JPH02299885A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To obtain excellent thermal transfer properties by providing a release layer based on a specific compound on a support and successively laminating an ink layer based on a colorant, a specific copolymer and a specific block copolymer and a fixability enhancing layer based on a specific resin to said release layer. CONSTITUTION:A release layer 2 based on either one of amide ester compound, an amide alcohol compound and a fatty acid diethanolamide compound respectively represented by formulae (I), (II), (III) is provided on a support and an ink layer 3 based on a colorant, an ethylene/ethyl acrylate or vinyl acetate copolymer (ethylene content : 70 - 90wt.%) with a melt index of 800 - 3,000g/10min and a styrene/isoprene/styrene and/or styrene/butadiene/styrene block copolymer is provided on said release layer and, further, a fixability enhancing layer 4 based on a resin with a glass transition point of 100 deg.C or more is laminated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent thermal transfer properties especially during high-density printing and high-speed printing, and can print high-resolution images not only on paper with high smoothness but also on paper with low smoothness. The present invention relates to a thermal transfer recording medium.

[Prior Art] In conventional thermal transfer recording methods, the transfer recording performance, that is, the print quality, is greatly affected by the surface smoothness of the recording medium, and although good printing is performed on highly smooth recording media, In the case of a low quality recording medium, the print quality may deteriorate significantly. However, even when using paper, which is the most typical recording medium, highly smooth paper is rather special, and ordinary paper has various degrees of unevenness due to entangled fibers. Therefore, in the case of paper with large surface irregularities, the hot-melted ink cannot penetrate into the paper fibers during printing and adheres only to the convex parts of the surface or evenly around them, resulting in the edges of the printed image being distorted. The image may not be sharp or part of the image may be missing, reducing print quality.

In addition, in order to improve print quality, it may be possible to use a heat-melting binder with a low melting point, but in this case, the heat-transferable ink layer remains viscous even at relatively low temperatures, resulting in poor storage stability. This causes inconveniences such as a decrease in the print quality and staining of the non-printing area of the recording medium.

There is also an example of adding a rubber elastic substance to the ink layer in an amount of 0.3 to IO beads to improve transferability to rough paper. but,
It was difficult to achieve the purpose of these because the rubber elastic material caused a decrease in thermal sensitivity or the ink was not clean (Japanese Patent Application Laid-Open No. 82-230872, 82-30083).
, 8O-225795).

In addition, there is a so-called bridge transfer method which is already known as a method for printing on rough paper. This is the same layer structure as in the present invention, but since the ink layer is transferred by contacting only the convex portions of the unevenness of the receiving paper, image fixing properties are poor and transfer failure occurs in large concave portions.

The above-mentioned conventional thermal transfer recording medium provided with a heat-fusible coloring material layer requires energy to melt and transfer the heat-fusible coloring material layer, especially when transferring in a short heating time such as during high-density printing or high-speed printing. There was a drawback that the image transfer rate and resolution were insufficient due to the lack of.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a high-resolution printed image not only on paper with high smoothness but also on paper with low smoothness, with excellent thermal transfer properties during high-density printing and high-speed printing. An object of the present invention is to provide a thermal transfer recording medium.

[Means for Solving the Problems] The thermal transfer recording medium of the present invention has the following general formula (I) on a support.
, (n), and (III) are provided as main components, and a copolymer of a coloring agent and vinyl acetate with a melt index of 8 from 0 to 3000 (
Ethylene content 70-9 (l weight %) and styrene-isobrene-styrene/and/or styrene-butadiene-
1. A thermal transfer recording medium comprising an ink layer containing a styrene block copolymer as a main component, and a fixing property improving layer containing a resin as a main component having a glass transition point of 100° C. or higher successively laminated thereon.

General formula (I) Niamide ester compound CH2 0COR3 However, R1 and R3 are linear or isosaturated hydrocarbons having 12 to 32 carbon atoms, R2 is H or C)i3 General formula (n) Amide alcohol compound R2 H20H However, R1 is a straight chain or isosaturated hydrocarbon having 12 to 32 carbon atoms, R2 is H or CM co-general formula (m) fatty acid jetanolamide compound CH2C
H20H CH2CH20H However, R is the number of carbon atoms! 3 to 41 linear acid, isoacid, antiisoacid and/or oxyacid residue.

Furthermore, in order to improve the adhesion of the release layer, an oxidized polyethylene wax with a melting point of 100°C or higher and a copolymer of vinyl acetate (ethylene-containing ff 170 to 90% by weight) with a melting point of 100°C or higher are used between the support and the thermal transfer layer. %) as a main component.

Further, the present invention is characterized in that any one layer on the support is composed of fine particles.

- The layer structure of the thermal transfer recording medium of the present invention is schematically explained as shown in FIGS. 1 and 2.

In the figure, 1 is a support, 2 is a release layer, 3 is an ink layer, 4 is a fixability improving layer, and 5 is an adhesive layer.

The oxidized polyethylene wax used in the adhesive layer of the present invention is preferably a flexible material with a melting point of 100°C or higher, preferably 110 to 130°C, and one melt ind.
Adhesion to the support is improved by using a copolymer of ethylene and ethyl acrylate or vinyl acetate (ethyl acrylate or vinyl acetate content 10-30%) of 10-500 g 710 m+10 Sox. Also, by combining oxidized polyethylene wax and a copolymer of ethylene and ethyl acrylate or vinyl acetate, not only the adhesion to the support is improved, but also the melt index of oxidized polyethylene wax and melt index 1O~500g/1Os is improved.
Due to the synergistic effect of the copolymer of ethylene and ethyl acrylate or vinyl acetate, the release layer on the adhesive layer is easily cut by the thermal energy of the thermal head, resulting in excellent transferability.

The mixing ratio of the oxidized polyethylene wax and the copolymer of ethylene and ethyl acrylate or vinyl acetate is preferably 90/10 to 30/70 by weight. The thickness of the adhesive layer is 0.405 to 3.0μ, preferably 0.5 to 1.5μ.
l is good.

The melt index used in the adhesive layer of the present invention is 10
- 800g/login, ethylene content 70-9
As the 0% ethylene-vinyl acetate copolymer, EVAFLEX-2 manufactured by Mikata DuPont Polychemical Co.
10 (MI=400g/10sin, VA=28
%), EVAFLEX-220 (Ml = 15
0g/login, VA-28%), EVAPLE
X-250 (Ml-15g/login, VA=
28%), EVAFLEX-310 (Ml-400
g/1o1n, VA-25%), EVAPLEX-4
10 (MI=400g/10sIn, VA-19
%), EVAPLEX-420 (old-150g/1
0ain, VA-19%), EVAFI, EX-4
50 (old -15g/l'Om!n SA-19
%), EVAPLEX-550 (old = 15g71
0sIn, VA-14%), etc.

Also, the melt index is 10-600g/! Os[n
.

As an ethylene-ethyl acrylate copolymer having an ethylene content of 70 to 90%, EEA-704 (formerly -275 g/LO) manufactured by Mikata-DuPont Polychemical Co., Ltd.
1n%EA-25%), EIEA-707 (M
l-25g/10sin s EA""' 17%).

In addition, as oxidized polyethylene wax, p Hochst-wax PED 121 113- manufactured by Hoechst & Co.
118Hoechst-1fax PED 153
115-12[]Hoehst-Wax PED 5
21 10B-108Hoechsc-Wax PE
D 522 100-105 and the like. As mentioned above, the adhesive layer of the present invention mainly contains oxidized polyethylene wax and ethylene-ethyl acrylate or ethylene-vinyl acetate copolymer, but in addition to these, if necessary, heat-melting substances such as Carnauba, paraffin, montan wax, etc. can be mixed.

The peeling layer of the present invention is provided to facilitate peeling of the coloring material layer from the support and to obtain a high-density printed image when the coloring material layer is melt-transferred. That is, the one-stage type (1
), the amide alcohol compound of general formula (II), and the fatty acid jetanolamide compound of general formula (III) have very small crystallinity and excellent transparency, and the molecules of these compounds are bulky. Because it has a long chain and an active functional group at its end, it has a high affinity with the heat-melting ink layer when melted, and because it is highly transparent, a high-density printed image can be obtained. be.

The amide ester compound of general formula (I) is synthesized by amidation and esterification through a dehydration reaction between 2 moles of higher fatty acids and 1 mole of amino alcohol. This reaction is
Esterification proceeds through amidation to produce the desired compound.

In selecting this compound, it is necessary not only to have an affinity for the above-mentioned solvents, but also to have various physical properties necessary for thermal transfer printing. It is suitable that the penetration degree as a parameter of hardness has a value of 0 to 20.

Higher fatty acids suitable for synthesizing amide ester compounds that satisfy the above physical properties include straight chain fatty acids having 12 to 30 carbon atoms, isofatty acids having 16 to 32 carbon atoms, and 2 to 30 carbon atoms.
It is one kind or a mixture of two or more kinds of 2 to 32 antiiso fatty acids.

On the other hand, monoethanolamine and monoisopropanolamine are suitable as the amino alcohol in terms of melting point and penetration.

Regarding the example of the compound synthesized using 2 moles of acid and amine, the raw material components and the physical properties of the synthesized compound are shown in Table 1 below.

Table 1 Synthesis row 'a Fluidity: ^, Good fluidity B, Fluidity when stirred C, Paste or solid The amide alcohol compound of general formula (n) is an amide formed by a dehydration reaction between a higher fatty acid and an amino alcohol. It is easily synthesized by chemical reaction. In selecting this compound, it is necessary not only to have an affinity for the above-mentioned solvents, but also to have various physical properties necessary for thermal transfer printing. It is suitable that the penetration degree as a parameter of hardness has a value of 0 to 20.

Higher fatty acids suitable for synthesizing amide alcohol compounds that satisfy the above physical properties include straight chain fatty acids having 12 to 30 carbon atoms, isofatty acids having 16 to 32 carbon atoms, and 2 to 32 carbon atoms.
One of 2 to 32 antiiso fatty acids or 2F! i
It is a mixture of the above.

On the other hand, monoethanolamine and monoisopropanolamine are suitable as the amino alcohol in terms of melting point and penetration.

The structures and properties of the compounds synthesized using the above acids and amines are shown in Table 2 below.

Table 2 Synthesis Examples Commercially available products are available from Yoken Fine Chemical Co. under the trade names Amizole CME%LME, PME, and SME.

The fatty acid jetanolamide compound of the general formula (III) can be obtained by dehydration condensation of higher fatty acids and jetanolamine, but it is desirable to use methyl esters of fatty acids in order to make the reaction proceed smoothly.

CH2C11z OHCH2CH2011 In selecting this compound, it is necessary to have various physical properties necessary for thermal transfer printing, especially a melting point of 60 to 110°C as a parameter of thermal properties and penetration as a parameter of hardness. It is suitable that the degree has a value of 0 to 20.

Straight chain or branched saturated hydrocarbons or oxy-saturated hydrocarbons having 13 or more carbon atoms are desirable as the fatty acid suitable for synthesizing jetanolamide that satisfies the above-mentioned physical properties. In particular, in order to have an irregular crystal grain shape in the solid phase, the fatty acid must not be a single fatty acid, but a mixture of two or more types with different carbon numbers, and the fatty acid must have a linear chain mixed with branched saturated hydrocarbons. is desirable. Suitable fatty acids that satisfy this requirement include hard lanolic acid, montanic acid, etc. extracted and purified from natural products.

For example, hard lanolin fatty acid jetanolamide (rising melting point 778°C, DSCSC Beeks 1'C content 12 (22
℃), fatty acid raw material, Yoshikawa Oil Co., Ltd., lanolin HH-73).

The main component is any of the above compounds. Further, as other binder components, conventionally known waxes and resins that melt by heating may be used as necessary. Examples of waxes include carnauba wax, auriculie wax, microcrystalline wax, paraffin wax, ceresin wax, montan wax, candelilla wax, shellac wax, wax wax, palm wax, beeswax, and low molecular weight polyethylene. Can be mentioned. Furthermore, if necessary, ethylene ethyl acrylate or ethylene-vinyl acetate copolymer or the like may be mixed and used.

When the release layer of the present invention has a fine particle structure, it is suitable for high-density printing and high-speed printing because it has excellent print quality, excellent transferability, and excellent one-dot reproducibility.

The fine particle structure of the present invention is formed by dispersing the wax described above in a solvent and coating it.

Examples of the solvent include toluene, xylene, ethyl acetate, methyl ethyl ketone, acetone, methanol, ethanol, isopropanol, ethyl cellosoneb, and cyclohexanone.

The size of the fine particles is preferably 0.01 to 0.8 μl, preferably 0.05 to 0.4 μl. (If it is too large, the thermal sensitivity will be lowered, and if it is too small, the one-dot reproducibility and transfer efficiency will be lowered.) The thickness of the release layer is 0.1 to 10 .mu.m, preferably 1 to 5 .mu.m.

The ink layer of the present invention has a colorant and a melt index of 80.
0~3000g710min, preferably 1000~
Copolymer of 2000g710sin of ethylene and ethyl acrylate or vinyl acetate (ethylene content 7
0 to 90 g (1% by weight, preferably 70 to 85% by weight)) and a block copolymer of styrene-isobrene=ren and/or styrene-butadiene-styrene to impart specific elasticity to the thermoplastic ink layer. . By doing so, it is possible to easily contact and adhere to the surface of the rough paper using the head pressure during printing. Furthermore, since the melt index is as high as floo ~3000g710min, it melts and flows in a short time, making it easy to wet the transferred material, and the content of ethyl acrylate or vinyl acetate in the copolymer is 10 to 30%. This ensures proper adhesion to paper.

Styrene - Isobrene - Styrene and/or Styrene -
A suitable block copolymer of butane diene-styrene has a hardness of 3 in Shore A (JISK6301).
0 to 60 elastic body and melt index 6 conditions (A
1~ in STM D123&) (8/1osin)
It is 500.

If the hardness is less than 30, an abnormal image will occur in OHP printing, and if it is greater than 60, the desired adhesion to rough paper irregularities cannot be achieved.

When the melt index is less than 1, the thermal sensitivity decreases,
Thermal transfer requires high energy. If it is greater than 500, it becomes difficult for the block copolymer to exhibit sufficient elasticity.

The melt index used in the ink layer of the present invention is 8.
00~3000g/1osin, ethylene content is 7'
As the ethylene-ethyl acrylate copolymer having a content of 0 to 90%, MB-910 (formerly =
1100g/io'mln, EA-28%) MB
-900 (old -1500g/10min, EA-2
3%).

Melt index is 800-3000g710sin
.

As an ethylene-vinyl acetate copolymer having an ethylene content of 70 to 90%, MB-850 (manufactured by Nippon Unicar Nakako Co., Ltd.) is used.
Ml -800g/fOmIn, VA-22%)
, MB-010 (old -1200g/LOWIn,
VA=25%), MB-080 (Ml-2500g
HAONn s v^-19%) and the like.

EVA and EEA are as defined above.

If the amount of copolymer is out of this range, it will mix with the block copolymer, reduce thermal sensitivity, cut off the ink,
It becomes impossible to transcribe. Melt index is 8
If it is smaller than 00, the thermal sensitivity will decrease and high energy will be required for thermal transfer, and if it is larger than 3000, it will not be possible to create a strong image on rough paper.

The ink layer of the present invention may also contain styrene and/or styrene derivatives, vinyl, acrylic, paraffin, polyethylene, candelilla, carnauba wax, etc., if necessary.

The mixing ratio of the block copolymer and the thermoplastic binder is appropriately selected depending on the printing conditions, but preferably the block copolymer is contained in an ao-eoi amount of 10 to 90% by weight, more preferably by an ao-eoi amount of 10 to 90%. be.

The layer thickness is 0.2-5μ, preferably 0.5-4μ.

As the coloring agent, it is preferable to use organic or inorganic dyes or pigments that have properties suitable for recording materials. For example, it is preferable to have a sufficient color density and not turn brown due to light, heat, humidity, etc. Further, it may be a substance that is colorless when not heated, but develops color when heated, or a substance that develops color when it comes into contact with a substance coated on a transfer target.

Specific examples include pigments and dyes such as carbon black, titanium dioxide, red iron oxide, Lake Red C1 Fast Sky Blue, benzidine yellow, phthalocyanine green, phthalocyanine blue, direct dyes, oil dyes, and basic dyes.

The ink layer of the present invention may be prepared by kneading a colorant and the above-described specific copolymer into a composition, and applying the composition to the surface of the release layer using an appropriate coating method.

As for the composition, the colorant and the above-mentioned specific copolymer are blended so that the weight of the colorant is 1 to 80%, preferably 5 to 30% of their total weight.

Further, the fine particle structure is formed by dispersing the composition in a solvent and coating it. Examples of the solvent include toluene, xylene, ethyl acetate, methyl ethyl ketone, acetone, methanol, ethanol, isopropanol, ethyl cellosolve, and cyclohexanone.

The thickness of the ink layer provided as above is 0.1 μ5
Approximately w1Oμ is appropriate, preferably 1μm to 5μ
− is.

When the ink layer of the present invention has a fine particle structure, it is easily cut during printing, has excellent transferability, and has excellent one-dot reproducibility, so that it is suitable for high-density printing and high-speed printing.

The size of the fine particles is 0.01 to 0.8 μ■,
Preferably it is 0.05 to 0.4 μm. If it is too large, thermal sensitivity will decrease, and if it is too small, one-dot reproducibility and transfer efficiency will decrease.

The fixing property improving layer of the present invention is mainly composed of at least one resin of styrene type and/or styrene derivative type, vinyl type, and acrylic type, and has a glass transition point of 100°C or higher, and optionally contains paraffin wax, polyethylene wax, and canned resin. It is also possible to add waxes such as Delilah wax and carnauba wax, and thermoplastic substances such as thermoplastic resins such as PE, PVC, EVA, and EEA.

The styrene resin of the present invention has a molecular weight [MW] of 85
,000 polystyrene (TglOO℃), and polystyrene derivatives include boron P-carbomethoxystyrene (TglOO℃).
g 131°C), polyP-cyanostyrene (Tg12
0°C), poly O-methylstyrene (12115°C), poly P-methylstyrene (Tg 101”c), poly 2,4-dimethylstyrene (Tgl 19°C), poly
2.5-dimethylstyrene (Tg 122°C), poly 3
．． 4-dimethylstyrene (Tg!02℃), polyP-
terL-butylstyrene (Tg118℃), polyP-phenylstyrene (Tg138℃), polyP-phenoxystyrene (TgLOQ℃), poly 2,5-difluorostyrene (Tg lol”c), polyP-chlorostyrene (72128℃) ), poly 2,5-dichlorostyrene (7g 130°C), poly 3,4-dichlorostyrene (Tg 138°C), poly 2,6-dichlorostyrene (Tg 167°C), poly α-vinylnaphthalene (7g 1
82℃), polyα-methylnaphthalene (Tg 180℃)
.

Polydivinylbenzene (7g10
6℃), polyvinyl formal (7g at 105℃), polyvinylcyclohexane (7g at 100℃), polymethyl methacrylate (7g at 105℃) as the acrylic resin
), isotactic polymethyl methacrylate) (T
g 115°C), poly tert-butyl methacrylate
) (7g 107℃), polyethylene glycol dimethacrylate (Tgl 16℃), polypentachlorophenylacrylate (7g 145℃), polyphenyl methacrylate (7g 110℃), polyP-cyanophenyl methacrylate (7g 150℃), polyP-cyanophenyl methacrylate (7g 150℃), polyP-cyanophenyl methacrylate (7g 150℃) Phenyl methacrylate (Tg 10B"c), poly P-cyanophenyl methacrylate) (7g 1211℃
), polymethacrylonitrile (Tg 120°C).

The fixability improving layer of the present invention is obtained by dispersing the composition in a solvent,
When the ink layer is coated on the surface, it has a fine particle structure.

Solvents include toluene, xylene, ethyl acetate, methyl ethyl ketone, acetone, methanol, ethanol,
Examples include isopropanol, ethyl cellosolve, and cyclohexanone.

The thickness of the fixing property improving layer provided as above is 0.1
Approximately 1 μm to 10 μm, preferably 1 μm to 10 μm
It is 5 μ■.

When the fixing property improving layer of the present invention has a fine particle structure, it is suitable for high-density printing and high-speed printing because it not only has good fixing properties but also is easy to tear during printing, has excellent transferability, and has excellent one-dot reproducibility. .

The size of the fine particles is o, 01-0.8μ,
Preferably it is 0.05 to 0.4μ. If it is too large, thermal sensitivity will decrease, and if it is too small, one-dot reproducibility and transfer efficiency will decrease.

Examples of the support for the thermal transfer recording medium of the present invention include relatively heat-resistant plastic films such as polyester, polycarbonate, triacetylcellulose, nylon, and polyimide, as well as glassine paper, condenser paper,
Examples include metal foil and the like and composites of the above materials.

Examples of the composite include an aluminum/paper board combination, metallized paper, or metallized plastic film. The thickness of the support is preferably about 2 to 15 microns when considering a thermal head as a heat source for thermal transfer, but it is preferable to use a heat source that can selectively heat the thermal transferable ink layer, such as a laser beam, for example. There are no particular restrictions in this case. 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. should be provided on the surface of the support that comes into contact with the thermal head. Accordingly, the heat resistance of the support can be improved, or a support material that could not be used conventionally can be used.

In addition to hot melt coating as a coating method and gravure coating, roll coating, air knife coating, and wire barcode as a solvent coating method, printing methods such as gravure printing, gravure offset printing, and silk screen printing may also be used.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Example 1 A polyester film having a thickness of 3.5 μm with a heat-resistant layer provided on the back side was coated with the compound No. 1 of Table 1 of General Formula 1) (■p74~
77℃) 15 parts by weight O paraffin wax (mp74.6℃) 5ffi parts O toluene
80 parts by weight of the composition was dispersed in a ball mill and a release layer with a thickness of 4 μm was formed using a gravure roll coating method, and then on the surface of the release layer, carbon black 1.5ffi 1 part O was applied.
Ethylene-ethyl acrylate copolymer [14B-91
0 (manufactured by Nippon Unicar, melt index 1100g
/login, EA content: 2-bond O block copolymer styrene-isoprene (40)-styrene (hardness: A3 g, melt index: 9, Califlex TR 1107, manufactured by Shell Chemical Co., Ltd.) 4.0 parts by weight O
A composition containing 90 parts by weight of toluene was dispersed in a ball mill and coated with a gravure roll to 3 μm.
Form an ink layer with a thickness of (1), and then on the surface: 5 parts by weight of polyP-methylstyrene (Tg LO1'C) 9 parts by weight of paraffin wax 5 parts by weight of methyl ethyl ketone 45 parts of toluene A fixability improving layer having a thickness of 2 μI was formed by dispersing and gravure roll coating to prepare a thermal transfer recording medium (A).

Example 2 In Example 1, the release layer composition was prepared by formula (1) No. 1 in Table 1. No. 1 in Table 1 instead of compound No. 1.

A thermal transfer recording medium (B) was prepared in the same manner except that the compound was changed to No. 5 (mp. 72-78° C.).

Example 3 In Example 1, the release layer composition was prepared from Table 1 No. of general formula CI). No. 1 in Table 1 instead of compound No. 1.

A thermal transfer recording medium (C) was prepared in the same manner except that the compound No. 6 (19.72 to 74°C) was used.

Example 4 In Example 1, the release layer composition was prepared by formula (I) No. 1 in Table 1. Table 2 No. of general formula (II) in place of compound 1
．． A thermal transfer recording medium (D) was prepared in the same manner except that one compound (sp. 83° C.) was used.

Example 5 In Example 4, the release layer composition was
Table No. No. in Table 2 instead of compound u.

A heat transfer recording medium (E) was prepared in the same manner except that 6 compounds (sp. 76 to 80°C) were used.

Example 6 In Example 4, the release layer composition was prepared according to Table 2 No. of general formula (n). In place of compound No. 1, compound No. 6 in Table 2 (1
A thermal transfer recording medium (P) was prepared in the same manner except that the temperature was changed to 2.63°C to 67°C.

Example 7 In Example 1, a hard lanolin fatty acid jetanolamide compound (mp, '11.
Thermal transfer recording medium (8℃) was prepared in the same manner except that the temperature was changed to
G) was created.

Example 8 In Example 1, the ink layer composition was changed to ethylene-vinyl acetate copolymer MB-010 (manufactured by Nippon Yujiriki) instead of ethylene-ethyl acrylate copolymer MB-910, and the melt index was 1200 g 710 sin.

A thermal transfer recording medium (1()) was prepared in the same manner except that the vinyl acetate content was changed to 25%.

Example 9 In Example 1, the block copolymer of the ink layer composition was changed to styrene-butadiene (40ffi%)-styrene (hardness Shore A49, melt index 22,
A thermal transfer recording medium (1) was prepared in the same manner except that the medium was changed to Califlex 7R4113 (manufactured by Shell Chemical Co., Ltd.).

Example 10 In Example 1, the fixing property improving layer composition was (10-1) instead of polyP-methylstyrene (Tg 101”C).
PolyP-chlorostyrene (Tg L28°C) - Thermal transfer recording medium (J) (to-2) Polyvinylcyclohexane (Tg 100
°C) to thermal transfer recording medium (K) (10-3) Polymethyl methacrylate (Tg 105
°C) ~ Thermal transfer recording medium (L) (10-4) Polyethylene glycol dimethacrylate (Tg 11B''c) ~ Thermal transfer recording medium (M) Example 1
1 O-oxidized polyethylene wax (manufactured by Hoechst Co., Ltd.) (Sop
: 113-118℃)
5 parts by weight O ethylene-ethyl acrylate copolymer A-
707 (made by Mitsui DuPont Polychemical Tochu) (melt index 25g710min, EA containing fl
17%) 51111 parts 0 toluene 90 parts by weight of the composition was dispersed in a ball mill and an adhesion improving layer with a thickness of 1 μm was formed using a gravure roll coating method, and then Example 1 was applied to the surface of the adhesion improving layer.
A thermal transfer recording medium (N) was prepared with the same configuration as in the above.

Example 12 In Example 11, ethylene-vinyl acetate copolymer was added to the ethylene-ethyl acrylate copolymer instead of -707 to EVAPLEX-410 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) (melt index 400 g/10 mIn).
A thermal transfer recording medium (0) was prepared in the same manner except that the material was changed to (vinyl acetate content: 19%).

Example 13 A thermal transfer recording medium (P) was prepared having the same structure as in Example 1 except that the release layer in Example 1 was changed to a hot melt coating method and a release layer coating was formed.

Example 14 A thermal transfer recording medium (Q) was prepared with the same configuration as in Example 1 except that the release layer and ink layer in Example 1 were changed to a hot melt coating method and a release layer coating film and an ink layer coating film were formed. Created.

Example 15 Example 1 except that the release layer, ink layer, and fixing property improving layer were changed to a hot melt coating method, and a releasing layer coating film, an ink layer coating film, and a fixing property improving layer coating film were formed. A thermal transfer recording medium (R) was prepared with the same configuration as Example 1.

Comparative Example 1 Compound No. 1 in Table 1 in Example 1 (mp74
Paraffin wax (sp74.6
A thermal transfer recording medium (a) was prepared in the same manner except that the temperature was changed to

Comparative Example 2 Ethylene-ethyl acrylate copolymer MB-910 of the ink layer in Example 1 [manufactured by Nippon Unicar Aji (Melt Index lloOg/Login, EA-2)
A thermal transfer recording medium (b) was prepared in the same manner except that only 8%)] was used.

Comparative Example 3 In Example 8, ethylene-vinyl acetate copolymer MB-010 (manufactured by Nippon Unicar Co., Ltd., melt index 1200 g/10 g In, vinyl acetate content 25
Thermal transfer recording medium (%) was used in the same manner except that only
C) was created.

Comparative Example 4 A thermal transfer recording medium (d) was prepared in the same manner as in Example 1 except that the fixability improving layer was not provided.

Thermal transfer recording medium (A) of the example obtained as described above
(R) and Comparative Example Thermal Transfer Recording Media (A) ~ (The pieces were printed on a thermal transfer printer (prototype machine...18 heads were wet) at a head energy of 14 s+J/dat and a printing speed of 1.
Printing was performed at 50 characters/second. As the transfer paper, paper with a Beck smoothness of 25 seconds was used. The printing results are shown in Table 3.

Table 3 o There is no image drop at all Δ m There is some image drop × I! i Image dropout and resolution〉 Clear paper stamp product〉 0 Solid printing on paper with smoothness of 10 to 30 seconds is perfectly effective Blocking〉 Probing state after storage at 100°C under temperature conditions [Effects] ] As is clear from the above description, the thermal transfer recording medium of the present invention has excellent thermal transfer properties during high-density printing and high-speed printing, and provides high-resolution printed images not only on paper with high smoothness but also on paper with low smoothness. be able to.

It also has excellent image fixing properties. Ribbon block king is also effective.

[Brief explanation of the drawing]

1 and 2 are diagrams schematically explaining the layer structure of the thermal transfer recording medium of the present invention. l...Support, 2...Peeling layer, 3...Ink layer,
4... Fixability improving layer, 5... Adhesive layer. 21 figures 2 figures

Claims (3)

[Claims] (1) The following general formulas (I), (II), (III) are applied on the support.
A release layer containing one of the compounds described in 1 as a main component is provided, and a colorant and a melt index of 800 to 3 are provided thereon.
000g/10min copolymer of ethylene and ethyl acrylate or vinyl acetate (ethylene content 70-9
0% by weight) and styrene-isobrene-styrene/and/
Alternatively, a thermal transfer characterized by providing an ink layer mainly composed of a block copolymer of styrene-butadiene-styrene, and further laminating in sequence a fixing property improving layer mainly composed of a resin having a glass transition point of 100°C or higher. recoding media. General formula (I): Amide ester compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 and R_3 are linear or isosaturated hydrocarbons having 12 to 32 carbon atoms, R_2 is H or CH_3 General formula (II) Amide Alcohol compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 is a straight chain or isosaturated hydrocarbon with 12 to 32 carbon atoms, R_2 is H or CH_3 General formula (III) Fatty acid diethanolamide compound ▲ Numerical formula, chemical formula, table, etc. etc.▼ However, R represents a linear acid, isoacid, antiisoacid, and/or oxyacid residue having 13 to 41 carbon atoms. (2) Between the support and the release layer, use oxidized polyethylene wax with a melting point of 100°C or higher and a melt index of 10 to 60.
Claim (1) further comprising an adhesive layer mainly composed of a copolymer of 0g/10min of ethylene and ethyl acrylate or vinyl acetate (ethylene content 70 to 90% by weight).
) The thermal transfer recording medium described in ). (3) The thermal transfer recording medium according to claim (1) or (2), wherein any one of the layers on the support is composed of fine particles.