JPH01120389A - Thermal transfer material and material to be thermally transferred, thermal transfer recording using these materials - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer material which allows formation of an image with high plasticity resistance and mechanical strength by providing a transfer recording layer consisting of acrylic resin with a glass transition point falling within a prearranged range, on a thermal transfer material. CONSTITUTION:A material to be thermally transferred consists of an image receiving layer based mainly on thermoplastic resin and lubricant on a support. A thermal transfer material is made of a transfer recording layer consisting of a coloring agent, a lubricant and a heat-melting substance on a heat-resistant support. The heat-melting substance contains linear saturated polyester formed by condensation polymerization of carboxylic acid component and diol component, and acrylic resin whose glass transition point Tg falls within a range of 50 deg.C-110 deg.C.The upper limit temperature of Tg of a thermal head which allows thermal transfer recording is max 110 deg.C. If acrylic resin at said temperature of max 50 deg.C is used, the chemical resistance, plasticity resistance and mechanical strength of an image which is thermally transferred and recorded cannot be added.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a thermal transfer material that can be thermally transferred by a thermal medium such as a thermal head, a thermal transfer material used in combination with the thermal transfer material, and a combination of the thermal transfer material and the thermal transfer material. The present invention relates to a thermal transfer recording method using a thermal transfer material, and more specifically, to a thermal transfer material and a thermal transfer material capable of forming an image having excellent plasticizer resistance, chemical resistance, and mechanical strength, and a thermal transfer recording method. It is something.

<Conventional technology and its problems> The thermal recording method has advantages such as a simple mechanism, dry type, and maintenance-free recording, so it is widely used in the fields of facsimiles and various printers. Recently, there has been an increase in the use of this thermal recording method to record visible information on substrates other than those made of paper, such as plastic substrates. Direct thermal recording and thermal transfer recording are examples of recording methods that can accommodate such uses. For direct thermal recording, a thermal medium using leuco dye has been proposed (
JP-A-59-199285) has been put into practical use.

However, since leuco dye is used, the reliability of the image after recording is affected, such as recoloring due to heating, discoloration and fading due to light, etc.
It also has the problem of lack of long-term storage stability.

As a method to solve this problem, a heat-sensitive recording medium using a metal vapor-deposited film has been proposed (Japanese Patent Application Laid-Open No. 1992-1988).
According to this proposal, the above-mentioned drawbacks are certainly improved, but in addition to drawbacks such as high printing energy and time-consuming printing, since the recording layer is a vapor-deposited metal film, It has drawbacks such as there is no contrast between the unimaged area and the imaged area, the background is metallic, and there is no whiteness. Therefore, its field of use is limited to special applications. As described above, the direct heat-sensitive recording type has drawbacks in the recording material itself, so its uses are limited, and only monochrome visible information can be obtained from the recording method.

On the other hand, in the thermal transfer recording type, a thermal transfer material consisting of a layer of heat-melting ink such as wax is superimposed on a transfer medium consisting of a plastic substrate with a porous ink absorbing layer.
This is a printing method that allows full-color visible information to be printed by changing the coloring agent in the ink layer of the thermal transfer material. However, if the image area is rubbed by hand, it will leave marks and stains, resulting in a lack of authenticity in the recorded image. If the stability of images after recording is improved, it would be desirable to expand the field of use without being limited to specific uses.

Means for Solving the Problems> The present invention was made in view of the above-mentioned shortcomings of the prior art, and its purpose is to record visible information (images) on a substrate made of plastic or the like using a heat medium such as a thermal head. It is an object of the present invention to provide a thermal transfer material, a thermal transfer material, and a thermal transfer recording method using the same, which are capable of forming images with excellent stability, particularly plasticity resistance, and mechanical strength.

The above purpose is to create a linear saturated polyester resin formed by condensation polymerization of a colorant, a dicarboxylic acid component, and a diol component on a heat-resistant support with a glass transition point in the range of 50°C to 110°C. "Thermal transfer material characterized by providing a transfer recording layer mainly composed of a heat-melting substance made of an acrylic resin and a lubricant"
A thermal transfer material characterized by having an image-receiving layer mainly composed of a thermoplastic resin in the temperature range of A transfer recording layer whose main components are a heat-melting substance made of a linear saturated polyester resin formed by condensation polymerization and an acrylic resin whose glass transition point is in the range of 50°C to 110°C, and a lubricant. A thermal transfer material characterized by a lubricant and a glass transition point of 50°C on a support.
and a thermal transfer target body characterized by being provided with an image-receiving layer mainly composed of a thermoplastic resin having a temperature in the range from 100° C. to 100° C.;
Thereafter, partial heating is performed in accordance with the printed image information from the support side of the thermal transfer material, and the transfer recording layer and the image receiving layer corresponding to the heated portion are selectively melted and thermally bonded to each other. A thermal transfer recording method characterized by forming a thermal transfer image on a transfer material.

” This can be achieved by

The present invention will be explained in detail below.

First, the thermal transfer material and the thermal transfer material will be described.

A thermal transfer material generally comprises a transfer recording layer containing a thermoplastic resin, a colorant, and a lubricant as main components on a heat-resistant support such as plastic. - On the other hand, the thermal transfer material used in combination with this thermal transfer recording material is generally one of the present invention, which is formed by providing an image-receiving layer mainly composed of a thermoplastic resin and a lubricant on a support such as plastic. The thermal transfer material is composed of a transfer recording layer comprising a colorant, a lubricant, and a heat-melting substance on a heat-resistant support such as plastic, as described above, and in particular, the heat-melting substance is dicarboxylic acid. A linear saturated polyester formed by condensation polymerization of a component and a diol component and a glass transition point (hereinafter abbreviated as Tg) of 50
It is characterized by being an acrylic resin with a temperature range of 110°C to 110°C. The saturated polyester is added to improve the adhesion of the transfer recording layer to a support such as a plastic, for example a polyester film. If the system does not contain saturated polyester, the adhesion between the support and the transfer recording layer will be weak, so during thermal transfer recording, the untransferred recorded area will peel off and transfer to the thermal transfer material, resulting in image breakage. becomes worse. In other words, it is added to improve cutting edges during transfer recording. The preferable addition amount is about 10 to 30 ml parts per 100 parts by weight of the heat-fusible substance.

The acrylic resin, which is another component of the heat-melting material, was selected to improve the reliability of the recorded image. Acrylic resin has the best plasticizer resistance among existing thermoplastic resins. By using this acrylic resin as a constituent material of the transfer recording layer, when a medium such as a soft PVC sheet or an eraser is brought into contact with the transferred and recorded image area,
The plasticizer contained in the medium etc. prevents scratches on the recording surface and transfer of recorded images to the medium. Furthermore, the glass transition point of the above acrylic resin was determined by the upper limit T
This is because g is appropriate for the thermal head, and the lower limit Tg is based on consideration of the durability of the transferred and recorded image.

Normally, the operating conditions for thermal heads are 300-400℃1
It is several n1s, and when converted to static temperature, it is about 130℃2
It will take about 5 seconds. Thermal transfer recording from a thermal transfer material using a thermoplastic resin as a heat-melting substance to a thermal transfer target material occurs when the temperature of the transfer recording layer reaches a rubber-like fluid state or higher, and when the temperature is lower than that, thermal transfer recording occurs. Based on these two findings that are not recorded, the upper limit temperature of Tg at which thermal transfer recording is possible under normal printing conditions (printing energy range that does not drastically reduce the life of the thermal medium such as a thermal head) was 110° C. or lower. The reason for setting the lower limit Tg to 50°C or higher is as follows.
This is because emphasis was placed on the durability of the image thermally transferred onto the thermal transfer material, which is the object of the present invention. If acrylic resin (34 resin) at a temperature of 50° C. or lower is used as a component of the heat-melting substance in the transfer recording layer, there will be problems with the chemical resistance and plasticity resistance of the thermally transfer recorded image, resulting in a lack of reliability of the image.

Ru.

Specific examples of the acrylic resins used in the present invention at temperatures from SO'C to 110°C include polyacrylic acid (T
g: 72°C), 2-methoxyethyl polyacrylate (Tg: 85°C), polymethyl acrylate (Tg: 85°C)
g: 100°C), polyacrylic acid-2-naphthyl (18
272°C), polyisobornyl acrylate 94°C), polymethyl methacrylate (Tg: 103°C), polyethyl methacrylate (Tg: 65°C), polyt-butyl methacrylate (Tg: 107°C), polymethacrylate Isobutyl methacrylate (Tg: 53°C), polyphenyl methacrylate (Tg: ilooC), copolymer of methyl methacrylate and alkyl methacrylate (however, the number of carbon atoms in the alkyl group is 2 to 6), polymethylchloroacrylate (Tg: 83 °C) Polyisopropyl-α-
chloroacryle) (Tg: 7biC), etc.

The lubricant, which is a component of the transfer recording layer of the thermal transfer material of the present invention, is a necessary component for improving transferability during thermal transfer and abrasion resistance of images recorded by thermal transfer. Addition of the lubricant improves the abrasion resistance of images recorded by thermal transfer, eliminates damage to the images due to scratches and other scratches, and provides durability against abrasion caused by erasers and the like.

Specific examples of lubricants used in the present invention include Teflon powder, polyethylene powder, animal-based, vegetable-based, mineral-based, and petroleum-based natural waxes, synthetic hydrocarbon-based, modified wax-based, aliphatic alcohols and acids. type, fatty acid ester and glyceride type, hydrogenated wax type, synthetic ketone, amine and amide type, chlorinated hydrocarbon type,
Examples include synthetic waxes such as synthetic animal waxes and alpha olefin waxes, and metal salts of higher fatty acids such as zinc stearate.

The colorant, which is a component of the transfer recording layer of the thermal transfer material of the present invention, is necessary for visualization, and by changing the type of colorant, a color visible image can be obtained. Coloring agents such as dyes and pigments can be used. In consideration of the weather resistance of the transferred and recorded image, inorganic and organic pigments are preferred, and specific examples include the following. Namely, titanium oxide, calcium carbonate, Hansa Yellow, Oil Yellow 2G, carbon blank, oil reflex, pyrazolone orange, oilette, red iron, anthraquinone violet, phthalocyanine blue, phthalocyanine green, aluminum powder, bronze powder, pearl essence, Bosho-mari etc. are used.

The composition ratio of the transfer recording layer mainly composed of the above-mentioned □ components is 40 to 80 parts by weight of the heat-melting substance and 10 to 30 parts by weight of the coloring agent to 100 parts by weight of the total solid content of the transfer recording layer. The lubricant is 5 to 30 parts.

Even if this transfer recording layer contains various additives in addition to the above-mentioned components, the characteristics of the present invention will not be affected in any way.

However, the amount added is 0 to 10 parts by weight based on 100i1i star parts of the above components.

The support used in the thermal transfer recording material of the present invention can be any support as long as it has heat-resistant strength, dimensional stability, and surface smoothness, but preferably 2 to 2.
A 10 μm polyester film with a layer provided on the back side to prevent sticking to the thermal head is used.

Next, the thermal transfer material of the present invention will be explained.

The thermal transfer material used in combination with the thermal transfer material of the present invention is formed by providing an image receiving layer mainly composed of a lubricant and a thermoplastic resin on a support such as paper, metal, or plastic sheet, preferably on a plastic sheet. Any thermoplastic resin can be used as long as it has a Tg in the range of 50°C to 100°C and is adhesive to the transfer recording layer of the thermal transfer material of the present invention. be. Preferably, in consideration of the chemical resistance and plasticizer resistance of the image-receiving layer, acrylic resins used in the transfer recording layer of the thermal transfer material are suitable. Depending on the type of plastic sheet that is the support for the transfer material, some sheets may not have adhesive properties with acrylic resin, so in that case, it is necessary to combine resins with good adhesive properties to impart adhesive properties.For example, polyester When using a sheet as a support, adhesion is imparted by adding a saturated polyester resin. The purpose of adding the lubricant here is to improve the abrasion resistance of the image-receiving layer. The amount added is 5 to 20 parts by weight per 100 parts by weight of the solid content of the image receiving layer.
Parts by weight are preferred. If too little lubricant is added, the abrasion resistance will be affected, and if too much, the adhesion during thermal transfer recording will be poor.

Hereinafter, a thermal transfer recording method using the thermal transfer material and thermal transfer target material having the above-described configuration will be described.

When recording, first, a thermal transfer material and a material to be thermally transferred are superimposed so that their transfer recording layer and image-receiving layer are in contact with each other. Next, partial heating is performed from the support side of the thermal transfer material according to the printed image information using a thermal medium such as a thermal head or a thermal pen. Then, the portion of the transfer record i1 layer corresponding to the heated portion is thermally melted, and at the same time, the thermoplastic resin in the image receiving layer is heated to a temperature of 7 g or more due to the thermal energy transmitted to the thermal transfer material via the thermal transfer material. be done. At this time, the heat-fused transfer recording layer and image-receiving layer are partially thermally and firmly adhered to form a thermally transferred image on the thermally transferred material.

The transferred and recorded image has excellent plasticizer resistance, chemical resistance (15), and mechanical strength.

<Effects of the Invention> As described above, according to the present invention, it is possible to print on a substrate such as Plus Ink using a heat medium such as a thermal head. In addition to providing basic characteristics such as color display and monochrome display, it can also impart durability, especially plasticizer resistance and mechanical strength, to the image thermally transferred to the transfer material, making it possible to improve It can be applied to a wide range of fields where conventional agents have not been able to advance, such as recording on Plus Thousand Tsuku, cards that require counterfeit prevention, variable information recording on sticker-less commuter passes, and balance display media for prepaid cards. can be used.

<Examples> Examples of the present invention will be shown below. In each example, "part" means part by weight.

<Example 1> 1) Preparation of thermal transfer material Composition of thermal transfer recording layer coating liquid [-, ff 77'-y'''1''I acrylic resin (Tg=105''C) 4 parts [Mitsubishi Rayon BR-801 Paraffin wax 0.5 parts Toluene/2-butanone (2/1) 30 parts A coating solution having the above composition was dispersed in a sand mill for 2 hours to obtain a transfer recording layer coating solution, and the dry weight was 1.5 g/+1. A thermal transfer material was obtained by coating and drying with a wire bar onto a 6μ polyester film, which had previously been provided with an anti-stinking layer on the back surface.

2) Preparation of thermal transfer material Composition of image-receiving layer coating liquid A coating liquid having the above composition was heated with a sand grinder for 30 minutes.
The image-receiving layer coating solution was dispersed for minutes, and the coating solution was applied onto a 250 μm white PVC sheet using a wire bar and dried so that the dry weight was tg/n (tg/n) to obtain a thermal transfer material.

<Example 2> 1) Preparation of thermal transfer material Composition of transfer recording layer coating liquid The coating liquid composed of the above composition was crushed and dispersed in a paint conditioner for 30 minutes to form a transfer recording layer! ! ! A thermal transfer material was obtained by applying the solution as a liquid onto a 4μ polyester film, which had been provided with an anti-stinking layer on the back surface, using a wire bar and drying so that the dry weight was 2 g/nf.

2) Preparation of thermal transfer material Composition of image-receiving layer coating liquid 17 o 7 /<'y9' 2
@B [, 7, F/2-7' months, 7 5
Part: A coating liquid having the above composition was dispersed in a Hyper for 30 minutes to obtain an image-receiving coating liquid, and the coating liquid was applied onto a 188μ white polyester sheet using a wire bar so as to have a dry weight of 2 g/rrf, and dried to obtain a thermal transfer material. I got it.

Comparative Example 1> Acrylic resin (Tg=6
A thermal transfer material was obtained in the same manner as in Example 2, except that the acrylic resin (Tg = 35°C) [Mitsubishi Rayon BR-65] was used. However, the same thermal transfer material as in Example 2 was used.

Comparative Example 2> The same as Example 2 except that the image receiving layer of the thermal transfer material of Example 2 was not applied.

<Evaluation of Examples 1 and 2 and Comparative Examples 1 and 2> The obtained thermal transfer material was placed on the thermal transfer material used in combination with a Toshiba thermal simulator (printing conditions, applied power 0.45W).
/dot, pulse width 2.5m5ON10FF), and the characteristics after recording were evaluated, and the results shown in Table 1 were obtained.

As is clear from Table 1, according to the present invention, it is possible to perform thermal transfer recording using a thermal medium such as a thermal head, and the durability (plasticity resistance, Abrasion resistant.

A thermal transfer recorded image with excellent scratch resistance and solvent resistance could be obtained.

*1 0.45 w/dot, 2.5mS 0N10
Regarding the transfer recording characteristics under FF printing conditions, the O mark is clearly transferred.

The X mark is faintly transferred and recorded.

*2 The state of the recording surface after being crimped with a plastic eraser (200g/cd) at 20°C and 60%RH and left for 2 days.

○ marks do not change. The X mark indicates image shift and intensity deterioration.

*3 Condition of recording surface after immersion in water and ethanol for 3 minutes.

The O mark does not change. X marks indicate elution and strength deterioration.

*4 50 with normal force using a plastic eraser
Discoloration of the image area when rubbed twice.

The O mark indicates an image. The image part of the X mark has disappeared.

*5 The degree of trailing on the image area when rubbed with a nail with normal force.

○ indicates no trailing. The X mark has a tail.

Patent applicant Toppan Printing Co., Ltd. Representative: Kazuo Suzuki

Claims (3)

[Claims] (1) A linear saturated polyester resin formed by condensation polymerization of a colorant, a dicarboxylic acid component, and a diol component on a heat-resistant support with a glass transition point of 50°C to 110°C.
1. A thermal transfer material comprising a transfer recording layer whose main components are a heat-melting substance made of an acrylic resin and a lubricant. (2) On the support, the lubricant and the glass transition temperature range from 50°C to 1
A thermal transfer material comprising an image receiving layer whose main component is a thermoplastic resin having a temperature in the range of 00°C. (3) A linear saturated polyester resin formed by condensation polymerization of a colorant, a dicarboxylic acid component, and a diol component on a heat-resistant support and a glass transition point of 50°C to 110°C.
A thermal transfer material comprising a transfer recording layer mainly composed of a heat-melting substance made of an acrylic resin and a lubricant having a glass transition temperature of 5.
A thermal transfer object characterized by being provided with an image receiving layer mainly composed of a thermoplastic resin having a temperature in the range of 0° C. to 100° C. is superimposed so that the transfer recording layer and the image receiving layer are in contact with each other, and then After that, partial heating is performed in accordance with the printed image information from the support side of the thermal transfer material, and the recording layer and image receiving layer corresponding to the heated portions are selectively melted and thermally bonded, and the thermal transfer material is heated. A thermal transfer recording method characterized by forming a thermal transfer image thereon.