JP2538196B2 - Transferr for thermal recording - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal recording transfer material (hereinafter abbreviated as transfer material) used for recording by thermal transfer.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter P)
When a polymer film such as ET) is used for the substrate 1, a so-called stick phenomenon occurs in which the substrate adheres to the thermal head due to thermal melting of the substrate due to a heat pulse of the thermal head or static electricity generated during running. As a result, the substrate does not run stably on the thermal head. Therefore, a heat-resistant protective layer is provided on the lower surface of the substrate (JP-A-55).
No. 7467), an anti-stick layer comprising an inorganic pigment having high lubricity and a resin material having thermosetting or high softening point is provided (JP-A-56-155794), which is a solid or semi-solid interface at room temperature. Proposals have been made such as providing a resin layer containing an activator or organic salts (JP-A-57-129789).

[0003]

However, not only the conventional melting type transfer body but also the running of the sublimation type transfer body in which the maximum recording energy is applied several times as much as the melting type transfer body is not stuck. The transfer material that runs in the direction is not obtained.

Further, due to the minute unevenness of several μ in the vicinity of the heating element of the thermal head, the polymer material or the additive is particularly scraped off at the non-uniform pressing of the platen and the thermal head, and the heating element is not removed. There is a problem that printouts (dropouts) occur in accumulated images.

In view of the above problems, it is an object of the present invention to obtain a transfer member that does not cause sticking, or a transfer member that does not cause sticking and does not cause dropout in an image.

[0006]

In order to solve the above problems, the transfer body of the present invention has a color material layer on the upper surface of a film-shaped substrate, and epoxy acrylate, urethane acrylate, silicone acrylate on the lower surface of the substrate. And an upper surface of a film-like substrate, which has a polymer composition layer formed of a polymer substance of a curable resin by at least one kind of light or electron beam selected from acrylate of polyacetal and a surfactant and a surfactant. Has a coloring material layer and has a polymer composition layer formed from a polymeric substance of a curable resin and a modified silicone oil on the lower surface of the substrate, or has a polymeric substance of the curable resin and a modified silicone oil. In the polymer composition layer formed from, the polymer substance is epoxy acrylate, urethane acrylate, or silicone. At least one light or electron beam curable resin selected from acrylates and polyacetal acrylates, or a polymer composition formed from a polymer substance of the curable resin and a modified silicone oil The layer is composed of synthetic amorphous silica, carbon black, alumina, titanium oxide,
The fine particles are formed by using fine particles having an average particle size of 0.5 μm or less selected from at least one selected from calcium silicate and aluminum silicate, and the ratio of the fine particles to the polymer substance is 5 to 100% by weight. The surface of the polymer composition layer is roughened.

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

[0008]

[Function] A polymer composition layer formed from a polymer substance of a resin curable by at least one light or electron beam selected from epoxy acrylate, urethane acrylate, silicone acrylate and acrylate of polyacetal, and a surfactant. Provides the polymer material with excellent heat resistance that is easily cured by light or electron beams in a short time and does not lose heat even under the recording conditions of a sublimation type transfer member,
Also, due to the slipperiness and antistatic properties of the surfactant, good running characteristics are exhibited without sticking. In addition, the polymer composition layer formed from the polymer substance of the curable resin and the modified silicone oil, the modified silicone oil is particularly excellent in lubricity and antistatic property, so that the recording condition of the sublimation type transfer member is improved. However, it shows good running characteristics without sticking.

Further, since the surface of the polymer composition layer roughened by adding the fine particles absorbs the sharp irregularities on the head, no deposit is generated on the heating element, resulting in dropout. Can be prevented. The particles serve the function of preventing dropout.

[0010]

EXAMPLES FIGS. 1 and 2 show schematic sectional views of transfer bodies of the present invention as examples.

In FIG. 1, 1 is a substrate of a transfer body, 2 is a color material layer formed thereon, and 3 is a polymer composition layer.
In FIG. 2, 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. In the polymer composition layer 6,
Further, it is effective to contain a liquid lubricant, a solid lubricant, or both a liquid lubricant and a solid lubricant, if necessary.

The material of the fine particles is not particularly limited, and various particles of metal, inorganic particles and organic particles can be used. For example, metal oxides, metal sulfides, metal carbides, metal nitrides, metal fluorides, graphite, fluorocarbons, carbon black, minerals, inorganic salts, organic salts, organic pigments, ethylene tetrafluoride, polyimide, etc. There are molecules, etc.

Particularly, synthetic amorphous silica, carbon black, alumina, titanium oxide, calcium silicate, aluminum silicate and the like are effective.

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, West Germany, aluminum oxide and titanium oxide (both produced by Nippon Aerosil Co., Ltd.) similarly produced by a vapor phase method. ) Etc.

Examples of hydrous silica or white carbon include, for example, "Carplex" by Shionogi Pharmaceutical Co., Ltd.,
Nippon Silica Industry Co., Ltd. “Nipseal”, Mizusawa Chemical Co., Ltd. “Shilton”, Tokuyama Soda Co., Ltd. “Fuinseal, Tokuseal” and the like are commercially available. Depending on the characteristics of the dye used, silica may react with the dye, so it is possible to use hydrophobic silica in which the silanol groups present in silica are chemically partially substituted with a methyl group or an organic silicon compound. .

The addition ratio of the fine particles to the polymer substance may be in the range of 0.1 to 200% by weight. In particular, it exhibits stable characteristics in the addition ratio of 5 to 100% by weight. The ultrafine particles are well dispersed by ultrasonic waves, a triple roll, a homogenizer and the like.

As for the size of the fine particles, the smaller the particle size is, the smaller the influence on the image quality is. The dropout hardly occurs particularly when the average particle size is 6 μm or less, which is desirable.

The material of the polymer substance is not particularly limited, and examples thereof include various thermoplastic resins, heat, light,
Various curable resins using electron beams or the like can be used. In particular, various curable resins are excellent in adhesiveness to the 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, the oligoacrylate curable resin exhibits excellent characteristics. In addition, the curable resin by light and electron beam is easily cured in a short time, and the unreacted resin on the back surface of the base material,
Since there is almost no transfer of a curing agent or the like, it is easy to prepare a long-sized transfer body and shows good characteristics. For example, a photocurable resin of an oligoacrylate light or electron beam, a photocurable resin of an epoxy resin using an aromatic diazonium salt, an aromatic iodonium salt, or an aromatic sulfonium salt catalyst is excellent.

Examples of oligoacrylates include polyol acrylates, polyester acrylates, epoxy acrylates, urethane acrylates, silicone acrylates and polyacetal acrylates, and examples of epoxy resins include vinyl cyclohexene dioxide and 3,4-epoxycyclohexylmethyl-.
There are cycloaliphatic epoxy resins such as 3,4-epoxycyclohexanecarboxylate. Further, 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 layer is not particularly limited. Generally, a polymer composition layer having a film thickness of 0.1 μm or more is easily obtained from the viewpoint of production and exhibits uniform properties.

Various well-known surfactants can be used as the surfactant. For example,
Various anionic surfactants such as carboxylates, sulfonates, sulfates, phosphates, etc., various aliphatic amine salts, aliphatic quaternary ammonium salts, aromatic quaternary ammonium salts, heterocyclic quaternary ammonium Various cationic surfactants such as salts, 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 fatty acid ester, fatty acid monoglyceride, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester and other ester type, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxy Various nonionic surfactants such as nitrogen-containing types such as ethylene alkylamine and alkylamine oxide, various betaine types,
Aminocarboxylic acid salt type, various amphoteric surfactants such as imidazoline derivatives, fluoroalkyl (C ₂ -C ₂₀ ) carboxylic acid, monoperfluoroalkyl (C ₆ -C ₁₆ ) ethyl phosphate, perfluorooctane sulfonic acid diethanolamide Various fluorine-containing surfactants such as, polyether modified silicone oil, carboxyl modified silicone oil, alkyl aralkyl polyether modified silicone oil, epoxy / polyether modified silicone oil, and other modified silicone oil, polyoxyalkylene glycol and silicone There are various silicone surfactants such as various copolymers.

Further, surfactants called polymer surfactants, organometallic surfactants, reactive surfactants and the like can also be used in the present invention.

Silicone-based and fluorine-based surfactants are particularly excellent, and when the above-mentioned surfactant and silicone-based or fluorine-based surfactant are used in combination, the effect of preventing sticking is excellent. Also, the HLB value is 3.0 or less and 3.0
The above effect is remarkable when two or more surfactants having HLB values separated by 3 or more are used in combination.

The liquid lubricant is a substance which is a 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, alkyldiphenylethane,
Synthetic oil such as phosphate ester, saturated hydrocarbon, animal and vegetable oil,
Mineral oil, ethylene glycol, propylene glycol,
Examples include glycols such as polyalkylene glycol, glycerin and glycerin derivatives, esters such as butyl stearate, and liquid paraffin.

The solid lubricant is a solid or semi-solid lubricant at 25 ° C. and 1 atm. For example, stearyl alcohol, various alcohols such as mannitol, stearic acid, fatty acids such as montanic acid, stearyl stearate,
Fatty acid esters such as cetyl palmitate and pentaerythritol tetrastearate, waxes such as microcrystalline wax and polyolefin wax, and aliphatic hydrocarbons such as partial oxides, fluorides and chlorides thereof, palmitic acid amide, ethylene bis Examples thereof include fatty acid amides such as stearic acid amide, metal soaps such as calcium stearate and aluminum stearate, graphite, molybdenum disulfide, ethylene tetrafluoride, carbon fluoride and talc.

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 and acetyl. Cellulose, cellulose derivatives such as cellophane, polyvinylidene fluoride, tetrafluoroethylene-
Propylene hexafluoride copolymer, fluorine-based polymer such as Teflon, ether-based polymer such as polyoxymethylene and polyacetal, olefin-based polymer such as polystyrene, polypropylene and methylpentene polymer, polyimide,
An imide-based polymer such as polyamideimide or polyetherimide can be used.

Particularly, the polyester polymer is useful because it is thin, has some heat resistance, and is inexpensive. Further, polymers such as imide polymers and amide polymers, which are more heat resistant than polyester polymers, are excellent in heat resistance when the transfer member is repeatedly used or used at high speed, and are useful as substrates.

The color material layer is not particularly limited, and various color material layer configurations used in the wax system, the sublimation dye system and the like can be used. Color materials include color formers as well as pigments and dyes. As a sublimable dye, 300
A dye that starts sublimation or evaporation at a temperature of not higher than 0 ° C. can be used, and examples thereof include a basic dye and a disperse dye.

Specific examples will be described below. Example 1 A PET film having a thickness of 12 μm was used as a substrate. Each coating solution (No. 1 to 1) having the composition shown in Table 1
No. 4) was produced. No. on the bottom surface of the PET film.
The coating liquid of No. 1 was applied with a wire bar, the solvent was evaporated with hot air at 60 ° C., and then the liquid was cured by irradiation with a high-pressure mercury lamp of 1 kW. No. 2 to No. The same procedure was performed for each coating solution of 4 to obtain a PET film having a polymer composition layer on the lower surface.

Next, an ink prepared by mixing 2 parts by weight of a sublimable dye represented by the following molecular structure, 4 parts by weight of polycarbonate and 100 parts by weight of methylene chloride was applied to the upper surface of the PET film processed as described above with a wire bar. After 60
Four types of transfer bodies were prepared by drying with hot air at ℃.

[0032]

Embedded image

Using each of the transfer members, recording was performed on activated clay-coated paper of A-5 plate 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 for one line: 33.3 ms Recording area: A-5 version This test result Is shown in Table 1. Coating liquid N according to the present invention
o. 1, No. 2 and No. The transfer body prepared from 3 is
Even at 8 ms, the vehicle ran stably without generating a stick. No. In No. 3, since it did not contain fine particles, dropout occurred in the first sheet of A-5 plate. On the other hand, Comparative Example No. The transfer body made from 4 is
A stick occurred in 3 ms. Further, since the transfer member was stuck and melted and cut, it was impossible to evaluate the dropout.

[0035]

[Table 1]

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 includes fine particles, a liquid lubricant, a solid lubricant, a surfactant and a polymer substance. Thereafter, in the same manner as in Example 1, the above coating liquid polymer composition layers were formed on the lower surface of the substrate, and the coloring material layer was formed on the upper surface to prepare three types of transfer bodies, and then the stick and the drop were formed. The recording power applied to the head during the out occurrence test is 0.
It carried out by raising to 77W. The test results are shown in Table 2.
Each coating liquid No. related to the present invention. 1 to No. Each of the transfer bodies prepared from No. 3 did not cause sticking even at 0.77 W for 8 ms, and had no dropout.

[0037]

[Table 2]

[0038]

As described above, the present invention provides a film-like group
There is a color material layer on the upper surface of the body, and a curable resin is on the lower surface of the base.
Of high molecular weight substance and modified silicone oil
A thermal recording transfer member having a polymer composition layer, or
There is a color material layer on the upper surface of the film-shaped substrate,
Synthetic amorphous silica, carbon black, alumina,
Titanium oxide, calcium silicate and aluminum silicate?
The average particle size of at least one selected from
Fine particles below and polymeric substance of curable resin and modified silicone
A polymer composition layer formed from oil and
The ratio of the particles to the polymer substance is 5 to 100% by weight.
And the surface of the polymer composition layer by the fine particles.
By the transfer body whose surface is roughened,
It is possible to obtain a transfer body that does not generate sticking or a transfer body that does not generate sticking and does not generate dropout in an image.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a thermal recording transfer member according to an embodiment of the present invention.

FIG. 2 is a schematic sectional view of a thermal recording transfer member according to an embodiment of the present invention.

[Explanation of symbols]

 1 Base 2 Coloring Material Layer 3 Polymer Composition Layer 4 Base 5 Coloring Material Layer 6 Polymer Composition Layer 7 Fine Particles 8 Surfactant

Claims (2)

(57) [Claims] 1. A color material layer is provided on the upper surface of a film-shaped substrate,
On the lower surface of the substrate, a high molecular weight curable resin and a modified silicone
With a polymer composition layer formed with
Transfer material for thermal recording. 2. A color material layer is provided on the upper surface of a film-shaped substrate,
On the lower surface of the substrate, synthetic amorphous silica, carbon black
Cu, alumina, titanium oxide, calcium silicate and silicic acid
At least one average particle size selected from aluminum
With fine particles of 0.5 μm or less and a polymeric substance of curable resin
Polymer composition layer formed from modified silicone oil
And the ratio of the fine particles to the polymer substance is 5
˜100% by weight, and due to the fine particles,
Transfer for thermal recording with roughened surface of child composition layer
body.