JPH01249386A - Thermosensitive transfer material - Google Patents

Abstract

PURPOSE:To form a non-repellent and uniformly strong coat and thereby eliminate back surface transfer of an ink layer without sticking by providing a protective layer consisting of a mixture of swelling inorganic stratified silicate, water-dispersant thermoplastic resin and organopolysiloxane of a specific weight ratio. CONSTITUTION:Swelling inorganic stratified silicate (a) is used as an inorganic coating component. In a protective layer, the silicate exists in the form of fine particles formed at least by partial interlayer separation using the swelling property. Water-soluble or water-dispersant thermoplastic resin (b) is thermoplastic resin which is dissolved, emulsified and suspended in water. Water-soluble or water-dispersant organopolysiloxane (c) is required to have a weight ratio of 1/20 to 5/1 for a/c and also 5/1 to 1/40 for a+c/b. This is because of an increase in coat fragility which is not desirable in terms of strength, if the weight ratio is larger than 5/1. If the weight ratio is smaller than 1/40, the sticking preventive effects are insufficient as an undesirable result.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermal transfer material, and particularly to a thermal transfer material suitable for use as a heat-melting type and a sublimation type thermal transfer ribbon.

[Prior Art] Conventionally, in a thermal transfer material having a transfer ink layer that melts or sublimates by heating on one side of a base H made of a plastic film, a vapor deposited layer is provided on the other side of the base material, Products with a heat-resistant protective layer made of thermosetting resin, or products with silicone oil, ethylene glycol, or surfactants added to thermosetting or heat-resistant resin, silicone and water-based polymers that dissolve or disperse in water. and/
Alternatively, those provided with a protective layer made of a reactive low molecular weight substance have been known.

[Problems to be Solved by the Invention] However, in the case of products with a vapor-deposited layer, the metal vapor deposition is a batch process, so the cost is inevitably high, and if it is thick enough to be effective in preventing sticking, the thermal conductivity will be poor. The drawback is that the resolution deteriorates due to the large size and increased heat diffusion.

On the other hand, those coated with a thermosetting resin or a heat-resistant resin do not cause sticking, but have the disadvantage that their slipperiness deteriorates to varying degrees as the temperature rises. Attempts have been made to add inorganic lubricants to improve this drawback, but in this case, the surface becomes too rough, resulting in poor adhesion to the heating head or poor heat transfer efficiency. There was a drawback.

On the other hand, when silicone oil, ethylene glycol, or surfactants are added to thermosetting or heat-resistant resins, the additives may diffuse and stain the dryer, or the coating film may be damaged over time. There was a drawback that slight differences in drying conditions could greatly change the way additives oozed out onto the surface. Also, in the case of silicone that dissolves and disperses in water and water-based polymers, coatings made of silicone will cause repellency, which will significantly worsen the appearance, and the repellency will cause sticking and deteriorate running performance. There were some drawbacks. Further, when a known surfactant 01 is used to improve this problem, disadvantages such as a decrease in coating film strength and back transfer of the ink layer occur.

The object of the present invention is to avoid the above-mentioned drawbacks, that is, to form a uniform coating film that does not repel even when using silicone that dissolves and disperses in water, and to prevent sticking and oozing of additives over time. Our goal is to provide a thermal transfer material (!-) that does not change and at the same time has excellent coating strength without volatilization of additives during the drying process, and is suitable for thermal transfer ribbons with no backside transfer of the ink layer. .

[Means for Solving the Problems] The present invention provides a biaxially oriented polynisder film with an in-layer that melts or blooms on one side and a protective layer on the other side. In the thermal transfer material, the protective layer is made of (a) a swellable inorganic layered silicate, (b) a water-soluble or water-dispersible thermoplastic resin, and (c) a water-soluble or water-dispersible Δlucanobolysiloxane. The l ratio [1)/(c) of (a) and (c) is from 1/20 to 5/1, and the weight ratio of (a)+(c)/(b) is from 5/1 to 1/
The core of the thermal transfer material is a layer obtained from a mixture of No. 40 and No. 40.

A biaxially oriented polyester film is used as the substrate of the thermal transfer material of the present invention, and polyester here is a general term for polymers having ester bonds as the main bond chain of the main chain. are polyethylene phthalate, polyethylene 2,6-naphthalate, and polyethylene α.

β-bis(2-chlorophenoxy)ethane 4,4°-dicarboxylate, poly-1-burene terephthalate, etc. Among these, polyethylene terephthalate is the most preferable from a comprehensive consideration of quality, operability, etc. . Therefore, hereinafter, we will proceed with the description using polyethylene terephthalate as a representative polyester.

Polyethylene terephthalate 1 to (hereinafter referred to as 41) in the present invention
(abbreviated as PET) is one in which 80 mol% or more, preferably 90 mol% or more, more preferably 95-[ru% or more] of ethylene terephthalate as a repeating unit, but within this limited amount range. , a part of the acid component and/or glycol component may be replaced with a third component as described below.

-Acid component- Isophthalic acid, 2,6-)-phthalene dicarboxylic acid, 1
．． 5-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4°-Schiffyl dicarboxylic acid, 4
゜4°-diphenylsulfonedicarboxylic acid, 4,4°-
Diphenyl ether dicarboxythoxybenzoic acid, adipic acid, azelaic acid, cepatic acid, hexahydroterephthalic acid, 1-nahydroisophthalic acid, ε-oxycaproic acid, trimellitic acid, trimesic acid, pyromellitic acid, α , β-bisphenoxyethane-4,4°-dicarboxylic acid, α,β-bis(2-chlorophenoxy)ethane-4,4°-dicarboxylic acid, 5-sodium sulfoisophthalic acid monoglycol component- propylene glycol, Dilene glycol, dinamelene glycol, decamethylene glycol, neopentyl glycol, 1,1-cyclohexane dimetatool, 1,4-cyclohexane dimethanol, 2,2-
Bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, diethylene glycol, triethylene glycol, pentaerythritol, trimethylolpropane, polyethylene glycol, etc.

PET also contains known additives, such as heat stabilizers, oxidation stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, and fillers. , a mold release agent, an antistatic agent, a nucleating agent, etc. may be added. The intrinsic viscosity of PET as described above (measured in orthochlorophenol at 25°C) is between 0.40 and 1.20.
, preferably 0.50 to 0.80, more preferably 0.
*b in the range of 55 to 0y75dl/u is suitable for the content of the present invention.

Next, the biaxially oriented polyester film as used in the present invention refers to a polyester sheet or film in an unstretched state.
2 in each of the so-called biaxial directions, the longitudinal direction and the width direction.
It is made by stretching about 5 to 5 times, and shows a biaxial orientation pattern in wide-angle X-ray diffraction.

The average surface roughness of this film is not particularly limited, but is 0.
04-0.4μm, preferably 0.05-0.30μm
It is desirable that =b is more preferably 0.06 to 0.25 μm.

The film thickness is usually 0.5 to 40 μm, preferably 1 μm to 8 μm.

When using a composite film, the number of layers or the method is not particularly limited, but it is possible to composite it by a composite extrusion method, an extrusion lamination method on a base film, a lamination method using various adhesives, etc. It's normal.

The melting or sublimating transfer ink constituting the transfer ink layer provided on one surface of the biaxially oriented polynisder film is also not particularly limited, and any known transfer ink may be used as appropriate. The heat-melting ink includes (1) wax with an appropriate melting point such as paraffin wax, microcrystalline wax, carnauba wax, (2) pigment, (3)
) The main ingredient is a softener such as oil, with various additives added as necessary. 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, as sublimable dyes, conventionally known sublimable bundles 1,
For example) iikenton Po1yester Ye
low-Y L (Made by Sangatsu Buntatsu, C, 1, Disper
s Yellow-42>, niayaset Yellow
low-G (Nippon Kayaku, C, 1, Dispers
Yellow-77), PTY-52 <Mitsubishi Kasei, C, I.

5olvent Yellow 4-1 > 9M1
kenton Poyester Red BSF (Mitsui Toatsu, C, 1, Dispers Red 111),
Niyaset Red B (Nippon Kayaku Co., Ltd., C, 1,
DiSpers Red B), PTR-54 (manufactured by Mitsubishi Kasei, C, 1, [)ispers Red50
), )Iikenton Poyester B
lue )” BL (Mitsui Toatsu, c, 1.[) ispe
rs Blue56), PTB-67 (Mitsubishi Kasei, C,1, Dispers Blue241>,
Kayaset Blue9 Q 5 (Nippon Kayaku, C, 1, S.

Event 112> etc. are given as a representative example.

As the binder resin for supporting the sublimable bundle 1 as described above, any conventionally known binder resin can be used, and preferred examples include ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, Cellulose resins such as cellulose acetate and cellulose acetate, vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinylpyrrolidone, and polyacrylamide, and polyesters are preferred from the viewpoint of heat resistance, dye migration, etc. be. Note that a release layer for preventing adhesion may be further applied to the surface of this sublimable coloring material layer.

The thickness of these heat-fusible and sublimable ink layers is not particularly limited, but is usually 0.1 to 15 μm, preferably 1 to 15 μm.
It is 8 μm.

The essence of the present invention is to use a swellable inorganic layered silicate as an inorganic coating component. Here, the term "swellable" refers to an inorganic layered silicate that has the property of "swelling" by coordinating water between the layers, and the coating layer of the coating film of the present invention utilizes this swelling property to at least partially It essentially exists in the form of yi fine particles formed by interlayer separation. In the swellable inorganic layered silicate 04 used in the present invention, the ratio of 3i to O of the tetrahedron is theoretical -[2;5 phyllokey r! It is an i-salt and has a crystal structure in which the crystal unit cell is repeated in the thickness direction, and a typical example thereof can be expressed by one chemical formula as follows.

Wo, 3~1.1 ×1.8~3.2 (S'3.5
~4.5010>21.8~2.2 Here, W: interlayer ion, one or more cationic ions X: ion at octahedral position, part of M02+ or M2+ q is 1 i + , F e 2+, Ni2+,
Mn.

An ion substituted with at least one ion selected from the group consisting of 2+AQ3+ and F3+.

0: Oxygen Z: One or two ions selected from F- or OH- Furthermore, in the present invention, Si4+ at the above-mentioned tetrahedral position is Qe34+, or a part of these is AQ, Fe'', The swollen 1/1 layered silicate according to the present invention also includes those purchased from J4 or the like.

Specific examples of these include natural products such as -[N Shichiri Fire I1~, Vermiculite I-, etc.] Tetrasilisic mica, taeniolite, and heta which are synthesized by melting or hydrothermally using the general formula 'Ii'. 1 ~ Rai! There are viscosity-based and mica-based minerals such as compounds such as ~.

Synthetic materials are particularly preferred because they have few impurities and have a uniform composition, resulting in uniform crystals.Among these, synthetic materials are preferred because they have excellent crystal flatness and large crystal size. Wx-0,1~x+0.1 2.8-x~3.2-x
LiXg (Si3.5~4.0010) "1.8~2.0 or Wx-0,1~x+0.1"g2.8-x~3.2-
x”X(Si3.5~.0O10) (OH)
1.3 to 2.0 (however, x is preferably 0.8 to 1.2). In addition, the interlayer ion W is not particularly limited as long as it is one or more cationic ions, but
Examples of force diionic ions include L i + , N a
+, /R2" R1-N-R3 (However, R1 is an alkyl group with 3 or more carbon atoms\R4 50 or less, R2-R4 is hydrogen or 1 carbon number
~10 alkyl groups), K+, or MC1, Ca
, alkaline earth metals such as Ba, and AQ. Among them, since the dispersibility in water is particularly good, y R2 "Rt-N-R3 or li+ accounts for 40% or more, preferably 60% or more, more preferably 80% or more and 90% of the interlayer ion\R4. It is preferable that the number of occupies is less than or equal to

The size of the swellable inorganic layered silicate is not particularly limited, but the average particle size measured by a sedimentation method is 0.05 μm to 1.0 μm.
A thickness in the range of 5 μm, preferably 0.1 μm to 8 μm, more preferably 0.15 μm to 3 μm is preferred because a uniform layer can be formed. Also, 50% of all particles,
Preferably 80%, more preferably 90% of the thickness is 80%.
0 Å or less, preferably 400 Å or less, more preferably 1
A thickness of 00 Å or less is more preferable because the surface of the coating layer becomes smooth. The thickness herein refers to the thickness of inorganic particles present in the cross section of the coding layer of the coating film.

The water-soluble or water-dispersible organopolysiloxane used in the present invention refers to those represented by the following general formulas (a) to (c).

? H3 -s r -R<c) Crystal [where X, Y and Z are integers of 1 to 5000, R is an alkyl group or hydroxyl group having 1 to 100 carbon atoms, Ro is an alkylene group or phenylene group having 1 to 10 carbon atoms , 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, water 1m, mercapto group,
One selected from a polyoxyalkylene group, an alkyl group containing a halogen, Ro゛ indicates one selected from an alkyl group having 1 to 100 carbon atoms, a polyoxyalkylene group, water MjA, and an alkyl group containing a halogen. . ] Specific examples include dimethylpolysiloxane oil, amine-modified silicone oil, amino-polyether-modified silicone oil, epoxy-modified silicone oil, and epoxy-modified silicone oil.
Polyether modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, alkyl and alkyl/aralkyl modified silicone oil, alkylφ
Examples include aralkyl/polyether-modified silicone oil, fluorine-modified silicone oil, alkyl/higher alcohol ester-modified silicone oil, methylhydrogen 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, amine/polyether-modified silicone oil, alcohol-modified silicone in terms of anti-sticking and noise prevention properties. Oils and emulsions thereof are preferred. Further, two or more of these may be mixed and used in any ratio. Additionally, a known crosslinking agent that reacts with the reactive group of the silicone oil may be used in combination.

The organopolysiloxane suitable for the present invention has a viscosity of 100 centistokes (hereinafter centistokes is abbreviated as C-8) or more and 5 million C-8 or less when measured at 25°C, preferably 500 C·S or more and 3 million centistokes or more. Those of C-8 or lower are preferred.

The water-soluble or water-dispersible thermoplastic resin (c
) refers to thermoplastic resins that are dissolved, emulsified, or suspended in water, other than organopolysiloxane. Examples of such thermoplastic resins include cellulose derivatives, gelatin, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, urethane resins, acrylic resins, ether resins, ester resins, olefin resins, and modified products thereof. Examples include resins that dissolve, emulsify, and suspend. In particular, those having good adhesion to polyester films are preferred, and for example, urethane resins, acrylic resins, and ester resins are preferably used.

The urethane resin is composed of polyols, polyisocyanates, chain extenders, etc., and is dissolved, emulsified, or suspended in water by introducing hydrophilic groups into the constituent components.

Also, a blocking agent for unreacted isocyanate of polyurethane,
For example, Chongya tiffi! sodium, ethyleneimine,
A method of blocking with ε-caprolactam, methyl ethyl ketoxime, etc. or dispersing in water can also be used.

The acrylic threads forming the acrylic resin include alkyl acrylate, alkyl methacrylate (alkyl groups include methyl group, ethyl group, n-propyl group,
(isobutyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.), acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid , β-unsaturated carboxylic acids having one or two carboxyl groups such as fumaric acid or their metal salts, an[nium salts], vinyl-substituted aromatic hydrocarbons such as styrene and α-edylsdyrene, acryloni α,β-unsaturated aliphatic nitriles such as tolyl and methacrylate, organic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride and vinylidene chloride, acrylamide, methacrylamide, N −
α,β-unsaturated carboxylic acid amides such as methyl-xyacrylamide, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate-1 and other α,β-unsaturated carboxylic acids. Examples include aminoalkyl esters of α,β-unsaturated carboxylic acids of polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and the like. One or two of the above monomers
Although it can be copolymerized using more than one species, it has functional groups such as hydrophilicity, water dispersibility, and adhesion to the base polyester film, such as a water base, an amide group, a carboxyl group, or a salt thereof. Preferably.

The ester resin is one obtained by polycondensing a dicarboxylic acid and a glycol component and is not particularly limited, but specific examples include the following.

The dicarboxylic acid component includes aromatic and aliphatic H1 alicyclic dicarboxylic acids, such as prephthalic acid, isophthalic acid,
Orthophthalic acid, 2.6-naphthalene dicarboxylic acid, adipic acid, zebacic acid, uccinic acid, glutaric acid, 1,3
-cyclopentadicarboxylic acid, dodecanedicarboxylic acid,
Abiraic acid and the like can be mentioned. In order to impart water solubility or water dispersibility, it is effective to use a dicarboxylic acid containing a sulfonic acid metal base as a copolymerization component.

For example, sulfoterephthalic acid, 5-sulfoisophthalic acid,
4-sulfoisophthalic acid, 4-sulfonaphthalene 2.7
-dicarboxylic acid, and metal salts such as 5[4-sulfophenonicy]isophthalic acid.

The glycol component to be reacted with the dicarboxylic acid component mentioned above is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms, and specific examples include ethylene glycol and 1,2-propylene glycol. ,1
．． 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hekylenediol,
These include 1,2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, 1,4-cyclohexane dimetatool, xylylene glycol, diethylene glycol, triethylene glycol, and the like. Polyethylene glycol, polypropylene glycol, or polytetramethylene glycol may be used as part of these glycol components. The polyester resin obtained from the above dicarboxylic acid and glycol components is used after being dissolved or dispersed in water.

In the present invention, the ff1ffi ratio (a
)/(c) is required to be 1/20 to 5/1.

If it is less than 1/20, the effects mentioned in the present invention will not be noticeable, which is not preferable, while if it is larger than 5/1, the coating layer will become brittle, which is not preferable.

When the weight ratio (a)/(c) is 115 to 1/1, the effects described in the present invention and the strength of the coating film are well balanced, and this is particularly preferred.

In addition, in the present invention, the above blending ratios (a) 1 and J, and (c
) d compound (a) + weight ratio of (c) and (b) (a) +
(c) /(b) must be 5/1 to 1/40.

If it is larger than 5/1, the strength of the coating film becomes brittle, which is not preferable, and if it is smaller than 1/40, the anti-sticking effect is not sufficient, which is not preferable. Weight ratio (
When a)+(c)/(b) is 1./1 to 1/10, the quality is well balanced and is particularly preferred.

The thickness of the protective layer in the present invention is not particularly limited, but it is usually in the range of 0.01 to 5 μm, preferably 0.02 to 1 μm, and more preferably 0.03 to 0.5 μm. In addition, the protective layer may contain known additives such as heat resistant agents, weather resistant agents, coloring agents, etc. within the range that does not impede the effects of the present invention.
Organic lubricants, surfactants, antistatic agents, etc. may be added.

Next, a typical method for manufacturing a thermal transfer material of the present invention will be described, but the present invention is not limited thereto. First, a biaxially oriented polyester film to be used as a base material is prepared. 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. Mix (a), (b), and (c) in a predetermined ratio on the film, add various additives as necessary, and apply a mixture using known methods such as gravure coating, reverse coating, and spray coating. After coating, 60℃~2
Dry at 50°C for about 1SeC to 15 minutes. In this case, the solvent is not particularly limited, but usually water, alcohol, or a mixture of water and alcohol is used. Next, the opposite side is coated with heat-melting or sublimation ink using the same method, and 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 separately formed and then laminated, but since the strength of the coating layer is somewhat insufficient, it is preferable to coat the coating layer directly onto the base film. The transfer ink layer can be coated by a known method such as barcode coating, reverse coating, gravure coating, etc., regardless of whether before or after the anti-sticking layer is coated.

Furthermore, since the base film is two-wheel stretched, it can be applied during the manufacturing process. Specifically, a coating layer is applied to at least one side of the film after being stretched in one direction, and after drying or while drying, the film is stretched in the right angle direction. In this method, the film is eroded and heat treated, or the film is stretched in the perpendicular direction, then re-stretched in the one direction and then heat treated.

In this way, when coating 15 during the film manufacturing process, coating 1
5. Since it is possible to set the drying temperature higher than in normal cases, it is possible to apply and dry at high speed, and by stretching, the swellable inorganic layered silicate in the coating film comes into contact with the film surface. Since they are oriented substantially parallel to each other, the volatilization prevention effect described in the present invention is more clearly exhibited, which is preferable.

[Effect of the invention] In the present invention, a swellable inorganic layered silicate! The use of salt made it possible to obtain the following effects.

(1) As a result of being able to significantly raise the oil volatilization temperature, A. It became possible to raise the temperature at which drying and heat treatment were performed, improving productivity.

B. The drying zone becomes clean because less oil evaporates.

(2) Even if the film is left in a roll, transfer to the back side is reduced, so the adhesion of the thermal transfer layer to the base paper is improved.

(3) The protective layer containing water-soluble and water-dispersible silicone was made into a uniform coating film without repelling without using a surfactant, which prevents sticking that occurs in uncoated areas due to repelling. This resulted in a coating film with excellent strength and no backside transfer of the ink layer.

Since the thermal transfer material of the present invention has the above-mentioned excellent effects,
It is suitable for use in word processors, facsimiles, personal computer printers, video printers, barcode ticket machines, label printers, typewriters, computer graphics, plain paper copiers, etc. for printing out characters or images.

[Method for evaluating properties and effects] (1) Film-forming property The coating property of the protective layer coating (repellency with an average diameter of 1 mm or more) was visually counted and judged according to the following criteria. The number of sea breams is 1 or less 7.2 is excellent, 2 to 5 pieces/m2
Good, 6 to 10 pieces/lT12, 11 or more pieces/W12
If it was good or better, there was no problem with sticking and it was considered to be a pass.

2) Sticking property and noise during running Evaluations were conducted using the line printer and sublimation printer shown below.

(a) Line type printer: A Mitsubishi Line Thermal Color Printer Model 0500F-10 was used to run and print at an applied voltage of 17V.

As a heat-melt transfer layer, the following composition was applied using a hot-melt coater to a thickness of 4 μm on the opposite side of the base film to the side on which the protective layer was provided.

Carnauba wax 100 parts Microcrystalline wax 30 parts Vinyl acetate-ethylene copolymer 15 parts FFI Carbon black
20Φ section (b) Transfer was performed using a sublimation printer: Sharp Color Video Printer GZ-PI 1 at an applied voltage of 14V.

As a sublimation type ink layer, the following composition was applied using a gravure coater to a thickness of 4 μm on the surface of the base film opposite to the protective layer.

Kayaset Blue 14 4 parts by weight (manufactured by Nippon Kayaku) Ethyl hydroxycellulose 6 parts by weight Methyl ethyl ketone 45 parts by weight Toluene
45 Market Department The above evaluations (a) and (b) were determined based on the following criteria.

(B) Anti-sticking properties ◎: Running is stable with no sticking at all.

O: Hardly any sticking.

△: Slight sticking occurs.

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

(b) Noise when driving ◎: Significantly small.

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

Δ: There is a very unpleasant noise.

X: The noise is extremely loud.

(3) Adhesion to the base film The anti-sticking layer is peeled off for 90' using a commercially available cellophane adhesive tape (manufactured by Chiban ■), and the area of the anti-sticking layer adhering to the cellophane tape after peeling is less than 20%: ○, 20
% or more and less than 50% is Δ, and 50% or more is X.

(4) Protective layer coating strength The protective layer surface of the thermal transfer material and the glass surface are overlapped and the load is 1k.
1401” at g, t), friction rotation for 5 minutes at 111 gt
The degree of abrasion of the coating film after drying was determined by the amount of abrasions adhering to the glass surface.

◎: No deposits at all.

O: Slight adhesion is observed.

△: More than 20% of the dry area has "excessive scrapes".

X: Over 50% of the IfllQ section has been scraped off.

(5) Improving the volatility of silicone Using TG-30M manufactured by Shimadzu Corporation, heat a given organopolysiloxane in air at a heating rate of 10'C/min.
The temperature at which % thermal weight loss occurs - "1" was measured.The increase in T1 for a given organopolysiloxane is 20°C or more and 40°C.
If it is less than ℃, [01, If it is 40℃ or more, [
◎], while if the temperature did not reach 20°C, it was rated 8 [x].

(6) Transfer to the inking surface The protective layer surface of the base film and the surface to be inked are overlapped and treated at 40°C, 85% RH under a load of 11 (g) for 48 hours, and the surface wetting tension of the surface to be inked is ASTM-
Judgment was made according to D-2578-67. If the surface wetting tension is 38 dyne/cm or more [◎1.34 dyne/cm]
/ cm or more and less than 38 dyne/cm [○], 3
Less than 4 dyne/cm and 32 tiyne/cm or more were determined as [Δ], and less than 32 c+dyne/cm was determined as [X].

(7) Rear transfer of ink layer A biaxially oriented polyester film with a protective layer provided on one side is provided with the transfer ink layer described above on the other side, and the protective layer surface and the ink layer surface are overlapped and 40 ℃85%
The ink layer was left in an RH atmosphere for 48 hours, and the degree of transfer of the ink layer to the surface of the protective layer was observed using an optical microscope with a magnification of 200 times, and evaluated using the following evaluation criteria. Those that do not allow transcription at all [
◎], cases where almost no transfer was observed were evaluated as [0], cases where clear transfer was observed in spots were evaluated as [△], and cases where transfer was significant were evaluated as [X].

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

Examples 1 to 7, Comparative Examples 1 to 4 Precipitated particles with a particle size of 0.5 to 1.5 μm (particles precipitated during polymerization) were mixed at 0.15 ui% and the average particle size was 1.5 μm.
Polyethylene terephthalate pellets (intrinsic viscosity 0.65 d
l/g) was dried in a vacuum at 180°C for 5 hours, then fed to an extruder, melted at 285°C, extruded into a sheet from a T-shaped nozzle, and wound around a cooling drum with a surface temperature of 50°C. The mixture was cooled and solidified. After this sheet was stretched 3.5 times in the longitudinal direction at approximately 95° C., one side of the film was subjected to corona discharge treatment in a carbon dioxide atmosphere, and the following composition A was coated on this G11 surface using a rod coating method. was applied at a concentration of 5%. This film was stretched 3.5 times in the width direction while drying at 110°C, and then subjected to tension heat treatment at 210°C for 10 seconds. The thickness obtained in this way was 6.5 μm,
A heat-melting ink layer or a sublimation ink layer with a thickness of about 4 μm was provided on a two-wheel stretched polyester film with a coating thickness of 0.2 μm, and 1 q of heat-sensitive transfer material was applied. The obtained thermal transfer material was evaluated as shown in the table.

Aiming Spring A (a) WMQ2 L i (S i 4010) F
2 (However, WG, tcHt - (cH2) 3 NH!
+) (b) 15-sulfoisophthalate terephthalate jlt
Polyester copolymer with intrinsic viscosity 0.65 dl/(l) consisting of Na (85/15 mol%) and ethylene glycol (c) Amino-polyether modified silicone oil (
Viscosity 1000 centistokes at 25°C measured with a B-type viscometer, amino acid content No. 5 wt%) Just a
), (b) and (c) are shown in the table. (a)
In the combined use system of (a) and (c), a mixture of (a) and (c) at 80° C. was used.

As shown in the table, excellent properties were exhibited only within the range of the present invention.

Comparative Example 5 A nonionic surfactant (polyoxyethylene stearyl ether, H
Example using the same composition except that LB15) was added to the coating solution at a concentration of 0.5%
In the same manner as above, a protective layer having the composition ratio shown in the table was formed and inked to prepare a heat-sensitive transfer material. Although the coating film forming properties of this thermal transfer material were improved by the use of a surfactant, the transfer properties to the ink surface and the back transfer properties of the ink layer were poor.

Claims (1)

[Claims] A heat-sensitive transfer material in which an ink layer that melts or sublimates upon heating is provided on one surface of a biaxially oriented polyester film, and a protective layer is provided on the other surface, the protective layer comprising (a) a swellable inorganic layered silicic acid; salt, (b) a water-soluble or water-dispersible thermoplastic resin, and (c) a water-soluble or water-dispersible organopolysiloxane, and the weight ratio (a)/(c) of (a) and (c) is 1. /20 to 5/1, and (a)
A thermal transfer material characterized in that the layer is obtained from a mixture having a weight ratio of +(c)/(b) of 5/1 to 1/40.