JP3002520B2 - Sublimation type thermal transfer body - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sublimation type thermal transfer member, and more particularly to a sublimation type thermal transfer member suitable for a speed difference mode method.

[Related Art] Conventionally, the following proposal has been made as a sublimation type thermal transfer member used in a speed difference mode method.

(1) A transfer member having a reactant composed of two or more reactive silicone oils having a reactive functional group on the surface of an ink layer (JP-A-2-2073).

(2) A transfer member having a reaction product of a resin having a reactive functional group and a linear hydrocarbon derivative having 12 or more carbon atoms
2078).

(3) A transfer body wherein the water-soluble or water-dispersible resin on the surface of the ink layer is a polymer compound containing a portion having a polydimethylsiloxane structure (JP-A-2-95888).

However, in the transfer body of the above (1), the silicone oil has no binder curing action, so that the ink layer is destroyed when the applied energy is high, and the storage stability of the ribbon is reduced due to the presence of unreacted oil. Is a disadvantage.

The transfer body (2) has no resin curing effect due to the linear hydrocarbon, and has the same disadvantages as the above (1).

(3) Since the solubility of the sublimable dye in water is small,
No sublimable dye is contained in the upper layer, which causes a problem of sensitivity reduction.

[Problem to be Solved by the Invention] The present invention solves the above-mentioned problems of the prior art, prevents sticking in the speed difference mode method, provides a transfer member that can be used many times without a decrease in sensitivity. What you want to do.

[Means for Solving the Problems] A configuration of the present invention for solving the above problems is a sublimation-type thermal transfer member described in the claims.

That is, the dye transfer contributing layer is a transfer body containing a reaction product of a water-insoluble resin having active hydrogen and a hydrolysis product of a silane coupling agent.

The relationship between the configuration of the sublimation-type thermal transfer member of the present invention and the operation thereof is as follows.

The laminate of the dye transfer contributing layer and the dye supply layer is a transfer body having multi-function.

(Japan Hard Copy '89 P205-P208) Since the contributing layer is a water-insoluble resin (soluble in organic solvent), an organic solvent with good solubility of sublimable dye is used as the ink solvent for the contributing layer. By ensuring the dye concentration in the inside, the sensitivity does not decrease.

By the crosslinking reaction between the hydrolysis product of the silane coupling agent and the active hydrogen of the resin, (i) the presence of the hydrolysis product of the silane coupling agent lowers the surface energy and provides lubricity.

(Ii) By the crosslinking reaction between the two, the contribution layer binder is cured, and the heat resistance, strength and the like are improved.

In addition, because this decomposition product has a three-dimensional structure,
The lubricity is improved by increasing the lubricating group ratio, and the degree of curing is increased by increasing the crosslink density.

As described above, the hydrolysis product of the silane coupling agent plays two roles of a lubricant and a curing agent, and further, the crosslinking with the resin causes a reduction in ribbon preservability due to instability of the conventional lubricant itself in the ink layer. Does not occur.

Next, the relationship between the dye transfer contributing layer and the dye supply layer will be described.

Means for facilitating the diffusion and supply of the sublimable dye from the dye supply layer to the transfer initiating layer include: I. a relation of the dye supply layer> the transfer contributing layer with respect to the dye concentration, and / or II. Regarding the diffusion coefficient in the inside, there is a means to make the relationship of the dye supply layer> the transfer contributing layer.
Further, as a specific method of operating the diffusion coefficient with respect to the above II, for example, Toyoko Sakai et al., Journal of the Textile Society of Japan Vol. 30, No. 12 (197
4); Norihiko Kuroki, “Dyeing Theory Chemistry,” published by Maki Shoten, p.503-
It is introduced in the 1st non-impact printing technology symposium paper collection 3-5. With reference to these, specific methods for realizing the above-mentioned means II include, for example, (1) Since the diffusion coefficient is affected by the energy suppression effect on dye diffusion due to hydrogen bonding between the dye and the organic binder, etc. A method of using an organic polymer material having a large number of proton-supplying groups or proton-accepting groups that are easily hydrogen-bonded to a sublimable dye as a binder of the transfer contributing layer. (2) The diffusion coefficient is such that the dye is dispersed. The organic binder has a glass transition or softening temperature dependency, and the lower the glass transition or softening temperature of the layer during printing in this process, the larger the diffusion coefficient becomes, and thus the organic binder in the dye supply layer. A method of using a substance having a lower glass transition temperature or a lower softening temperature than that of the transfer contributing layer as the agent; (3) having a compatibility with at least one organic binder in the dye supply layer, and A method in which a plasticizer incompatible with all the organic binders therein is contained in the dye supply layer; (4) a method in which the above methods (1), (2) and (3) are appropriately combined. However, it is needless to say that the method is not limited to these methods as long as the above relationship of the diffusion coefficient is satisfied.

The means I and / or II are useful in designing the material formulation of the dye supply layer and the transfer contributing layer in the present invention, and it is easy to confirm whether or not the intended improvement is realized by these effects. As a method, the same amount of coating is formed as a single layer on a substrate in each of the prescriptions of the dye supply layer and the transfer contributing layer, and each is superimposed on a separate image receiving layer.
There is a method of selecting each layer such that when a constant sublimation temperature is applied, the sublimation transfer amount satisfies the relationship of dye supply layer> transfer layer.

Next, the thickness of the transfer contributing layer is generally 0.05 to 5 μm,
Preferably it is 0.1 to 2 μm. The thickness of the dye supply layer is generally 0.1 to 20 μm, preferably 0.5 to 10 μm.

Known sublimable dyes, binders and the like used in the transfer contributing layer and the dye supply layer of the present invention can be used.

The sublimable dye is a dye that sublimates or vaporizes at 60 ° C. or higher, and may be any dye that is mainly used in thermal transfer printing such as disperse dyes and oil-soluble dyes.For example, CI Disperse Yellow 1,3,8 , 9,16,41,54,60,77,116 etc., CI
1,4,6,11,15,17,55,59,60,73,83
Such as CI Disperse Blue 3,14,19,26,56,60,64,
72,99,108, CI Solvent Yellow 77,116, CI Solvent Red 23,25,27, CI Solvent Blue 36,83,105, etc. It can also be used.

Thermoplastic or thermosetting resin is used for the binder used in the dye supply layer, and among the resins having relatively high glass transition point or high softening property, for example, vinyl chloride resin, vinyl acetate resin, Polyamide, polyethylene,
Examples include polycarbonate, polystyrene, polypropylene, acrylic resin, phenol resin, polyester, polyurethane, epoxy resin, silicone resin, fluorine resin, butyral resin, melamine resin, natural rubber, synthetic rubber, polyvinyl alcohol, and cellulose resin.

These resins can be used alone, but several kinds may be mixed or a copolymer may be used.

Further, when making a difference with respect to the glass transition or softening temperature between the dye transfer contributing layer and the dye supply layer, a resin or a natural or synthetic rubber having a glass transition temperature of 0 ° C. or less, or a softening temperature of 60 ° C. or less is preferable. Include syndiotactic 1,2-polybutadiene (commercially available as JSR RB810,820,830 Nippon Synthetic Rubber); olefin copolymers and terpolymers containing acid or non-acidic acid (commercially available as Dexon XEA-7, Dexon Chemical); Ethylene-vinyl acetate copolymer (400 & 400A, 405, 43 as commercial products)
0, Allied Fibers &Plastics; P-3
307 (EV150), p-2807 (EV250), DuPont Mitsui Polychemical); low molecular weight polyolefin polyol and its derivatives (commercially available products: Polytail H, HE Mitsubishi Kasei Kogyo; brominated epoxy resin (YDB-340,400,500,600 Toto Kagaku)) Novolak type epoxy resin (YDCN-701,702,70)
3 Toto Chemical); Thermoplastic acrylic solution (Tynalnal LR1075,1080,1081,1082,1063,1079 Mitsubishi Rayon); Thermoplastic acrylic emulsion (LX-400, LX-45)
0 Mitsubishi Rayon); Polyethylene oxide (Alcox E-30,45, Alcox R-150,400,1000 Meisei Chemical); Caprolactone polyol (Placcel H-)
1,4,7, Daicel Chemical Industries) and the like, and in particular, polyethylene oxide and polycaprolactone polyol are practically useful, and the thermoplastic or thermosetting resin described above and one or more of the above It is preferable to use it in a mixed form.

The dye concentration of the transfer contributing layer is usually 5 to 80%, preferably 10 to 80%.
About 60%.

The dye concentration of the dye supply layer is preferably from 5 to 80%, but when a dye concentration gradient is provided between the dye transfer contributing layer and the dye supply layer, the dye concentration is 1.1 to 1.0%. It is desirably 5 times, preferably 1.5 to 3 times.

In order to stably supply the dye for a long time and maintain good printing characteristics, the dye supply layer preferably contains at least an undissolved particulate sublimable dye. Here, the undissolved particulate dye means a dye which is not completely dissolved in the organic binder after application and drying of the ink (organic binder + sublimator dye + solvent) at the time of forming the ink layer, and which precipitates as particles. However, the presence of the undissolved particulate dye differs depending on the solvent even with the same binder and dye. The presence or absence of the undissolved particulate dye can be easily identified by an electron microscope after forming the dye supply layer. The particle size of the undissolved particulate dye varies depending on the layer thickness of the dye supply layer,
It is from 01 μm to 20 μm, preferably from 1.0 μm to 5 μm.

Further, the dye state in the dye transfer contributing layer is that it is dispersed in a monomolecular state which actually contributes to the transfer, preventing the occurrence of transfer density unevenness and the dye concentration between the dye supply layer and the dye transfer contributing layer. It is desirable to keep the gradient stable.

As the base sheet, a film such as a condenser paper, a polyester film, a polystyrene film, a polysulfone film, a polyimide film, or a polyamide film is used. Between the base sheet and the dye supply layer, if necessary, a conventional adhesive layer is used. A conventional heat-resistant lubricating layer may be provided on the back surface of the base sheet, if necessary.

So far, an example in which the dye layer is divided into two layers has been described. However, if an appropriate difference in dye transfer amount is generated and the function separation intended by the present invention can be achieved, the dye layer can be formed into a multilayer of two or more layers. It is.

Although the above description has been made with reference to a recording method using a thermal head, the transfer medium of the present invention is a recording method in which recording heat energy is applied by a method other than the thermal head, for example, a thermal printing plate, a laser beam, or It can also be used for a method using Joule heat generated in a medium such as a substrate. Among them, using Joule heat generated in the medium,
The so-called energized thermal transfer method is best known, for example, U.S. Patent No. 4,103,066, JP-A-57-14060, JP-A-57-11
080 or JP-A-59-9096.

When used in the current transfer method, as a substrate, a resin such as polyester, polycarbonate, triacetylcellulose, polyamide, polyimide, or aromatic polyamide having relatively high heat resistance, aluminum, copper, iron, tin, zinc, nickel, Metal powders such as molybdenum and silver and / or conductive powders such as carbon black are dispersed to adjust the resistance to an intermediate value between insulators and good conductors. Alternatively, a sputtered material may be used. The thickness of these substrates is desirably about 2 to 15 μ in consideration of Joule heat conduction efficiency.

In the case of using the laser light transfer method, a material that absorbs laser light and generates heat may be selected as the substrate. For example, a conventional thermal transfer film containing a light-absorbing heat converting material such as carbon or an absorbing layer formed on the front and back surfaces of a substrate is used.

Examples of the binder for the contributing layer include water-insoluble resins having active hydrogen, such as polyvinyl butyral, cellulosic resin, polycarbonate, aromatic polyester, vinyl chloride-vinyl acetate copolymer, polyvinyl folimal, polyester polyol, polyether polyol, and acrylic polyol. , Polyurethane polyols and the like can be used,
Polyvinyl butyral is preferred.

Also, the binder material is hydrophobic. The reason is that although the content of the contributing layer is smaller than that of the supply layer, it is advantageous to have the dye in a dissolved state in terms of sensitivity. Is dependent on the dye concentration.

The hydrolysis product of the silane coupling agent in the present invention may be partially or completely hydrolyzed.

The hydrolysis product of the silane coupling agent is formed by adding a bifunctional silane coupling agent or a trifunctional silane coupling agent as appropriate and adding water and an acid or alkaline catalyst in an organic solvent. Can be

Examples of the bifunctional silane coupling agent include dimethylchlorosilane, diphenyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane and the like can be used.

As trifunctional silane coupling agents, methyltrichlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, vinyltriethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like can be used. Among these, preferably, a bifunctional and trifunctional silane coupling agent is mixed to obtain a silane coupling agent hydrolysis product having a three-dimensional structure.

The partial hydrolysis product of the silane coupling agent thus prepared is present in an amount of 0.5% by weight or more and less than 50% by weight, preferably 1.0% by weight or more and less than 25% by weight based on the contributing layer binder. Added and used.

EXAMPLES Hereinafter, the present invention will be described more specifically based on the following examples. In addition, the amount (part) of each component in the following description is part by weight.

Thickness 6 having a 1 μm thick silicone resin-based heat-resistant layer
Using a wire bar on the aromatic polyamide film of 1.0 μm, a 1.0 μm thick intermediate adhesive layer and then a dye supply layer
It was coated to a thickness of 4.5 μm, and a dye transfer contributing layer was further applied thereon to a thickness of 1.0 μm to form an ink layer, and was thermally cured at 60 ° C. for 24 hours to produce a recording medium.

However, the compositions of the intermediate adhesive layer forming liquid and the dye supply layer forming liquid in the examples and comparative examples are all the same, and the compositions are as follows.

(Composition of adhesive layer forming solution) Polyvinyl butyral resin BX-1 [manufactured by Sekisui Chemical Co., Ltd.] 10 parts Diisocyanate coronate L [manufactured by Nippon Polyurethane Industry Co., Ltd.] 5 parts Toluene 95 parts Methyl ethyl ketone 95 parts (Dye supply layer formation Liquid composition) Polyvinyl butyral resin BX-1 7 parts Polyethylene oxide resin Alcox R-400
[Meisei Industry Co., Ltd.] 3 parts Sublimation dye Kayaset Blue 714 [Nippon Kayaku Co., Ltd.]
Manufacture] 30 parts Diisocyanate coronate L 3 parts Toluene 95 parts Methyl ethyl ketone 95 parts Example 1 (Synthesis of partial hydrolysis product of silane coupling agent) 24.0 g of dimethyldimethoxysilane, 13.6 g of methyltrimethoxysilane, 50 g of toluene and 50 g of methylethylketone
And 3 ml of 1% sulfuric acid was added to carry out hydrolysis for 3 hours. This liquid is referred to as Liquid A.

(Composition of the contributing layer forming liquid) Polyvinyl butyral resin BX-1 10 parts Liquid A 1 part Curing accelerator (dibutyltin dilaurate) 0.1 part Kayaset Blue 714 8 parts Toluene 95 parts Methyl ethyl ketone 95 parts Example 2 (silane coupling agent) Synthesis of Hydrolysis Product) 24.0 g of dimethyldimethoxysilane and 9.5 g of vinyltriethoxysilane were dissolved in a mixed solution of 50 g of toluene and 50 g of methyl ethyl ketone, and 10 ml of 1% sulfuric acid was added to carry out hydrolysis for 3 hours.

150 ml of water and 50 ml of toluene are added to this solution,
Stir for hours. After completion, the toluene layer was separated and dried over anhydrous sodium sulfate overnight, and then toluene was distilled off to obtain 18.5 g of an oily hydrolysis product. Dioxane 5
Use diluted to 0%. This liquid is referred to as Liquid B.

(Composition of Contributing Layer Forming Solution) Polyvinyl Butyral Denka Butyral # 4000-2
[Manufactured by Denki Kagaku Kogyo KK] 10 parts Solution B 1 part Curing accelerator (dibutyltin dilaurate) 0.1 part Dye: Kayaset Blue 714 8 parts Toluene 95 parts Methyl ethyl ketone 95 parts Example 3 (Partial hydrolysis of silane coupling agent) Synthesis of Product) 24.4 g of diphenyldimethoxysilane and 20.4 g of methyltrimethoxysilane were dissolved in a mixed solution of 50 g of toluene and 50 of methyl ethyl ketone, and 3 ml of 1% sulfuric acid was added to carry out hydrolysis for 3 hours. This liquid is referred to as liquid C.

(Composition of the contributing layer forming liquid) Cellulose acetate butyrate CAB381-0.5 [manufactured by Eastman Kodak Co., Ltd.] 10 parts C liquid 2 parts Curing accelerator (dibutyltin dilaurate) 0.1 part Kayaset Blue 714 8 parts Toluene 95 parts Methyl ethyl ketone 95 parts Example 4 (Synthesis of Partial Hydrolysis Product of Silane Coupling Agent) 24.0 g of dimethyldimethoxysilane 11.1 g of γ-aminopropyltriethoxysilane was dissolved in a mixture of 50 g of toluene and 50 g of methyl ethyl ketone, and 3 ml of 1% sulfuric acid was added. In addition, hydrolysis was performed for 3 hours. This liquid is referred to as Liquid D.

(Composition of contribution layer forming liquid) Ethyl cellulose [manufactured by Kanto Chemical Co., Ltd.] 10 parts D liquid 1 part Hardening accelerator (dibutyltin oxide) 0.1 part Kayaset Blue 714 8 parts Toluene 95 parts Methyl ethyl ketone 95 parts Comparative Example 1 Example Except that liquid A and the curing accelerator were omitted in 1, all were the same.

Comparative Example 2 (Composition of Contribution Layer Forming Solution) Polyvinyl Butyral BX-1 10 parts Amino-modified silicone SF-8417 [Toray Silicone Co., Ltd.] 1 part Epoxy-modified silicone oil SF-8411 [Toray Silicone Co., Ltd.] 1 part Kayaset Blue 714 8 parts Toluene 95 parts Methyl ethyl ketone 95 parts Comparative Example 3 Comparative Example 2 is the same except that the epoxy-modified silicone is omitted and the amino-modified silicone is 2 parts.

Comparative Example 4 (Composition of Contribution Layer Forming Solution) Partially saponified polyvinyl alcohol grafted with polydimethylsiloxane 10 parts Water 75 parts Ethanol 75 parts However, partially saponified polyvinyl alcohol grafted with polydimethylsiloxane was prepared as follows.

After radical copolymerization of 98 parts of vinyl acetate with 2 parts of a macromonomer having vinyl silane introduced at one end of a terminal diol type polydimethylsiloxane having a molecular weight of about 5600, the vinyl acetate was saponified with a molar fraction of 60%.

Further, a mixture having the following composition was sufficiently mixed and dispersed as an image receiving paper to prepare a coating solution [A] for a dye receiving layer.

[Solution A] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer (VAGH; manufactured by Union Carbide) 10 parts Isocyanate (Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 5 parts Amino-modified silicone (SF-8417; manufactured by Toray Silicone Co., Ltd.) 0.5 part Epoxy-modified silicone (SF-8411; manufactured by Toray Silicone Co., Ltd.) 0.5 part Toluene 40 parts Methyl ethyl ketone 40 parts Next, [solution A] was applied to a thickness of about 150 μm using a wire bar.
m on synthetic paper (trade name: Yupo FPG-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.) and dried at a drying temperature of 75 ° C. for 1 minute to form a dye receiving layer having a thickness of about 5 μm. Further, the mixture was stored at 80 ° C. for 3 hours and cured to prepare an image receiving medium of the present invention.

 The above was recorded at a thermal head resolution of 12 dots / mm, an applied energy of 0.64 mj / dot, an applied power of 0.16 w / dot, and a receiver speed of 8.5 mm / s and an ink sheet speed of 1.2 mm / s.

 The results are shown in the table below.

The recording density was measured by a reflection densitometer RD-918 (manufactured by Macbeth).

In the soil test, the sample after the storage test in a constant temperature bath at 60 ° C. for 100 hours was passed through a printer without heating, and the contamination of the receiving paper was visually evaluated.

[Effects of the Invention] The effects of the present invention described above are summarized as follows.

(1) In a transfer material having two layers of multi-function, a certain sublimable dye can be contained in the contributing layer by the water-insoluble resin, and the sensitivity does not decrease. In addition, by containing a reaction product of a resin having active hydrogen and a partial hydrolysis product of a silane coupling agent, lubricity and curing are improved, and in a speed difference mode method, a good multi-layer without sticking occurs. A record is obtained.

(2) Since the partial hydrolysis product has a three-dimensional structure, lubricity and curing are improved, and sticking is less likely to occur.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-95888 (JP, A) JP-A-2-241793 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (2)

(57) [Claims] 1. A sublimation-type thermal transfer body comprising a dye supply layer and a dye transfer contributing layer in which a sublimable dye is dispersed in an organic binder in order from the substrate side. A sublimation-type thermal transfer member, wherein the contributing layer contains a reaction product of a water-insoluble resin having active hydrogen and a hydrolysis product of a silane coupling agent. 2. The sublimation-type thermal transfer member according to claim 1, wherein the hydrolysis product of the silane coupling agent is a substance having a three-dimensional structure.