JPH115375A - Thermal transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance heat resistance and adhesion properties for a base material by forming an antisticking layer of specific contents of an acrylic silicone graft copolymer and copolymerized polyester, in a thermal transfer recording material with a heat sensitive ink layer formed on one of the faces of a base material and the antisticking layer formed on the other face. SOLUTION: This thermal transfer recording material is available for not only an ink ribbon for bar code but also various use applications in thermal transfer recording process. In the thermal ink transfer recording material with a heat sensitive ink layer formed on one of the faces of a base material and an antisticking layer formed on the other face, the antisticking layer is formed of 70-99.5 pts.wt. of an acrylic silicone graft copolymer and 30-0.5 pts.wt. of copolymerized polyester. In this case, the content of the copolymerized polyester is 1-20 wt.% of the total weight of the acrylic silicone graft copolymer and the copolymerized polyester. Further, the acrylic silicone graft copolymer to be used is such one as having an acrylic polymer at a glass transition temperature of 80 deg.C or higher as a basic component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording material having a stick prevention layer having excellent heat resistance and excellent adhesion to a substrate. It is suitably used for various thermal transfer recording applications such as an ink ribbon.

[0002]

2. Description of the Related Art Thermal transfer recording materials are used in printers, recorders and the like of various office equipment employing the thermal transfer recording system. In the thermal recording method, the recording paper, which is the material to be transferred, is brought into contact with the thermal ink layer provided on the substrate film, and a pulse signal is emitted from the thermal head on the opposite side of the ink layer, and the ink layer passes through the substrate film. Is heated, and the heated ink layer is transferred to recording paper by melting or sublimation to form a recorded image. The thermal recording method is a recording method which has advantages such as no noise during printing, excellent heat resistance and chemical resistance of printing, and excellent storage stability.

In the thermal transfer recording material, a part of the base film is melted due to the high temperature of the thermal head, and the molten resin adheres to the thermal head, so that the transfer of the base film becomes defective. There is a problem of so-called sticking, which makes it difficult to transfer characters, figures, and the like to recording paper. Therefore, in order to solve this problem, it is common practice to provide an anti-stick layer on the surface of the substrate film in contact with the thermal head. Conventionally, a metal layer such as aluminum, a silicone resin layer, a paraffin layer, a thermosetting resin layer, and the like have been adopted as a stick prevention layer in the thermal transfer recording material, but all have insufficient stick prevention effects. However, there were problems such as poor workability, poor adhesion to a base material, poor film formability, and corrosion of a thermal head, and the utility was poor.

Further, in recent years, there has been a strong demand for clearer and more precise printing, and accordingly, the voltage applied to the thermal head has been increased, and a higher heat resistance has been required for the stick prevention layer of the thermal transfer recording material. And high adhesion to the base film, and further improvement of the heat resistance of the stick prevention layer accompanying the thinning of the base film is required. For the purpose of satisfying such demands, it has been proposed to use an acryl-silicone graft copolymer as a stick prevention layer of a thermal transfer recording material (JP-A-62-30082, JP-A-62-30082). JP-A-63-37620 and JP-A-2-274596. However, the stick prevention layer made of the conventional acrylic-silicone-based graft copolymer described above is still insufficient in heat resistance and adhesion to the substrate film, and has further improved heat resistance and adhesion to the substrate. There is a need for a thermal transfer recording material.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a stick prevention layer which is more excellent in heat resistance and adhesion to a substrate, and the components in the stick prevention layer during thermal transfer. Sticks to the thermal head, or sticks (adhesion) to the thermal head with a stick prevention layer
The object of the present invention is to provide a high-quality heat-sensitive transfer recording material free of heat.

[0006]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the stick prevention layer of the heat-sensitive transfer recording material was replaced with an acrylic-silicone-based graft copolymer and a copolymerized polyester. When formed using a specific ratio, the heat resistance of the stick prevention layer is further improved, and the adhesion of the stick prevention layer to the base material is further improved. The inventors have found that a thermal transfer recording material can be obtained and completed the present invention.

That is, the present invention provides a heat-sensitive transfer recording material comprising a base material having a heat-sensitive ink layer on one surface and a stick prevention layer on the other surface. -Based graft copolymer 7
0-99.5 parts by weight and copolymerized polyester 30-
A thermal transfer recording material comprising 0.5 part by weight.

In the thermal transfer recording material of the present invention, the content of the copolymerized polyester in the stick prevention layer is 1 to 20 based on the total weight of the acryl-silicone graft copolymer and the copolymerized polyester.
The preferred embodiment includes a thermal transfer recording material which is in a weight%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The acrylic-silicone-based graft copolymer (hereinafter sometimes referred to as "graft copolymer (A)") constituting the stick prevention layer in the thermal transfer recording material of the present invention comprises an acrylic polymer as a main component. And a graft copolymer containing a silicone polymer as a branch component.

The acrylic polymer constituting the trunk component of the graft copolymer (A) mainly comprises a unit based on a (meth) acrylic monomer selected from (meth) acrylic acid esters or (meth) acrylic acid. Preferably a component,
Specifically, the (meth) acrylic monomer unit is preferably contained in an amount of 50% by weight or more based on the total amount of the constituent units of the acrylic polymer. When the proportion of the (meth) acrylic monomer unit in the acrylic polymer constituting the trunk component is less than 50% by weight, the heat resistance of the stick prevention layer may be insufficient. As the (meth) acrylic monomer, methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate and isobornyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; Lactone-modified hydroxy (meth) acrylate; acrylic acid, methacrylic acid, and the like.

The acrylic polymer constituting the trunk component of the graft copolymer (A) has a structural unit derived from one or more other radically polymerizable monomers, if necessary. It may be. In this case, examples of other radically polymerizable monomers include styrene, (meth) acrylonitrile, vinyl acetate, (meth) acrylamide, itaconic acid, and maleic acid.

The acrylic polymer constituting the trunk component of the graft copolymer (A) may be vinyltriethoxysilane or γ-methacryloxy, if necessary, in addition to the above-mentioned radical polymerizable monomer. Organosilicon monomers such as propyltrimethoxysilane, allyl methacrylate, structural units derived from bifunctional monomers such as diallyl phthalate,
It may be present in such a small amount that gelation does not occur during the production of the graft copolymer (A).

In the graft copolymer (A), the acrylic polymer constituting the trunk component has a glass transition temperature (hereinafter, sometimes abbreviated as “Tg”) of 80 ° C. or more, which prevents sticking. This is desirable because the heat resistance of the layer can be further improved. Herein, the term Tg stem component of the graft copolymer (A) (acrylic polymer), Tg _1, Tg ₂ relates homopolymer of each monomer constituting the acrylic polymer is a stem component , Tg ₃ ,... And the weight ratio of the monomer in the acrylic polymer as the main component, are calculated by the following formula.

[0014]

1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / T
g ₃ + ... [wherein Tg is the glass transition point of the acrylic polymer constituting the trunk component of the graft copolymer (A), Tg ₁ , Tg ₂ ,
Tg ₃ ,... Are the glass transition points of the homopolymers of the monomers constituting the acrylic polymer, W ₁ , W ₂ , W ₃ ,.
Represents the weight ratio of each monomer in the acrylic polymer. Note that Tg calculated here is an absolute temperature. ]

[0015] A typical example of the silicone-based polymer constituting the branch component of the graft copolymer (A) is polydiorganosiloxane, and more specifically, for example, polydimethylsiloxane, polydiethylsiloxane and the like. Dialkylsiloxane; polyalkylphenylsiloxane such as polymethylphenylsiloxane and polyethylphenylsiloxane; and polydiarylsiloxane such as polydiphenylsiloxane. The branch component of the graft copolymer (A) can be formed from one or more of the above-mentioned polydiorganosiloxanes. Among them, the silicone polymer serving as a branch component is preferably polydimethylsiloxane from the viewpoint of lubricity of the stick prevention layer.

The silicone polymer which constitutes a branch component of the graft copolymer (A) has a molecular weight of 1,000 to 1,000.
00 is preferred. When the molecular weight of the silicone polymer is less than 1000, the properties of the silicone polymer such as lubricity and releasability become difficult to be exhibited in the stick prevention layer. On the other hand, when the molecular weight exceeds 100000, the hardness of the stick prevention layer decreases. As a result, the durability of the thermal transfer recording material during running tends to deteriorate.

In the graft copolymer (A), the proportion of the silicone polymer constituting the branch component is preferably 5 to 60% by weight. When the proportion of the silicone polymer is less than 5% by weight, the lubricity and the like are reduced, and the transferability of the heat-sensitive transfer recording material is easily reduced.
If it exceeds 0% by weight, the adhesion to the substrate is reduced and the durability tends to be poor.

The method for producing the graft copolymer (A) used for the stick prevention layer is not particularly limited, and the graft copolymer having a trunk component composed of a (meth) acrylate polymer and a branch component composed of a silicone polymer can be used. Any method may be used as long as it can produce a polymer. Although not limited, the graft copolymer (A)
Is, for example, a radical copolymerization of (meth) acrylic acid ester and / or (meth) acrylic acid and, if necessary, other radical polymerizable monomer together with a silicone macromonomer having a (meth) acryloyl group at a terminal. Can be obtained. In that case, a known method can be applied to the radical copolymerization, and for example, a known method such as a radiation irradiation method and a method using a radical polymerization initiator can be used. Among them, a polymerization method using a radical polymerization initiator is preferably adopted from the viewpoint of easiness of polymerization operation, easiness of controlling the molecular weight of the resulting silicone-based graft copolymer, and the like. It may be performed by any method such as a solution polymerization method, a bulk polymerization method, and an emulsion polymerization method.

As the above radical polymerization initiator, any of those used in general radical polymerization can be used, and an appropriate one may be selected according to the polymerization method.
For example, an inorganic radical polymerization initiator such as ammonium persulfate, peroxyketal, hydroperoxide,
Dialkyl peroxide, diacyl peroxide,
Organic peroxides such as peroxydicarbonate and peroxyester, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-
Methylbutyronitrile), azobis (cyclohexane-
Organic radical polymerization initiators such as azo compounds such as 1-carbonitrile) can be exemplified. Among them, organic peroxides and azo compounds having a low decomposition temperature are preferred in that a relatively low polymerization temperature can be adopted, side reactions are suppressed, and a graft copolymer having a clear structure is obtained with high purity. In particular, azo compounds are preferred.

The amount of the radical polymerization initiator used is generally
The amount is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the total weight of the polymerizable component. Generally, the polymerization temperature is preferably from 50 to 150 ° C,
60-100 degreeC is more preferable. The polymerization time is usually about 5 to 25 hours.

When the block copolymer (A) is produced by an ultraviolet irradiation method, polymerization may be carried out using a known sensitizer, and the block copolymer (A) may be produced by an electron beam irradiation method. In the case of production, the block copolymer (A) can be obtained only by electron beam irradiation without using a sensitizer.

In the thermal transfer recording material of the present invention, the other component constituting the stick prevention layer, the copolymerized polyester [hereinafter sometimes referred to as “copolymerized polyester (B)”] has a glass transition temperature of −30. ℃ -50
C. is preferably used. If the glass transition temperature of the copolymerized polyester (B) exceeds 50 ° C., the degree of adhesion of the stick prevention layer containing the same to the substrate will be low, making it difficult to obtain the desired thermal transfer recording material. In addition, the glass transition temperature of the copolyester (polyester) referred to in this specification is JIS K712.
Refers to the glass transition temperature measured by DSC (differential scanning calorimeter) according to 1.

In the present invention, as the copolymerized polyester (B), any copolymerized polyester having a glass transition temperature of -30 ° C. to 50 ° C. can be preferably used. For example, an aromatic dicarboxylic acid component, an aliphatic A copolymerized polyester obtained by using a raw material component mainly composed of a dicarboxylic acid component and an alkylene glycol; a copolymerized polyester obtained by reacting an aromatic oxycarboxylic acid component and an aliphatic oxycarboxylic acid component; Examples thereof include copolymerized polyesters obtained by polymerization. In the present invention, one or more of the above-described copolymerized polyesters can be used.

Among them, in the present invention, as the copolymerized polyester (B), a copolymerized polyester obtained using a raw material component mainly comprising an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component and an alkylene glycol component [hereinafter referred to as It may be referred to as “copolymerized polyester (b)”] from the viewpoint of easy availability and easy production. The method for producing the copolymerized polyester (b) more preferably used in the present invention is not limited at all, and any method may be used as long as it is produced according to a conventionally known production technique for this type of polyester. For example, an aromatic dicarboxylic acid component, A raw material component mainly composed of an aliphatic dicarboxylic acid component and an alkylene glycol component,
According to a conventionally known method, it can be produced by employing a transesterification method or a direct esterification method.

Examples of the aromatic dicarboxylic acid component that can be used in the production of the copolymerized polyester (b) include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; wherein the aromatic nucleus is an alkyl group, a halogen atom or a nitrile group. And the above-mentioned aromatic dicarboxylic acids substituted with other substituents; anhydrides of the above-mentioned aromatic dicarboxylic acids,
Examples thereof include ester-forming derivatives such as lower alkyl esters and halides. The copolymerized polyester (b) may have a structural unit derived from one or more of the above-mentioned aromatic dicarboxylic acid components.

Examples of the aliphatic dicarboxylic acid component which can be used in the production of the copolymerized polyester (b) include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, anhydrides thereof, lower alkyl esters, Examples include ester-forming derivatives such as halogenation, and the copolymerized polyester (b) can have a structural unit derived from one or more of the above-described aliphatic dicarboxylic acid components. .

The alkylene glycol component which can be used for producing the copolymerized polyester (b) includes, for example,
Ethylene glycol, diethylene glycol, 1,4-
Examples thereof include butanediol, 1,6-hexanediol, neopentyl glycol, and polyethylene glycol. The copolymerized polyester (b) has a structural unit derived from one or more of the above-described alkylene glycol components. Can be.

Further, the copolymerized polyester (B) may be used in an amount not to impair the object of the present invention, if necessary, and
Trifunctional or higher carboxylic acid components (for example, trimellitic acid,
It may have a structural unit derived from trimellitic anhydride, pyromellitic anhydride, etc.) and / or a structural unit derived from a trifunctional or higher alcohol component (eg, trimethylolpropane, pentaerythritol, etc.).

In the thermal transfer recording material of the present invention, the blending ratio of the graft copolymer (A): copolyester (B) in the stick prevention layer is 99.5: 0.5-7.
It is necessary that the weight ratio be 0:30, and 99: 1
Preferably, the ratio is 80:20. When the proportion of the copolyester (B) is less than 0.5% by weight based on the total weight of the graft copolymer (A) and the copolyester (B), the adhesion of the stick prevention layer to the substrate is poor. As a result, a phenomenon occurs in which the stick prevention layer is scraped off by the thermal head during printing, which adversely affects printability. On the other hand, when the proportion of the copolymerized polyester (B) exceeds 30% by weight based on the total weight of the graft copolymer (A) and the copolymerized polyester (B),
The glass transition temperature of the entire stick prevention layer is lowered,
The heat resistance of the stick prevention layer is reduced, causing a stick phenomenon to the thermal head and a blocking during transfer of the thermal transfer recording material during thermal transfer.

In the heat-sensitive transfer recording material of the present invention, the stick preventing layer contains other components, if necessary, together with the above-mentioned graft copolymer (A) and copolymerized polyester (B). You may. For example, a polyvalent isocyanate compound and / or a melamine-based curing agent can be used in combination with the graft copolymer (A) and the copolymerized polyester (B), and in this case, the graft copolymer (A) may have a functional group such as a hydroxyl group. When it has a group, the stick preventing layer can be cross-linked and cured by the polyvalent isocyanate compound and / or the melamine-based curing agent. When the graft copolymer (A) has a hydrolyzable functional group bonded to a silicon atom, for example, when a catalyst such as dibutyltin dilaurate is used in combination, the stick preventing layer is crosslinked using the functional group. Can be cured.

Further, when an inorganic filler such as talc, calcium carbonate, carbon black, silica powder or the like is contained in the stick preventing layer, the heat resistance thereof can be improved. By imparting lubricity to the layer, the transferability of the thermal transfer recording material can be improved. Further, an antistatic agent or the like may be contained in the stick prevention layer.

In the thermal transfer recording material of the present invention, the type of the substrate is not particularly limited, and any substrate conventionally used in thermal transfer recording materials can be used.
Films and sheets made of polyester such as polyethylene terephthalate, nylon, polycarbonate, polypropylene, cellophane, etc.
Examples of the base material include condenser paper and cellophane paper. Among them, a polyethylene terephthalate film or sheet is preferably used as the substrate from the viewpoint of mechanical strength, cost and the like.

The method for forming the stick prevention layer on the substrate is not particularly limited, and any method capable of forming the stick prevention layer to a uniform thickness is conventionally known in the production of thermal transfer recording materials. Either method may be used. Although not particularly limited, for example, a solution or dispersion is prepared by dissolving or dispersing the graft copolymer (A), the copolymerized polyester (B), and optionally other components in an organic solvent, an aqueous medium, or the like. Then, after coating it on the surface of the substrate using a gravure roll coater, reverse roll coater, air knife coater or the like, a stick prevention layer can be formed by a method of drying by heating.

From the viewpoint of flexibility, thermal transfer efficiency of the thermal head, cost, etc., the amount of the solid applied to the stick prevention layer is preferably 0.01 to ² g / m ² in terms of the solid content. More preferably, it is 0.05 to 1 g / m ² .

In the heat-sensitive transfer recording material of the present invention, the content and type of the heat-sensitive ink layer provided on the surface opposite to the stick prevention layer on the substrate are not particularly limited, and the heat-sensitive transfer recording material conventionally used in heat-sensitive transfer recording materials is not limited. Any of the ink layers may be used. The thermal ink layer is usually formed using a polymer composition containing a dye or pigment.

Although not particularly limited, when the heat-sensitive transfer recording material of the present invention is a hot-melt transfer material,
In general, a hot-melt ink is prepared by blending a dye or pigment with a thermoplastic polymer, and a heat-sensitive ink layer is formed using the hot-melt ink. At this time, the type of dyes and pigments to be contained in the thermal ink layer is not particularly limited, and one or more conventionally known organic dyes and inorganic dyes and pigments can be used in the thermal transfer recording material. Although not limited, examples of organic dyes and pigments include, for example, azo dyes, anthraquinones,
Known organic dyes and pigments belonging to indigoid-based and cyanine-based dyes and the like, and inorganic dyes and pigments include carbon black and the like. Further, as the thermoplastic polymer used in the hot-melt ink, for example, polyethylene,
Polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, vinyl acetate-vinyl chloride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylate- Acrylamide copolymer, styrene-butadiene copolymer, poly (meth)
Acrylic ester, polyacrylonitrile, acrylonitrile-vinyl acetate copolymer, polyvinyl acetate, cellulosic resin, polyvinyl butyral, polyvinyl acetoacetal, polyamide, copolyester, and the like, and one of the thermoplastic polymers described above. Alternatively, two or more kinds can be used.

When the heat-sensitive transfer recording material of the present invention is a sublimation-type heat transfer material, the heat-sensitive ink layer may be formed using a sublimation-type ink composed of a polymer composition containing a sublimation-type dye. The type of the sublimation dye used at this time is not particularly limited, and any of the conventionally known sublimation dyes can be used in the thermal transfer recording material. Specific examples of sublimation dyes include MSRed G and Macrolex as red dyes.
Red and the like. Further, examples of the yellow dye include holon brilliant yellow 6GL, macrolex yellow 6G, and the like. As blue dyes, Kayaset Blue 714, Holon Brilliant Blue SR
And the like. As the polymer used for the sublimation type ink, various thermoplastic polymers similar to those described above for the hot melt type ink can be used.

The formation of the heat-sensitive ink layer on the substrate can be carried out by the same method as described above for the formation of the stick prevention layer on the substrate. For example, a dye or pigment as described above, a thermoplastic polymer, and optionally other necessary additives are added to an appropriate solvent to prepare a solution or dispersion, which is then subjected to a gravure roll coater, a reverse roll coater, an air knife coater, or the like. Is used, a heat-sensitive ink layer can be formed on the substrate by coating the surface of the substrate opposite to the surface on which the stick prevention layer is to be formed, followed by drying by heating. Generally, the thickness of the heat-sensitive ink layer is preferably about 0.2 to 5 μm,
The amount of the dye / pigment contained in the thermal ink layer is 5 to 90.
It is preferable that the amount is about% by weight.

[0039]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. In the following examples, “parts” indicates “parts by weight”. In addition, the silicone macromonomer used in each example, that is, FM07
25, AK-32 and X-22-174DX are all macromonomers having a methacryloyl group at the terminal of dimethylpolysiloxane.

Reference Example 1 [Production of Acrylic-Silicone Graft Copolymer (a ₁ )] A silicone macromonomer (manufactured by Chisso Corporation) was placed in a flask equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube. FM0725 "; molecular weight 10,000) 20 parts, methyl methacrylate 60 parts, butyl methacrylate 10
Part, 2-hydroxyethyl methacrylate 5 parts, methacrylic acid 5 parts, azobisisobutyronitrile 1.0 part and methyl ethyl ketone 100 parts, and the mixture was maintained at 70 ° C. for 3 hours while bubbling nitrogen thereto. 0.5 part of lonitrile was added, and the mixture was further heated at the same temperature for 3 hours to produce a solution of an acrylic-silicone-based graft copolymer having a nonvolatile content of 50%. The component Tg is 90.5
° C.) [hereinafter "acrylic - silicone-based graft copolymer (a _1)" hereinafter] were collected as solids.

Reference Example 2 [Production of Acrylic-Silicone Graft Copolymer (a ₂ )] As a polymerizable component, a silicone macromonomer (“AK-32” manufactured by Toagosei Co., Ltd .; molecular weight 30,000) 30
, Methacrylate, 60 parts, butyl methacrylate, 5 parts, and acrylic acid, 5 parts, and polymerization was carried out in the same manner as in Reference Example 1 to obtain an acrylic-silicone-based graft copolymer (Tg of the trunk component was 97.4). ° C) [hereinafter referred to as “acryl-silicone graft copolymer (a ₂ )”
It was manufactured.

Reference Example 3 [Production of Acrylic-Silicone Graft Copolymer (a ₃ )] As a polymerizable component, a silicone macromonomer (“X-22-174DX” manufactured by Shin-Etsu Chemical Co., Ltd .; molecular weight 500)
0) 40 parts, methyl methacrylate 35 parts, styrene 1
0 parts, butyl acrylate 5 parts and methacrylic acid 10
Of the acrylic-silicone-based graft copolymer (Tg of the trunk component is 87.5 ° C.) [hereinafter referred to as “acryl-silicone-based graft copolymer (a)”. ₃ ) "].

Reference Example 4 [Acrylic copolymer (c)]
Production of Acrylic copolymer using 75 parts of methyl methacrylate, 13 parts of butyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate and 6 parts of methacrylic acid as polymerizable components in the same manner as in Reference Example 1. A polymer (Tg: 90.0 ° C.) [hereinafter referred to as “acrylic copolymer (c)”] was produced.

Reference Example 5 [Production of Copolyester (b ₁ )] A flask equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube was charged with 83.5 parts of dimethyl terephthalate and 70.4 parts of isophthalic acid. , Adipic acid 19.5 parts, ethylene glycol 62.2 parts, neopentyl glycol 104.2
Parts, zinc acetate 0.20 parts and tetrabutyl titanate 0.20 parts were charged under a nitrogen gas stream,
After performing the esterification reaction at 4 ° C. for 4 hours, the temperature is increased and the pressure is reduced, and the reduced pressure reaction is performed at 210 to 250 ° C. and 5 mmHg to obtain a copolymerized polyester [hereinafter referred to as “copolymerized polyester (b ₁ )”]. Manufactured. When the composition analysis of the copolymerized polyester (b ₁ ) thus obtained was performed,
45 mol% of terephthalic acid units, 42 mol% of isophthalic acid units and 13 mol% of adipic acid units are financed as acid units, and ethylene glycol units are 49 as glycol units.
It had mol% and 51 mol% neopentyl glycol units. The glass transition temperature of the copolymerized polyester (b ₁ ) was 45 ° C.

Example 1 [Production of Thermal Transfer Recording Material] (1) A polyester film (4.5 μm, made of diamond foil) was used as a base film, and a bar coater was used on one surface of the polyester film. acrylic prepared in reference example 1 - silicone-based graft copolymer (a ₁₎ 100 parts of copolymerized polyester produced in reference example 5 (b ₁₎
2 parts were dissolved and dissolved in 2000 parts of methyl ethyl ketone and 60 parts of cyclohexanone, and then applied and dried to form a 0.1 μm-thick stick prevention layer. (2) Red dye (MSR manufactured by Mitsui Toatsu Chemicals, Inc.
ed G ") 5 parts, polyvinyl acetal resin (" S-flex KS-5 "manufactured by Sekisui Chemical Co., Ltd.) 3 parts,
A solution for a heat-sensitive ink layer was prepared using 70 parts of toluene and 22 parts of methyl ethyl ketone, and the solution was applied using a bar coater to the opposite surface of the base film on which the stick prevention layer was formed in (1) above, and dried. A heat-sensitive transfer recording material was manufactured by forming a heat-sensitive ink layer having a thickness of 0.3 μm.

Example 2 [Production of Thermal Transfer Recording Material] (1) In Example 1 (1), instead of 100 parts of the acryl-silicone graft copolymer (a ₁ ),
100 parts of the acrylic-silicone graft copolymer (a ₂ ) produced in Reference Example 2 was used, and instead of 2 parts of the copolymer polyester (b ₁ ) produced in Reference Example 5, a copolymer polyester (b ₂ ) was used. (Toyobo Co., Ltd. “Byron 500”; glass transition temperature 4 ° C.) A stick prevention layer having a thickness of 0.1 μm was formed on the base film in the same manner as in (1) of Example 1 except that 5 parts were used. Was formed. (2) Next, in the same manner as in (2) of Example 1, a heat-sensitive ink layer having a thickness of 0.3 μm was formed on the opposite surface of the base film to manufacture a heat-sensitive transfer recording material.

<< Example 3 >> [Production of Thermal Transfer Recording Material] (1) In Example 1 (1), instead of 100 parts of the acryl-silicone graft copolymer (a ₁ ),
100 parts of the acrylic-silicone graft copolymer (a ₃ ) produced in Reference Example 3 was used, and instead of 2 parts of the copolymer polyester (b ₁ ) produced in Reference Example 5, copolymer polyester (b ₃ ) was used. (Toa Gosei Co., Ltd. "Aronmelt PES340"; glass transition temperature -20 ° C) Prevention of stick of 0.1 µm thickness on base film in the same manner as (1) of Example 1 except that 15 parts were used. A layer was formed. (2) Next, in the same manner as in (2) of Example 1, a heat-sensitive ink layer having a thickness of 0.3 μm was formed on the opposite surface of the base film to manufacture a heat-sensitive transfer recording material.

Comparative Example 1 [Production of Thermal Transfer Recording Material] (1) As a solution for forming a stick prevention layer, 100 parts of the acrylic-silicone graft copolymer (a ₁ ) produced in Reference Example 1, methyl ethyl ketone Using a solution prepared from 1900 parts and 60 parts of cyclohexanone,
A stick prevention layer having a thickness of 0.1 μm was formed on the base film in the same manner as in (1) of Example 1. (2) Next, in the same manner as in (2) of Example 1, a heat-sensitive ink layer having a thickness of 0.3 μm was formed on the opposite surface of the base film to manufacture a heat-sensitive transfer recording material.

Comparative Example 2 [Production of Thermal Transfer Recording Material] (1) As a solution for forming a stick prevention layer, 100 parts of the acrylic-silicone graft copolymer (a ₁ ) produced in Reference Example 1 was used. 50 parts of polymerized polyester (b ₃ ) (“Aronmelt PES340” manufactured by Toagosei Co., Ltd .; glass transition temperature −20 ° C.), methyl ethyl ketone 2000
A 0.1 μm-thick stick prevention layer was formed on the substrate film in the same manner as in Example 1, (1), using the solution prepared from 1 part and 60 parts of cyclohexanone. (2) Next, in the same manner as in (2) of Example 1, a heat-sensitive ink layer having a thickness of 0.3 μm was formed on the opposite surface of the base film to manufacture a heat-sensitive transfer recording material.

Comparative Example 3 [Production of Thermal Transfer Recording Material] (1) Reference Example 4 was used instead of an acrylic-silicone graft copolymer as a solution for forming a stick prevention layer.
100 parts of the acrylic copolymer (c) produced in the above, 10 parts of the copolymerized polyester (b ₁ ) produced in Reference Example 5, 2000 parts of methyl ethyl ketone, and cyclohexanone 60
A 0.1 μm-thick stick prevention layer was formed on the base film in the same manner as in (1) of Example 1 using the solution prepared from the section. (2) Next, in the same manner as in (2) of Example 1, a heat-sensitive ink layer having a thickness of 0.3 μm was formed on the opposite surface of the base film to manufacture a heat-sensitive transfer recording material.

<< Test Examples >> (1) Printing was performed on each of the thermal transfer recording materials obtained in Examples 1 to 3 and Comparative Examples 1 to 3 under the following conditions.

[Printing conditions] Printer: POSTWORD manufactured by Casio Computer Co., Ltd.
HX-1. Printing speed: 5000 mm / min. Printing travel distance: 1000 m. Transfer paper: Fine paper with a Beck smoothness of 50 seconds.

(2) The adhesion state of the stick prevention layer to the thermal head after printing in the above (1) and the stick phenomenon (damage to the stick prevention layer) were examined as follows. The results were as shown in FIG.

[Observation and Evaluation of Adhesion State of Stick Prevention Layer Component to Thermal Head] Metallurgical Microscope (ELIZA)
Manufactured by MICRO-SCANNER ACE), the state of adhesion of the components of the stick preventing layer to the thermal head was observed, and evaluated according to the evaluation criteria described in Table 1 below.

[0055]

[Table 1] [Evaluation criteria for adhesion state of components of stick prevention layer] ：: No change is observed compared to the unused state. Δ: Almost unused state by wiping with alcohol. X: The stick prevention layer component adhered to the thermal head surface and could not be wiped off with alcohol.

[Evaluation of Stick Phenomenon] The phenomenon that the surface of the stick prevention layer of the thermal transfer sheet in contact with the thermal head surface melts during printing and fuses to the thermal head (stick phenomenon) is evaluated according to the following evaluation criteria. evaluated.

[0057]

[Table 2] [Evaluation criteria for stick phenomenon] ：: No stick phenomenon was observed. Δ: A little stick phenomenon occurred. X: The thermal transfer recording material was broken (the base material was broken).

[0058]

[Table 3] Composition of stick prevention layer ¹⁾ Thermal head state of adhesion to stick phenomenon (part) Example 1 (a ₁ ) / (b ₁ ) = 100/2 100 Example 2 (a ₂ ) / (b ₂ ) = 100 / 5 ○ ○ Example 3 (a ₃ ) / (b ₃ ) = 100/15 ○ ○ Comparative Example 1 (a ₁ ) = 100 △ ○ Comparative Example 2 (a ₁ ) / (b ₃ ) = 100/50 ○ △ Comparative Example 3 (c) / (b ₁ ) = 100/10 × △ 1) Composition of stick prevention layer (a ₁ ): acrylic-silicone graft copolymer (a ₁ ) (a ₂ ) produced in Reference Example 1: acrylic-silicone graft copolymer (Reference Example 2) a ₂₎ (a _3): acrylic prepared in reference example 3 - silicone-based graft copolymer _{(a 3) (b 1)} : a polyester copolymer prepared in reference example _{5 (b 1) (b 2} ): commercially available Copolymerized polyester (Vylon 500; Tg = 4 ° C.) (b ₃ ): Commercial copolymerized polyester (Aronmelt PES340; Tg = −20 ° C.) (c): Acrylic copolymer (c) produced in Reference Example 5

From the results in Table 3 above, the acrylic-silicone graft copolymer and copolyester were
In the heat-sensitive transfer recording materials of Examples 1 to 3 having the stick prevention layer formed in the range of 70:30 to 99.5: 0.5 (weight ratio), the stick prevention layer is heat-resistant and has a good effect on the substrate. It can be seen that the adhesion of the components in the stick prevention layer to the thermal head was not observed and the stick phenomenon did not occur. On the other hand, the thermal transfer recording material of Comparative Example 1 having a stick prevention layer consisting only of the acrylic-silicone-based graft copolymer (a ₁ ) produced in Reference Example 1 without using the copolymerized polyester, It can be seen that the components are attached to the head. Further, in the heat-sensitive transfer recording material of Comparative Example 2 having a stick prevention layer in which the ratio of both the acrylic-silicone-based graft copolymer and the copolymerized polyester is out of the range of the present invention, a stick phenomenon occurs. . Then, in the thermal transfer recording material of Comparative Example 3 in which an acrylic polymer was used instead of the acrylic-silicone graft copolymer and the stick prevention layer was formed from the acrylic polymer and the copolymerized polyester, the component adhesion to the thermal head was reduced. It can be seen that the stick phenomenon is also remarkable.

[0060]

As described above, the heat-sensitive transfer recording material of the present invention having a stick prevention layer using the acrylic-silicone-based graft copolymer and the copolymerized polyester in a predetermined ratio has the heat resistance of the stick prevention layer and the ability to adhere to the substrate. Adhesion is good, and when thermal transfer is performed, clear and precise printing can be performed without sticking of the stick preventing layer component to the thermal head and sticking phenomenon of the stick preventing layer to the thermal head. it can. Therefore, the thermal transfer recording material of the present invention can be effectively used for printers and recorders of various office equipment employing the thermal transfer recording system by utilizing the above-mentioned characteristics.

Claims (5)

[Claims] 1. A heat-sensitive ink layer on one surface of a substrate,
In a heat-sensitive transfer recording material having a stick prevention layer provided on the other surface, the stick prevention layer is composed of 70 to 99.5 parts by weight of an acryl-silicone graft copolymer and 30 to 0.5 parts by weight of a copolyester. A heat-sensitive transfer recording material characterized by comprising: 2. The thermal transfer according to claim 1, wherein the content of the copolymerized polyester in the stick prevention layer is 1 to 20% by weight based on the total weight of the acrylic-silicone-based graft copolymer and the copolymerized polyester. Recording material. 3. The graft copolymer comprising an acrylic polymer having a glass transition temperature of 80 ° C. or higher as a main component and a silicone polymer as a branch component, wherein the acrylic-silicone graft copolymer constituting the stick prevention layer is used. 3. The heat-sensitive transfer recording material according to claim 1, which is a unified material. 4. The heat-sensitive transfer recording material according to claim 1, wherein the copolyester constituting the stick prevention layer is a copolyester having a glass transition temperature of −30 to 50 ° C. 5. The thermal transfer recording according to claim 4, wherein the copolymerized polyester constituting the stick preventing layer is a copolymerized polyester obtained by a reaction of an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component and an alkylene glycol component. material.