JP3178619B2 - Master film for thermal transfer recording - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a master film for thermal transfer recording, and more particularly to a master film for thermal transfer recording which can be used repeatedly. More specifically, a heat-sensitive solid ink of a so-called melting type or sublimation type is heated and melted and transferred to a master film for thermal transfer recording (hereinafter referred to as “inking”). The present invention relates to a master film for thermal transfer recording, which is used in a method of transferring to a transfer-receiving medium (hereinafter, referred to as “image transfer”).

[0002]

2. Description of the Related Art The thermal transfer recording system is rapidly growing because the equipment is inexpensive, low-noise, excellent in operability, pollution, etc. as compared with other non-impact recording systems. What should be pointed out is that there is a strong demand for lower cost consumables while maintaining image quality higher than the current level. For this reason, various proposals have been made for a recording medium for a thermal transfer master using an intermediate transfer member. As a recording medium for thermal transfer which is repeatedly used, a film using an organic material as it is (JP-B-59-16932),
Stainless steel with a through hole (JP-B-59-36)
879), a stainless steel having a through-hole and an organic film adhered thereto (JP-A-62-48).
594) is known.

[0003]

Among these, those using a film made of an organic material as it is have a problem that the molten ink is not transferred uniformly onto the film, that is, the inking property is poor. In a stainless steel having a through hole, there is a problem that the melted ink stains the head, the efficiency of the head is reduced, and the transfer efficiency is reduced, that is, the image transferability is poor. When an organic film is applied to stainless steel with through holes, the thermal transfer coefficient between the stainless steel and the organic film differs when heated with a thermal head, so the image transferability tends to be poor and the film is easily peeled. There is.

The present invention has been made to solve the above problems, and has good inking properties and good image transfer properties even when used repeatedly.
An object of the present invention is to provide a master film for thermal transfer recording, which can provide a clear image stably and does not stain the head.

[0005]

According to the present invention, there is provided a master film for thermal transfer recording according to the present invention, wherein the master film for thermal transfer recording comprises a resin having no melting point and a high thermal conductivity. It is composed of an a layer consisting of particles, and B layer made of high thermal conductivity particles less content than without resin and a layer melting point
The layer B is provided on both sides of the layer A.

The layer A of the master film for thermal transfer recording of the present invention must contain particles having high thermal conductivity. If the particles do not contain high heat conductive particles, heat transfer at the time of transfer is poor, so that high printing energy is required, and high-speed image transfer cannot be performed. Examples of the high thermal conductive particles include carbon black, tin oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride and the like, and carbon black is particularly preferred in terms of economy. The amount of the high thermal conductive particles is 0.5% by weight to 150% by weight based on the weight of the polymer.
Is more preferable, more preferably 1% to 100% by weight,
More preferably, the content is 3% by weight to 80% by weight. If it is less than 0.5% by weight, heat transfer is not sufficient, and as described above, printing energy is increased, and it is difficult to increase the speed. 150
If the content is more than 10% by weight, the mechanical properties of the film are remarkably deteriorated, causing a problem in handling. The primary particle size of the particles to be added is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

Further, in the present invention, it is necessary to laminate a layer B containing less heat-conductive particles than the layer A on both sides of the layer A containing the particles having a high heat conductivity. If the layer B is not laminated, the durability of the head is deteriorated and clear image transfer cannot be performed, and the adhesion between the master film and the ink is increased, so that the releasability of the ink is deteriorated and the ink comes off. Image transfer cannot be performed . A layer / B layer 2
In a layer structure in which the ink layer is formed on the A layer side and the head is in contact with the B layer side, the durability of the head is improved, but the adhesion between the master film and the ink is increased and the releasability of the ink is poor and clear image transfer is performed. Can not do. Further, in a structure in which an ink layer is formed on the layer B side and the head contacts the layer A side, clear image transfer can be performed, but the durability of the head is not sufficient.
The layers need to be provided on both sides of the layer A. The three-layer structure of B / A / B makes it possible to improve the durability of the head, facilitate the transfer of inking and ink to paper, and form a clear image transfer. It becomes possible.

[0008] The amount of the high thermal conductive particles in the layer B is used to optimize the inking property and the releasability of the master film, and to prevent the head from being stained by the falling off of the high thermal conductive particles by the head. Therefore, it is necessary to make the content less than that in the layer A, and it is not necessary to substantially contain the same.

[0009] The master film for thermal transfer recording of the present invention must be made of a heat-resistant resin having no melting point. A resin having a melting point (for example, a resin made of polyethylene terephthalate or the like) is easily melted by heating the head portion during printing ("hot stick property").
Problem).

In the present invention, the heat-resistant resin having no melting point means a heat-resistant resin which does not melt even when the temperature is raised. For example, it is a resin that decomposes and carbonizes without melting when the temperature is increased, and the temperature at the time of 5% weight loss by thermogravimetry (TG) in air is a melting point measuring instrument or
It is a resin composed of a polymer having a melting point lower than that measured by a differential scanning calorimeter (DSC). Such heat-resistant resin, for example, aromatic polyamide, aromatic polyimide,
Aromatic polyamide imide, polyparabanic acid, etc. may be mentioned, but aromatic polyamide and aromatic polyimide resins are particularly preferred.

The aromatic polyamide contains at least 50 mol%, preferably at least 70 mol%, of -NH-Ar ₁ -NHOC-Ar ₂ -CO- or -HN-Ar ₁ -CO- as a basic structural unit. Those comprising a polymer are preferred. Here, Ar ₁ is
In the formula, Ar ₂ is represented by Chemical formula ₂ .

[0012]

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[0013] In the chemical formula 1, R, X, Y, W is a halogen group, an alkyl group or a C ₁ nitro group, C ₁ -C ₃
-C ₃ alkoxy groups, Z is _{-CO -, - CH 2 -,} -
O- or _{-SO 2 -, p, q,} m, n is 0 to 3, l is 0 or 1.

[0014]

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In the above formula 2, S is a halogen group, a nitro group, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ alkoxy group, and r and t are 0-4.

The aromatic polyamide is obtained by a reaction between an acid chloride and a diamine, or a reaction between an isocyanate and a carboxylic acid.

Taking a combination of an acid chloride and a diamine as an example, as the monomer, the acid chloride side has a terephthalic acid chloride, an isophthalic acid chloride, and a halogen, nitro, alkyl, or alkoxy group in the aromatic nucleus thereof. Examples thereof include 2-chloroterephthalic acid chloride, 2-chloroisophthalic acid chloride, 2,5-dichloroterephthalic acid chloride, 2-nitroterephthalic acid chloride, and 2-methylisophthalic acid chloride. On the diamine side, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylketone, 3 , 3'-Diaminodiphenylketone, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) benzene, benzidine, and those having the above substituents on the aromatic nucleus thereof, for example, 2-chloro
-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-m-phenylenediamine, 2-methyl-m-phenylenediamine, 3,3 ' -Dimethylbenzidine etc.

Taking a combination of isocyanate and carboxylic acid as an example, the isocyanate side has phenylene-1,4-
Diisocyanate, phenylene-1,3-diisocyanate, diphenylketone-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, diphenylsulfone -4,4'-
Diisocyanates and those having the above substituents on these aromatic nuclei, for example, toluylene-2,6-diisocyanate, toluylene-2,4-diisocyanate and the like are included. On the carboxylic acid side, there are terephthalic acid, isophthalic acid, and those having a substituent on the aromatic nucleus.

In the above aromatic polyamide, the copolymer component of less than 50 mol% is not particularly limited, and may contain an ester bond, a urethane bond, an imide bond, a heterocyclic bond and the like. In order to obtain a film having excellent mechanical properties and heat resistance, the polymer has an intrinsic viscosity (a value measured at 30 ° C. as a 100 ml solution of 0.5 g of the polymer in N-methylpyrrolidone containing 2.5% by weight of lithium bromide). ) Is preferably from 0.5 to 6.0.

On the other hand, as is well known, the aromatic polyimide is preferably one mainly composed of one represented by the following structural unit.

[0021]

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Here, R ₁ has at least one aromatic ring and preferably has 25 or less carbon atoms, and two carbonyl groups forming an imide ring are bonded to adjacent carbon atoms. Organic group. In the formula, -R
_2- is a divalent organic group, which is represented by the general formula H ₂ NR ₂
It is derived from an aromatic diamine having —NH ₂ . The R ₁ group is provided by an aromatic tetracarboxylic acid component having the general formula 4

[0023]

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The following are typical examples of such an aromatic tetracarboxylic acid. Pyromellitic dianhydride, 3,3'-4.4'-bisphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenedicarboxylic anhydride, 2,
2-bis (3,4-dicarboxyphenyl) ether dianhydride, pyridine-2,3,5,6-tetracarboxylic dianhydride,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride or these tetracarboxylic esters.

On the other hand, as the aromatic diamine, it is preferable that two amino groups are bonded via at least one carbon, and that R ₂ contains at least one aromatic ring. And the number of carbon atoms is preferably 25 or less, for example, paraxylylenediamine, metaphenylenediamine, benzidine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3'-dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3 '
-Dimethoxybenzidine, 1,4-bis (3-methyl-5-aminophenyl) benzene and the like. It goes without saying that these acid components and amine components are used alone or in combination.

The term "polyamide imide" refers to a polymer having an amide group in a polyimide main chain.
For example, various polymerization such as polymerization of aromatic tricarboxylic anhydride and diamine, polymerization of aromatic tetracarboxylic anhydride containing amide bond and diamine, polymerization of aromatic tetracarboxylic anhydride and diamine containing amide bond, and the like. The structural unit also has various types, and various known types can be used. For example, those having a structural unit as shown in the following Chemical Formula 5 can be mentioned.

[0027]

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Here, R ₃ is a trivalent organic group containing at least one aromatic ring, preferably has 25 or less carbon atoms, and is derived from an aromatic tricarboxylic anhydride. R ₄ is a divalent organic group, preferably has 25 or less carbon atoms, and is derived from a diamine. Examples of the tricarboxylic anhydride include trimellitic anhydride. Examples of the diamine include the various aromatic diamines described above used for polyimide.

The polymers of the layer A and the layer B of the master film of the present invention may be the same or different, but are preferably the same.

The thickness of the laminated film of the present invention is from 1 μm to 5 μm.
0 μm is preferred, and more preferably 3 μm to 30 μm. If the thickness is less than 1 μm, the film will have poor mechanical properties and will not be practically usable due to poor handling properties. On the other hand, when the thickness is more than 50 μm, the thermal conductivity of the film is reduced, so that the image transferability is deteriorated, or the transfer energy is increased, which is not suitable for high speed operation. The thickness ratio of the laminated film is preferably in the range of A layer / B layer = 1/1 to 1 / 0.01, more preferably 1 / 0.7 to 1 / 0.05. Here, the thickness of the layer B represents the total value of both sides of the layer A. 1
When the ratio is more than / 1, heat transfer is deteriorated and image transferability is deteriorated, or transfer energy is increased, which is not preferable. Conversely, if the ratio is less than 1 / 0.01, the adhesion between the master film and the ink is too good, and the releasability of the ink is poor, causing ink to be missing during transfer.

The surface roughness (Rp) of the layer B of the master film of the present invention is preferably in the range of 0.001 μm to 2 μm. More preferably, it is in the range of 0.005 μm to 1 μm. More preferably 0.01 μm to 1.0 μm
m. When Rp is less than 0.001 μm, the surface of the master film B layer becomes too smooth, and the inking property deteriorates, or the friction with the head becomes large, causing sticking and further, the film is scraped. The purpose of the present invention cannot be achieved because the head is soiled. On the other hand, if Rp exceeds 2 μm, clear image transfer cannot be performed due to loss of color in printing or energy loss. Further, there is a problem that the head or the film is scraped, which is not preferable.

The thermal conductivity of the laminated film of the present invention is 3.
It is preferably at least 0 × 10 ⁻⁴ (cal / cms ° C.). It is more preferably at least 3.5 × 10 ⁻⁴ (cal / cms ° C.). 3.0 × 1
If it is less than 0 ^-4 (cal / cms ° C), the printing energy is undesirably increased.

In the master film of the present invention, the strength in at least one of the vertical and horizontal directions is 0.5.
kg / mm ² or more is preferable. More preferably, it is 3 kg / mm ² or more. If it is less than 0.5 kg / mm ² , it will not be able to withstand the tension at the time of transfer, which may cause breakage.

Further, in the master film of the present invention, the Young's modulus in at least one of the longitudinal and transverse directions is preferably at least 300 kg / mm ² , more preferably at least 400 kg / mm ² . 300 kg / mm ²
If it is less than 10, the film has a weak waist, which causes a problem in handling.

The surface tension of the master film of the present invention is as follows:
It is preferably 20 dyn / cm or more and 100 dyn / cm or less. More preferably, 30 dyn / cm or more, 80 dy
n / cm or less. If it is less than 20 dyn / cm, the inking property is poor, and if it exceeds 100 dyn / cm, the adhesion between the film and the ink is too good, and the transfer of the ink to paper or the like is poor.

Further, the heat shrinkage of the laminated film of the present invention at 200 ° C. is preferably 5% or less, more preferably 3%.
It is as follows. If it exceeds 5%, the film shrinks due to heat during transfer, and wrinkles occur, making continuous use impossible.

It is to be noted that the master film of the present invention may contain other components in addition to the above-mentioned components as long as the object of the present invention is not impaired. Also, known additives, for example, heat stabilizers, oxidation stabilizers, weather stabilizers, ultraviolet absorbers, lubricants, pigments, dyes, organic or inorganic fine particles, fillers, release agents, antistatic agents, A nucleating agent may be contained.

Next, a method for producing the master film of the present invention will be described, but the present invention is not limited thereto. In order to achieve the present invention, a film is formed by containing particles having high thermal conductivity in a solution of aromatic polyamide, aromatic polyimide, polyamic acid (polyimide precursor), or aromatic polyamideimide. Particles are added to the B layer as needed.

First, an aromatic polyamide, which is composed of an acid chloride and a diamine, may be used in an aprotic organic polar solvent such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) or dimethylformamide (DMF). And is synthesized by solution polymerization or interfacial polymerization using an aqueous solvent. When acid chloride and diamine are used as monomers, hydrogen chloride is produced as a monomer in the polymer solution.In order to neutralize this, an inorganic neutralizing agent such as calcium hydroxide, calcium carbonate, lithium carbonate, or ethylene oxide is used. , Propylene oxide, ammonia,
An organic neutralizing agent such as triethylamine is added. The reaction between the isocyanate and the carboxylic acid is performed in an aprotic organic polar solvent in the presence of a catalyst. These polymer solutions may be directly used as a stock solution for forming a film, or the polymer may be isolated once and then redissolved in the above solvent to prepare a stock solution. In some cases, an inorganic salt such as calcium chloride, magnesium chloride, or lithium chloride is added as a dissolution aid to the film forming stock solution.
The polymer concentration in the stock solution is preferably about 2 to 40% by weight.

On the other hand, a solution of aromatic polyimide or polyamic acid is obtained as follows. That is, the polyamic acid can be prepared by reacting a tetracarboxylic dianhydride with an aromatic diamine in an aprotic organic polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like. The aromatic polyimide can be prepared by heating a solution containing the above-mentioned polyamic acid or adding an imidizing agent such as pyridine to obtain a polyimide powder, which is dissolved in a solvent again. The polymer concentration in the film forming stock solution is preferably about 5 to 40% by weight.

The following methods can be used for incorporating high thermal conductive particles such as carbon black, but are not limited thereto. (1) The high thermal conductive particles are dispersed in a solvent in which the polymer is soluble and added to the polymer solution. Alternatively, the isolated polymer is added to the dispersion solution and dispersed. (2) Polymerization is carried out after dispersing a highly thermally conductive substance in a polymerization solvent before polymerization. (3) The high thermal conductive particles are added to the polymer solution as powder or together with a solvent and dispersed. Examples of the dispersing device include a colloid mill, a three-roll mill, a kneader, an ultrasonic dispersing machine, a sand mill, and a ball mill.

Further, when the film surface is too smooth only by adding the high thermal conductive particles, it is preferable to keep the particles in the stock solution for film formation. Here, the particles are not particularly limited, but may be SiO ₂ , TiO ₂ , ZnO, Al ₂
Inorganic and organic materials such as O ₃ , CaSO ₄ , BaSO ₄ , CaCO ₃ , zeolite, silicone particles and Teflon particles are used. The particle size is preferably 0.1 to 10 μm, and the amount of addition is preferably 0.1 to 5% by weight.

The film-forming stock solution prepared as described above is formed into a film by a so-called solution film-forming method such as a wet method, a dry-wet method, and a dry method. When the film is formed by a wet method, a method in which the stock solution is directly extruded from a die into a film-forming bath, or is once extruded onto a support such as a drum, and the whole support is introduced into the wet bath can be adopted. This bath is generally composed of an aqueous medium, and may contain an organic solvent or an inorganic salt in addition to water. In the wet bath, an organic solvent, an inorganic salt, and the like are extracted, and the film is stretched in the longitudinal direction of the film. Next, drying, transverse stretching, and heat treatment are performed, and these treatments are generally performed at 100 ° C. to 500 ° C. for 1 second to 30 seconds.
Minutes.

When a film is formed by a dry-wet method, a stock solution is extruded from a die onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer to dry until the thin film has self-holding property. I do. Drying conditions are from room temperature
300 ° C, within 60 minutes. The film after the dry process is peeled from the support and introduced into the wet process,
Desalting, desolvation, and the like are performed in the same manner as in the above wet method, and further, stretching, drying, and heat treatment are performed to form a film.
In the case of employing a dry process, a film which is dried on a drum or an endless belt and has self-holding properties is peeled off from these supports, and is stretched in the longitudinal direction of the film. Further, drying, stretching, and heat treatment for removing the residual solvent are performed, and these treatments are performed at 150 to 500 ° C. for 1 to 30 minutes.

The film formed as described above is stretched during the film forming process, and the stretching ratio is 0.9 to 3.0 (area ratio). Is defined as a value obtained by dividing by the area of the film. 1 or less means relaxation.) In order to improve the thermal conductivity and maintain the mechanical properties and the thermal properties. When the area ratio is larger than 3.0, the mechanical properties are improved, but the thermal conductivity and the thermal properties are unfavorably deteriorated.
The method for adjusting the surface properties of the film is controlled by the type and amount of the high thermal conductive particles, the dispersing method, the film forming conditions, and the like.

To form the laminated film of the present invention, A
Two types of film forming stock solution corresponding to the layer side and film forming stock solution corresponding to the layer B side were prepared by a known method, for example, as shown in JP-A-56-162617, in a merging tube or in a base. And B /
It can be formed by laminating A / B. Alternatively, it is acceptable to form a film by film-forming solution of any one performs desolvation cast other membrane-forming solution thereon, on this is al, laminating in the same way the method Can be. In particular, when laminating in a junction tube or a base, the viscosity of the stock solution is 100 to 10
It is preferable to adjust to be 000 poise. If it is smaller than this range, the liquids tend to mix with each other before the undiluted liquid comes out of the die, which is not preferable. Further, it is desirable that the viscosities of the liquids in the respective layers are the same, but there may be a slight difference in viscosity, and it is preferable that the difference in viscosity is targeted at 50% or less.

Further, when a dry method or a dry / wet method is adopted,
Each liquid may mix during the drying process. The undiluted solution cast on the support once decreases in viscosity when heated,
Thereafter, the viscosity increases again as the solvent evaporates. However, when the viscosity falls below 10 poise, the respective liquids are easily mixed. Therefore, it is necessary to sufficiently adjust the drying conditions so that the viscosity does not drop below 10 poise, preferably below 50 poise. is there. For example, a method of increasing the drying temperature in at least two stages can be adopted.

Although the laminated film of the present invention is manufactured as described above, it is preferable to perform a glow discharge treatment and a corona discharge treatment for further improving the inking property.

[Method of Use] The film of the present invention thus obtained is used by inking one of its surfaces. The use form is a drum-shaped,
Endless drum shape, ribbon shape, endless ribbon shape,
A sheet shape, an endless sheet shape, or the like can be appropriately selected. If necessary, the surface to be inked within the range satisfying the characteristics of the present invention may be provided with ink adhesiveness, ink releasability, antistatic property, or inking. It is possible to impart lubricity and lubricity to the surface opposite to the surface to be formed.

As the heat-sensitive solid ink of the present invention, known inks are generally used, and monochrome and color inks can be used. Further, any of a so-called fusion type and sublimation type can be used. . Among them, a melt type ink is preferable.

[0051]

According to the master film for thermal transfer recording of the present invention, the resin having no melting point has a layer A composed of high thermal conductive particles , and the resin having no melting point has high thermal conductive particles having a smaller content than the layer A. As a result of the structure in which the layer B is laminated on both sides of the layer A , the following effects are obtained.

The master film can be used repeatedly, and an inexpensive master film can be obtained. In addition, since high thermal conductive particles are included, thermal efficiency is improved, so that speed can be increased and transfer energy can be reduced.

[0053]

[0054]

[Method of measuring characteristics and method of evaluating effects]
The method for measuring characteristics and the method for evaluating effects in the present invention are as follows. (1) Thermal conductivity Measured at 25 ° C. by laser flash method using TC-700 manufactured by Vacuum Riko Co., Ltd.

(2) Surface Roughness Using a surface roughness measuring instrument, SE-3E, manufactured by Kosaka Seisakusho, a measurement length of 4 mm was measured under the condition of a cutoff value of 0.08 mm, and the roughness curve was measured from the center line of the chart. Of the maximum height Rp was calculated. The film is measured by fixing it to a glass cylinder having an outer diameter of 80 mm with cellophane.

(3) Inking properties and image transfer properties The following hot-melt ink solids are heated and melted and transferred to the surface of the heat-resistant film, and the inking properties are then transferred. To evaluate the image transferability. Note that plain paper was used as the transfer paper. [Hot-melt ink composition] Carnauba wax: 100 parts by weight Microcrystalline wax: 30 parts by weight Vinyl acetate / ethylene copolymer: 15 parts by weight Carbon black: 20 parts by weight Uniform over the entire surface Δ: There is a slightly non-uniform part on the ink surface. X: The ink surface is non-uniform. Criteria for image transferability were as follows: 印字: clear printing was obtained. 少 し: printing had a slightly unclear portion. X: printing was unclear, and ○ was good.

(4) Head Staining Property After printing 10,000 sheets under the condition (3),
The head was removed, and the stained and worn state of the head was observed with a 100-fold optical microscope. When the contaminated area of the head portion was less than 30%, the head contamination was [O], when it was 30% or more, [Δ], and when it was less than 30%, it could not be removed by wiping with ethyl alcohol [X]. The occurrence of scratches on the head was observed, and those without any scratches were marked with [○] for the head abrasion, and those with scratches were marked with [x]. Both the head stainability and the head abrasion were evaluated as [O], and the head stainability was evaluated as [O].

(5) Hot Stick Property The vehicle was run under the conditions of the above (3), and judged according to the following criteria. ◎: No sticking was observed, the running property was extremely good, and clear printing was obtained. ：: There is no problem in running properties, and normal printing can be performed, but a slight stick occurs in the solid printing portion. Δ: Running, but normal printing was not possible. ×: No running at all. ○ The above was regarded as good.

[0060]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following Examples 1 5 and the characteristics in Comparative Example 1 to 5 are summarized in Table 1, also the practical test results shown in Table 2.

Example 1 45 liters of dehydrated N-methylpyrrolidone and 0.3 mole of 2-chloro-p-phenylenediamine in a molar ratio of 0.3
4,4'-Diaminodiphenyl ether corresponding to the molar ratio was dissolved under stirring, cooled to 10 ° C, and 2-chloroterephthalic chloride corresponding to a 1.0 molar ratio was added thereto, followed by stirring for 2 hours. Thereafter, 96 mol% of sufficiently purified calcium carbonate was added per generated hydrogen chloride, and the mixture was stirred at 70 ° C. for 2 hours, and then neutralized by adding 7 mol% equivalent of aqueous ammonia. 1/3 of this polymer solution
Was extracted, and N-methylpyrrolidone was added so that the solution viscosity became 3000 poise at 30 ° C. On the other hand, in the remaining 2/3 solution, carbon black was added to the polymer in Table 1.
To obtain a homogeneous solution. 3 more
N-methylpyrrolidone was added so as to be 3000 poise at 0 ° C. Each of the obtained polymer solutions was uniformly cast at 30 ° C. through a 30 μm-cut filter onto a metal drum at a temperature of 30 ° C. using a merging tube so that the liquid containing carbon black became a central layer. It dried for about 10 minutes in the atmosphere of ° C. The film was peeled from the drum and stretched 1.1 times in the longitudinal direction while continuously immersed in a water bath at 30 ° C. for about 10 minutes. Further, the film was introduced into a tenter and stretched 1.1 times in the width direction at 320 ° C. to obtain an aromatic polyamide film having a thickness of 15 μm. Tables 1 and 2 show the thickness configuration and characteristics of the three-layer film.

Example 2 40 mol% of paraphenylenediamine and 60 mol% of 3,4'-diaminodiphenyl ether were used as an amine component, and 100 mol% of terephthalic acid chloride was used as an acid component to polymerize in N-methylpyrrolidone. And dried by removing the hydrochloric acid by-product. A part of this polymer and N-methylpyrrolidone were placed in a kneader, LiCl was added at 20% by weight per polymer, and carbon black was further added to the concentration shown in Table 1 to obtain a uniform solution.
Further, the remaining polymer and N-methylpyrrolidone were put into a kneader, and LiCl was added and dissolved at 20% by weight per polymer. This was cast onto a metal drum through a 30 μm-cut filter in the same manner as in Example 1, dried, and then introduced into water. The film was stretched 1.2 times in the longitudinal direction in water, then introduced into a tenter, and stretched 1.2 times in the width direction at 320 ° C. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

Example 3 80 mol% of 2-chloro-p-phenylenediamine and 4,4
20 mol% of 4'-diaminodiphenylmethane as an amine component, 60 mol% of terephthalic acid chloride and 40 mol% of isophthalic acid chloride as acid components are polymerized in N-methylpyrrolidone. The polymer was isolated by pouring into water. After washing and removing hydrogen chloride produced as a by-product,
Vacuum dried to obtain a dried polymer. Part of this polymer and N-
Methylpyrrolidone was placed in a kneader, LiCl was added at 30% by weight per polymer, and tin oxide was further added to the concentration shown in Table 1 to obtain a homogeneous solution. Further, the remaining polymer was dissolved in a solution containing N-methylpyrrolidone and 30% by weight of LiCl per polymer. This is the same as in Example 1 3
It was cast on a metal drum through a 30 μm-cut filter as a layer, dried, and then introduced into water. The film was stretched 1.10 times in the longitudinal direction in water, then introduced into a tenter and stretched 1.15 times in the width direction at 330 ° C. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

Example 4 4,4'-Diaminodiphenyl ether (DAE) was dissolved in dehydrated N-methylpyrrolidone and cooled to 20 ° C. Pyromellitic anhydride was added in an equimolar amount to DAE and reacted for 2 hours to complete the polymerization. A part of this solution was taken out and adjusted to have a solution viscosity of 3000 poise at 30 ° C. Further, carbon black was added to the remaining polymer solution so as to have a concentration shown in Table 1 to obtain a uniform solution.
This was cast into a three-layer form as in Example 1 and cast on a metal drum through a 30 μm-cut filter.
It was dried for a minute and peeled off from the drum. The stretching ratio is the longitudinal direction,
It is 1.0 times in both width directions. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

Example 5 A polymer was prepared in the same manner as in Example 1, and a stock solution was prepared so that the amount of carbon black was 5% by weight and 40% by weight per polymer. A film was obtained by exactly the same method except that the film was changed as follows. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

Comparative Example 5 Using the polymer obtained in Example 1, a film having a two-layer structure consisting of only a carbon-containing layer and a polymer layer was obtained by a merging tube. Tables 1 and 2 show the thickness configuration and characteristics of the two-layer film.

COMPARATIVE EXAMPLE 1 A single film was obtained from the solution in Example 1 to which no carbon black was added. The characteristics of the film are as shown in Tables 1 and 2.

Comparative Example 2 A single film was obtained from a solution containing carbon black without using the three-layer structure in Example 1. Table 1 shows the film characteristics.
It is as shown in Table 2.

Comparative Example 3 A film was obtained in exactly the same manner as in Example 1, except that the thickness of the three layers of the film was changed. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

Comparative Example 4 A film was obtained in exactly the same manner as in Example 4 except that the film was not passed through. Tables 1 and 2 show the thickness configuration and characteristics of the obtained three-layer film.

As shown in Tables 1 and 2, the master film for thermal transfer recording satisfying the requirements of the present invention is excellent in inking property, image transfer property , head stain property, hot stick property and clear image. It can be seen that it can be obtained stably.

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[Table 1]

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[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-3980 (JP, A) JP-A-2-299882 (JP, A) JP-A-61-92893 (JP, A) JP-A 62-980 39292 (JP, A) JP-A-63-237989 (JP, A) JP-A-4-105994 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5 / 38-5 / 40

Claims (3)

(57) [Claims] 1. A master film for thermal transfer recording which is used repeatedly, wherein the master film for thermal transfer recording contains a resin having no melting point and an A layer comprising high thermal conductive particles , a resin having no melting point and less than the A layer. is composed of a B layer made of the amount of the high thermal conductive particles, the B layer is a
A master film for thermal transfer recording characterized by being provided on both sides of a layer . 2. The method according to claim 1, wherein the layer B contains substantially high thermal conductive particles.
2. The master film for thermal transfer recording according to claim 1, wherein said master film is made of a resin . 3. The resin having no melting point is an aromatic polymer.
3. The master film for thermal transfer recording according to claim 1, which is a imide or an aromatic polyimide .