JPH011586A - Thermal transfer recording medium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermal transfer recording medium. More particularly, the present invention relates to a thermal transfer recording medium having a backing layer.

[Background of the Invention] Conventionally, the back side of a thermal transfer recording medium used in a thermal transfer recording method has a material that prevents the occurrence of so-called sticking phenomenon and so-called blocking phenomenon, and improves the runnability of the thermal transfer recording medium. In order to do this, a backing layer is provided.

Various resins such as acrylic resins, polyester resins, and cellulose derivatives are generally used as resin components forming such backing layers. As the powdery substance, inorganic powders such as silica powder, boron nitride powder, talc, and aluminum dioxide powder are generally used.

However, according to the inventor's study, since the inorganic powder has high hardness, it may damage the mounting of the thermal head etc. that comes into contact with this backing layer, and in such a case, the service life of the thermal head may be shortened. It was found that the period was shortened. Furthermore, inorganic powders generally have low dispersibility in resin components, and even if an attempt is made to incorporate all of the inorganic powder into resins that are widely used as backing layer resins, they may not be well dispersed. Such poorly dispersed inorganic powder may come off during running and contaminate the inside of the device. Furthermore, inorganic powders with poor dispersion.

Prolonged contact between the backing layer and the kA, 8 transfer colorant layer may cause it to adhere to the surface of the thermal transfer colorant layer, reducing print quality.

Furthermore, these inorganic particles have very poor dispersibility even in resin components such as silicone resins that have good heat resistance, and it is difficult to disperse them well by ordinary methods. Therefore, at present, the use of powder particles added to a backing layer made of a resin having good heat resistance such as a silicone resin has not been specifically studied.

On the other hand, heat-sensitive transfer recording methods using heat-sensitive transfer recording media have traditionally had the problem of insufficient printability on transfer media with low surface smoothness (so-called "rough paper"). In order to solve this problem, a method of increasing the printing energy to a very high level to improve the printing quality on rough paper is being considered.

The thermal energy in this case is much higher than the printing energy on a transfer medium with a high surface smoothness, so a thermal transfer recording medium with a backing layer formed from a conventionally used resin component was used. In some cases, a new problem arises in that thermal deformation occurs in the thermal transfer recording medium, such as wrinkles in the printed area due to thermal energy during transfer.

When the heat-sensitive transfer recording medium deformed in this way is wound up, the winding diameter after use becomes larger than the winding diameter before use (a becomes thicker). Therefore, when using a thermal transfer recording medium used for such high-energy transfer by storing it in a cassette, the increase in the winding diameter due to the thickening of the thermal transfer recording medium after use is deducted in advance. The recording medium, the thermal tape, must be housed in a cassette.

The thermal transfer recording medium used in the form of a cassette is advantageous because it has a large amount of printing for a negative-volume cassette. However, leaving an extra space in the cassette in consideration of the roll thickness while maintaining the size of the conventional cassette is disadvantageous in terms of print amount. However, if extra space is given to conventional cassettes to take into account the roll thickness, the cassettes will become larger and, by extension, the printers will become larger.

[Object of the Invention] An object of the present invention is to provide a thermal transfer recording medium with improved anti-blocking performance and anti-stacking performance.

A further object of the present invention is to provide a thermal transfer recording medium that has improved anti-blocking performance and anti-stacking performance and also exhibits good runnability.

In addition, the present invention not only effectively prevents sticking and blowing, but also has extremely heat-resistant properties, such as less damage such as thermal deformation due to heating during printing, and less thickening when wound up after printing. The purpose is to provide a good thermal transfer recording medium.

[Means for achieving the above object] The structure of the present invention for achieving the above object has a heat-sensitive transfer colorant layer on one side of a support, and a backing layer on the other side of the support. The backing layer contains a resin having a siloxane bond in one molecule and/or a cured product of the resin, and an organic powder.

1. Support 1. The support used in the thermal transfer recording medium of the present invention preferably has heat-resistant strength, high dimensional stability, and high surface smoothness.

Materials forming the support include, for example, papers such as plain paper, condenser paper, laminated paper, and coated paper, resin films such as polyethylene, polyethylene terephthalate, polystyrene, polypropylene, and polyimide, and composites of paper and resin films. Any of these can be suitably used, such as a metal sheet such as a body and a metal sheet such as aluminum foil.

The thickness of the support is usually less than 60 lm in order to obtain good thermal conductivity. In the present invention, especially 1.
Preferably, it is within the range of 5 to 15 m. In order to improve the adhesive properties of the backing layer (or heat-sensitive transfer colorant layer), the surface of the support may be subjected to corona discharge treatment, glow discharge treatment, other electric shock treatment, flame treatment, ultraviolet irradiation treatment, etc.
Surface treatments such as oxidation treatment and saponification treatment may be performed, or rough undercoating processing may be performed.

-Backing layer- The backing layer is provided on the surface of the support on which the heat-sensitive transfer colorant layer is not provided.

The backing layer contains a resin having a siloxane bond in its molecules as a resin component.

Examples of the resin having a siloxane bond in the molecule include an organopolysiloxane resin represented by the following formula (I), a resin in which a part of R in the following formula (I) is an epoxy group, an olefin group, an ether group, a hydroxyl group, or a fluorine group. Modified polysiloxane resins substituted with t substituents having atoms, amino groups, mercapto groups, etc., and organopolysiloxanes in which a part of the resin, such as urethane resins, acrylic resins, and polyester resins, is represented by the following formula (I) Examples include silicone-modified resins modified with resins or the above-mentioned modified polysiloxane resin components.

However, in the above formula CI), R represents a lower alkyl group, and n is within the range of 10 to 10,000.

Among these resins that have siloxane bonds in their molecules,
A resin having a softening point (according to ASTM-D-1525, the same applies hereinafter) of 60° C. or higher (more preferably 80° C. or higher) can be suitably used.

Specific examples of the modified polysiloxane resin used in the present invention include those represented by the following formulas (1) to (6).

・・・・・・・・・・・・(3) Me He Me (CI+2)aSl+ ・・・・
...---(6) In addition, m, n, a, b, c and X in the above formulas (1) to (6) are integers of 0 or more, and m and n are It cannot be 0 at the same time, R1
represents an alkyl group, and R2 and R3 represent a divalent bonding group. Further, Me represents a methyl group.

The silicone-modified resin that can be used in the present invention is preferably one in which the content of organopolysiloxane resin or modified polysiloxane resin in the resin component is within the range of 5 to 40% by weight.

Furthermore, among the silicone-modified resins, a silicone-modified urethane resin in which a part of the urethane resin is modified with the above-mentioned organopolysiloxane resin component or modified polysiloxane resin is most preferable.

Among the silicone-modified urethane resins mentioned above, it is suitable...
・・・・・・(7) ・・・・・・・・・(8) However, in the above formulas (7) and (8), p and q are integers greater than or equal to 0, and q is never 0 at the same time, and R' is any of the divalent bonding groups represented by the following formulas (9) to (12).

・・・・・・・・・・・・・・・ (9) ・・・・・・・・・・・・・・・ (10)・・・・・・
・・・・・・・・・(11)・・・・・・・・・・・・
(12) In the above formulas (9) to (12), S represents an integer.

The ratio of the urethane resin part to the silicone resin part in the silicone-modified urethane resin is usually 99:]
to 5:95 (preferably 95:5 to 10:90).

It is also possible to use a resin having a siloxane bond in the molecule as described above as a resin component constituting the backing layer, but this has not been done yet]! In No. 1, at least one resin is selected from among polyester resin, polyamide resin, cellulose derivative, acrylic resin, and polyether sulfone resin as the second resin component, and the resin having a siloxane bond in the molecule is selected. They can also be used together.

As the polyester resin, common thermoplastic polyester resins and copolymers containing polyester resin components can be used. In particular, in the present invention, the number average molecular weight is 5000 to too much.

(particularly preferably in the range of toooo to 2[1000]), and has a softening point of 706C or higher (particularly preferably 100
A material having a tensile strength (ASTM D6:18-61T) of 150 kg/crn or more when formed into a film can be suitably used.

As the polyamide resin, ordinary ones can be used. Examples of such polyamide resins include nylon 6, nylon 8, nylon 11, nylon 66 and nylon 610, as well as copolymers containing the polyamide resin component of the rod.

Among these polyamide resins, the number average molecular weight is 1oo
A polyamide resin having a softening point of 706°C or more (particularly preferably 110°C or more) can be suitably used.

Examples of the cellulose derivatives include cellulose esters such as acetylcellulose, nitrocellulose and acetylbutylcellulose, and cellulose ethers such as ethylcellulose, methylcellulose, benzylcellulose and carboxymethylcellulose.

Examples of the acrylic resin include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, acrylamide, homopolymers of these derivatives, and the various acrylic monomers and vinyl acetate and vinyl chloride. Examples include copolymers with styrene, maleic anhydride, and the like.

Among various acrylic resins, the number average molecular weight is 5]0
~7001]00 (particularly preferably Yen000~500
00) and a softening point of 70°C or higher (particularly preferably 90°C or higher).

Examples of the polyether sulfone resin described in +iii include resins represented by the following formula,
In the above formula, R1 to R8 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Particularly in the present invention, a hydrogen atom is preferred. Also,
The average molecular weight is usually in the range of 100 to 500. In addition, the polyethersulfone resin may contain other repeating units such as bisphenol A in an amount of 50 mol% or less in addition to the repeating units represented by the above formula.

In particular, in the present invention, the second resin component is
Preferably, cellulose derivatives and/or polyester resins are used. In particular, when a silicone-modified urethane resin is used as the resin component having a siloxane bond in the molecule, it is particularly preferable to use nitrocellulose. In this case, it is preferable that the nitrocellulose has a nitrogen content in the range of 11.5 to 12.2%. This is a silicone-modified urethane resin or a relatively soft resin with a high elastic modulus, and nitrocellulose °
This is because both are resins with relatively high hardness, and by using both together, it is possible to form a strong and highly flexible backing layer.

The backing layer can be formed by adding, as a binder, the above-mentioned resin having a siloxane bond in its molecules, and, if necessary, the above-mentioned second resin component. Furthermore, the backing layer can be made into a cured or crosslinked product by adding aziridine, a polyisocyanate compound, a catalyst, or the like to these resins. In the present invention, it is particularly preferable to use a polyisocyanate compound.

Polyisocyanate compounds that can be used in the present invention include aromatic polyisocyanate compounds, alicyclic polyisocyanate compounds and aliphatic polyisocyanate compounds.

Examples of aromatic polyisocyanate compounds include:
Tolylene diisocyanate (TD+), 4.4°-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), metaxylylene diisocyanate (MXDI), and adducts of these polyisocyanate compounds with active hydrogen compounds. It is preferable that the average molecular weight is within the range of 100 to 3000.

Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate (IIMDI), trimethylhexamethylene diisocyanate (TMDI), and adducts of these polyisocyanate compounds with active hydrogen compounds. Furthermore, examples of alicyclic polyisocyanate compounds among aliphatic polyisocyanate compounds include methylcyclohexane-2,4-cyisocyanate [structural formula; C1+, ]4
,4-methylenebis(cyclohexyl isocyanate) [417W formula; Ofl:N+CI+2+NGO],
Mention may be made of inphorone diisocyanate and adducts of these polyisocyanate compounds with active hydrogen compounds.

Among these aliphatic polyisocyanate compounds and adducts of these polyisocyanate compounds and active hydrogen compounds, those with a molecular weight of 1O (1 to 3000
It is within the range of Furthermore, among the aliphatic polyisocyanate compounds, acyclic polyisocyanate compounds and adducts of these compounds and active hydrogen compounds are preferred.

In the present invention, the polyisocyanate compounds may be used alone or in combination of two or more. In particular, by using an aromatic polyisocyanate compound and another polyisocyanate compound in combination, it becomes possible to control the curing rate.

When using a polyisocyanate compound, the amount of the polyisocyanate compound to be added is determined by the weight of the resin having a siloxane bond in the molecule (and when using a second resin component, the total weight of the second resin component). The weight ratio of 驕) and the amount of polyisocyanate compound used is 50:50 to 9.
It is preferable to set it within the range of 9:l. When the amount of the polyisocyanate compound used is less than the above range, curing tends to be insufficient, and when it exceeds the above range, the runnability of the thermal transfer recording medium is reduced by 1 fe. Furthermore, it is particularly preferable to use the polyisocyanate compound in the above weight ratio within the range of 80:20 to 99:l.

In addition, when using an aromatic polyisocyanate compound as a curing rate regulator, the mixing ratio of the aromatic polyisocyanate compound is usually 20 to 80% by weight based on the total weight of the polyisocyanate compound used. Set within range.

In the present invention, common aziridine compounds can be used.

In addition, in the present invention, organic metals (
For example, cobalt naphthenate, tetra-n-methyltin), inorganic metal salts (eg, stannic chloride), or organic amines (eg, methylamine) can also be used.

Further, resins having siloxane bonds in their molecules can be cured by forming crosslinks using a catalyst. Catalysts that can be used in the present invention include, for example, platinum catalysts, tin catalysts, and 1-lead catalysts.

By adding a catalyst, a resin having siloxane bonds in one molecule and a second resin or a cured product are formed. In this case, a curing agent such as a polyisocyanate compound may or may not be used. In this case, the amount of catalyst used is 1.Usually, the amount of catalyst used is 1! ,
[It is less than 1% by weight.

The backing layer is a cured product formed from a vA resin having a siloxane bond in the molecule and/or a resin having a siloxane bond in the molecule, a second resin component optionally used, and a polyisocyanate compound. Or the crosslinked product is usually 20% by weight or more (particularly preferably 50% by weight or more, more preferably 80% by weight)
(above)) Including.

When using a second resin component, the resin component having a siloxane bond in the molecule and the second resin component are usually
It is used in a weight ratio of IQ:9Q to '10:10. The ratio is preferably 20:80 to '10:10, particularly preferably 50:50 to 85:15, and even more preferably 60:40 to 85:15.

A. The backing layer of the thermal transfer recording medium of 1!11 contains an organic powder.

The Ja powder that can be used in the present invention can be broadly classified into heat-resistant penta-alpha powder and non-heat-resistant alpha powder. In the present invention, from the viewpoint of reducing damage to the thermal transfer recording medium due to heating during printing, the following is achieved. IY
It is preferable to use 1N organic powder.

This ITI# thermal organic powder can be further broadly classified into heat-resistant resin powder and heat-resistant non-resin powder.

Here, examples of the heat-resistant resin powder include benzoguanamine resin powder, melamine resin powder, and resin powder having a siloxane bond in the molecule.

Examples include polyfluorinated olefin resin powder, polyolefin resin powder, polyester resin powder, polyimide resin powder, polyamide resin powder, epoxy resin powder, and cellulose resin powder.

Furthermore, examples of the heat-resistant non-resin powder include organic pigment powder such as phthalocyanine pigments.

As the benzoguanamine resin powder, for example, a normal benzoguanamine resin powder can be used, and further, a resin powder obtained by a reaction such as methylolization, methylenization, or alkyl etherification of benzoguanamine resin can also be used. . In addition, a resin obtained by copolymerizing benzoguanamine with urea, melamine, phenol, etc. may also be used. In addition, resins similar to benzoguanamine resins using the compound represented by the following formula as a starting material may also be used. It comes.

H2 These benzoguanamine-based resins can be pulverized by a conventional method using a ball mill or the like to form the powder used in the present invention.

Among such benzoguanamine-based resin powders, those made porous so that the ratio of true specific gravity/bulk specific gravity is within the range of 1.3 to 8 have particularly good thermal properties against resin components and solvents. Therefore, it is preferable because it can be dispersed well.

As the melamine resin powder used in the present invention, a melamine resin produced by a conventional method and pulverized by the same method as described above can be used.

As the resin powder having a siloxane bond in the molecule, the above-mentioned resin powder having a siloxane bond in the molecule can be used.

In addition, polyfluorinated olefin resin powder is a resin obtained by polymerizing monomers such as olefins in which at least one hydrogen atom has been replaced with a fluorine atom, and such resins include, for example, tetrafluorinated Ethylene resin, tetrafluoroethylene/hexafluoropropylene copolymer resin, tetrafluoroethylene/perfluoroalkoxyethylene copolymer resin, trifluorochloride ethylene resin, tetrafluoroethylene/
Mention may be made of ethylene copolymers, vinylidene fluoride resins and vinyl fluoride resins. These fluororesins can be used alone or in combination of two or more.

Further, as the polyolefin resin powder, polyester resin powder, polyimide resin powder, and polyamide resin powder, ordinary ones can be used.

The phthalocyanine pigment, which is a heat-resistant non-resin powder that can be used as an organic powder in the present invention, usually has the formula (C
o 84 N 2 ) Rn. Here, R is ll, Na, K, Cu, Ag, Be
, Mg, Ca, Zn, Cd, Ha, tlg, AJl
, Ga, Ir, La, Nd, Ss, Eu, Gd, Dy
, tlo.

Er, Th, Tm, Yb, 1. u, Ti, Sn,
llf, Pb, V, Sb, Cr, Mo, U,
Mn, Fe, (:o, Ni, llh, Pd, O
Examples include atoms such as 5 and pt. n is O~2. The phthalocyanine pigments include α, β, γ,
Crystal types such as π, χ, and () are known, but
In the present invention, any crystal type can be used. Furthermore, in the above formula, a phthalocyanine pigment that substitutes a halogen atom such as chlorine can also be used.

In the present invention, among the heat-resistant resin powder and heat-resistant non-resin powder, considering the dispersibility of the resin having a siloxane bond in the molecule, which is the binder of the backing layer, among the heat-resistant resin powder, Resin powder with siloxane bonds, polyfluorinated olefin resin powder,
Benzoguanamine resin powders and melamine resin powders are preferred, and among the thermal non-resin powders, phthalocyanine pigments are preferred.

These heat-resistant resin powders and heat-resistant non-resin powders exhibit approximately the same effects in terms of properties such as blocking resistance and staking resistance. However, the backing layer runs while contacting the running system of the device (e.g., thermal head, support ball) during printing, so in order to give the thermal transfer recording medium good runnability, the backing layer must be It is desirable that the friction coefficient of the layer be within a certain range. Therefore, among the heat-resistant resin powders and heat-resistant non-resin powders used in the present invention, powders with slipperiness (
It is preferable to use a lubricating powder), and examples of such lubricating powder include the aforementioned resin powders having siloxane bonds in the molecule and polyfluorinated olefin resin powders.

That is, the coefficient of friction (JL value) of the surface of a backing layer made by using a resin having a siloxane bond in its molecules as a binder resin and adding the above-mentioned organic powder to it is usually:
It becomes 0.3 or less. By using a resin powder having a siloxane bond and/or a polyfluorinated olefin resin powder as the organic powder, the coefficient of friction (final value) of the surface of the backing layer can be made 0.15 or less.

Furthermore, when comparing a resin powder having a siloxane bond and a polyfluorinated olefin resin powder as the Ja-based powder, there is a tendency for the coefficient of friction to be lower when the polyfluorinated olefin resin powder is used.

In the present invention, a resin having a siloxane bond in the molecule is used as the binder resin forming the backing layer, but the contact between the backing layer, which does not contain organic powder, and the running system is surface contact. The contact between the backing layer of the thermal transfer recording medium of the present invention containing organic powder and the running system is basically point contact. Therefore, even if the backing layer-forming resin and the powder-forming resin are made of the same resin component, the difference in the form of their presence in the backing layer will cause them to have poor Plotskiff resistance,
#The effects on various properties such as sticking property, running performance, and heat resistance are completely different.

There is no particular restriction on the shape of the organic powder used in the present invention,
For example, spherical, ellipsoidal, and rectangular shapes may be used, but in the present invention, spherical or ellipsoidal shapes are preferred. This is because the surface of the backing layer containing spherical powder or ellipsoidal powder comes into good point contact with the traveling system, and the friction coefficient of the backing layer surface is reduced.

The organic powder used in the present invention usually has an average powder diameter of 0.01 JLm or more (preferably 0, old to 1.0 JLm or more).
Within the range of 0 pm, more preferably 0. O1~0.5
gm) is used. If a powder containing a large maximum powder diameter is used, the surface roughness of the backing layer may become too high.
．． 8. Transfer of the softening colorant layer to the surface may reduce printability. Also, the diameter of the uniform powder is 0.011L.
If it is smaller than m, the surface of the backing layer will become too smooth,
The anti-blocking performance and anti-state king properties may not be sufficiently improved.

Furthermore, among the above-mentioned organic powders, it is preferable to use one having a Mohs hardness of 7 or less.

If the hardness is higher than this, the device may be damaged by running. Further, in consideration of the difference in hardness from that of a device such as a thermal head, it is preferable that the Mohs hardness is 6 or less (more preferably 5 or less). The hardness of the organic powder can be selectively determined depending on the characteristics of the material, the powder manufacturing method, and the like.

Existence 43 in the backing layer! quality powder ffi ffl
The ratio is usually in the range from 0.1 to 50% by weight, based on the total amount of this layer.

In particular, when heat-resistant non-resin powder is used, the content of the heat-resistant non-resin powder in the backing layer is usually 1.3.
'l'f amount % or less (preferably 5% by weight or less, more preferably 0.1 to 3% by weight). If the amount of amorphous powder is too large, the state of dispersion may deteriorate. moreover,
The content ratio of the resin having a siloxane bond in the molecule and the heat-resistant non-resin powder in this layer is 75:25 to 99.
．． 9: It is preferable to set within the range of 0.1.

Further, when heat-resistant resin powder is used, the content of the heat-resistant resin powder is usually in the range of 1 to 30% by weight. Furthermore, the content ratio of the resin having siloxane bonds in the molecule and the heat-resistant resin powder in this layer is
It is preferable to set it within the range of 50:50 to 99:l.

In addition to the above components, the backing layer may contain additives such as waxes, surfactants, higher fatty acid derivatives, higher aliphatic alcohols, higher aliphatic ethers, and phosphoric acid esters. The amount of these components is the total amount based on the total amount of components forming the backing layer, and is usually
It is within the range of 1 to 20% by weight (preferably 1 to 9% by weight).

The thickness of the backing layer is usually 0.01 μm or more, and in practical terms, it is preferably within the range of O,OS to 0.51 Lm. Furthermore, the layer thickness is generally made thicker than the average organic powder used. It is preferable to make the layer thickness twice or more (preferably twice or more) with respect to the average powder diameter of the powder used, in order to effectively contain the amorphous powder in the backing layer. If the layer thickness is doubled, the powder may easily come off during running, or it may come off during storage and transfer to the heat-sensitive transfer colorant layer, resulting in a decrease in printing + Z quality.

As a method for attaching the backing layer to the support, for example, a method of solvent coating with a coating liquid in which the above-mentioned backing layer composition is dispersed in a solvent can be used. The solvent used at this time may be any solvent that dissolves or disperses each component to form a coating liquid. For example,
Paraffin solvents such as n-hexane, ligroin, isoparaffin, aromatic solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isotutyl ketone, alcohol solvents such as methanol, ethanol, propatool, butanol, etc. , ester solvents such as ethyl acetate, organic solvents such as special solvents such as dimethylformamide and dimethyl sulfoxide, and mixed solvents thereof may also be used.

For coating, any coating technique can be employed, such as a reverse roll coater method, an extrusion coater method, a gravure coater method, or a wire bar coating method.

Further, when using a curing agent or curing catalyst such as a polyisocyanate compound, a curing step such as a heating step may be provided to accelerate the curing reaction.

Unlike inorganic powders that are commonly used as fillers for backing shoes, organic powders exhibit good dispersibility even in resin components that have siloxane bonds in their molecules. Therefore, when preparing the backing layer of the thermal transfer recording medium of the present invention, the organic powder can be easily dispersed in the coating liquid, so that the organic powder is in a good dispersed state in the backing layer.

Furthermore, by using a polyisocyanate compound to make the hand-inking layer into a cured or crosslinked resin,
The backing layer now has better iIt thermal properties and durability. In addition, by using a resin having a siloxane bond in the molecule together with a second resin component, and further using a curing agent such as a polyisocyanate compound,
The backing layer has good durability and its coefficient of friction is low.

The surface of the thus applied hawking layer is roughened to correspond to the amorphous powder. Therefore, the backing layer is mainly in the form of one turn! E makes point contact with the heat-sensitive transfer colorant layer, and also makes point contact with the thermal head during running.

- Thermal transfer colorant The heat-sensitive transfer colorant layer is usually prepared by dispersing a colorant such as carbon black in a heat-melting substance such as wax and/or a mature RQ plastic resin such as polyethylene-vinyl acetate copolymer. This is a layer.

The thickness of the heat-sensitive transfer colorant layer is usually 15 square meters or less (preferably within the range of 1 to 67 square meters).

The thermal transfer colorant layer of the thermal transfer recording medium of the present invention may contain materials commonly used in this layer.

1. Other matters regarding the thermal transfer recording medium - The shape of the thermal transfer recording medium of the present invention is not particularly limited, and can be formed into a desired shape such as a tape shape.

Furthermore, the thermal transfer recording medium of the present invention can be used in the same way as ordinary ones.

For example, a tape-shaped thermal transfer recording medium is used while being stored in a cassette or the like in a wound state.

[Effects of the Invention] Since the backing layer of the thermal transfer recording medium of the present invention contains a resin having a siloxane bond in one molecule and an organic powder, the surface of the backing layer is roughened and the thermal transfer coloring is improved. Since the agent layer and the backing layer come into point contact, and the resin component does not exhibit adhesive properties, the blocking resistance is improved, such as by raising the temperature at which blocking occurs. Furthermore, the contact with the thermal head is point contact, and the heat resistance of the resin is also good, which improves the anti-stacking performance.

In addition, the surface of the backing layer is moderately roughened,
Furthermore, since the resin forming this layer has a siloxane bond, the coefficient of friction (#L value) of the surface of the backing layer is low, and the thermal transfer recording medium of the present invention has good running performance. In particular, a backing layer obtained by using a combination of silicone-modified resin and nitrocellulose as resin components and curing these resin components with a polyisocyanate compound has good durability and heat resistance, and has good durability and heat resistance. Due to its characteristics and roughening with the powder, the coefficient of friction is extremely low and it exhibits particularly good running properties.

As described above, in the heat-sensitive transfer recording medium of the present invention, the organic powder is well dispersed, so that the aluminous powder does not come off or adhere to the surface of the heat-sensitive transfer colorant layer during running or storage. . Further, the powder used is an organic powder,
Furthermore, since the hardness is low, the unevenness on the surface of the backing layer will not be transferred to the surface of the heat-sensitive transfer colorant layer, and the printing quality will not deteriorate.

Furthermore, since the thermal transfer recording medium of the present invention includes a backing layer in direct contact with the thermal head or a highly heat-resistant resin having a siloxane bond in its molecules, and an organic powder,
Even if the printing energy is increased to improve the printing quality on rough paper, the damage to the thermal transfer recording medium is minimized by the action of the resin and powder. Therefore, the difference between the winding diameter of the thermal transfer recording medium before printing and the winding diameter after printing becomes very small, and the winding thickness is reduced, so there is no need to provide excessive extra space in the cassette, and The space can be used effectively.

(The following is a blank space) [Example] Next, Examples and Comparative Examples of the present invention will be shown. In addition, in the Examples and Comparative Examples below, the expression "parts" represents "parts by weight."

(Example 1) A para-kink layer coating composition (■
) 2 parts by weight dissolved in 98 parts by weight of an organic solvent (toluene/methyl ethyl ketone (weight ratio) = 1/l) was applied using a wire bar to a thickness of O,:l JLm. Then, it was cured at 50° C. for 60 hours to form a backing layer.

Backing...1'l I (Solid content equivalent weight (hereinafter the same)) Silicone modified polyurethane resin (average molecular r: approx. 20,000 Silicon component content: 21% by weight)...20
Part Nitrocellulose (112 substances)・・・・・・・・・
...80 parts polyisocyanate compound (product name: Desmodur Shi, manufactured by Nippon Polyurethane)...
15 parts benzoguanamine resin powder (average particle size: 0.3 JLm Mohs hardness: 4 true specific gravity: L35 new specific gravity/bulk specific gravity: 3.38)
...2 parts Next, on the support without the backing layer, a heat-softening F3 coating composition having the composition described below was applied using a wire bar to a film thickness of 2.0 μm. A heat-softening layer was formed, and a heat-sensitive transfer recording medium was manufactured.

H - Cloth acrylic resin・・・・・・・・・・・・・・・・・・・
・・・・・・50 parts paraffin wax [melting point 70℃
]・・・・・・・・・25 parts carnauba wax・・・・・・
・・・・・・・・・・・・・・・・・・10 parts carbon black・・・・・・・・・・・・・・・・・・・・・
25 parts (Comparative Example 1) A thermal transfer recording medium was produced in the same manner as in Example 1, except that the same amount of nitrocellulose used in Example 1 was further added instead of the silicone-modified polyurethane resin.

(Comparative Example 2) A thermal transfer recording medium was produced in the same manner as in Example 1, except that alumina powder (average particle size: 0.2 pm, Mohs hardness: 9) was used instead of pentzguanamine resin powder. It should be noted that when preparing the backing layer coating composition, alumina powder is very difficult to mix.
The mixing time was 10 times longer than that in Example 1.

(Example 2) In Example 1, phthalocyanine pigment (average particle size: 0, :lILm
, except that Mohs hardness: 5) was used.

A thermal transfer recording medium was produced in the same manner.

90 m of the obtained thermal transfer recording medium was placed in a cassette, and the blocking start temperature at a load of 80 g/crrf was measured by the temperature gradient method.

100 rolls of the obtained thermal transfer recording medium were recorded (printed) using a thermal printer (24 dot serial head, platen pressure 250 g hat, platen rubber hardness 70'') at a printing speed of 40 cps, and the occurrence of sticking was evaluated. did.

In Table 1, samples with good sticking resistance are marked with 0, and samples with sticking are marked with x.

In addition, after running, the running system was visually observed to see if there were any scratches. The results are listed in Table 1.

L Hill Stand 1 100 rolls of cassettes similar to those used in the evaluation of blocking resistance described in L were prepared and run using the above thermal printer.

In Table 1, indicate the cases where no change was observed in the running speed.
The changes observed in the running speed are indicated by an X.

11 Plate 1 The friction coefficient of the backing layer surface of the obtained thermal transfer recording medium was measured.

The measurement results are listed in Table 1.

Table 1 (Example 3) In Example 1, a coating solution was prepared using the backing layer coating composition ([) described below. 8. Apply the cloth liquid to a thickness of Q: 1 gm, and then
A thermal transfer recording medium was produced in the same manner except that heating was performed at 120° C. for 21 minutes to form an occlusion layer.

Para-kink value: Right V force "Sewing" 2 ri + 1 Silicone resin (5P-212V, manufactured by Dainichiseika [Manufactured by Dainichiseika]...
...80 parts fluororesin powder (average particle size: 0.2 mm, trade name Nilpuron, manufactured by Taikin Dai) ......
20 parts (Comparative Example 3) A thermal transfer recording medium was prepared in the same manner as in Example 3, except that the backing layer was formed using the backing layer P1 fabric composition (m-c) described below. was manufactured.

Harakink fake; = m-c silicone resin (5P-2+2V, made by Dainichiseika ■)・・・・・・・・・
100 parts (Example 4) A thermal transfer recording medium was produced in the same manner as in Example 1, except that a backing layer was formed using the backing layer coating composition (IV) described below.

Backing ・、■ Silicone resin (5D-7226, Toray Silicone ■51)---・φ
ψ・・・φ・70 parts Fluororesin powder (average particle size: 0.2 m, trade name: Nilbron, manufactured by Daikin) ・・・・・・・・・
...20 parts platinum catalyst (platinum content = 5% by weight) ...
- 10 parts (Example 5) In Example 1, backing layer coating 71 described below
A thermal transfer recording medium was produced in the same manner except that the backing layer was formed using Composition (V).

Packing g, 2 = y Silicone resin (5P-203V, manufactured by Dainichiseika ■)・・・・・・・・・
...70 parts fluororesin powder (V average particle size: 0.2 m, trade name Nilkan, manufactured by Daikin) ......
...20 parts polyester resin (Ba4a 200, manufactured by Toyobo Co., Ltd.)...
10 parts (Comparative Example 4) A thermal transfer recording medium was prepared in the same manner as in Example 5, except that the backing layer was formed using the backing layer coating composition (VC) described below. Manufactured.

Harakinbuto, right V-C silicone resin (5P-203V, made of large viscosity ■)...
・・・・・・70 parts polyester resin (Byron 200, manufactured by Toyobo ■) ・・・・・・・・・
30 parts (Example 6) A thermal transfer recording medium was prepared in the same manner as in Example 1 except that the backing layer was formed using the backing layer coating composition ¥k (Vl) described below. Manufactured.

Backing...! 1■ Silicone resin (5P-2105, Dainichiseika ■W＞・・・・・・・・・
...40 parts fluororesin powder (V average particle diameter = 0.2 m, product name: LeBlon, manufactured by Daikin) ......
・・・・・・15 parts Nitrocellulose (Product name: Selva, manufactured by Asahi Kasei)・・・・・・・・・・・・
・・40 parts polyisocyanate compound (D-70, manufactured by Dainichiseika ■)・・・・・・・・・・・・
...5 parts (Comparative Example 5) A thermal transfer recording medium was produced in the same manner as in Example 5 except that the backing layer was formed using the backing layer coating composition (VI-1c) described below. .

-VT-IC Silicone resin (5P-2105, manufactured by Dainichiseika Co., Ltd.)...
...40 parts nitrocellulose (product name: Selva, manufactured by Asahi Kasei Mari) ......
・・55 parts polyisocyanate compound (D-70, large [manufactured by I Viscous ■)・・・・・・・・・・・・・
...5 parts (Comparative Example 6) A thermal transfer recording medium was produced in the same manner as in Example 5, except that the backing layer was formed using the parakink layer coating composition (Vl-2C) described below. did.

Harakink, surface roughness (VI-2C” fluororesin powder (average particle size = 0.2 m, product name: LeBron, manufactured by Daikin) ・・・・・・・・・
・・・・・・15 parts Nitrocellulose (Product name: T-Luba, manufactured by Asahi Kasei ■)・・・・・・・・・
...80 parts polyisocyanate compound (D-70, manufactured by Daio Seika ■)
...5 copies of the obtained thermal transfer recording medium were rolled with a diameter of 38 mm.
It was wound around a core in layers and housed in a cassette.

The obtained thermal transfer recording medium was transferred to a word processor thermal printer (prototype No. 2, manufactured by Konishiroku Photo Industry ■).
(24 dot real head, platen pressure: 200g
/head, applied energy: 38■J/to, rad, platen rubber hardness: :lO'), solid printing was performed on Subicabond paper with a smoothness of 10 seconds at a printing speed of 20cps, and a torque of 50g/c■ I rolled it up.

After the thermal transfer recording medium in the cassette is used up, the cassette is disassembled and the diameter of the wound thermal transfer recording medium is measured.

The results are shown in Table 2.

The meanings of the symbols in Table 2 are as follows.

◎・-・Less than 40mm ○・・・・・・40m- or more 42m■ Within the range of unskinned △・
...within the range of 42 + am or more and less than 44 cm x ・
・・・・・・44m The obtained thermal transfer recording medium was used for printing using the above apparatus. Separately, a thermal transfer recording medium manufactured under the same conditions was heated at 55°C. After storage for 24 hours, printing was performed under the same conditions to compare the printing quality of the two.

The results are shown in Table 2.

The meanings of the symbols in Table 2 are as follows.

Niece-j l Main seedling and side A ◎・・・ One dot is well reproduced with no difference in density between the two.

○: Some dots are missing on the thermal transfer recording medium after storage, but the print quality is almost good.

△... The thermal transfer recording medium after storage has some dots missing, and the print quality is poor.

×: Dots are missing or scratches appear on the thermal transfer recording medium after storage, and the print quality is significantly degraded.

90 m of the obtained thermal transfer recording medium was placed in a cassette,
100 rolls of this cassette were run using the above thermal printer. Fluctuations in running speed were visually observed.

L-　　L-Okatate'' ◎・・・・・・No change is observed in the running speed.

O: There is almost no change in the running speed.

Δ: There is no change in running speed or any decrease in printing performance.

X...The running speed fluctuates, and the print quality also fluctuates due to the fluctuation.

Stiffening The obtained thermal transfer recording medium was recorded (printed) under the same printing conditions as those used in the above evaluation of winding thickness, and the occurrence of sticking was evaluated.

The results are shown in Table 2.

The meanings of the symbols in Table 2 are as follows.

L-E Sticking C ◎・・・・・・・・・Sticking is not observed at all.

○...The thermal transfer recording medium may be slightly fused to the thermal head, but there is no noticeable difference in printability or running performance.

△・・・・・・Thermal △, The heat-sensitive transfer recording medium often adheres to the sheet, resulting in a decrease in runnability.

X: The thermal transfer recording medium is frequently fused to the thermal head, leading to a decrease in running performance and a decrease in printing performance.

(71) measured the friction coefficient of the backing layer surface of the thermal transfer recording medium.

The measurement results are listed in Table 2.

(Margin below) Table 2

Claims (8)

[Claims] (1) In a thermal transfer recording medium having a heat-sensitive transfer colorant layer on one side of a support and a backing layer on the other side of the support, the backing layer is a resin having a siloxane bond in the molecule. and/or a thermal transfer recording medium comprising a cured product of the resin and an organic powder. (2) The thermal transfer recording medium according to claim 1, wherein the content of organic powder in the backing layer is within the range of 0.1 to 50% by weight based on the total weight of the layer. (3) The thermal transfer recording medium according to claim 1 or 2, wherein the organic powder is a heat-resistant organic powder. (4) The thermal transfer recording medium according to claim 3, wherein the organic powder is a heat-resistant resin powder having slipperiness. (5) The thermal transfer recording medium according to claim 1, wherein the resin having a siloxane bond in the molecule is a modified polysiloxane resin or a silicone modified resin. (6) The thermal transfer recording medium according to claim 1, wherein the cured product of the resin having a siloxane bond in the molecule is a reaction cured product of a resin having a siloxane bond and a polyisocyanate compound. (7) The cured product of the resin component containing a resin having a siloxane bond in the molecule is a reaction cured product of a resin having a siloxane bond in the molecule, a cellulose derivative and/or a polyester resin, and a polyisocyanate compound. A thermal transfer recording medium according to claim 1. (8) The thermal transfer recording according to claim 1, wherein the content of the resin having a siloxane bond in the molecule or the cured product of the resin in the backing layer is 20% by weight or more of the total weight of the backing layer. Medium.