JPS60131297A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To enhance a sticking-preventing effect, by a method wherein a sticking-preventing layer comprising a specified mono-, di- or tri-(polyoxyethylene alkyl ether) phosphate is provided on the lower side of a film base. CONSTITUTION:A thermal transfer layer is provided on the upper side of the film base, and the sticking-preventing layer is provided on the lower side of the film base to produce a thermal transfer recording material. The sticking-preventing layer is constituted of a layer of one of mono-, di- and tri-(polyoxyethylene alkyl ether) phosphates of general formulas I , II, III, IV and V and a layer of a combination of at least one of the mono-, di- and tri-(polyoxyethylene alkyl ether) phosphates of general formulas I , II, III, IV and V with a phosphate of general formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel thermal transfer recording material, and more particularly to a thermal transfer recording material having a thermal transfer layer on the upper surface of a film base and a stick prevention layer on the lower surface.

[Prior art]

2. Description of the Related Art Heat-sensitive transfer recording materials have been known in which a heat-melting ink layer containing a colorant or a layer containing a heat-reactive color-forming reaction component is provided on a base material such as paper or a plastic film. For those with a heat-melting ink layer, a colored image can be obtained by overlaying paper as a receptor sheet and thermally printing from the bottom surface of the substrate with a thermal head to transfer the molten ink onto the receptor sheet. On the other hand, those having a heat-reactive color-forming reaction component-containing layer have a layer containing paper or a reaction component that reacts with the color-forming reaction component under heat to form a color as a receptor layer. A colored image can be formed on the receiving sheet surface by overlapping the sheets and performing thermal printing from the bottom surface of the substrate using a thermal head.

By the way, when a plastic film is used as the base material in such a thermal transfer recording material, the melting point of the plastic film is at most about 200 to 300°C and the heat distortion temperature is about 100°C, whereas the thermal head Since the surface temperature of the thermal head reaches a high temperature of 400° C. or more, the thermal head has a problem in that sticks occur and fused plastic film adheres to the thermal head, resulting in so-called stick residue.

In addition, in order to prevent such sticks, the bottom surface of the plastic film (the contact surface of the thermal head) should be
It has also been proposed to provide an anti-stick layer. For example, it has been proposed to use a metal layer, a heat-resistant resin layer, a penztriazole layer, an ethyl cellulose layer containing sodium stearyl sulfonate, a polyester resin layer containing stearic acid, etc. as a stick prevention layer (for example, (See Japanese Patent Application Laid-open No. 143152/1983). However, if the amount of these anti-stick layers is too small, sufficient anti-stick effect cannot be obtained, and if the amount of adhesion is too large, thermal sensitivity may decrease due to increased heat capacity, or the anti-stick layer may This has disadvantages such as new generation of sticks and stick scum.

〔the purpose〕

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and its object is to provide a thermal transfer recording material having an anti-stick layer that exhibits a high anti-stick effect with a small amount of adhesion.

〔composition〕

A ninth aspect of the present invention to achieve the above object is to provide a stick prevention layer consisting of mono-, di-, or tri-(polyoxyethylene alkyl ether) esters having a specific structural formula, alone or in combination. be. That is, according to the present invention, in a heat-sensitive transfer recording material having a heat-sensitive transfer layer on the upper surface of a film base material and a stick prevention layer on the lower surface of the film base material, the stick prevention layer is formed by the following formulas (1), (2), and (2). A layer consisting of at least one of (7) a mono represented by ■, formula ■ or formula ■, :) or tri(polyoxyethylene alkyl ether) phosphate ester, or the following formula 11 formula ■, formula ■, formula ■ or a combination of at least one of tri(polyoxyethylene alkyl ether) phosphates and tri(polyoxyethylene alkyl ether) phosphates represented by the following formula (■): A heat-sensitive stencil paper is provided, which is characterized in that it uses a layer consisting of a thin layer.

6- Formula ■ Formula ■ Formula ■ Formula ■ Formula V Formula ■ In each of the above formulas, R means an alkyl group or an alkenyl group, X means a hydrogen atom or an alkali metal, and 2, m and n are each 1 to 10 means the number of

Alkyl or alkenyl groups usually have 8 to 24 carbon atoms.
Preferably it is a linear or branched one with 12 to 18 atoms, and typical examples of the alkali metal include sodium or potassium. The range of 6 to 6 is preferable.

The phosphate ester type surfactant used in the present invention exhibits a high stick prevention effect even with a very small amount of adhesion, and the amount of adhesion is 0.01 to 0.5 t to the film base material.
/m2, preferably 0.05 to 0.3 t/m2 is sufficient. In addition, to form a stick prevention layer made of a phosphate ester type surfactant on a substrate, the surfactant is dissolved in a suitable solvent such as water, ethanol, methanol, ethyl acetate, methyl ethyl ketone, or other organic solvent. This can be done by applying it on top and drying it. In this case, the concentration of phosphate ester type surfactant in the solvent is 0.
, 1 to 5 weights, preferably 0.5 to 3 weights, and drying conditions may be 70 to 100°C for 10 to 50 seconds.

As the film base material used in the present invention, conventionally known base films can be used as they are, and the type thereof is not particularly limited. Typical examples thereof include polyester films, polyamide films, polyolefin films, polycarbonate films, cellulose films, etc., and the thickness thereof is usually about 2 to 50 μm, preferably about 3 to 10 μm.

Furthermore, in the present invention, conventionally known heat-sensitive transfer layers can be used as the heat-sensitive transfer layer formed on the film base material, and the type thereof is not particularly limited, and a non-reactive type or a reactive type can be arbitrarily used. Examples of the reactive type include a transfer layer made of hot-melt ink, and examples of the reactive type include a transfer layer containing one of the reactive components of a color-forming reaction system in the following combinations. can be mentioned.

(1) Leuco dye, color developer (electron-accepting substance), and 9
- combinations (2) of long chain aliphatic iron salts such as ferric stearate and ferric myristylate with phenols such as tannic acid, gallic acid and ammonium salicylate; (3) Heavy wire mesh, such as silver, lead, mercury, thorium sulfates, sulfates and Ha-tetrathionate, sodium thiosulfate,
Combination with sulfur compounds such as thiourea, (4) -? A combination of noble metal salts of organic acids such as silver henate and silver stearate with aromatic organic reducing agents such as protocatechuic acid, spiroin□dane, and hy-10quinone; (5) Lead caproate is lead larginate. , a combination of an organic acid lead salt such as lead behenate and a thiourea derivative such as ethylenethiourea, N-dodecylthiourea.

10- When using a thermal transfer recording material having a reactive thermal transfer layer as described above, the receiving sheet that receives the transfer is:
A sheet having a receptor layer containing a reactive component that causes color development by reacting with a reactive component contained in a thermal transfer layer of a color-forming reaction system consisting of the combination described above is used. For example, when the thermal transfer layer contains a leuco dye, a receiving sheet containing a color developer such as a phenolic substance can be used as the receiving sheet.

Further, the color-forming reaction system consisting of a combination of the two types of reaction components described above can be contained in the thermal transfer layer in a state in which the color-forming reaction is prevented in advance. A thermal transfer recording material having thermal transfer 1# containing such a color-forming reaction component can transfer an image consisting of a melted deposit of a color-forming reaction product onto paper as a receiving sheet by thermal transfer. Here, to explain the formation method using a non-reactive heat-sensitive transfer layer as an example, a composition consisting of a coloring agent, a binder agent, etc. is hot-melt coated on a film base material, or the composition is coated in an appropriate solvent. The dispersed coating solution can be solvent coated to form a layer of about 1 to 20 microns. As the colorant, any of various dyes or pigments such as carbon black, which have been conventionally used in the field of copying paper, can be used, and as the binder, waxes such as carnauba wax, wood wax, and beeswax can be used. I can do it.

Further, the thermal transfer recording material of the present invention can be used in any desired shape, such as a typewriter ribbon or a wide tape like a line printer.

〔Example〕

A heat-sensitive transferable ink composition having the following component composition was applied and dried on the upper surface of a polyester film having a thickness of 6μ to form a heat transfer layer having a thickness of 4μ.

Carnauba wax 20 parts by weight Nono rough-in wax (M65°C) 30 # oxidized wax 10 Vaseline 10 Carbon black 20 Next, apply the anti-stick agent shown in Table 1 on the underside of the polyester film in solution form with a wire par. Diameter 0.1■)
Apply and dry using -1° to N11LG-2.
Each product was obtained. Also, in the table, Zui F-1 and N11F-
Product No. 2 is a product obtained according to JP-A-5.7-129789, and products N11G-1 and N11G-2 are products obtained according to JP-A-58-74355. In addition, as a comparative product, the anti-stick layer, which requires heat curing, was excluded from the experiment. Furthermore, in this example, the amount of stick prevention layer deposited was extremely small (0.5 as a reference value).
% liquid is 0.03~O, 0.05t/m2.1 liquid is 0.03~0.
06 to 0.1f/1n2), and in consideration of measurement errors, the amount of adhered anti-stick layer was expressed using the concentration of the coating liquid in Table 1. Further, the diameter of the wire parr used for coating was O.1 wφ.

14-Table 1 In addition, since it is difficult to separate the surfactant odors shown in the above-mentioned products of the present invention, it also contains a small amount of A-1 and B-2, as well as B-1 and B-2. Also D-1 and D-
Sample 2 is available.

Next, paper as a receiving sheet was placed on the thermal transfer layer surface of each of the thermal transfer materials obtained as described above, and a thermal head was used as a heating means to apply a heat amount of 0.8 mJ/dot from the stick prevention layer surface. In addition, we perform thermal printing,
A transferred image was obtained on a receiving sheet. In this case, the feeding speed (running speed) of the thermal transfer recording material to the thermal head was 12 crn/sec. The following table shows the performance evaluation results of each product when thermal transfer was performed in this manner.

Note that the evaluation items shown in Table 2 mean the following.

(1) Stickiness Indicates the presence or absence and size of stickiness (stickiness) of the product with respect to the thermal head.

(2) Drivability Indicates the difficulty level of feeding the transfer material tape ribbon.

(If the ribbon sticks, it will not be able to feed smoothly, and if severe, it will break.) (3) Substrate residue adhesion The presence or absence of adhesion of the polyester film residue used as the base material to the thermal head and its size are shown.

(4) Adhesion of anti-stick agent scum Shows the presence or absence and size of adhesion of anti-stick agent scum to the thermal head.

(0 running performance □ Indicates the degree of deterioration in print quality.

(Cleaning is required if debris adheres to the thermal head and accumulates. If you print without cleaning,
In addition, the type of alkyl group and the number of oxyethylene units of the phosphate ester type surfactant used as the anti-stick agent in the present invention are changed to improve the quality of the product. When carried out in the same manner as in the example, almost the same results as above were obtained.

〔effect〕

The thermal transfer recording material of the present invention can be used as a thermal transfer paper, a thermal transfer ribbon, a thermal stencil for digital platemaking, etc., and has the following advantages.

(1) The anti-stick agent used in the present invention can achieve a good anti-stick effect with a very small amount of application, so
Not only the base film melt) but also the anti-stick agent itself hardly ever adheres or deposits on the thermal head.

(2) Due to the properties of the phosphate ester type surfactant used in the present invention, the adsorption force (ion adsorption) to the film surface is strong (because the oil film strength is high), so it is hardly removed by contact with the head. It does not stick to the surface as scum.

(3) Since the anti-stick agent used in the present invention does not need to be thermally cured, it can be applied by normal coating and drying operations.

(4) Since the anti-stick agent used in the present invention has an antistatic effect, it prevents dirt and dust from adhering to the product surface due to static electricity, and also prevents adhesion between products due to static electricity.

(5) The anti-stick agent used in the present invention does not need to be used in combination with the binder resin, so the amount of application can be kept to an extremely low level, preventing a decrease in the thermal sensitivity of the product, and preventing the sticking residue of the binder resin itself from adhering to the thermal head. Does not cause any problems.

21- Procedural amendment January 25, 1980 Mr. Kazuo Wakasugi, Commissioner of the Patent Office■, Indication of the case, Patent Application No. 238983, filed in 1982, 2, Name of the invention, Thermal transfer recording material 3, Person making the amendment, Case and Relationship Patent Applicant Address 1-3-6 Nakamarigome, Ota-ku, Tokyo Name (67
4) Ricoh Co., Ltd. -4, Agent 5, Date of amendment order (voluntary) Showa (Ship date: Showa) & Subject of amendment: Scope of claims and Detailed explanation of the invention in the specification Contents of Z amendment 1) The scope of patent claims will be amended as shown in the attached sheet.

2) Correct "thermal stencil paper" on the last line of page 6 to "thermal transfer recording material."

Above 2, Claims A heat-sensitive transfer layer on the top surface of the film base material! In a thermal transfer recording material having a stick prevention layer on the lower surface of the film base, the stick prevention layer is formed by the following formula 11 formula (■), formula (2),
A layer consisting of at least one mono-, di-, or tri(polyoxyethylene alkyl ether) phosphate ester represented by formula ■ or formula ■, or the following formula 11 formula ■, formula ■, formula ■, or formula ■ The material represented by this material is a layer consisting of a combination of at least one kind of tri(polyoxyethylene alkyl ether) phosphate ester and a tri(polyoxyethylene alkyl ether) phosphate ester represented by the following formula (■). Thermal transfer recording material which is characterized in that it is used Formula I Formula ■ 2 ■ Formula ■ Formula V Formula ■ (However, in each of the above formulas, R means an alkyl group or an alkenyl group, and X is a hydrogen atom and nine is an alkali metal. and l, m and n each mean a number from 1 to 10).

2-

Claims (1)

[Scope of Claims] In a thermal transfer recording material having a heat-sensitive transfer layer on the upper surface of a film base and a stick prevention layer on the lower surface of the film base, the stick prevention layer is formed by the following formula (■), formula (2), or formula ■,
A layer consisting of at least one mono-, di-, or tri(polyoxyethylene alkyl ether) phosphate represented by formula ■ or formula ■, or a layer represented by the following formula 11 formula ■, formula ■, formula ■, or formula V Use a layer consisting of a combination of at least one of tri(polyoxyethylene alkyl ether) phosphate and tri(polyoxyethylene alkyl ether) phosphate represented by the following formula (■). Heat-sensitive stencil paper formula 1 characterized by 2, m and n each mean a number from 1 to 10).