JP3219286B2 - Washing-resistant thermal transfer recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an thermal transfer recording material which combines a thermal transfer recording medium body and the transferred object, particularly, resistance to dry cleaning, water washability and ironing resistance, etc.
The present invention relates to a washing-resistant thermal transfer recording material which provides an excellent image (sometimes collectively referred to as "washing-resistance") and is particularly useful for clothing labels.

[0002]

2. Description of the Related Art Labels for handling and displaying clothes, labels for cleaning, and the like must be able to withstand washing while the labels are attached to the clothes, and withstand the heat of a hot press or an iron. That is, it is necessary to have washing resistance. As a general method of producing such a conventional label “clothing label”, there are (1) a method in which recording is performed on a woven fabric by letterpress printing using a curable printing ink, and heat treatment, light irradiation, and the like are performed as necessary. ) A pattern, characters, etc. are formed in reverse on the release support in advance,
Method of transferring to woven fabric by heat or the like (described in JP-B-61-44077), (3) Method of recording on woven fabric by ink jet method using liquid ink (described in JP-A-60-71767) And (4) a method of writing a liquid ink on a woven fabric with a writing implement or the like (described in JP-A-56-14137).

However, in these methods, (1)
And (2) is suitable for mass production because of printing,
It is unsuitable for small quantities and various kinds, and has the disadvantage that it takes a long time to record (print). In the above (3), various kinds are small and excellent in quickness, but are limited to a special woven fabric in terms of ink bleeding, and require a drying step. In the above (4), since it is a manual operation, it is not suitable for complicated designs and fine characters, and has a drawback that workability is not good. In addition to these, a transfer image obtained by a conventional ink sheet (thermal transfer recording medium) generally includes an ink component containing a cleaning solvent (water, warm water, 1,1,1-
(Trichloroethane, perchren, naphtha, etc.), which has the disadvantage of being easily removed by washing because it contains substances that are easily attacked.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, has good washing resistance, and provides a transferred image with excellent resolution, and is particularly useful for clothing labels. and it provides a resistance to washing thermal transfer recording material which combines a resistance to washing thermal transfer recording medium body and the transferred object.

[0005]

A first aspect of the present invention is a washing-resistant heat transfer recording medium , in which a colorant and a melting point (D
Ink layer by SC method) is mainly composed of 80 to 150 ° C. of polyamides resins are characterized by being provided. It is desirable that a release layer containing wax as a main component is provided between the support and the ink layer.

A second aspect of the present invention relates to a washing-resistant thermal transfer recording material .
In the above , the colorant and melting point on the support (by DSC method)
Is characterized by using a combination of a thermal transfer recording medium provided with an ink layer mainly composed of a polyamide resin at 80 to 150 ° C. and an object to be transferred whose ink receiving surface is mainly composed of a polyamide resin and has a Beck smoothness of 500 seconds or more. And

The inventors of the present invention have conducted much research on a thermal transfer recording medium which is useful as a clothing label or the like and has a good washing quality with a washing resistance. It has been confirmed that the above-mentioned problem can be achieved by using an ink sheet (thermal transfer recording medium) containing a polyamide resin whose main component is in the range of 80 to 150 ° C. It has also been found that the polyamide resin having a melt viscosity at 150 ° C. in the range of 500 to 5000 Pa · S is particularly effective. The present invention has been made based on such findings.

Hereinafter, the present invention will be described in more detail. As described above, the thermal transfer recording medium of the present invention has a configuration in which a specific ink layer is formed on a support. Further, as described above, the thermal transfer recording material of the present invention has a configuration including a combination of a specific ink sheet and a specific transfer target.

First, the description of the thermal transfer recording medium (ink sheet) of the present invention proceeds. The support used in the ink sheet is a plastic film having a thickness of about 3 to 10 μm, for example, a polyester film, a polycarbonate film, or the like. , A polyimide film, a wholly aromatic polyamide film, a polyetheretherketone film, a polysulfone film, and the like.

As a colorant in the ink layer, carbon black, other generally known inorganic pigments, organic dyes and pigments are used. Among them, the use of carbon black is particularly preferred.

The polyamide resin has a melting point (according to DSC method) of 80
Those having a temperature in the range of -150 ° C are used as the binder.
The “melting point (according to DSC method)” here is a differential calorimeter (DSC)
It is a main melting peak temperature when measured by using. By using a polyamide as a copolymer, compared to a homopolymer, a decrease in crystallinity and a accompanying decrease in melting point,
Further, the melt viscosity can be reduced, which is desirable as a binder for a thermal transfer recording medium. And polyamide resin (including modified polyamide resin) is methanol,
It is very easy to handle because it dissolves in alcohol such as ethanol and IPA (it does not dissolve in the cleaning solvent). On the other hand, the homopolymer dissolves in formic acid, concentrated sulfuric acid, phenol, cresol and the like, but does not dissolve in other general-purpose solvents, so that it is practically difficult to disperse and apply.

The following are examples of such polyamide resins.

[0013]

[0014]

[0015]

Of these resins, the lower the melting point and the lower the melt viscosity, the better the amount of the copolymer component, the better. However, if the crystallization is reduced too much, the material becomes sticky. Copolymers are easier to handle.

It is desirable that these polyamide resins have a melt viscosity at 150 ° C. in the range of 500 to 5000 Pa · S. If the melt viscosity is less than 500 Pa · S, the iron resistance deteriorates. On the other hand, if the melt viscosity is more than 5000 Pa · S, the cut of the print deteriorates, which is not preferable.

The polyamide resin as a binder of such ink layer is intended more desirably particulate and its particle size is 0.1~2μm preferably 0.1~0.5μm
Is appropriate .

In order to make the polyamide resin into particles, for example, the resin (polyamide copolymer) may be dissolved in a mixed solvent of methanol and toluene, and the resulting solution may be dispersed and emulsified in water with stirring. .

By making the polyamide resin into a particulate form, the heated portion and the non-heated portion of the ink layer are sharply cut, the energy for cutting is reduced, and the thermal sensitivity is increased.

The ratio of the colorant / polyamide resin in the ink layer is 30/70 to 70 by weight in the case of a continuous layer system.
/ 30, more preferably 40/6
0 to 60/40. The ratio of the colorant / polyamide resin in the ink layer is 5/95 in the case of a particulate system.
７０70/30, more preferably 1/70/30
0/90 to 50/50. If the ratio of the colorant is higher than this, the ink tends to fall off from the support or the rub resistance of the formed image becomes insufficient. Conversely, if the ratio of the colorant is smaller than this, the cohesive force of the ink layer becomes remarkably large, and the tomochi phenomenon (for example, a phenomenon in which the middle part of the letter "" is transferred by being surrounded by the surrounding part). ) Occurs.

In addition, other substances (eg, resin, wax, surfactant, etc.) may be contained in the ink layer, if necessary, for the purpose of improving sensitivity, preventing the ink layer from falling off the support, and improving dispersibility. Can be added, but should be in a minimum amount so as not to reduce the washing resistance. The ink layer material is used by dispersing it in a suitable solvent, or is melt-dispersed and coated on a support. The amount of ink layer attached is 0.
It is 1 to 3.0 g / m ^2, preferably 0.5 to 2.0 g / m ² .

The thermal transfer recording medium according to the present invention is preferably provided with a release layer mainly composed of wax between the support and the ink layer.

Examples of such waxes include natural waxes such as beeswax, carnauba wax, whale wax, wood wax, candelilla wax, rice bran wax, montan wax, etc .: paraffin wax, microcrystalline wax, oxidized wax, ozokerite, ceresin Synthetic waxes such as polyester wax, polyethylene wax and the like are preferably used. In addition to these waxes, higher fatty acids such as margaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, freunic acid, and behenic acid: higher alcohols such as stearyl alcohol and behenyl alcohol: esters such as fatty acid esters of sorbitan:
Amides such as stearinamide and oleinamide can be used as appropriate.

In addition, rubbers such as isoprene rubber, butadiene rubber, ethylene propylene rubber, butyl rubber, and nitrile rubber are added in order to increase the elasticity of the release layer (to improve the adhesion between the ink sheet and the transfer-receiving member). And / or adding resins such as an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer in order to impart adhesiveness to the release layer (to prevent the release layer from falling off). Is also good.

The coating weight of the release layer, 0.5 to 8 g / m ² preferably from 1 to 5 g / m ^2. The release layer may be hot-melt-coated, but it is preferable to apply it by dispersing it in a solvent and apply it in the form of particles.

[0027] If necessary, an undercoat layer may be provided between the support and the release layer. The undercoat layer has an uneven surface and a larger surface area than a smooth one, thereby increasing the adhesion area between the undercoat layer and the release layer, improving the adhesive force between these two layers, and simultaneously performing thermal transfer. In this case, it is effective to make the release layer easy to cut.

The thermal transfer recording medium of the present invention may be provided with a stick prevention layer, if necessary, on the surface opposite to the ink layer.

As the transfer object used in combination with the thermal transfer recording medium of the present invention, paper, film, cloth, etc. can be used. The paper is preferably made of a resin or the like subjected to a water-resistant treatment, synthetic paper, or the like. As the cloth, artificial fibers such as rayon, Bemberg, acetate, nylon, and polyester, natural fibers such as cotton and silk, or blended fibers of these, and nonwoven fabrics thereof can be used. About film, polyester film,
Polyolefin films, acetate films, polycarbonate films, polyimide films, and the like can be used.

[0030] a transfer member of the present invention, the ink layer in the thermal transfer recording medium is as a main component a colorant and a polyamide resin, a main component Toshikatsu Bekk smoothness of the polyamide resin to the respective material to be transferred onto the 500 The one provided with a receiving layer for at least seconds, or the one to be transferred itself is made of a polyamide resin and has a Beck smoothness of 500 seconds or more.
You. By doing so, the cleaning resistance and the iron resistance can be further improved. This is because (i) there is no void and the resolution of the transferred image is good, (ii) the contact area with the transferred object is large, and the force applied during washing is small, and (iii) heat is transmitted efficiently. , Etc.

In order to make the Beck smoothness of the receiving layer 500 seconds or more, the density (the degree of density of warp and weft (expressed by the number of yarns per inch)) when the substrate of the transfer object is cloth is used. Increase the thickness of the yarn, reduce the thickness of the yarn, heat and / or
Alternatively, it is possible to take measures such as crushing the fibers by applying pressure, laminating a polyamide resin film, or the like. In addition,
Can be applied to paper and film as a base material.

The use of a polyamide resin for the thermal transfer recording medium itself is described in JP-A-63-78791 and JP-A-2-92587. However, unlike the ink layer, the former is used as an adhesive layer, and the ink layer is mainly composed of a colorant and a thermoplastic resin, and is intended to produce a barcode having good friction resistance. In the latter case, a polyamide resin is added to improve the friction resistance of the transfer ink surface, and the main component of the binder resin is a wax or the like as in the former case. The focus is on creating good barcodes. That is, no consideration is given to washing resistance, ironing resistance, etc.

[0033]

EXAMPLES All parts and percentages are by weight. For convenience, the thermal transfer recording medium is referred to as an “ink sheet”.

Example 1 A mixture consisting of 10 parts of silicone rubber (30%), 90 parts of toluene and 90 parts of a curing agent (CAT-PL-8, manufactured by Shin-Etsu Chemical Co., Ltd.) was coated on one surface of a polyester film having a thickness of about 4.5 μm. It was applied and dried to provide a stick prevention layer having a thickness of about 0.1 μm. Further, a mixed solution having the following composition was prepared, applied to the polyester film surface opposite to the stick prevention layer, and dried to form an ink layer of about 1.0 g / m ² . Thermal transfer recording media (comparative examples for ink layers 9, 10 and 11) were prepared.

(Composition of Ink Layer 1) Carbon black 5 parts No. 1 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 2) Carbon black 5 parts No. 3 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 3) Carbon black 5 parts No. 4 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 4) Carbon black 5 parts No. 5 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 5) Carbon black 5 parts No. 7 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 6) Carbon black 5 parts No. 9 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 7) Carbon black 5 parts No. 10 polyamide resin 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (Composition of ink layer 8) Carbon black 5 parts Polyamide resin No. 12 5 parts Methanol / toluene (= 1/1) mixed solvent 90 parts (composition of ink layer 9) Carbon black 5 parts 6 nylon 5 parts Phenol 90 parts (composition of ink layer 10) Carbon black 7.5 Part Acrylic resin 7.5 parts Methyl ethyl ketone 85 parts (Composition of ink layer 11) Carbon black 7.5 parts Styrene resin 7.5 parts Toluene 85 parts

On the other hand, (A) (B) (C)
(D) Seven types of transfer recipients (E), (F) and (G) were prepared. (A) Nylon 6 2.4 parts Calcium chloride 1.6 parts Methanol 16 parts The composition which consists of nylon base cloth (190
The coated layer was coated and dried, washed with water and dried again to provide a receptor layer having an adhesion amount of about 10 g / m ² . The Beck smoothness was 47 seconds. (B) An object to be transferred which is exactly the same as the above (A) except that a nylon base cloth of 210 lines × 210 lines / square inch and 70 denier is used. Beck smoothness of the receiving layer is 3
50 seconds. (C) the amount of the receptor layer attached is from about 10 g / m ² to about 20 g / m ^2;
A transferred body identical to the above (A) except that m ² was changed. The Beck smoothness of the receiving layer was 500 seconds. (D) The object of (C) is an object to be transferred obtained by subjecting a base fabric to calendering in advance. Beck smoothness of the receiving layer is 12
00 seconds. (E) Nylon 6 film (Beck smoothness∞) (F) Laminating the film of (E) above on high quality paper (Beck smoothness∞) (G) Water resistant paper

A thermal transfer printer (line-type head,
Printing was performed with an applied energy of 10 to 25 mj / mm ² ), an appropriate printing energy (sensitivity) was determined, and a transferred image was created and tested. The results are summarized in Table 1.

Example 2 The same stick preventing layer as in Example 1 was provided on one side of a polyester film having a thickness of about 4.5 μm, and the other polyester side was carnauba wax (10% toluene dispersion) 85 parts polybutadiene rubber (5% toluene solution) The mixed liquid consisting of 15 parts was dried with a wire bar to a dry adhesion amount of about 1.0.
g / m ² and dried at 40 ° C. for 1 minute to form a release layer. Also, a mixed solution having the following composition was prepared, applied on the release layer, applied so that the dry adhesion amount was about 1.0 g / m ² , and dried to prepare a thermal transfer recording medium. 6/66/12 Nylon Copolymer (mp 120 ° C.) 15 parts Isopropyl alcohol 25 parts Toluene 25 parts Methanol 5 parts A mixture consisting of 5 parts was heated to 50 ° C. with stirring to dissolve. After dissolution, 30 parts of water was added little by little while continuing stirring to prepare an emulsion of polyamide resin. To 100 parts of this emulsion, 10 parts of carbon black (50% methanol dispersion) was added and mixed to prepare an ink layer forming liquid. An ink sheet 12 was prepared in the same manner as in Example 1 except that this was used.

Example 3 A mixture consisting of 10 parts of 6/610/12 nylon copolymer (mp 100 ° C.), 10 parts of methanol, 25 parts of toluene, 25 parts of water and 40 parts of water was emulsified in the same manner as in Example 2; 5 parts of carbon black (50% methanol dispersion) was added to 100 parts and mixed to prepare an ink layer forming liquid. An ink sheet 13 was prepared in the same manner as in Example 2 except that this was used.

Example 4 An ink layer forming liquid was prepared by adding 10 parts of a carnauba wax emulsion (solid content: 20%) to 110 parts of the forming liquid of Example 2. An ink sheet 14 was prepared in the same manner as in Example 2 except that this was used.

Example 5 A mixture of 15 parts of 6/66/12 nylon copolymer (mp 120 ° C.), 40 parts of toluene, 40 parts of methanol was heated to 50 ° C. while stirring to dissolve the mixture, and carbon black was added thereto. 15 parts were added and dispersed in a ball mill for 5 hours to prepare an ink layer forming liquid. An ink sheet 15 was prepared in the same manner as in Example 2 except that this was used.

Example 6 A mixture of 10 parts of 6/610/12 nylon copolymer (mp 100 ° C.), 25 parts of methanol, 25 parts of toluene was heated to 50 ° C. while stirring to dissolve the mixture, and carbon black was added thereto. 10 parts were added and dispersed in a ball mill for 5 hours to prepare an ink layer forming liquid. An ink sheet 16 was prepared in the same manner as in Example 2 except that this was used.

The ink transfer sheets (A), (B), and (C) used in Example 1 were the same as those used in Example 1.
Tables 1 (D), (E), (F) and (G), and the results of tests performed with a thermal transfer printer are shown in Table 1.

[Table 1] (Note 1) Water washability test JIS L-0844A-3 Dry cleanability test JIS L-0860 (However, the solvent is 1,1,1-trichloroethane and the temperature is 25
° C. (* 2) Image sharpness ◎: Extremely good ○: Good △: Normal ×: Poor (Note 3) Water-resistant washing resistance, dry cleaning resistance, alkali resistance ◎: Image does not fall off at all ○: Image hardly falls off Δ: Image dropped slightly ×: Image dropped completely (Note 4) Decoding rate measurement A vertical bar was printed with code 39, and the decoding rate was measured.

[0044]

According to the thermal transfer recording material of the present invention, the following effects can be obtained. (1) An image excellent in washing resistance (water, hot water, dry cleaning) can be obtained. (2) Good heat sensitivity and the same image washing resistance as (1) can be obtained. (3) because the main component and transferring the image formed by combined is more than Beck smoothness 500 seconds polyamide resin to the transfer body is performed, better results are obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-128992 (JP, A) JP-A-63-197095 (JP, A) JP-A-1-259988 (JP, A) JP-A-63-16995 54283 (JP, A) JP-A-3-24993 (JP, A) JP-A-61-244593 (JP, A) JP-A-2-3378 (JP, A) JP-A-3-58888 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (4)

(57) [Claims] 1. A thermal transfer recording medium comprising a support and an ink layer mainly composed of a polyamide resin having a colorant and a melting point of 80 to 150 ° C. (according to a DSC method), and an ink receiving surface mainly composed of a polyamide resin. Washing-resistant thermal transfer recording material characterized by being used in combination with an object to be transferred having a Beck smoothness of 500 seconds or more. 2. A polymer for an ink layer of the thermal transfer recording medium.
The resin according to claim 1, wherein the resin is in the form of particles.
Washing-resistant thermal transfer recording material. 3. The method according to claim 1, wherein the thermal transfer recording medium comprises a support,
A release layer containing wax as a main component was provided between the layers.
3. The resistance according to claim 1 or 2, wherein
Washable thermal transfer recording material. 4. The ink layer of the thermal transfer recording medium according to claim 1, wherein
500~5000Pa · S der melt viscosity at 0.99 ° C. of Mid resin
4. The resistance according to any one of claims 1 to 3, wherein
Washable thermal transfer recording material.