JPH0911635A - Thermal transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer recording material capable of a printing image good in transfer properties and excellent in scratch resistance. SOLUTION: A hot-melt ink layer consisting of an epoxy resin, a colorant and a spherical silica powder and/or a mica powder and containing 50wt.% or more of one or more kind of the epoxy resin selected from a group consisting of tetraphenolethane tetraglicydyl ether, cresole novolac polyglicydyl ether, bisphenol A diglicydyl ether and bisphenol F diglicydyl ether is provided on a base material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer recording material for forming an image having excellent fastness.

[0002]

2. Description of the Related Art Conventional thermal transfer recording materials are generally capable of printing images of good quality on a base material coated with a hot-melt ink containing wax as a main component of a vehicle or on paper having poor surface smoothness. A hot-melt ink containing a resin as a main component of the vehicle is applied for forming or forming an image having good scratch resistance.

In recent years, thermal transfer recording materials have been used to print barcodes and the like used in the management of parts and products in the manufacturing process in manufacturing factories, product management in the distribution field, and article management in the field of use. Bar code printers and label printers are being used. In the case of bar codes used in the field of distribution and the like, since there are many occasions of rubbing, particularly good scratch resistance is required.

In addition to bar codes, outdoor advertisements, election posters, general posters, standing signs, stickers, catalogs, pamphlets, calendars, etc. in the commercial printing field, light packaging bags, foods, beverages, medicines, paints, etc. in the packaging field. In the field of clothing, such as container labels and bundling tapes, quality transfer labels, process control labels, product control labels, etc., heat transfer printers have come to be used. Scratch resistance is required.

[0005]

However, in the case of a conventional thermal transfer recording material using a heat-meltable ink mainly composed of wax, the transferability is good, but the obtained image has a scratch resistance. Was inferior. Further, in the case of a thermal transfer recording material using a heat-meltable ink containing a resin such as an ethylene-vinyl acetate copolymer as a main vehicle, the scratch resistance of the obtained image is relatively good,
The melt viscosity was high and the transferability was inferior to the wax-based one.

In view of the above points, an object of the present invention is to provide a thermal transfer recording material capable of forming an image having good transferability and excellent scratch resistance.

[0007]

The present invention comprises (1) an epoxy resin, a colorant, and spherical silica powder and / or mica powder on a substrate, wherein the epoxy resin is tetraphenolethane tetraglycidyl ether. , Cresol novolac polyglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether 1
The present invention relates to a thermal transfer recording material comprising a heat-meltable ink layer containing 50% by weight or more of one or more resins.

The present invention further comprises (2) the content of the spherical silica powder and / or mica powder in the hot-melt ink layer is 5 to 70% by weight. The present invention relates to a thermal transfer recording material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The hot-melt ink layer of the present invention contains a specific epoxy resin, a colorant, and spherical silica powder and / or mica powder. By blending the spherical silica powder or mica powder, the hardness of the ink layer made of the epoxy resin is increased, thereby improving the scratch resistance of the printed image and improving the sharpness of the ink layer at the time of transfer. It Further, since the silica powder has a spherical shape, the ink easily flows during the transfer, which is advantageous for the transfer.

The spherical silica powder preferably has an average particle size of 0.05 to 15 μm, especially 0.1 to 10 μm. If the average particle size is less than the above range, sufficient abrasion resistance tends not to be obtained, while if it exceeds the above range, transferability tends to be poor. From the standpoint of transferability, spherical silica powder is particularly preferably spherical silica powder.

The mica powder has an average particle size of 0.
It is preferably in the range of 05 to 15 μm, especially 0.1 to 10 μm. If the average particle size is less than the above range, sufficient abrasion resistance tends not to be obtained, while if it exceeds the above range, transferability tends to be poor.

The spherical silica powder and the mica powder may be used alone or as a mixture. From the viewpoint of transferability, it is preferable to use spherical silica powder, especially true spherical silica powder alone.

The content of the spherical silica powder and / or mica powder in the hot-melt ink layer is 5 to 70.
% (Weight%, the same applies hereinafter), especially 40 to 60% is preferable. If the content of the powder is less than the above range, the effect of improving the scratch resistance of the printed image may not be sufficiently exhibited. On the other hand, if it is more than the above range, the transferability tends to be poor.

The epoxy resin used in the present invention is tetraphenol ethane tetraglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A.
One or two or more selected from the group consisting of diglycidyl ether and bisphenol F diglycidyl ether is contained in an amount of 50% or more, more preferably 70% or more.

Among the epoxy resins, the above-mentioned four kinds of specific epoxy resins are preferable because they have good transferability.

In the present invention, it is particularly preferable that the total amount of the epoxy resin is composed of the specific epoxy resin, but it is not always necessary, and the epoxy resin containing 50% of the specific epoxy resin, especially 70% or more is contained. If so, the desired effect is achieved. If the content of the specific epoxy resin in all the epoxy resins is less than the above range, the dispersibility of the pigment in the vehicle will be poor, and the transferability will be poor.

The above-mentioned tetraphenol ethane tetraglycidyl ether (hereinafter sometimes abbreviated as TPETGE) is one of the polyfunctional epoxy resins represented by the formula (I) and has a softening point in the range of 92 ° C.

[0018]

Embedded image

The cresol novolac polyglycidyl ether (hereinafter sometimes abbreviated as CNPGE) is a kind of polyfunctional epoxy resin, and in the present invention, it has the formula (II):

[0020]

Embedded image

Those represented by (in the formula, m is usually an integer of 3 to 7) are preferred. The CNPGE used in the present invention includes a mixture having different values of m. CNPGE preferably has a softening point in the range of 60 to 120 ° C.

The above-mentioned bisphenol A diglycidyl ether (hereinafter sometimes abbreviated as BPADGE) is a kind of bifunctional epoxy resin, and in the present invention, it has the formula (III):

[0023]

Embedded image

(In the formula, n is usually an integer of 0 to 13)
Is preferably represented. BPA used in the present invention
DGE also includes mixtures of different values of n.
As BPADGE, those having a softening temperature in the range of 60 to 140 ° C are preferable.

The bisphenol F diglycidyl ether (hereinafter sometimes referred to as BPFDGE) is a kind of bifunctional epoxy resin, and in the present invention, it has the formula (I
V):

[0026]

Embedded image

(In the formula, p is usually an integer of about 0 to 33) is preferable. BP used in the present invention
FDGE also includes a mixture of two or more different p values in formula (IV). 60 to 1 for BPFFDGE
Those having a softening point in the range of 40 ° C. are preferable.

Examples of other epoxy resins which can be used in combination with the above specific epoxy resin in the present invention include the following.

(1) Glycidyl ether type brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, naphthol modified cresol novolak polyglycidyl ether Examples include ether.

(2) Glycidyl ether / ester type p-oxybenzoic acid glycidyl ether / ester and the like.

(3) Glycidyl ester type phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester and the like can be mentioned.

(4) Glycidyl amine type glycidyl aniline, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane and the like can be mentioned.

(5) Linear aliphatic epoxy type Examples include epoxidized polybutadiene and epoxidized soybean oil.

(6) Alicyclic epoxy type 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate and the like can be mentioned.

The other epoxy resins may be used alone or in combination of two or more. As the other epoxy resin, those having a softening temperature of 60 ° C. or higher are preferable. However, if the softening temperature of the entire vehicle becomes 60 ° C. or higher by mixing with another epoxy resin or the specific epoxy resin, the liquid Epoxy resin can also be used.

The vehicle may be blended with a heat-melting resin other than the epoxy resin as long as the object of the present invention is not impaired. Examples of such a heat-fusible resin include an ethylene-vinyl acetate copolymer resin, an ethylene-alkyl (meth) acrylate copolymer resin, a phenol resin,
Examples thereof include styrene-acrylic copolymer resin, polyester resin and polyamide resin. The other heat-meltable resin is preferably used in an amount of 15% or less, particularly preferably 5% or less of the total amount of the vehicle.

The vehicle preferably has a softening temperature in the range of 60 to 120 ° C. from the viewpoint of storage stability and transferability of the thermal transfer recording material.

The content of the vehicle in the heat fusible ink layer is preferably 10 to 90%, more preferably 20 to 70% from the viewpoint of transferability and the like.

The colorant used in the present invention includes carbon black, azo pigments (insoluble azo, azo lake, condensed azo pigment), phthalocyanine pigments, nitro pigments, nitroso pigments, anthraquinone pigments, nigrosine pigments. , Quinacridone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments, titanium white, calcium carbonate, various organics such as barium sulfate,
Inorganic pigments can be used. A dye may be used in combination for adjusting the color tone. The content of the colorant in the ink layer is 5 to 20%, preferably 5 to 15%.

When a subtractive color mixture is used to form a multicolored or full-color image, yellow, magenta, and cyan colorants, and if necessary, a black colorant are used.

Transparent pigments are preferably used as the yellow, magenta and cyan colorants. As the black colorant, an opaque pigment is usually used.

Examples of the yellow transparent pigment include naphthol yellow S, Hansa yellow 5G, Hansa yellow 3G, Hansa yellow G, Hansa yellow GR, Hansa yellow A, Hansa yellow RN, Hansa yellow R, benzidine yellow, benzidine yellow G, benzidine yellow GR,
One or more organic pigments such as permanent yellow NCG and quinoline yellow lake can be used.

Examples of magenta transparent pigments include Permanent Red 4R, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Carmine FB, Resole Red, and Permanent Red F5.
One or more organic pigments such as R, brilliant carmine 6B, pigment scarlet 3B, rhodamine lake B, rhodamine lake Y, alizarin lake, and quinacridone red can be used.

As the transparent cyan pigment, for example, one or more organic pigments such as Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue and fast sky blue can be used.

Here, the transparent pigment means a pigment which, when dispersed in a transparent vehicle, gives a transparently colored ink.

As the black pigment, for example, one or more of inorganic pigments such as carbon black having an insulating property and conductivity and organic pigments such as aniline black can be used.

In addition to the above-mentioned components, a dispersant and the like can be appropriately blended in the heat-meltable ink layer in the present invention.

The hot-melt ink layer in the present invention is dissolved in a solvent which dissolves an epoxy resin or dispersed in a solvent which does not dissolve an epoxy resin, and further contains a colorant, a spherical silica powder and / or a mica powder, and the like. The additive can be dissolved and dispersed to prepare a coating solution, and the coating solution is applied onto a substrate and dried.

The coating amount of the heat-meltable ink layer in the present invention (in terms of solid content, the same applies hereinafter) is usually 0.02 to 5 g / m.
² , more preferably 0.5 to 3 g / m ² .

Examples of the substrate include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polybutylene naphthalate and polyarylate film, polycarbonate film, polyamide film, aramid film, polyether sulfone film, Polysulfone film, polyphenylene sulfide film, polyetheretherketone film,
A polyetherimide film, a modified polyphenylene ether film, a polyacetal film, and various plastic films which are generally used as a film for a substrate of an ink ribbon of this type can be used. Also, high-density thin paper such as condenser paper can be used. The thickness of the substrate is usually about 1 to 10 μm, and the range of 1 to 6 μm is preferable from the viewpoint of reducing thermal diffusion and enhancing resolution.

When the thermal transfer recording material of the present invention is used in a thermal transfer printer equipped with a thermal head, a silicone resin, a fluororesin, a nitrocellulose resin, or the like is formed on the back surface of the base material (the surface on the side in sliding contact with the thermal head). It is necessary to provide a conventionally known stick-preventing layer made of various heat-resistant resins modified by, for example, silicone-modified urethane resin, silicone-modified acrylic resin, or a mixture of these heat-resistant resins with a lubricant. preferable.

The thermal transfer recording material of the present invention includes a thermal transfer recording material for forming a single color image and a color thermal transfer recording material for forming a multicolor or full color image by utilizing subtractive color mixture. Be done.

A thermal transfer recording material for forming a monochromatic image is a monochromatic thermofusible ink layer provided on a substrate. As the color of the heat-fusible ink layer, black, red, blue,
Examples include green, yellow, magenta, and cyan.

One embodiment of a color thermal transfer recording material for forming a multicolor or full color image is
On a single substrate, a yellow heat-meltable ink layer, a magenta heat-meltable ink layer, a cyan heat-meltable ink layer, and, if necessary, a black heat-meltable ink layer are arranged side by side. . There are various modes for arranging the ink layers of the respective colors, which are appropriately selected according to the type of the printer.

FIG. 1 is a partial plan view showing an example of the thermal transfer recording material of the above embodiment. In FIG. 1, on a single substrate 1, a yellow heat-fusible ink layer 2Y, a magenta heat-fusible ink layer 2M, and a cyan heat-fusible ink layer 2C are arranged side by side. The ink layers 2Y, 2M, and 2C each have a fixed size, and are arranged in the longitudinal direction of the base material 1 repeatedly in a fixed order as one repeating unit U. The order in which the three color ink layers are arranged in the repeating unit U is appropriately determined according to the transfer order of each color. A black ink layer may be added to the repeating unit U.

Another embodiment of a color thermal transfer recording material for forming a multicolor or full color image is 1
Of a first heat-meltable ink layer provided on one substrate
Thermal transfer recording material, a second thermal transfer recording material having a magenta heat-fusible ink layer provided on another substrate, and a third thermal transfer having a cyan heat-fusible ink layer provided on another base material It consists of a recording material and, if necessary, a fourth set of thermal transfer recording material provided with a black heat-meltable ink layer on another substrate.

When the thermal transfer recording material for color image formation is used, a multicolor or full color image excellent in scratch resistance can be obtained. Furthermore, since the hot-melt ink layers of the respective colors in the present invention have good superposition properties, a color image with good color reproducibility can be obtained.

To form a printed image using the thermal transfer recording material of the present invention, the ink layer of the thermal transfer recording material is superposed on the transferred material, and thermal energy is applied to the ink layer imagewise. A thermal head is generally used as a heat source for applying thermal energy, but any known one such as a laser beam, an infrared flash, and a hot pen can be used.

When the transfer target has a three-dimensional shape that is not a sheet, and the surface is a curved surface, thermal transfer by laser light is advantageous because heat energy can be easily applied.

The formation of a multicolor or full-color image using the thermal transfer recording material for color image formation of the present invention is usually carried out by a thermal transfer printer in accordance with the separated color signals of the multicolor image, that is, the yellow signal, the magenta signal and the cyan signal. , Yellow ink dots, magenta ink dots, and cyan ink dots are sequentially transferred in a predetermined order to form a yellow separated image, a magenta separated image, and a cyan separated image on the image receptor. . The transfer order of the yellow, magenta, and cyan ink dots can be arbitrarily selected. In the case of a normal multi-color or full-color image, a three-color separation image is formed in accordance with the three-color signal, whereas when there are only two color signals, a corresponding two-color separation image is formed.

Thus, (A) a region where a color is developed by subtractive color mixing of at least two kinds of yellow, magenta and cyan, or (B) the region of (A) and yellow, magenta and cyan. A multicolor color image including an area formed by a combination with at least one type of monochrome area can be obtained. Here, the red color is at the overlapping portion of the yellow ink dot and the magenta ink dot, the green color is at the overlapping portion of the yellow ink dot and the cyan ink dot, and the blue color is at the overlapping portion of the magenta ink dot and the cyan ink dot. In addition, a black color is presented at the overlapping portion of the yellow ink dot, the magenta ink dot, and the cyan ink dot.

In the above description, the black color is obtained by superimposing the yellow ink dots, the magenta ink dots, and the cyan ink dots, but it is possible to obtain the black color only with the black ink dots without using the three color ink dots. You can

The black ink dots may be made to have a black color by superimposing them on at least one of yellow ink dots, magenta ink dots, and cyan ink dots, or on at least two of them being superposed.

When a printed image is formed using the thermal transfer recording material of the present invention, the printed image may be directly formed on a target transferred material, but it is previously printed on a sheet-shaped transferred material (image receiving material). After forming an image, the image-receiving member may be attached to a target transfer-receiving member by an appropriate means such as an adhesive.

[0065]

Next, the present invention will be described with reference to examples.

Examples 1 to 8 and Comparative Examples 1 to 4 A 5 μm thick polyethylene terephthalate film was coated on one side with a stick-preventing layer made of a silicone resin and having a coating amount of 0.25 g / m ² , and on the opposite side, Table 1 Apply the ink coating liquid shown in 1), dry at 70 ° C, and apply 2
A heat-meltable ink layer of g / m ² was formed to obtain a heat transfer recording material.

In Table 1, the average particle diameters of the spherical silica powder and the mica powder were measured with a laser diffraction particle size distribution analyzer SALD-1100 manufactured by Shimadzu Corporation.

[0068]

[Table 1]

Using each of the above-mentioned thermal transfer recording materials, silver namema manufactured by Lintec Co., Ltd. (aluminum was vapor-deposited on one side of a polyester film) by a thermal transfer type bar code printer (B-30 manufactured by Tech Co., Ltd.), and an adhesive was applied on the silver namemer. A bar code pattern is printed on a layer-provided one, which is printed on the surface of a polyester film) under the following conditions, and the obtained printed image has transferability, scratch resistance (clocking resistance, smear resistance). Sex) was evaluated.

Applied energy: 22.6 mJ / mm ² Printing speed: 2 inches / second Platen pressure: Strong The results are shown in Table 2.

[Transferability] RJS for the obtained printed image
Reading was determined by a bar code reader (CODER SCAN II) manufactured by ENTERPRISES, INC. The criteria for the barcode reader are as follows.

○ It is completely readable. △ Partially readable. × Unreadable.

[Scratch Resistance (Clocking Resistance)] Under the conditions shown below, the printed image after the test was read by a bar code reader in the same manner as described above.

Testing machine: A. Atlas Electric Device Co. A. A. T. C. C. Crockmeter Model CM-1 Friction material: Cotton cloth Pressure: 500 g / cm ² times: 300 times reciprocation [Scratch resistance (smear resistance)] The same as the above for the printed image after the test under the following conditions. The reading was judged by a code reader.

Test machine: Love tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. Friction material: Corrugated cardboard Pressure: 250 g / cm ² times: 300 reciprocations

[0076]

[Table 2]

[0077]

INDUSTRIAL APPLICABILITY The thermal transfer recording material of the present invention provides an image having excellent transferability and scratch resistance, and is useful for printing bar codes and the like.

[Brief description of the drawings]

FIG. 1 is a partial plan view showing an example of the arrangement of ink layers of each color in an embodiment of the thermal transfer recording material of the present invention.

[Explanation of symbols]

 Reference Signs List 1 base material 2Y yellow ink layer 2M magenta ink layer 2C cyan ink layer

Claims (2)

[Claims] 1. A substrate comprising an epoxy resin, a colorant, and spherical silica powder and / or mica powder, wherein the epoxy resin is tetraphenolethane tetraglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A diglycidyl. A thermal transfer recording material comprising a heat-meltable ink layer containing 50% by weight or more of one or more resins selected from the group consisting of ether and bisphenol F diglycidyl ether. 2. The thermal transfer recording material according to claim 1, wherein the content of the spherical silica powder and / or the mica powder in the hot-melt ink layer is 5 to 70% by weight.