JP4381243B2 - Thermal transfer ribbon - Google Patents

Description

  The present invention relates to a thermal transfer ribbon having improved heat resistance and slipperiness. More specifically, the present invention relates to a thermal transfer ribbon capable of high-speed printing and high image quality by coating one surface of a base material with a polyamideimide resin having heat resistance and slipperiness.

  When a thermoplastic film such as a polyester film is used as the base material of the thermal transfer sheet, the base film is fused and stuck to the thermal head during printing, or the thermal transfer sheet is torn due to lack of slipperiness. There is a problem that printing wrinkles occur.

  In order to solve these problems, Patent Document 1 discloses a heat-resistant thermal transfer ribbon in which a polyamideimide resin is coated on at least one surface of a polyester film. However, although the heat resistance is high, there is a problem that the thermal transfer sheet is torn due to lack of slipperiness. In order to solve this problem, Patent Document 2 discloses a thermal transfer ribbon in which slipperiness is improved by modifying polyamide with polyfunctional silicone. Patent Document 3 discloses a thermal transfer ribbon in which heat resistance and slip properties are improved by copolymerizing or modifying polyamideimide with a silicone compound, and Patent Document 4 discloses a similar polyamideimide composition. . However, it is difficult to say that the glass transition temperature of the resin used in the examples sufficiently satisfies the heat resistance of 260 ° C. at the maximum. Further, Patent Document 5 discloses a thermal transfer ribbon that improves slipperiness by copolymerizing specific silicone and lowers the surface tension of the heat-resistant resin to increase slipperiness, but the resin used in the examples Although the glass transition temperature was 260 ° C. at the maximum and the slipperiness was improved, the heat resistance was insufficient.

  In recent years, there has been a tendency to increase the printing speed in order to shorten the throughput time of the printer. Therefore, in order to obtain a desired printing density in a short time, the printing energy per unit time must be increased, the thermal burden on the thermal transfer ribbon is becoming increasingly severe, and the above problems are becoming more serious. .

JP-A-7-179077 JP 7-314929 A JP-A-8-244369 Japanese Patent Laid-Open No. 8-113647 JP 2002-212290 A

  An object of the present invention is to provide a thermal transfer ribbon that can withstand high-speed printing and high image quality by imparting excellent heat resistance and slipperiness to the thermal transfer ribbon.

  The present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is the following thermal transfer ribbon.

（Ｒ₁、Ｒ₂は２価のアルキル基又はアリール基を表し、Ｘは水酸基、アミノ基、カルボキシル基、エポキシ基、チオール基、メタクリル基、フェノール性水酸基を表す。ｎは１以上の整数である。）

（Ｒ₃は１価のアルキル基又はアリール基を示す。Ｒ₄は２価以上５価以下のアルキル基又はアリール基である。ＹはＲ₄に含まれる炭素に結合しており、水酸基、アミノ基、カルボキシル基、エポキシ基、チオール基、メタクリル基、フェノール性水酸基から選ばれる官能基を表す。ｎは１以上の整数であり、ｋは１以上４以下の整数を表す。） (1) In a thermal transfer ribbon in which at least one surface of a base film is coated with a polyamideimide resin, the polyamideimide resin is copolymerized with a silicone compound of the following formula 1 and / or formula 2, and the logarithmic viscosity is 0 A thermal transfer ribbon characterized by having a glass transition temperature of 270 ° C. or higher and 400 ° C. or lower.

(R ₁ and R ₂ represent a divalent alkyl group or aryl group, X represents a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, or a phenolic hydroxyl group. N is an integer of 1 or more. is there.)

(R ₃ represents a monovalent alkyl group or aryl group. R ₄ represents a divalent to pentavalent alkyl group or aryl group. Y is bonded to the carbon contained in R ₄ , A functional group selected from a group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, and a phenolic hydroxyl group, n is an integer of 1 or more, and k is an integer of 1 to 4.

(2) The number average molecular weight of the silicone compound of formula 1 and / or formula 2 is 1000 or more and 13000 or less, and the copolymerization amount of the silicone compound of formula 1 and / or formula 2 is 0.1 out of the whole polyamideimide resin. The thermal transfer ribbon according to (1), wherein the thermal transfer ribbon is at least 30% by weight.

（Ｒ₅、Ｒ₆は水素又は１価のアルキル基もしくはアリール基を示す。）

（Ｒ₇、Ｒ₈は水素又は１価のアルキル基もしくはアリール基を示す。） (3) The thermal transfer ribbon according to (1) or (2), wherein the polyamideimide resin has a structure of Formula 3 and / or Formula 4.

(R ₅ and R ₆ represent hydrogen or a monovalent alkyl group or aryl group.)

(R ₇ and R ₈ represent hydrogen or a monovalent alkyl group or aryl group.)

(4) The thermal transfer ribbon according to (3), wherein the structure of Formula 3 and / or Formula 4 is contained in an amount of 20 to 80 mol% in 100 mol% of the amine component of the polyamideimide resin.

(5) The polyamideimide resin for thermal transfer ribbon coating according to any one of (1) to (4).

(6) A thermal transfer ribbon is produced by applying a solution containing the polyamideimide resin according to any one of (1) to (4) to a solvent containing N, N-dimethylformamide and / or N, N-dimethylacetamide. A method for producing a thermal transfer ribbon, comprising:

  The thermal transfer sheet of the present invention can provide a thermal transfer ribbon that can withstand high-speed printing and high image quality by imparting excellent heat resistance and slipperiness.

（Ｒ₁、Ｒ₂は２価のアルキル基又はアリール基を表し、Ｘは水酸基、アミノ基、カルボキシル基、エポキシ基、チオール基、メタクリル基、フェノール性水酸基を表す。ｎは１以上の整数である。）

（Ｒ₃は１価のアルキル基又はアリール基を示す。Ｒ₄は２価以上５価以下のアルキル基又はアリール基である。ＹはＲ₄に含まれる炭素に結合しており、水酸基、アミノ基、カルボキシル基、エポキシ基、チオール基、メタクリル基、フェノール性水酸基から選ばれる官能基を表す。ｎは１以上の整数であり、ｋは１以上４以下の整数を表す。） The present invention will be described in detail below. According to the present invention, in a thermal transfer ribbon in which at least one surface of a base film is coated with a polyamideimide resin, the polyamideimide resin is copolymerized with a silicone compound of the following formula 1 and / or formula 2, and the logarithmic viscosity is 0: A thermal transfer ribbon characterized by having a glass transition temperature of 270 ° C. or higher and 400 ° C. or lower.

(R ₁ and R ₂ represent a divalent alkyl group or aryl group, X represents a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, or a phenolic hydroxyl group. N is an integer of 1 or more. is there.)

(R ₃ represents a monovalent alkyl group or aryl group. R ₄ represents a divalent to pentavalent alkyl group or aryl group. Y is bonded to the carbon contained in R ₄ , A functional group selected from a group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, and a phenolic hydroxyl group, n is an integer of 1 or more, and k is an integer of 1 to 4.

  In the present invention, slip properties are imparted by copolymerizing the silicone compound of the formula 1 and / or the formula 2 with the polyamide-imide resin. Since these compounds have poor compatibility with the polyamideimide resin, the film of the resin alone becomes opaque. As a result, the components of Formula 1 and Formula 2 having lubricity are likely to appear on the resin surface, and the friction coefficient can be further reduced. When the silicone compound of Formula 1 or Formula 2 is copolymerized with a polyamideimide resin, it may be used either in combination of two or alone. The amount of copolymerization is 0.1 wt% or more and 30 wt% or less of the entire polyamideimide resin, preferably 2 wt% or more and 20 wt% or less, more preferably 3 wt% or more and 15 wt% or less. If it exceeds 30% by weight, there may be a problem that the heat resistance is deteriorated, and if it is less than 0.1% by weight, the slipperiness may be deteriorated. The number average molecular weight of the silicone compounds of Formula 1 and Formula 2 is 2000 or more and 13000 or less, but preferably 3000 or more and 8000 or less. When the number average molecular weight is less than 2000, even if copolymerized with polyamideimide, phase separation does not occur and the friction coefficient may not decrease. On the other hand, if it exceeds 13,000, it may be difficult to copolymerize with polyamideimide.

  Specific examples of the silicone compound of Formula 1 include X-22-161A, X-22-161B, KF-8012, KF-8008 and other terminal diamine types manufactured by Shin-Etsu Chemical Co., Ltd., X-22-163A, X-22. -163B, X-22-163C and other terminal epoxy types, X-22-162C, X-22-3701E, X-22-3710 and other terminal carboxyl group types, KF-6001, KF-6002, KF- Examples thereof include both terminal hydroxyl groups such as 6003. Specific examples of the silicone compound of the formula 2 include one-terminal bifunctional hydroxyl group types such as X-22-176B, X-22-176D, and X-22-176DX. In addition to the above, examples of the terminal functional group include a thiol group, a methacryl group, a phenolic hydroxyl group, and the like. From the viewpoint of reactivity, an amino group, a hydroxyl group, and a carboxyl group are preferable. Further, when the formula 1 and the formula 2 silicone compound are compared, it is preferable to use the formula 2 because the slipperiness can be further improved.

  The polyamide-imide resin used in the present invention desirably has a glass transition temperature of 270 ° C. or higher and 400 ° C. or lower, preferably 300 ° C. or higher and 360 ° C. or lower. Below 270 ° C, there may be a problem with heat resistance. Moreover, if it is 400 degreeC or more, the solubility of a polyamideimide may become low and handling may become difficult. The logarithmic viscosity is desirably 0.2 dl / g or more and 2.0 dl / g, preferably 0.2 dl / g or more and 1.0 dl / g, more preferably 0.3 dl / g or more and 0.7 dl / g or less. If it is less than 0.2 dl / g, the resin becomes brittle, and as a result, the coating layer may crack upon contact with the thermal head. Moreover, when it exceeds 2.0 dl / g, there exists a possibility that the viscosity of a polyamidoimide resin solution may become high, and handling may become difficult.

  Polyamideimide resin copolymerized with the silicone compound of Formula 1 and / or Formula 2 is an isocyanate method produced from an acid component and an isocyanate component, or an acid chloride method produced from an acid chloride and an amine, an acid component and an amine component However, the isocyanate method is preferred from the viewpoint of production cost.

  Although it is desirable to use trimellitic anhydride as the acid component used in the synthesis of the polyamideimide resin, a part of it can be replaced with another polybasic acid or its anhydride. For example, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, propylene glycol bistrimellitate and their anhydrides, Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene), 1,4 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethanedicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid, Le acid, diphenyl sulfone dicarboxylic acid, diphenylether dicarboxylic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid. Among these, trimellitic anhydride, pyromellitic acid, and benzophenone tetracarboxylic anhydride are preferable from the viewpoint of heat resistance.

  In addition, a urethane group can be introduced into the molecule by replacing part of the trimellitic acid compound with glycol. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and hexanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of the above dicarboxylic acids. And polyesters having terminal hydroxyl groups synthesized from one or more of the above glycols.

（Ｒ₅、Ｒ₆は水素または１価のアルキル基もしくはアリール基を示す。）

（Ｒ₇、Ｒ₈は水素または１価のアルキル基もしくはアリール基を示す。）
また、フェニレンジアミン、トルエンジアミン、４，４’−ジアミノジフェニルメタン、トリジン、ナフタレンジアミン、イソホロンジアミン等のジアミン及びこれらのジイソシアネートが好ましく、更に好ましくはナフタレンジアミン、トリジン及びこれらのジイソシアネートであり、共重合量は２０モル％〜８０モル％、好ましくは３０モル％〜７０モル％、更に好ましくは４０モル％〜６０モル％である。２０モル％未満では耐熱性が悪くなる問題が生じる可能性あり、又８０モル％を超えると溶剤溶解性が悪くなることがある。 Examples of the diamine (diisocyanate) component used in the synthesis of the polyamideimide resin of the present invention include phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, benzidine, and xylidine. Aromatic diamines such as range amine, tolylenediamine and tolidine, and diisocyanates thereof, aliphatic diamines such as ethylene diamine, propylene diamine and hexamethylene diamine, and diisocyanates thereof, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, Examples thereof include alicyclic diamines such as isophorone diamine and 4,4′-dicyclohexylmethane diamine, and diisocyanates thereof. In these, the diisocyanate which has a component of Formula 3 and Formula 4 from a heat resistant and reactive point is preferable.

(R ₅ and R ₆ represent hydrogen or a monovalent alkyl group or aryl group.)

(R ₇ and R ₈ represent hydrogen or a monovalent alkyl group or aryl group.)
Also preferred are diamines such as phenylenediamine, toluenediamine, 4,4′-diaminodiphenylmethane, tolidine, naphthalenediamine, isophoronediamine, and their diisocyanates, more preferably naphthalenediamine, tolidine, and their diisocyanates. Is 20 mol% to 80 mol%, preferably 30 mol% to 70 mol%, more preferably 40 mol% to 60 mol%. If it is less than 20 mol%, there may be a problem that the heat resistance is deteriorated, and if it exceeds 80 mol%, the solvent solubility may be deteriorated.

  The polyamide-imide resin used in the present invention is preferably used after being dissolved in a low boiling point solvent so that it can be easily dried during the production of the thermal transfer ribbon. Specifically, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, ether solvents such as tetrahydrofuran and diethyl ether, and ketone solvents such as cyclopentanone and cyclohexanone. It is preferable to contain 60% by weight or more of these components in 100% by weight of the solvent composition. In particular, N, N-dimethylformamide and / or N, N-dimethylacetamide are preferable from the viewpoint of solubility. N-methyl-2-pyrrolidone, γ-butyrolactone, and the like having a boiling point exceeding 200 ° C. may not be able to completely remove the solvent during the production of the thermal transfer ribbon. As a result, the solvent is not contained in the ink layer when the ribbon is stored in roll form. May cause a problem of lowering image quality.

  Manufacture of polyamide-imide resin includes amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, lactones such as γ-butyrolactone, N, N-dimethylimidazolidinone, etc. It can be easily produced by stirring in an imidazole solvent while heating to 60 to 200 ° C. In this case, amines such as triethylamine, diethylenetriamine, triethylenediamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and halogenated sodium fluoride, potassium fluoride, cesium fluoride, etc. Metals, organic bases such as sodium methoxide and sodium ethoxide, and inorganic bases such as sodium hydroxide and potassium hydroxide can also be used as catalysts. From the viewpoint of preventing corrosion of the thermal head with these catalysts, a catalyst containing no metal or halogen is preferred. The amount of the catalyst is preferably 0.1 mol% or more and 10 mol% or less, more preferably 0.5 mol% or more and 5 mol% or less with respect to 100 mol% of the acid component.

Although there is no restriction | limiting in the preparation of the raw material at the time of manufacture, (1) Collective preparation of an acid and isocyanate (2) After adding an excess acid and isocyanate, an isocyanate is further added.
(3) After adding an acid and excess isocyanate, an acid is further added.
And the like.

  The method for copolymerizing the silicone compound is not particularly limited, and examples thereof include a method in which silicone is added together with other raw materials, a method in which silicone is added later, and a method in which silicone is added and copolymerized after completion of the reaction.

  In addition, the polyamidoimide resin solution polymerized to replace the polyamidoimide resin with a low boiling point solvent is put into a poor solvent for the polyamidoimide resin and mixed with a high boiling polar solvent (coagulation bath). After reprecipitation and drying, the solvent may be replaced by re-dissolving in a different solvent.

  In order to effectively elute high boiling polar solvents and adjust the elution rate, alcohol solvents such as ethylene glycol and triethylene glycol, hydrocarbon solvents such as toluene and xylene, ketone systems such as acetone and methyl ethyl ketone Solvents, ether solvents such as dioxane and ethylene glycol dimethyl ether, and ester solvents such as methyl acetate and ethyl acetate may be added to the resin composition and the coagulation bath.

  Furthermore, elution of the high boiling polar solvent can be further accelerated by lowering the polymer concentration of the resin composition and increasing the temperature of the coagulation bath. The coagulation bath used in the present invention is most preferably water.

  The method of charging the resin composition into the coagulation bath is not particularly limited, but it is preferable to discharge the resin composition from a fine nozzle for continuous and efficient production.

  The re-precipitated polymer is filtered, and after removing the solvent with a centrifugal dehydrator or the like, it is dried. Drying can be performed by a usual method such as hot air drying or vacuum drying.

  There is no particular limitation on the means for redissolving, and it can be dissolved by an ordinary method. For example, a solvent is put into a container, and a dry polymer is added little by little at room temperature or under heating while stirring.

  The polyamide-imide resin used in the present invention is excellent in heat resistance, slipperiness, but in order to further improve slipperiness, as an organic lubricant, silicone oil, higher fatty acid, higher fatty acid ester, various surfactants or fluorine These compounds may be used alone or in admixture of two or more. Examples of the inorganic lubricant include talc, kaolin, mica, sekiboku, glass stone, gypsum, blues stone, graphite, calcium carbonate, molybdenum disulfide and the like. In addition, other resins such as polyester resins, polyamide resins, polyurethane resins, acrylic resins, melamine resins, phenol resins, epoxy resins, polyfunctional isocyanates, curing agents, coloring, etc. You may mix | blend an agent etc.

As a method of applying the polyamideimide resin to the thermal transfer ribbon of the present invention, a polyamideimide resin composition (solution) is coated on a base material such as polyethylene terephthalate, polyethylene naphthalate film, aramid film, polyphenylene sulfide, polyimide film, etc. Apply with a coater, kiss coater, reverse roll coater, etc. The coating amount in this case is preferably 0.01 to 1.0 g / m ² . The lower limit is more preferably 0.05 g / m ^2, more preferably from 0.1 g / m ^2. On the other hand, the more preferable upper limit is 0.8 g / m ² , and further preferably 0.6 g / m ² . If the coating amount is less than 0.01 g / m ² , the effect on heat resistance, slipperiness, etc. may be weak. If it exceeds 1.0 g / m ² , the effect is saturated, which may be disadvantageous in terms of cost. Moreover, you may give an anchor coat for the adhesive improvement of a base film and a polyamide-imide resin composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. The evaluation shown in the examples was measured by the following method.

1. Logarithmic viscosity Reprecipitation, filtration, and drying of polyamideimide polymerization solution from a polyamideimide polymerization solution using a solution of 0.5 g of polyamideimide resin dissolved in 100 ml of N-methyl-2-pyrrolidone at 25 ° C. in an Ubbelohde viscosity tube at 25 ° C. It was measured.

2. Glass transition temperature A polyamideimide resin solution was cast on a polyester film and semi-dried to obtain a film. The film was attached to a 300 mm × 200 mm metal frame and dried at 200 ° C. for 8 hours to obtain a 30 μm polyamideimide resin film. The sample length inflection point when a polyamideimide film having a measurement width of 5 mm and a length of 15 mm is measured with a Rigaku thermomechanical analyzer (PTC10A) using a tensile load method under conditions of a weight of 2 g and 10 ° C./min is the glass transition temperature. It was.

3. Coefficient of dynamic friction When a stainless steel plate having a width of 5 cm, a length of 10 cm and a weight of 200 g is placed on the film surface coated with polyamideimide resin, and this plate is slid at a speed of 200 mm / min using Toyo Baldwin Tensilon. A value obtained by gradually reducing the stress generated at 200 g was used.

4). Heat resistance After coating a polyamideimide resin with a dry film thickness of 1 μm and drying at 120 ° C. for 10 minutes with aluminum foil, heat-sealer TP-701-B made by tester industry, pressurizing and heating at 320 ° C., 0.1 MPa for 1 second The peeling resistance was compared.
○: Peel off from aluminum foil almost without resistance △: Peel off from aluminum foil but heavy peeling ×: Does not peel off from aluminum foil

Example 1
In a reaction vessel equipped with a nitrogen introduction tube and a cooling device, 1 mol of trimellitic anhydride, 0.5 mol of o-tolidine diisocyanate, 0.5 mol of diphenylmethane diisocyanate, KF-6003 (both end hydroxyl group polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., The number average molecular weight 5100) is 10% by weight with respect to the polymer, 1,8-diazabicyclo [5.4.0] -7-undecene 0.01 mol as a catalyst, N, N-dimethylacetamide as a solvent, and solid content concentration After reacting at 30% at 100 ° C. for 2 hours, it was reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. The silicone copolymerization amount of the obtained polyamideimide resin is 10% from the preparation, the logarithmic viscosity is 0.76 dl / g, the glass transition temperature is 300 ° C., the dynamic friction coefficient is 0.07, the blocking resistance is ○, the dynamic friction coefficient The blocking resistance was good and it was suitable as a back coating agent for thermal transfer ribbons.

Example 2
In a reaction vessel equipped with a nitrogen introduction tube and a cooling device, 1 mol of trimellitic anhydride, 0.5 mol of naphthalene diisocyanate, 0.5 mol of diphenylmethane diisocyanate, X-22-176DX (one end hydroxyl group bifunctional polydimethyl by Shin-Etsu Chemical Co., Ltd.) 7% by weight of siloxane, number average molecular weight 3500) with respect to the polymer, 0.02 mol of potassium fluoride as a catalyst, N, N-dimethylacetamide as a solvent, and reaction at 100 ° C. for 2 hours at a solid content concentration of 30% And reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. Silicone copolymerization amount of the obtained polyamideimide resin is 10% from the charged amount, logarithmic viscosity is 0.84 dl / g, glass transition temperature is 320 ° C., dynamic friction coefficient is 0.07, blocking resistance is ○, dynamic friction coefficient The blocking resistance was good and it was suitable as a back coating agent for thermal transfer ribbons.

Comparative Example 5
5 mol of trimellitic anhydride, 1 mol of diphenylmethane diisocyanate, KF-6002 (both terminal hydroxyl group polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3200) are added to a reaction vessel equipped with a nitrogen introduction tube and a cooling device. % By weight, 0.018 mol of 1,8-diazabicyclo [5.4.0] -7-undecene as a catalyst, N, N-dimethylacetamide as a solvent, and reaction at 100 ° C. for 2 hours at a solid content concentration of 30% And reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. The logarithmic viscosity was 0.50 dl / g, the glass transition temperature was 275 ° C., the dynamic friction coefficient was 0.09, the blocking resistance was Δ, and although the blocking resistance was slightly inferior, it was suitable as a back coating agent for thermal transfer ribbons. .

Example 4
In a reaction vessel equipped with a nitrogen introduction tube and a cooling device, 1 mol of trimellitic anhydride, 0.7 mol of naphthalene diisocyanate, 0.3 mol of tolylene isocyanate, 1,8-diazabicyclo [5.4.0] -7 as a catalyst. -0.02 mol of undecene was added, and N, N-dimethylacetamide was added and reacted at a solid content concentration of 20% at 100 ° C for 1 hour, and then X-22-176DX (single-end bifunctional hydroxyl group polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd. The number average molecular weight 3500) was 20% by weight based on the polymer, and the mixture was reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. The logarithmic viscosity was 0.55 dl / g, the glass transition temperature was 330 ° C., the dynamic friction coefficient was 0.05, and the anti-blocking property was ◯, which was suitable for the backcoat agent of the thermal transfer ribbon.

Comparative Example 6
A reaction vessel equipped with a nitrogen inlet tube and a reflux condenser was charged with 1 mol of trimellitic anhydride, 1.01 mol of isophorone diisocyanate, and 0.02 mol of potassium fluoride together with γ-butyrolactone to a monomer concentration of 50% by weight. . After this solution was reacted at 100 ° C. for 2 hours with stirring, silicone X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd .; hydroxyl group-containing polydimethylsiloxane number average molecular weight 3500) was adjusted to 9% by weight with respect to the polymer. In addition, after reacting for 1 hour, it was further reacted at 180 ° C. for 3 hours. This solution was cooled to room temperature while being diluted to 25% with N-methyl-2-pyrrolidone, then poured into water while stirring, reprecipitated and filtered, and dried with hot air at 60 ° C. The obtained polymer was dissolved in tetrahydrofuran to obtain a varnish. The logarithmic viscosity was 0.53 dl / g, the glass transition temperature was 285 ° C., the dynamic friction coefficient was 0.07, and the anti-blocking property was Δ, which was suitable as a back coating agent for thermal transfer ribbons.

Comparative Example 1
After charging 1 mol of trimellitic anhydride, 0.99 mol of diphenylmethane diisocyanate and N, N-dimethylacetamide as a solvent in a reaction vessel equipped with a nitrogen introduction tube and a cooling device, the mixture was reacted at 100 ° C. for 2 hours at a solid content concentration of 30%. And reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. The silicone copolymerization amount of the obtained polyamideimide resin is 0% from the preparation, logarithmic viscosity is 0.58 dl / g, glass transition temperature is 290 ° C., dynamic friction coefficient is 0.35, blocking resistance is Δ, dynamic friction coefficient Therefore, it was not suitable as a back coating agent for thermal transfer ribbons.

Comparative Example 2
A reaction vessel equipped with a nitrogen inlet tube and a reflux condenser is charged with 0.5 mol of trimellitic anhydride, 0.5 mol of cyclohexanedicarboxylic acid, 1.01 mol of isophorone diisocyanate, and 0.02 mol of sodium methoxide together with γ-butyrolactone. The monomer concentration was 50% by weight. After this solution was reacted at 100 ° C. for 2 hours with stirring, silicone X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd .; hydroxyl group-containing polydimethylsiloxane number average molecular weight 3500) was adjusted to 9% by weight with respect to the polymer. In addition, after reacting for 1 hour, it was further reacted at 180 ° C. for 3 hours. This solution was cooled to room temperature while being diluted to 25% with N-methyl-2-pyrrolidone, then poured into water while stirring, reprecipitated and filtered, and dried with hot air at 60 ° C. The obtained polymer had a logarithmic viscosity of 0.51 dl / g, a glass transition temperature of 257 ° C., a dynamic friction coefficient of 0.07, and a blocking resistance of x, which was unsuitable for a thermal transfer ribbon backcoat agent.

Comparative Example 3
In a reaction vessel equipped with a nitrogen introduction tube and a reflux condenser, 1 mol of trimellitic anhydride, 0.91 mol of diphenylmethane diisocyanate, X-22-176DX (single terminal hydroxyl group bifunctional polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd., number average molecular weight 3500) ), 0.02 mol of potassium fluoride as a catalyst was added to 3% by weight with respect to the polymer, and N, N-dimethylacetamide was added as a solvent and reacted at 100 ° C. for 2 hours at a solid content concentration of 30%. And reacted at 150 ° C. for 3 hours. Cooled and diluted with N, N-dimethylacetamide to a solids concentration of 20%. The obtained polyamideimide resin had a logarithmic viscosity of 0.15 dl / g, and the glass transition temperature could not be measured because the film was brittle. Although the dynamic friction coefficient was 0.10 and the blocking resistance was Δ, the coating layer was peeled off due to the brittleness at the time of blocking resistance measurement, which was unsuitable for the back coating agent for the thermal transfer ribbon.

Comparative Example 4
In a reaction vessel equipped with a nitrogen introduction tube and a cooling device, 1 mol of trimellitic anhydride, 0.99 mol of diphenylmethane diisocyanate, X-22-176F (one end hydroxyl group bifunctional polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd., number average molecular weight 14000) 20 g (0.001 mol) of N-methyl-2-pyrrolidone as a solvent was added and reacted at a solid content of 30% at 100 ° C. for 2 hours and then at 150 ° C. for 3 hours. It was attached to the wall and copolymerization was difficult.

  The thermal transfer sheet of the present invention can provide a thermal transfer ribbon that can withstand high-speed printing and high image quality by imparting excellent heat resistance and slipperiness.

Claims (6)

In the thermal transfer ribbon in which at least one surface of the base film is coated with a polyamideimide resin, the polyamideimide resin is a copolymerized silicone compound of the following formula 1 and / or formula 2, and the formula 3 and / or formula A thermal transfer ribbon having a structure of 4 , a logarithmic viscosity of 0.2 dl / g or more and 2.0 dl / g or less, and a glass transition temperature of 300 ° C. or more and 360 ° C. or less .

(R ₁ and R ₂ represent a divalent alkyl group or aryl group, X represents a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, or a phenolic hydroxyl group. N is an integer of 1 or more. is there.)

(R ₃ represents a monovalent alkyl group or aryl group. R ₄ represents a divalent to pentavalent alkyl group or aryl group. Y is bonded to the carbon contained in R ₄ , A functional group selected from a group, a carboxyl group, an epoxy group, a thiol group, a methacryl group, and a phenolic hydroxyl group, n is an integer of 1 or more, and k is an integer of 1 to 4.

(R ₅ and R ₆ represent hydrogen or a monovalent alkyl group or aryl group.)

(R ₇ and R ₈ represent hydrogen or a monovalent alkyl group or aryl group.) The number average molecular weight of the silicone compound of formula 1 and / or formula 2 is 1000 or more and 13000 or less, and the copolymerization amount of the silicone compound of formula 1 and / or formula 2 is 0.1% by weight or more of the whole polyamideimide resin The thermal transfer ribbon according to claim 1, wherein the thermal transfer ribbon is 30% by weight or less. The thermal transfer ribbon according to claim 1 or 2 , wherein the structure of Formula 3 and / or Formula 4 is contained in an amount of 20 to 80 mol% of 100 mol% of the amine component of the polyamideimide resin. The thermal transfer ribbon according to any one of claims 1 to 3, wherein the structure of Formula 3 and / or Formula 4 is contained in 30 to 70 mol% of 100 mol% of the amine component of the polyamideimide resin. The polyamideimide resin for thermal transfer ribbon coating according to any one of claims 1 to 4. A thermal transfer ribbon is produced by applying a solution containing the polyamideimide resin according to any one of claims 1 to 4 to a solvent containing N, N-dimethylformamide and / or N, N-dimethylacetamide. Manufacturing method of thermal transfer ribbon.