JPH0536239B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a heat-sensitive recording transfer body used for recording by thermal transfer, and is particularly used for high-speed recording using electronic devices such as thermal heads and laser beams. Conventional structure and problems Conventionally, this recording method used a transfer body containing a highly stable dye for transfer printing of polyester fibers. It was difficult to obtain sufficient color density using the thermal energy of a normal thermal head. Furthermore, although ionic dyes containing highly sublimable color formers can provide sufficient color density, they have problems with storage stability. In addition, the transfer substrate made of an inexpensive and homogeneous film used to obtain a homogeneous image is coated with a lubricating inorganic pigment or a solid material to prevent it from adhering to the head, especially when a thermal head is used as a recording means. It has been proposed to provide a resin layer containing a to semi-solid surfactant. However, in the above composition, when maximum recording energy is applied to the transfer member after washing the thermal head with acetone or the like, the polyethylene terephthalate film melts and breaks due to the large static frictional resistance at the start of running. OBJECTS OF THE INVENTION The purpose of the present invention is to obtain a transfer body for thermal recording that can obtain sufficient color density by using a dye that is stable and has excellent sublimation ability, and that can run stably and continuously without the film melting and cutting. do. Structure of the Invention The transfer body of the present invention has a coloring material layer containing at least one kind of sublimable dyes represented by the following general formulas (), (), and () on one side of the substrate, and the other side It has a composition layer consisting of a liquid lubricating substance and a polymeric substance. (In the formula, X is a hydrogen atom or a methyl group, R and
(R' represents a methyl group, an ethyl group, a linear or branched propyl group, or a butyl group, respectively).The specific structure will be described in detail. The coloring material layer is composed of two or more sublimable dyes having different substituents among the general formula (), (), or (). The coloring material layers on three sides having different hues each containing at least one type of sublimable dye selected from the general formulas (), (), and () are sequentially arranged. The coloring material layers on the three sides contain at least one sublimable dye selected from the general formulas (), (), and (), and at least one dye selected from each of the general formulas (), (), and (). The fourth coloring material layer is arranged in a plane-sequential manner. Furthermore, the polymer composition layer is composed of a liquid lubricating substance, a polymer substance, and fine particles, and the surface of the polymer composition layer is roughened by the fine particles. With the above structure, the coloring material layer containing the dye having the chemical structure described above has excellent storage stability, and with the addition of the effect of the thin film base, sufficient color density and hue can be obtained. Gives excellent recorded images. Furthermore, since the film runs stably without melting and cutting, images can be continuously recorded. Description of Examples Examples of the present invention will be described below. The figure shows a schematic cross-sectional view of a transfer body as an example of the present invention. A coloring material layer 2 is provided on the upper surface of the substrate 1, and a polymer composition layer 3 is provided on the lower surface. Specific examples of the sublimable dyes represented by the general formulas (), (), and () include the following. Those exhibiting a cyan color represented by () 1,5-bis(methylamino)-4,8-naphthoquinone, 1,5-bis(ethylamino)-4,
8-naphthoquinone, 1,5-bis((n)-propylamino)-4,8-naphthoquinone, 1,5-bis((iso)-propylamino)-4,8-naphthoquinone, 1,5-bis( (n)-butylamino)-4,
8-naphthoquinone, 1,5-bis((iso)-butylamino)-4,8-naphthoquinone, 1-methylamino-5-ethylamino-4,8-naphthoquinone, 1-methylamino-5-(n) -Propylamino-4,8-naphthoquinone, 1-methylamino-
5-(n)-Butylamino-4,8-naphthoquinone, 1-methylamino-5-(iso)-propylamino-4,8-naphthoquinone, ethylamino-5
-(n)-Propylamino-4,8-naphthoquinone, 1-ethylamino-5-(n)-butylamino-4,8-naphthoquinone, 1-(n)-propylamino-5-(n)-butyl Amino-4,8-naphthoquinone. Yellow color represented by () 4-(2,2-dicyanovinyl)-N,N-dimethylaniline, 4-(2,2-dicyanovinyl)-
N,N-diethylaniline, 4-(2,2-dicyanovinyl)-N,N-di(n)-propylaniline, 4-(2,2-dicyanovinyl)-N,N-di(iso)- Propylaniline, 4-(2,2-dicyanovinyl)-N,N-di(n)-butylaniline,
4-(2,2-dicyanovinyl)-N,N-di(iso)-butylaniline, 4-(2,2-dicyanovinyl)-N,N-di(sec)-butylaniline,
3-Methyl-4-(2,2-dicyanovinyl)-
N,N-dimethylaniline, 3-methyl-4-
(2,2-dicyanovinyl)-N,N-diethylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N,N-di(n)-propylaniline, 3
-methyl-4-(2,2-dicyanovinyl)-N,
N-di(iso)-propylaniline, 3-methyl-
4-(2,2-dicyanovinyl)-N,N-di(n)-butylaniline, 3-methyl-4-(2,
2-dicyanovinyl)-N,N-di(iso)-butylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N,N-di(sec)-butylaniline,
4-(2,2-dicyanovinyl)-N-ethyl-N
-(n)-Propylaniline, 4-(2,2-dicyanovinyl)-N-ethyl-N-(n)-butylaniline, 4-(2,2-dicyanovinyl)-N-methyl-N-( n)-propylaniline, 4-(2,
2-dicyanovinyl)-N-methyl-N-(n)-
Butylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N-methyl-N-(n)-propylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N-methyl- N-(n)-butylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N-ethyl-N-(n)-propylaniline,
3-Methyl-4-(2,2-dicyanovinyl)-N
-Ethyl-N-(n)-butylaniline. Those exhibiting a magenta color represented by () 4-tricyanovinyl-N,N-dimethylaniline, 4-tricyanovinyl-N,N-diethylaniline, 4-tricyanovinyl-N,N-di(n) -Propylaniline, 4-tricyanovinyl-N,N-di(iso)-propylaniline, 4-tricyanovinyl-N,N-di(n)-butylaniline, 4-tricyanovinyl-N,N- di (iso)
-butylaniline, 4-tricyanovinyl-N,
N-di(sec)-butylaniline, 3-methyl-4
-tricyanovinyl-N,N-dimethylaniline, 4-tricyanovinyl-N-methyl-N-
(n)-propylaniline, 4-tricyanovinyl-N-methyl-N-(n)-butylaniline, 4-
Tricyanovinyl-N-ethyl-N-(n)-propylaniline, 4-tricyanovinyl-N-ethyl-N-(n)-butylaniline, 4-tricyanovinyl-N-ethyl-N-(iso )-butylaniline, 4-tricyanovinyl-N-ethyl-N-
(sec)-butylaniline, 4-tricyanovinyl-N-(n)-propyl-N-(n)-butylaniline, 3-methyl-4-tricyanovinyl-N-methyl-N-ethylaniline. The ink for forming the coloring material layer can be prepared by mixing the pigment represented by the general formula () or () or () with a resin having a high melting point or softening point and a solvent or a solvent such as water. Further, non-sublimable particles, surfactants, etc. can also be added to the coloring material layer. As the resin for preparing the above ink,
Inks used in ordinary printing inks may be used, such as rosin-based, phenol-based, xylene-based, petroleum-based, vinyl-based, polyamide-based, alkyd-based, nitrocellulose-based, alkylcellulose, alkylcelluloses, ether-based, ester-based, etc. Oil-based resins or aqueous resins such as maleic acid-based, acrylic acid-based, casein, silica, glue, etc. can be used, but more specifically, polycarbonate, polysulfone, polyphenylene oxide, polyarylate, which have a high melting point or softening point. , cellulose derivatives, etc. are particularly effective. In addition, solvents for ink preparation include alcohols such as methanol, ethanol, propanol, and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene, and xylene, and esters such as butyl acetate. , ketones such as acetone, methyl ethyl ketone, and cyclohexanone, hydrocarbons such as ligroin, cyclohexane, and kerosene, and halogenated hydrocarbons such as dimethylformamide, methylene chloride, chlorobenzene, and chloroform, but when using aqueous resins. Water or a mixture of water and the above-mentioned solvents can also be used. The liquid lubricant substance is a lubricant or surfactant that is liquid at 25° C. and 1 atm and has lubricating properties. For example, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, fluorine silicone oil, and various other modified silicone oils (epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, polyether-modified, alkyl-modified・Aralkyl/polyether modified, epoxy/polyether modified, etc.), silicone-based lubricating substances such as copolymers of silicone and organic compounds such as polyoxyalkylene glycol, fluorine-based lubricating substances such as fluoroalkyl compounds, polyglycerin oleate,
Examples include fatty acid esters such as polyoxyethylene sorbitan monolaurate, alkylbenzenes, polybutenes, alkylnaphthalenes, alkyldiphenylethanes, phosphoric acid esters, synthetic oils such as polyalkylene glycol oils, saturated hydrocarbons, animal and vegetable oils, mineral oils, and the like. As liquid lubricating substances, silicone-based and fluorine-based lubricating substances are particularly excellent. Further, when a lubricant such as silicone oil and a surfactant having antistatic properties such as polyether-modified silicone oil are used in combination, an excellent effect on running stability is exhibited. The liquid lubricating substance is present inside and on the surface of the polymer composition layer. The curable polymer substances used in the polymer composition layer are various resins that are curable by heat, light, electron beams, or the like. Various curable resins have good adhesion to the substrate and good heat resistance. Examples include silicone resins, epoxy resins, unsaturated aldehyde resins, urea resins, unsaturated polyester resins, alkyd resins, furan resins, oligoacrylates, and the like. Among these, oligoacrylate cured resins exhibit excellent properties. In addition, the resin cured by light or electron beams is easily cured in a short time, and there is almost no transfer of unreacted resin, curing agent, etc. to the back surface of the base material, making it easy to produce long transfer bodies. , exhibiting good properties.
For example, light- or electron beam-curable resins of oligoacrylates, or photo-curable resins of epoxy resins catalyzed by aromatic diazonium salts, aromatic iodonium salts, or aromatic sulfonium salts are excellent. Examples of oligoacrylates include polyol acrylate, polyester acrylate, epoxy acrylate, urethane acrylate, silicone acrylate, polyacetal acrylate, etc. Epoxy resins include vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxy There are cycloaliphatic epoxy resins such as cyclohexane carboxylate. Further, a reactive diluent such as tetrahydrofurfuryl acrylate or lauryl acrylate may be added to the resin. The film thickness of the polymer composition is not particularly limited. Generally, from a production standpoint, polymer compositions with a film thickness of 0.1 μm or more are easily obtained and exhibit uniform characteristics. The substrate used in the present invention is not particularly limited, but a polymer film is particularly useful.
For example, ester polymers such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, amide polymers such as nylon, cellulose derivatives such as acetyl cellulose and cellophane,
Polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, fluorocarbon polymers such as Teflon, ether polymers such as polyoxymethylene and polyacetane, olefin polymers such as polystyrene, polyethylene, polypropylene, and methylpentene polymers. Polymers, imide-based polymers such as polyimide, polyamideimide, polyetherimide, etc. can be used. In particular, polyester polymers are useful because they are thin, have a certain degree of heat resistance, and are inexpensive.
In addition, imide-based, amide-based, and other polymers whose substrates are more heat resistant than polyester polymers are useful because they have excellent heat resistance when the transfer body is used repeatedly or at high speeds. When the polymer composition layer of the present invention further contains fine particles in addition to the liquid lubricating substance and the polymeric substance, the following effects can be obtained. That is, the polymer composition layer consisting of a liquid lubricating substance and a polymeric substance is scraped away by the uneven portions existing near the heating element of the thermal head, and deposits are generated near the heating element. This deposit obstructs heat transfer from the head to the transfer member, resulting in white lines (dropouts) on the recorded image. On the other hand, the polymer composition layer containing fine particles and whose surface is roughened by the fine particles absorbs sharp irregularities on the head and does not generate dusty deposits near the heating element. As a result, dropouts do not occur in the eyelid image. Fine particles exhibiting such effects are not particularly limited, and various metal, inorganic, and organic particles can be used. For example, metal oxides, metal sulfides, metal carbides, metal nitrides, metal fluorides, graphite, carbon fluoride, carbon black, minerals,
Examples include inorganic salts, organic pigments, tetrafluoroethylene, and polymers such as polyimide. In particular, synthetic amorphous silica, carbon black, alumina, titanium oxide, molybdenum disulfide, boron nitride, carbon fluoride, calcium silicate, aluminum silicate, etc. are effective. Synthetic amorphous silica includes anhydrous silica and hydrated silica. As the anhydrous silica, ultrafine particles produced by a gas phase method are useful. For example, high-purity ultrafine particulate silica (product name: Aerosil, Nippon Aerosil Co., Ltd.) developed by West German Degussa, aluminum oxide and titanium oxide (both produced by Nippon Aerosil Co., Ltd.) similarly produced by a gas phase method. ) etc. As hydrated silica or white carbon,
For example, Shionogi & Co., Ltd. “Carplex”,
It is commercially available under names such as Nippon Silica Kogyo Co., Ltd.'s ``Nipseal'', Mizusawa Chemical Industry Co., Ltd.'s ``Silton'', and Tokuyama Soda Co., Ltd.'s ``Fain Seal'' and Tokuseal. Silica may react with the dye depending on the characteristics of the dye used, so hydrophobic silica is used, in which the silanol groups present in silica are chemically partially substituted and bonded with methyl groups or organic silicon compounds. be able to. Addition ratio of fine particles to polymeric substance is 0.1~
It can be used in a range of 200% by weight. especially,
It shows stable characteristics when the addition ratio is in the range of 5 to 100% by weight. Ultrafine particles are well dispersed by ultrasonic waves, triple rolls, homogenizers, and the like. As for the size of the fine particles, it is preferable that the smaller the particle size, the less the influence on the image quality, and especially when the average particle size is 6 μm or less, dropout hardly occurs. The fine particles are contained inside and on the surface of the polymer composition layer. A more specific example will be described. Example 1 A polyethylene terephthalate (PET) film with a thickness of 6 μm is used as the substrate. Coating liquid No. 1 having the composition shown in the table was applied to one side of the film using a wire bar, and after evaporating the solvent with hot air at 60℃, it was irradiated with a 1KW high-pressure mercury lamp and cured. Ta.
PET films each having a cured polymer composition layer on one side were prepared using coating solutions No. 2 to No. 4 in the same manner. Next, sublimable dye 5 represented by the following structural formula (1)
Parts by volume, 5 parts by volume of polycarbonate, 100 parts by volume of dichloromethane and 10 parts by volume of silica particles (average particle size 5 μm)
After agitating the dispersion liquid consisting of volume parts with a ball mill, the other side of the above-mentioned film was coated with a wire bar to obtain four types of transfer bodies. After wiping the surface of the thermal head with acetone, images were drawn on recording paper (A5 size) coated with a layer containing polyester and an inorganic substance using the above transfer body. The recording conditions were as follows. Main scanning and sub-scanning linear density: 4 dots/mm Recording power: 0.7 W/dot Head heating time: 8 ms The test results are shown in the table.

【table】

[Table] From the table, it can be seen that coating liquids No. 1 and No. 2 according to the present invention run stably without causing any stick even if a head heating time of 8 ms is given at the start of recording, but comparative example No. 3 , 4 had high static frictional resistance and the film melted and broke at the start of running. Furthermore, in the case of the transfer body using coating liquid No. 2 containing fine particles (TiO ₂ ), there was no occurrence of dropouts that would cause white lines on the image. The color density of the recorded images obtained in Experiment No. 1 and 2 is
A high concentration of 1.65 was obtained. Example 2 For each of the cyan, yellow, and mazedan sublimable dyes represented by the structural formulas (1), (2), and (3), 5 parts by volume of the dye and 5 parts by volume of polysulfon were added.
After stirring an ink consisting of 100 parts by volume of monochlorobenzene in a ball mill, Experiment No. 1 in the table was prepared.
The above inks were separately applied to the other side of a PET substrate having a polymer composition layer prepared on one side, thereby obtaining three types of transfer bodies. As a result of recording under the recording conditions of Example 1, the recording density was 1.65 for cyan, 1.60 for magenta, and 1.1 for yellow. Next, the three types of transfer materials were wound around a test tube and heated to 40°C.
After storing for 100 hours in a temperature and humidity environment of 90% RH, the recorded density was measured, and the results were cyan 1.60 and magenta.
1.60, yellow 1.04. Comparative Example 1 In place of the dye used in Example 2, 5 parts by volume of a basic dye represented by the following formula was used, and the ink preparation, transfer body preparation, and transfer recording method were carried out in the same manner as in Example 2. Using. As a result of storing the transfer member under the same temperature and humidity test conditions as in Example 2, the cyan color density of 1.55 before the test decreased to 1.1 after storage. Effects of the Invention As described above, the thermal recording transfer member of the present invention has excellent storage stability, provides sufficient color density, and can continuously record images with high recording density because the film runs stably without melting and cutting. Can be recorded. Furthermore, full-color images can be obtained using three types of transfer bodies that develop colors in cyan, magenta, and yellow.

[Brief explanation of drawings]

The figure is a schematic cross-sectional view of a transfer body in one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Coloring material layer, 3...Polymer composition layer, 4...Liquid lubricating substance.

Claims (1)

[Claims] 1. The following general formulas (), (),
At least one of the sublimable dyes represented by ()
It has a coloring material layer containing types, (In the formula, X represents a hydrogen atom or a methyl group, and R and R' represent a methyl group, an ethyl group, a linear or branched propyl group, or a butyl group, respectively.) A liquid lubricating substance and a curable substance are placed on the other side. A transfer body for thermal recording having a polymer composition layer made of a polymer substance. 2. The thermal recording transfer body according to claim 1, wherein the coloring material layer contains two or more sublimable dyes having different substituents in the general formula. 3. The method according to claim 1, wherein three colorant layers containing at least one type of sublimable dye selected from the general formulas (), (), and () and having different hues are sequentially arranged. Transfer body for thermal recording. 4 Containing at least one sublimable dye selected from the general formulas (), (), ()
The thermosensitive device according to claim 1, wherein the coloring material layer on the surface and the fourth coloring material layer made of at least one type selected from each of (), (), and () are arranged sequentially on the surface. Recording transfer material. 5. The polymer composition layer according to claim 1, wherein the polymer composition layer contains a liquid lubricant substance, a curable polymer substance, and fine particles, and the surface of the polymer composition layer is roughened by the fine particles. Transfer body for thermal recording.