JPH02182486A - Heat transfer recording sheet - Google Patents

Abstract

PURPOSE:To print in a matte without gloss easily without reducing printing quality and transfer density by incorporating two types or more of resins of nonsolubility or partial solubility of heat fusible inks so that the resins respectively become island phase and sea phase, and selectively retaining the island phase in a base material at the time of heat transfer printing. CONSTITUTION:A heat transfer recording sheet contains two types or more resins of nonsolubility or partial solubility with heat fusible ink, and the resins cause microphase isolation to form an island and structure. The rein for forming the island phase desirably includes, for example, saturated polyester resin or polyamide resin of dimer acid base, and the resin for forming the sea phase desirably includes, for example, olefin resin such as polyethylene, polypropylene, polybutene, etc. The resin for forming the island phase has excellent adhesive with a polyester film of a base material, and the resin for forming the sea phase has excellent adhesive to an image receiving sheet. As a result, the heat application of the heat transfer recording sheet, i.e., the peeled part (aggregation breakage) is roughed to generate matte of a printing face.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal transfer recording sheet that provides matte printing without gloss. More specifically, the present invention relates to a thermal transfer recording sheet that provides matte-like printing, excellent adhesion between the base material and ink, and high-quality printed images.

[Conventional technology]

In recent years, thermal transfer recording, in which a complete image is formed on plain paper using a thermal printer, thermal facsimile, etc., has been actively developed. This thermal transfer recording is relatively easy to maintain due to its simple device mechanism, and has low price and maintenance costs. It also uses low energy to produce clear and durable recordings, and uses multi-colored ink sheets, making it relatively easy to maintain. It has been widely used recently because color recording is easily possible.

In particular, the usage of monochrome type thermal transfer recording sheets is increasing due to the spread of thermal printers for word processors, thermal facsimile machines, and the like.

However, printed images recorded by thermal printers generally have high gloss. In multi-color recording, as in fields such as graphic design and full-color copying, in addition to the precision of the recording, beauty is also required, and the glossiness of the image greatly contributes to these characteristics. nru.

On the other hand, monochrome type records are often used in areas such as character recording and copying. In this case, when it comes to reading printed images, the higher the gloss, the more fatigue the human eye feels, and this is one of the points to be improved in thermal transfer recording. That is, in monochrome type thermal transfer recording, there is a strong demand for matte printing without gloss.

In response to such a situation, there are many known techniques for thermal transfer recording that provides smooth, matte printing.

For example, as in Japanese Patent Application Laid-Open No. 60-101084, the surface of the base film on the side where heat-melting ink/[1- is to be provided is matted by Sandgelast treatment, or by kneading fine particles and forming a film. discloses a method to do so.

Further, as in Japanese Patent Application Laid-Open No. 56-164891, a method is disclosed in which a matting agent is completely mixed into a heat-melting thermal ink.

Furthermore, Japanese Patent Application Laid-Open No. 101083/1983 discloses a method of providing a matte layer on a base film.

In addition, Japanese Patent Application Laid-Open No. 62-263090 is cited as a transfer type heat-sensitive recording material capable of obtaining halftones. Here, the transfer type thermosensitive recording material is constructed to include a resin A having a strong adhesive strength with a base material and a resin B having a weak adhesive strength.

When the base material is a polyester film, the resin A is at least 1 m selected from the group of saturated polyester, ethylene/vinyl acetate copolymer resin, and 7 silicone resins, and the resin B is vinyl chloride/acetic acid. At least one type selected from the group of vinyl copolymer resin, vinyl acetate resin, acrylonitrile/phenol copolymer resin, and acrylonitrile/styrene copolymer resin is exemplified.

However, in the cited example, the objective is to achieve high image quality and high constant layer property, but it is concerned with the fixing property due to abrasion of the recording material on the image receiving paper after transfer.

That is, in the transfer-type heat-sensitive recording material of the cited example, resins A and B are both peeled off from the base material during transfer, and one of the resins is intended to have high fixability. Further, in the cited example, halftones are given, and in the examples, all ink coatings are solvent coatings.

[Problems to be Solved by the Invention] The patent publications cited in the above-mentioned prior art have various problems.

The method of sandblasting the surface of the base film has the drawbacks of reduced strength of the film itself and increased cost. Fine particles? The method of kneading and forming a film has the disadvantage that the degree of matting cannot be increased unless a large amount of fine particles are kneaded.

In addition, in the method of mixing a matting agent into the ink, the matting agent is generally a white inorganic pigment, and if a small amount of matting agent is used, it is difficult to produce a matting effect, whereas if a large amount is added, the print quality and transfer density will be affected. The disadvantage is that a decrease in

Furthermore, in the method of forming a matte layer on a base film, the matte layer ink is a material consisting of a binder and an inorganic pigment, and in order to produce a matting effect, it is necessary to increase the matte depth of the matte layer. There is a drawback that the particle size of the inorganic pigment must be increased or the total amount used must be increased.

[Means to solve all problems]

The present invention provides a thermal transfer recording sheet 1 which solves all the conventional drawbacks and provides matte printing without gloss.

That is, the thermal transfer recording sheet provided by the present invention is as follows:
2 The heat-melting inks are incompatible or partially compatible with each other
The resin in the heat-melting ink undergoes microphase separation to form an island-sea structure, which is an unrestricted mixture state, and the resin becomes an island phase and an S phase, respectively, and the thermal transfer It is characterized in that the island phase selectively remains on the base material during printing.

The resin forming the island phase has a melt viscosity of 5 at 120°C.
It is a saturated polyester resin with a poise of 0 poise or less, and the resin forming the groove phase is one or more selected from the group of olefin resins such as polyethylene, polypropylene, and polybutene, or their derivatives, and the heat-melting ink is In the formulation, the saturated polyester resin is contained in an amount of 10 to 40 percent by weight, and the olefin resin gold is contained in an amount of 40 to 70 percent by weight. It is a dimer acid-based polyamide resin with a poise of 50 poise or less, and the resin forming the groove phase is one or more selected from the group of orange-based resins such as polyethylene, polypropylene, and polybutene, or derivatives thereof. In the formulation of the heat-melting ink, the polyamide resin has a total content of 10 to 10%.
It is characterized by containing 40% by weight of the vinyl resin and 40 to 70% by weight of the vinyl resin.

Further, it is characterized in that the base material is a polyester film.

Furthermore, the thermal transfer recording sheet and the image receiving paper? The printed image obtained by thermal transfer recording in combination is a matte printed image, and the matte printed image has a 60 degree specular Motozawa degree (hereinafter referred to as glossiness) measured by the specular gloss measurement method specified in JIs Z8741. ) 30 or less.

The present invention will be explained in detail below.

The thermal transfer recording sheet of the present invention is made by coating a heat-melting ink on one side of a base material, and is combined with an image receiving paper to print a thermal head. When printed using this method, a matte-like printed image with no gloss is produced on the image-receiving paper.

In addition, the thermal transfer recording sheet of the present invention has other advantages in that it has excellent adhesion to the substrate and printability that allows high-quality printed images to be obtained.

That is, the purpose of the thermal transfer recording sheet of the present invention is to provide matte printing properties without gloss.

In the present invention, the achievement of the above object is considered to be related to the state at the interface between the heat-melting ink applied to the base material of the thermal transfer recording sheet and the base material.

In the case of normal thermal transfer recording, the heat-melting ink applied to the substrate is completely peeled off from the substrate and transferred to image-receiving paper. Since the base material generally has a highly smooth interface like a mirror surface, the next printed image that is transferred to the receiver paper will reflect the surface condition of the base material and will be glossy. Can you make full use of this idea to get money from matte printing? The method aimed at is the method of providing matte Mk on a substrate according to the above-mentioned nine examples disclosed in Japanese Patent Application Laid-open No. 101083/1983. Here, by reproducing the state of the matte layer on the bottom surface of the printed image, matte-like printing is provided.

In contrast to such methods, in the present invention, when the thermal transfer recording sheet and image receiving paper are peeled off after thermal printing, complete peeling is achieved between the base material surface of the thermal transfer recording sheet and the heat-melting ink. The heat-fusible ink itself undergoes total cohesive failure (between the thermal transfer recording sheet and the image receiving paper, it breaks and peels off), and the surface of the transferred printed image becomes matte-like by breaking and peeling. It is.

More specifically, in the thermal transfer recording sheet of the present invention, the heat-melt ink contains two or more resins that are incompatible or partially compatible with each other, and the resins in the heat-melt ink cause microphase separation. It forms an island-sea structure, which is a state of unrestricted and mixed conditions.

Although the exact reason is not clear, the resin forming the island phase has excellent adhesion to the polyester film that is the base material, and the resin forming the groove phase has excellent adhesion to the receiver paper. In the V-melted ink due to the heat from the Searle head, near the interface with the base material, the island phase resin, which has excellent adhesive strength with the base material, selectively migrates to the base material side and forms a friendly state. , so-called non-uniform interfaces within the ink no.

After thermal printing, the thermal transfer recording sheet is overlaid and peeled off from the image-receiving paper. At this time, peeling occurs at uneven interfaces within the ink layer. (Destruction) The raised area has irregular irregularities, so-called roughened surface n7, and it is thought that the printed surface becomes matte. In addition, it is thought that the minute irregularities of the island phase resin remaining on the base material also promote the matting of the printed surface.

Based on this principle, the thermal transfer recording sheet of the present invention can provide matte printing without gloss. The purpose of the present invention can be achieved as long as the material constituting the island phase is a heat-fusible material that has a high adhesive strength to the base material, but saturated polyester resins and dimer acid-based polyamide resins are particularly preferred in the present invention.

These have adhesive strength with the base material, and as the molecular weight increases, the adhesive strength increases, but as the molecular value increases, the softening point and melt viscosity also increase, and the black phase in the hot melt ink increases. It becomes difficult for the island-sea structure, which is the unrestricted-basin state that occurred, to fully form.

In the heat-melting ink of the present invention, the resin forming the island phase is 1
A saturated polyester resin having a melt viscosity at 20° C. of 50 poise or less, or a lurid or dimer acid-based polyamide resin is desirable. At this time, the resin forming the island phase is preferably one or more selected from olefin resins such as polyethylene, polypropylene, and polybutene, or their rust conductors, from the viewpoint of compatibility, melt viscosity, and softening point. .

By the way, the reason why the resin content of the thermally meltable ink of the present invention is outside the specified range can be explained as follows. When the amount of the island phase resin is less than the lower limit of 10% by weight, the absolute amount of the resin that migrates to the substrate side during thermal printing is small, and the formation of a nonuniform interface is insufficient, so that cohesive failure does not occur. That is, since the surface of the base material is reproduced as it is, first, the printed image becomes glossy, which is not suitable for the purpose of matte printing of the present invention. In addition, if it is larger than the upper limit of 40ifi percent, the melt viscosity of the entire ink increases,
tm, because the adhesive force between the hot melt ink and the base material is too thick,
When the thermal transfer recording sheet and image receiving paper are peeled off after heating printing, cohesive failure occurs within the ink layer, but the amount of ink remaining on the thermal transfer recording sheet after peeling is large, and the printing quality is significantly reduced.

In the present invention, the printed image obtained by thermal transfer recording by combining a thermal transfer recording sheet and an image receiving paper is JIS Z8.
? It is desirable that the matte printed image has a 60 degree specular gloss of 30 or less as measured by the specular gloss measurement method specified in No. 41. When the glossiness is higher than 30, it does not meet the purpose of the matte printed image of the present invention and tends to give a feeling of visual fatigue.

Next, the materials used will be explained in more detail.

The base material can be thin paper such as capacitor paper, typewriter paper, tracing paper, sosei paper, cellophane paper, or even synthetic resin film such as polyester film, polyimide film, polyethylene film, polycarbonate film, Teflon film, etc. Alternatively, the thermal head is used after being heat-resistant treated to prevent a glaze layer from forming.

Among these examples, polyester film is particularly preferred for the purpose of the present invention.

The ink used in the heat-melting ink layer of the present invention includes a heat-melting substance, a colorant, a binder, a softener, etc.
However, when using it, you can use it according to your needs.

Island phases and resins that form island phases include polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins, polyvinyl resins, polyvinyl chloride resins, cellulose resins, and polyvinyl alcohol. Examples thereof include saturated polyester resins, petroleum resins, terpene resins, polystyrene resins, polyolefin resins, and nidistomers, but those suitable for the purpose of the present invention are particularly saturated polyester resins, polyamide resins, and Olefin resins or derivatives thereof are desirable. However, this does not limit the use of the above-mentioned materials in combination with other waxes, such as rice wax, wood wax, candelilla wax,
Vegetable waxes such as carnauba wax, animal waxes such as lanolin, beeswax, spermaceti wax, shellac wax, mineral waxes such as montan wax, osikelite, shellac, petroleum waxes such as paraffin wax, microcrystalline wax, oxidation Examples include paraffin wax, synthetic hydrocarbon waxes such as low-molecular polyethylene, and fatty acid amide waxes such as ricinoleamide, lauric acid amide, erucic acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, and ethylene bisstearic acid amide. be able to.

Metallic soaps include sodium stearate, sodium palmitate, potassium laurate, potassium myristic, calcium stearate, zinc stearate,
Examples include metal salts of higher fatty acids such as aluminum stearate and magnesium stearate.

Coloring agents include dyes and pigments such as oil bath dyes, disperse dyes, and colored pigments, which may be selected depending on the need. Specific examples are given below, but are not limited to these and include only 2.
It may be used in combination with more than one building.

Oil-soluble dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, and 7-talocyanine dyes. To give a more specific example, the azo dye is Solvent Yellow 2 (C, 1, 11020, hereinafter in parentheses indicates C, I At-) Solvent Orange 1
(11920), Solvent Red 24 (26105)
, Solvent Brown 3 (11360), etc., and Solvent Yellow 19 (1390) as an azo metal complex dye.
0A), Solvent Orange 5 (18745A), Solvent Red 8 (12715), Solvent Brown 3
7. Solvent Black 123 (12195) etc.
Solvent violet 1 is an anthraquinone dye.
3 (60725), Nrupentozu 4/, 7i□i (6!
Solvent Blue 25 (61565) is a phthalocyanine dye.
74350) etc. 〇 Examples of disperse dyes include aminoazo, aminoanthraquinone dyes, and nidroarylamine dyes. To give a more specific example, the aminoazo dye is Disverse Yellow 3 (C, zl, 11855, hereinafter C, I in parentheses).

), Disbirds Orange 3 (11005),
Disbirds Red 1 (11110), Disbirds Violet 24 (11200), Dispersion Blue 4
There are 4 etc. Aminoanthraquinone dyes include Disbirds Orange 11 (60700), Disbirds Red 4 (60755), Disbirds Violet 1 (
61100) and Disperse Blue 3 (61505).

Examples of nidroarylamine dyes include Dis, +-Zuerrow 1 (1θ345) and 42 (IQ338).

Colored pigments include azo pigments (seven azo, bisazo, and azo pigments), dyeing lake pigments (acidic dye lakes, basic dye lakes, and mordant dye lake pigments), nitro pigments, nitrone pigments, phthalocyanine pigments, and high-grade pigments. Examples include (infectious dye pigments, gold-M complex salt pigments, color pigments, isoindolinone pigments, quinacridone pigments), etc. To give a more specific example, examples of azo pigments include No Nzaero G (C, 1, 11680, hereinafter C,
1.Ku? ), Hansa Yellow R (12710), Pyrazolone Red B (21120), Nokuichi Manent Red R (12085), Lake Red C (15585), Brilliant Carmine 6B (15850), Permanent Amine FB (12490) C or higher monoazo pigment), Benzidine Yellow G (21090), Benzidine Yellow G
R (211o0), Permanent Yellow NCR (200
40) (the above bisazo pigments), chromophthal yellow,
Examples include chromophthalic red (azo pigment).

As a dyeing lake pigment, quinoline yellow lake (47
005), Nio7 Lake (45380), Alkaline Blue Lake (42750A, 42770A) (above acid dye lake pigments) Rhodamine Lake B (45170),
Meternoku Iolet Lake (42535), Victoria Blue Lake (44045), Malachite Green Lake (42000) C or higher basic dye lake pigment), Alizarin Lake (58000) (mordant dye lake pigment)
and so on. Naphthol Yellow 5 (1) as a nitro pigment
0316), Pigment Green B as a nitrone pigment
(10006), Naphthol Clean B (10020)
, as phthalocyanine pigments, metal-free 7 thalocyanine blue (74ioo), phthalocyanine blue (741
60) and Phthalocyanine Green (74260). As a high-grade pigment, anthrapyrimidine yellow (
6B420), Zundanslen Brilliant Orange G
K (59305), Indus Stretch λ-R8 (69800), Chikuindigo Red B (733
00) (vat dye pigments), nickel azoero=(
12775) metal complex salt pigment), Tokirylene Red (711
40), -4'J Len Scarlet (71137) (perylene pigment), Isoindolinone Yellow (inindolinone pigment), Quinacridone Red Y (46500)
, quinacridone magenta (73915), etc. In addition, carbon black (C) is used as a black pigment.

1.77265).

As the binder, either a water-bathable binder or a non-water-bathable binder can be used.

Specific examples of such binders are illustrated below, but the binder is not limited thereto, and two or more types may be used in combination.

As the binder, for example, polyvinyl alcohol,
Methylcellulose, gelatin, hydroxyethylcellulose, carboxymethylcellulose, gum arabic, starch and its bound conductor, casein, polyvinylpyrrolidone, butyral resin, ethylene ethyl acrylate, styrene-butadiene copolymer, vinyl acetate resin, vinyl acetate copolymer , acrylic resin, methyl methacrylic resin, styrene/acrylonyl tri, ethylene-vinyl acetate compound, polyester 4] resin, petroleum resin, and the like.

Examples of softeners include mineral oil, dibutyl phthalate, dioctyl phthalate, mineral spirit, liquid paraffin, and the like.

In addition to the heat-melting substances, colorants, binders, and softeners listed above, additives such as surfactants, dispersants, antistatic agents, antioxidants, and ultraviolet absorbers may be added.

In the thermal transfer recording sheet of the present invention, the heat-melting ink If
Coating machines used to coat the substrate include known coaters such as hot melt coaters, air knife coaters, roll coaters, blade coaters, and bar coaters, as well as flexography, gravure, etc. Known printing machines may also be used.

For coating the # agent, a general bath agent can be used, and for example, methanol, ethanol, isopropyl alcohol, toluene, methyl ethyl ketone, acetone, ethyl acetate, etc. can be used as appropriate.

The thickness of the heat-melting ink layer formed on the base material is 1 to 15
μ vortex preferably 2-10sv+a, more preferably 3-10sv+a
[Function] The thermal transfer recording sheet according to the present invention is composed of two or more resins that are incompatible or partially compatible with each other, and the resins in the heat-melt ink cause microphase separation. The main feature is that the heat-melting ink layer is entirely coated to form an island f6 structure in a non-uniformly mixed state.

The thermal transfer recording sheet of the present invention having such a characteristic sound can obtain a matte-like printed image with low gloss on the receiving paper, and also has excellent adhesion between the base material and the ink and high quality. The effect of not being able to obtain a printed image? Motsu.

Hereinafter, the present invention will be specifically explained with reference to Examples. still,
Is "%" in the examples a heavy ik percentage? [Example] Example 1 As an island phase resin, molecular 77000, melting point 81 ° C., 120
All polyester resins with a melt viscosity of 40 poise at °C were used, and the primary and island phase resins were molecules [5
000, using all polyethylene resin with a melting point of 100℃, each material with the following composition t Sand Grinding at 130℃
At a temperature of 1 minute (i? 2 hours), a heat-melting ink was obtained.
．． Obtained on the non-coated side of the polyester film with 2μ grooves
A hot melt ink layer was applied using the hot melt ink using a hot melt coater to a coating thickness of 4 μm to obtain a thermal transfer recording sheet.

Carbon black 15% saturated polyester resin 40% polyethylene resin
40% petroleum resin (melting point near 0℃) 5
% In this way, we obtained a thermal transfer recording paper (manufactured by Mitsubishi Paper Mills, product name: TTR-T).
When superimposed on the paper and printed characters and solids at 1.3 mJ/dos using Matsushita Electronics' mH thermal head printing system, a clear and matte-like printed image was obtained on the receiving paper. The layering properties between the material and the ink were also excellent.

The evaluation results are shown in Figure 1.

Example 2 A hot-melt ink using the same material as in Example 1 and having the following composition? A thermal transfer recording sheet was obtained by coating, and printing was carried out in the same manner as in Example 1. The evaluation results are shown in Cloth 1.

Carbon black 15% saturated polyester resin 20% polyethylene resin
60% petroleum resin (melting point 70°C) 5% Example 3 As island phase resin, molecule f4000, melting point 75°C, 120
A saturated polyester resin having a melt viscosity of 25 poise at °C was used, the same polyethylene resin as in Example 1 was used as the island phase resin, and a heat-melting ink having the same formulation as in Example 1 was coated for thermal transfer. Recording Sea)k Obtain, Example 1
Print the length in the same manner as above.

The evaluation results are shown in Cloth 1.

Example 4 The same saturated polyester resin as in Example 1 was used as the island phase resin. The island phase resin used has a molecular weight of 3000 and a melting point of 7.
A thermal transfer recording sheet was obtained by using an olefin resin derivative consisting of a copolymer of α-olefin and maleic anhydride at 0°C and applying a heat-melting ink having the following composition, and the same procedure as in Example 1 was carried out. The 0 evaluation result for printing is shown in 1.

Carpump Chic 15% saturated polyester resin 40% saturated resin derivative
40% petroleum resin (melting point 70°C) 5% Example 5 The same saturated polyester resin as in Example 1 was used as the island phase resin, and as the island phase resin, molecule t9ooo, 8 points 7
The same procedure as in Example 4 was carried out using all the olefin resin derivatives made of a copolymer of α-olefin and maleic anhydride at 0°C.
Printing was carried out in the same manner as in Example 1 using thermal transfer recording 7-7 using a blended heat-melting ink. The evaluation result is fi
Comparative Example 1 All of the same materials as in Example 1 were used, and a heat-melting ink having the following formulation was applied, and printing was carried out in the same manner as in Example 1 on a thermal transfer recording sheet.

The evaluation results are shown in Table 1.

Carbon black 15% saturated primary polyester resin 5% polyethylene resin
75% petroleum resin (melting point 70°C) 5% Comparative Example 2 All the same materials as in Example 1 were used, all of the heat-melt ink was coated with the following formulation, and the whole book was printed on a thermal transfer recording sheet in the same manner as in Example 1. did.

The evaluation results are shown in Table 1.

Carbon black 15% saturated polyester resin 60% polyethylene resin
20% petroleum resin (melting point 70℃) 5%
Comparative Example 3 As the island phase resin, molecule fil O000, melting point 90°C,
A saturated polyester resin with a melt viscosity of 60 poise at 120° C. was used, the same polyethylene resin as in Example 1 was used as the island phase resin, and the heat-melt ink with the same formulation as in Example 1 was completely coated. A thermal transfer recording sheet 1f was obtained and printed in the same manner as in Example 1.The evaluation results are shown in Table 1.

Example 6 As an island phase resin, molecular 72000. lfi point 89℃, 1
A polyamide resin with a melt viscosity of 45 poise at 20°C was used, and the same polyethylene resin gold as in A1 Example 1 was used as the island phase resin, and the heat-melt ink gold was coated with the following composition to make a thermal transfer self-recording sheet. The entire book was printed in the same manner as in Example 1.

The evaluation results are shown in 2.

Carbon blank 15% polyamide resin 40% polyethylene resin
40% petroleum resin (melting point 70℃) 5%
Example 7 Using the same material as in Example 6, a thermal transfer recording sheet tf was obtained by coating the entire sheet with heat-melting ink having the following formulation, and printing was carried out in the same manner as in Example 1.

The rod value results are shown in Thorn 2.

Carbon black 15% polyamide resin 20% polyethylene resin
60% petroleum resin (melting point 70.”C)
5% pJ Meishi #8 As island phase resin, molecule fil O00, melting point 89℃, 1
A polyamide resin with a melt viscosity of 30 poise at 20°C was used, the same polyethylene resin as in Example 1 was used as the island phase resin, and a heat-melt ink with the same formulation as in Example 6 was applied to perform thermal transfer recording. A sheet was obtained and printed in the same manner as in Example 1.

The evaluation results are shown in Cloth 2.

implementation? lJ9 The same polyamide resin as in Example 6 was used as the island phase resin, all the same olefin resin derivatives as in Example 4 were used as the island phase resin, and a hot melt ink with the following formulation was applied. A thermal transfer recording sheet was obtained and printed in the same manner as in Example 1.

The evaluation results are shown in Table 2.

Carbon black 15% polyamide resin 40% resin derivative
4094 petroleum resin (melting point 70℃) 5
% Example 10 The same polyamide resin as in Example 6 was used as the island phase resin, the same olefin resin or conductor as in Example 5 was used as the island phase resin, and the heat treatment with the same formulation as in Example 9 was used. A thermal transfer recording sheet was obtained by completely applying the meltable ink, and printing was carried out in the same manner as in Example 1.

The evaluation results are shown in Precept 2.

Comparative Example 4 Using the same material as in Example 6, a thermal transfer recording sheet was obtained by completely coating the heat-melting ink with the following formulation, and printing was carried out in the same manner as in Example 1.

The evaluation results are shown in Table 2.

Carbon black 15% polyamide resin 5% polyethylene resin
75% petroleum resin (melting point 70℃)
5% Comparative Example 5 A thermal transfer recording sheet was prepared by using the same material as in Example 6 and fully coating the heat-melting ink with the following formulation. 7 tons were printed in the same manner as in Example 1.

The evaluation results are shown in Table 2 and are 7t.

Carbon black 15% polyamide resin 60% polyethylene resin
20% petroleum resin (melting point 70℃) 5
% Comparative Example 6 As island phase resin, molecule 115000, melting point 107°C, 1
A polyamide resin with a melt viscosity of 65 poise at 20°C was used, and the same polyethylene resin as in Example 1 was used as the Kushima phase resin, and the heat-melt ink with the same formulation as in Example 6 was applied. A thermal transfer recording sheet was obtained, and printing was carried out in the same manner as in Example 1.

The evaluation results are shown in Table 2.

Evaluation method ■ Glossiness evaluation method Measure the 60 degree specular gloss specified by JIS Z8741 using a glossmeter (Nippon Denshoku Kogyo NG, product name: ND-1001)
DP).

(2) Ink + lB Adhesive Thermal Transfer Recording Sheet)'kl The film was grasped by hand 0 times to observe the peeling tL of the heat-melting ink layer from the base material.

■Printability Thermal transfer recording paper (Mitsubishi Paper @ Back, Product name: TTR-
On the thermal transfer recording sheet of Example 1, the character pattern and solid printing were performed using an under-desk Paneriko parts-shu thermal head printing device at an applied energy of L3 mJ/dot, and the ink dense layer on the base material was visually observed. It has excellent properties and produces clear, matte-like printed images.

The thermal transfer recording sheet of Example 2 had a saturated polyester resin content of 20% in the thermal transfer recording sheet of Example 1.
Toshifc, case, has excellent ink adhesion to the substrate,
A clear and matte printed image was obtained. The thermal transfer recording sheet of Example 3 uses a lower molecular weight saturated polyester resin than the second saturated polyester resin used in the thermal transfer recording sheet of Example 1, and has superior ink layer density to the base material.
, a clear and matte 5M printed image was obtained n 7t .

The thermal transfer recording sheet of Example 4.5 has excellent ink adhesion to the substrate by using olefin resin derivatives with different molecular weights in place of the polyethylene resin used in the thermal transfer recording sheet of Example 1. , a clear and matte-like printed image can be obtained.

In the thermal transfer recording sheet of Comparative Example 1, the saturated polyester resin distribution i' in the thermal transfer recording sheet of Example 1 was set to 5% and 7? In this case, the island-sea structure, which is a non-uniformly mixed state, is insufficiently formed in the heat-fusible ink, that is, the formation of the island-sea structure in the heat-fusible ink layer between the island phase resin and the island phase resin is insufficient. The ink was not formed sufficiently, the ink adhesion to the substrate was poor, and the printed image was also glossy.

The thermal transfer recording sheet of Comparative Example 2 has a saturated polyester resin content of 60% in the thermal transfer recording sheet of Example 1, and the melt viscosity of the ink is increased and the ink layering force on the substrate is strong. Because it is too much, there are many white spots and scratches on the printed surface, and the printing performance is poor.

The thermal transfer recording sheet of Comparative Example 3 was obtained by using a high molecular weight saturated polyester resin instead of the saturated polyester resin used in the thermal transfer recording sheet of the example.
It was not possible to prepare an ink due to the high melt viscosity.

The thermal transfer recording sheet of Example 6 had excellent ink adhesion to the substrate, and a clear and matte printed image was obtained. The thermal transfer recording sheet of Example 7 has a polyamide resin content of 20% in total as in the thermal transfer recording sheet of Example 6, and has fn in ink adhesion to the substrate and a clear and matte printed image. The thermal transfer recording sheet of Example 8 is made of a polyamide resin with a lower molecular value than the polyamide resin used in the thermal transfer recording sheet of Example 6, and has superior ink adhesion to the substrate. A clear and matte-like printed image was obtained. Example 9.
By using olefin resin derivatives with different molecular weights in the thermal transfer recording sheet No. 10 in place of the polyethylene resin used in the thermal transfer recording sheet of Example 6,
The ink had excellent adhesion to the substrate, and a clear and matte printed image was obtained.

The thermal transfer recording sheet of Comparative Example 4 is the same as the thermal transfer recording sheet of Example 6, in which the polyamide resin content per 1 ft is 5%. The adhesion of the ink to the substrate was poor, and the printed image was also glossy.

The thermal transfer recording sheet of Comparative Example 5 is the same as the thermal transfer recording sheet of Example 6 in which the polyamide resin content is 60% gold, and the melt viscosity of the ink increases, and sufficient dispersion and mixing cannot be performed. It was also not possible to coat the surface.

In the thermal transfer recording sheet of Comparative Example 6, a high molecular weight polyamide resin was used in place of the polyamide resin used in the thermal transfer recording sheet of Example 6, and the melt viscosity was so high that it was impossible to prepare an ink. [Effects of the Invention] As described above, the thermal transfer recording sheet of the present invention has lower gloss of printed images and superior matte printability than conventional thermal transfer recording sheets, and is of extremely high industrial significance. be.

[Brief explanation of the figure]

FIGS. 1 and 2 are micrographs (400 times magnification) of the ink-coated surfaces of the thermal transfer recording sheets of Example 1 and Comparative Example 1, respectively. In the figure, the white part is the island phase resin, and the black part is the island phase resin.

In FIG. 1, it is clear that the entire island-sea structure is formed due to the microphase separation according to the present invention. On the other hand, in Figure 2, it can be seen that the formation of the island-sea structure is insufficient.

Claims (7)

[Claims] (1) In a thermal transfer recording sheet formed by coating a heat-melting ink on one side of a base material, the heat-melting ink contains two or more types of resins that are incompatible or partially compatible with each other, and The resin in the ink forms an island-sea structure, which is a heterogeneous mixed state in which microphase separation occurs, and the resin becomes an island phase and a sea phase, respectively, and the island phase selectively remains on the base material during thermal transfer printing. A thermal transfer recording sheet characterized by: (2) The resin forming the island phase is a saturated polyester resin with a melt viscosity of 50 poise or less at 120°C, and the resin forming the sea phase is an olefin resin such as polyethylene, polypropylene, polybutene, or a derivative thereof. The thermal transfer recording sheet according to claim 1, characterized in that it is one or more selected from the group of. (3) The thermal transfer recording sheet according to claim 2, wherein the heat-melting ink contains 10 to 40 weight percent of the saturated polyester resin and 40 to 70 weight percent of the olefin resin. (4) The resin forming the island phase is a dimer acid-based polyamide resin with a melt viscosity of 50 poise or less at 120°C, and the resin forming the sea phase is polyethylene,
Olefin resins such as polypropylene and polybutene,
2. The thermal transfer recording sheet according to claim 1, wherein the thermal transfer recording sheet is one or more selected from the group consisting of: or its derivatives. (5) In the formulation of the hot-melt ink, the amide resin is 10 to 40% by weight, and the olefin resin is 4% by weight.
5. The thermal transfer recording sheet according to claim 4, wherein the thermal transfer recording sheet contains 0 to 70% by weight. (6) The thermal transfer recording sheet according to claim 1, wherein the base material is a polyester film. (7) The thermal transfer recording sheet according to claim 1, wherein the printed surface has a 60 degree specular gloss of 30 or less as measured by a specular gloss measuring method specified in JIS Z8741.