compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol. In the present invention, the melting point or softening point of the above-mentioned heat-meltable substance is 10 to 150.
Those at ℃ are preferred.

In the present invention, it is usually preferable to select the total amount of the additives to be added in the range of 0.1 to 30% by weight based on the binder resin.

The thickness of the image receiving layer is usually selected in the range of 3 to 30 μm, preferably 5 to 20 μm.

The image receiving layer may be a single layer,
Alternatively, if necessary, a multilayer structure having two or more layers having the same composition or different compositions may be provided.

-Other Layers-In the invention, an intermediate layer (undercoat layer) is provided between the image-receiving layer and the support for the purpose of imparting properties such as heat insulating property, barrier property, cushioning property and adhesive property. Is preferred.

As the resin forming the intermediate layer, polyurethane resin, polyester resin, polybutadiene resin, poly (meth) acrylic acid ester resin, epoxy resin, polyamide resin, rosin-modified phenol resin, terpene phenol resin, ethylene-vinyl acetate copolymer Examples include coalesce, polyolefin-based resin, cellulose-based resin, gelatin, and casein.

In order to provide cushioning property,
The intermediate layer is preferably a layer containing microbubbles.

As a method for forming a layer containing fine bubbles, in the case of a coating method, a method of coating and drying a coating liquid containing bubbles by mechanical stirring, and a coating liquid containing a foaming agent are applied. After drying, a method of foaming a foaming agent, a method of applying and drying hollow fine particles, a solvent that dissolves the resin described above, and a solvent having a higher boiling point than the solvent and having an affinity for the solvent Formed by a method of mixing a solvent that is not soluble in the resin, coating and drying, or a method of coating and drying a coating solution mixed with a high boiling point solvent, dipping it in the solvent, and then dissolving the high boiling point solvent. can do. In the case of the laminating method, a resin melting composition containing a foaming agent is laminated and then heated to foam, a method of laminating a molten composition containing hollow fine particles, and fine particles are added to the composition forming the intermediate layer. A method in which the molten composition is contained, extruded, stretched in at least one axial direction to form a sheet containing microbubbles, and then laminated on a support;
It can be formed by a method of melting and kneading a component soluble in a solvent and a component insoluble in the solvent, laminating the components, and then immersing the component in a solvent to dissolve the dissolved component. In addition, a sheet-shaped composition that has been foamed in advance may be attached via an adhesive or the like.

Furthermore, JP-A-61-270192 and JP-A-61-2701.
No. 92, No. 63-56489, No. 63-87286, No. 63-122593,
JP-A-1-145192, 1-280586, 2-89690, 2-2
No. 41740, No. 2-248289, No. 3-76687, etc., an intermediate layer having a porous structure between the support and the image-receiving layer, or JP-A-61-144394, Same as 61-258793
No. 61, No. 61-279582, No. 62-146693, No. 62-151393,
As described in JP-A-63-153194, JP-A-64-5885, JP-A-64-26497, etc., an intermediate layer made of a resin having cushioning property between a support and an image receiving layer, 62-1585,
62-21590, 64-27996, JP 1-280585, 1-
As described in 301283, 2-99389, etc.,
A method and constitution of a barrier layer or the like between the support and the image receiving layer can also be preferably used in the present invention.

The above-mentioned intermediate layer is usually 0.001 to 30 μm.
It is suitable to select m, preferably 0.01 to 25 μm.

The intermediate layer described above may be a single layer or, if necessary, may be provided as a multi-layer structure of two or more layers having the same composition or different compositions to separate the functions. good.

Further, the surface of the image receiving layer is overcoated with a silicone resin, a fluorine resin, waxes or the like for the purpose of preventing fusion between the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet. The layers may be laminated. Further, JP-A-60-101090, 61-102293, 61
-127392, 61-244589, 61-258785, 62-2012
No. 90, No. 62-231797, No. 63-56489, JP-A 1-159289
No. 1-229689, 1-247196, 1-291990, 2-
67193, 2-92592, 2-154184, 2-255381,
As described in JP-A-2-258389, on the image receiving layer, a method and a structure for providing an overcoat layer for preventing fusion with the ink layer and improving the storage stability of the dye are also provided. It can be preferably used in the invention.

On the surface opposite to the image receiving layer (on the laminate layer when the laminate layer is provided), antistatic, prevention of plural sheets serving, slipperiness imparting, prevention of adhesion to other image receiving layer, curling prevention, writing A backing layer may be provided for the purpose of improving the property.

For the purpose of antistatic, it is preferable to add the antistatic agent described in the section of the image receiving layer additive.

In order to prevent plural sheets from being served, to impart slipperiness, and to prevent adhesion to other image-receiving layers, it is preferable to add an antistatic agent and / or a filler or pigment described in the section of image-receiving layer additive.

To prevent curling, it is preferable to use a heat-resistant resin having a small thermal deformation or a resin cured by heat or ionizing radiation after forming the backing layer.

As the heat resistant resin, methyl cellulose,
Cellulosic resins such as nitrocellulose, polystyrene, styrene resins such as styrene-acrylonitrile copolymer, acrylic resins such as polymethylmethacrylate and polyacrylic acid, polyester resins such as polyethylene terephthalate, polycarbonate, polyarylate, polyacetal. , Polysulfone, polyether sulfone, polyether nitrile, polyether ether ketone, modified polyphenylene oxide, polyoxybenzylene, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, polyparabanic acid resin and the like.

In order to impart writability, it is preferable to contain the filler or pigment described in the section of the image receiving layer additive.

Further, JP-A-61-295085 and 61-51490
No. 62, No. 62-152793, No. 61-170391, No. 63-122593,
63-218397, 64-44781, JP-A-1-99888, 1-
271289, 2-63893, 2-113992, 2-219691
The method and structure of providing a backing layer on the surface of the support opposite to the image receiving layer as described in JP-A No. 2-252584 and the like can also be preferably used in the present invention.

When the above-mentioned overcoat layer and backing layer are provided, the thickness of each is usually 0.01 to 10 μm.
It is preferable to select in the range of m.

Each of the layers described above may be a single layer or, if necessary, may be provided as a multi-layered structure of two or more layers having the same composition or different compositions to separate the functions. ..

-Manufacturing of image-receiving sheet for heat-sensitive transfer recording-For the image-receiving sheet for heat-sensitive transfer recording, the components for forming the image-receiving layer are dispersed or dissolved in a solvent to prepare a coating solution for the image-receiving layer,
A coating method in which the surface of a support or an intermediate layer is coated with the coating liquid for the image receiving layer and dried, or a mixture having the components for forming the image receiving layer is melt extruded and laminated on the surface of the support or the intermediate layer by hot-melt coating. Extrusion lamination method, after forming the image receiving layer on the peelable sheet,
It can be formed by a transfer method or the like in which heating and / or pressurization is laminated on the support or the intermediate layer.

As the solvent used in the above coating method, water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene), ketones ( For example, acetone, methyl ethyl ketone), ester solvents (eg ethyl acetate, butyl acetate, etc.), ethers (eg tetrahydrofuran, dioxane), chlorine solvents (eg chloroform, trichloroethylene), amide solvents (eg dimethylformamide, N-methyl). Pyrrolidone), dimethyl sulfoxide and the like.

For the above-mentioned coating, conventionally known surface-sequential separate coating method using a gravure roll, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted.

The image receiving layer may be formed on the entire surface of the support or the intermediate layer, or may be formed on a part of the surface, if necessary.

Further, other layers can be provided by the same method as the method of forming the image receiving layer.

In the present invention, when the adhesive strength between the image receiving layer or the intermediate layer laminated on the support is insufficient, the surface to be laminated is treated before providing the layer to be laminated. Preferably, the surface treatment method includes corona discharge treatment, flame treatment, ozone treatment,
UV treatment, radiation treatment, roughening treatment, chemical treatment,
Known resin surface modification techniques such as low temperature plasma treatment and grafting treatment can be applied as they are.

(2) Thermal transfer recording ink sheet and method for producing the same The thermal transfer recording ink sheet basically comprises an ink layer laminated on a support.

-Support-As the support, any material may be used as long as it has good dimensional stability and can withstand heat during recording with a thermal head, but thin paper such as condenser paper or glassine paper, polyethylene terephthalate, Polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone,
A heat resistant plastic film such as polyvinyl alcohol cellophane or polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm.

The shape of the support is not particularly limited,
For example, a wide sheet or film, a narrow tape or a card, or any other shape.

-Ink Layer- The ink layer contains, as essential components, at least a pigment formed by forming a salt with a phenolic hydroxyl group and / or a nitrogen-containing organic base, and a binder.

1. Thermal Diffusible Dye The dye of the present invention is not particularly limited as long as it is a dye having a phenolic hydroxyl group and / or a salt formed with a nitrogen-containing organic base.

As the dye having a phenolic hydroxyl group, dyes such as azo dyes, azomethine dyes and anthraquinone dyes conventionally used in heat-sensitive transfer materials can be used. In addition, JP-A-3-83685, JP -836
No. 87, No. 3-83688, No. 3-83689, No. 3-90397, No. 3-9
2385, 3-92386, and 3-114890, and further, compounds I-1 to I-16 and pages 13 to 16 described in Japanese Patent Application No. 3-258005, pages 9 to 11. Described compounds C-1 to C-
17, M-1 to C-10, Y-2, Y-4, Y-5 and the like can also be preferably used.

The dye formed by forming a salt with a nitrogen-containing organic base is not particularly limited as long as it can form a salt with a nitrogen-containing organic base, and azo dyes and azomethine dyes conventionally used in heat-sensitive transfer materials. , Anthraquinone dyes, etc. (eg Kinki Chemical Society: Functional Dye Subcommittee Material No. 1
Dyes and their derivatives described on pages 6, 34 to 35,
In particular, a derivative having a phenolic hydroxyl group is preferable in view of the point described later).

Among these dyes, a dye having a phenolic hydroxyl group is preferable in order to form a salt with a nitrogen-containing organic base while maintaining high sensitivity (high transferability of the dye). Also, in the case of forming an image using a basic compound and / or a mordant, a dye having a phenolic hydroxyl group is preferable from the viewpoint of achieving both high transferability and mordability. As the dye having a phenolic hydroxyl group, a derivative of the phenolic hydroxyl group of the above-mentioned dye, JP-A-3-83685, 3-8
3687, 3-83688, 3-83689, 3-90397, 3
-92385, 3-92386, 3-114890, etc. are mentioned.

A particularly preferable dye having a phenolic hydroxyl group is a dye represented by the following general formula (2).

[0111]

[Chemical 2]

Specific examples thereof include JP-A-3-83685,
3-83687, 3-83688, 3-83689, 3-90397
Nos. 3-92385, 3-92386 and 3-114890, and further, compounds I-1 to I-16 described in Japanese Patent Application No. 3-258005, pages 9-11. , Compound C-described on pages 13 to 16
1 to C-17, M-1 to C-10, Y-2, Y-4, Y-5
Etc. can also be used suitably.

The nitrogen-containing organic base forming the dye salt is preferably an organic base having a pka of 9 or more, and examples thereof include primary to tertiary alkylamines (eg octylamine, cyclohexylamine, dibutylamine, pyrrolidine, triethylamine). Etc.). Examples of particularly preferable organic bases include compounds represented by the following general formula (1). These compounds include amidine, guanidine, guanidine derivatives, and vinyl-type derivatives thereof.

[0114]

[Chemical 3]

In the formula, R ₁ , R ₂ and R ₃ are hydrogen atoms or
It represents an alkyl group, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, an amino group (including an alkyl-substituted amino group) or a guanidine group. Also, R ₁ and R ₂ and / or R ₃ and R ₄
May combine with each other to form a ring. X represents a vinyl group, and n represents 0 or 1.

Specific examples of the base represented by the above general formula (1) include compounds B-1 to B described in JP-A-64-3654, pages 3-4.
In addition, compounds A-1 to A-42 described in Japanese Patent Application No. 3-258005, pages 18 to 20, and the like can be preferably used.

Further, in the present invention, it is preferable to use a dye salt composed of a dye and a nitrogen-containing organic base, from the viewpoints of storability and reactivity.

Further, as the dye contained in the ink layer of the present invention, one or more kinds of conventionally used cyan dye, magenta dye and yellow dye other than the above dyes may be used in combination.

Examples of such cyan dyes include conventionally known naphthoquinone dyes, anthraquinone dyes, azomethine dyes, indoaniline dyes, and magenta dyes, anthraquinone dyes, azo dyes, azomethine dyes, and the like. Examples of yellow dyes include methine dyes, azo dyes, quinophthalone dyes, and anthryothothiazole dyes.

The dye is usually contained in the ink layer forming composition.
It is 20 to 90% by weight, more preferably 30 to 80% by weight. Further, the dye having a phenolic hydroxyl group and / or the dye forming a salt with a nitrogen-containing organic base is usually 50 to 100% by weight, and further 70 to 100% by weight in the whole dye contained in the ink layer. Weight percent is more preferred.

2. Binder As a binder for the ink layer, a cellulose addition compound,
Cellulose resins such as cellulose ester and cellulose ether; polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral and other polyvinyl acetal resins, polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, styrene resins, poly (meth) acrylic Examples include acid-based esters, vinyl-based resins such as poly (meth) acrylic acid and (meth) acrylic acid copolymers, rubber-based resins, ionomer resins, olefin-based resins, polyester resins, and the like.

Among these resins, a polyvinyl acetal resin or a cellulose resin having excellent storage stability is preferable.

Each of the above-mentioned various binders may be used alone or in combination of two or more.

The binder is usually contained in the ink layer-forming composition in an amount of 10 to 80% by weight, preferably 70 to 20% by weight.

3. Other optional components Further, various additives can be appropriately added to the ink layer.

Basically, an additive that can be added to the image receiving layer can be appropriately selected and used. As the additive, for example, silicone resin, silicone oil (reaction hardening type is also acceptable), silicone modified resin, fluororesin, surfactant, and releasable compound such as wax, fine metal powder,
Fillers such as silica gel, metal oxides, carbon black, and resin fine powders, curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylics, or epoxies), antistatic agents, and transfer Of a hot-melting material for promoting heat transfer, such as wax or higher fatty acid ester, is disclosed in JP-A-59-10699.
Examples thereof include compounds described in No. 7.

The amount of the additive is usually 0 to 30% by weight, more preferably 0 to 20% by weight in the ink layer forming composition.

-Other Layers- The heat-sensitive transfer recording dye-providing material is not limited to a two-layer structure comprising a support and an ink layer, and other layers may be formed.

For example, JP-A-59-48188, JP-A-60-224590, JP-A-61-209195 and JP-A-63195195 have been used for the purpose of preventing fusion with a heat-sensitive transfer recording image receiving material and settling (blocking) of a dye. -1
An overcoat layer may be provided on the surface of the ink layer as described in No. 02992, JP-A 1-281987, No. 2-2073, No. 2-2075.

Further, for the purpose of improving the adhesiveness to the ink layer on the support and preventing the transfer and dyeing of the dye to the support side,
JP-A-59-124890, JP-A-60-232996, JP-A-61-261090,
62-128792, 62-196184, 63-45089, 63-1
It may have an undercoat layer as described in 35288, 63-134281 and the like. Further, on the back surface of the support (the side opposite to the ink layer), for the purpose of running stability, heat resistance, antistatic, etc., JP-A-60-82387, 60-94390, 60
-115486, 60-184883, 60-219094, 61-2795
No. 95, No. 62-251192, No. 62-284784, No. 63-212587
No. 63, No. 63-214483, No. 64-1586, No. 64-11887, No. 64
A backing layer as described in JP-A-11888, JP-A-1-214475 and JP-A-2-239973 may be provided.

The thickness of the overcoat layer, the undercoat layer and the backing layer is usually 0.1 to 1 μm.

-Production of Ink Sheet for Thermal Transfer Recording- For the ink sheet for thermal transfer recording, an ink layer-forming coating liquid is prepared by dispersing or dissolving the various components forming the ink layer in a solvent, It can be produced by applying this to the surface of the support or the adhesive layer and drying.

The binder may be used by dissolving one kind or two or more kinds in a solvent or dispersing it in a latex form.

Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, butyl acetate and the like.

For the coating, a conventionally known surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted.

The ink layer may be formed as a layer containing a monochromatic dye on the entire surface or a part of the surface of the support, or a yellow ink layer containing a dye forming a yellow dye image. , A magenta ink layer containing a dye forming a magenta dye image and a cyan ink layer containing a dye forming a cyan dye image are formed on the entire surface or a part of the surface of the support at a constant repetition along the plane direction. It may be formed in.

Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed.

With respect to the black ink layer, a clear image can be obtained by either the thermal diffusion transfer type or the thermal fusion transfer type.

The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm.

Incidentally, the ink sheet for thermal transfer recording may be formed with perforations or provided with detection marks for detecting the positions of areas having different hues, thereby facilitating use.

(3) Formation of Image (Thermal Transfer Recording) To form an image, the ink layer of the thermal transfer recording ink sheet and the image receiving layer of the thermal transfer recording image receiving sheet are superposed to form an ink layer and an image receiving layer. Imagewise heat energy is applied to the interface.

Then, the dye in the ink layer is thermally diffused (vaporized or sublimated) by an amount corresponding to the applied thermal energy.
Then, as a result of being transferred to the image receiving layer side and being received, an image is formed on the image receiving layer.

In the present invention, a thermal transfer recording ink sheet having an ink layer containing at least a dye having a phenolic hydroxyl group and / or a dye formed by forming a salt with a nitrogen-containing organic base, and white fine particles as a base material are included. An image is formed by combining an image-receiving sheet for thermal transfer recording containing at least a basic compound and / or a mordant in the image-receiving layer formed on the laminate layer containing polypropylene as a main component.

Therefore, the image formed at the time of thermal transfer is
Since there is a laminated layer containing polypropylene containing white fine particles as a main component under the image receiving layer, sufficient heat is retained in the image receiving layer and the image is transferred at a high density onto the image receiving sheet for thermal transfer recording. You can

Further, in the image-receiving sheet for heat-sensitive transfer recording of the present invention, since sufficient heat is supplied to the image-receiving layer, the dye is stabilized by the basic compound and / or the mordant, and the light and heat during storage are kept. Not only is it possible to reliably prevent the dye from bleeding, but it is also excellent in image storability.

Further, in the constitution of the present invention, since the laminate layers are present on both sides of the substrate, curling after printing is prevented.

As a heat source for giving the heat energy,
Although a thermal head is generally used, a known one such as a current-carrying head, a laser beam, an infrared flash, and a hot pen can be used.

When a thermal head or an energizing head is used as a heat source for applying heat energy, the applied heat energy can be changed continuously or in multiple steps by modulating the applied voltage or pulse width.

When laser light is used as a heat source for giving heat energy, the heat energy to be given can be changed by changing the light amount and irradiation area of the laser light by using an optical system such as a lens. In this case, in order to easily absorb the laser light, a laser light absorbing material (for example, in the case of a semiconductor laser, carbon black or a near infrared absorbing substance) is used in the ink layer and / or
Alternatively, it may be present near the ink layer and further on the surface of the image receiving layer.

When a laser beam is used, it is preferable that the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet are sufficiently brought into close contact with each other.

If a dot generator with a built-in acousto-optic element is used, it is possible to give heat energy according to the size of the halftone dot.

When an infrared flash lamp is used as a heat source for giving heat energy, it is preferable to heat through a colored layer such as black as in the case of using laser light.

Alternatively, the heating may be carried out through a pattern or a halftone dot pattern in which the gradation of the image such as black is continuously expressed, or it corresponds to the negative of the above-mentioned pattern and a colored layer of one surface such as black. You may heat by combining a negative pattern. The thermal energy may be applied from the thermal transfer recording ink sheet side, the thermal transfer recording image receiving sheet side, or both sides, but if the effective use of thermal energy is prioritized. It is desirable to carry out from the side of the thermal transfer recording ink sheet.

By the above thermal transfer recording, an image of one color can be recorded on the image receiving layer of the thermal transfer recording image receiving sheet. For example, yellow, magenta, cyan and, if necessary, a black thermal transfer recording ink sheet are used. By sequentially replacing and performing thermal transfer according to each color, it is possible to obtain a color image having a color photographic tone, which is a combination of the colors. In this case, the use of the thermal transfer recording ink sheet having the areas formed separately for each color has the advantage of eliminating the need to replace the thermal transfer recording ink sheet as described above, thus reducing the size of the apparatus. From the aspect of the above, it can be suitably adopted.

Further, after forming an image by the method described above, heat treatment may be carried out by the method described above for the purpose of further improving the image storability (particularly the fixing property). For example, heat treatment may be performed over the entire image forming surface using a portion of the ink sheet where the ink layer is not provided, or heat treatment such as a heat roll may be newly performed. Further, when the near infrared ray absorbent is contained, the image forming surface may be exposed by using an infrared flash lamp.

It is also possible to change the shape of the image surface by heating and pressing the surface of the image. In this case, the method described in JP-A-2-215569, JP-A-2-238986 and JP-A-2-249657 can be used. Further, an apparatus as described in Japanese Patent Application No. 3-231020 can be preferably used for changing the shape of the image surface.

[0157]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" represents "parts by weight as active ingredients" unless otherwise specified.

(Examples 1 to 42) 1. Image-Receiving Sheet for Thermal Transfer Recording The image-receiving sheet for thermal transfer recording shown in the table was produced as follows.

<Substrate> a: Transparent polyethylene terephthalate film having a thickness of 125 μm [S, manufactured by Diafoyle Hoechst Co., Ltd.] b: White polyethylene terephthalate film containing a white pigment having a thickness of 125 μm [Diafoyle Hoechst Co., Ltd.]
W410] c; 150 μm thick white polyethylene terephthalate film [W 900J, manufactured by Diafoyle Hoechst Co., Ltd.] d; 60 μm thick, 50 μm thick on both sides, 50 μm white on both sides of Beck smoothness 150 seconds Polyethylene terephthalate film (D900 foil Hoist Co., Ltd., W900J)
Was laminated with a urethane adhesive to form a base material.

E; thickness 150 μm, Bekk smoothness 10 on both sides
0 second quality paper.

F; thickness 150 μm, Bekk smoothness 20 on both sides
0 second quality paper.

G; thickness 125 μm, Bekk smoothness 30 on both sides
0 second quality paper.

<Laminating composition (composition containing polypropylene as the main component)> The following composition containing polypropylene as the main component was melted and sufficiently kneaded, and then the composition was placed on the substrate.
Hot melt extrusion lamination was performed so as to have a thickness of 10 to 50 μm, and a laminate layer containing polypropylene as a main component was formed on the substrate.

A: Density of 0.90 g / cm ³ containing 5 parts of titanium oxide having an average particle size of 0.3 μm, melt florate 9 g / 10 mi
n polypropylene.

B; Density of 0.90 g / cm ³ , containing 12 parts of titanium oxide having an average particle size of 0.3 μm, melt florate of 7 g / 10 mi
n polypropylene.

C; Crosslinked styrene-acrylic hollow resin particles having an average particle size of 0.4 μm (JSR hollow particles SX863 (P), manufactured by Japan Synthetic Rubber Co., Ltd.) 12 parts in density 0.90 g / cm ³ , melt florate 7g / 10min polypropylene.

D; 7 parts of titanium oxide having an average particle size of 0.3 μm and crosslinked styrene-acrylic hollow resin particles having an average particle size of 0.4 μm (JSR hollow particles SX863 (P), manufactured by Japan Synthetic Rubber Co., Ltd.)
Containing 5 parts of density 0.90 g / cm ³ , melt florate 7
g / 10min polypropylene.

<Laminating composition (composition for laminating on the side opposite to the image receiving layer)> The following composition is melted,
After sufficiently kneading, hot-melt extrusion lamination was performed on the base material so that the thickness was 10 to 50 μm, and a laminate layer was formed on the base material.

A: Density of 0.91 g / cm ³ , melt florate of 7.0 g / 1 containing 10 parts of titanium oxide having an average particle size of 0.3 μm
0min low density polyethylene.

B; Same as composition for laminating b).

C; 10 parts of titanium oxide having an average particle size of 0.3 μm and an antistatic agent [Nippon Yushi-Seiya Ltd., Elegan S-100]
Low density polyethylene with a density of 0.91 g / cm ³ and melt flow rate of 7.0 g / 10 min.

D; 12 parts of titanium oxide having an average particle size of 0.3 μm and an antistatic agent [Matsumoto Yushi-Seiyaku Co., Ltd., Elex 33]
4] 1.5 parts of polypropylene having a density of 0.90 g / cm ³ and a melt flow rate of 7 g / 10 min.

<Primer Layer> The following primer layers were provided, with the primer layer on the surface of the substrate on which the image receiving layer was laminated as A and the primer layer on the substrate opposite to the image receiving layer as B.

A; Alkyl titanate in ethyl acetate [Organix PC-426 manufactured by Matsumoto Trading Co., Ltd.]
A solution of 5 parts of is applied and dried to form a primer layer with a thickness of 0.1 μm.

B: A composition containing ethylene-vinyl acetate copolymer as a main component in toluene [manufactured by Toyo Morton Co., Ltd.,
Adcoat AD-1790-15] was dissolved in 10 parts to form a primer layer having a thickness of 0.5 μm.

C; A solution of 5 parts of polyethyleneimine [Epomin P-1000 manufactured by Nippon Shokubai Co., Ltd.] dissolved in water was applied and dried to form a primer layer having a thickness of 0.1 μm.

D; A solution of 10 parts of a polybutadiene resin [Citabond 180 manufactured by Nippon Soda Co., Ltd.] dispersed in water was applied and dried to form a primer layer having a thickness of 0.3 μm.

E; Methyl ethyl ketone, urethane resin [Takelac A-367H, manufactured by Takeda Pharmaceutical Co., Ltd.] / Hardening agent, Takenate A-7, manufactured by Takeda Pharmaceutical Co., Ltd. = 7
Dissolve 10 parts at a composition ratio of / 3, apply and dry, thickness 0.3 μm
After forming the primer layer of 1 above and providing the above-mentioned laminate layer, aging at 40 ° C for 72 hours.

<Surface treatment> a: Corona discharge treatment of the surface.

B; Flame treatment of the surface with a molar ratio of air / methane = 105/100.

C; The surface is ultraviolet light (low wavelength type: 189n
m) irradiate for 10 minutes and UV treatment.

D; Radiation treatment was performed by irradiating the surface with an electron beam from an electron beam accelerator of 750 kv.

<Intermediate Layer> The following intermediate layers were formed with a thickness of 20 μm in a to d) and 0.2 μm in e to f).

A: Styrene-butadiene latex [JSR Latex 0617 manufactured by Japan Synthetic Rubber Co., Ltd.]
The intermediate layer was formed by coating and drying on a support.

B; Polyurethane resin [Takeda Pharmaceutical Co., Ltd.
Manufactured by Takelac T] 15 parts to 100 parts of a solution prepared by dissolving 15 parts by toluene / isopropyl alcohol = 2/1,
40 parts of water was mixed, and a slightly cloudy solution was applied on a support and dried to form a porous intermediate layer.

C; The following intermediate layer forming composition was dissolved in dimethylformamide in an amount of 30 parts and coated on a support.
After being dipped for 2 seconds to be solidified, it was dipped in hot water at 80 ° C. to make it porous, and dried to form a porous intermediate layer.

Polyester: 74 parts [Unitika Co., Ltd., Elitel UE-3690] Butyltin laurate: 4 parts [Akishima Chemical Co., Ltd., BL-42A] Barium-zinc organic compound: 4 parts [Akishima Chemical Co., Ltd., LT701B] Silica:・ ・ ・ ・ ・ ・ ・ ・ 4 parts [Average particle size; 0.015 μm] Calcium carbonate ・ ・ ・ ・ ・ ・ ・ ・ 4 parts [Average particle size; 0.2 μm] d; After forming an intermediate layer similar to a, urethane resin was added to methyl ethyl ketone [Takeda Pharmaceutical Co., Ltd.
Manufactured by Takelac A-367H] / hardener [Takenate A-7 manufactured by Takeda Yakuhin Kogyo Co., Ltd.]: 10 parts of a coating solution dissolved at a composition ratio of 7/3 is laminated to form a 2.0 μm thick adhesive layer. Forming,
After transferring the intermediate layer by thermocompression bonding to the support, 72 at 40 ° C
Formed by aging for time.

E; An intermediate layer was formed by coating and drying an aqueous solution containing 5% of a hardening agent in gelatin and having a solid content of 10%.

F; 2.5 parts of a solution of titanium-modified aqueous resin [manufactured by Matsumoto Kosho Co., Ltd., Organix WS680, 11% of active ingredient] in a solution of water / methanol = 8/32 was applied and dried to obtain an intermediate Layers were formed.

<Image Receiving Layer> An image receiving layer-forming composition having the following composition was added to distilled water, methyl ethyl ketone / methyl cellosolve /
Cyclohexanone = 80/10/10 or dioxane / Methylcellosolve / Cyclohexanone = 80/10/10 dissolved in a solid content of 10 parts, and by wire bar coating method, the thickness after drying becomes 10 μm Apply and dry to form an image-receiving layer.

A; Water-soluble polyester resin: 6 parts [Vylonal MD1200, manufactured by Toyobo Co., Ltd.] Mordant: 2 parts [Chemical B-1] Colloidal silica: 1.5 parts [Snowtex 40 manufactured by Nissan Chemical Industries, Ltd.] Modified silicone oil ........................ 0.5 part [KF355, manufactured by Shin-Etsu Chemical Co., Ltd.] b; polyvinyl butyral resin: 6 parts [manufactured by Denki Kagaku Co., Ltd.] , Denka Butyral # 6000-EP] Polyether polyol ・ ・ ・ ・ ・ ・ ・ ・ 1.5 parts [Desmophen 550U, manufactured by Sumitomo Bayern Urethane Co., Ltd.] Mordant ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ 2 parts [Chemical B-2] Modified silicone resin ・ ・ ・ ・ ・ ・ ・ ・・ 0.5 parts [Shin-Etsu Chemical Co., Ltd., X-24-8300] c; Styrene-based resin: 7.5 parts [Mitsui Toatsu Chemical Co., Ltd.] , Lightac-A 200PC] Mordant ・ ・ ・ ・ ・ ・ ・ ・ 2 parts [Chemical B-3] Modified silicone resin ・ ・ ・ ・ ・ ・ ・ ・..0.5 parts [Shin-Etsu Chemical Co., Ltd., X-24-8300] d; Phenoxy resin ... 7.5 parts [Union Carbert, PKHH] Mordant: 2.0 parts [Chemical B-4] Modified silicone resin: 0.5 parts [Shin-Etsu] Chemical Industry Co., Ltd., X-24-8310] e; Polycarbonate resin ... 6.5 parts [Mitsubishi Gas Chemical Co., Ltd., Iupilon Z-100] Mordant ...・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ ・ 2.0 parts [Chemical B-5] Phthalates alkyl ester ・ ・ ・ ・ 1.0 part [Dahachi Chemical Co., Ltd., DOP] Modified silicone resin .............. 0.5 part [X-24-8300, manufactured by Shin-Etsu Chemical Co., Ltd.] After forming the following image-receiving layer on release paper, urethane resin [Takeda Chemical Industries, Ltd. ), Takelac A-367H] / hardener [Takeda Pharmaceutical Co., Ltd.,
Takenate A-7] = 7/3 of a coating solution dissolved at a composition ratio of 7/3 is laminated to form an adhesive layer having a thickness of 3.0 μm, which is thermocompression-bonded onto a support and / or an intermediate layer to form an image receiving layer. After being transferred, it was formed by aging at 40 ° C. for 72 hours.

F; Similar to the image receiving layer of a.

Similar to the image-receiving layer of g; c.

H; Same as the image receiving layer of e.

[0195]

[Chemical 4]

2. Ink sheet for thermal transfer recording The following ink layer forming composition was dissolved in a mixed solvent of methyl ethyl ketone / dioxane / cyclohexanone = 4/4/2 at a solid content of 5% to prepare an ink layer forming coating liquid,
A 6 μm-thick polyethylene terephthalate film [Lumirror F53N manufactured by Toray Industries, Inc.] as a support has a corona discharge-treated surface and an ink layer-forming coating liquid of 1 μm after dried by a wire bar coating method. After coating and drying, a nitrocellulose solution containing 50% by weight of a silicone resin [Daiichi Seika Co., Ltd., Dialomer SP-712] on the back surface not treated with corona is dried by a wire bar coating method. The ink sheet for heat-sensitive transfer recording shown in the table was produced by applying the coating solution to a thickness of 0.3 μm, drying it, and performing back treatment coating.

A: Thermal diffusible dye [Chemical D-1] / polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX
−1] = 60/40 b; Thermal diffusible dye [Chemical D-2] / Polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BL-1] = 60 /
40 c; Thermal diffusible dye [Chemical D-3] / Polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX-1] / Silicone modified resin [Sumitomo Bakelite Co., Ltd., Sumiresin Excel CRC-7235] = 65/30/5 d; Thermal diffusible dye [Chemical D-4] / Polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX-1] / Silicone modified resin [Sumitomo Bakelite Co., Ltd., Sumiresin Excel CRC] -7245] = 60/38/2 e; Thermal diffusible dye [Chemical D-5] / Polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX-1] / Silicone modified resin [Sumitomo Bakelite Co., Ltd., Sumiresin Excel CRC-7225] = 60/36/4 f; thermal diffusible dye [Chemical D-6] / polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX-1] / isocyanate [ This Polyurethane Industry Co., Ltd., Coronate HX] = 60/45/5 g; Thermal diffusion dye [Chemical D-7] / Polyvinyl butyral [Sekisui Chemical Co., Ltd., S-REC BX-1] / Silicone modified resin [Sumitomo Bakelite Co., Ltd., Sumirejin Excel CRC-7225] = 60/36/4

[0198]

[Chemical 5]

[0199]

[Chemical 6]

3. Formation of Image First, the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet are superposed so that the former ink layer surface and the latter image receiving layer surface are in contact with each other to support the thermal transfer recording ink sheet. From the body side, a thermal head was applied under the following conditions to form an image.

Next, the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet were peeled off, and the image was transferred onto the thermal transfer recording image receiving sheet.

After recording the image, the transfer density on the surface of the image receiving layer, the heat resistance of the image, the light resistance, the fixing property and the bleeding prevention property are
The following criteria evaluated. The results are shown in Table 1.

Linear density of main scanning and sub scanning: 8 dots / mm Recording power: 0.6 W / dot Heating time of thermal head: 20 msec (applied energy about 11.2 × 10 ⁻³ J) to 2 msec (applied energy about 1.12 × 10 ^-3 J), the heating time was adjusted stepwise.

[Transfer density]: Reflection density OD with an optical densitometer
Measure the value.

A ... OD value is 2.0 or more B ... OD value is 1.5 to 2.0 C ... OD value is 1.0 to 1.5 D ... OD value is 1.0 or less.

[Transfer sensitivity]: Reflection density of 1.0 with an optical densitometer
The applied energy (E) that gave

A ... E <4.8 × 10 ^-3 [J] B ... 4.8 × 10 ^-3 [J] ≦ E <5.2 × 10 ^-3 [J] C ... 5.2 × 10 ^-3 [J] ≤ E <5.6 x 10 ^-3 [J] D ... 5.6 x 10 ^-3 [J] ≤ E [Curl]: Measure with a curl gauge and convert the radius of curvature to m It was expressed by the reciprocal X (0 to 0.5 before printing).

A ... X <0.5 B ... 0.5 ≦ X <1 C ... 1 ≦ X <2 D ... 2 ≦ X [Fixability of dye]: An image was recorded. The thermal transfer recording image-receiving sheet faces the thermal transfer recording image-receiving sheet of the present invention on which no image is recorded, and a load of 40 g / cm ² is applied to the thermal transfer recording image receiving sheet at 60 ° C.
・ After leaving for 48 hours, measure the optical density of the dye transferred to the thermal transfer recording image-receiving sheet on which no image was recorded.

A .... Transferred dye concentration <0.05 B .... 0.05 ≦ transferred dye concentration <0.10 C .... 0.10 ≦ transferred dye concentration <0.15 D .... 0.15 ≦ transferred dye concentration Density [Prevention of dye bleeding]: The image-receiving image-receiving sheet for thermal transfer recording is left at 60 ° C for 1 week, and then the degree of bleeding at the edge is measured with a microdensitometer.

A: No bleeding was observed B: Some bleeding was recognized C: Some bleeding was observed (Comparative Examples 1 to 7) In the constitution of the image-receiving sheet for thermal transfer recording, A composition containing polypropylene as a main component containing white fine particles on the image-receiving layer side, is melted by changing to the following:
Thermal kneading transfer recording was carried out in the same manner as in Example except that hot-melt extrusion lamination was performed on the substrate so that the thickness of the substrate was 10 to 50 μm after sufficient kneading, and the laminate layer was formed on the substrate. An image receiving sheet for use was produced, and an image was formed using the above-mentioned thermal transfer recording ink sheet.

E; Hot melt extrusion
No laminating layer by laminating. f; Density 0.90 g / cm ³ , Melt Florate 9 g / 10 min
Polypropylene.

G; Density of 0.91 g / cm ³ , melt flow rate of 7.0 g / 1, containing 10 parts of titanium oxide having an average particle size of 0.3 μm.
0min low density polyethylene.

H: Density of 0.91 g / cm containing 10 parts of cross-linked styrene-acrylic hollow resin particles [JSR hollow particles SX863 (P) manufactured by Japan Synthetic Rubber Co., Ltd.] having an average particle diameter of 0.4 μm.
^3. Low density polyethylene with melt flow rate 7.0g / 10min.

[0214]

[Table 1]

[0215]

As shown in Table 1, the present invention comprises an ink layer containing a dye having a phenolic hydroxyl group or a dye salt formed by forming a salt with a nitrogen-containing organic base, a basic compound and / or a mordant. By using the heat-sensitive transfer material contained therein, a high-sensitivity and high transfer density can be obtained, and further, an image-receiving sheet for heat-sensitive transfer recording excellent in image storability which does not cause curling after image formation and a suitable manufacturing method thereof can be obtained. It was

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Watanabe 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (6)

[Claims] 1. An ink layer of a thermal transfer recording ink sheet having an ink layer containing, on a support, a dye having at least a phenolic hydroxyl group and / or a dye salt consisting of at least a dye and a nitrogen-containing organic base, and an image receiving layer. Face the image-receiving layer of the image-receiving sheet for thermal transfer recording containing at least a basic compound and / or a mordant, and heat according to the image information to form a dye image according to the image information on the image-receiving layer. In the heat-sensitive transfer image-forming material, as the image-receiving sheet for heat-sensitive transfer recording, a laminate layer having a thickness of 5 to 50 μm and containing polypropylene containing white fine particles as a main component is provided on the surface of the base material on which the image-receiving layer is laminated. An image-receiving sheet for heat-sensitive transfer recording characterized by using a support. 2. The image-receiving sheet for thermal transfer recording according to claim 1, wherein an intermediate layer is further provided between the laminate layer containing polypropylene as a main component containing the white fine particles and the image-receiving layer. 3. A support having a laminate layer containing white fine particles having a thickness of 5 to 50 μm on the surface of the base material opposite to the surface on which the image receiving layer is laminated is used. 1. An image-receiving sheet for heat-sensitive transfer recording according to 1. 4. A resin composition containing polypropylene as a main component containing white fine particles in a thickness of 5 to 50 μm is hot-melt extruded and laminated by a melt extrusion method on a substrate directly or after a primer treatment. A laminate layer is formed by doing so, and on this laminate layer,
A method for producing an image-receiving sheet for thermal transfer recording, which comprises laminating an image-receiving layer containing a basic compound and / or a mordant by a coating method and / or a laminating method directly or after surface treatment. 5. The laminated layer as described above is directly or surface-treated, and then an intermediate layer is formed by a coating method and / or a laminating method, and the intermediate layer is directly or surface-treated and then the coating method and / or Or by the laminating method,
The method for producing an image-receiving sheet for thermal transfer recording according to claim 4, wherein an image-receiving layer containing a basic compound and / or a mordant is laminated. 6. A resin composition containing white fine particles in an amount of 5 to 50, which is opposite to the surface on which the above-mentioned image receiving layer is laminated, is directly or after a primer treatment is applied by a melt extrusion method.
The laminated layer is formed by hot melt extrusion lamination having a thickness of μm.
A method for producing the image-receiving sheet for heat-sensitive transfer recording described.