JPH0630974B2 - Transfer material for thermal recording - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transfer member for heat-sensitive recording used for recording by thermal transfer.

Configuration of Conventional Example and Problems Thereof FIG. 1 is a schematic cross-sectional view of a thermal recording transfer member (hereinafter abbreviated as transfer member). Reference numeral 1 is a substrate of a transfer body, 2 is a color material layer formed thereon, and 3 is a polymer composition layer.

When a polymer film such as polyethylene terephthalate (hereinafter abbreviated as PET) is used for the substrate 1, so-called stick development in which the substrate adheres to the thermal head due to heat melting of the substrate due to heat pulse of the thermal head or static electricity generated during running Occur. As a result, the substrate does not run stably on the thermal head.

Therefore, a heat-resistant protective film is provided on the lower surface of the substrate (Japanese Patent Laid-Open No. Sho 61-96).
55-7467), an anti-stick layer comprising an inorganic pigment having high lubricity and a thermosetting or high softening point resin material is provided (JP-A-56-155794), which is solid or semi-solid at room temperature. It has been proposed to provide a resin layer containing a surfactant or an organic salt (Japanese Patent Laid-Open No. 57-129789).

However, although various proposals for the stick have been made for the fusion type transfer body, in the case of the sublimation type transfer body, a few μ in the vicinity of the heating element of the thermal head is newly added.
Due to the minute unevenness of m, the polymer material or the additive is particularly scraped off at the place where the pressure of the platen and the thermal head is not uniform, which causes a problem that printouts (dropouts) occur on the heating element due to accumulation on the heating element. did.

OBJECT OF THE INVENTION It is an object of the present invention to solve the above-mentioned conventional drawbacks and to provide a transfer member which does not drop out in an image and does not stick.

The transfer member of the present invention has a coloring material layer on the upper surface of a film-shaped substrate, and is selected from synthetic amorphous silica, carbon black, alumina, titanium oxide, calcium silicate and aluminum silicate on the lower surface of the substrate. There is a polymer composition layer formed of at least one kind of fine particles, a surfactant and a polymer substance of a curable resin, and the surface of the polymer composition layer is roughened by the fine particles. .

Further, if necessary, a liquid lubricant, a solid lubricant, or both a liquid lubricant and a solid lubricant are further added to the polymer composition layer.

The interfacial lubricant prevents sticking, and the fine particles function to prevent dropout.

That is, the surface of the polymer composition layer roughened by adding 5 to 100% by weight of fine particles having an average particle diameter of 0.5 μm or less to the polymer substance absorbs sharp irregularities on the head. Since deposits are not generated on the heating element, and as a result, dropouts can be prevented from occurring, the stick preventing effect of the surfactant can be fully utilized.

Further, the stick is more effectively prevented by using a combination of a surfactant and a liquid lubricant, or a surfactant and a solid lubricant, or a surfactant, a liquid lubricant and a solid lubricant.

Description of Examples Examples of the present invention will be described below.

FIG. 2 shows a schematic sectional view of a transfer body as an embodiment of the present invention. The color material layer 5 is provided on the upper surface of the substrate 4, and the polymer composition layer 6 is provided on the lower surface. The polymer composition layer 6 is composed of fine particles 7, a surfactant 8 and a polymer substance. The fine particles 7 are contained so as to be exposed not only inside the polymer composition layer 6 but also on the surface.

It is also effective that the polymer composition layer 6 further contains a liquid lubricant, a solid lubricant, or both a liquid lubricant and a solid lubricant, if necessary.

As fine particles, synthetic amorphous silica, carbon black,
At least one selected from alumina, titanium oxide, calcium silicate and aluminum silicate can be used.

Synthetic amorphous silica includes anhydrous silica and hydrous silica. Ultrafine particles prepared by a vapor phase method are useful as anhydrous silica. For example, high-purity ultrafine particle silica (trade name: Aerosil, Nippon Aerosil Co., Ltd.) developed by Degussa in West Germany, aluminum oxide and titanium oxide similarly produced by the vapor phase method (both are Nippon Aerosil Co., Ltd.). ) Etc.

As hydrous silica or white carbon, for example,
Shionogi Pharmaceutical Co., Ltd. “Carplex”, Nippon Silica Industry Co., Ltd. “Nipseal”, Mizusawa Chemical Co., Ltd. “Shilton”, Tokuyama Soda Co., Ltd. “Fineseal, Tokuseal” are commercially available.

Since silica may react with the dye depending on the characteristics of the dye used, it is preferable to use hydrophobic silica in which a silanol group present in silica is chemically partially substituted with a methyl group or an organic silicon compound. it can.

The addition ratio of the fine particles to the polymer substance shows stable characteristics in the range of 5 to 100% by weight. The ultrafine particles are well dispersed by ultrasonic waves, a triple roll, a homogenizer and the like. The smaller the particle size, the smaller the influence on the image quality, and the dropout does not occur at all when the average particle size is 0.5 μm or less, which is desirable.

As the polymer substance, various curable resins by heat, light, electron beam or the like can be used. Various curable resins have good adhesiveness to a substrate and heat resistance.

For example, there are silicone resin, epoxy resin, unsaturated aldehyde resin, urea resin, unsaturated polyester resin, alkyd resin, furan resin, oligoacrylate and the like.

Among them, a cured resin of oligoacrylate shows excellent characteristics. In addition, since the cured resin by light and electron beam 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, it is easy to prepare a long transfer body. ,
Shows good properties. For example, light of oligoacrylate,
Alternatively, an electron beam curable resin, an aromatic diazonium salt, an aromatic iodonium salt, or an epoxy photocurable resin with an aromatic sulfonium salt catalyst is excellent.

Examples of the oligo acrylate include polyol acrylate, polyester acrylate, epoxy acrylate, urethane acrylate, silicone acrylate, and polyacetal acrylate. Examples of the epoxy resin include vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl-
There are cycloaliphatic epoxy resins such as 3,4-epoxycyclohexanecarboxylate.

Also, a reactive diluent such as tetrahydrofurfuryl acrylate or lauryl acrylate may be added to the resin for use.

The film thickness of the polymer composition is not particularly limited. Generally, a polymer composition having a film thickness of 0.1 μm or more is easily obtained from the viewpoint of production and exhibits uniform properties.

As the surfactant, various well-known surfactants can be used.

For example, various anionic surfactants such as carboxylic acid salts, sulfonic acid salts, sulfuric acid ester salts, and phosphoric acid ester salts, various aliphatic amine salts, aliphatic quaternary ammonium salts, aromatic quaternary ammonium salts, heterocyclic 4 Various cationic surfactants such as primary ammonium salt, ether type such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, ether ester type such as polyoxyethylene sorbitan fatty acid ester, polyethylene glycol Ester type such as fatty acid ester, fatty acid monoglyceride, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkyl ester Amines, various nonionic surfactants if the nitrogen type such as alkylamine oxide, various betaine type, aminocarboxylic acid salt, various amphoteric surfactants such as imidazoline derivatives, fluoroalkyl (C ₂ ~C ₂₀₎ carboxylic acid , Monoperfluoroalkyl (C _{6 to} C ₁₆ ) ethyl phosphate, various fluorocarbon surfactants such as perfluorooctane sulfonic acid diethanolamide, polyether modified silicone oil, carboxyl modified silicone oil, alkylaralkyl polyether modified silicone oil , Various modified silicone oils such as epoxy / polyether modified silicone oil, and various silicone surfactants such as various copolymers of polyoxyalkylene glycol and silicone.

Furthermore, surfactants called polymer surfactants, organometallic surfactants, reactive surfactants, etc. can also be used in the present invention.

Silicone and fluorine surfactants are particularly excellent,
When the above-mentioned surfactant is used in combination with the silicone-based or fluorine-based surfactant, the effect of preventing sticking is excellent. Also, the HLB value is 3.0 or less and 3.0 or more, or HL
The effect is remarkable when two or more surfactants whose B values are 3 or more apart are used together.

The liquid lubricant is a substance that is liquid at 25 ° C. and 1 atm and exhibits lubricity.

For example, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, silicone-based oil such as fluorosilicone oil, alkylbenzene, polybutene, alkylnaphthalene,
Synthetic oils such as alkyldiphenylethane and phosphoric acid esters, saturated hydrocarbons, animal and vegetable oils, mineral oils, glycols such as ethylene glycol, propylene glycol and polyalkylene glycol, glycerin and glycerin derivatives,
Esters such as butyl stearate, liquid paraffin, etc.

The solid lubricant is a solid or semi-solid lubricant at 25 ° C. and 1 atm. For example, various alcohols such as stearyl alcohol and mannitol, fatty acids such as stearic acid and montanic acid, fatty acid esters such as stearyl stearate, cetyl palmitate and pentaerythritol tetrastearate, waxes such as microcristan wax and polyolefin wax, and Aliphatic hydrocarbons such as partial oxides, fluorides and chlorides, fatty acid amides such as palmitic acid amide, ethylene bisstearic acid amide, metallic soaps such as calcium stearate and aluminum stearate, graphite, molybdenum disulfide, tetrachloride There are ethylene fluoride, carbon fluoride, talc, etc.

The substrate used in the present invention is not particularly limited as long as it is a polymer film, and examples thereof include ester polymers such as polyethylene terephthalate, polyethylene naphthalate and polycarbonate, amide polymers such as nylon, acetyl cellulose and cellophane. Cellulose derivatives such as polyvinylidene fluoride, tetrafluoroethylene-6-propylene propylene copolymer, fluorine-based polymers such as Teflon,
Ether-based polymers such as polyoxymethylene and polyacetal, polystyrene, polyethylene, polypropylene,
An olefin-based polymer such as methylpentene polymer, an imide-based polymer such as polyimide, polyamideimide, or polyetherimide can be used.

In particular, polyester polymers are useful because they are thin, have some heat resistance, and are inexpensive.

In addition, imide type, which is more heat resistant than polyester type polymer,
Polymers such as amides can be used when the transfer body is used repeatedly.
It is useful as a substrate because it has excellent heat resistance when used at high speeds.

The color material layer is not particularly limited, and various color material layer configurations used in a wax method, a sublimation dye method, or the like can be used. Color materials include color formers as well as pigments and dyes. As the sublimable dye, a dye that starts sublimation or evaporation at 300 ° C. or lower can be used.
There are basic dyes and disperse dyes.

Hereinafter, it will be described more specifically.

Example 1 A PET film having a thickness of 12 μm was used as a substrate. Each coating liquid having the composition shown in Table 1 (No. 1 to No. 4)
Was produced.

No. on the lower surface of the PET film. 1 coating solution was coated with a wire bar, the solvent was evaporated with hot air at 60 ° C., and then the coating was irradiated with a high pressure mercury lamp of 1 KW to cure it. No. 2 to No. Four
The same procedure was performed for each of the coating liquids in Example 1 to obtain a PET film having a polymer composition layer on the lower surface.

Next, 2 parts by weight of a sublimable dye represented by the following molecular structure,
An ink prepared by mixing 4 parts by weight of polycarbonate and 100 parts by weight of methylene chloride was applied on the upper surface of the PET film processed as described above with a wire bar and then dried with hot air at 60 ° C. to prepare four types of transfer bodies.

Using each of the transfer members, recording was performed on an A-5 version activated clay-coated paper under the following thin film type thermal head recording conditions.

Main and sub-scanning linear density: 4 dots / mm Recording power: 0.7 W / dot Head heating time: 2-8 ms Recording time per line: 33.3 ms Recording area: A-5 version This test result is shown in Table 1. Show. Coating liquid N according to the present invention
o. 1, No. In No. 2, no sticking occurred even at 8 ms, and no dropout occurred. on the other hand,
Comparative Example No. In No. 3, the transfer body was melted and cut by sticking in 3 ms, and thus it was impossible to evaluate dropout.
In addition, Comparative Example No. In No. 4, a dropout that causes a white line (non-printed portion) on the image was generated on the first A-5 plate.

Example 2 A PET film having a thickness of 9 μm was used as a substrate. In each coating solution shown in Table 2, in addition to the solvent and the sensitizer, No.
No. 1 contains fine particles, a liquid lubricant, a surfactant and a polymer substance. No. 2 contains fine particles, a solid lubricant, a surfactant and a polymer substance. 3 is fine particles, liquid lubricant, solid lubricant,
Contains surfactants and polymeric substances. Hereinafter, in the same manner as in Example 1, a polymer composition layer was formed on the lower surface of the substrate from each of the above-mentioned coating liquids, and a color material layer was formed on the upper surface to prepare three types of transfer bodies. The dropout occurrence test was conducted by increasing the recording power applied to the head to 0.77W. The test results are shown in Table 2. Coating liquid No. 1 according to the present invention. 1-No. No. 3 produced no stick even at 0.77 W and 8 ms, and no dropout occurred.

EFFECTS OF THE INVENTION As described above, since the transfer body of the present invention has no dropout in the image and does not stick, it is possible to provide a large number of high-quality and inexpensive images, and further, it can be used for high-speed recording.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view of a conventional thermal recording transfer member, and FIG. 2 is a schematic sectional view of a thermal recording transfer member according to an embodiment of the present invention. 4 ... Substrate, 5 ... Color material layer, 6 ... Polymer composition layer, 7
... fine particles, 8 ... surfactant.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyoshi Taguchi 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) Reference JP-A-56-155794 (JP, A) JP-A-58-101095 (JP, A) JP 58-171992 (JP, A) JP 57-129789 (JP, A)

Claims (6)

[Claims] 1. A color material layer is provided on the upper surface of a film-shaped substrate,
On the lower surface of the substrate, formed from at least one kind of fine particles selected from synthetic amorphous silica, carbon black, alumina, titanium oxide, calcium silicate and aluminum silicate, a surfactant and a polymeric substance of curable resin. A thermal recording transfer member having a polymer composition layer, and the surface of the polymer composition layer being roughened by the fine particles. 2. The thermal recording transfer member according to claim 1, wherein the polymer composition layer further contains a liquid lubricant. 3. The heat-sensitive recording transfer member according to claim 1, wherein the polymer composition layer further contains a solid lubricant. 4. The thermal recording transfer member according to claim 1, wherein the polymer substance is an oligoacrylate. 5. The transfer material for heat-sensitive recording according to claim 1, wherein the polymer substance is an epoxy resin which is photocured using an aromatic diazonium salt, aromatic iodonium salt or aromatic sulfonium salt catalyst. 6. The transfer material for heat-sensitive recording according to claim 1, wherein the polymer substance is an epoxy resin which is photocured using an oligoacrylate salt, an aromatic iodonium salt, or an aromatic sulfonium salt catalyst.