JPH03274187A - Resin type thermal transfer recording material - Google Patents

Abstract

PURPOSE:To improve heat-responding properties of the title material and to make the material accurate and transferable by forming the material through laminating a peeling layer mainly composed of wax and a thermal transfer recording layer containing a resin binder, colorant and antifriction agent on a support and by forming the resin binder from the mixture of specific high-molecular weight and low-molecular weight resins. CONSTITUTION:In a resin type thermal transfer recording material formed by laminating a peeling layer 2 mainly composed of wax and a thermal transfer recording layer 3 containing a resin binder, colorant and antifriction agent in this order on a heatresisting support 1, the resin binder is composed of the mixture of a high-molecular weight resin of 50-110 deg.C glass transition point and 8000 or more molecular weight and a low-molecular weight resin of 60-150 deg.C softening point and 500-5000 molecular weight. Desirably, 20-70wt.% of the high molecular weight resin is contained in the whole quantity of the resin component of the thermal transfer recording layer 3. Under 20wt.%, when the resin is formed into a coating, the coating is low in viscosity so that swimming of the coating occurs in the case of applying said coating. Therefore, it is difficult to form a thermal transfer recording layer 3 with uniform film thickness. Also, when 70wt.% is exceeded, the resulting material deteriorates in heat-responding properties.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a resin-type thermal transfer recording material.

More specifically, it can be transferred to the plastic surface of plastic cards, etc., and can be transferred with high precision (prior technology).On a heat-resistant support, a release layer mainly composed of wax, a resin binder, a colorant, and A resin-type thermal transfer recording material is well known in which a thermal transfer recording layer containing an anti-wear agent is laminated in this order (Japanese Patent Application Laid-open No. 1-141788). A resin having a glass transition point of 50 to 110°C is used as the binder.

For transfer, a transfer recording material is placed on the plastic surface of the transfer target, a thermal head is pressed against the back side of the transfer recording material, and selective heating is performed to soften the thermal transfer layer in the heated area and increase adhesive strength. At the same time, the release layer is melted and fluidized, and only the release layer and the thermal transfer recording layer are transferred. As a result, printing or printing of characters, symbols, figures, etc. becomes possible.

(Problem H to be solved by the invention) However, since the release layer melts at a lower temperature than the softening of the thermal transfer recording layer, when the thermal transfer recording layer softens, not only the release layer in the heated area but also the There was a problem in that the surrounding release layer also melted and was transferred. As a result,
Sufficiently accurate transfer was not possible, and precise image formation was impossible.

Further, when the release layer was heated to such an extent that it melted, the thermal transfer recording layer did not soften, making transfer impossible, and the transfer sensitivity was not sufficient.

(Means for Solving the Problem) In order to solve this problem, the present invention provides a release layer containing wax as a main component, a resin binder, a colorant, and an anti-wear agent on a heat-resistant support. In a resin type thermal transfer recording material in which thermal transfer recording layers are laminated in this order, the resin binder is a high molecular weight resin having a glass transition point of 50 to 110°C and a molecular weight of 8000 or more, and a softening point of 60 to 150°C.
The present invention provides a resin type thermal transfer recording material characterized by being made of a mixture of low molecular weight resins having a molecular weight of 500 to 5000.

The present invention will be explained below with reference to the drawings. FIG. 1 of the drawings shows a sectional view of a resin-type thermal transfer recording material.

As you can see from the diagram. The resin-type thermal transfer recording material of the present invention includes:
It consists of three layers: a support (1), a release layer (2), and a thermal transfer recording layer (3).

The support (1) supports the release layer (2) and the thermal transfer recording layer (3). It requires heat resistance, dimensional stability, and surface smoothness to withstand the heat of the thermal head during transfer and not deform.

Although any plastic film can be used as the support (1), a two-wheel stretched polyester film is commonly used in terms of heat resistance, dimensional stability, and the like. The thickness is 2-1
0 μm is sufficient.

The thermal head comes into contact with the back surface of the support (1), and the thermal transfer recording layer (3) comes into contact with it when it is wound up, so it prevents sticking to the thermal head and prevents prodding when it is wound up. Therefore, the support (
1) It is desirable to provide an anti-sticking layer (11) on the back surface.

As the anti-sticking layer (11), a silicone modified resin is used in which a silicone intermediate condensate having an alkoxy group (methoxy group, ethoxy group, etc.) at the end is condensed with acrylic resin, epoxy resin, polyester resin, acrylic resin, etc. can. For example, KR manufactured by Shin-Etsu Chemical Co., Ltd.
218 etc. Further, the anti-sticking layer (11) may be formed of a mixture of such a silicone-modified resin or a heat-resistant binder such as nitrocellulose and silicone oil. Alternatively, a two-layer anti-sticking layer (11) may be formed by separately applying silicone modified resin and silicone oil.

The anti-sticking layer (11) can be formed by gravure coating, roll coating, reverse coating, etc. to a thickness of 0.1 to 5μ.
It is sufficient to apply it to a thickness of m.

The release layer (2) melts during thermal transfer to facilitate transfer. As described later, the transfer is performed using a thermal transfer recording layer (3).
) becomes a rubber-like fluid state due to the heat of the thermal head, generates adhesive force, and adheres to the surface of the transferred object. If the release layer (2) is not present, the thermal transfer recording layer (3) will also develop adhesive force to the support (1) during this thermal transfer, making transfer difficult.

The release layer (2) needs to be easily melted by heating with a thermal head. For this reason, the melting point is 60~
The main component is wax at 120°C. However, if it is made of wax alone, the support (1) and the release layer (2)
It is desirable to mix a small amount of a resin component with a low softening point because the adhesive strength of the adhesive is poor and the adhesive may fall off inadvertently.

As the wax, paraffin wax, carnauba wax, Montanwa wax, higher fatty acid, higher alcohol, higher fatty acid amide, higher fatty acid ester, etc. can be used.

As the resin having a low softening point, epoxy resin, low molecular weight polystyrene, ethylene-vinyl acetate copolymer, polyamide resin, polyurethane resin, polyester resin, petroleum resin, etc. can be used. The amount added may be 0 to 20% by weight based on the total solid content of the release layer (2).

The release layer (2) can be formed by melting and coating the material (hot melt coating). Alternatively, it may be dissolved or dispersed in a solvent and coated (solvent coat).As the solvent, aromatic hydrocarbons such as toluene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and alcohol solvents such as isopropyl alcohol are used. can. Solvent coating can be done by methods such as gravure coating, roll coating, barcode coating, and blade coating. Peeling layer (2) is 0°5-2.0μm
It should be formed to a thickness of .

The thermal transfer recording layer (3) is a layer that is transferred to the surface of the object to be transferred to form a colored image. Transfer is performed by the heat of the thermal head turning the thermal transfer recording layer (3) into a rubber-like fluid state, producing adhesive force and adhering to the surface of the object to be transferred.

The thermal transfer recording layer (3) mainly contains a colorant and a resin binder. The coloring agent imparts color to the transferred image (the image formed on the surface of the transfer target by transfer), and the resin binder makes the transfer possible.

Known dyes or pigments can be used as the colorant. In order to ensure the weather resistance of the transferred image, organic or inorganic pigments are preferred. For example, titanium oxide, calcium carbonate, Hansa Yellow Oil Yellow 2G, carbon blank,
Oil blank, Villa Solon Orange, Oil Red,
These include hengara, anthraquinone high ollent, phthalocyanine green, aluminum powder, bronze powder, pearl powder, magnetic powder, etc.

The resin component should be selected from a high molecular weight resin with a glass transition point of 50-110'C and a low molecular weight resin with a softening point of 60-150'C.

High molecular weight resins can be transferred by the heat of the thermal head, but if the glass transition point exceeds 110"C, transfer will not be possible under normal conditions, and transfer will place an excessive burden on the thermal head and thermal transfer recording material. Furthermore, if the glass transition point is less than 50°C, the image stability of the transferred image will be poor.The molecular weight is usually 8,000 or more.

Such high molecular weight resins include polyester resins; vinyl chloride resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resins, and modified vinyl chloride-vinyl acetate copolymer resins; polyacrylic acid, polyacrylic acid-2- Methoxyethyl, polymethyl acrylate, polyacrylic acid-
2-naphthyl, polyisobornyl acrylate, polyacrylonitrile, polyacrylonitrile, polymethylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polyisobutyl methacrylate, polyphenyl methacrylate, methacrylic acid Acrylic resins such as copolymers of methyl and alkyl methacrylate (alkyl group has 2 to 6 carbon atoms); polystyrene, polyvinyltoluene, polyvinyltoluene, styrene-butadiene copolymer, styrene-alkyl methacrylate (however, the alkyl group has 2 to 6 carbon atoms); Vinyl resins such as copolymers with 1 to 6 carbon atoms; nylon-6,6, nylon-6,7, nylon-6,8, -1
-Iron-6,9, Nylon 6.10, -j-Iron 6
．． 12, polyamide resins such as Nai 07-10, and polyacetal resins such as polyvinyl butyral and polyvinyl acetal.

In addition, polyester refers to polyvalent carboxylic acid and polyvalent 7/
l/ ] -7+/ (7) Wi The main component of carboxylic acid in the resin obtained by polymerization is terephthalic acid. Also, the main component of alcohol is ethylene glycol.

Other carboxylic acids include aromatic carboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoquinethane dicarboxylic acid, and diphenylsulfone dicarboxylic acid; fatty acids such as hexahydroxyterephthalic acid and hexahydroxycisophthalic acid. Examples include cyclic carboxylic acids; aliphatic carboxylic acids such as adipic acid, sebacic acid, and azelaic acid; and oxyacids such as p-β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and ε-oquincabronic acid. In addition, other alcohols include propylene glycol, 1,4-butanediol, 1
4-Dicyclohexane dimetatool, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene gellicol, diethylene glycol, 1. ■-Cyclohexanedimethylol, 14-cyclohexanedimethylol, 22-bis(4-β-hydroxyethoxophenylyopropane, bis(4-β-hydroxyethoxyphenyl)sulfonecyclohexanediol, 14-bis(β-
Examples include hydroxyethoxy)henzen and 1,3-bis(β-hydroxyethoxy)henzen.

The low molecular weight resin lowers the softening point of the entire thermal transfer recording layer (3) and improves thermal responsiveness, and as a result, the release layer (
2) can be transferred at the same time as it is melted, thereby preventing the peeling layer (2) around the heated portion from melting and improving the transfer accuracy. For this reason, it is necessary to use a material with a softening point of 150° C. or lower. In addition, in order to ensure the image stability of the transferred image, the softening point must be 60°C or higher.6The molecular weight is usually 500 to 5,000.

Such low molecular weight resins have a softening point of 60 to 100°C,
A polyester resin having a molecular weight of 2,000 to 5,000 can be used.

Also, softening point 60-150'' C1 molecular weight 600-200
0 petroleum resin can also be used. For example, C7-based copolymers of styrene, vinyltoluene, α-methylstyrene, and indene have a softening point of 80 to 150°C and a molecular weight of 600 to 1.
500 petroleum resin. Alternatively, isoprene, piperylene, 2-methylbutene-1,2-methylbutene-2
Softening point of copolymer etc. 70-100' C1 molecular weight 80
It is a C3 petroleum resin with a molecular weight of 0 to 2000. Further, C3 and C7 copolymer resins having a softening point of 60 to 100°C can also be used.

Alternatively, it may be an epoxy resin. For example, it is a copolymer of bisphenol A and epichlorohydrin having a softening point of 65 to 170°C and a molecular weight of 900 to 5,000. Moreover, a brominated epoxy resin or an epoxy novolac resin may be used.

Ketone resins can also be used. For example, softening point 70
It is a copolymer of ketone and formaldehyde at ~130°C.

Additionally, coumaron resin can also be used. For example, softening point 7
It is a coumaron-indene copolymer with a temperature of 0 to 160°C and a molecular weight of 600 to 1000.

Additionally, xylene resin can also be used. For example, a copolymer of xylene and formaldehyde.

In addition, low molecular weight styrene resins, polyamide resins, and acrylic resins can also be used.

It is desirable that the high molecular weight resin is contained in an amount of 20 to 70% by weight based on the total amount of resin components of the thermal transfer recording layer (3). If it is less than 20% by weight, the viscosity of the paint will be low when it is made into a paint, and the paint will swim even when applied, making it difficult to form a thermal transfer recording layer (3) with a uniform thickness. Also, 70% by weight
Exceeding this results in poor thermal response. Note that the remainder is a low molecular weight resin.

In addition, it is necessary to mix an abrasion resistant material into the thermal transfer recording layer (3). In addition to improving the resistance to abrasion caused by copying scratches, this also reduces the tensile elongation at break of the thermal transfer recording layer (3) and improves the transfer accuracy. In other words, if the abrasion resistant material is not mixed, the thermal transfer recording layer (3) in the area heated during transfer and the thermal transfer recording layer (3) around it
will adhere to each other, making accurate transfer impossible.

Abrasion-resistant materials include animal wax, plant-based Yonox,
Natural waxes such as mineral waxes and petroleum waxes; base hydrocarbon waxes, camphorax, aliphatic alcohol and acid ester waxes, fatty acid ester and glyceride waxes, hydrogenated waxes, synthetic ketone waxes, amines or amides wax, chlorinated hydrocarbon wax,
Synthetic waxes such as platform animal waxes and α-olefin waxes: Metal salts of higher fatty acids such as zinc stearate;
Teflon powder; polyethylene powder, polypropylene powder, etc. can be used.

The thermal transfer recording layer (3) can be formed by mixing a colorant, a resin component, an abrasion resistant material, and other necessary additives, dissolving or dispersing the mixture in a solvent to form a paint, and applying the mixture. The mixing ratio may be 10 to 30 parts by weight of the colorant, 40 to 80 parts by weight of the resin component, and 5 to 30 parts by weight of the abrasion resistant material. 0 to 10 parts by weight of other additives may be mixed. In order to prevent swimming during coating, it is desirable to use 15 to 50% by weight of the solvent, with the total amount of these solids and solvent being 100%. As the solvent, general-purpose paint solvents such as aromatic hydrocarbons, ketones, and alcohols can be used. Application is by barcode, blade coat, air knife coat, gravure coat, solvent coat such as roll coat.

Dry film thickness 0.5-4. It is sufficient to apply it to the thickness of OIIm.

The thermal transfer recording material according to the present invention can be transferred onto a plastic surface using heat from a thermal head. For example, PVC resin, polystyrene, polycarbonate,
These include polyester, acrylic resin, ABS resin, etc.

Alternatively, it is a coated paper or a transfer material whose surface is coated with a thermoplastic resin having a glass transition point of 50 to 110°C. The object to be transferred may be a rolled sheet, a sheet in the form of a sheet, or a card shape.

Transfer involves applying a thermal transfer recording layer (
3) This is possible by bringing the surfaces into contact, applying a thermal head to the back surface of the thermal transfer recording material, and selectively heating the heating element of the thermal head.

The transfer conditions may be similar to those of conventional thermal heads, such as applied power Q, 3 W/dot, and pulse width 2.5.
ms e c (ONloFF), do with density 6
Dot/mm is fine.

(Example 1) (1) Support.

Thickness 6 with 0.1μm coating of KR218 on the back
．． Omm Nitsumugi stretched polyethylene terephthalate film.

(2) Release layer.

(a) Composition.

Rice wax 2°0 parts by weight Polyester wax 1.0 parts by weight Toluene 15.0 parts by weight (b) Thickness. 1.0 μm.

(c) Application method. Gravure coat.

(3) Thermal transfer recording layer.

(a) Resin acid composition.

Methacrylic acid ester (glass transition point 55°C) 77 parts by weight (molecular weight 60000) Petroleum resin 33 parts by weight (softening point 8
0°C) (Molecular placement piece 1000) (b) Colorant.

Carbon black.

(c) wear-resistant material; teflon powder (d) Thermal transfer recording layer composition.

Resin component 8.0 parts by weight Colorant
2.0 parts by weight Abrasion resistant material 0.
5 parts by weight (e) solvent.

(1) Composition.

Methyl ethyl ketone 50 parts by weight Toluene 50 parts by weight (ii) Mixing amount.

of the above resin components, colorants, and wear-resistant materials. 50 parts by weight for a total of 100 parts by weight Quantity part.

(f) Application method: Gravure coating.

(g) Thickness: 2.5 μm (dry).

(4) Transcription.

(a) Transferee.

250 μm thick white polyvinyl chloride sheet (b) transfer conditions.

Applied power: 0.3W/dot.

Pulse width 2.5m5ec (ONloFF) dat density 6dot/mm.

(c) Transfer shape.

Transferred in a mesh pattern with mesh spacing of approximately 1mm.

(d“) Results.

It was transferred in a mesh pattern along the mesh.

(Comparative example) (1) Support.

Same as Example 1.

(2) Release layer.

Same as Example I.

(3) Thermal transfer recording layer.

(a) Resin component composition.

Methacrylic acid ester (Glass transition point 55°C) (Molecular placement piece 60000) (b) Colorant.

carbon blank.

(c) Abrasion resistant material.

teflon powder (d) Thermal transfer recording layer composition.

Same as Example 4.

(e) Solvent.

Same as Example 1.

77 parts by weight (f) Application method: Gravure coating.

(g) Thickness 2.5μm (dry) *(4)
Transcription.

(a) Transferee.

Same as Example 1.

(b) Transcription conditions.

Same as Example 1.

(c) Transfer shape.

Same as Example 1.

(d) Results.

The images were transferred to the center of the mesh at a rate of several tens of times. When adhesive tape was adhered onto this and then peeled off, only the ink in the center of the mesh adhered to the adhesive tape and was peeled off.

(Example 2) (1) Support.

Same as Example 1.

(2) Release layer.

(a) Composition.

Rice wax 6.0 parts by weight Carnauba wax 4.0 parts by weight Polyamide resin 2.0
Weight part (b) Thickness, 2.0 μm.

(C) Coating method. Real melt coat.

(3) Thermal transfer recording layer.

(,a) Resin component composition.

Styrene-acrylic copolymer (glass transition point 100°C) 40 parts by weight (molecular weight 70,000) Epoxy resin 60 parts by weight (softening point 8
3°C) (Molecular placement piece 1000) (b) Colorant.

Carbon black.

(c) Abrasion resistant material.

Zinc stearate.

(d) Thermal transfer recording layer composition.

Resin component 6.0 parts by weight Colorant
1.5 parts by weight wear-resistant material 1.
0 parts by weight (e) Solvent.

Methyl ethyl ketone.

50 parts by weight based on 100 parts by weight of the total amount of the resin component, colorant, and anti-wear material.

(f) Application method: Gravure coating.

(g) Thickness: 2.0 μm (dry).

(4) Transcription.

(a) Transferee.

White polyester sheet with a thickness of 188 μm.

(b) Transcription conditions.

Same as Example 1.

(c) Transfer shape.

Transferred into a mesh shape with mesh spacing of approximately 1mm.

(d) Results.

It was transferred in a mesh pattern along the mesh.

(Example 3) (1) Support.

Same as Example 1.

(2) Release layer.

(a) Composition.

Paraffin wax 8゜ Ethylene-vinyl acetate copolymer 1゜ Toluene 80° 0 parts by weight 5 parts by weight 0 parts by weight (b) Thickness. 2. OAIm.

(c)? 1 cloth method. Hot melt coat.

(3) Thermal transfer recording layer.

(a) Resin component composition.

Polyester (glass transition point 65°C) 33 parts by weight (molecular weight 15000) Polyester 77 parts by weight (softening point 8
7°C) (Molecular weight: 4000) (b) Colorant.

Carbon black.

(c) Abrasion resistant material.

polyethylene powder (d) Thermal transfer recording layer composition.

Resin component 7.0 parts by weight Colorant
1.5 parts by weight Abrasion resistant material 0.7
5 parts by weight (e) solvent.

(i) &fl precepts.

Methyl ethyl ketone 33 parts by weight Toluene 77 parts by weight (11) Mixing amount.

of the above resin components, colorants, and wear-resistant materials. 50 parts by weight for a total of 100 parts by weight Quantity part.

(i Application method: Roll coating.

(g) Thickness: 1.8 μm (dry).

(4) Transcription.

(a) Transferee.

Same as Example 2.

(b) Transcription conditions.

Same as Example 1.

(c) Transfer shape.

Transferred into a mesh pattern with a mesh spacing of 1mm.

(d) Results.

It was transcribed in a mesh pattern according to the lines.

(Example 4) (1) Support.

Thickness 6 with 0.1μm coating of KR21B on the back.
．． 0mm two-wheel stretched polyethylene terephthalate film.

(2) Release layer.

(a) Composition.

Rice wax 2.0 parts by weight Polyester wax 1.0 parts by weight Ketone resin 0.
5 parts by weight Toluene 15.0 parts by weight (b)
Thickness: 0.8 μm.

(c) Coating method, gravure coating.

(3) Thermal transfer recording layer.

(a) Resin component composition.

Vinyl chloride-vinyl acetate copolymer (glass transition point 70°C) 50 parts by weight (molecular weight 35,000) Ketone resin 50! if part (softening point
95°C) (molecular weight 1000) (b) Colorant.

Carbon black.

(c) Abrasion resistant material.

polypropylene powder (d) Thermal transfer recording layer composition.

Resin component 6.0 parts by weight Colorant
2.0 parts by weight Abrasion resistant material 0.
6 parts by weight (e) solvent.

(i) Composition.

Methyl ethyl ketone 77 parts by weight Methyl isobutyl ketone 33 parts by weight (ii) Mixing amount.

of the above resin components, colorants, and wear-resistant materials. 50 parts by weight for a total of 100 parts by weight Quantity part.

(f) 2 cloth method: Gravure coating.

(g) Thickness: 1.5 μm (dry).

(4) Transcription.

(a) Transferee.

Same as Example 1.

(b) Transcription conditions.

Same as Example 1.

(c) Transfer shape.

Transferred into a mesh shape with mesh spacing of approximately 1mm.

(d) Results.

It was transferred in a mesh pattern along the mesh.

FIG. 1 is a sectional view of a thermal transfer recording material.

(1)-----One support (2) --- Peeling layer (3) - One thermal transfer recording layer

Claims (1)

[Claims] (1) In a resin-type thermal transfer recording material, which is formed by laminating a release layer containing wax as a main component and a thermal transfer recording layer containing a resin binder, a colorant, and an anti-wear agent in this order on a heat-resistant support. , wherein the resin binder is a mixture of a high molecular weight resin having a glass transition point of 50 to 110°C and a molecular weight of 8000 or more and a low molecular weight resin having a softening point of 60 to 150°C and a molecular weight of 500 to 5000. Material.