JP3071206B2 - Thermal transfer recording medium - Google Patents

Description

The present invention relates to a high-sensitivity thermal transfer recording medium having excellent scratch resistance, abrasion resistance, heat resistance and print quality,
The present invention relates to a thermal transfer recording medium suitable for price tags for clothing.

[Prior Art] Conventionally, a thermal transfer layer (ink layer) of a thermal transfer recording medium has an ink layer containing an emulsified resin at a minimum modeling temperature of 40 ° C. or higher (JP-A-63-57679);
A composition containing a styrene / methyl methacrylate / butyl acrylate copolymer as a main component (JP-A-62-23779)
No.); a styrene / methacrylic ester copolymer / polymethacrylate / polyvinyl chloride resin and a colorant laminated on a permeable protective layer composed of a mixture of a styrene / methacrylic ester copolymer and a polyvinyl chloride resin. It has an ink layer composed of a mixture (JP-A-62-179992)
No.); having an ink layer composed of a mixture of a (meth) acrylate polymer and a colorant laminated on a permeable protective layer composed of a chlorinated polyolefin resin (JP-A No.
No. 63-42891).

However, when the conventional ink layer is used for a price tag for clothing or the like, there is a drawback that the image is blurred or stained due to the heat of the hot press.

That is, in JP-A-63-57679, the minimum film formation temperature is 40
A resin having a temperature of not less than 100 ° C. does not always have good heat resistance, blocking at about 100 ° C., bleeding of an image, and staining. In addition, high glass transition points (T
The resin emulsion of g) also has a high minimum film forming temperature and poor thermal sensitivity. In particular, in a hot press at 180 ° C. or higher, an image blurs and stains occur. In addition, the adhesiveness to the transferred object is poor,
If you rub strongly, the image will easily fall off. Also, if a low-melting wax is used as the binder, the image will be blurred by hot pressing and stains will occur, making it impossible to use it as a price tag for clothing.
JP-A-62-23779, JP-A-62-17992, JP-A-63
In -42891, when the Tg is increased, the hot press resistance is improved but the sensitivity is decreased. When the Tg is decreased, the sensitivity is increased, but the hot press resistance is deteriorated. Further, hot press resistance is not good because chlorinated polyolefin is used for the protective layer.

In order to solve these problems, a heat transferable ink layer containing at least a water-soluble resin and a surfactant is provided on the support, and a layer near the support surface contains more surfactant than the water-soluble resin. A thermal transfer recording medium has been proposed (JP-A-63-29308). In such a thermal transfer recording medium, the particle properties near the support surface of the thermal transfer ink become strong, while the particle properties near the surface facing the transfer paper become weak, so that various properties such as transfer property, friction resistance and scratch resistance are obtained. Although it is excellent in performance, heat resistance is not sufficient, and further improvement in hot press resistance, transferability, friction resistance and scratch resistance has been desired.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal transfer recording medium capable of overcoming the above-mentioned problems of the prior art and obtaining a transferred image having excellent scratch resistance, friction resistance, hot press resistance and heat resistance.

[Means for solving the problem]

According to the present invention, on the support, the thermoplastic resin, the melting point
At 30 to 60 ° C., a thermal transfer recording medium provided with a thermal transfer layer having a HLB value of 3 to 12 and a surfactant and a colorant as main components is provided. A thermal transfer recording medium is provided, wherein the thermal transfer layer is provided on a release layer mainly composed of wax having a softening point of 50 to 130 ° C.

That is, the main feature of the present invention is that, as a component of the thermal transfer layer, a melting point of 30 to 60 ° C. together with a thermoplastic resin and a colorant, HL
The point is that a surfactant having a B value of 3 to 12 was used.

A thermal transfer recording medium having such a thermal transfer layer satisfies all requirements of scratch resistance, friction resistance and heat resistance.

 Hereinafter, the present invention will be described in more detail.

As the thermoplastic resin used in the thermal transfer layer of the present invention, various resins having a melting point or softening point of 200 ° C. or less, for example, acrylic resin, methacrylic resin, styrene resin, vinyl acetate resin, vinyl chloride resin, vinylidene chloride resin, polyester resin , A polyether resin, a polyamide resin, a polyacetal resin, an epoxy resin, a terpene resin, a rosin resin, or a copolymer thereof. For the thermal transfer layer, one kind or a plurality of thermoplastic resins having different melting points, softening points or glass transition points may be used.

As the wax having a melting point or softening point of 50 to 130 ° C. used for the release layer, for example, carnauba wax, montan wax, ozokerite, microcrystalline wax,
Rice wax, ceresin wax, paraffin wax, polyethylene wax, sasol wax, hydrogenated castor oil, and the like. The thickness of the release layer is preferably from 0.1 to 3 μm. Further, such a release layer is formed by hot melt application or application of a liquid dissolved and dispersed in water or an organic solvent.

The surfactant used in the thermal transfer layer of the present invention has a melting point of 30 to 60 ° C. and an HLB value of 3 to 12, preferably 3 to 12.
Nine.

Examples of such a surfactant include polyoxyethylene stearyl ether, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan destearate,
Glycerol monostearate and the like.
It can be used as a species or a mixture of two or more.

Surfactants whose melting point and HLB value do not satisfy the above ranges are insufficient in the surface energy of the melted ink or the penetrability of the ink to the object to be transferred and the adhesion of the ink to the object to be transferred. Cannot achieve the purpose of the term.

In the present invention, the amount of the surfactant used is not particularly limited, but is preferably 30 parts by weight or more, and more preferably 50 to 150 parts by weight, per 100 parts by weight of the thermoplastic resin.

Colorants include carbon black, red bengara, lake red C, fast sky blue, benzidine yellow, phthalocyanine green, phthalocyanine blue,
Pigments such as direct dyes, oil dyes and basic dyes, dyes and the like can be used, and it is preferable to add about 10 to 20% by weight to the entire thermal transfer layer.

In the thermal transfer layer, a plasticizer may be used as needed to adjust the melting point or softening point. Examples of such a plasticizer include dimethyl phthalate,
Examples include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl adipate, diethyl glycol benzoate, butyl stearate, and triphenyl phosphate.

The thickness of the thermal transfer layer is suitably about 0.5 to 3 μm. Further, the present invention has a melting point or softening point between the support and the thermal transfer layer.
A release layer containing wax at 50 to 130 ° C. as a main component may be provided.

Since such a release layer has a function of forming a wax layer on the surface of a transferred image while improving transfer efficiency during thermal transfer, a thermal transfer recording medium provided with such a release layer only gives a clear transfer image. In addition, the action of the wax improves the hot press resistance (becomes difficult to transfer to others), and also improves the friction resistance.

If the melting point or softening point of the release layer is lower than 50 ° C., heat energy at the time of transfer is consumed for melting the wax, and transfer of the thermal transfer layer is deteriorated. On the other hand, if the melting point or the softening point is higher than 130 ° C., the releasability during transfer deteriorates.

A lubricant may be added to the release layer and / or the thermal transfer layer. Particularly preferred are inorganic lubricants and organic lubricants having a melting point of 140 ° C. or higher.

Examples of the inorganic lubricant include talc, mica powder, molybdenum disulfide, graphite, etc., having an average particle size of 0.1 to 5 μm, and 5 to 20 μm.
Add in the range of weight%.

The organic lubricant has a melting point of 140 ° C. or higher and includes lithium stearate, magnesium stearate, calcium stearate, strontium stearate, barium stearate, calcium laurate, barium laurate, lithium 12-hydroxystearate, lithium 12-hydroxystearate Metallic soaps such as calcium phosphate and dibasic lead stearate, N, N'-ethylenebis-12-hydroxystearic acid amide, N, N'-ethylenebislauric acid amide, N, N'-methylenebisstearic acid amide , N, N'-ethylenebisstearic acid amide, N, N '
N-substituted fatty acid amides such as hexamethylene bisoleic acid amide, N, N'-distearyl adipamide, N, N'-distearyl terephthalic acid amide, polytetrafluoroethylene, silicone resin, etc. weight%
Add within the range. These are dissolved in a layer forming liquid or used in the form of particles of about 0.1 to 5 μm.

〔Example〕

The present invention has been described above with reference to examples and comparative examples. Parts are parts by weight.

Example 1 The following composition solution was applied to a 4.5 μm-thick polyethylene terephthalate film, and a 2.0 μm-thick thermal transfer layer was provided.
A thermal transfer recording medium of the present invention was prepared.

Ethyl methacrylate / acrylonitrile copolymer emulsion (Tg 70 ° C, solid content 50%) 80 parts 3,6-dimethyl-4-octyne-3,6-diol (HLB3
40 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol (HLB5-7 mp.50 ° C) 20 parts Carbon black dispersion 20 parts Example 2 4.5 μm thickness The following composition liquid was applied to a polyethylene terephthalate film of, and a 2.2 μm thick thermal transfer layer was provided.
A thermal transfer recording medium of the present invention was prepared.

Ethyl methacrylate / acrylonitrile copolymer emulsion (Tg 70 ° C, solid content 50%) 70 parts n-butyl acrylate / methyl methacrylate copolymer emulsion (Tg 20 ° C, solid content 50%) 10 parts 3,6-dimethyl-4-octyne -3,6-diol 20 parts Carbon black dispersion 20 parts Example 3 The following composition was applied on a 4.5 μm thick polyethylene terephthalate film to provide a 2 μm thick release layer.

Carnauba wax 10 parts Toluene (dispersed in a ball mill for 24 hours) 90 parts On this release layer, a 2.2 μm thick thermal transfer layer similar to that of Example 1 was provided to prepare a thermal transfer recording medium of the present invention.

Example 4 The following composition was applied on a polyethylene terephthalate film having a thickness of 4.5 μm to form a release layer having a thickness of 3 μm.

Carnauba wax 90 parts Ethylene / vinyl acetate copolymer (120 ° C. hot melt coating) 10 parts On this release layer, a 20 μm-thick thermal transfer layer similar to that of Example 2 was provided to prepare a thermal transfer recording medium of the present invention.

Comparative Example 1 Instead of 3,6-dimethyl-4-octyne-3,6-diol, diethylene glycol monolaurate (HLB4 to 7,
mp. 17-18 ° C), except that a thermal transfer recording medium of Comparative Example 1 was prepared in the same manner as in Example 2.

Comparative Example 2 Instead of 3,6-dimethyl-4-octyne-3,6-diol, polyoxyethylene stearate (HLB16.7, mp.
-48 ° C.), except that the heat transfer recording medium of the present invention was prepared in the same manner as in Example 2.

Comparative Example 3 In Example 1, 3,6-dimethyl-4-octyne-3,6-diol and 2,4,7,9-tetramethyl-5-decyne-4.7-diol were removed from the thermal transfer layer forming solution. A heat transfer recording medium of Comparative Example 3 was prepared in the same manner as in Example 1 except for the above.

Comparative Example 4 In Example 3, 3,6-dimethyl-4-octyne-3,6-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol were added from the thermal transfer layer forming solution. A thermal transfer recording medium of Comparative Example 4 was prepared in the same manner as in Example 3 except that the thermal transfer recording medium was omitted.

In each of the above Examples and Comparative Examples, the following composition liquid was applied on the side of the support opposite to the side on which the thermal transfer layer was provided, and the thickness was 0.1 μm.
m of the anti-stick layer was provided.

Silicon rubber (30%) 10 parts Toluene 90 parts Curing agent 0.1 part A thermal transfer printer (line type head, print energy 10-25
mJ / mm ² ), printing was performed on a sheet to be transferred, and the following test was performed.

Hot press test (JIS L 0850) Friction test (JIS L 0849) Scratch test (pencil hardness test) The results are shown in Table 1. The transfer paper used was ibest paper.

[Effects of the Invention] As described above, the thermal transfer recording medium of claim (1) satisfies all requirements of scratch resistance, friction resistance, hot press resistance, and heat resistance. In the thermal transfer recording medium of the present invention, a specific release layer is provided between the support and the thermal transfer layer of the present invention, so that the hot press resistance and the scratch resistance are further improved. .

Continuation of front page (56) References JP-A-63-82781 (JP, A) JP-A-63-57284 (JP, A) JP-A-63-293085 (JP, A) JP-A-62-20765 (JP, A) , A)

Claims (2)

(57) [Claims] 1. A thermoplastic resin having a melting point of 30 to 60 on a support.
A thermal transfer recording medium comprising a thermal transfer layer mainly composed of a surfactant and a colorant having an HLB value of 3 to 12 at ℃. 2. A thermal transfer device according to claim 1, wherein a release layer mainly composed of wax having a melting point or softening point of 50 to 130 ° C. is provided between the support and the thermal transfer layer. recoding media.