CN101048290A - Thermal transfer sheet and protective layer transfer sheet - Google Patents

Abstract

The invention provides a thermal transfer sheet and a protective layer transfer sheet. It is intended to provide a sheet of excellent transfer performance, in particular, a thermal transfer sheet that excels in transfer sensitivity and adhesion between base material and dye layer and that can be used in high-speed photographic printing with high transfer sensitivity, being capable of providing a photographic print of high density and high clearness, and a protective layer transfer sheet that excels in transfer performance, being markedly low in the generation of static electricity at the time of transfer. Further, it is intended to provide a photographic print that excels in antistatic performance, plasticizer resistance and transparency. There is provided a sheet with a base material, in particular, a thermal transfer sheet (I) comprising a laminate of, sequentially arranged, a base material, an underlayer and a dye layer, or a protective layer transfer sheet (II) comprising a base material and, detachably superimposed on at least part of the surface thereof, a protection transfer laminate including a conductive layer, characterized in that the underlayer and conductive layer are each one produced using colloidal inorganic pigment ultrafine particles.

Description

Hot transfer piece and protective layer transfer printing sheet

Technical field

The present invention relates to hot transfer piece and protective layer transfer printing sheet.

Background technology

As utilizing hot transfer printing to form the method for image, known have and will overlap to form the thermal diffusion type transfer printing mode (subliming type thermal transfer mode) of full-colour image as the thermal diffusion type hot transfer piece of recording materials and hot transfer printing imaging film, described thermal diffusion type hot transfer piece has supported thermal diffusion type dye (subliming type dyestuff) on base materials such as plastic foil, other base materials such as described hot transfer printing imaging film paper or plastic foil are provided with the receiving layer of above-mentioned dyestuff.

About hot tranfer recording mode, along with the development of the high speed of the print speed printing speed of thermal transfer printer, produced the problem that hot transfer piece so far can't obtain enough gradation of drop-out colour (print Concentrated degree) gradually based on sublimation transfer.

As the hot transfer piece that has improved printing concentration, the known hot transfer piece that the intermediate layer is set between substrate sheets and dye coating.

As the hot transfer piece that is provided with the intermediate layer, for example known have the hot transfer piece of the hydrophily barrier that contains polyvinylpyrrolidone and polyvinyl alcohol that is provided as priming coat between dye coating and the substrate sheets and at Ranvier's membrane and contain be provided with between the recording layer of subliming type dyestuff contain diffusion coefficient less than recording layer in (for example with reference to the patent documentation 1 and the patent documentations 2) such as hot transfer pieces in intermediate layer of subliming type dyestuff of diffusion coefficient of contained sublimation dye.Yet also there is the problem that can't obtain to print the sufficiently high photographic printed material of concentration (print thing, photographic print) in these hot transfer pieces.

Put down in writing following hot transfer piece in the patent documentation 3: on base material, form the layer that obtains by evaporation metal or metal oxide, on this layer, dye film is set again.But this hot transfer piece exists can't obtain to print the sufficiently high photographic printed material of concentration and the special device of needs causes manufacturing cost to uprise during owing to evaporation problem.

Put down in writing between base material and dye coating the hot transfer piece of the easy adhesive layer of the copolymer that the homopolymers that contains the N-vinylpyrrolidone or N-vinylpyrrolidone and other compositions are set in the patent documentation 4.Except above-mentioned each polymer, can also mix aluminium oxide, silica etc. in this easy adhesive layer, but these compounds not to contain.And, in the hot transfer piece of patent documentation 4, have the inadequate problem of dye transfer efficient.

Put down in writing the ethanolic solution of coating aminopropyl trialkoxy silane between the base material of hot transfer piece and dye coating or 1-propanol solution embodiment in the patent documentation 5 as priming coat.But, owing to used thicker base material, the problem of transfer printing sensitivity variation when having high speed printing.

Put down in writing the priming coat that copolymers such as making polymer with inorganic main chain that the IVb family metal oxide forms and acryloyl-oxy alkoxy silane reacts and forms in the patent documentation 6.The problem that exists in the priming coat of patent documentation 6 records is: cause hear resistance insufficient owing to having the organic chain that is derived from above-mentioned copolymer, and owing to have above-mentioned inorganic main chain, unstable so easily be hydrolyzed.

Further be in the situation of base material with the plastic foil in thermal diffusion type hot transfer piece, base material is because heating of bearing during print (print, photographic printing) and stress (tension) and there is the problem that produces the print fold in deterioration.

In order to address this problem, as plastic film substrate, knownly have based on longitudinal stretching method (Zai Longitudinal extension method once more) etc. improve the vertically height stretching base material (for example with reference to patent documentation 7 and patent documentation 8) of the drawing process of the stretching ratio of (length direction), in the described method of longitudinal stretching once more, when the film processed base material, the biaxially-stretched film that alongst stretches with width is further stretched along its length.

But, because this height stretching base material needs special film making process, the problem that existence can't avoid cost to improve.And, in recent years,, there is trend to the fire damage increase of base material along with the high speed of the printing that utilizes thermal transfer printer, the problem of hear resistance and intensity variation just progressively appears in the existing hot transfer piece.

On the other hand, be main purpose the image that utilizes thermal transfer mode to obtain is given durability, use the hot transfer piece set in advance matcoveredn, carry out the transfer printing of this protective layer so that protective layer to be set after utilizing the sensible heat printer to form image on image.But, this protective layer when peeling away, hot transfer piece can be produced a large amount of static, and produce transfer printing body and hot transfer piece thus and in the sensible heat printer, transport bad problem.

In order to address this problem; possesses antistatic layer in the protective layer (protection transfer printing layer) that has scheme to propose to make to be arranged on the hot transfer piece; this antistatic layer contains antistatic additive such as conductive metal oxide such as surfactant as quaternary ammonium salt, zinc antimonates, and has proposed this antistatic additive and can be included in the protective layer or adhesive layer that constitutes the protection transfer printing layer (for example with reference to patent documentation 9).But this antistatic additive is under the situation of quaternary ammonium salt surface active agent etc., and surfactant is discharged into the outermost of protection transfer printing layer and influences the problem of transfer printing and problem that plasticizer resistance properties worsens etc. when having long-term the use.

In order to solve the problem of quaternary ammonium salt surface active agent, proposed to comprise the protective layer hot transfer piece (for example with reference to patent documentation 10) that the electric conductivity protective layer of electric conductivity inorganic substances forms by setting, described electric conductivity inorganic substances are by with SnO ₂Acicular crystals such as conductive agents such as/Sb class processing potassium titanate obtain.

But conductive agent is under the situation of inorganic particulate such as metal oxide, the problem of if addition is too much, then exist the transparency of protective layer to lose, becoming turbid etc.

Above-mentioned antistatic additive (conductive agent) all needs to form layer with binder resin.But, used and had following two problems in the antistatic layer that contains conductive agent of binder resin: (1) is because must consideration when setting mixing ratio and the cohesive of substrate sheets or other layers, addition to conductive agent is restricted, so in order to obtain desired antistatic effect needs coating weight to a certain degree; (2) the necessary compatibility of considering conductive agent and adhesive makes restricted to making up.

As the protective layer transfer film, proposed to be provided with the transfer film of the hot transfer printing resin bed that constitutes by laminate, in the described laminate, transparent resin bed, plasticizer resistance properties resin bed, Thermoadhesive resin bed are arranged by base material film one side lamination successively.Wherein, as the plasticizer resistance properties resin bed, when the resin that uses the ammonium salt that in the acrylic compounds copolymer resins, imports as polar group, sulfonate, acetate etc. to form, think that its antistatic behaviour is excellent (for example with reference to patent documentation 11).But the plasticizer resistance properties resin bed that imports polar group in the acrylic compounds copolymer resins is inadequate sometimes.

Patent documentation 1: the spy opens flat 5-131760 communique

Patent documentation 2: the spy opens clear 60-232996 communique

Patent documentation 3: the spy opens clear 59-78897 communique

Patent documentation 4: the spy opens the 2003-312151 communique

Patent documentation 5: the spy opens clear 63-135288 communique

Patent documentation 6: the spy opens flat 5-155150 communique

Patent documentation 7: the spy opens flat 8-230032 communique

Patent documentation 8: the spy opens flat 11-188791 communique

Patent documentation 9: the spy opens flat 11-105437 communique

Patent documentation 10: the spy opens the 2003-145946 communique

Patent documentation 11: the spy opens flat 11-156567 communique (claim 1, [0031])

Summary of the invention

In view of above-mentioned present situation, the object of the present invention is to provide the good sheet material of a kind of transfer printing and a kind of antistatic behaviour, plasticizer resistance properties and excellent photographic printed material (the print thing of the transparency, photographicprint), the good sheet material of described transfer printing is hot transfer piece and protective layer transfer printing sheet, the transfer printing of described hot transfer piece is highly sensitive, the cohesive of base material and dye coating is good, and can be used for high speed printing (print, photographic printing), can access the high photographic printed material of distinctiveness of high concentration; The transfer printing of described protective layer transfer printing sheet is good, few static that produces when transfer printing.

The present invention relates to a kind of sheet material, it is the sheet material that contains base material, this sheet material is characterised in that, it is hot transfer piece (I) or protective layer transfer printing sheet (II), described hot transfer piece (I) is lamination base material, substrate layer and dye coating and form successively, and described protective layer transfer printing sheet (II) strippingly has the protection transfer printing laminate that contains conductive layer on the part surface at least of base material; Wherein said substrate layer and conductive layer form by using colloid shape inorganic pigment ultra micron.

The present invention relates to a kind of hot transfer piece (hereinafter being sometimes referred to as " hot transfer piece (1) "), it is characterized in that, this hot transfer piece forms successively on a face of base material and contains ultramicronized substrate layer of colloid shape inorganic pigment and dye coating.

The present invention relates to a kind of hot transfer piece (hereinafter being sometimes referred to as " hot transfer piece (2) "), this hot transfer piece is by lamination base material, prime coat (hereinafter being sometimes referred to as " substrate layer ") and dye coating obtain successively, this hot transfer piece is characterised in that, described prime coat forms by using colloid shape inorganic pigment ultra micron, the substrate intensity of described base material is more than or equal to 3.5, less than 4.0, and this substrate intensity is with the fracture strength S on the length direction ₁(MPa) and elongation at break S ₂(MPa) ratio S ₁/ S ₂Represent.

In this specification, sometimes above-mentioned hot transfer piece (1) and hot transfer piece (2) are generically and collectively referred to as " hot transfer piece of the present invention ".

The present invention relates to a kind of protective layer transfer printing sheet; it is characterized in that; this protective layer transfer printing sheet strippingly has protection transfer printing laminate on the part surface at least of substrate sheets, described protection transfer printing laminate contains the conductive layer by using colloid shape inorganic pigment ultra micron to form.

The present invention relates to a kind of protective layer transfer printing sheet; it is characterized in that; this protective layer transfer printing sheet strippingly has protection transfer printing laminate on the part surface at least of substrate sheets; described protection transfer printing laminate contains by the conductive layer that uses the inorganic pigment ultra micron to form, and described conductive layer does not contain binder resin.

The present invention relates to a kind of photographic printed material, it is characterized in that, the protective layer transfer printing sheet transfer printing of this photographic printed material the application of the invention forms protection transfer printing laminate, and the parts of images surface obtains to cover at least.

Description of drawings

Fig. 1 is the cross-sectional of a preferred forms of expression hot transfer piece of the present invention (1).

Fig. 2 is the sectional view of an example of expression hot transfer piece of the present invention (2).

Fig. 3 is the sectional view of an example of expression protective layer transfer printing sheet of the present invention.

Fig. 4 is the figure of an example that expression has the protective layer transfer printing sheet of the present invention of adherent layer.

Fig. 5 is the sectional view of an example that expression is provided with the protective layer transfer printing sheet of the present invention of painted thermal transfer ink layer.

Symbol description

The 1a base material

2a contains the ultramicronized substrate layer of colloid shape inorganic pigment

The 3a dye coating

The heat-resisting slip layer of 4a

The 1b base material

The 2b prime coat

The 3b dye coating

The heat-resisting slip layer of 4b

The 1c substrate sheets

The 2c adherent layer

3c protection transfer printing laminate

The 4c protective layer

The 5c conductive layer

The 6c adhesive layer

The heat-resisting slip layer of 7c

The 2d base material

The 3d conductive layer

The 4d protective layer

The painted thermal transfer ink layer of 5d

6d protection transfer printing laminate

The 7d adhesive layer

The 8d certification mark

The heat-resisting slip layer of 10d

The specific embodiment

Describe the present invention below in detail.

Sheet material of the present invention is above-mentioned hot transfer piece (I) or protective layer transfer printing sheet (II), and this sheet material is characterised in that described substrate layer and conductive layer form by using colloid shape inorganic pigment ultra micron.

As above-mentioned hot transfer piece (I), can enumerate hot transfer piece of the present invention etc.

As above-mentioned protective layer transfer printing sheet (II), can enumerate protective layer transfer printing sheet of the present invention etc.

Have substrate layer and the conductive layer that uses colloid shape inorganic pigment ultra micron to form owing to sheet material of the present invention; so have the feature of transfer printing excellence; but to its concrete feature, with shown in the explanation of relevant hot transfer piece of the present invention described later and protective layer transfer printing sheet of the present invention.

1. hot transfer piece (1)

A specific embodiment as shown in Figure 1 is such, the structure of hot transfer piece of the present invention (1) is: the face of the side of base material 1a is provided with heat-resisting slip layer 4a, be formed with successively on the face of the opposite side of base material 1a and contain ultramicronized substrate layer 2a of colloid shape inorganic pigment and dye coating 3a, described heat-resisting slip layer 4a makes the sliding property of thermal head good and can prevent to adhere to.

Below, each layer that constitutes hot transfer piece of the present invention (1) is elaborated.

(base material)

Base material as the hot transfer piece that uses among the present invention (1), so long as existing known have to a certain degree hear resistance and the base material of intensity get final product, for example can enumerate PETG [PET], polybutylene terephthalate (PBT) [PBT], 1,4-gathers cyclohexylene dimethylene terephthalate, PEN polyester such as [PEN]; Polyolefin such as polyethylene, polypropylene; Polyamide such as aramid fiber, nylon; Polyphenylene sulfide; Polystyrene; Polysulfones; Merlon; Polyvinyl alcohol; Cellophane; Cellulose derivatives such as cellulose acetate; Polyvinyl chloride; Polyvinylidene chloride; Polyimides; Fluorine resin; Plastic foils such as ionomer.

The thickness of above-mentioned base material is generally 0.5 μ m～50 μ m, is preferably about 1 μ m～10 μ m.

In the above-mentioned base material, for the fracture strength S on the length direction ₁(MPa) and elongation at break S ₂(MPa) ratio S ₁/ S ₂Represented substrate intensity is not particularly limited, and is preferably 3.5～5.0, more preferably more than or equal to 3.5, less than 4.0.

In this specification, above-mentioned fracture strength and elongation at break are the values of measuring according to JIS C 2151.

In the above-mentioned base material, often carry out adhesion process to being used to form the face that contains ultramicronized substrate layer of colloid shape inorganic pigment and dye coating.For the plastic foil of above-mentioned base material, if be formed with the thin layer of inorganic oxide in the above, then because the cohesive of the thin layer of base material and inorganic oxide etc. have deficiency easily slightly, so preferably carry out adhesion process.

As this adhesion process, can directly use known surface modification of resin technology such as Corona discharge Treatment, fiery scorching processing, ozone treatment, UV treatment, radioactive ray processing, roughening processing, chemicals processing, plasma treatment, low-temperature plasma processing, primary coat (primer) processing, grafting processing.And, also can share two or more these processing methods.Above-mentioned primary coat is handled and can followingly be carried out: for example when melt extruding the formation plastic foil, to stretching coating primary coat liquid on the film, carry out stretch processing afterwards again.

Among the present invention, consider and improve base material and the adaptation that contains the ultramicronized substrate layer of colloid shape inorganic pigment, in above-mentioned adhesion process, preferably can operate simply and the Corona discharge Treatment or the plasma treatment that can not raise the cost.

(containing the ultramicronized substrate layer of colloid shape inorganic pigment)

Containing in the ultramicronized substrate layer of colloid shape inorganic pigment between base material that is arranged at hot transfer piece of the present invention (1) and dye coating, can use existing known compound as colloid shape inorganic pigment ultra micron.

As above-mentioned colloid shape inorganic pigment ultra micron, can enumerate for example silica (colloidal silica); Metal silicate such as alumina silicate, magnesium silicate; Metal oxide-type such as aluminium oxide or hydrated alumina (alumina sol, colloidal alumina, cationic aluminum oxide or its hydrate, pseudobochmite etc.), magnesia, titanium oxide; Carbonate such as magnesium carbonate; Or the like.In the above-mentioned hot transfer piece (1), preferred especially colloidal silica, alumina sol, more preferably alumina sol.

The ultramicronized size of above-mentioned colloid shape inorganic pigment is expressed as below the 100nm with average primary particle diameter, is preferably below the 50nm, especially preferably uses the ultra micron of primary particle size as 3nm～30nm, can give full play to the effect of substrate layer thus.

The ultramicronized shape of colloid shape inorganic pigment of the present invention can be spherical, needle-like, tabular, featheriness or arbitrary shape such as amorphous.And, can use be treated to acid type so that be easy to carried out surface-treated colloid shape inorganic pigment ultra micron etc. with the colloidal sol shape is dispersed in colloid shape inorganic pigment ultra micron in the aqueous solvent, the electric charge that makes particulate obtains after as positive charge colloid shape inorganic pigment ultra micron or to particulate.

And the coating adaptability when considering the coated substrate layer as the coating fluid of substrate layer, preferably reduces coating fluid viscosity so that it has flowability.

Contain above-mentioned colloid shape inorganic pigment ultra micron in the formation of substrate layer of the present invention, substrate layer can form as follows: do not use the resin as adhesive, utilize intaglio plate rubbing method, rolling method, silk screen print method, utilized the existing known formation method coatings such as reverse rolling method of intaglio plate by the inorganic pigment ultra micron is dispersed in the coating fluid that forms in the aqueous solvent with the colloidal sol shape, and carry out drying, form substrate layer thus.

Aqueous solvent in the above-mentioned coating fluid can be to mix with alcohol such as isopropyl alcohols and the aqueous solvent that obtains.Above-mentioned coating fluid does not make the existing method of water different with for example only using alcohol, and its steady dissolution, dispersion stabilization excellence can be used as coating fluid well.

In the above-mentioned coating fluid, preferred colloid shape inorganic pigment ultra micron is 0.1 mass parts～50 mass parts with respect to this coating fluid of 100 mass parts.

Also can not contain binder resin in the above-mentioned substrate layer.

Coating weight when so the substrate layer that forms is dry is generally 0.02g/m ²～1g/m ²Or 0.02g/m ²～1.0g/m ², be preferably 0.03g/m ²～0.3g/m ²About, 0.1g/m more preferably ²About.

Substrate layer of the present invention forms as follows: use by above-mentioned inorganic pigment ultra micron is dispersed in the coating fluid that forms in the aqueous solvent with collosol state, this coating fluid is coated on the base material, under 90 ℃～130 ℃ temperature, carry out heated-air drying etc., remove moisture so that it becomes gel by the colloidal sol shape, form substrate layer thus.Therefore, substrate layer of the present invention does not carry out the processing of firing based on general sol-gel process.

Like this; containing the ultramicronized substrate layer of colloid shape inorganic pigment is formed between base material and the dye coating as diaphragm; can improve the cohesive of base material and dye coating; when carrying out hot transfer printing by heating, can prevent the unusual transfer printing of dye coating on hot transfer printing imaging film with hot transfer printing imaging film is combined.In addition, because this substrate layer constitutes by being difficult for the colloid shape inorganic pigment ultra micron of quilt from the dyeing of dye coating, can prevent during print that dyestuff is transferred to substrate layer by dye coating, make the dyestuff receiving layer one side diffusion of thermotropism transfer printing imaging film effectively, transfer printing sensitivity in the time of can improving print thus improves printing concentration.

(dye coating)

In the hot transfer piece of the present invention (1), on the face of the opposite side of the base material that is provided with heat-resisting slip layer on the one side, dye coating is set across above-mentioned substrate layer.This dye coating can be made of the simple layer of monochrome, perhaps is being concatenated to form the dye coating that comprises more than dyes in different colors two-layer on the same one side of same base material by face order (Cis To of face).

Dye coating in the above-mentioned hot transfer piece (1) is to utilize adhesive arbitrarily to support hot metastatic dyestuff and the layer that forms.

As the dyestuff that in above-mentioned hot transfer piece (1), uses, can enumerate the dyestuff that melted by heating, diffusion or distillation are shifted, for example be the existing known dyestuff that in sublimation transfer type hot transfer piece, uses, these dyestuffs may be used to the present invention, select but will wait according to color, printing sensitivity (lettering sensitivity), light resistance, keeping quality and the dissolubility in adhesive.

Be not particularly limited as above-mentioned dyestuff, can enumerate for example diarylmethanes class pigment; Triarylmethane class pigment; The thiazoles pigment; Portion spends cyanines class pigment; Methine class pigment (methines: methine) such as pyrazolone methine; Indoaniline class pigment; Azomethine class pigments such as acetophenone azomethine, pyrazoles azomethine, imidazoles azomethine, imidazo azomethine, pyridone azomethine; Xanthene class pigment; Oxazine class pigment; Cyanogen such as dicyano styrene, tricyano-styrene methylene base class pigment; The thiazide pigment; The azines pigment; The acridine pigment; Benzeneazo class pigment; (ジ ズ ア ゾ dizazo) waits azo class pigment for pyridone azo, thiophene azo, isothiazole azo, pyrroles's azo, ピ ラ one Le ア ゾ (pyrraleazo), imidazoles azo, thiadiazoles azo, triazole azo, two diazonium; Spiro-pyrans class pigment; Indoline spiro-pyrans (indoline spiropyran) class pigment; The Material of Fluoran pigment; Rhodamine lactams pigment; Naphthoquinones class pigment; Anthraquinone pigments; Quinophthalone class pigment etc.

Be not particularly limited as the adhesive in the above-mentioned dye coating, can use existing known resin binder.

As above-mentioned resin binder, cellulosic resins such as preference such as methylcellulose, ethyl cellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropyl cellulose, cellulose acetate, cellulose butyrate; Vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyethylene acetal, polyvinylpyrrolidone, polyacrylamide; Polyester resin; Phenoxy resin; Or the like.

As above-mentioned resin binder, wherein, even consider that transferring postpone in high temperature, super-humid conditions also can keep aspect substrate layer and dye coating fusible the preferred high resin of cohesive.As the high resin of above-mentioned cohesive, can enumerate the resin that for example polyvinyl butyral, polyethylene acetal, polyvinyl acetate, polyester resin, cellulosic resin etc. have hydroxyl, carboxyl etc.

As the resin binder in the above-mentioned dye coating, can also further enumerate the antistick characteristic graft copolymer.Above-mentioned antistick characteristic graft copolymer can be used as antitack agent to be added with above-mentioned resin binder.

At least a antistick characteristic segment that the glycerol polymerization on the main chain of the polymer that constitutes above-mentioned resin binder of above-mentioned antistick characteristic graft copolymer is selected from polysiloxanes segment, fluorocarbon chain section, fluorinated hydrocarbons segment and chain alkyl segment forms.

As above-mentioned antistick characteristic graft copolymer, wherein preferred graft polysiloxane segment on the main chain that contains the polyethylene acetal and the graft copolymer that obtains.

In the above-mentioned dye coating, except above-mentioned dyestuff, above-mentioned adhesive, can also add silane coupler.

In above-mentioned dye coating, add in the situation of silane coupler, it is believed that silanol group that produces owing to the silane coupler hydrolysis and the hydroxyl generation condensation that is present in the inorganic compound on substrate layer surface, thereby the cohesive of dye coating and substrate layer is improved.And silane coupler has under the situation of epoxy radicals, amino etc., and the hydroxyl of itself and resin binder or carboxyl etc. react and carry out chemical bonding, can improve the intensity of dye coating itself thus, aggegation destruction of dye coating etc. when preventing hot transfer printing etc.

As above-mentioned silane coupler, for example can enumerating, γ-NCO propyl trimethoxy silicane, γ-NCO propyl-triethoxysilicane etc. contain the compound of NCO; Gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-beta-aminoethyl-γ-An Jibingjisanyiyangjiguiwan, γ-phenyl amino propyl trimethoxy silicane etc. contain amino compound; γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc. contain the compound of epoxy radicals; Or the like.

In the above-mentioned dye coating, both can only add a kind of above-mentioned silane coupler, also can add more than 2 kinds.

In the above-mentioned dye coating,, can also further add existing known various additives except above-mentioned dyestuff, above-mentioned adhesive, and the silane coupler that adds as required.

As above-mentioned additive, for example can enumerate for the coating adaptability of the antistick characteristic that improves dye coating and hot transfer printing imaging film or printing ink and organic fine particles of Tissuemat E that adds etc., inorganic particles etc.

Above-mentioned dye coating can form usually as follows: the additive that adds above-mentioned dyestuff, adhesive and use as required in appropriate solvent, suitably dissolve or disperse each composition to prepare the dye coating coating fluid, this dye coating coating fluid of coating on substrate layer forms dye coating after the drying then.

As the coating process of above-mentioned dye coating, for example can enumerate woodburytype, silk screen print method, utilize the reverse rolling method of intaglio plate etc., wherein preferred intaglio plate rubbing method.

Can be coated with above-mentioned dye coating coating fluid makes drying coated amount be preferably 0.2g/m ²～6g/m ²Or 0.2g/m ²～6.0g/m ²About, 0.3g/m more preferably ²～3g/m ²Or 0.3g/m ²～3.0g/m ²About.

(heat-resisting slip layer)

Hot transfer piece of the present invention (1) can be provided with heat-resisting slip layer to prevent adhesion that heat was caused or the harmful effects such as (lettering わ) of printing fold owing to thermal head on the face of the opposite side of the side with being provided with dye coating of base material.

As the resin that forms above-mentioned heat-resisting slip layer, use existing known resin to get final product, can enumerate for example polyvinyl butyral resin, polyethylene acetyl acetate resin, mylar, vinyl chloride vinyl acetate copolymer, polyether resin, polybutadiene, SB, polyalcohols such as acrylic acid polyalcohols, urethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, the prepolymer of urethanes or epoxy, Nitro cellulose resin, nitrocellulose resin, cellulose ethanoate propionic ester resin, the cellulose acetate butyrate resin, cellulose ethanoate hydrogen diene phthalic acid ester resin, the cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamide-imide resin, polycarbonate resin, chlorinated polyolefin resin etc.

Except that above-mentioned heat-resistant resin, can also add the sliding property that sliding property imparting agent improves thermal head in the above-mentioned heat-resisting slip layer usually.

As above-mentioned sliding property imparting agent, can enumerate for example silicone polymers such as phosphate, metallic soap, silicone oil, graphite powder, fluorine class graft polymers, silicone graft polymers, acrylic acid silicone graft polymers, acrylic acid silica alkane, aryl siloxanes etc.

In above-mentioned heat-resisting slip layer, both can only add a kind of above-mentioned sliding property imparting agent, also can add more than 2 kinds.

In addition, also can replace in above-mentioned heat-resisting slip layer, mixing the operation of sliding property imparting agent at the above-mentioned sliding property imparting agent of coating on the above-mentioned heat-resisting slip layer.

Except heat-resistant resin with the above-mentioned sliding property imparting agent that adds as required, can also in above-mentioned heat-resisting slip layer, add additives such as crosslinking agent, antitack agent, organic dust, inorganic powder.

Can improve hear resistance, filming property and adaptation etc. when for example, in above-mentioned heat-resisting slip layer, adding crosslinking agent such as polyisocyanate compounds.And, can improve the mobility of thermal head when in above-mentioned heat-resisting slip layer, adding antitack agent, organic dust or inorganic powder.As above-mentioned antitack agent, can enumerate wax, higher fatty acid amides, ester, surfactant etc.Can enumerate fluorine resin etc. as above-mentioned organic dust.Can enumerate silica, clay, talcum, mica, calcium carbonate etc. as above-mentioned inorganic powder.

As above-mentioned heat-resisting slip layer, be preferably the layer that in polyalcohols (for example polyalcohols macromolecular compound), contains polyisocyanate compounds and phosphate compounds, more preferably in above-mentioned these compositions, add filler.

Heat-resisting slip layer can form as follows: dissolve or disperse the resin of above-mentioned explanation, sliding property imparting agent and filler etc. with appropriate solvent, prepare heat-resisting slip layer coating fluid, with for example woodburytype, silk screen print method, utilized the formation methods such as reverse rolling method of intaglio plate that this coating fluid is coated on the substrate sheets, and carry out drying.The coating weight of heat-resisting slip layer represents to be preferably 0.1g/m with solid constituent ²～3g/m ²Or 0.1g/m ²～3.0g/m ²

(other)

Identical with hot transfer piece of the present invention described later (2), hot transfer piece of the present invention (1) can be on substrate sheets and the face dye coating homonymy has the protection transfer printing layer according to the mode (Cis To of face) that is the face order with dye coating.

Hot transfer piece of the present invention (1) can utilize existing known sensible heat printer to be transferred at hot transfer printing imaging film etc. and form desired images on the material.

2. hot transfer piece (2)

As shown in Figure 2, hot transfer piece of the present invention (2) is for example by constituting from base material lamination prime coat 2b successively and dye coating 3b on the face of the side of base material 1b.And, heat-resisting slip layer 4b also can be set on the another side of base material 1b.

Below each layer that constitutes hot transfer piece of the present invention (2) described.

(base material)

In the base material of the present invention, by the fracture strength [S on the length direction ₁And elongation at break [S (MPa)] ₂(MPa)] ratio [S ₁/ S ₂] represented substrate intensity is more than or equal to 3.5, less than 4.0.

The value of above-mentioned substrate intensity is high more, and intensity and hear resistance are excellent more.

In the past, as the base material that is used for hot transfer piece, consider the troubles such as print fold that the heating when preventing owing to print causes, and selected the high base material of above-mentioned substrate intensity usually, preferred above-mentioned substrate intensity is the base material more than 4.0.But, as described later, the transfer printing sensitivity of hot transfer piece of the present invention (2) is good, can be in low-yield print down, thereby can use the lower base material of substrate intensity in above-mentioned scope, even use such base material also not to be prone to because heating during print or the trouble that stress caused.

As base material of the present invention, illustrative plastic foil in the preferred above-mentioned hot transfer piece (1), wherein more preferably polyester, polyolefin etc., further preferred PET, PBT, PEN etc.

The present invention is when application, in order to improve substrate intensity based on above-mentioned definition, as the base material in the thermal diffusion type hot transfer piece, think and be necessary to use the contour stretching base material of film that has carried out biaxial stretch-formed processing and further carried out stretch processing (longitudinal stretching once more) along the longitudinal direction, but because the base material of hot transfer piece (2) also can have lower substrate intensity, even thereby the film that after biaxial stretch-formed processing, does not stretch once more, also can make the heat transfer film of transfer printing sensitivity excellence.

Base material thickness in the above-mentioned hot transfer piece (2) can suitably be set so that its intensity and hear resistance reach suitable degree according to its kind, base material thickness is preferably about 2.5 μ m～6 μ m or 2.5 μ m～6.0 μ m, be limited to 4 μ m or 4.0 μ m under preferred, be limited to 5.5 μ m on preferred.

For substrate intensity based on above-mentioned definition, generally there is the low more trend of the thin more intensity of base material thickness, but for the base material in the hot transfer piece (2), as long as substrate intensity is in above-mentioned scope, so can dwindle thickness.

In this specification, can utilize micrometer (MFC-191, Nikon society produces) to measure the thickness of 10 overlapping base materials, utilize the value of measuring to ask to count in and state base material thickness.

Be not particularly limited for above-mentioned base material,, can carry out various surface treatments such as easy adhesion process in order to improve the cohesive with prime coat.

Above-mentioned easy adhesion process can be undertaken by for example being coated with resin described later and it is solidified on base material.

As the resin that can be used in above-mentioned easy adhesion process, can enumerate polyester resin, acrylic resin, polyurethanes resin, alkyd based resin.In above-mentioned easy adhesion process, can in above-mentioned resin, add compound, chelate of melamine compounds, isocyanate ester compound, epoxy compounds, Han You oxazolyl etc.

For the coating weight of the easy adhesive layer that forms by above-mentioned easy adhesion process, preferred drying coated amount is 0.1g/m ²Below.Degree of irregularity for the coating weight of easy adhesive layer, consider thermal head mobility, prevent to print aspects such as spot, for example when this base material be under the situation of stretched film, preferably the crawling on MD direction and the TD direction all average coating weight ± 5% in.

(prime coat)

Prime coat lamination in the hot transfer piece of the present invention (2) is between above-mentioned base material and dye coating described later.

Above-mentioned prime coat both can lamination on base material, also can lamination in lamination on the above-mentioned easy adhesive layer on the base material, but preferably be located at the below of pasting dye coating.

Prime coat in the above-mentioned hot transfer piece (2) forms by using colloid shape inorganic pigment ultra micron.

As above-mentioned colloid shape inorganic pigment ultra micron, can use above-mentioned existing known compound, in above-mentioned prime coat, oxide-based and the carbonate of preferable alloy, more preferably metal oxide-type, further preferred aluminium oxide or hydrated alumina, wherein, alumina sol most preferably.In the above-mentioned prime coat, as the also suitable colloidal silica that uses of colloid shape inorganic pigment ultra micron.

Above-mentioned prime coat both can only use a kind of above-mentioned colloid shape inorganic pigment ultra micron to form, and can use also that above-mentioned colloid shape inorganic pigment ultra micron forms more than 2 kinds.

Colloid shape inorganic pigment ultra micron in the prime coat can be a shape arbitrarily, consider the intensity of the hot transfer piece of gained, the described ultramicronized average grain diameter of using in preferred this ultramicronized average grain diameter of colloid shape inorganic pigment and the above-mentioned hot transfer piece (1) is in same scope, and, in order to be easy to be distributed in the aqueous solvent, also can carry out above-mentioned various processing with the colloidal sol shape.

Colloid shape inorganic pigment ultra micron in the above-mentioned prime coat can be for example alumina sol 100 (daily output chemical industry society produce), alumina sol 200 commercially available products such as (daily output chemical industry society produce).

According to whiteness, give purposes such as disguise, toning, above-mentioned prime coat can have various pigment, dyestuff, fluorescent whitening agent and other additives in the scope that does not influence transfer printing sensitivity.

Above-mentioned prime coat can form in for example following mode: dispersion colloid shape inorganic pigment ultra micron uses this coating fluid to be coated with on base material or above-mentioned easy adhesive layer to form the prime coat coating fluid in aqueous medium, and dry.

Above-mentioned prime coat coating fluid can not contain water, but preferably contains water, also can contain water and water-miscible organic solvent.If the prime coat coating fluid contains water, then do not make the existing method of water different with for example only using alcohol, its steady dissolution, dispersion stabilization excellence can be suitable for use as coating fluid.

In the above-mentioned prime coat coating fluid, colloid shape inorganic pigment ultra micron is preferably 0.1 mass parts～50 mass parts with respect to this coating fluid of 100 mass parts, more preferably below 20 mass parts.Above-mentioned prime coat also can not contain binder resin.

Among the present invention, can be 0.05g/m with dried coating weight ²～10g/m ²The amount primer coating layer coating fluid of scope, in order to obtain the hot transfer piece of transfer printing sensitivity and excellent strength, be 0.05g/m preferably with dried coating weight ²Above amount is coated with, and, consider manufacturing cost, dried coating weight is preferably 5g/m ²Following amount, more preferably 3g/m ²Below.

That is, compare, in the prime coat among the present invention,, also can access the hot transfer piece of excellent strength even use a spot of colloid shape inorganic pigment ultra micron with the existing ultramicronized prime coat of colloid shape inorganic pigment that do not use.

Above-mentioned drying is carried out heated-air drying etc. usually, so that colloid shape inorganic pigment ultra micron becomes the desiccant gel shape by the colloidal sol shape.Because the prime coat among the present invention forms through above-mentioned drying process, so colloid shape inorganic pigment ultra micron is in the state of set, the hear resistance of prime coat and excellent strength.

(dye coating)

The formation of the dye coating in the hot transfer piece of the present invention (2) and preparation method are identical with dye coating in the above-mentioned hot transfer piece (1).Above-mentioned hot transfer piece (2) is preferably the thermal diffusion type.

(heat-resisting slip layer)

Also can be further in the hot transfer piece of the present invention (2) with the substrate surface of the relative side of face that forms above-mentioned prime coat etc. on heat-resisting slip layer is set.

Above-mentioned heat-resisting slip layer be for prevent to adhere to or during hot transfer printing such as print fold the problem that heat caused owing to thermal head be provided with.

Heat-resisting slip layer in the above-mentioned hot transfer piece (2) contains heat-resistant resin, have with hot transfer piece (1) in the identical formation of heat-resistant resin layer.

Except above-mentioned heat-resistant resin, can add the sliding property that sliding property imparting agent improves thermal head in the above-mentioned heat-resisting slip layer usually.In addition, also can replace in above-mentioned heat-resisting slip layer, mixing the operation of sliding property imparting agent at the above-mentioned sliding property imparting agent of coating on the above-mentioned heat-resisting slip layer.Identical with hot transfer piece (1), except heat-resistant resin with the above-mentioned sliding property imparting agent that adds as required, can also in above-mentioned heat-resisting slip layer, add various additives.

Can come the heat-resisting slip layer in the above hot transfer piece of lamination (2) by the heat-resisting slip layer coating fluid of coating on the face opposite of base material and dry with dye coating one side is set.

Above-mentioned heat-resisting slip layer can form usually as follows: the above-mentioned sliding property imparting agent and the additive of above-mentioned heat-resistant resin and interpolation as required are added in the appropriate solvent, dissolving or disperse each composition, prepare heat-resisting slip layer coating fluid, should be coated on the base material by heat-resisting slip layer coating fluid afterwards, and dry.

Can enumerate illustrative method in the coating of above-mentioned dye coating as the rubbing method of above-mentioned heat-resisting slip layer coating fluid, wherein preferred intaglio plate rubbing method.

Can be coated with above-mentioned heat-resisting slip layer coating fluid, make drying coated amount be preferably 0.1g/m ²～3g/m ², this drying coated amount is 1.5g/m more preferably ²Below.

(protection transfer printing layer)

Hot transfer piece of the present invention (2) can be on substrate sheets and the face dye coating homonymy has the protection transfer printing layer according to the mode that is the face order with dye coating.

Be not particularly limited as above-mentioned protection transfer printing layer, for example can enumerate the existing known protection transfer printing layer that constitutes with laminate etc., described laminate has transparent resin bed, plasticizer resistance properties resin bed and Thermoadhesive resin bed by base material side lamination successively.Above-mentioned protection transfer printing layer also can contain conductive layer and replace above-mentioned plasticizer resistance properties resin bed.

Various resins in above-mentioned transparent resin bed, above-mentioned plasticizer resistance properties resin bed and above-mentioned Thermoadhesive resin bed are not particularly limited, as long as deterioration does not take place during each comfortable print, can use to have known resin now.As above-mentioned conductive layer, can enumerate the conductive layer that for example uses above-mentioned colloid shape inorganic pigment ultra micron to form.

As the protection transfer printing layer in the above-mentioned hot transfer piece (2), preferably constitute the protection transfer printing laminate of protective layer transfer printing sheet of the present invention described later.

(print)

Hot transfer piece of the present invention (2) can utilize existing known sensible heat printer to be transferred at hot transfer printing imaging film etc. and form desired images on the material.And, when hot transfer piece of the present invention (2) also has the protection transfer printing layer, except transfer printing forms desired image, can also be to desired field transfer printing protection transfer printing layer.

Be not particularly limited as above-mentioned hot transfer printing imaging film, can enumerate the imaging film that the receiving layer with dye-acceptancy for example is set on existing known base material.

Be not particularly limited as the base material in the above-mentioned hot transfer printing imaging film, can enumerate for example common paper, good quality paper, translucent drawing paper, plastic foil etc.

Receiving layer in the above-mentioned hot transfer printing imaging film can adopt rubbing method and utilize thermal head or the forming method of hot-rolling etc. waits and forms.In addition, in the above-mentioned hot transfer printing imaging film,, just receiving layer needn't be set as long as base material itself has dye-acceptancy.

Above-mentioned hot transfer printing imaging film can be a shape arbitrarily such as card, postcard, passport, notepaper, report paper, notebook, catalogue.

Condition of photographic printing among the present invention is not particularly limited, and can suitably set according to the formation of employed hot transfer piece (2), hot transfer printing imaging film etc.

As mentioned above, because hot transfer piece of the present invention (2) transfer printing sensitivity excellence, so also can access the high photographic printed material of printing concentration even under low energy condition, carry out print, troubles such as also being difficult for producing the print fold even print speed accelerates.

Hot transfer piece of the present invention (2) for example can be made and the photographic printed material that has equal printing concentration by the resulting photographic printed material of existing thermal diffusion type hot transfer piece with existing 80% energy.

3. protective layer transfer printing sheet

As a form of protective layer transfer printing sheet of the present invention, for example shown in Figure 3, on the face of the side of substrate sheets 1c, have protection transfer printing laminate 3c, and heat-resisting slip layer 7c is set on another face of substrate sheets 1c.In form shown in Figure 3, among the above-mentioned protection transfer printing laminate 3c by substrate sheets one side lamination matcoveredn 4c successively, conductive layer 5c and adhesive layer 6c.

In the protective layer transfer printing sheet of the present invention, above-mentioned protection transfer printing laminate 3c also can be arranged on the above-mentioned substrate sheets 1c across adherent layer 2c for example as shown in Figure 4.

In addition, if substrate sheets 1c is good with the antistick characteristic of protection transfer printing laminate 3c, the formation of then above-mentioned adherent layer 2c is not necessary.

Below each layer that constitutes protective layer transfer printing sheet of the present invention described.

(substrate sheets)

As the substrate sheets in the protective layer transfer printing sheet of the present invention, can directly use and be used for the existing used identical substrate sheets of substrate sheets of hot transfer piece.Being not particularly limited for above-mentioned substrate sheets, can be through various surface-treated substrate sheets such as easy adhesion process.

As above-mentioned substrate sheets, plastic foils such as preference such as PETG polyester such as [PET], Merlon, polyamide, polyimides, cellulose acetate, polyvinylidene chloride, polyvinyl chloride, polystyrene, fluorine resin, polypropylene, polyethylene, ionomer; Stationeries such as cellophane cover, kraft capacitor paper, waxed paper; Cellophane etc.

And above-mentioned substrate sheets also can be with the composite membrane after the material laminations two or more in above-mentioned plastic foil, stationery and the cellophane.

The thickness that can suitably set above-mentioned substrate sheets according to material is so that its intensity and hear resistance are comparatively appropriate, but this thickness is preferably about 2.5 μ m～100 μ m.

(adherent layer)

In the protective layer transfer printing sheet of the present invention, good for the transfer printing that makes protection transfer printing laminate, preferably the zone of the protection of the formation in the surface of substrate sheets transfer printing laminate is provided with adherent layer.

As the resin that forms above-mentioned adherent layer, so long as existing known antistick characteristic resin, resin all is fine arbitrarily, for example can enumerate wax class, silicone wax, silicone resin, silicone modified resin, fluorine resin, contain fluorine modified resin, polyvinyl alcohol, acrylic resin, heat cross-linking epoxy-amino resins and heat cross-linking alkyd-amino resins etc.

Among the present invention, above-mentioned adherent layer both can contain a kind of resin, also can contain the resin more than 2 kinds.

Above-mentioned adherent layer can form in for example following mode: above-mentioned antistick characteristic resin dissolves is obtained the adherent layer coating fluid in solvent; utilizing the zones that are formed with protection transfer printing laminate of methods in substrate surface such as existing known intaglio plate rubbing method, the reverse rubbing method of intaglio plate to be coated with above-mentioned adherent layer coating fluid, to make thickness (dried standard) be about 0.5 μ m～5 μ m, and carry out drying.

Crosslinking agent of can be with above-mentioned antistick characteristic resin and adding as required or catalyst dissolution in appropriate solvent such as MEK, toluene, isopropyl alcohol to prepare above-mentioned adherent layer coating fluid.The preferred solid component concentration of above-mentioned adherent layer coating fluid is about 5 quality %～50 quality %.

Above-mentioned adherent layer can suitably be selected following adherent layer: be transferred to the adherent layer of transfer printing body, the adherent layer (non-transfer printing adherent layer) that (2) residue in substrate sheets one side, the adherent layer that (3) aggegation destroys etc. during (1) hot transfer printing; but consider the aspects such as transfer printing stability of lustrous surface, protection transfer printing laminate, preferred (2) non-transfer printing adherent layer.In the protective layer transfer printing sheet of the present invention; when protecting the transfer printing laminate when the adherent layer of non-transfer printing is arranged on the substrate sheets; this moment is if carry out hot transfer printing; then since protection transfer printing laminate be transferred to the image that is formed on the transfer printing body above become the protective layer of this image; and adherent layer is stayed substrate sheets one side, thereby can improve the antistatic behaviour and the transparency of gained photographic printed material.

And, if wish after transfer printing, to obtain the protective layer of delustring, then can be by in adherent layer, adding various particles or delustering being carried out on the surface of protective layer one side of adherent layer handled and make surperficial rough-shape attitude.

(protection transfer printing laminate)

Protective layer transfer printing sheet of the present invention strippingly has protection transfer printing laminate on the part surface at least of substrate sheets.

In the above-mentioned protection transfer printing laminate, usually on the surface of a side of substrate sheets by substrate sheets one side lamination successively (I) protective layer, (II) conductive layer and (III) adhesive layer.

Above-mentioned (I) protective layer to be formed at the image on the transfer printing body and to be transferred on this image in order to protect usually, and this protective layer can use existing known any resin, so long as durability and the excellent resin of the transparency get final product.

As the resin in above-mentioned (I) protective layer, can enumerate for example acrylic resin, cellulosic resin, polyethylene acetate resin, mylar etc.

Above-mentioned (I) protective layer can form in for example following mode: with above-mentioned resin dissolves be dispersed to appropriate solvent or dispersion liquid in make protective layer coating solution, utilize above-mentioned existing known method that coating fluid is coated on and make thickness (dry back standard) be 0.5g/m on the surface of adherent layer ²～5g/m ²About, and carry out drying.

Above-mentioned protective layer coating solution can similarly prepare with above-mentioned adherent layer coating fluid.Consider transfer printing, preferred above-mentioned protective layer does not contain quaternary ammonium salt surface active agent.

As the 1st mode in the protective layer transfer printing sheet of the present invention, above-mentioned (II) conductive layer uses colloid shape inorganic pigment ultra micron and forms.In the protective layer transfer printing sheet of the present invention,, above-mentioned (II) conductive layer forms, so the barrier of protection transfer printing laminate and transfer printing height and plasticizer resistance properties are good owing to being to use colloid shape inorganic pigment ultra micron.

As above-mentioned colloid shape inorganic pigment ultra micron, can enumerate for example illustrative example in above-mentioned hot transfer piece (1), wherein preferred electric conductivity colloid shape inorganic pigment ultra micron.

As above-mentioned electric conductivity colloid shape inorganic pigment ultra micron, can use for example metal silicate such as alumina silicate, magnesium silicate; Metal oxide-type such as aluminium oxide or hydrated alumina (alumina sol, colloidal alumina, cationic aluminum oxide or its hydrate, pseudobochmite etc.), magnesia, titanium oxide; Carbonate such as magnesium carbonate; Deng existing known compound, but preferable alloy is oxide-based and carbonate, more preferably metal oxide-type, further preferred aluminium oxide or hydrated alumina, especially preferred alumina sol.

Because (II) conductive layer of above-mentioned the 1st mode as protective layer transfer printing sheet is to use colloid shape inorganic pigment ultra micron to form, so needn't contain binder resin, considers the coating weight that can reduce the conductive layer coating fluid, does not preferably contain binder resin.

Among the present invention, for the ease of being distributed in the aqueous solvent with the colloidal sol shape, thereby above-mentioned colloid shape inorganic pigment ultra micron both can mix dispersion stabilizers such as hydrochloric acid, acetate and be treated to acid type, can also be surface treated particulate with the electric charge cationization of particulate also.

Colloid shape inorganic pigment ultra micron among the present invention can be for example alumina sol 100 (daily output chemical industry society produce), alumina sol 200 commercially available products such as (daily output chemical industry society produce).

As the 2nd mode of protective layer transfer printing sheet of the present invention, (II) of the present invention conductive layer can use the inorganic pigment ultra micron to form, and (II) conductive layer does not contain binder resin.As above-mentioned inorganic pigment ultra micron, except above-mentioned colloid shape inorganic pigment ultra micron, also can be that the spy opens the described acicular crystal electric conductivity of 2003-145946 communique inorganic substances etc., even but consider the aspect of not using its film forming of binder resin also excellent, preferred colloid shape inorganic pigment ultra micron, and, consider the aspect of excellent electric conductivity, preferred electric conductivity inorganic pigment ultra micron, more preferably electric conductivity colloid shape inorganic pigment ultra micron.

Above-mentioned (II) conductive layer both can be use in the 1st mode of protective layer transfer printing sheet of the present invention above-mentioned colloid shape inorganic pigment ultra micron and the conductive layer that forms more than a kind or 2 kinds, also can be use in the 2nd mode of protective layer transfer printing sheet of the present invention above-mentioned inorganic pigment ultra micron and the conductive layer that forms more than a kind or 2 kinds.

Contain the ultramicronized average grain diameter of the above-mentioned ultramicronized inorganic pigment of colloid shape inorganic pigment and be generally below the 100nm, be preferably below the 50nm, be preferably 3nm～30nm especially.

Contain the ultramicronized average grain diameter of the above-mentioned ultramicronized inorganic pigment of colloid shape inorganic pigment in above-mentioned scope the time, can access the very excellent protective layer transfer printing sheet of antistatic behaviour.

In this specification; not indicating for (II) conductive layer is under the situation of any mode in the 1st mode of protective layer transfer printing sheet of the present invention or the 2nd mode; this moment is as (II) conductive layer, be in the 1st mode of protective layer transfer printing sheet of the present invention and the 2nd mode the explanation carried out of common item.

According to whiteness, give purposes such as disguise, toning, above-mentioned (II) conductive layer can have various pigment, dyestuff, fluorescent whitening agent, other additives in the scope that does not influence electric conductivity.

Above-mentioned (II) conductive layer can form in for example following mode: make the inorganic pigment ultra micron be dispersed into collosol state in aqueous medium; form the conductive layer coating fluid; use this coating fluid on above-mentioned (I) protective layer, to be coated with and drying, form (II) conductive layer thus.

As the aqueous medium in the above-mentioned conductive layer coating fluid, can enumerate the mixed liquor of water-soluble alcohols such as water, isopropyl alcohol, water and water-soluble alcohol etc.

In the above-mentioned conductive layer coating fluid, the preferred inorganic pigments ultra micron is 1 mass parts～300 mass parts with respect to the aqueous medium of 100 mass parts.

Because above-mentioned (II) conductive layer can not contain binder resin, thereby compare with the conductive layer that the conductive layer coating fluid (obtaining by dispersed electro-conductive agent in binder resin) that uses in the past forms, the present invention (II) conductive layer can be with the less desired electric conductivity of coating weight acquisition.In the protective layer transfer printing sheet of the present invention, owing to having (II) conductive layer that can form, so can be transferred to transfer printing body by the protective layer that the transparency is high with less coating weight.

Above-mentioned conductive layer coating fluid can be with dried coating weight at 0.1g/m ²～10g/m ²The amount of scope be coated with, consider the aspect of giving excellent antistatic behaviour, can be preferably 0.15g/m with above-mentioned coating weight ²More than, 0.2g/m more preferably ²Above amount is coated with.In addition, consider that antistatic behaviour is abundant, can be preferably 5g/m with above-mentioned coating weight ²Below, 3g/m more preferably ²Following amount is coated with.

Above-mentioned drying can be carried out heated-air drying etc. usually so that the inorganic pigment ultra micron becomes the desiccant gel shape by the colloidal sol shape.

Above-mentioned (III) adhesive layer is formed on the face with respect to substrate sheets one side of above-mentioned (II) conductive layer, has the effect that improves the adaptation of protection transfer printing laminate and transfer printing body after the transfer printing.

Above-mentioned (III) adhesive layer can utilize the existing known adhesive of sensible heat arbitrarily to form, but is that 50 ℃～80 ℃ thermoplastic resin forms by glass transition temperature preferably.

As above-mentioned thermoplastic resin, can enumerate for example ultraviolet-absorbing resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, mylar, polycarbonate resin, butyral resin, polyamide, vinyl chloride resin etc.

Above-mentioned (III) adhesive layer can similarly form with above-mentioned adherent layer.

In the protective layer transfer printing sheet of the present invention, protection transfer printing laminate is to demonstrate 1 * 10 under 60% the environment at 23 ℃, relative humidity ⁵Ω/～1 * 10 ¹⁰The surface resistivity of Ω/, this surface resistivity is preferably 1 * 10 ⁶Ω/～5 * 10 ⁹The scope of Ω/.

In this specification; the surface resistivity of above-mentioned protection transfer printing laminate is to be determined as follows the value that obtains: utilize high resistivity to measure machine (Hiresta IP MCP-HT250; DIAINSTRUMENTS society produces); according to JIS K 6911, be that 23 ℃, relative humidity are under 60% the environment surface of the protection transfer printing laminate before forming image to be measured in temperature.

In the protective layer transfer printing sheet of the present invention, owing to have the protection transfer printing laminate that demonstrates the surface resistivity in the above-mentioned scope, thereby its excellent antistatic property, troubles such as static can appear when being transferred to transfer printing body producing hardly.

(heat-resisting slip layer)

Heat-resisting slip layer in the protective layer transfer printing sheet of the present invention, the mobility of thermal head etc. when improving hear resistance and print and on the face with respect to protection transfer printing laminate one side of above-mentioned substrate sheets, use thermoplastic resin to form.

As above-mentioned thermoplastic resin, the preferred polyester resinoid; The polyacrylate resinoid; The polyvinyl acetate esters resin; The styrene-acrylate resinoid; The polyurethanes resin; Polyolefin resin such as polythylene resin, polypropylene-based resin; Polystyrene resins; Polyvinyl chloride resin; The polyethers resin; Polyamide-based resin; Polyimide based resin; The polyamideimides resin; Polycarbonate resin; Polyacrylate resin; Polyacrylamide resin; Corvic; The polyvinyl butyral resin; Thermoplastic resin such as polyethylene acetate resins such as polyethylene acetyl acetate resin and their silicone modifier etc. are considered aspects such as hear resistance, more preferably polyamideimides resin or its silicone modifier etc.

In order to carry high-slip, above-mentioned heat-resisting slip layer can also add hot antitack agents such as wax, high fatty acid amide, ester, metallic soap, silicone oil, surfactant except that containing above-mentioned thermoplastic resin; Organic dusts such as fluorine resin; Various additives such as inorganic particulate such as silica, clay, talcum, calcium carbonate.

Above-mentioned heat-resisting slip layer can be by preparing heat-resisting slip layer coating fluid, being coated with this coating fluid and dry formation.

Above-mentioned heat-resisting slip layer coating fluid both can be the coating fluid that only contains above-mentioned thermoplastic resin, also can be also to mix the coating fluid that has added additive and formed as required except above-mentioned thermoplastic resin.

Consider excellent protective layer transfer printing sheets such as can obtaining hear resistance, the thickness of above-mentioned heat-resisting slip layer is preferably 2g/m with the solid constituent canonical representation ²Below, 0.1g/m more preferably ²～1g/m ²

(painted thermal transfer ink layer)

Protective layer transfer printing sheet of the present invention both can be the transfer printing sheet that above-mentioned protection transfer printing laminate only is set on substrate sheets, also can be the transfer printing sheet that above-mentioned protection transfer printing laminate and painted thermal transfer ink layer are set by the face order on same of substrate sheets.

That is to say; protective layer transfer printing sheet of the present invention also can be following form: have above-mentioned protection transfer printing laminate on the part surface of substrate sheets; have painted thermal transfer ink layer according to being face mode in proper order with above-mentioned protection transfer printing laminate on the surface of above-mentioned substrate sheets, this painted thermal transfer ink layer is monochromatic above sublimable dye layer or monochromatic above hot-melt type coloring agent layer.

In the protective layer transfer printing sheet of the present invention; also on the substrate sheets according to being provided with under the situation of painted thermal transfer ink layer by the mode that is face order with above-mentioned protection transfer printing laminate; can the usability thermal printer desired image be formed at and be transferred on the material, also can be needed on the desired image field by protection transfer printing laminate simultaneously.

Above-mentioned sublimable dye layer can utilize existing known method to be formed by known sublimable dye and known binder resin, for example, can form equally with above-mentioned hot transfer piece (1) etc.

Above-mentioned hot-melt type coloring agent layer can utilize existing known method to be formed by hot melt property materials such as known pigment and known waxes.

Can enumerate following transfer printing sheet as protective layer transfer printing sheet of the present invention; this transfer printing sheet is for having protection transfer printing laminate on the part surface of substrate sheets; and the hot transfer piece that on the surface of described substrate sheets, has painted thermal transfer ink layer according to the mode that is face order with described protection transfer printing laminate; described painted thermal transfer ink layer is monochromatic above sublimable dye layer or monochromatic above hot-melt type coloring agent layer; wherein said protection transfer printing laminate comprises conductive layer and further comprises protective layer; the following formation of described protective layer transfer printing sheet: on the part surface of a side of described substrate sheets, described protective layer is set and forms laminate; on all surfaces of the side that is provided with described protective layer of described laminate, described conductive layer is set, on this conductive layer and the zone of described protective layer below not being in described painted thermal transfer ink layer is set then.

The formation of each layers such as base material, conductive layer and painted thermal transfer ink layer in the described protective layer transfer printing sheet is identical with above-mentioned protective layer transfer printing sheet.

Described protective layer transfer printing sheet is owing to have described conductive layer, thereby the cohesive of base material and painted thermal transfer ink layer is good, can carry out hot transfer printing at a high speed, and the unusual transfer printing of painted thermal transfer ink layer on imaging film can not occur.

The preferred implementation of above-mentioned protective layer transfer printing sheet is provided with protective layer 4d as shown in Figure 5 on the face top of base material 2d, on this protective layer 4d and be not provided with on the base material 2d of protective layer 4d conductive layer 3d is set all sidedly.And; also can on conductive layer 3d, adhesive layer 7d be set according to the zone that the mode of protective layer 4d below being in is provided with; under this situation, these three layers of protective layer 4d, conductive layer 3d, adhesive layer 7d are transferred to transfer printing body as protection transfer printing laminate 6d.And, on base material 2d and the face face opposite side that is provided with protective layer 4d, heat-resisting slip layer 10d can be set, when this heat-resisting slip layer is set, can prevents with the thermal head fusion and improve mobility etc.

And when the outmost surface of protection transfer printing laminate 6d was provided with adhesive layer 7d, transfer printing and cohesive on transfer printing body were improved.And; in the different place, formation zone of shifting laminate 6d with protection; between protection transfer printing laminate 6d and next protection transfer printing laminate 6d; be sequentially set with painted thermal transfer ink layer by face; preferably be provided with weld layer (Y), magenta dye layer (M) and the cyan dye layer (C) of painted thermal transfer ink layer 5d, the unit 9d (not shown) that contains tricolored painted thermal transfer ink layer 5d and protection transfer printing laminate 6d preferably is concatenated to form on the length direction of protective layer transfer printing sheet.Further, also can be between weld layer (Y) and the magenta dye layer (M), between magenta dye layer (M) and the cyan dye layer (C), between cyan dye layer (C) and the protection transfer printing laminate 6d and between protection transfer printing laminate 6d and the weld layer (Y) certification mark 8d is set.

Above-mentioned protective layer 4d, adhesive layer 7d and certification mark 8d can be existing known compositions, for example can to open the 2003-312151 communique identical with the spy.

(transfer printing etc.)

Protective layer transfer printing sheet of the present invention also is provided with under the situation of above-mentioned painted thermal transfer ink layer, can form image on transfer printing bodies such as for example hot transfer printing imaging film, further can transfer printing protection transfer printing laminate.

Among the present invention, above-mentioned protection transfer printing laminate both can be needed on all surfaces of formed image, also can only be needed on specific part.

Photographic printed material with following feature also is one of the present invention, in this photographic printed material, uses protective layer transfer printing sheet transfer printing of the present invention to form at least part surface of protection transfer printing layered product with overlay image.Protection transfer printing laminate in the photographic printed material of the present invention is to use protective layer transfer printing sheet of the present invention to form, and has the conductive layer (II) that uses the inorganic pigment ultra micron to form, so barrier height and plasticizer resistance properties are good.Therefore, even photographic printed material of the present invention and the resin Long contact time that contains plasticizer such as polyvinyl chloride also can make the dyestuff in the dyestuff receiving layer shift hardly, can keep image.

Hot transfer printing imaging film as the transfer printing that can be used for above-mentioned protective layer transfer printing sheet is not particularly limited, and can enumerate the imaging film of introducing when describing for for example hot transfer piece of the present invention (1).

Can use protective layer transfer printing sheet of the present invention to make card-like such as ID card, identity card, driving license.

Except image informations such as photos, above-mentioned card-like also can contain Word message.

Among the present invention, on above-mentioned card-like, form in the situation of Word message, can form this literal information, form image informations such as photo in the sublimation transfer mode in heat fusing transfer printing mode.

Embossing, signature, IC storage, magnetosphere, holographic and other printings etc. can also further be set on above-mentioned card-like, also embossing, signature, magnetosphere etc. can be set after the transfer printing laminate is protected in transfer printing.

When using protective layer transfer printing sheet formation image of the present invention or protecting the transfer printing of transfer printing laminate; both can set the proper transfer condition and carry out dye transfer and the transfer printing of protection transfer printing laminate on different respectively thermal transfer printers, also the printing energy that can suitably adjust on same printer in each transfer printing carries out above-mentioned two kinds of transfer printings.

Protective layer transfer printing sheet of the present invention also can utilize heating plate, hot-die sheet, hot-rolling, circuit heater, iron etc. to carry out transfer printing, and is not limited to thermal transfer printer.

Because sheet material of the present invention has above-mentioned formation, so transfer printing is good.Wherein, hot transfer piece of the present invention and base material or dye coating all have good cohesive, can carry out hot transfer printing with high speed, and dye coating can be to the unusual transfer printings of imaging film.Further, dyestuff was transferred to substrate layer from dye coating when above-mentioned hot transfer piece can prevent print, dyestuff is spread to receiving layer one side from imaging film effectively, so the transfer printing in the print was highly sensitive, can improve printing concentration.Especially, because hot transfer piece of the present invention (2) uses the lower base material of substrate intensity to form, thereby can not utilize high stretch process to make, can make the photographic printed material of film originally with the one-tenth that is lower than existing thermal diffusion type hot transfer piece.

Because protective layer transfer printing sheet of the present invention has above-mentioned formation, its transfer printing and excellent antistatic property can produce troubles such as static hardly when being transferred to transfer printing body.Therefore, utilize protective layer transfer printing sheet of the present invention can obtain the photographic printed material of the transparency, plasticizer resistance properties and excellent antistatic property.

Enumerate embodiment below and comparative example further describes the present invention.In addition, except specified otherwise, part or % in the article are standard with the quality.

Every data in each embodiment and each comparative example are measured with following steps.

1. base material thickness

Utilize micrometer (MFC-191, Nikon society produces) to measure the thickness of 10 overlapping base materials, utilize the value of measuring to ask the calculation base material thickness.

2. fracture strength and elongation at break

Measure according to JIS C 2151.

Embodiment 1

Be to utilize the intaglio plate rubbing method to be coated with the substrate layer coating fluid 1 of following composition on PETG (PET) film of 4.5 μ m at the thickness as base material, making drying coated amount is 0.06g/m ², dry back forms substrate layer.

Utilize the intaglio plate rubbing method to be coated with the dye coating coating fluid of following composition above the substrate layer at this, making drying coated amount is 0.7g/m ², dry back forms dye coating, has made the hot transfer piece of embodiment 1.

In addition, on the surface of the opposite side of above-mentioned base material, formed heat-resisting slip layer in advance as follows: utilize the intaglio plate rubbing method to be coated with the heat-resisting slip layer coating fluid of following composition, so that drying coated amount is 1.0g/m ², dry back forms heat-resisting slip layer.

＜substrate layer coating fluid 1 〉

50 parts of colloidal silicas (ス ノ one テ Star Network OXS, particle diameter is 4nm～6nm, daily output chemical industry (strain) production)

25 parts in water

25 parts of isopropyl alcohols

＜dye coating coating fluid 〉

C.I. solvent blue 63 (エ ス レ Star Network BX-1, ponding chemical industry (strain) is produced) is 6.0 parts

3.0 parts of polyvinyl butyral resins (エ ス レ Star Network BX-1, ponding chemical industry (strain) is produced)

45.5 parts of MEKs

45.5 parts of toluene

＜heat-resisting slip layer coating fluid 〉

13.6 parts of polyvinyl butyral resins (エ ス レ Star Network BX-1, ponding chemical industry (strain) is produced)

0.6 part of polyisocyanate curing agent ( ケ ネ one ト D218, military field pharmaceutical industries (strain) is produced)

0.8 part of phosphate (プ ラ イ サ one Off A208S, the first industrial pharmacy (strain) is produced)

42.5 parts of MEKs

42.5 parts of toluene

Embodiment 2

Substrate layer in the hot transfer piece that will make among the embodiment 1 changes into the following composition, operation similarly to Example 1, the hot transfer piece of making embodiment 2.

＜substrate layer coating fluid 2 〉

50 parts of alumina sols (daily output chemical industry (strain) is produced for alumina sol 200, featheriness form)

25 parts in water

25 parts of isopropyl alcohols

Embodiment 3

Substrate layer in the hot transfer piece that will make among the embodiment 1 changes into the following composition, operation similarly to Example 1, the hot transfer piece of making embodiment 3.

＜substrate layer coating fluid 3 〉

25 parts of alumina sols (daily output chemical industry (strain) is produced for alumina sol 520, boehmite plate crystal form)

37.5 parts in water

37.5 parts of isopropyl alcohols

Comparative example 1

Use the base material of the PET film identical, and on the face of the opposite side of this base material, be pre-formed heat-resisting slip layer similarly to Example 1 with embodiment 1 condition.On the relative face of the face with being provided with heat-resisting slip layer of this base material, utilize the intaglio plate rubbing method directly to be coated with the dye coating coating fluid that uses among the embodiment 1, so that drying coated amount is 0.7g/m ², dry back forms dye coating, has made the hot transfer piece of comparative example 1.

Comparative example 2

Use the base material of the PET film identical, and on the face of the opposite side of this base material, be pre-formed heat-resisting slip layer similarly to Example 1 with embodiment 1 condition.On the relative face of the face with being provided with heat-resisting slip layer of this base material, utilize the intaglio plate rubbing method to be coated with the adhesive layer coating fluid 1 of following composition, so that drying coated amount is 0.06g/m ², dry back forms adhesive layer.And then, on this adhesive layer, form the dye coating identical with embodiment 1, made the hot transfer piece of comparative example 2.

＜adhesive layer is formed liquid 1 〉

10 parts of polyvinylpyrrolidone resins (K-90, ISP society produces)

100 parts in water

100 parts of isopropyl alcohols

Comparative example 3

Use the base material of the PET film identical, and on the face of the opposite side of this base material, be pre-formed heat-resisting slip layer similarly to Example 1 with embodiment 1 condition.On the relative face of the face with being provided with heat-resisting slip layer of this base material, utilize the intaglio plate rubbing method to be coated with the adhesive layer coating fluid 2 of following composition, so that drying coated amount is 0.06g/m ², dry back forms adhesive layer.And then, on this adhesive layer, form the dye coating identical with embodiment 1, made the hot transfer piece of comparative example 3.

＜adhesive layer is formed liquid 2 〉

3 parts in mylar (WR-961, Japanese synthetic chemical industry (strain) is produced)

50 parts in water

50 parts of isopropyl alcohols

Test example 1

Hot transfer piece for embodiment 1～3 and comparative example 1～3 is determined as follows.

＜reflection density 〉

Use each embodiment of above-mentioned making and the hot transfer piece of comparative example, combined with the P-400 printer that OLYMPUS company produces with special-purpose hot transfer printing imaging film, carry out print under the following conditions, utilize Macbeth reflection of the concentration RD-918 to measure reflection density.

(condition of photographic printing)

Thermal head: KGT-217-12MPL20 (KYOCERA's (strain) production)

Heater average electrical resistance: 2994 (Ω)

Main scanning direction print density (character-display unit): 300dpi

Sub scanning direction print density: 300dpi

Add electric power: 0.10 (w/dot)

1 line period: 5 (msec)

Printing beginning temperature: 40 (℃)

Applying pulse (gradation control method): the test printing machine that uses the multiple-pulse mode, it can be changed into 0 to 255 and has the editing pulse number that 1 line period is divided into 256 parts pulse length in 1 line period, the dutycycle (duty ratio) of each editing pulse is fixed in 70%, the umber of pulse of each line period is divided into 15 parts by 0 to 255.15 grades of different energy can be provided thus.

Reflection density when the photographic printed material in the various embodiments described above and the comparative example is measured concentration maximum (the 255th tonal gradation).

The bonding strength of＜dye coating 〉

Use the hot transfer piece of above-mentioned making, sticking glass paper self-adhesive tape on dye coating (registration mark is セ ロ テ one プ) is also comforted repeatedly with thumb and to be pressed 2 times, tear immediately afterwards, observation is torn back adhesive tape one side and whether is adhered to dye coating, thus the bonding strength of dye coating is estimated.

Estimate with following standard.

Zero: do not observe adhering to of dye coating.

△: only observe adhering to of some dye coatings.

*: observe adhering to of dye coating at whole face.

＜antistick characteristic evaluation 〉

Under the condition of photographic printing identical with the situation of measuring above-mentioned reflection density, with photographic printed material all is that solid (tonal gradation 255/255: the print pattern concentration maximum) carries out print, and whether the dye coating of perusal hot transfer piece and hot transfer printing imaging film heat takes place merge or unusual transfer printing (dye coating of promptly ining succession is transferred to hot transfer printing imaging film) does not take place after the print.

Estimate with following standard.

Zero: heat does not take place and merges in dye coating and hot transfer printing imaging film, and unusual transfer printing does not take place.

*: the heat fusion takes place or unusual transfer printing takes place in dye coating and hot transfer printing imaging film.

The evaluation result of the measurement result of above-mentioned reflection density, the bonding strength of dye coating and antistick characteristic is shown in following table 1.

[table 1]

	Substrate layer	Reflection density	The bonding strength of dye coating	Antistick characteristic is estimated
					Embodiment 1	Colloidal silica	2.39	△	○
Embodiment 2	Alumina sol	2.56	○	○
					Embodiment 3	Alumina sol	2.3	○	○
Comparative example 1	-	2.16	×	×
					Comparative example 2	The polyvinylpyrrolidone resin	2.15	○	○
Comparative example 3	Mylar	1.93	○	○

By The above results as can be known, in the hot transfer piece of embodiment 1～3, be provided with between base material and dye coating and contain the ultramicronized substrate layer of colloid shape inorganic pigment, the reflection density of described hot transfer piece all is more than 2.30, to be high concentration.And the hot transfer piece among the embodiment 1～3 has all obtained good result aspect antistick characteristic, and dye coating is also no problem for the cohesive of base material.

In the hot transfer piece of comparative example 1,2,3, do not contain the ultramicronized substrate layer of colloid shape inorganic pigment owing between base material and dye coating, be provided with, thereby above-mentioned reflection density can not satisfy the condition as the photographic printed material of high concentration less than 2.2.And, in the comparative example 1, at dye coating for the problem that exists aspect the antistick characteristic of the cohesive of base material and dye coating and hot transfer printing imaging film in the practicality.

Embodiment 4

Except using PETG [PET] film (thickness is 4.0 μ m, and substrate intensity is 3.5) as beyond the base material, operate similarly to Example 1, make the hot transfer piece of embodiment 4.

Embodiment 5

Except using PET film (thickness is 4.5 μ m, and substrate intensity is 3.5) as beyond the base material, operate similarly to Example 1, make the hot transfer piece of embodiment 5.

Embodiment 6

Except using PET film (thickness is 4.5 μ m, and substrate intensity is 3.7) as beyond the base material, operate similarly to Example 2, make the hot transfer piece of embodiment 6.

Embodiment 7

Except using PET film (thickness is 4.5 μ m, and substrate intensity is 3.5) as beyond the base material, operate similarly to Example 3, make the hot transfer piece of embodiment 7.

Comparative example 4

Except using PET film (thickness is 4.5 μ m, and substrate intensity is 3.5) as beyond the base material, similarly operate with comparative example 1, make hot transfer piece.

Comparative example 5

Except using PET film (thickness is 4.5 μ m, and substrate intensity is 4.0) as beyond the base material, similarly operate with comparative example 1, make hot transfer piece.

Test example 2

Hot transfer piece for embodiment 4～7 and comparative example 4～5 carries out following test.

1. the highest printing concentration

Use subliming type thermal transfer printer (メ ガ ピ Network セ Le III, ア Le テ Star Network society produces) and the certified products developing-out paper of above-mentioned printer, carry out print with the cyan solid pattern, utilize reflection of the concentration Macbeth RD-918 (C filter) that the photographic printed material that obtains is measured, ask the highest printing concentration of calculation.

In addition, the gray value of print data is 100% solid with 255 tonal gradations, and the gray value during print is this pattern with respect to the external energy of maximum external energy (for example, if the gray value during print is 210 grades divided by 255 ratio, 210/255=0.823 then, promptly 83% is solid).

Can be by change the gray value when regulating above-mentioned print arbitrarily with Photo Shop.

2. the fold gray value does not appear

In the photographic printing method of record, per 5 grades ground changes gray value, carries out the print of solid pattern in above-mentioned 1., in the time of will occurring than fold a little less than the energy of one-level be made as and the fold gray value do not occur.

Evaluation result is in table 2 illustrate.

[table 2]

	Use base material		Substrate layer (prime coat)	The print data
						Thickness (μ m)	Substrate intensity	The highest printing concentration (OD value)	The fold gray value does not appear
	Embodiment 4	4.0		3.5	Substrate layer 1					2.20	200
Embodiment 5			4.5			3.5	Substrate layer 1	2.20	200
	Embodiment 6	4.5		3.7	Substrate layer 2					2.25	200
Embodiment 7			4.5			3.5	Substrate layer 3	2.20	200
	Comparative example 4	4.5		3.5	Do not have					1.80	200
Comparative example 5			4.5			4.0	Do not have	2.20	255

By the result as can be known, though the substrate intensity of the photographic printed material that obtains among the embodiment 4～7 is lower, only be 3.5 or 3.7, also can obtain with substrate intensity be 4.0 comparative example 5 the highest equal printing concentration.On the other hand, compare with the highest printing concentration of the photographic printed material that obtains among the embodiment 4～7, the highest printing concentration of the photographic printed material that is obtained by the hot transfer piece of the comparative example 4 that does not have substrate layer of the present invention is relatively poor.

Embodiment 8

Utilize the intaglio plate rubbing method to be coated with the heat-resisting slip layer coating fluid of following composition on substrate sheets (thickness is 4.5 μ m for PETG [PET] film, the production of Toray society), making drying coated amount is 0.5g/m ², dry back forms heat-resisting slip layer.

＜heat-resisting slip layer coating fluid 〉

50.0 parts of polyamide-imide resins (HR-15ET, Japan weaving society produces)

50.0 parts of polyamidoimide silicone resins (HR-14ET, Japan weaving society produces)

10.0 parts of stearoyl trbasic zinc phosphates (LBT-1830 is refining, and Sakai chemistry society produces)

10.0 parts of zinc stearates (GF-200, Japanese grease society produces)

3.0 parts in mylar (バ イ ロ Application 220, Japan weaving society produces)

10.0 parts of inorganic fillers (talcum, average grain diameter are 4.2 μ m)

Then, utilize the intaglio plate rubbing method to be coated with the protective layer coating solution A of following composition on the face of the relative side with heat-resisting slip layer of substrate sheets, making drying coated amount is 1.0g/m ², dry back forms protective layer.

＜protective layer coating solution A 〉

50 parts of acrylic resins (ダ イ ヤ Na one Le BR-83, RAYON society of Mitsubishi produces)

25 parts of MEKs

25 parts of toluene

Then, utilize the intaglio plate rubbing method to be coated with the conductive layer coating fluid A of following composition on above-mentioned protective layer, making drying coated amount is 0.2g/m ², dry back forms conductive layer.

＜conductive layer coating fluid A 〉

50 parts of alumina sols (daily output chemical industry society produces for alumina sol 100, hydrochloric acid stable type)

25 parts in water

25 parts of isopropyl alcohols

And then, on above-mentioned conductive layer, utilize the intaglio plate rubbing method to be coated with the adhesive layer coating fluid of following composition, making drying coated amount is 1.5g/m ², obtain the protective layer transfer printing sheet of embodiment 8 after the drying.

＜adhesive layer coating fluid 〉

69.6 parts in mylar (バ イ ロ Application 700, Japan weaving society produces)

With 17.4 parts of the acrylic copolymers of reactive ultra-violet absorber reaction bonded (PUVA-50M-40TM, big  chemistry society produces)

25 parts of silica (サ イ リ シ ア 310, Silysia society of Fuji produces)

Embodiment 9

Except the conductive layer coating fluid A that the conductive layer coating fluid B that uses following composition replaces using among the embodiment 8, operate similarly to Example 8, obtain the protective layer transfer printing sheet of embodiment 9.

＜conductive layer coating fluid B 〉

50.0 parts of alumina sols (daily output chemical industry society produces for alumina sol 200, acetate stable type)

25.0 parts in water

25.0 parts of isopropyl alcohols

Embodiment 10

On the protective layer transfer printing sheet of making in embodiment 8, utilize the intaglio plate rubbing method to be coated with the adherent layer coating fluid of following composition between substrate sheets and protective layer, making drying coated amount is 1.0g/m ², obtain adherent layer after the drying, in addition, operate similarly to Example 8, obtain the protective layer transfer printing sheet of embodiment 10.

＜adherent layer coating fluid 〉

45.7 parts of silicone modified acroleic acid resinoids (セ Le ト Star プ 226, DAICEL chemistry society produces)

8.5 parts of Al catalysts (セ Le ト Star プ CAT-A, DAICEL chemistry society produces)

22.9 parts of MEKs

22.9 parts of toluene

Comparative example 6

In the protective layer transfer printing sheet of in embodiment 8, not making, be provided with the conductive layer, operate similarly to Example 8, obtain the protective layer transfer printing sheet of comparative example 6.

Comparative example 7

Except the protective layer coating solution B that uses following composition replace using among the embodiment 8 protective layer coating solution A and be not provided with the conductive layer, operation similarly to Example 8 obtains the protective layer transfer printing sheet of comparative example 7.

＜protective layer coating solution B 〉

50 parts of acrylic resins (ダ イ ヤ Na one Le BR-83, RAYON society of Mitsubishi produces)

25 parts of needle-like conductive inorganic substances (FSS-10M, the former テ Network of stone ノ society produces)

37.5 parts of MEKs

37.5 parts of toluene

(FSS-10M is for containing the conductive material of tin oxide (being doped with antimony).Solid constituent is 30%, and draw ratio is 20～30.)

Comparative example 8

Except the protective layer coating solution C that uses following composition replace using among the embodiment 8 protective layer coating solution A and be not provided with the conductive layer, operation similarly to Example 8 obtains the protective layer transfer printing sheet of comparative example 8.

＜protective layer coating solution C 〉

50 parts of acrylic resins (ダ イ ヤ Na one Le BR-83, RAYON society of Mitsubishi produces)

25 parts of quaternary ammonium salt surface active agents (ス テ イ サ イ De, ACL society produces)

37.5 parts of MEKs

37.5 parts of toluene

Protective layer transfer printing sheet to embodiment 8～10 and comparative example 6～8 carries out following test.

1. transparent

Use Y (Huang), M (fuchsin), C (green grass or young crops) three look subliming type hot transfer pieces; utilize printer (CP-2000; Mitsubishi Electric society produces) on special-purpose developing-out paper, stamp and deceive solid image; obtain photographic printed material; use the protective layer transfer printing sheet of embodiment 8～10 or comparative example 7～8; utilize the transfer printing protection on photographic printed material of above-mentioned printer to shift laminate, the difference of the photographic printed material concentration that the situation of this moment and protective layer transfer printing sheet by comparative example 6 are obtained is confirmed, estimates according to following evaluation criterion.In addition, above-mentioned photographic printed material concentration is that to utilize colorimeter (Macbeth densimeter RD-918, Macbeth society system) be to measure near 2.0 to obtain to the O.D. value.

(evaluation criterion)

Zero: though be lower than the photographic printed material that is obtained by comparative example 6, the photographic printed material concentration difference is less than 5%.

△: the photographic printed material concentration than the photographic printed material that is obtained by comparative example 6 is low, and its concentration difference is less than 10% scope more than or equal to 5%.

*: the photographic printed material concentration than the photographic printed material that is obtained by comparative example 6 is low, and its concentration difference is more than 10%.

2. transfer printing

Use printer and the special-purpose developing-out paper identical, under the condition identical, protect the transfer printing of transfer printing laminate, obtain photographic printed material thus with above-mentioned 1. with above-mentioned 1., this photographic printed material of perusal, and estimate according to following standard.

(evaluation criterion)

Zero: protection transfer printing laminate is transferred fully.

*: the transfer printing of protection transfer printing laminate has part to be interrupted.

3. plasticizer resistance properties

Each photographic printed material that protection transfer printing laminate is arranged for the method transfer printing that utilizes above-mentioned 1.; soft PVC sheet (the production ア of the Mitsubishi Chemical society Le ト ロ Application of plasticizer will be added with; #480; thickness is 400 μ m) coincide with above-mentioned each photographic printed material; apply the load of 40g to the per unit square centimeter; preserved 60 hours down in 50 ℃ environment, perusal since the damage (dyestuff transfer) of the photographic printed material that plasticizer causes estimate according to following evaluation criterion.

(evaluation criterion)

Zero: do not confirm dyestuff and shift.

△: the dyestuff on the soft PVC sheet shifts less.

*: the dyestuff on the soft PVC sheet shifts more.

4. surface resistivity

Utilize high resistivity to measure machine (Hiresta IP MCP-HT250; DIA INSTRUMENTS society produces); according to JIS K 6911; in temperature is that 23 ℃, relative humidity are the voltage that applies 100V under 60% the environment, and the protection transfer printing laminate that forms on the protective layer transfer printing sheet before the image is measured applying the surface resistivity of voltage after 10 seconds.And profit uses the same method the surface resistivity of protecting the transfer printing laminate to be needed on the photographic printed material that forms on the image is measured.

Each evaluation result is in table 3 illustrate.

[table 3]

	The transparency	Transfer printing	Plasticizer resistance properties	The surface resistivity of protection transfer printing laminate (Ω/)	The surface resistivity of photographic printed material (Ω/)
						Embodiment 8	○	○	○	3×10 8	3×10 8
Embodiment 9	○	○	○	5×10 9	5×10 9
						Embodiment 10	○	○	○	3×10 8	3×10 8
Comparative example 6	○	○	△	Super scope	Super scope
						Comparative example 7	×	○	△	6×10 9	6×10 9
Comparative example 8	△	×	×	7×10 10	7×10 10

The transfer printing of the protective layer transfer printing sheet of embodiment 8～10 is good, and surface resistivity is low, and, the transparency of resulting photographic printed material and plasticizer resistance properties excellence, surface resistivity is also lower.

On the other hand, can confirm by the result, the surface resistivity height of the protective layer transfer printing sheet of comparative example 6～8, the plasticizer resistance properties of resulting photographic printed material is bad.Especially, the transparency of the photographic printed material that obtains in comparative example 7 and the comparative example 8 is also relatively poor, and the transfer printing of the protective layer transfer printing sheet that obtains in the comparative example 8 is also relatively poor.

Industrial utilizability

Because sheet material of the present invention has above-mentioned formation, so transfer printing is good. Wherein, hot transfer piece of the present invention and base material or dye coating all have good cohesive, can carry out hot transfer printing with high speed, and dye coating can be to the unusual transfer printings of imaging film. Further, dyestuff was transferred to substrate layer from dye coating when above-mentioned hot transfer piece can prevent print, can effectively carry out imaging film to the dye diffusion of receiving layer one side, so the transfer printing in the print was highly sensitive, can improve printing concentration. Especially, because hot transfer piece of the present invention (2) forms with the lower base material of substrate intensity, thereby can not utilize high stretch process to make, can originally make with the one-tenth that is lower than existing thermal diffusion type hot transfer piece the photographic printed material of film.

Because protective layer transfer sheet of the present invention has above-mentioned formation, thereby its transfer printing and excellent antistatic property, can produce hardly the troubles such as static when being transferred to transfer printing body. Therefore, utilize protective layer transfer sheet of the present invention can obtain the photographic printed material of the transparency, plasticizer resistance properties and excellent antistatic property.

Claims (16)

1. sheet material, it is the sheet material that contains base material, this sheet material is characterised in that, it is hot transfer piece (I) or protective layer transfer printing sheet (II), described hot transfer piece (I) is lamination base material, substrate layer and dye coating and form successively, and described protective layer transfer printing sheet (II) strippingly has the protection transfer printing laminate that contains conductive layer on the part surface at least of base material; Wherein said substrate layer and conductive layer form by using colloid shape inorganic pigment ultra micron.

2. a hot transfer piece is characterized in that, in this hot transfer piece, forms successively on a face of base material and contains ultramicronized substrate layer of colloid shape inorganic pigment and dye coating.

3. hot transfer piece as claimed in claim 2 wherein, further is provided with heat-resisting slip layer on the opposite face of the side with being provided with described dye coating of described base material.

4. as claim 2 or 3 described hot transfer pieces, it is characterized in that described colloid shape inorganic pigment ultra micron is colloidal silica or alumina sol.

5. as claim 2 or 3 described hot transfer pieces, wherein, described colloid shape inorganic pigment ultra micron is an alumina sol.

6. hot transfer piece, this hot transfer piece is by lamination base material, prime coat and dye coating obtain successively, this hot transfer piece is characterised in that, described prime coat forms by using colloid shape inorganic pigment ultra micron, the substrate intensity of described base material is more than or equal to 3.5, less than 4.0, and this substrate intensity is with the fracture strength S on the length direction ₁(MPa) and elongation at break S ₂(MPa) ratio S ₁/ S ₂Represent.

7. hot transfer piece as claimed in claim 6, this hot transfer piece are the hot transfer piece of thermal diffusion type.

8. protective layer transfer printing sheet; it is characterized in that; this protective layer transfer printing sheet strippingly has protection transfer printing laminate on the part surface at least of substrate sheets, described protection transfer printing laminate contains the conductive layer by using colloid shape inorganic pigment ultra micron to form.

9. protective layer transfer printing sheet as claimed in claim 8, wherein, described colloid shape inorganic pigment ultra micron is an alumina sol.

10. protective layer transfer printing sheet; it is characterized in that; this protective layer transfer printing sheet strippingly has protection transfer printing laminate on the part surface at least of substrate sheets; described protection transfer printing laminate contains by the conductive layer that uses the inorganic pigment ultra micron to form, and described conductive layer does not contain binder resin.

11. protective layer transfer printing sheet as claimed in claim 10, wherein said inorganic pigment ultra micron is an alumina sol.

12. as each described protective layer transfer printing sheet of claim 8～11, wherein, described protection transfer printing laminate is across the adherent layer of non-transfer printing and be arranged on the substrate sheets.

13. as each described protective layer transfer printing sheet of claim 8～12, wherein, described protection transfer printing laminate is by forming in substrate sheets one side lamination protective layer, conductive layer and adhesive layer successively.

14. as each described protective layer transfer printing sheet of claim 8～13; wherein; this protective layer transfer printing sheet has protection transfer printing laminate on the part surface of substrate sheets; and on the surface of described substrate sheets, having painted thermal transfer ink layer according to being face mode in proper order with described protection transfer printing laminate, described painted thermal transfer ink layer is monochromatic above sublimable dye layer or monochromatic above hot-melt type coloring agent layer.

15. protective layer transfer printing sheet, this protective layer transfer printing sheet is each described protective layer transfer printing sheet of claim 8～12, it is the hot transfer piece that has painted thermal transfer ink layer according to the mode that is the face order with described protection transfer printing laminate having on the part surface of substrate sheets on protection transfer printing laminate and the surface in described substrate sheets, and described painted thermal transfer ink layer is monochromatic above sublimable dye layer or monochromatic above hot-melt type coloring agent layer; Wherein,

Described protection transfer printing laminate comprises conductive layer and further comprises protective layer;

Described protective layer transfer printing sheet forms as follows: on the part surface of a side of described substrate sheets described protective layer is set and forms laminate; on all surfaces of the side that is provided with described protective layer of described laminate, described conductive layer is set, on this conductive layer and the zone of described protective layer below not being in described painted thermal transfer ink layer is set then.

16. a photographic printed material is characterized in that, this photographic printed material is to protect the transfer printing laminate to obtain with the part surface at least of overlay image by using each described protective layer transfer printing sheet transfer printing of claim 8～16 to form.

Images