CN1827392A - Thermal transfer receiver, method for producing the same, method for recording image, and recorded image - Google Patents
Thermal transfer receiver, method for producing the same, method for recording image, and recorded image Download PDFInfo
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- CN1827392A CN1827392A CN 200610004548 CN200610004548A CN1827392A CN 1827392 A CN1827392 A CN 1827392A CN 200610004548 CN200610004548 CN 200610004548 CN 200610004548 A CN200610004548 A CN 200610004548A CN 1827392 A CN1827392 A CN 1827392A
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Abstract
The objects of the present invention are to provide a thermal transfer receiver adapted to form transferred images excellent in solvent resistance and superior in wear resistance, a method for producing the thermal transfer receiver, a method for recording an image, and a recorded image. The objects may be attained by the thermal transfer receiver which comprises a support and a receiving layer disposed on the support, and the receiving layer contains a polyethyleneimine derivative, a thermoplastic resin, and a crosslinker.
Description
Technical field
The present invention relates to a kind of hot transfer printing acceptor and manufacture method, recording method and record body that forms transferred image with excellent solvent resistance and rub resistance.
Background technology
With thermal printing head hot tranfer recording medium is heated, the method that makes Yin Mo be transferred to formation image on the acceptor is known for people, and is applied to the making as labels such as nameplates.
Under the environment that uses the organic solvent as methyl ethyl ketone (MEK), use described label occasion, requirement is transferred to image on the label not by this organic solvent cancellation.
In the past, as having the excellent seal China ink transfer printing and the acceptor of resistance rerum natura, can enumerate and open flat 5-286227 communique, spy as the flat 4-115995 communique of Japan Patent Publication Laid-Open, spy and open flat 8-43994 communique and specially open that disclosed in the flat 8-58250 communique to use ethene at receiving layer be the acceptor of oligomer resin.
Again, the acceptor with coating layer of being made up of the addition polymers of the aziridine of unsaturated carboxylic acid olefin copolymer and poly-imines based polymer is disclosed in the flat 2002-113959 communique of Japan Patent Publication Laid-Open.
Yet according to these motions, the solvent resistance that is formed at the image on receiving layer or the coating layer is still not talkative fully.
Have, for obtaining the solvent resistance of transferred image, the someone attempts adding the same a kind of resin with excellent solvent resistance in Yin Mo and receiving layer again.For example, a kind of specific polyolefinic method of using has been proposed on No. 2533456 communique of Japan Patent in seal inkwood fat and receiving layer.Again, open on the 2001-199171 communique, proposed a kind of method ink layer and receiving layer interpolation Fypro at flat 4-347688 communique of Japan Patent Publication Laid-Open and spy.But present situation is, in these motion methods, also can't obtain tolerating the solvent resistance of the image of very severe service condition.
Again, in having the acceptor of receiving layer, for improving the crocking resistance of image, the someone has considered to improve the intensity of receiving layer, for example, the method for bottom is set between receiving layer and support.
Specifically, proposition is provided with the method for the bottom that comprises uv-hardening resin and (opens clear 61-112693 communique with reference to the spy between receiving layer and support, the spy opens clear 61-121993 communique, Te Kaiping 1-228890 communique, Te Kaiping 1-244890 communique, the spy opens flat 2-223495 communique and the spy opens flat 4-275194 communique).In addition, propose between receiving layer and support, to be provided with the method for the bottom that comprises thermmohardening type resin.
Yet the shortcoming of these motions is, the insufficient strength of receiving layer be the more important thing is, the solvent resistance that is arranged at the image on the receiving layer is low.
Summary of the invention
The present invention puts forward for solving the existing problem of above-mentioned prior art, the objective of the invention is to, a kind of hot transfer printing acceptor that forms the transferred image with excellent solvent resistance and crocking resistance is provided, use the recording method of this acceptor, and on hot transfer printing acceptor, form the record images body by this recording method.
To achieve these goals, the present invention proposes following scheme:
(1) a kind of hot transfer printing acceptor, described hot transfer printing acceptor comprises support, and is sequentially with bottom and receiving layer on this support, it is characterized in that:
Described receiving layer contains polyethylenimine derivates, thermoplastic resin and crosslinking agent.
(2) in the hot transfer printing acceptor of (1), it is characterized in that described support is made of plastic sheeting.
In the hot transfer printing acceptor of (1), it is characterized in that (3) described support is the polyester film of proportion 0.9-1.2.
(4) in the hot transfer printing acceptor of (1), it is characterized in that the support of described support for forming by stacked many films of bond layer.
In the hot transfer printing acceptor of (4), it is characterized in that (5) at least a of film that constitutes support is pet film.
(6) in the hot transfer printing acceptor of (4), it is characterized in that between the film that constitutes support, having metal level.
(7) in the hot transfer printing acceptor of (4), it is characterized in that at least one face of support, having metal level.
In the hot transfer printing acceptor of (1), it is characterized in that (8) described bottom contains the salt and the crosslinking agent of ethylene-methacrylic acid copolymer.
(9) in the hot transfer printing acceptor of (1), it is characterized in that described bottom contains ultraviolet curing resin and pigment.
In the hot transfer printing acceptor of (9), it is characterized in that (10) described ultraviolet curing resin contains at least a in urethane acrylate and the epoxy acrylate.
(11) in the hot transfer printing acceptor of (1), it is characterized in that described bottom contains thermohardening type resin and pigment.
In the hot transfer printing acceptor of (11), it is characterized in that (12) described thermohardening type resin is to be selected from least a in epoxy resin, melamine resin and the unsaturated polyester resin.
In the hot transfer printing acceptor of (1), it is characterized in that (13) described underlayer thickness is 0.5-3.0 μ m.
In the hot transfer printing acceptor of (1), it is characterized in that (14) thermoplastic resin in the receiving layer is the salt of ethylene-methacrylic acid copolymer.
In the hot transfer printing acceptor of (1), it is characterized in that (15) crosslinking agent in the receiving layer is an epoxide.
(16) in the hot transfer printing acceptor of (1), it is characterized in that receiving layer contains inorganic pigment, this inorganic pigment is at least a in calcium carbonate and the calcined kaolin.
In the hot transfer printing acceptor of (16), it is characterized in that (17) particle diameter of inorganic pigment is 0.5-4.0 μ m.
In the hot transfer printing acceptor of (1), it is characterized in that (18) the receiving layer surface is 200-3000 second based on the smoothness of JIS P8119.
In the hot transfer printing acceptor of (1), be characterised in that (19) thickness of receiving layer is 0.3-8.0 μ m.
(20) in the hot transfer printing acceptor of (1), it is characterized in that, between support and bottom, be provided with metal level.
(21) a kind of manufacture method of hot transfer printing acceptor is characterized in that, described method comprises:
Bottom forms operation, and coating contains the bottom coating fluid of resin and water at least on support, forms bottom;
Receiving layer forms operation, and coating contains the receiving layer coating fluid of polyethylenimine derivates, thermoplastic resin, crosslinking agent and water on this bottom, forms receiving layer.
(22) a kind of record method is characterized in that:
Use hot tranfer recording medium and hot transfer printing acceptor, described hot tranfer recording medium is to be sequentially with the peel ply that contains wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer on support at least, and described hot transfer printing acceptor is to be sequentially with bottom and to contain polyethylenimine derivates, thermoplastic resin, and the receiving layer of crosslinking agent on support;
The receiving layer of the ink layer of above-mentioned hot tranfer recording medium and above-mentioned hot transfer printing acceptor is superimposed, carry out hot transfer printing.
(23) a kind of record body is characterized in that:
Use hot tranfer recording medium and hot transfer printing acceptor, described hot tranfer recording medium is to be sequentially with the peel ply that contains wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer on support at least, and described hot transfer printing acceptor is to be sequentially with bottom and to contain polyethylenimine derivates, thermoplastic resin, and the receiving layer of crosslinking agent on support;
The receiving layer of the ink layer of above-mentioned hot tranfer recording medium and above-mentioned hot transfer printing acceptor is superimposed, carry out hot transfer printing, by this record method, on hot transfer printing acceptor, form image.
Hot transfer printing acceptor of the present invention comprises support, and is sequentially with bottom and receiving layer on this support, and described receiving layer contains polyethylenimine derivates, thermoplastic resin and crosslinking agent.According to hot transfer printing acceptor of the present invention, the image that is transferred on this hot transfer printing acceptor has excellent tolerance for methyl ethyl ketone (MEK) equal solvent, and has excellent rub resistance.
The manufacture method of hot transfer printing acceptor of the present invention comprises:
Coating contains the bottom coating fluid of resin and water at least on support, and the bottom that forms bottom forms operation;
Coating contains the receiving layer coating fluid of polyethylenimine derivates, thermoplastic resin, crosslinking agent and water on this bottom, to form the operation of receiving layer.
According to recording method of the present invention, use:
Hot tranfer recording medium, it is to be sequentially with the peel ply that contains wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer on support at least;
Above-mentioned hot transfer printing acceptor of the present invention;
The receiving layer of the ink layer of above-mentioned hot tranfer recording medium and above-mentioned hot transfer printing acceptor is superimposed, carry out hot transfer printing.Its result can write down and makes the image that is formed on the receiving layer have image for the tolerance of the excellence of MEK equal solvent and excellent rub resistance.
According to above-mentioned recording method of the present invention, record body of the present invention forms image on above-mentioned hot transfer printing acceptor of the present invention.
The specific embodiment
Below, present invention will be described in detail with reference to the accompanying embodiment, in following examples, though to inscape, kind, combination waits has done various qualifications,, these only exemplify, and the present invention is not limited thereto.
Hot transfer printing acceptor
Hot transfer printing acceptor of the present invention has support, is sequentially with bottom and receiving layer and constitutes on this support, also has metal level, and other layers optionally.
Receiving layer
Above-mentioned receiving layer contains polyethylenimine derivates, thermoplastic resin and crosslinking agent, also contains inorganic pigment, and other compositions optionally.
Polyethylenimine derivates
As above-mentioned polyethylenimine derivates, can enumerate: as polymine (making the polymer of aziridine ring-opening polymerisation), on the side chain of other polymer of acrylic acid series polymeric compounds etc., make the polymine of polymine glycerol polymerizationization polymer-modified, polymine modified acroleic acid based polymer etc.Nationality can improve the tolerance of image for methyl ethyl ketone (MEK), toluene, dimethylbenzene equal solvent especially by the interpolation of such polyethylenimine derivates.
The content of above-mentioned polyethylenimine derivates in described receiving layer, % is advisable with the 5-75 quality, is more preferably 20-60 quality %.If above-mentioned content is less than 5 quality %, it is low then to improve the solvent resistance effect sometimes, and above-mentioned content surpasses 75 quality %, and then its resistance to water may be low.
Thermoplastic resin
As above-mentioned thermoplastic resin and without particular limitation, can do corresponding the selection according to purpose, for example can enumerate water-soluble resin, emulsion and aqueous dispersion etc.
As above-mentioned water-soluble resin, can enumerate for example partly-hydrolysed polyvinyl alcohol, fully saponified polyvinyl alcohol, by the polyvinyl alcohol of modified polyethylene alcohol such as carboxyl, carboxylic acid sodium, sodium sulfonate, acetoacetyl, cation radical etc.; The starch or derivatives thereof; Cellulose derivative as methoxyl group cellulose, hydroxyethylcellulose, carboxylic first collection cellulose, methylcellulose, ethyl cellulose etc.; As polyacrylic acid, Sodium Polyacrylate, polyvinylpyrrolidone, acrylamide and acrylic acid ester copolymer, acrylamide and acrylic acid ester-metering system acid ter-polymer, the alkali salt of styrene-maleic anhydride copolymer, the alkali salt of isobutene-copolymer-maleic anhydride, polyacrylamide, mosanom, gelatin etc.
As above-mentioned emulsion or aqueous dispersion, can enumerate, as polyvinyl acetate resin, polyurethane resin, SB, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic acid series copolymer, polyacrylate, polymethacrylates, vinyl chloride-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, the salt of ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, polyvinylacetate-acrylic copolymer, ethene-vinyl acetate-acrylic copolymer, urethane-modified polyethylene, vinyl-acrylate copolymer, ethylene-propylene copolymer, ethylene-vinyl chloride copolymer, vinyl acetate-ethylene-vinyl chloride copolymer, polyester etc.
These thermoplastic resins can use separately, also can mix more than two kinds and use.
Wherein, be preferably the salt of mylar, polyurethane resin, methyl methacrylate butadi ene copolymer, ethylene-methacrylic acid copolymer, good especially is ethylene-methacrylic acid copolymer.
As above-mentioned mylar, its molecular weight is 10,000-25, and 000, and vitrification point (Tg) is advisable with 40-80 ℃.Particularly, can use Off ァ イ Application テ Star Network ス, the ペ ス レ ジ Application A of high terebinth corporate system etc. of バ イ ロ Na one Le of Toyo Boseki K.K's system, the black chemical industry of big Japan's seal society system.
As above-mentioned polyurethane resin, be preferably and use polyester-type, polyether-type, ester-ether type and vitrification point at 35-75 ℃ polyurethane resin.Particularly, can use the Ha イ De ラ Application etc. of the ス one パ one Off レ Star Network ス of the first industrial pharmacy society system, the black chemical industry of big Japan's seal society system.
As above-mentioned methyl methacrylate butadi ene copolymer, can enumerate, as the vitrification point of carboxylated copolymer at-70～20 ℃.Particularly, can use ラ Star Network ス one, the Japanese A ﹠amp of the black chemical industry of big Japan's seal society system; ス マ one テ ッ Network ス, the Na Le ス etc. of L corporate system.
The salt of above-mentioned ethylene-methacrylic acid copolymer is got the part of methacrylic acid by Na, K, Ca, Zn, NH
3Deng cation between strand, form crosslinked structure.Wherein, be preferably at least a salt that contains among Na, K and the Zn.Be preferably the methacrylic acid that contains the 15-25 quality % that has an appointment in the copolymer again.Have, be preferably, this salt partly is that the 25-75 quality % in the methacrylic acid of described copolymer is neutralized and the salt that forms.
Usually, be dissolved in the common solvent, therefore, in the present invention, should use the salt that is machined in the ethylene-methacrylic acid copolymer in the aqueous dispersion because the salt of ethylene-methacrylic acid copolymer is very difficult.Wherein, be preferably, the salt of ethylene-methacrylic acid copolymer does not use dispersant but the dispersion of self-emulsifying.Use the dispersion of dispersant or water-soluble resin forced emulsification, its dispersant or water-soluble resin can produce baneful influence to resistance to water, the solvent resistance of image.
As the salt of above-mentioned ethylene-methacrylic acid copolymer, can use the commercially available prod, as this commercially available prod, can enumerate ケ ミ パ one Le S-650, S-659 etc. as Mitsui Chemicals, Inc's system.
The content of above-mentioned thermoplastic resin in described receiving layer is advisable with 20-70 quality %.If described content is less than 20 quality %, then the intensity of receiving layer may descend, and surpasses 70 quality %, and then the solvent resistance of image may be low.
Crosslinking agent
For improving the solvent resistance of described receiving layer, in receiving layer, add crosslinking agent.
As described crosslinking agent, can enumerate, as carbodiimides, oxazoline, isocyanates, melamine compound, epoxide, multivalent metal salt etc.Wherein, good especially is epoxide.As this epoxide, be preferably the aliphatic epoxy compound, the epoxide equivalent of described epoxide is advisable with 150-200mg/eq.
The content of above-mentioned crosslinking agent in described receiving layer is advisable with 0.5-20 quality %, is more preferably 1-5 quality %.If described content is less than 0.5 quality %, then crosslinked meeting is insufficient, if surpass 20 quality %, then unreacted reactant can increase, and solvent resistance is low.
Inorganic pigment
As inorganic pigment, can enumerate as calcium carbonate, magnesium carbonate, silica, calcium silicates, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, calcined kaolin, talcum etc.Wherein, good especially is calcium carbonate, calcined kaolin.This calcium carbonate is preferably the alkali matter calcium carbonate of calcite type.
The particle diameter of above-mentioned inorganic pigment is advisable with 0.5-4.0 μ m, is more preferably 1.0-4.0 μ m.If above-mentioned particle diameter is less than 0.5 μ m, the solvent resistance that then is transferred to the image on the receiving layer sometimes is low, and particle diameter surpasses 4.0 μ m, then may make the fineness of transferred image low.
The content of above-mentioned inorganic pigment is advisable with 10-80 quality %, is more preferably 30-70 quality %.If less than 10 quality %, then the solvent resistance of transferred image may be low, and above 80 quality %, then the opacity of receiving layer increases, in the occasion that makes translucent acceptor and the back side occasion that the metal evaporation layer makes the silver color acceptor is set, possibly can't obtains good transparency and silvery appearance.
Have again, optionally, also can contain the additive of the lubricant, defoamer etc. of higher fatty acids slaine and alkene wax etc. at above-mentioned receiving layer.
The thickness of above-mentioned receiving layer is advisable with 0.3-8.0 μ m, is more preferably 1.0-8.0 μ m.If above-mentioned thickness less than 0.3 μ m, then is difficult to form the receiving layer of homogeneous sometimes, and thickness surpasses 8.0 μ m, and receiving layer is peeled off from support easily because of friction.
Again, the smoothness on above-mentioned receiving layer surface (JIS P-8119) is advisable with 200-3000 second, is preferably 200-1500 second, is more preferably 200-500 second.If above-mentioned surface smoothness was less than 200 seconds, then the fineness of image is low sometimes, and surpasses 3000 seconds, and then the solvent resistance of image may be low.
(JIS P-8119) becomes the 200-3000 method of second as the smoothness that makes above-mentioned receiving layer surface, have (1) to use the method for surface roughening film as support, or (2) adds the method for pigment etc. to receiving layer.
Support
As the support of above-mentioned hot transfer printing acceptor, be advisable to use plastic sheeting.
As above-mentioned support, be preferably the polyester film that proportion is 0.9-1.2 again.
The proportion of common mylar is about about 1.4, but the polyester film as using so then because of shock-absorbing capacity is lower, can cause the crocking resistance of image low.
As the method that obtains 0.9-1.2 proportion, have when forming film, make it to produce the method in trickle cavity.
If above-mentioned proportion is less than 0.9, then the intensity as support is low, if proportion surpasses 1.2, then shock-absorbing capacity is low, can cause the crocking resistance of print image to descend.
As the polyester resin film of above-mentioned proportion, just like polyester film of the white low-gravity type of the Le ミ ラ one of, the Network リ ス パ one of Toyo Boseki K.K's system, eastern Lei Co., Ltd. system etc. at 0.9-1.2.
As the material of above-mentioned support, can enumerate as polyester, polyethylene, polypropylene, polyvinyl chloride, polyether sulfone, polyphenylene sulfide, PEI, polyether-ether-ketone, polyimides, nylon, vinylon etc.
Also can use the synthetic paper of resin such as polyolefin coated or polyester on body paper again.
Wherein, good especially is the plastic sheeting of its surface roughening.On the plastic sheeting of such surface roughening, receiving layer is set, can further improve solvent resistance.The smoothness of roughened surface (JISP-8119) is preferably the second at 100-300.
Method as the surface roughening that makes above-mentioned plastic sheeting, the method that useful annular knurl roller is handled plastic sheeting (roughness is regulated and can be undertaken by the adjusting of the decorative pattern roughness of annular knurl roller), with a large amount of fine particles is jetted to plastic sheeting, make it roughening grit-blasting treatment process (but the adjusting nationality of roughness by the winding-up granular size and the change of amount carry out) etc.Again, also can use in the manufacturing process of plastic sheeting the coarse film of mixed grain that mixes and form into the roughening agent.
Again,, be preferably, use the support that forms via superimposed many films of bond layer as above-mentioned support.Such support is because of having suitable elasticity, when on its surface receiving layer being set, even be subjected to powerful wiping, the destruction of the image on the receiving layer can not taken place yet or come off.
Each stacked film both can be an identical type, also can be variety classes, considered from intensity, hear resistance and cost aspect, was advisable to use pet film.
By on the surface of support or constitute between the film of this support metal level is set, can make the hot transfer printing acceptor of silver color again.Above-mentioned metal level can use metals such as aluminium, silver, zinc, but to use aluminium desirable especially.As on the surface of support or constitute the method that metal level is set between the film of this support, can enumerate as using the galvanoplastic of chemical plating etc., and physical vapor depositions such as vacuum evaporation, ion plating, sputtering method, beam method, and the chemical vapor deposition method of hot CVD, plasma CVD, optical cvd, laser CVD etc. etc. is provided with the method for metal level.Above-mentioned metal layer thickness is advisable with 0.001-10 μ m, is more preferably 0.01-1 μ m.
The thickness of each stacked film is advisable with 5-75 μ m, is more preferably 10-50 μ m.
As the bonding agent that forms above-mentioned bond layer and without particular limitation, can be from suitably select for use according to purpose the known bonding agent in the past.For example, can use carbamide resin, melamine resin, phenolic resin, epoxy resin, vinyl acetate is that resin, vinyl acetate acrylic copolymer, EVA are that resin, acrylic resin, polyvinylether resin, vinyl chloride vinyl acetate are that resin, polystyrene resin, polyester based resin, polyurethane series resin, polyamide-based resin, (gathering) chloridized polyolefin are arbitrary bonding agent of resin, polyvinyl butyral resin, acrylate based copolymer, methacrylate ester copolymer, natural rubber system, cyanoacrylate system, silicone-based etc.
Also can add curing agent, plasticizer, filler as required at above-mentioned bond layer, prevent aging agent etc.
The thickness of above-mentioned bond layer is advisable with 1-20 μ m.
The thickness of the support by superimposed above-mentioned many films of bond layer is advisable with 20-300 μ m, is more preferably 25-250 μ m.
Again,, can use transparent or semitransparent material, on its at least one face, the metal evaporation layer is set, make the acceptor of silver color as the plastic sheeting of above-mentioned support.
Above-mentioned metal evaporation series of strata are used the metal of aluminium, silver, zinc etc., the metal level that is formed on support by the method for vacuum evaporation, electron beam spraying plating, sputtering method etc.Wherein, as the metal on the metal evaporation layer, the good especially aluminium that is to use.
The thickness of above-mentioned metal evaporation layer is advisable with 0.01-0.1 μ m.
Bottom
Between above-mentioned receiving layer and above-mentioned support, bottom is set.
As described bottom, be preferably the salt that contains ethylene-methacrylic acid copolymer and the priming coat of crosslinking agent.Nationality can improve the adhesive strength of support and receiving layer by the setting of described bottom.
The salt and the crosslinking agent that are used for the ethylene-acrylic acid copolymer of above-mentioned bottom can use as the same salt and the crosslinking agent that are used in receiving layer.Above-mentioned crosslinking agent is added to suitable for the salt of ethylene-acrylic acid copolymer with 0.5-5.0 quality %.
Again, above-mentioned bottom preferably contains ultraviolet curing resin and pigment.As this ultraviolet curing resin, can enumerate, for example, urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylic ester oligomer, polyalcohol acrylate oligomer etc.Have again, optionally, also can add acrylate monomer simultaneously with these oligomer.Also can add and be used to improve ultraviolet reactive sensitizer.Can use the ュ ニ デ イ Star Network of the black chemical industry of big Japan's seal society system etc. as these ultraviolet curing resins.
Again, above-mentioned bottom is advisable to contain thermohardening type resin and pigment.Can enumerate as this thermohardening type resin, for example, phenolic resin, carbamide resin, melamine resin, alkyd resins, acrylic resin, unsaturated polyester resin, diallyl phthalate, epoxy resin, polyurethane resin etc.Can use a kind of of these resins separately or mix two kinds of uses.Wherein, good especially is to use epoxy resin, melamine resin, unsaturated polyester resin or their combination.
Have again, optionally, can add and solidify required curing agent and curing accelerator.As curing agent, can enumerate as peroxidating methyl ethyl ketone, cyclohexanone peroxide, benzoyl peroxide etc.As curing accelerator, can there be cobalt naphthenate, dimethyl to replace phenylamino etc.
As the pigment that makes an addition to above-mentioned bottom, for example can use the inorganic pigment of calcium carbonate, magnesium carbonate, silica, calcium silicates, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, calcined kaolin, talcum etc.Can use organic pigment as acrylic resin particle, urea-formaldehyde resins particle, melamine resin particle, silicone resin particle, PTFE particle etc. etc. again.
The average grain diameter of the pigment of above-mentioned bottom is advisable with 0.5-4.0 μ m.Less than 0.5 μ m, then the concavo-convex degree of bottom surface is not enough, can reduce the cementability of bottom and receiving layer as the average grain diameter of above-mentioned bottom pigment, if surpass 4.0 μ m, then the fineness of transferred image descends.
The ratio of the ultraviolet curing resin of above-mentioned bottom or thermohardening type resin and pigment (portions of resin pigment) is advisable with 90: 10～50: 50 based on quality criteria.Less than 10, then the concavo-convex degree of bottom surface is not enough, can reduce the cementability of bottom and receiving layer as the ratio of pigment.On the other hand, if the pigment ratio surpasses 50, then the intensity of bottom may descend.
Optionally, also can add lubricant, dispersant, defoamer etc. in the above-mentioned bottom.
The thickness of above-mentioned bottom is advisable with 0.5-3.0 μ m.Be more preferably 1.0-2.0 μ m.Less than 0.5 μ m, then the raising effect of the cementability of bottom and receiving layer is low as the thickness of above-mentioned bottom, if surpass 3.0 μ m, then the solvent resistance of transferred image can descend.
Again, according to the present invention, the occasion at the hot transfer printing acceptor of wishing to get silver color is preferably between support and the bottom metal level is set.
Described metal level is made up of metals such as aluminium, silver, zinc.Wherein, good especially is aluminium.
Method to set up as above-mentioned metal level has, and for example uses the galvanoplastic of chemical plating etc.; Physical vapor deposition as vacuum evaporation, ion plating, sputtering method, beam method etc.; And as the chemical vapor deposition method of hot CVD, plasma CVD, optical cvd, laser CVD etc. etc.
Above-mentioned metal layer thickness is advisable with 0.001-10 μ m, is more preferably 0.01-1 μ m.
Again, also can hot transfer printing acceptor with the opposition side one side that receiving layer is set, sequential cascade is provided with bond layer, peeling paper, takes this, and hot transfer printing acceptor can be processed into the form that can be adhered to by the label on the convered structure.
Hot transfer printing acceptor of the present invention comprises support, bottom, receiving layer, and comprises that optionally the integral thickness of set bond layer etc. is advisable with 40-250 μ m again, is more preferably 70-150 μ m.Less than 40 μ m, then the intensity of acceptor is low as above-mentioned thickness, destroys easily; If surpass 250 μ m, then be pasted on by occasion on the sticky object as label, tangled easily and come off.
The manufacture method of hot transfer printing acceptor
The manufacture method of hot transfer printing acceptor of the present invention comprises following operation:
Bottom forms operation, is coated with the bottom coating fluid that contains resin and water on support at least, forms bottom;
Receiving layer forms operation, and coating contains the receiving layer coating fluid of polyethylenimine derivates, thermoplastic resin, crosslinking agent and water on this bottom, forms receiving layer;
Optionally, also can comprise other operations.
As the resin in the above-mentioned bottom coating fluid, as mentioned above, can enumerate salt, ultraviolet curing resin, thermohardening type resin of ethylene-methacrylic acid copolymer for example etc.
Coating process as above-mentioned receiving layer coating fluid and bottom coating fluid for example can use, and rotary rubbing method, contrary roller rubbing method, touches any method that rubbing method, continous way mould are coated with method, metering rubbing method, knife coating etc.
The coating amount of above-mentioned receiving layer is preferably 0.3～3.0g/m
2, be more preferably 0.5～1.0g/m
2If the coating amount of described receiving layer is less than 0.3g/m
2, then the intensity of receiving layer can reduce, and surpasses 3.0g/m
2, then the solvent resistance of image is low.
Recording method
Recording method of the present invention system uses hot tranfer recording medium and described hot transfer printing acceptor of the present invention, makes the receiving layer of the ink layer of described hot tranfer recording medium and described hot transfer printing acceptor superimposed, carries out hot transfer printing.
As above-mentioned heat-transferring method and without particular limitation, can do corresponding suitably selection according to purpose.For example, can enumerate the heater means of thermal printing head and laser etc.
Hot tranfer recording medium
The stacked above one another at least of tying up to above-mentioned hot tranfer recording medium on the support contains the peel ply of wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer forms, and also can optionally be provided with other layers.Thus, can obtain having the transferred image of more excellent solvent resistance.
Ink layer
The salt of the ethylene-methacrylic acid copolymer in the above-mentioned ink layer can use the same salt of salt of ethylene-methacrylic acid copolymer with the receiving layer that is used for hot transfer printing acceptor.
In the above-mentioned ink layer, except that the salt of ethylene-methacrylic acid copolymer, can use other resins.
As above-mentioned other resins, can enumerate water-soluble resin, emulsion and aqueous dispersion etc.As above-mentioned water-soluble resin, can enumerate: as partly-hydrolysed polyvinyl alcohol, fully saponified polyvinyl alcohol, by the polyvinyl alcohol of modified polyethylene alcohol such as carboxyl, sodium sulfonate group, acetoacetyl, cation radical etc.; The starch or derivatives thereof; The methoxyl group cellulose, hydroxyethylcellulose, carboxymethyl cellulose, methylcellulose, the cellulose derivative of ethyl cellulose etc.; As polyacrylic acid, Sodium Polyacrylate, polyvinylpyrrolidone, acrylamide and acrylic acid ester copolymer, acrylamide and acrylic acid ester-metering system acid ter-polymer, the alkali salt of styrene-maleic anhydride copolymer, the alkali salt of isobutene-copolymer-maleic anhydride, polyacrylamide, mosanom, gelatin etc.
As above-mentioned emulsion or aqueous dispersion, can enumerate, as polyvinyl acetate, polyurethane, SB, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic acid series copolymer, polyacrylic acid, polyacrylate, polymethacrylates, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinylacetate-acrylic copolymer, ethene-vinyl acetate-acrylic copolymer, urethane-modified polyethylene, copolymer in cinnamic acrylic ester, ethylene-propylene copolymer, ethylene-vinyl chloride copolymer, vinyl acetate-ethylene-vinyl chloride copolymer, polyester etc.
For improving hot transfer printing performance and resolution ratio, can optionally add various interpolation materials in the above-mentioned ink layer.For example, the synthetic wax class of the fatty acid amide of wax shape, various lubricant, alkene wax etc. be can add,, hot transfer printing performance and resolution ratio taken this to improve as the natural waxes of candelila wax and Brazil wax etc.Again, the lubricant of this moment except that the phosphate etc., also can use the resin particle class of silicone resin, TFE and fluoroalkyl ether resin etc.
As the colouring agent that can be used for above-mentioned ink layer, can be according to desired tone etc., use carbon black, organic pigment, inorganic pigment or from various dyestuffs, suitably select to use.
The thickness of above-mentioned ink layer is advisable with 0.5-6 μ m, is more preferably 0.8-3 μ m.
Peel ply
Above-mentioned peel ply contains bonding agent and wax, optionally also can contain other compositions and form.When the heat energy that applies from thermal printing head, this peel ply is peeled off from the support of ink layer easily, keeps good thermal sensitivity.Again, in transferred image, peel ply is positioned on the ink layer, and the protection ink layer is avoided the influence of solvent.
As above-mentioned bonding agent, can enumerate ethylene-vinyl acetate copolymer for example, polyamide, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetal, cellulose derivative, polyvinyl chloride, isobutene rubber, butadiene rubber, EP rubbers, butyl rubber, nitrile rubber etc.
As above-mentioned wax, can enumerate as beeswax, spermaceti, haze tallow, rice health wax, Brazil wax, candelila wax, montan wax, alkene wax, Tissuemat E, OPE, sour modified polyethylene wax, microwax, sour wax, ceresine, ceresin, ester type waxes, Heptadecanoic acide, laurate, tetradecanoic acid, palmitic acid, stearic acid, furancarboxylic acid, mountain Yu acid, stearyl alcohol, docosyl alcohol, sorbitan, stearmide, oleamide etc.
The thickness of above-mentioned peel ply is advisable with 0.2-0.3 μ m, is more preferably 1.0-2.0 μ m.
As the support in the above-mentioned hot tranfer recording medium, and without particular limitation, can directly use known film or paper.For example, be preferably, can use polyester as PETG etc.; As the hear resistance of Merlon, triacetyl cellulose, nylon, polyimides etc. plastic sheeting preferably; Viscose film (glassine paper); Template etc.
In hot tranfer recording medium, also can optionally protective layer be set at the back side of support again.When thermal printing head applied heat energy, this protective layer can protect support to avoid the influence of high temperature, except hear resistance high thermoplastic resin and thermohardening type resin, also can use ultraviolet curing resin and electron ray curing type resin.As being applicable to the resin that forms protective layer, can enumerate as fluororesin, silicone resin, polyimide resin, epoxy resin, phenolic resin, melamine resin etc.These resins can use the film shape.
In addition, by the hear resistance that protective layer can significantly improve support is set, therefore,, also can use to be considered to the support that should not use by this protective layer is set in the past.
More than ink layer of Xiang Shuing and peel ply can pass through the heat seeling coating method, and the rubbing method of use solvent etc. is laminated on the support and forms.By this rubbing method setting the layer integral thickness be advisable with 0.1-10 μ m, be more preferably 0.5-6.0 μ m.
The record body
Record body of the present invention forms image by above-mentioned recording method of the present invention on hot transfer printing acceptor.
Record body of the present invention has the transferred image of solvent resistance and rub resistance excellence, therefore, even under the environment that uses the organic solvent as methyl ethyl ketone (MEK), also can use no problemly.
Below, be described more specifically the present invention for embodiment.In following giving an example, " part " expression " mass parts ", " % " expression " quality % ".
Embodiment A-1
(1) making of hot tranfer recording medium
The pet film of preparing thick 4.5 μ m is as support, (Toray, ダ ゥ コ one ニ Application グ, silicone corporate system SD7226) is coated on an opposite side that has been coated with ink layer coating fluid one side with silicone rubber, make its drying, dried thickness is 0.35 μ m, makes the support with heat-resisting slip layer.
Peel ply coating fluid prescription
The toluene dispersion liquid of Brazil wax (solid constituent 10%) ... 90 parts
The toluene solution of ethylene-vinyl acetate copolymer (vinyl acetate amount 28 quality %, MFR=15dg/ branch)
(solid constituent 10%) ... 10 parts
The peel ply coating fluid of above-mentioned prescription is coated ink layer one side of support, make its drying, dried thickness is 1.0 μ m, and peel ply is set.
Ink layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 62 parts
The aqueous dispersion of carbon black (solid constituent 38%) ... 22 parts
Water ... 16 parts
The ink layer coating fluid of above-mentioned prescription is coated on the above-mentioned peel ply, made its drying, dried thickness is 0.8 μ m, and ink layer is set, and makes hot tranfer recording medium.
(2) making of hot transfer printing acceptor
Bond layer coating fluid prescription
Polyurethane series aqueous dispersion (big Japan refine industrial society system, ノ Application ソ Le ボ Application De WA-377) ... 72 parts
Curing agent (big Japan refine industrial society system, ノ Application ソ Le ボ Application De C-96) ... 2 parts
Water ... 26 parts
Bond layer coating fluid with above-mentioned composition, be coated with on the sided corona treatment face of the delustring polypropylene film (Toray Co., Ltd. system, ト レ Off ァ Application YM 11) of the thickness 20 μ m of sided corona treatment in its one side, make its drying, become 3.0 μ m thickness, form bond layer.Polypropylene film (the system パ イ レ of Toyo Boseki K.K Application P-2261) with this bonding agent aspect coating thickness is 20 μ m then, 40 ℃ of heat treatments 2 days, makes support.
Bottom coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 71.9 part
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.6 part
Water ... 27.5 part
With the bottom coating fluid of above-mentioned composition, on the delustring polypropylene film face of above-mentioned support, be coated with, drying, forming thickness is the bottom of 1.5 μ m.
Receiving layer coating fluid prescription
Calcined kaolin (ENGELHARD corporate system, aqueous dispersion ANSILEX) (particle diameter 0.8 μ m, solid constituent 25%) ... 34 parts
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 31 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.5 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%) ... 9 parts
Water ... 25.5 part
With the receiving layer coating fluid of above-mentioned composition, be coated on the above-mentioned bottom, drying, forming thickness is the receiving layer of 1.0 μ m.Again, the smoothness on receiving layer surface (JIS P8119) is 2,100 seconds.
Embodiment A-2
With the bond layer coating fluid that uses in the embodiment A-1, (eastern Lei Co., Ltd. system is coated with on sided corona treatment face S105), makes its drying through the pet film of the thickness 25 μ m of sided corona treatment in its one side, dried thickness is 3.0 μ m, forms bond layer.Delustring polypropylene film (the system polyester film E-3120 of Toyo Boseki K.K) with this bonding agent aspect coating thickness is 12 μ m after the applying, 40 ℃ of heat treatments 2 days, makes support.
Bottom coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 71.9 part
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.6 part
Water ... 27.5 part
With the bottom coating fluid of above-mentioned composition, on the delustring polypropylene film face of above-mentioned support, be coated with, drying, formation thickness is the bottom behind the 1.5 μ m.
Receiving layer coating fluid prescription
The aqueous dispersion of calcite type precipitated calcium carbonate (oil absorption 40cc/100g) (particle diameter 3.0 μ m, solid constituent 25%) ... 34 parts
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 31 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.5 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%) ... 9 parts
Water ... 25.5 part
With the receiving layer coating fluid of above-mentioned composition, be coated on the above-mentioned bottom, drying, forming thickness is the receiving layer of 1.0 μ m.Again, the smoothness on receiving layer surface (JIS P8119) is 2,000 seconds.
Hot tranfer recording medium is identical with embodiment A-1.
Embodiment A-3
Bond layer coating fluid with embodiment A-1 use, in pet film (Japan メ ラ イ ジ Application グ corporate system of its one side through the thickness 25 μ m of aluminium-vapour deposition processing, メ Le ミ one S) is coated with on the aluminium-vapour deposition treated side, make its drying, dried thickness is 3.0 μ m, forms bond layer.Delustring pet film (the system polyester film E-3120 of Toyo Boseki K.K) with this bonding agent aspect coating thickness is 12 μ m after the applying, 40 ℃ of heat treatments 2 days, makes support.
As embodiment A-2, bottom and receiving layer are set on above-mentioned support.The smoothness on receiving layer surface (JIS P8119) is 2,000 seconds.
Embodiment A-4
In embodiment A-1, except the support used thickness is that in addition, other make hot transfer printing acceptor as embodiment A-1 for the pet film (ュ ニ チ カ corporate system, エ Application Block レ ッ ト S-38LS) of 38 μ m.The smoothness on receiving layer surface (JIS P8119) is 1,500 second.
Hot tranfer recording medium is identical with embodiment A-1.
Comparative examples A-1
In embodiment A-1, except the prescription of receiving layer coating fluid adopt following, other make hot transfer printing acceptor as embodiment A-1.The smoothness on receiving layer surface (JIS P8119) is 2,100 seconds.
Hot tranfer recording medium is identical with embodiment A-1.
Receiving layer coating fluid prescription
Calcined kaolin (ENGELHARD corporate system, aqueous dispersion ANSILEX) (particle diameter 0.8 μ m, solid constituent 25%) ... 40 parts
Carboxylated SBR latex (big Japanese Yin Mo KCC system, LACSTAR DS-205, solid constituent 50%) ... 20 parts
Water ... 40 parts
Then, use prepared hot tranfer recording medium and hot transfer printing acceptor, print, estimate solvent resistance and rub resistance as described below by following condition.It the results are shown in table 1.
Print conditions
Printer: Zebra corporate system 96XiIII
Print speed: 2 inch per seconds
Print energy: Tone (tone) 26
Solvent resistance (MEK tolerance)
Cotton with impregnation methyl ethyl ketone (MEK) adds 100g/cm
2Load, image is observed in wiping 100 times, by following benchmark evaluation, solvent uses MEK.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image can not interpretation.
1: the result of friction test, image cancellation.
Rub resistance
Stainless steel with thick 0.5mm applies the load of 3.0gf to it, and wiping image 50 times is observed image, by following benchmark evaluation.
3: the result of friction test, with no change before the test.
2: the result of friction test, but image interpretation, but damage is arranged slightly.
1: the result of friction test, image is peeled off.
Table 1
| Anti-MEK | Rub resistance | |
| Embodiment A-1 | 5 | 3 |
| Embodiment A-2 | 5 | 3 |
| Embodiment A-3 | 5 | 3 |
| Embodiment A-4 | 4 | 2 |
| Comparative examples A-1 | 1 | 1 |
From the result of table 1, can understand that the image that uses embodiment A-1 to make to each hot transfer printing acceptor of A-4 not only has excellent tolerance for MEK, and has the excellent rub resistance to image.
Embodiment B-1
(1) making of hot tranfer recording medium
The pet film of preparing thick 4.5 μ m is as support, at the opposition side that has been coated with ink layer coating fluid side, coating silicone rubber (Toray ダ ゥ コ one ニ Application グ silicone corporate system SD7226), make its drying, make that dried thickness is 0.35 μ m, makes the support with heat-resisting slip layer.
Peel ply coating fluid prescription
The toluene dispersion liquid of Brazil wax (solid constituent 10%) ... 90 parts
The toluene solution (solid constituent 10%) of ethylene-vinyl acetate copolymer resin (vinyl acetate amount 28 quality %, MFR=15dg/ branch) ... 10 parts
The peel ply coating fluid of above-mentioned prescription is coated ink layer one side of support, and making it dried thickness is 1.0 μ m, forms peel ply.
Ink layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 62 parts
The aqueous dispersion of carbon black (solid constituent 38) ... 22 parts
Water ... 16 parts
The ink layer coating fluid of above-mentioned prescription is coated on the above-mentioned peel ply, made its drying, making it dried thickness is 0.8 μ m, and ink layer is set, and makes hot tranfer recording medium.
(2) making of hot transfer printing acceptor
The prescription of bottom coating fluid
Polyester acrylate (the black chemical industry of big Japan's seal Co., Ltd. system, ュ ニ デ イ ッ Network V-3021) ... 16 parts
Silica (marshy land chemistry society system, P-603) ... 4 parts
Methyl ethyl ketone (MEK) ... 80 parts
With the bottom coating fluid of above-mentioned composition, be coated on the polyester film (E5100, thickness 50 μ m) of Toyo Boseki K.K's system, make it dry, dried thickness is 1.5 μ m.Then, handled for 10 seconds, make its curing, form bottom with high-pressure mercury-vapor lamp (80W/cm).
Receiving layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 31 parts
Carbodiimides (Misshin Spinning Co., Ltd's system, E-20) ... 2 parts
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
3 parts
Water ... 64 parts
The receiving layer coating fluid of above-mentioned composition is coated on the above-mentioned bottom, makes it dry, dried thickness is 2.5 μ m, forms receiving layer, makes hot transfer printing acceptor.
Embodiment B-2
Bottom coating fluid prescription
Polyester acrylate (the black chemical industry of big Japan's seal Co., Ltd. system, ュ ニ デ イ ッ Network V-4221) ... 16 parts
Silica (marshy land chemistry society system, P-603) ... 4 parts
Methyl ethyl ketone (MEK) ... 80 parts
With the bottom coating fluid of above-mentioned composition, be coated on the polyester film of thickness 50 μ m of Toray Co., Ltd. system, make it dry, dried thickness is 1.5 μ m.Then, handled for 10 seconds, make its curing, form bottom with high-pressure mercury-vapor lamp (80W/cm).
Receiving layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 31 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 1 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
3 parts
Water ... 65 parts
Receiving layer coating fluid with above-mentioned composition is coated on the above-mentioned bottom, makes it dry, and dried thickness is 2.5 μ m, forms receiving layer, makes hot transfer printing acceptor.
Identical in hot tranfer recording medium and the Embodiment B-1.
Embodiment B-3
In Embodiment B-2, except using the prescription of following prescription as the bottom coating fluid, other make hot transfer printing acceptor as Embodiment B-2.Identical in hot tranfer recording medium and the Embodiment B-1.
Bottom coating fluid prescription
Epoxy acrylate (the black chemical industry of big Japan's seal Co., Ltd. system, ュ ニ デ イ Star Network V-5500) ... 16 parts
Silica (marshy land chemistry society system, P-603) ... 4 parts
Methyl ethyl ketone (MEK) ... 80 parts
Embodiment B-4
In Embodiment B-2, except using the prescription of following prescription as the receiving layer coating fluid, other make hot transfer printing acceptor as Embodiment B-2.Identical in hot tranfer recording medium and the Embodiment B-1.
Receiving layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 15 parts
Calcium carbonate water dispersion liquid (particle diameter 2.5 μ m, solid constituent 25%) ... 16 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 1 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
3 parts
Water ... 65 parts
Comparative example B-1
In Embodiment B-1, except bottom is not set, be provided with on the polyester film outside the receiving layer, other make hot transfer printing acceptor as Embodiment B-1.Identical in hot tranfer recording medium and the Embodiment B-1.
Reference example B-1
In Embodiment B-1, except using following prescription as the bottom coating fluid prescription, other make hot transfer printing acceptor as Embodiment B-1.Identical in hot tranfer recording medium and the Embodiment B-1.
Bottom coating fluid prescription
Polyester water dispersion (Toyo Boseki K.K's system, バ イ ロ Na one Le MD-1200, solid constituent 34%) ... 47 parts
Silica (marshy land chemistry society system, P-603) ... 4 parts
Water ... 49 parts
Comparative example B-2
In Embodiment B-1, except using the prescription of following prescription as the receiving layer coating fluid, other make hot transfer printing acceptor as Embodiment B-1.Identical in hot tranfer recording medium and the Embodiment B-1.
Receiving layer coating fluid prescription
The aqueous dispersion of calcium carbonate (particle diameter 1.5 μ m, solid constituent 25%) ... 40.0 part
Polyester water dispersion (Toyo Boseki K.K's system, バ イ ロ Na one Le MD-1200, solid constituent 34%) ... 29.4 part
Water ... 30.6 part
Then, use prepared hot tranfer recording medium and hot transfer printing acceptor, print, estimate solvent resistance and rub resistance as described below by following condition.It the results are shown in table 2.
Print conditions
Printer: Zebra corporate system 96XiIII
Print speed: 2 inch per seconds
Print energy: Tone 26
Solvent resistance
With the excellent impregnation solvent of cotton 0.5cc, coat on the transferred image after, to this sample 100g/cm in addition
2Load, image is observed in wiping 200 times, by following benchmark evaluation.Solvent uses MEK.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image, but can not interpretation.
1: the result of friction test, image cancellation.
Rub resistance
To the stainless steel bar of diameter 1mm, add the load of 3.0gf, in this state, wiping image 100 times is observed image, by following benchmark evaluation.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image, but can not interpretation.
1: the result of friction test, image cancellation.
Table 2
| Anti-MEK | Rub resistance | |
| Embodiment B-1 | 3 | 4 |
| Embodiment B-2 | 4 | 5 |
| Embodiment B-3 | 4 | 5 |
| Embodiment B-4 | 5 | 5 |
| Comparative example B-1 | 3 | 1 |
| Reference example B-1 | 2 | 2 |
| Comparative example B-2 | 1 | 3 |
Can confirm that from the result of table 2 image that uses Embodiment B-1 to make to each hot transfer printing acceptor of B-4 not only has excellent tolerance for MEK, and with sharp keen object brute force wiping the time, also not destroy image.
Embodiment C-1
(1) making of hot tranfer recording medium
The pet film of preparing thick 4.5 μ m is as support, at the opposition side that has been coated with ink layer coating fluid side, coating silicone rubber (Toray ダ ゥ コ one ニ Application グ silicone corporate system SD7226), make its drying, dried thickness is 0.35 μ m, makes the support with heat-resisting slip layer.
Peel ply coating fluid prescription
The toluene dispersion liquid of Brazil wax (solid constituent 10%) ... 90 parts
The toluene solution (solid constituent 10%) of ethylene-vinyl acetate copolymer resin (vinyl acetate amount 28 quality %, MFR=15dg/ branch) ... 10 parts
The peel ply coating fluid of above-mentioned prescription is coated ink layer one side of support, make it dry, dried thickness is 1.0 μ m.
Ink layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 62 parts
The aqueous dispersion of carbon black (solid constituent 38%) ... 22 parts
Water ... 16 parts
The ink layer coating fluid of above-mentioned prescription is coated on the above-mentioned peel ply, made it dry, dried thickness is 0.8 μ m, and ink layer is set, and makes hot tranfer recording medium.
(2) making of hot transfer printing acceptor
Bottom coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 71.9 part
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.6 part
Water ... 27.5 part
With the bottom coating fluid of above-mentioned composition, the thickness that is coated on Toyo Boseki K.K's system is the polyester film of 50 μ m (K1212, proportion 1.1), makes it dry, and dried thickness is 1.5 μ m, forms bottom.
Receiving layer coating fluid prescription
Calcined kaolin (ENGELHARD corporate system, aqueous dispersion ANSILEX) (particle diameter 0.8 μ m, solid constituent 25%) ... 40 parts
Polyester water dispersion (Toyo Boseki K.K's system, バ イ ロ Na one Le MD-1245, solid constituent 30%) ... 20 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 1 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
10 parts
Water ... 29 parts
Receiving layer coating fluid with above-mentioned composition is coated on the above-mentioned bottom, makes it dry, and dried thickness is 3.0 μ m, forms receiving layer.The smoothness on receiving layer surface (JIS P8119) is 1,400 second.
Embodiment C-2
In Embodiment C-1, except used thickness be the mylar (Toray Co., Ltd. system, E63, proportion 1.0) of 50 μ m as outside the support, other make hot transfer printing acceptor as Embodiment C-1.The smoothness on receiving layer surface (JIS P8119) is 1,300 second.
Identical in hot tranfer recording medium and the Embodiment C-1.
Embodiment C-3
In Embodiment C-1, except using the prescription of following prescription as the receiving layer coating fluid, other make hot transfer printing acceptor as Embodiment C-1.The smoothness on receiving layer surface (JIS P8119) is 950 seconds.
Identical in hot tranfer recording medium and the Embodiment C-1.
Receiving layer coating fluid prescription
The aqueous dispersion of calcite type precipitated calcium carbonate (oil absorption 40cc/100g) (particle diameter 3.0 μ m, solid constituent 25%) ... 40 parts
Polyester water dispersion (Toyo Boseki K.K's system, バ イ ロ Na one Le MD-1245, solid constituent 30%) ... 20 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 1 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
10 parts
Water ... 29 parts
Embodiment C-4
In Embodiment C-1, except using the prescription of following prescription as the receiving layer coating fluid, other make hot transfer printing acceptor as Embodiment C-1.The smoothness on receiving layer surface is 950 seconds (JISP8119).
Identical in hot tranfer recording medium and the Embodiment C-1.
Receiving layer coating fluid prescription
The aqueous dispersion of calcite type precipitated calcium carbonate (oil absorption 40cc/100g) (particle diameter 3.0 μ m, solid constituent 25%) ... 34 parts
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 31 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 0.5 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
9 parts
Water ... 25.5 part
Embodiment C-5
In Embodiment C-4, be that mylar (Toray Co., Ltd. system, E63, the proportion 1.0) surface of 50 μ m imposes film that aluminium-vapour deposition handles as outside the support except using at thickness, other make hot transfer printing acceptor as Embodiment C-4.The smoothness on receiving layer surface is 900 seconds (JISP8119).
Identical in hot tranfer recording medium and the Embodiment C-1.
Reference example C-1
In Embodiment C-1, except used thickness be the mylar (Toray Co., Ltd. system, S10, proportion 1.4) of 50 μ m as outside the support, other make hot transfer printing acceptor as Embodiment C-1.The smoothness on receiving layer surface is 1450 seconds (JIS P8119).
Identical in hot tranfer recording medium and the Embodiment C-1.
Comparative example C-1
In Embodiment C-1, except bottom is not set, and impose outside the receiving layer coating fluid of following prescription, other make hot transfer printing acceptor as Embodiment C-1.The smoothness on receiving layer surface is 1300 seconds (JIS P8119).
Identical in hot tranfer recording medium and the Embodiment C-1.
Receiving layer coating fluid prescription
Calcined kaolin (ENGELHARD corporate system, aqueous dispersion ANSILEX) (particle diameter 0.8 μ m, solid constituent 25%) ... 40 parts
SB latex (Japanese A ﹠amp; The L corporate system, SR-100, solid constituent 51%)
20 parts
Water ... 40 parts
Then, use prepared hot tranfer recording medium and hot transfer printing acceptor, print, estimate solvent resistance and rub resistance as described below by following condition.It the results are shown in table 3.
Print conditions
Printer: Zebra corporate system 96XiIII
Print speed: 2 inch per seconds
Print energy: Tone 25
Solvent resistance (anti-MEK)
With the excellent impregnation solvent of cotton 0.5cc, coat on the transferred image after, to this sample 100g/cm in addition
2Load, image is observed in wiping 50 times, by following benchmark evaluation.Solvent uses MEK.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image, but can not interpretation.
1: the result of friction test, image cancellation.
Rub resistance
The stainless steel bar of diameter 0.5mm is applied the load of 3.0gf, and in this state, wiping image 50 times is by following benchmark evaluation.
3: the result of friction test, with no change before the test.
2: the result of friction test, but image interpretation, but damage is arranged slightly.
1: the result of friction test, image is peeled off.
Table 3
| Anti-MEK | Rub resistance | |
| Embodiment C-1 | 3 | 3 |
| Embodiment C-2 | 4 | 3 |
| Embodiment C-3 | 4 | 3 |
| Embodiment C-4 | 5 | 3 |
| Embodiment C-5 | 5 | 3 |
| Reference example C-1 | 4 | 1 |
| Comparative example C-1 | 1 | 2 |
From the result of table 3, can confirm that the image that uses Embodiment C-1 to make to each hot transfer printing acceptor of C-5 not only has excellent tolerance for MEK, and has excellent image rub resistance.
Embodiment D-1
(1) making of hot tranfer recording medium
The pet film of preparing thick 4.5 μ m is as support, at the opposition side that has been coated with ink layer coating fluid side, coating silicone rubber (Toray ダ ゥ コ one ニ Application グ silicone corporate system SD7226), make its drying, dried thickness is 0.35 μ m, makes the support with heat-resisting slip layer.
Peel ply coating fluid prescription
The toluene dispersion liquid of Brazil wax (solid constituent 10%) ... 90 parts
The toluene solution (solid constituent 10%) of ethylene-vinyl acetate copolymer resin (vinyl acetate amount 28 quality %, MFR=15dg/ branch) ... 10 parts
The peel ply coating fluid of above-mentioned prescription is coated ink layer one side of support, make it dry, dried thickness is 1.0 μ m, and peel ply is set.
Ink layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 62 parts
The aqueous dispersion of carbon black (solid constituent 38%) ... 22 parts
Water ... 16 parts
The ink layer coating fluid of above-mentioned prescription is coated on the above-mentioned peel ply, made it dry, dried thickness is 0.8 μ m, and ink layer is set, and makes hot tranfer recording medium.
(2) making of hot transfer printing acceptor
Bottom coating fluid prescription
Thermohardening type resin: the mixture of epoxy resin and melamine resin (the black chemical industry of big Japan's seal Co., Ltd. system, SF409, solid constituent 37%) ... 35 parts
Calcium carbonate (average grain diameter 0.6 μ m) ... 7 parts
Methyl ethyl ketone (MEK) ... 58 parts
The bottom coating fluid of above-mentioned composition is coated on the polyester film (E5100, thickness 50 μ m) of Toyo Boseki K.K's system, makes it dry, dried thickness is 0.8 μ m.Then, with 150 ℃ of heat treatments that imposed for 30 seconds, form bottom.
Receiving layer coating fluid prescription
The salt of ethylene-methacrylic acid copolymer (Mitsui Chemicals, Inc's system, ケ ミ パ one Le S-650, solid constituent 27%) ... 15 parts
Calcium carbonate water dispersion liquid (Toyo Boseki K.K's system, particle diameter 2.5 μ m, solid constituent 25%) ... 16 parts
Epoxide (epoxide equivalent 160mg/eq, solid constituent 100%) ... 1 part
Polymine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application P-1000, solid constituent 30%)
3 parts
Water ... 65 parts
The receiving layer coating fluid of above-mentioned composition is coated on the above-mentioned bottom, makes it dry, dried thickness is 0.5 μ m, and receiving layer is set, and makes hot transfer printing acceptor.The smoothness on receiving layer surface is 2,200 seconds.
Embodiment D-2
In embodiment D-1, except using the prescription of following prescription as the bottom coating fluid, other make hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 2,300 seconds.
Bottom coating fluid prescription
Thermohardening type resin: the mixture of unsaturated polyester resin and melamine resin (the black chemical industry of big Japan's seal Co., Ltd. system, SF-C-329, solid constituent 43%) ... 29 parts
Calcium carbonate (average grain diameter 0.6 μ m) ... 7 parts
Curing agent (the black chemical industry of big Japan's seal Co., Ltd. system, SP Ha one De Na one B) ... 1 part
Methyl ethyl ketone (MEK) ... 63 parts
Embodiment D-3
Bottom coating fluid prescription
Thermohardening type resin: the mixture of unsaturated polyester resin and melamine resin (the black chemical industry of big Japan's seal Co., Ltd. system, SF-C-329, solid constituent 43%) ... 36 parts
Polymethyl methacrylate is cross-linking agent grain (Nippon Shokubai Co., Ltd's system, MA1002, average grain diameter 2.5 μ m) ... 7 parts
Curing agent (the black chemical industry of big Japan's seal Co., Ltd. system, SP Ha one De Na one B) ... 1 part
Methyl ethyl ketone (MEK) ... 59 parts
The bottom coating fluid of above-mentioned composition is coated on the polyester film (E5100, thickness 50 μ m) of Toyo Boseki K.K's system, makes it dry, dried thickness is 1.5 μ m.Then, with 150 ℃ of heat treatments that imposed for 30 seconds, form bottom.
Then, on resulting bottom,, receiving layer is set, makes hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 1,200 second.
Comparative Example D-1
In embodiment D-1, except bottom is not set, be provided with on the polyester film outside the receiving layer, other make hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 4800 seconds.
Reference example D-1
In embodiment D-1, except using the prescription of following prescription as the bottom coating fluid, other make hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 3,500 seconds.
Bottom coating fluid prescription
Thermohardening type resin: the mixture of epoxy resin and melamine resin (the black chemical industry of big Japan's seal Co., Ltd. system, SF-409, solid constituent 37%) ... 47 parts
Methyl ethyl ketone (MEK) ... 53 parts
Reference example D-2
In embodiment D-1, except using the prescription of following prescription as the bottom coating fluid, other make hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 2,400 seconds.
Bottom coating fluid prescription
Polyester is polyurethane aqueous dispersion body (the black chemical industry of big Japan's seal Co., Ltd. system, Ha イ De ラ Application AP-10, a solid constituent 30%) ... 43 parts
Calcium carbonate (average grain diameter 0.6 μ m) ... 7 parts
Water ... 50 parts
Comparative Example D-2
In embodiment D-1, except using following prescription as the receiving layer coating fluid prescription, other make hot transfer printing acceptor as embodiment D-1.Identical among hot tranfer recording medium and the embodiment D-1.The smoothness on receiving layer surface is 2300 seconds.
Receiving layer coating fluid prescription
Calcium carbonate water dispersion liquid (particle diameter 2.5 μ m, solid constituent 25%) ... 40 parts
SBR latex (Japanese A ﹠amp; The L corporate system, SN-348, solid constituent 48%) ... 21 parts
Water ... 39 parts
Use above-mentioned hot tranfer recording medium that makes and hot transfer printing acceptor, print, estimate solvent resistance and rub resistance as described below by following condition.It the results are shown in table 4.
Print conditions
Printer: Zebra corporate system 96XiIII
Print speed: 2 inch per seconds
Print energy: Tone 26
Solvent resistance (anti-MEK)
With the excellent impregnation solvent of cotton 0.5cc, coat on the transferred image after, to this sample 100g/cm in addition
2Load, image is observed in wiping 200 times, by following benchmark evaluation.Solvent uses MEK.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image can not interpretation.
1: the result of friction test, image cancellation.
Rub resistance
With the stainless steel bar of diameter 0.5mm, under the state that adds the 3.0gf load, wiping image 100 times is by following benchmark evaluation.
5: the result of friction test, with no change before the test.
4: the result of friction test, but image interpretation, but damage is arranged slightly.
3: the result of friction test, but image interpretation, but damage is arranged.
2: the result of friction test, residual image can not interpretation.
1: the result of friction test, image cancellation.
Table 4
| Anti-MEK | Rub resistance | |
| Embodiment D-1 | 3 | 4 |
| Embodiment D-2 | 4 | 5 |
| Embodiment D-3 | 5 | 5 |
| Comparative Example D-1 | 3 | 1 |
| Reference example D-1 | 3 | 1 |
| Reference example D-2 | 2 | 2 |
| Comparative Example D-2 | 1 | 3 |
Can confirm that from the result of table 4 the hot transfer printing acceptor of each of embodiment D-1 to D-3 not only has excellent tolerance for MEK, and with sharp keen object brute force wiping the time, also not destroy image.
According to hot transfer printing acceptor of the present invention, transfer printing can obtain noting down body from the image of hot tranfer recording medium, and the image that is formed at receiving layer has excellent tolerance for the MEK equal solvent, and has excellent rub resistance.
Above with reference to description of drawings embodiments of the invention, but the present invention is not limited to the foregoing description.Can do all changes in the technology of the present invention thought range, they all belong to protection scope of the present invention.
Claims (23)
1. hot transfer printing acceptor, described hot transfer printing acceptor comprises support, and is sequentially with bottom and receiving layer on this support, it is characterized in that:
Described receiving layer contains polyethylenimine derivates, thermoplastic resin and crosslinking agent.
2. hot transfer printing acceptor as claimed in claim 1 is characterized in that described support is made of plastic sheeting.
3. hot transfer printing acceptor as claimed in claim 1 is characterized in that described support is the polyester film of proportion 0.9-1.2.
4. hot transfer printing acceptor as claimed in claim 1 is characterized in that, the support of described support for forming by stacked many films of bond layer.
5. hot transfer printing acceptor as claimed in claim 4 is characterized in that, at least a of film that constitutes support is pet film.
6. hot transfer printing acceptor as claimed in claim 4 is characterized in that, has metal level between the film that constitutes support.
7. hot transfer printing acceptor as claimed in claim 4 is characterized in that, has metal level at least one face of support.
8. hot transfer printing acceptor as claimed in claim 1 is characterized in that described bottom contains the salt and the crosslinking agent of ethylene-methacrylic acid copolymer.
9. hot transfer printing acceptor as claimed in claim 1 is characterized in that described bottom contains ultraviolet curing resin and pigment.
10. hot transfer printing acceptor as claimed in claim 9 is characterized in that, described ultraviolet curing resin contains at least a in urethane acrylate and the epoxy acrylate.
11. hot transfer printing acceptor as claimed in claim 1 is characterized in that described bottom contains thermohardening type resin and pigment.
12. hot transfer printing acceptor as claimed in claim 11 is characterized in that, described thermohardening type resin is to be selected from least a in epoxy resin, melamine resin and the unsaturated polyester resin.
13. hot transfer printing acceptor as claimed in claim 1 is characterized in that, described underlayer thickness is 0.5-3.0 μ m.
14. hot transfer printing acceptor as claimed in claim 1 is characterized in that the thermoplastic resin in the receiving layer is the salt of ethylene-methacrylic acid copolymer.
15. hot transfer printing acceptor as claimed in claim 1 is characterized in that the crosslinking agent in the receiving layer is an epoxide.
16. hot transfer printing acceptor as claimed in claim 1 is characterized in that receiving layer contains inorganic pigment, this inorganic pigment is at least a in calcium carbonate and the calcined kaolin.
17. hot transfer printing acceptor as claimed in claim 16 is characterized in that, the particle diameter of inorganic pigment is 0.5-4.0 μ m.
18. hot transfer printing acceptor as claimed in claim 1 is characterized in that, the receiving layer surface is 200-3000 second based on the smoothness of JISP8119.
19. hot transfer printing acceptor as claimed in claim 1 is characterized in that, the thickness of receiving layer is 0.3-8.0 μ m.
20. hot transfer printing acceptor as claimed in claim 1 is characterized in that, is provided with metal level between support and bottom.
21. the manufacture method of a hot transfer printing acceptor is characterized in that, described method comprises:
Bottom forms operation, and coating contains the bottom coating fluid of resin and water at least on support, forms bottom;
Receiving layer forms operation, and coating contains the receiving layer coating fluid of polyethylenimine derivates, thermoplastic resin, crosslinking agent and water on this bottom, forms receiving layer.
22. a record method is characterized in that:
Use hot tranfer recording medium and hot transfer printing acceptor, described hot tranfer recording medium is to be sequentially with the peel ply that contains wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer on support at least, and described hot transfer printing acceptor is to be sequentially with bottom and to contain polyethylenimine derivates, thermoplastic resin, and the receiving layer of crosslinking agent on support;
The receiving layer of the ink layer of above-mentioned hot tranfer recording medium and above-mentioned hot transfer printing acceptor is superimposed, carry out hot transfer printing.
23. a record body is characterized in that:
Use hot tranfer recording medium and hot transfer printing acceptor, described hot tranfer recording medium is to be sequentially with the peel ply that contains wax, the ink layer that contains the salt of colouring agent and ethylene-methacrylic acid copolymer on support at least, and described hot transfer printing acceptor is to be sequentially with bottom and to contain polyethylenimine derivates, thermoplastic resin, and the receiving layer of crosslinking agent on support;
The receiving layer of the ink layer of above-mentioned hot tranfer recording medium and above-mentioned hot transfer printing acceptor is superimposed, carry out hot transfer printing, by this record method, on hot transfer printing acceptor, form image.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP055331/05 | 2005-03-01 | ||
| JP055330/05 | 2005-03-01 | ||
| JP2005055330A JP4327749B2 (en) | 2005-03-01 | 2005-03-01 | Receptor for thermal transfer recording and recording method |
| JP061396/05 | 2005-03-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827392A true CN1827392A (en) | 2006-09-06 |
| CN100441426C CN100441426C (en) | 2008-12-10 |
Family
ID=36946019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100045489A Expired - Fee Related CN100441426C (en) | 2005-03-01 | 2006-01-27 | Thermal transfer receiver, method for producing the same, method for recording image, and recorded image |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4327749B2 (en) |
| CN (1) | CN100441426C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101758678A (en) * | 2008-12-24 | 2010-06-30 | 株式会社Uviinc | Transfer paper with ultraviolet offset printing layer and ultraviolet enhancement layer and preparation method thereof |
| CN103419522A (en) * | 2013-07-23 | 2013-12-04 | 霍虾 | Method for making thermal transfer paper |
| CN104245343A (en) * | 2012-02-20 | 2014-12-24 | 艾利丹尼森公司 | Multilayer film for multi-purpose inkjet systems |
| CN104968855A (en) * | 2013-05-30 | 2015-10-07 | 丁斗镐 | Method for printing fabric or leather goods, and printed matter printed by using same |
| CN105026503A (en) * | 2012-12-28 | 2015-11-04 | 艾利丹尼森公司 | Topcoat compositions, coated substrates, and related methods |
| CN110382245A (en) * | 2017-03-01 | 2019-10-25 | 凸版印刷株式会社 | Heat-sensitive transfer recording medium |
| CN112118964A (en) * | 2018-10-03 | 2020-12-22 | 惠普发展公司，有限责任合伙企业 | Thermal transfer printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108327416B (en) * | 2018-04-16 | 2023-07-28 | 江苏学泰印务有限公司 | Water-based environment-friendly thermal transfer film and preparation method thereof |
| JP7015226B2 (en) * | 2018-09-27 | 2022-02-02 | 積水化成品工業株式会社 | Styrene composite polyethylene resin foamed particles, their manufacturing method and foamed molded product |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2175516A (en) * | 1985-04-16 | 1986-12-03 | Canon Kk | Recording medium |
| GB8909250D0 (en) * | 1989-04-24 | 1989-06-07 | Ici Plc | Receiver sheet |
| US5977263A (en) * | 1992-12-10 | 1999-11-02 | 3M Innovative Properties Company | Thermal transfer compositions, articles and graphic articles made with same |
| GB9301429D0 (en) * | 1993-01-25 | 1993-03-17 | Ici Plc | Receiver sheet |
| JP4357108B2 (en) * | 2000-10-06 | 2009-11-04 | 株式会社ユポ・コーポレーション | Image receiving film for printing and thermal transfer |
| GB0108199D0 (en) * | 2001-04-02 | 2001-05-23 | Dupont Teijin Films Us Ltd | Multilayer film |
| EP1295729A3 (en) * | 2001-09-25 | 2003-05-14 | Oji Paper Co., Ltd. | Water-resistant and organic solvent-resistant recording sheet |
| DE60309106T2 (en) * | 2002-08-05 | 2007-05-10 | Ricoh Co., Ltd. | Receiving paper for thermal transfer recording and method of manufacture |
| US20060257593A1 (en) * | 2002-10-01 | 2006-11-16 | J P Haenen | Coated printing sheet and process for making same |
-
2005
- 2005-03-01 JP JP2005055330A patent/JP4327749B2/en not_active Expired - Fee Related
-
2006
- 2006-01-27 CN CNB2006100045489A patent/CN100441426C/en not_active Expired - Fee Related
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| CN101758678A (en) * | 2008-12-24 | 2010-06-30 | 株式会社Uviinc | Transfer paper with ultraviolet offset printing layer and ultraviolet enhancement layer and preparation method thereof |
| CN104245343B (en) * | 2012-02-20 | 2017-02-22 | 艾利丹尼森公司 | Multilayer film for multi-purpose inkjet systems |
| CN104245343A (en) * | 2012-02-20 | 2014-12-24 | 艾利丹尼森公司 | Multilayer film for multi-purpose inkjet systems |
| CN105026503B (en) * | 2012-12-28 | 2018-02-06 | 艾利丹尼森公司 | Overcoat compositions, the substrate of coating and correlation technique |
| CN105026503A (en) * | 2012-12-28 | 2015-11-04 | 艾利丹尼森公司 | Topcoat compositions, coated substrates, and related methods |
| US9868313B2 (en) | 2012-12-28 | 2018-01-16 | Avery Dennison Corporation | Topcoat compositions, coated substrates, and related methods |
| US10486450B2 (en) | 2012-12-28 | 2019-11-26 | Avery Dennison Corporation | Topcoat compositions, coated substrates, and related methods |
| CN104968855A (en) * | 2013-05-30 | 2015-10-07 | 丁斗镐 | Method for printing fabric or leather goods, and printed matter printed by using same |
| CN104968855B (en) * | 2013-05-30 | 2017-07-21 | 丁斗镐 | The printing process of fabric or leather and fur products and the printed matter printed using this method |
| CN103419522B (en) * | 2013-07-23 | 2016-04-13 | 霍虾 | A kind of preparation method of heat-transferring printing paper |
| CN103419522A (en) * | 2013-07-23 | 2013-12-04 | 霍虾 | Method for making thermal transfer paper |
| CN110382245A (en) * | 2017-03-01 | 2019-10-25 | 凸版印刷株式会社 | Heat-sensitive transfer recording medium |
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| US11442393B2 (en) | 2018-10-03 | 2022-09-13 | Hewlett-Packard Development Company, L.P. | Heat transfer printing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100441426C (en) | 2008-12-10 |
| JP2006239910A (en) | 2006-09-14 |
| JP4327749B2 (en) | 2009-09-09 |
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