JPH05169838A - Infrared heating type thermal transfer recording sheet - Google Patents

Abstract

PURPOSE:To obtain sharp recorded matter with high density, in the title sheet having a layer containing a thermal transfer dye and an infrared absorbing substance by using a phthalocyanine or naphthalocyanine compound represented by a specific chemical formula as the infrared absorbing substance. CONSTITUTION:A thermal transfer recording sheet using infrared laser as a heating means is obtained by providing a layer containing a thermal transfer dye and an infrared absorbing substance on a base film. This recording sheet is heated to transfer the dye to an image receiving sheet to perform recording. In this case, a phthalocyanine or naphthalocyanine compound represented by general formula (wherein R<1>-R<4> are an alkyl group which may be substituted or -(C2H4O)nY, A is group IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VB, VIII metal of the Periodic Table or a compound containing the metal and Y is a hydrogen atom or an aryl group) is used as the infrared absorbing substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording sheet used for heat-sensitive transfer recording, particularly dye transfer type heat-sensitive transfer recording.

[0002]

2. Description of the Related Art A dye-transfer type heat-sensitive transfer recording is a heat-sensitive transfer sheet in which a heat-sensitive transfer sheet having a coloring material layer containing a heat transferable dye on a base film and an image-receiving sheet having a dye-receiving layer on the surface are superposed. Is a recording method in which the dye in the heat-sensitive transfer sheet is transferred to the image-receiving sheet by heating to record. This recording method is applied to full-color image recording such as a video printer because the transfer amount of the dye can be controlled by the amount of heating energy and gradation can be expressed.

Conventionally, as a heating means for the transfer sheet, a line type thermal head in which a heating resistor element which generates heat in response to an electric signal is formed in a line on a substrate is used. However, it is difficult to uniformly form a large number of heating resistor elements on the substrate, which makes it difficult to manufacture a large thermal head, and it is difficult to record an image on a large screen. In addition, since there is a limit to the formation density of the heating resistor elements, there is a problem in image recording that requires high resolution.

In order to solve the problems of these thermal heads, it has been proposed to use laser light as a heating means. As the laser light, a semiconductor laser that is small and obtains high energy is particularly advantageous. Currently, there are semiconductor lasers having a transmission wavelength of 650 to 850 nm in the red to near infrared region, but those in the near infrared region of 750 to 850 nm are mainly used. In order to heat the transfer sheet by using these semiconductor lasers as a heating means, it is necessary to include a photothermal conversion substance that absorbs laser light and converts the absorbed light into heat energy in the transfer sheet. The photothermal conversion substance used here is very important because it directly affects the recording sensitivity of the transfer sheet and also affects the quality of the recorded image. The photothermal conversion substance is required to have the following characteristics.

Good absorption efficiency of laser light Good conversion efficiency of absorbed light into heat Good solubility or dispersibility in solvent or water, good stability of coating liquid, film Easy to coat ・ Stable when the transfer sheet is stored, and does not adversely affect the dyes used together ・ No heat transfer, or very small compared to dyes As the conversion substance, for example, JP-A-63-
319191, JP-A-58-16888, JP-A-2-2
074 and many others have been proposed. However, these products do not always satisfy all the above-mentioned characteristics, and more excellent products are demanded.

[0006]

DISCLOSURE OF THE INVENTION The present invention uses an infrared absorbent having a specific structure as a photothermal conversion substance having excellent characteristics in thermal transfer recording using infrared rays such as an infrared semiconductor laser as a heating means. In other words, it is an object of the present invention to provide a heat-sensitive transfer recording sheet having good transfer sensitivity and capable of providing a high quality recorded matter.

[0007]

The heat-sensitive transfer recording sheet of the present invention has a layer containing a heat transferable dye and an infrared absorbing substance on a base film, and the infrared absorbing substance is represented by the following general formula (I).

[0008]

[Chemical 3]

(Wherein R ¹ , R ² , R ³ and R ⁴ are optionally substituted alkyl groups, — (C ₂ H ₄ O) _n Y or

[0010]

[Chemical 4]

A is the group IB, IIA of the periodic table
Group, Group IIB, Group IIIA, Group IIIB, Group IVA, Group
It represents a metal belonging to Group IVB, Group VB and Group VIII or a compound containing the metal. Here, X represents a halogen atom, Y represents a hydrogen atom, an aryl group or an optionally substituted alkyl group, n represents an integer value of 1 to 4, m represents 0, 1 or 2, and Z represents Z. Represents a hydrogen atom, a carboxylic acid group, a carboxylic acid ester group, an aryl group, an optionally substituted alkyl group or an optionally substituted alkoxy group. ) Is a phthalocyanine or naphthalocyanine compound.

The contents of the present invention will be described in detail below. First, the infrared absorbent represented by the general formula (I) will be described. Specific examples of the phthalocyanine-based compound and the naphthalocyanine-based compound represented by the general formula (I) include those shown in Table 1. These substances are known substances and are disclosed in JP-A-1-304991. , JP-A-62-39286 and the like.

Since these compounds have an absorption band having a large absorption intensity in the wavelength band of 700 to 900 nm, it is known that the absorption efficiency of infrared laser light is good and the heat conversion efficiency of absorbed light is also good. It was By the way, when the present inventors try to use these compounds as an infrared absorber of the recording sheet, the coating liquid is easy to prepare because the solubility in the solvent used for the thermal transfer recording sheet is large,
In particular, it has no adverse effect on the dye, has good storage stability of the coating liquid and transfer sheet, and has a very small thermal transfer property as compared with the dye, and even in high-speed recording where high heat energy is applied, the image receiving paper itself. The present invention has been completed by finding that it is not transferred to the recording medium and does not deteriorate the recording image quality.

In the general formula (I), the substituents OR ¹ , O
The ring to which R ² , OR ³ or OR ⁴ is bonded is

[0015]

[Chemical 5]

If BZ,

[0017]

[Chemical 6]

When it is, it is expressed as NP, and the substitution position is defined as above. or,

[0019]

[Chemical 7]

"-Ph" is abbreviated as "-Ph", and "(p)" means substitution at the para position of the phenyl group. Unless otherwise specified, R ¹ = R ² = R ³ = R ⁴ .

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

Next, the transfer sheet of the present invention will be described. In the transfer sheet of the present invention, the layer containing the infrared absorbing substance may be formed at any position of the base film, but it is formed on the same side as the color material layer containing the heat transferable dye. It is advantageous, and it is more advantageous to use it by mixing it with a dye in the color material layer.

When forming a coloring material layer containing an infrared absorbing material in the coloring material layer, an ink is prepared by dissolving the infrared absorbing material in a medium together with a dye and a binder in the form of fine particles. Apply ink to the base film,
It can be carried out by drying. As the binder for preparing the ink, cellulose-based, acrylic acid-based,
Starch-based and epoxy-based water-soluble resins and acrylic resins, methacrylic resins, polystyrene, polycarbonate, polysulfones, polyether sulfones, polyvinyl butyral, ethyl cellulose, acetyl cellulose,
Examples thereof include resins soluble in organic solvents such as polyester, AS resin, and phenoxy resin.

As a medium for ink preparation, in addition to water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, fragrances such as toluene, xylene and chlorobenzene. Group, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methylene chloride,
Chlorine solvents such as chloroform and trichlorethylene,
Ethers such as tetrahydrofuran and dioxane,
Examples thereof include organic solvents such as N, N-dimethylformamide and N-methylpyrrolidone.

The heat transferable dye may be any one as long as it can be transferred to the receiving layer by the action of heat, and azo dyes and anthraquinone dyes which have been proposed for heat transfer sheets for conventional thermal heads. Dyes, azomethine dyes, methine dyes, indoaniline dyes, quinophthalone dyes and the like can be used. Infrared absorber,
The amount of the dye and the binder used is 1 to 200% by weight, preferably 10 to 10% by weight of the infrared absorber with respect to the dye.
0% by weight, and 10 to 500% by weight, preferably 50 to 200% by weight, of the pigment is suitable for the binder.

In the above ink, in addition to the above components, if necessary, organic or inorganic non-sublimable fine particles, dispersant, antistatic agent, defoaming agent, antioxidant, viscosity modifier, release agent. Etc. can be added. The thickness of the color material layer is 0.1 to 10 μm
Is suitable, and preferably 0.5 to 5 μm.

As the base film of the transfer sheet, a film of transparent plastic having good heat resistance such as polyester, polycarbonate, polyamide, polyimide, polyaramid is suitable, and the thickness thereof is in the range of 3 to 200 μm. I can name it. Of the above base films, the polyethylene terephthalate film is particularly advantageous in consideration of mechanical strength, solvent resistance, economy and the like.

In the transfer sheet of the present invention, a dye-permeable protective layer may be further formed on the above color material layer, if necessary. As a method for applying the ink to the base film, a gravure coater, a reverse roll coater, a rod coater, an air doctor coater or the like can be used.

[0031]

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

[0032]

Table 1 Example 1 a) Preparation of ink Infrared absorber Compound (1) of Table 1 2 g Chromium 1,1,2-tricyano-2- (p-ethyl 8 g butylaminophenyl) ethylene cellulose acetate 10 g ( Product name: L-30; Daicel Chemical Co., Ltd. product) Methyl ethyl ketone 80 g ──────────────────────────────────── Total 100 g The mixture having the above composition was treated with a paint conditioner for 10 minutes to prepare an ink.

B) Preparation of Transfer Sheet The above ink was applied onto a polyethylene terephthalate film (6 μm thick) using a wire bar and dried (dry film thickness of about 1 μm) to obtain a transfer sheet.

C) Preparation of image receptor 10 parts of vinyl chloride / vinyl chloride resin (product name: VYHD; Union Carbide product), amino-modified silicone (product name: KF-3)
93; product of Shin-Etsu Chemical Co., Ltd.) Synthetic paper containing 0.5 parts, 15 parts of methyl ethyl ketone, and 15 parts of xylene (product name: YUPO FPG150; product of Oji Yuka Co., Ltd.)
Apply with a wire bar and dry (dry film thickness about 5 μm),
Further, it was produced by treating in an oven at 80 ° C. for 30 minutes.

D) Transfer recording The transfer sheet was superposed so that the ink-coated surface of the transfer sheet was in contact with the surface of the image receiving layer of the image receiving member, and was wound around a drum having a diameter of 250 mm so that the image receiving member was in contact with the drum (vacuum was sucked from the inside of the drum. Furthermore, a transparent cover film of polyethylene terephthalate having a thickness of 25 μm was further adhered onto the transfer sheet so that the transfer sheet and the image receiver were in close contact with each other.) While the drum was rotated, the transmission wavelength of 830
Transfer recording was performed under the following conditions while continuously irradiating a semiconductor laser beam of nm.

[0036]

[Table 5] Equipment used: manufactured by Matsushita Electric Industrial Co., Ltd., model number LN
98100PR Drum rotation speed: 500 rpm Laser light output: 80 mW Laser light spot diameter: 4 μm Recording line density: 100 lines / mm

By the transfer recording under the above-mentioned conditions, a uniform and clear magenta-colored recorded matter was obtained. The color density of the recorded matter was 1.30 as measured by a densitometer TR-927 manufactured by Macbeth.

Example 2 Instead of the dye of Example 1 in the preparation of the ink, dye 1,
Ink preparation, transfer sheet preparation, image receptor preparation and transfer recording were carried out in the same manner as in Example 1 except that 8 g of 1-dicyano-2- (p-diethylamino-o-methylphenyl) ethylene was used. A uniform and clear yellow-colored recording material having a density of 1.35 was obtained.

Example 3 Instead of the dye of Example 1 in the preparation of the ink, dye o-
Acetamide-N- (p-diethylamino-o-methylphenyl) p-quinoneimine [acetamide is in the ortho position with respect to the carbon atom bonded to the oxygen atom of quinone]
Ink preparation, transfer sheet preparation, image receptor preparation and transfer recording were carried out in the same manner as in Example 1 except that 8 g was used to obtain a uniform and vivid cyan recording material having a color density of 1.25. ..

Example 4 In preparation of the ink, 0.2 g of true spherical silicon resin particles (average diameter 2.0 μm) was added to the components of Example 1 to prepare an ink, and a transfer sheet was prepared. The production of the image receptor and the transfer recording are carried out in the same manner as in Example 1, and the color density is 1.
20 uniform and vivid magenta colored recordings were obtained.

Example 5 A transfer sheet was prepared by further coating an aqueous solution of polyvinyl alcohol on the color material layer of the transfer sheet prepared in Example 1 to form a protective layer of about 0.1 μm. Using this transfer sheet, transfer recording was carried out in the same manner as in Example 1 to obtain a uniform and clear magenta color recorded product having a color density of 1.10.

Example 6 Instead of the infrared absorber of Example 1 in the preparation of the ink,
Ink was prepared, a transfer sheet was prepared, an image receptor was prepared and transfer recording was carried out in the same manner as in Example 1 except that 2 g of the infrared absorbent shown in Table 2 was used. I got a record.

Comparative Example Instead of the infrared absorber of Example 1 in the preparation of the ink,
Ink preparation, transfer sheet preparation, image receptor preparation and transfer recording were carried out in the same manner as in Example 1 except that 2 g of the infrared absorbent shown in Table 2 was used, and the results shown in Table 2 were obtained.

[0044]

[Table 6] * Ni-compound has the following structure

[0045]

[Chemical 8]

[0046]

When the heat-sensitive transfer sheet of the present invention is used,
A semiconductor infrared laser can be used as a heating means to obtain a high density and clear recorded matter.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kurose 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (1)

[Claims] 1. A sheet used for heat-sensitive transfer recording having a layer containing a heat transferable dye and an infrared absorbing substance on a base film, wherein the infrared absorbing substance has the following general formula (I): ) [Chemical 1] (Wherein R ¹ , R ² , R ³ and R ⁴ are optionally substituted alkyl groups, — (C ₂ H ₄ O) _n Y or Where A is Periodic Table Group IB, Group IIA, IIB
It represents a metal belonging to Group IIIA, Group IIIA, Group IIIB, Group IVA, Group IVB, Group VB and Group VIII or a compound containing the metal. Here, X represents a halogen atom, and Y
Represents a hydrogen atom, an aryl group or an optionally substituted alkyl group, n represents an integer value of 1 to 4, m represents 0, 1 or 2, Z represents a hydrogen atom, a carboxylic acid group,
It represents a carboxylic acid ester group, an aryl group, an optionally substituted alkyl group or an optionally substituted alkoxy group. ] An infrared heating type thermal transfer recording sheet characterized by being a phthalocyanine or naphthalocyanine compound represented by