JPS63191677A - Heat-sensitive transfer material - Google Patents

Abstract

PURPOSE:To stabilize feeding at the time of printing, reduce noise, suppress exfoliation of a coated film and contamination of a thermal head and ensure clear printing, by providing an anti-sticking layer comprising a vinylidene chloride copolymer and an organopolysiloxane in a specified ratio and having a specified thickness on a side of a base film opposite to the side of an ink layer. CONSTITUTION:A heat-fusible or sublimable transfer ink layer is provided on one side of a plastic film, and an anti-sticking layer comprising a mixture of (A) a vinylidene chloride copolymer and (B) an organopolysiloxane and having a (B)/(A) weight ratio of 0.01-8 and a thickness of 0.03-3 mum is provided on the other side. The vinylidene chloride copolymer may be any copolymer prepared from vinylidene chloride and a comonomer by a known method. The organopolysiloxane may be, for example, a silicone oil or a modified silicone oil into which a functional group has been introduced for imparting compatibility with the resin used therewith, hydrophilicity, reactivity, adsorption properties, lubricity or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal transfer material, and more particularly to a thermal transfer material that prevents sticking during printing and runs smoothly.

[Background Art] In recent years, recording media suitable for various hard copy devices have been put into practical use as we move toward a highly information-oriented society.

In particular, thermal printers, which use heat to melt thermofusible ink that is solid at room temperature and transfer it to transfer paper, have strict requirements such as small size, light weight, low noise, and high speed printing. Conventional thermal transfer materials based on plastic film have drawbacks such as a phenomenon (sticking) that occurs due to their lack of heat resistance, which causes fusion with the thermal head and significantly impedes running performance. This problem has become even more noticeable due to the accompanying increase in applied voltage and multicolor printing. To prevent this sticking, methods include adding inorganic particles such as siloids and calcium carbonate to roughen the surface to reduce contact with the thermal head, and mixing lubricants such as wax as an anti-sticking layer on the opposite side of the ink surface. A method of providing a thermoplastic resin layer or a fluororesin layer has been proposed.

[Problems to be Solved by the Invention] A thermal transfer material using a plastic film as a base material is fused to a thermal head, which significantly impedes running or, in extreme cases, makes it impossible to run. In addition, when using plastic film whose surface has been roughened with inorganic particles, if the surface is roughened to the extent that it prevents sticking, the ink layer will not be sufficiently transferred to the paper, resulting in unclear prints and rough surfaces. When the degree of oxidation is reduced, there are drawbacks such as significant noise during running.

Although layers containing lubricants such as wax or fluororesin are effective in preventing sticking, the toughness of the coating film is poor and the adhesion to the base plastic film is poor. The paint film may fall off during running, contaminating the thermal head, or may be insufficient in terms of noise during running.

The object of the present invention is to provide a thermal transfer material that does not have the above-mentioned drawbacks, that is, has no sticking, excellent adhesion to a plastic film as a base material, low noise during printing, and clear printing performance. There is a particular thing.

[Means for Solving the Problems] The object of the present invention is to provide a transfer ink layer on one side of a plastic film that melts or sublimates when heated;
The other surface is made of a mixture of (A>vinylidene chloride copolymer and (B) organoborisiloxy→none, and (B)
)/(A> weight ratio is 0°01~8, thickness is 0.03~
This is achieved by a heat-sensitive transfer material characterized by providing an anti-sticking layer with a thickness of 3 μm.

As the base plastic film in the thermal transfer material of the present invention, a publicly known PlusDeck film can be used as appropriate.

Typical examples include polynisdel film, polycarbonate film, tri-7cetyl cellulose film,
Cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film,
Examples include polyolefin films. However, from the viewpoint of cost and heat resistance, it is preferable to use polynisdel film, polycarbonate film, and polyphenylene sulfide film.
A polynisdel film is preferable in terms of dimensional stability, etc. Among polyester films, a polynisdel film is preferred, and among polyester films, a polynitride film consisting of a copolymer of polyethylene derephthalate-1 to (hereinafter abbreviated as PET) and a PE-cholic acid component of 90 mol% or more is preferable. Axial stretched film (
Hereinafter, the two-wheel stretched film will be abbreviated as BO film. ) are particularly suitable.

The thickness of the plastic film is not particularly limited, but is usually 0.5 μm or more and 40 μm or less, preferably 1 μm or more and 10 μm or less. Furthermore, the base film has a tensile elastic modulus of 100 to 25°C, 65% rh, measured using a Tensilon type tensile tester at a tensile speed of 200 mm/min.
2000kLj/1TllT12. The heat shrinkage rate measured at 120°C is preferably 2% or less. The plastic film may be roughened on one or both sides using inorganic particles to provide slipperiness, but in this case, if the surface is extremely rough, the ink layer may not be transferred to the transfer paper. JIS-BO6 is sufficient and the printing becomes unclear.
Center average roughness Ra) measured according to 01-1976
is 0.005 to 0.4 μm, maximum surface roughness (Rt) is 0
．． It is preferable to use a material having a diameter of 0.05 to 4 μm or less.

The base plastic film may contain dispersed additives such as a weathering agent, a color toner, a matting agent, an antistatic agent, and a flame retardant, as long as the object of the present invention is not impaired. The surface of the rough film may be subjected to discharge treatment, primer treatment, antistatic treatment, matting treatment, flame retardant treatment, coloring, etc.

The melting or sublimating transfer ink constituting the transfer ink layer provided on one side of the base plus deck film is not particularly limited either, and any known one can be used as appropriate. The main components of the hot-melt ink are (1) a wax with an appropriate melting point such as paraffin wax, microcrystalline wax, or carnauba wax, (2) a pigment, and (3) a softener such as oil. Typical examples include those to which various additives are added depending on the requirements. Typical pigments used in this case include organic pigments such as azo pigments, phthalocyanine pigments, dyeing lakes, condensed polycyclic pigments, nitrone pigments, and alizarin lakes. On the other hand, sublimable inks mainly include (1) cellulose-based water-soluble acrylics such as hydroxyethyl cellulose, polyvinyl alcohol, or polyamide-based resins, (2) sublimable dyes of yellow, magenta, and cyan. A typical example is one containing additives. Representative examples of sublimable dyes include disperse dyes, basic dyes, and oil-soluble dyes. The thickness is not particularly limited, but is usually 0.1 to 15 μm, preferably 1 to 6 μm.
It is m.

The thermal transfer material of the present invention has (A) vinylidene chloride copolymer and (B) on the opposite side of the ink layer of the base plastic film.
) A layer made of a mixture of organopolysiloxanes is provided, where (A>vinylidene chloride copolymer is a monomer copolymerized with vinylidene chloride by a known method. Although not particularly limited, representative examples include vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylic acid ester copolymer, and vinylidene chloride-methacrylic acid ester copolymer. Examples include merging.

Among these, nylidene chloride-7-acrylonitrile copolymer and vinylidene chloride-acrylic acid ester copolymer are preferred from the viewpoint of adhesion to the base plastic film, particularly PET-BO film. A three-dimensional or four-dimensional copolymer containing these in combination with acrylic acid, methacrylic acid, crotonic acid, etc. may also be used. It may also be a vinylidene chloride copolymer copolymerized or grafted with a reactive group.

The ratio of vinylidene chloride and the copolymerized component is 100 parts by weight or more of the copolymerized component to 1 part of vinylidene chloride, preferably 100 parts by weight or more, preferably 5 parts by weight or more, preferably 30 parts by weight or more. This is suitable in terms of adhesion to the base plastic film.

The vinylidene chloride copolymer may have a degree of polymerization sufficient to form a film by itself, and the polymer average molecular weight is 500.
0 to 1 million, preferably 20,000 to 800,000. Vinylidene chloride copolymer is dissolved in a general-purpose organic solvent,
Alternatively, any emulsion can be used.

Used as a mixed component with vinylidene chloride copolymer (
B) As the organopolysiloxane, compatibility with silicone oil and resin to be blended, hydrophilicity, reactivity,
Examples include modified silicone oils into which various functional groups have been introduced for the purpose of imparting adsorption properties, lubricity, etc.

Representative examples of organopolysiloxanes applicable to the present invention are represented by the following general formulas (a) to (c).

R''...(c) [However, ×, Y, and Z are integers of 1 to 5000, R is an alkyl group having 1 to 100 carbon atoms or a water group, and R' is an alkylene group having 1 to 10 carbon atoms. group, a phenylene group, a cyclohexylene group, an ether group, R'' is hydrogen, an alkyl group having 1 to 100 carbon atoms, an epoxy group, an amino group,
carboxyl group, phenyl group, hydroxyl group, mercapto group,
A group selected from a polyoxylene alkyl group, a halogen-containing alkyl group, and R''' is a group selected from a C1-100 alkyl group, a polyoxylene alkyl group, a hydroxyl group, and a halogen-containing alkyl group. ] Specific examples include dimethylpolysiloxane oil, amine-modified silicone oil, epoxy-modified silicone oil,
Epoxy/polyether modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, alkyl and alkyl◆aralkyl modified silicone oil,
Examples include alkyl/aralkyl/polyether-modified silicone oil, fluorine-modified silicone oil, alkyl/higher alcohol ester-modified silicone oil, methylhydrogene, polysiloxane oil, phenylmethyl silicone, and emulsified products thereof. Dimethylpolysiloxane oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, polyether-modified silicone oil, amino-modified silicone oil and emulsions thereof are preferred in terms of anti-sticking properties and noise-preventing properties. Further, two or more of these may be mixed and used in any ratio. Furthermore, it is particularly preferable to use various crosslinking agents that react with the reactive groups of the silicone oil in view of stain resistance.

Organopolysiloxanes suitable for the present invention have a viscosity measured at 25° C. of 100 to 5 million C-8, preferably 200 OC-S to 3 million C-8. Those of C-8 or lower are preferred.

(A) Vinylidene chloride copolymer and (B) organopolysiloxane are mixed at any ratio using a common organic solvent or water, and the effect of the present invention is that (B/A> weighting is 0). It appears when B/A> is 0.01 to 8, preferably 0.1 to 5, more preferably 0.2 to 1.
If it is less than 01, the anti-sticking effect is not sufficient and the noise during printing is also large. If it exceeds 8, it is not preferable because the adhesion to the base plastic film may be poor or the coating film may become sticky and have poor runnability. Excellent effects are exhibited only when (B/A) is within the range of the present invention.

The thickness of the anti-sticking layer of the present invention is 0.03 μm or more and 3 μm or less, preferably 0.1 μm or more and 1 μm or less. If it is less than 0.03 μm, it is insufficient in terms of preventing sticking and noise, and even if it is applied more than 3 μm, the sticking improvement effect will not increase and the toughness of the coating film and the clarity of the print will decrease. It is not desirable because

Further, anti-blocking agents, lubricants, pigments, coloring agents such as dyes, plasticizers, light and heat stabilizers, surfactants, etc. may be added to this coating layer within a range that does not impair the effects of the present invention.

Next, a typical thermal transfer manufacturing method of the present invention will be described, but the present invention is not limited thereto. First, prepare a plastic film as a base material. This film may be subjected to corona discharge treatment in air or other various atmospheres, if necessary. Anchor treatment may be performed using a known anchor treatment agent such as urethane resin or epoxy resin, but this is usually not necessary. An anti-sticking layer was coated on the film using a known method such as gravure coating, reverse coating, spray coating, etc., for 1 sec at 60°C to 250°C.
Let dry for about 15 minutes. In this case, the solvent is not particularly limited, but usually water, alcohol, or a mixture of water and alcohol is used.

Subsequently, heat-melting or sublimation ink is applied to the opposite side in the same manner, and then dried at a predetermined temperature. These coats may be performed in any order, and of course may be performed simultaneously. Alternatively, a coating layer may be formed separately and then applied or laminated, but since the strength of the coating layer is somewhat insufficient, it is preferable to directly coat the base film.

The transfer ink layer can be coated by a known method such as bar coating, reverse coating, gravure coating, etc., regardless of whether before or after the anti-sticking layer is applied.

Moreover, when the base film is biaxially stretched, it is also possible to apply it during the manufacturing process. Specifically, an example is as follows: 1. An anti-sticking layer is coated on at least one side of a unidirectionally stretched polyester film.
Shun stretched in the right angle direction after drying or while drying,
There is a method in which heat treatment is performed, or alternatively, after stretching in the perpendicular direction, stretching is performed again in the one direction and then heat treatment is performed.

Although the present invention can fully exhibit its effects by either the former method or the latter method, the latter method is preferred in terms of the toughness of the anti-sticking layer and economical efficiency.

[Effects of the Invention] The present invention provides the following excellent properties by providing a vinylidene chloride copolymer and an organopolysiloxane in a specific ratio and a specific thickness as an anti-sticking layer on the opposite side of the ink layer of the base film. I was able to enjoy the effect.

(1) Sticking does not occur during printing and running is stable.

2) The noise during printing is extremely low.

(3) Because of the high adhesion to the base film, there is little chance of paint film falling off or contamination of the thermal head.

<4) Printing is clear.

Since the thermal transfer material of the present invention has the above-mentioned excellent effects, it is particularly suitable for use in facsimile machines, bar code printers, graphic printers, automatic ticket issuing machines, and the like.

[Method for evaluating characteristics and effects] Sticking properties, noise during running, and print clarity were evaluated using a serial printer and a line printer shown below.

(a) Serial printer 2 Sharp Shoin WD300
Print voltage 10V, 12V using F type word processor
I ran it and printed it.

(b) Line printer: Mitsubishi line thermal color printer G500F-10 type, applied voltage 17V
I ran it and printed it.

The evaluations of (a) and (b) above were determined based on the following criteria.

(1) Anti-sticking property ◎: Running is stable with no sticking at all.

Q: I almost never stick.

Δ: Slight sticking occurs.

X: Sticking is so severe that it becomes impossible to drive.

(2) Noise when driving ◎: Significantly small.

○: There is some noise, but it is hardly noticeable.

Δ: There is quite audible noise.

×: The noise is extremely loud.

<3) Print clarity ◎: No peeling, fading, or deformation at all.

Q: It is easy to handle and does not fade or deform.

Δ: Slightly deformed characters are seen.

X: Deformation is significant and difficult to handle.

(4) Adhesion to the base film When the anti-sticking layer is peeled off by 90' using a commercially available cellophane adhesive tape manufactured by Chiban Co., Ltd., the area of the anti-sticking layer adhered to the cellophane tape after peeling is less than 20%. ○,
The case of 20% or more and less than 50% was set as Δ, and the case of 50% or more was set as X.

[Example] Next, the present invention will be explained based on examples.

Examples 1 to 3, Comparative Examples 1 to 2 Polyethylene terephthalate biaxially stretched film with a raw area of 5 μm (tensile modulus: 400 to 9/mm2, Ra/R
t: 0.15 μm/1.30 μm> An anti-sticking layer with the following composition is applied to one side of the film with a thickness of 0.2 after drying.
Apply 5 μm. Drying was performed at 110°C for 1 minute.

(A> Nylidene chloride/acrylonitrile (93w 7w
t%) copolymer (weight average molecular weight: 200,000) emulsion (B) epoxy/polyether modified silicone oil (
Viscosity 3500C・5 (25℃) measured with a B-type viscometer,
Epoxy content: 0.5 wt%) The compositions (A> and (B) above) were mixed at the weight ω ratio shown in Table 1 and the concentration was adjusted with water.This coating liquid was applied using a gravure coater, and after drying. , and 11 parts of carnauba wax 100ff and 3 parts of macrocrystalline wax on the other side.
0 parts by weight, 15 parts by weight of vinyl acetate-ethylene copolymer,
A thermal transfer material shown in Table 1 was prepared by applying a heat-melting ink containing 20 parts by weight of carbon black to a thickness of 5 μm.

(Comparative Example 1) where the ratio of B/A> was less than the range of the present invention resulted in sticking and noise, and the printing was unclear.Also, when the ratio exceeded the range of the present invention (Comparative Example 2), there was no close contact. The object of the present invention could not be achieved due to insufficient properties and stickiness of the coating film. (Good characteristics were shown only when B/A> was within the range of the present invention.

Examples 4 to 6, Comparative Examples 3 to 4 (1q thermal transfer material was prepared in the same manner as in Example 1, except that the ratio of B/A> was 0.3 and the coating thickness was changed.Coating thickness In Comparative Example 3), which did not fall within the scope of the present invention, sticking and noise were significant, and printing performance was also poor. In addition, in Comparative Example 4), which was coated beyond the scope of the present invention, there was no sticking or noise, but the adhesion was poor, resulting in contamination of the thermal head, and the total thickness was thick, resulting in some areas of printing being unclear. Ta. Good properties were exhibited only when the coating thickness was within the range of the present invention.

Example 7 Thermal transfer materials shown in Table 1 were obtained in the same manner as in Example 1 except that an emulsion of dimethylborisiloxane oil (viscosity: 1,000,000 C-S) was used as Luganopolysiloxane A. As shown, thermal transfer materials with good properties were obtained even when the type of organoborisiloxane was changed.

Example 8 Polyethylene terephthalate with an intrinsic viscosity of 0.62 was
It was melted at 80°C and extruded onto a cooling drum at about 60°C. Further, it was stretched 3.5 times by roll stretching in the longitudinal direction at 80°C.
After corona discharge treatment in air, a water-based repaint as shown in Example 8 was applied.

After coating, continuously stretch 3.5 times in the transverse direction at 110'C.
Heat treatment was performed at 20'C to obtain a biaxially stretched polyester film having a film thickness of 5 μm and a coating thickness of 0.25 μm. A heat-melting ink was applied to the opposite side of the film to the coated side in the same manner as in Example 1 to obtain a heat-sensitive transfer material. This thermal transfer material was found to exhibit good properties with no problems in both line type and serial type printers.

Claims (1)

[Claims] A transfer ink layer that melts or sublimates when heated is provided on one side of the plastic film, and the other side is made of a mixture of (A) vinylidene chloride copolymer and (B) organopolysiloxane, and (B) /(A) weight ratio is 0
．． 01-8, a thermal transfer material characterized by being provided with an anti-sticking layer having a thickness of 0.03-3 μm.