JPH02258295A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To improve the abrasion resistance to material of high hardness and the resistance to a variety of chemicals by employing a colorant and acrylonitrile- or methacrylate-based copolymer as an ink layer on a substrate. CONSTITUTION:A colorant and an ink layer are provided on a substrate. A acrylonitrile- or metacrylate-based copolymer is used as a material being a main component of the ink layer. The copolymer mainly contains acrylonitrile or metacrylate, and a compound represented by formula I is used for another monomer. With respect to the molecular weight of the copolymers, an average molecular weight is 2,000 to 1,000,000 and a molecular weight in numerical average is 1,000 to 500,000 in a value on polystyrene conversion. To prepare the copolymers, benzoyl peroxide, for instance, is used as a radial initiator, and they are polymerized under an appropriate temperature and solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermal transfer recording medium capable of producing images with improved abrasion resistance, heat resistance, and chemical resistance.

[Conventional technology]

Conventionally, thermal transfer recording media have a softening temperature of 60 to 110°C.
An ink layer comprising an epoxy resin and a colorant is known (Japanese Patent Publication No. 6G-59159). According to this method, it is possible to obtain records with primary color development and excellent storage stability and abrasion resistance on various recording surfaces such as plain paper, plastic, and metal foil.

[Problems to be Solved by the Invention] However, in the above thermal transfer recording medium, the softening point of the epoxy resin constituting the ink layer is 60 to 110°C.
Therefore, it has the disadvantage of being inferior in heat abrasion resistance. That is, when an image exposed to a high temperature, for example 70° C., is rubbed with, for example, cardboard, the image becomes distorted and it is difficult to read it.

In addition, the image surface of ink using epoxy resin has a drawback that it has poor lubricity and easily falls off when it comes into contact with highly hard objects such as metal edges and nails.

Furthermore, the above-mentioned epoxy resins have poor chemical resistance; for example, they are resistant to industrial alcohol, oils such as engine oil and brake oil, kerosene, car wax, toluene, xylene, and perchloromethane used in dry cleaning. It was insufficient.

In view of these circumstances, it is an object of the present invention to provide a thermal transfer recording medium that has improved abrasion resistance and chemical resistance and is capable of producing highly reliable printed images. A further object of the present invention is to provide a thermal transfer recording medium that prevents the ink layer from falling off at low temperatures.

Still another object of the present invention is to provide a thermal transfer recording medium with improved thermal sensitivity.

[Means for Solving the Problems] The present inventor has conducted extensive research in order to solve the above problems, and found that it is possible to adopt an acrylonitrile- or methacrylonitrile-based copolymer as the constituent material of the ink layer. It was discovered that this method is effective, leading to the present invention.

That is, the present invention provides (1) a thermal transfer recording medium characterized by having an ink layer on a base material whose main components are a colorant and a copolymer mainly containing an acrylonitrile or methacrylonitrile monomer; (2) 4-thermal transfer characterized by being constructed by sequentially laminating on a base material a lubrication agent layer, an ink layer whose main component is a copolymer mainly composed of a colorant and an acrylonitrile or methacrylonitrile monomer. A recording medium, (3) a thermal transfer recording medium formed by providing an adhesion improver layer on a base material and further forming each layer described in (1) and (2) above, (4) further comprising an ink layer and This is a thermal transfer recording medium provided with a sensitivity enhancer layer mainly composed of a heat-melting substance and/or a heat-softening substance.

In the present invention, as the base material supporting the above-mentioned ink layer, conventionally known films and papers can be used as they are, and for example, materials with relatively good heat resistance such as polyester, polycarbonate, triacetylcellulose, nylon, and polyimide can be used. Plastic film, cellophane, parchment paper, etc. can be suitably used. The thickness of the support should be 2 when considering a thermal head as a heat source during thermal transfer.
It is desirable that the temperature is 15 μ-, but there is no particular limitation if a heat source such as a laser beam that can selectively heat the thermally transferable ink layer is used. In addition, when using a thermal head, a heat-resistant protective layer made of silicone resin, fluororesin, polyimide resin, epoxy resin, phenol resin, melamine resin, nitrocellulose, etc. can be provided on the surface of the support that comes into contact with the thermal head. The heat resistance of the support can be improved, or a base material that could not be used conventionally can be used.

Further, as the colorant used in the present invention, an appropriate colorant can be selected from carbon black, organic pigments, inorganic pigments, or dyes depending on the required color tone.

In the present invention, a copolymer based on acrylonitrile or methacrylonitrile is used as the main material of the ink layer.

This copolymer mainly contains acrylonitrile or methacrylonitrile, and has the general formula (1) as another copolymer.
The following can be used. Specific examples include acrylonitrile-methyl methacrylate, acrylonitrile-methyl acrylate, acrylonitrile-ethyl methacrylate, acrylonitrile-ethyl acrylate, acrylonitrile-n-butyl methacrylate, acrylonitrile-glycidyl methacrylate, acrylonitrile-glycidyl acrylate, acrylonitrile-2-hydroxyethyl methacrylate, Copolymers of acrylonitrile-1so-butyl methacrylate, acrylonitrile-tert-butyl methacrylate, acrylonitrile-2-hydroxypropyl methacrylate and all the above combinations of acrylonitrile and methacrylonitrile.

Among the above copolymers, compositions that are particularly excellent in terms of heat resistance, chemical resistance, and abrasion resistance, and can be easily manufactured industrially include acrylonitrile-glycidyl methacrylate, acrylonitrile-methyl methacrylate, and acrylonitrile-ethyl It is methacrylate.

In addition to the above, various other vinyl monomers may be used as comonomers to form a terpolymer without departing from the object of the present invention. As such a monomer, a terpolymer of the following general formula (II) is preferable.

This copolymer can be represented by the following general formula.

R2ClI2 (1) C1l,.

However, the functions of the comonomers R+:H or CH3 R2:H or CH3, C2H5°C3HT, C4I9, and C2H50H are as follows.

(Meth)acrylic acid ester: Provides thermoplasticity, Tg control, chemical resistance, (meth)acrylonitrile: Provides chemical resistance, mechanical strength, heat resistance Glycidyl (meth)acrylate: Adhesion The composition ratio of the comonomers for imparting properties, crosslinking properties, and heat resistance is preferably within the following range.

1:m:n! XIEl ratio-(0~H): (10
~70): (0~80), more preferably (10
~60) : (20~60) : (10~
60).

If this compositional balance is lost, sufficient mechanical strength cannot be ensured, and problems such as deterioration of chemical resistance and curling of the ink layer occur.

The molecular weight of these copolymers affects the melt viscosity and influences the sensitivity during thermal transfer. Therefore, the molecular weight of these copolymers is the weight average molecular weight in polystyrene equivalent values determined by GPC! i1 (hereinafter referred to as π"W') 2000 to 10
00,000, number average molecular weight (hereinafter referred to as "■") 1000 to 5
00,000, more preferably WW: 3,000 to 500,000, below ■!
500,000 to 250,000.

The copolymer can be easily prepared by known methods. For example, using a radical initiator such as benzoyl peroxide or azobisisobutyronitrile as a polymerization initiator,
It is obtained by polymerization at an appropriate temperature and in a solvent. These compositions can also be synthesized by emulsion polymerization using conventionally known methods, and can also be used as emulsions.

When using a copolymer having a curable functional group obtained by using glycidyl methacrylate or the like as the second or third polymer, an appropriate thermosetting agent is contained in the ink layer. Also good.

Typical examples include phenols, such as phenolic resins, primary amines, secondary amines, and amine complex compounds (
Examples include complex compounds of Lewis acids, particularly boronic trifluorides, and amines (eg, BF3C2H5.Nl2), organic acids, organic acid anhydrides, and the like. Theoretically, it is sufficient to use an amount of the curing agent containing a chemical equivalent of a functional group such as a glycidyl group of the copolymer to be cured.

A lubrication agent is a substance that can increase the lubricity of the surface of a thermally transferred image. This lubricity reduces the coefficient of wear on all objects such as metal, cardboard, and wood, and serves to avoid stress concentration on the ink in the image area.

In this way 1. Lubricant agents function to impart lubricity to the above-mentioned copolymers, such as lubricants such as waxy fatty acid amides and phosphoric acid esters, and waxes such as natural paraffin wax, carredellilla wax, and carnauba wax. oils such as silicone oils and perfluoroalkyl ethers, oils such as silicone resins and perfluoroalkyl ethers, resins such as silicone resins and fluoroalkyl ether resins, PTFE
, 5iCSSiOz and other lubricity imparting particles.

Among these, carnauba wax is the most effective substance for achieving both mechanical strength and lubricity of the ink.

The amount added is suitably 1 to 30% by weight based on the copolymer.

The above-mentioned lubricity imparting agent may be used by being added to the ink layer, but as a measure to further improve functionality, it is preferable to provide a lubricity imparting agent layer between the base material and the ink layer. The above-mentioned substances are used for this lubricant layer, but in this case paraffin wax and carnauba wax are most preferred. For example, when using carnauba wax, 0.3
A layer with a thickness of ~2.0 μl can exhibit sufficient functionality.

Additives such as a flexibility imparting agent, a thermal sensitivity modifier, etc. can be used as additives to the above-mentioned main components of the ink layer. Examples of such materials include plasticizers such as DOP, softeners such as EVA, EEA, and synthetic rubber, and thermoplastic resins such as acrylic resins and polyester resins that do not deteriorate wear resistance.

The thickness of the ink layer is appropriately set depending on the smoothness of the recording paper, similarly to the sensitivity improver layer described later. 1.0 to 2.0 for polyester films with infinite smoothness.
5μ is sufficient to form a strong image and has good thermal sensitivity. Also, for coated paper and high-quality paper, 2.5 to 4
．． A value of about 0μ is good in terms of image quality, and in those with a sensitivity improver layer, it is 1.5 to 3.0μ.
degree is preferred.

The thermal transfer recording medium of the present invention, which is formed by laminating the above ink layer, lubricant layer, and ink layer, can be used for low-temperature printing, for example, at 0°C.
In order to prevent ink from falling off during printing in an environment, an adhesion improver layer can be provided between the base material and the ink layer or between the base material and the lubrication agent layer. The adhesion promoter layer may be thermally transferred or may remain on the substrate. The adhesion improver is preferably a substance that exhibits flexibility at room temperature, such as resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acetate, acrylate copolymer, ethylene-vinyl chloride copolymer, polyvinyl butyral, natural rubber, synthetic rubber, etc. type is used.

When thermally transferring this layer, 30 to 70% by weight of waxes having an appropriate melting point, such as paraffin wax and carnauba wax, may be blended. Thickness is 0.2~
1.0μ is appropriate.

By using the thermal transfer recording medium having the above structure, it is possible to obtain images with improved abrasion resistance and heat resistance. Furthermore, a large amount of applied energy is required to obtain a close-up image of fine line breaks and a good solid image. When printing with a printer with a printing speed of 10cs/5eas and a platen pressure of 50g/c, a good image can be obtained with 20aJ/we'' when printing on a highly smooth recording medium such as film. In the case of coated paper that is less smooth than film, such as mirror coated paper, 25 J/as2
A good image cannot be obtained unless the applied energy is .

In the case of a general thermal transfer recording medium mainly composed of wax, a good image can be obtained by applying energy of 13 aJ/as' for film and 16 mJ/am2 for mirror coated paper.

Therefore, in order to transfer a good image to paper with a lower smoothness than mirror coated paper, even more applied energy is required, which increases the cost of the printing device and lowers the heat resistance of the base material and/or the heat-resistant protective layer. A material with higher heat resistance is required, which increases the cost of the thermal transfer recording medium. Furthermore, in order to increase the speed of recording, even higher applied energy than the above is required, and increasing the speed of recording is not desirable.

Therefore, in order to improve the thermal sensitivity while substantially maintaining the abrasion resistance and heat resistance of the image, a sensitivity improving layer can be further provided on the ink layer.

The sensitivity improving layer in the present invention is mainly composed of a heat-melting substance and/or a heat-softening substance, and such a heat-melting substance has a melting point of 60 to 130°C and 140°C.
Waxes having a melt viscosity of 1000 cps or less are preferable, and specific waxes include paraffin wax, carnauba wax, candelilla wax, and polyethylene wax. In addition, heat-softening substances include ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, acrylic resin, polyester resin, especially branched polyester resin, etc. suitable.

These resins alone can be sufficiently effective as materials for the sensitivity enhancer layer, but in order to improve surface properties, increase printing speed, and print on low-smoothness paper, carnauba wax and paraffin may be used. Heat-melting substances such as wax, candelilla wax, polyethylene waxes, fatty acid amides, etc. may be added. In addition, the heat-melting substance can be used alone, but when the sensitivity improver layer is composed of these waxes alone, the smoother the recording material, the better the metal edge abrasion resistance and hardness resistance. Since 2H abrasion resistance may be lowered, in such a case, it is not preferable to use a wax alone, and it is preferable to use the above-mentioned thermosoftening resin in combination.

The melt viscosity of the sensitivity improver, which influences thermal sensitivity, is preferably 50 to 5000 cps at 140°C using a B-type rotational viscometer. In addition, the ratio of heat-melting substance/thermo-softening substance is 95
A range of 15 to O/100 is preferable.

Further, the thickness of the sensitivity improver layer is sufficient if it is the minimum thickness required for the connection tube for its purpose, and it is better to be as thin as possible so as not to reduce the mechanical strength. On the other hand, when recording on paper with low smoothness, in order to improve the appearance of thin lines or solid areas, it is necessary to make the ink layer as thick as possible without reducing the thermal sensitivity, so that the effect of unevenness of the paper on the transferability of the ink layer is minimized. It is preferable to avoid this. From the above points, the thickness of the sensitivity improver layer is o, i-1,5μ layer, more preferably 0.3 to 1
．． It is preferable that the thickness be 0 μm.

[Example] Further, the present invention will be explained in detail with reference to Examples. Inks were prepared at 20% solids in methyl ethyl ketone unless otherwise noted.

Example 1 The following components were used as ink layer components.

Colorant: Rikiichi, Bonblack 20 parts by weight Copolymer dimethyl methacrylate ψ acrylonitrile conjugate (weight ratio 70:30) [TW: 6400.1 piece:
aeoo) 70 parts by weight Lubricant agent: carnauba wax A 4.5 μm thick polyester film was used as the base material.

The above composition was applied as an ink layer to this base material so as to have a mist of 3.0 μm and was dried to obtain a thermal transfer recording medium of the present invention.

Example 2 An ink layer was formed in the same manner as in Example 1 except that the copolymer in the composition was replaced with the following substance.

Copolymer: Methyl methacrylate/acrylonitrile (
! 11 quantity ratio 50:50) ET'v'': 7700, r?
iJ: 4100] Example 3 The following components were used as ink layer components.

Colorant 2 carbon black 2 Offl E 1 part Copolymer: Same components as in Example 1 76 parts by weight Lubricant agent: 4 parts by weight Silicone oil 3.0 pm as an ink layer on the same base material as used in Example 1 The coating was applied to a thick layer and dried to obtain a thermal transfer recording medium.

Example 4 A mixed wax of carnauba wax and paraffin wax (
A coating solution prepared by dispersing (weight ratio 1:1) in toluene was applied and dried to a thickness of 1 μm.

On this layer, a composition obtained by removing the lubricant from the ink composition used in Example 1 was applied as an ink layer component to a thickness of 2.5 μm and dried to obtain a thermal transfer recording medium.

Example 5 Same as Example 1 - 1:1ff of ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150) and carnauba wax as an adhesion improver layer on the substrate
Coating liquid with lJ1 ratio dispersed in toluene to a thickness of 0.5μ
It was obtained by coating and drying to obtain the desired amount.

On this layer, apply the ink composition of Example 1 and four balls to a thickness of 265 μm.
A thermal transfer recording medium was obtained by coating and drying so as to give -. This thermal transfer recording medium was rubbed by hand to see if the ink came off, and most of it remained on the base material, confirming the effectiveness of the adhesion improver layer.

Example 6 The following components were used as ink layer components.

Blue agent: Carbon black 20 parts by weight Copolymer: Same substance as in Example 1 57 parts by weight Additives: Softening agent (styrene butadiene rubber) 3 parts by weight Heat sensitivity modifier (linear polyester resin) 1 part by weight Lubrication Imparting agent: carnauba wax 10 parts by weight A thermal transfer recording medium was prepared using the same composition as in Example 1.

An example fink layer was formed in the same manner as in Example Full 1 except that the copolymer in the composition was replaced with the following substance.

Copolymer nigericidyl methacrylate-acrylonitrile (weight ratio 50:50) [πW: 3QQQ, IJT: 3900) Example 8 The copolymer in the composition of Example 1 was replaced with the following substance as the ink layer. It was formed in the same manner.

Copolymer: glycidyl methacrylate-methacrylonitrile (weight ratio BO: 40) [If: 10,000, πW: 49,001.

Comparison f'llll As the ink layer component, the following material containing a so-called thermofusible wax as the main component was used.

Colorant: Carbon black 20 parts by weight Binder: Paraffin wax (melting point 68°C) 40 parts by weight Carnauba wax (melting point 81"C) 20 parts, 2 parts Ethylene-vinyl acetate copolymer (vinyl acetate 28%, melt index 250) 10 parts by weight An ink was prepared with the above composition at 15% solids in toluene.

Using the same base material as in Example 1, the above composition was applied and dried so that the ink layer had a thickness of 3.0 p, to obtain a thermal transfer recording medium as a comparative example.

Comparative Example 2 A so-called thermoplastic resin was used as an ink layer component.
The following substance containing 0-59159 listed substance) as the main component was used.

Colorant: 20 parts by weight of carbon black Binder: Bisphenol A epoxy resin (Epicoat 10
02, softening point 77-78°C, manufactured by Shell Chemical Co., Ltd.) 80ff
Using the same base material as in Example 1, the above composition was applied and dried to form an ink layer having a thickness of 3.0 μm to obtain a thermal transfer recording medium as a comparative example.

[Comparative Evaluation Results] In the printing test, a polyester film (PET) whose release surface was treated with adhesive to form a label shape and mirror coated paper (coated paper) were used. The printing conditions are as follows.

Printing conditions> Thermal head two-part glaze thin film head type platen pressure: 150g/cl Peeling angle of thermal transfer recording medium: 30° with respect to the transfer paper
Peeling torque value: 200g Applied energy: lO~30 mJ/am” Printing speed:
LOcm/sac The various performances that were comparatively evaluated are as follows.

Thermal sensitivity: Applied energy heat abrasion resistance with no fading of fine lines in mirror coating Place the printed sample on a glass plate in a bath set at 0°C, and cover the printed surface with corrugated paper at aOg/c*
A reciprocating love test was carried out at a speed of m5Nc layers/see, and the number of times the image became illegible was recorded.

Hardness 2H1q Abrasion resistance: A love test was conducted using a 2H hardness objective with approximately It/am2, and the same number of exposed paper surfaces was recorded.

Metal edge abrasion resistance: Using a stainless steel edge of about it/cs' as an objective, a rubbing test was conducted in the same manner, and the number of times the transferred paper surface was exposed was recorded.

Chemical resistance: A cotton swab was soaked with 0.51% of the various solvents listed below, and a rub test was performed under a load of 10 g 7 am 2 m, and the number of times required to expose the surface of the paper to be transferred was recorded. An image printed on PET was used.

Chemicals> ■ Ethanol ■ Brake oil ■ Kerosene ■ Compound car wax ■ Toluene ■ Xylene ■ Parkrene Example 9 The following were used as ink layer components.

Colorant 2 Carbon black 2 Offi parts Copolymer 2 General formula (n) l:m:n (lllllffi ratio)
-55:25:2G (However, sentence, RI of n: CH3,
m R1:H.

R2:CH3) ['FfN:6100, "Down-F 320G]7Off
i parts oil lubricant: carnauba wax 10 parts by weight A polyester film with a thickness of 4.5 μm was used as the base material. The above composition was applied to this base material as an ink layer to a thickness of 3.0 μm and dried to obtain a thermal transfer recording medium of the present invention.

Example 10 An ink layer was formed in the same manner as in Example 9 except that the terpolymer in the composition was replaced with the following substance.

Copolymer di general formula (n) l:s:n-45:30:
25 (However, RI of sentence: CH3, R2: CHs
, m's R1:H, n's R1:CH3) [1; rW: 690G, M1': 38001 Example 11 Example 9 was used as the ink layer component. A thermal transfer recording medium was obtained in the same manner as in Example 7 by adding 1.5 parts by weight of a latent thermosetting agent BF3.C2H3NH2 to the composition.

Example 12 The following components were used as ink layer components.

Colorant: 20 parts by weight of carbon black Copolymer: 76 parts by weight of the same components as in Example 9 Lubricant: 4 parts by weight Silicone oil On the same substrate as used in Example 9, an ink layer of 3.0 μl thickness was applied. The mixture was coated and dried to obtain a thermal transfer recording medium.

Example 13 A lubrication agent layer was formed on the same base material as in Example 9 to a thickness of 1 μm using a coating liquid containing carnauba wax dispersed in toluene.
It was coated, dried, and formed.

A composition obtained by removing the lubricant from the ink composition used in Example 9 was applied onto this layer as an ink layer component and dried to a thickness of 2.5 μm to obtain a thermal transfer recording medium.

Example 14 On the lubrication agent layer prepared in Example 13, a composition from Example 11 with the lubrication agent removed was applied as an ink layer component to a thickness of 2.5 μm, dried, and thermally transferred. Obtained a recording medium.

Example 15 Same as Example 9 - Ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150) on the substrate
A coating solution prepared by dispersing a 1:1 weight ratio of carnauba wax and carnauba wax in toluene was applied to a thickness of 0.3 μm and dried to form an adhesion improver layer.

The same ink composition as in Example 1 was applied on the main layer to a thickness of 2.5 μm.
A thermal transfer recording medium was obtained by coating and drying so as to give -. This thermal transfer recording medium was rubbed by hand to see if the ink came off, and most of it remained on the base material, confirming the effectiveness of the adhesion improver layer.

Example 16 The following components were used as ink layer components.

Antique coloring agent dicarbon black 20 parts by weight Ternary copolymer: Same substance as Example 9 57 parts by weight Additives: Softener (styrene butadiene rubber) 3 parts by weight Heat sensitivity modifier (linear polyester resin) 10 parts by weight Part Lubricant agent: Carnauba wax 10 parts by weight A thermal transfer recording medium was prepared using the same composition as in Example 1.

Example 1 A fink layer was formed in the same manner as in Example 9 except that the terpolymer in the composition was replaced with the following substance.

Copolymer nigericidyl methacrylate-acrylonitrile-2-hydroxyethyl methacrylate (weight ratio: 50: 40: 10) [T
'w = 20,000, ``■: 10,000] [Comparative evaluation results] The printing test used a polyester film (PET) in an 8-bell shape with adhesive applied to the release surface, and mirror coated paper (coated paper). The printing conditions are as follows.

Printing conditions> Thermal head: Partial glaze thin film head type Platen pressure: 150g/el Peeling angle of thermal transfer recording medium: 30° with respect to the transfer paper
Degree peeling torque value: 200g Applied energy: 10~30 layers J/■■2 Printing speed:
10cm/see The comparatively evaluated performances are as follows.

Thermal sensitivity RTT: Printing without fading of fine lines in mirror coating Energy heat abrasion resistance: Place the print sample on a glass plate in a tank set at 100°C, and cover the print surface with corrugated paper at 80g/cm
A reciprocating love test was performed at a load of ' and a speed of 30 cs/sec, and the number of times the image became illegible was recorded.

Hardness a'2H abrasion resistance: A love test was performed using a 2H hardness objective of about it/cm2, and the number of times the transferred paper surface was exposed was recorded.

Metal edge abrasion resistance: Using a stainless steel edge of about I L/c 2 as an objective, a rubbing test was conducted in the same manner, and the number of times the transferred paper surface was exposed was recorded.

Steam iron resistance: Place a cotton cloth on the printed surface of the print sample and apply a 100g7 steam iron set at 150°C.
cm' for 10 seconds. Thereafter, the transferability of the ink to the cotton fabric was visually evaluated.

Evaluation Criteria> Heat Resistance: Using a Teflon tape attached to the tip of an iron set at a temperature of 200°C, a rubbing test was performed under a load of 300 g/cs', and the number of times the image became illegible was recorded.

Chemical resistance: A cotton swab was soaked with 0.51% of the various solvents listed below, and a rubbing test was performed under a load of 10 g/as', and the number of days required to expose the transfer paper surface was recorded. An image printed on PET was used.

Chemicals> ■Ethanol ■Brake oil ■Kerosine ■Compound human car wax ■Toluene ■Xylene ■Perkleen No transfer at all, faint transfer
Transfer Example 18 The following components were used as ink layer components.

Colorant: 20 parts by weight of carbon black Copolymer: Methyl methacrylate/acrylonitrile copolymer (
Weight ratio 70:30) [WW, [14QQ, "■: 3
B00170 parts by weight Lubricant agent: carnauba wax 10 parts by weight A 4.5 μl thick polyester film was used as the base material. The above composition was applied as an ink layer to this base material so as to have a thickness of 2.0μ and dried. Ethylene-vinyl acetate copolymer (vinyl acetate content 40% by weight, melt flow rate 70g/5in) was used as a sensitivity improver layer component. 20 parts by weight of carnauba wax 80 parts by weight were prepared as a 10% solids solution in toluene (the same applies hereinafter unless otherwise specified). The composition was coated on the ink layer in an amount of 1.0 μl and dried to provide a sensitivity improver layer, thereby obtaining a thermal transfer recording medium.

Example 19 An ink layer was formed in the same manner as in Example 18 except that the copolymer in the composition was replaced with the following substance.

Copolymer: Acrylonitrile in methyl methacrylate (
Weight ratio 50:50) [1grv near 700, rl'r-41H) Example 20 As a sensitivity improver layer, ethylene-ethyl acrylate copolymer (ethyl acrylate content!! [ffi%) 30ffi parts paraffin wax 155 〒 70ffi ffi
It was formed in the same manner as in Example 18, except for changing the part.

Example 21 A lubrication agent layer was formed on the same base material as in Example 18 by coating and drying it to a thickness of 1.0 μm using a coating liquid in which carnauba wax and paraffin wax (weight ratio 1:1) were dispersed in toluene. did.

On this layer, a composition obtained by removing the lubricant from the ink composition used in Example 18 was applied as an ink layer component to a thickness of 2.5 μ- and dried, and further on the ink layer was used in Example 18 to improve sensitivity. The agent layer was coated to a thickness of 0.5 μm and dried to obtain a heat-sensitive transfer recording medium.

Example 22 A coating liquid containing a 3 near weight ratio of ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150) and carnauba wax dispersed in toluene was used as an adhesion improver layer on the same base material as in Example 18. was coated and dried to a thickness of 0.5 μm.

The same ink composition as in Example 18 was applied on the main layer to a thickness of 2.5 mm.
The ink layer was coated and dried to a thickness of 0.5 μm, and then the sensitivity improver layer used in Example 18 was coated and dried to a thickness of 0.5 μm on the ink layer to obtain a thermal transfer recording medium. This thermal transfer recording medium was rubbed by hand to see if the ink came off, and most of it remained on the base material, confirming the effectiveness of the adhesion improver layer.

Example 23 The following components were used as ink layer components.

Blue agent dicarbon black 20 parts by weight Copolymer: Same substance as Example 18 57 parts by weight Additives: Softening agent (styrene butadiene rubber) 3 parts by weight Heat sensitivity modifier (linear polyester resin) 10 parts by weight Lubrication Imparting agent: carnauba wax 10 parts by weight A thermal transfer recording medium was prepared in the same manner as in Example 18 except that the ink layer had the above composition.

Example 24 Bottom as ink layer components: 9. I used the later one.

Colorant: 20 parts by weight of carbon black terpolymer of general formula (II) l:s:n (ffi ratio)
-55:25:20 (However, !, R1:CH3 of n,
R+ of m: H, R2: CH3) [77″'v: 6100, rFJ: 320017
Off amount part Lubricity imparting agent: Carnauba wax 10 parts by weight A thermal transfer recording medium was prepared in the same manner as in Example 18 except that the ink layer had the above composition.

Example 25 An ink layer was formed in the same manner as in Example 24 except that the terpolymer in the composition was replaced with the following substance.

Copolymer: l:s:n=45:3 in the composition of Example 24
0:25 [11r: 8900, rl'r: 3
8001 Example 26 Example 24 was used as the ink layer component.

Latent thermosetting agent BF3C2R5Nl2 for its composition
A thermal transfer recording medium was obtained in the same manner as in Example 24 by adding 1 part of 1.5ff11i.

Example 27 A thermal transfer recording medium was obtained in the same manner as in Example 20 except that Example 24 was used as the ink layer component of Example 20.

Example 28 The procedure was the same as in Example 24 except that a composition obtained by removing the lubricant from the ink composition used in Example 24 was used as the ink layer component in Example 21.

Example 29 On the lubrication agent layer prepared in Example 28, a composition from Example 26 with the lubrication agent removed was applied as an ink layer component to a thickness of 2.5 μl, and dried. The same sensitivity improver layer as in Example 24 is provided on the ink layer.

Example 30 Same as Example 18 - Ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150)
) and carnauba wax (1=1 weight ratio) dispersed in toluene was applied to a thickness of 0.3 μm and dried to form an adhesion improver layer.

An ink layer and a sensitivity improver layer similar to those in Example 24 are provided on this layer. This thermal transfer recording medium was rubbed by hand to see if the ink came off, and most of it remained on the base material, confirming the effectiveness of the adhesion improver layer.

[Comparative Evaluation Results] In the printing test, mirror coated paper (coated paper) and art coated paper whose release surface was treated with adhesive to form a label shape were used.

The printing conditions and the comparative evaluation results of various characteristics were the same as those performed in Examples 1 to 8.

Evaluation Results〉 Evaluation Results〉 0 There was no lubricity and the material was easily caught on corrugated paper.

Example 31 The following components were used as ink layer components.

Rejuvenating agent dicarbon black 20ffi parts Copolymer: Methyl methacrylate/acrylonitrile copolymer (weight ratio 70:3G) [W: 8400, ■:
3800] 7011 parts by weight Lubricant agent: Carnauba wax 10 parts by weight A polyester film with a thickness of 4.5 μm was used as the base material. The above composition was applied to this base material in an amount of 2.0 μl as an ink layer, dried, and the dibasic acid was phthalic anhydride, and the diols were ethylene glycol, neopentyl glycol, and trimethylolpropane (acid and alcohol). A branched polyester resin (melt viscosity at 140°C of 15,000
cps), the above composition was coated on the above ink layer to a thickness of 1.0 .mu.m and dried to provide a sensitivity improver layer, thereby obtaining a thermal transfer recording medium.

Example 32 An ink layer was formed in the same manner as in Example 31 except that the copolymer in the composition was replaced with the following substance.

Copolymer: Methyl methacrylate/acrylonitrile (
Weight ratio 50:50) ['□" 2 7700, 'i""N": 4+
00] Example 33 A sensitivity improver layer was formed in the same manner as in Example 31 except that the branched polyester resin in the composition was replaced with the following substance.

Branched polyester resin: A compressed compound of adipic acid and phthalic anhydride as dibasic acids and 1,6-hensandiol, ethylenezolicol, and trimethylol glycol as diols (ratio of acid and alcohol: ffi amount 50:50. Three types of alcohol ratio 1:
1:1). Melt viscosity at 140°C is 2800
0cps.

Example 34 A lubrication agent layer was formed on the same base material as in Example 31 by coating and drying it to a thickness of 1.0 μm using a coating liquid in which carnauba wax and paraffin wax (weight ratio 1:1) were dispersed in toluene. did.

On this layer, a composition obtained by removing the lubricant from the ink composition used in Example 31 was applied as an ink layer component to a thickness of 2.5μ, dried, and then the sensitivity improver used in Example 33 was applied on the ink layer. A layer was coated to a thickness of 0.5 μl and dried to obtain a sensitive/thermal transfer recording medium.

Example 35 Same as Example 31 - ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150) and carnauba wax in a 3-7 weight ratio were dispersed in toluene as an adhesion improver layer on the base material. A coating liquid was applied and dried to a thickness of 0.5 μm.

The same ink composition as in Example 31 was applied on the main layer to a thickness of 2.5 mm.
The ink layer was coated and dried to a thickness of 0.5 μm, and the sensitivity improver layer used in Example 31 was coated and dried on the ink layer to a thickness of 0.5 μm to obtain a thermal transfer recording medium. This thermal transfer recording medium was rubbed by hand to see if the ink came off, and most of it remained on the base material, confirming the effectiveness of the adhesion improver layer.

Implemented flq36 The following components were used as ink layer components.

Colorant: 20 parts of carbon black Copolymer: 57 parts by weight of the same substance as in Example 31 Additives: 3 parts by weight of softener (styrene butadiene rubber) Heat sensitivity: J3u agent (linear polyester resin ff1l10
Part by weight Lubricating agent: Carnauba wax 10 parts by weight A thermal transfer recording medium was prepared in the same manner as in Example 31 except that the ink layer had the above composition.

Example 3 The following components were used as ink layer components.

Colorant: Carbon black 20 parts by weight Copolymer general formula (IIJ l:s:n (weight ratio) -55:2
5:20 (However, sentence, R1:H of m.

RI of n: CH3, R2 of n: CH3) [vr'vr:
A thermal transfer recording medium was prepared in the same manner as in Example 31 except that the ink layer had the above composition.

Example 38 An ink layer was formed in the same manner as in Example 37 except that the terpolymer in the composition was replaced with the following substance.

Copolymer: composition of Example 37 l:s:n-45:30
:25 ['Frvr: 6900, Vr'Fr: 3
800] Example 39 Example 37 was used as the ink layer component.

Latent thermosetting agent BF3C2H3NH2 for its composition
A thermal transfer recording medium was obtained in the same manner as in Example 37 by adding 1.5 parts by weight.

Example 40 A thermal transfer recording medium was obtained in the same manner as in Example 33 except that Example 37 was used as the ink layer component.

Example 41 A thermal transfer recording medium was obtained in the same manner as in Example 34, except that a composition obtained by removing the lubricant from the ink composition used in Example 37 was used as the ink layer component.

Example 42 On the lubricity imparting agent layer prepared in Example 41, a composition from Example 39 with the lubricity imparting agent removed was applied as an ink layer component to a thickness of 2° and 5 μm, and then dried. The same sensitivity improver layer as in Example 37 is provided on the ink layer.

Example 43 On the same substrate as in Example 31, ethylene-vinyl acetate copolymer (vinyl acetate 40%, melt index 150
) and carnauba wax dispersed in toluene in a 1:1 weight ratio was applied and dried to a thickness of 0.3 μm to form an adhesion improver layer.

On this layer, an ink layer and a sensitivity improver layer similar to those in Example 37 were provided. When this thermal transfer recording medium was rubbed by hand, the ink fell off, but almost all of it remained on the base material.
The effect of the adhesion improver layer was confirmed.

[Comparative evaluation results] The same conditions as in Examples 7 to 17 were used.

Evaluation results: Otori: It had no lubricity and was prone to getting caught on cardboard.

Evaluation Results> [Effects of the Invention] As explained above, by using an acrylonitrile- or methacrylonitrile-based copolymer according to the structure of the present invention, it is possible to improve the abrasion resistance of images, especially the abrasion resistance against high-hardness materials, and various other properties. The reliability of printed images can be greatly improved, such as by significantly improving resistance to chemicals.

Claims (5)

[Claims] (1) A thermal transfer recording medium characterized by having an ink layer on a base material, the main components of which are a colorant and a copolymer composed of units represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 is H or CH_3; m is an integer; X is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is the same as above; R_2, R_3 are H, C
H_3, C_2H_5, C_3H_7, C_4H_9,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, C_2H_4OH
;n, n_1, n2 are integers)] (2) A thermal transfer recording medium having a lubricity imparting agent layer provided on a base material and an ink layer according to claim (1) thereon. (3) A thermal transfer recording medium having an adhesion improver layer provided on a base material and each layer according to claim (1) or claim (2) thereon. (4) The thermal transfer recording medium according to any one of claims (1) to (3), further comprising a sensitivity improver layer mainly composed of a heat-melting substance and/or a heat-softening substance on the ink layer. . (5) Claim (4) wherein the heat-melting substance and/or the heat-softening substance is selected from the group consisting of wax, polyester, acrylic resin, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. The thermal transfer recording medium described above.