CN101746168B - Basal membrane for hydraulic transfer printing - Google Patents
Basal membrane for hydraulic transfer printing Download PDFInfo
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- CN101746168B CN101746168B CN2009102463967A CN200910246396A CN101746168B CN 101746168 B CN101746168 B CN 101746168B CN 2009102463967 A CN2009102463967 A CN 2009102463967A CN 200910246396 A CN200910246396 A CN 200910246396A CN 101746168 B CN101746168 B CN 101746168B
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Abstract
The invention provides a basal membrane for hydraulic transfer printing, which has good transfer printing adaptability and good dissolution and dispersion of the polyvinyl alcohol film and can improve the productivity. The invention relates to a basal membrane for hydraulic transfer printing, containing a polyvinyl alcohol film, wherein, the polyvinyl alcohol film contains a polyvinyl alcohol resin, the polyvinyl alcohol resin contains a polyvinyl alcohol resin (A1), with the viscosity of the 4 wt.% aqueous solution being 15 to 50 mPa.s at 20 DEG C, and a polyvinyl alcohol resin (A2) with the viscosity of the 4 wt.% aqueous solution being 1 to 10 mPa.s at 20 DEG C.
Description
Technical field
The present invention relates to float on liquid level, the particularly water surface and use, can the pattern that be printed on the film surface successfully be transferred to the basal membrane for hydraulic transfer printing that is transferred on the thing.
Background technology
All the time; As surface printing method of patterning at stereo shaping thing with complex surface shape; Known have a following method: use on the surface of basement membrane, to have the transfer film that forms figuratum printed layers; Making above-mentioned transfer film is after top mode floats on the liquid level (water surface) with the printing aspect, pushes the predetermined formed body (being transferred thing) that is used for the hectographic printing layer from the top, the printed layers of transfer film is transferred to the surface of formed body through hydraulic pressure.As this basal membrane for hydraulic transfer printing; Use is with the polyvinyl alcohol film of polyvinyl alcohol resin as the formation material; Consider from the viewpoint of film strength, use usually under 20 ℃, 4 weight % viscosity in aqueous solution are the polyvinyl alcohol resin film of 25～50mPas.
In addition, in such liquid pressure transfer method, various basement membranes are studied according to its purpose.For example; Patent documentation 1 has proposed the polyvinyl alcohol basement membrane that the polyvinyl alcohol resin by average degree of polymerization 300～3000, average 50～97 moles of % of saponification degree constitutes; In addition, also proposed two kinds of averages degree of polymerization, the average different polyvinyl alcohol resin of saponification degree are carried out blend.In addition, the polyvinyl alcohol film that superelevation degree of polymerization polyvinyl alcohol resin and the average degree of polymerization that has proposed average degree of polymerization more than 3200, average 65～95 moles of % of saponification degree in the patent documentation 2 is lower than 3200, the polyvinyl alcohol resin of average saponification degree 65～95 moles of % mixes.In addition, carboxyl that the polyvinyl alcohol resin that has also proposed to contain 70～98 moles of % of average saponification degree in the patent documentation 3 and average 70 moles of % of saponification degree are above and/or sulfonic group modified polyvinyl alcohol resin and boron compound and the polyvinyl alcohol film that forms.
Patent documentation 1: japanese kokai publication sho 55-25330 communique
Patent documentation 2: japanese kokai publication hei 7-117327 communique
Patent documentation 3: TOHKEMY 2003-11590 communique
Summary of the invention
But the liquid pressure transfer method of disclosed use polyvinyl alcohol film in the above-mentioned patent documentation is though can obtain good pattern, the dissolving of the polyvinyl alcohol film after the transfer printing or dispersed insufficient.The dissolving of the polyvinyl alcohol film after the transfer printing or dispersed when insufficient; There is the protective layer that is used to protect the surface after the residual polyvinyl alcohol film of patterned surfaces part, the transfer printing and is coated with part problem such as come off sometimes, thereby needs better Film Fractionation or dispersiveness.
And then when adopting following printing transferring method, said printing transferring method is: form the hydrophobicity transfer printing layer that dissolves in organic solvent in membrane surface; And then make basement membrane be positioned at the below and float on the surface, after activating agent makes above-mentioned transfer printing layer activation, will be transferred thing in coating on the above-mentioned transfer printing layer by being pressed on the above-mentioned transfer printing layer; Transfer printing layer is transferred to is transferred the thing surface, remove basement membrane then, then; The thing that is transferred through transfer printing there being above-mentioned transfer printing layer is implemented the active energy beam irradiation and is added pine at least a, and transfer printing layer is solidified, and fixes thereby will be transferred to the pattern that is transferred on the thing; Since there is not moisture to get into from cured layer one side, therefore, aspect the swelling behavior of transfer film; The dissolubility of basement membrane becomes problem especially, needs dissolving or dispersed better basement membrane.
The present invention In view of the foregoing carries out, and it is good that its purpose is to provide not only hectographic printing to fit property, and the dissolving of polyvinyl alcohol film or dispersed good, the basal membrane for hydraulic transfer printing that can boost productivity.
In order to achieve the above object, the inventor furthers investigate repeatedly, and the resin that is conceived to basement membrane is formed; And be that the center is studied with it; The result finds, through containing intermediate molecular weight and at least two kinds of low-molecular-weight, that molecular weight varies in size polyvinyl alcohol resins are formed as the resin that constitutes the polyvinyl alcohol film, and hectographic printing characteristic good not only; And the dissolving of the polyvinyl alcohol film after the transfer printing or dispersed good, thereby accomplished the present invention.
Purport of the present invention is described below.
1. basal membrane for hydraulic transfer printing; Contain the polyvinyl alcohol film; It is characterized in that; Said polyvinyl alcohol film contains polyvinyl alcohol resin, said polyvinyl alcohol resin contain under 20 ℃, 4 weight % viscosity in aqueous solution be the polyvinyl alcohol resin (A1) of 15～50mPas and under 20 ℃, 4 weight % viscosity in aqueous solution are the polyvinyl alcohol resin (A2) of 1～10mPas.
2. as (1) described basal membrane for hydraulic transfer printing, it is characterized in that, polyvinyl alcohol resin (A2) under 20 ℃, 4 weight % viscosity in aqueous solution than polyvinyl alcohol resin (A1) under 20 ℃, 4 weight % viscosity in aqueous solution are little by 5～50%.
3. like (1) or (2) described basal membrane for hydraulic transfer printing, it is characterized in that the use level of polyvinyl alcohol resin (A2) is 10～50 weight portions with respect to polyvinyl alcohol resin (A1) 100 weight portions.
4. like each described basal membrane for hydraulic transfer printing in (1)～(3), it is characterized in that the average saponification degree of polyvinyl alcohol resin (A1) is 70～98 moles of %, the average saponification degree of polyvinyl alcohol resin (A2) is 70～98 moles of %.
5. each described basal membrane for hydraulic transfer printing as in (1)～(4) is characterized in that the difference of the average saponification degree of the average saponification degree of polyvinyl alcohol resin (A1) and polyvinyl alcohol resin (A2) is 3 moles below the %.
6. like each described basal membrane for hydraulic transfer printing in (1)～(5), it is characterized in that the thickness of polyvinyl alcohol film is 20～50 μ m.
7. like each described basal membrane for hydraulic transfer printing in (1)～(6), be used for liquid pressure transfer method, in the said liquid pressure transfer method; Form in membrane surface and to dissolve in the hydrophobicity transfer printing layer of organic solvent, and then make basement membrane be positioned at the below and float on the surface, after the coating activating agent makes above-mentioned transfer printing layer activation on the above-mentioned transfer printing layer; To be transferred thing by being pressed on the above-mentioned transfer printing layer, and transfer printing layer will be transferred to be transferred the thing surface, remove basement membrane then; Then; The thing that is transferred through transfer printing there being above-mentioned transfer printing layer is implemented the active energy beam irradiation and is added pine at least a, and transfer printing layer is solidified, and fixes thereby will be transferred to the pattern that is transferred on the thing.
Basal membrane for hydraulic transfer printing of the present invention has the dissolving or the dispersed good effect of the polyvinyl alcohol film after hectographic printing characteristic good not only but also the transfer printing; And; Thereby adopting when implementing the active energy beam irradiation and adding at least a method of pining for transfer printing layer to be solidified to be transferred to the fixing printing transferring method of the pattern that is transferred on the thing; Bring into play significant excellent results, can be widely used in the hydraulic transfer printing purposes of the internal and external ornament thing of automobile and the extraneous adornment of mobile phone, various electric equipment products, building materials, family, daily necessities etc.
The specific embodiment
Below, the present invention is carried out detailed explanation.
Basal membrane for hydraulic transfer printing of the present invention (below, only abbreviate basement membrane sometimes as) comprises the polyvinyl alcohol film.
Among the present invention, so-called " comprising the polyvinyl alcohol film ", also comprise the also range upon range of situation that other layer (film or film etc.) arranged except that the polyvinyl alcohol film, common, how only to use the polyvinyl alcohol film as basement membrane.
The polyvinyl alcohol film is to use polyvinyl alcohol (being designated hereinafter simply as PVA) resinoid to form film like and obtain; Among the present invention; As the PVA resinoid, be contain under 20 ℃, 4 weight % viscosity in aqueous solution be the PVA resinoid (A1) of 15～50mPas and under 20 ℃, 4 weight % viscosity in aqueous solution are the PVA resinoid of the PVA resinoid (A2) of 1～10mPas.
At this, so-called PVA class is meant PVA self or the product of PVA after various material modified modifications for example, and its modification degree is generally 20 moles below the %, is preferably 15 moles below the %, more preferably 10 moles below the %.
As above-mentioned material modified, for example can enumerate: olefines such as ethene, propylene, isobutene, α-octene, α-laurylene, α-octadecylene; Unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid or its salt or list or dialkyl etc.; Nitrile such as acrylonitrile, methacrylonitrile, amide-types such as acrylamide, Methacrylamide; Alkene sulfonic acid or its salt such as vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid; The alkyl vinyl ethers; Polyoxyalkylene (methyl) allyl ethers such as polyoxyethylene (methyl) allyl ether, polyoxypropylene (methyl) allyl ether; Polyoxyalkylene (methyl) acrylic acid ester such as polyoxyethylene (methyl) acrylic acid ester, polyoxypropylene (methyl) acrylic acid ester; Polyoxyalkylene (methyl) acrylamides such as polyoxyethylene (methyl) acrylamide, polyoxypropylene (methyl) acrylamide; Polyoxyethylene [1-(methyl) acrylamide-1,1-dimethyl propyl] ester, polyoxyethylene vinyl ethers, polyoxypropylene vinyl ethers, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinyl amine, polyoxypropylene vinyl amine, two acryloyl group pyroracemamides (diacryl acetone amide), N acrylamide methyl trimethoxy ammonium chloride, pi-allyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, dimethyl-allyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride etc.These other monomers can use separately or two or more combination is used.
In addition; As the PVA resinoid; Also preferably use to have 1 on the side chain, the PVA resinoid of 2-diol bond has 1 on the above-mentioned side chain; The PVA resinoid of 2-diol bond can obtain through for example following method: (1) is with vinylacetate and 3; The method of the copolymer saponification of 4-diacetoxy-1-butylene, (2) with the method for the copolymer saponification of vinylacetate and vinylethylene carbonate and decarboxylation, (3) with vinylacetate and 2,2-dialkyl group-4-vinyl-1, the copolymer saponification of 3-dioxolanes and the method for ketalization, (4) are with method of the copolymer saponification of vinylacetate and allylin etc.
The PVA resinoid (A1) that uses among the present invention under 20 ℃, 4 weight % viscosity in aqueous solution need be 15～50mPas, are preferably 15～45mPas, are preferably 16～40mPas especially.PVA resinoid (A1) if 4 weight % viscosity in aqueous solution too small, the undercapacity of film then, meeting and become the reason of breaking in the use, if viscosity is excessive, then dissolubility is insufficient.
In addition, above-mentioned under 20 ℃, 4 weight % viscosity in aqueous solution measure according to JIS K 6726.
In addition, the average saponification degree of PVA resinoid (A1) is preferably the scope of 70～98 moles of %, is preferably the scope of 75～95 moles of % especially, further the scope of preferred 80～90 moles of %.Average saponification degree is crossed when low or too high, and dissolubility all has the tendency of reduction.
In addition, the resinoid average saponification degree of above-mentioned PVA is measured according to JIS K 6726.
Above-mentioned PVA resinoid (A1) can suitably be selected from commercially available article usually and obtain.
The PVA resinoid (A2) that uses among the present invention under 20 ℃, 4 weight % viscosity in aqueous solution need be 1～10mPas, are preferably 2～9mPas, are preferably 3～8mPas especially.PVA resinoid (A2) if 4 weight % viscosity in aqueous solution too small, then be difficult to make stabilized resins, if viscosity is excessive, then improves deliquescent effect and disappear.
In addition, the average saponification degree of PVA resinoid (A2) is preferably the scope of 70～98 moles of %, is preferably the scope of 75～95 moles of % especially, further is preferably the scope of 80～90 moles of %.Average saponification degree is crossed when low or too high, all has film and produces inner muddy and cause the tendency of bad order.
Above-mentioned PVA resinoid (A2) can suitably be selected from commercially available article usually and obtain.
Among the present invention; When 4 weight % viscosity in aqueous solution of comparison PVA resinoid (A1) and 4 weight % viscosity in aqueous solution of PVA resinoid (A2); Consider that from dissolubility and film strength aspect 4 weight % viscosity in aqueous solution of preferred PVA resinoid (A2) are littler by 5～50% than 4 weight % viscosity in aqueous solution of PVA resinoid (A1), preferred little by 10～50% especially; Further preferred little by 15～47%, especially preferred little by 15～30%.Compare with 4 weight % viscosity in aqueous solution of PVA resinoid (A1), when 4 weight % viscosity in aqueous solution of PVA resinoid (A2) are too small, have the tendency that is difficult to obtain resin, during too greater than preset range, the deliquescent effect of improving is had the tendency that diminishes.
In addition; Relatively during the average saponification degree of the average saponification degree of PVA resinoid (A1) and PVA resinoid (A2); Consider that from the good aspect of film appearance preferably its difference is 3 moles below the %, is preferably 2 moles especially below the %; Further be preferably 1.5 moles below the %, especially preferably in fact almost do not have difference.When the difference of this average saponification degree is excessive, the inner muddy big tendency that becomes is arranged.
In addition; Content ratio for PVA resinoid (A1) and PVA resinoid (A2); Consider that from film strength and dissolubility aspect preferably with respect to PVA resinoid (A1) 100 weight portions, PVA resinoid (A2) is 10～50 weight portions; Be preferably 10～40 weight portions especially, further preferred 15～35 weight portions.PVA resinoid (A2) if content very few, the deliquescent tendency that effect disappears of improving is then arranged, if too much, the not enough tendency of film strength is arranged then.
In addition, among the present invention, should and with above-mentioned PVA resinoid (A1) and PVA resinoid (A2), but can also be further also with PVA resinoid (A1) and PVA resinoid (A2) PVA resinoid in addition.
Like this, in the present invention, should use PVA resinoid (A1) and PVA resinoid (A2) to form PVA class film, when forming film, cooperate plasticizer usually as the PVA resinoid.
As this plasticizer, for example can enumerate: glycerols such as glycerine, diglycerol, triglycerin; Aklylene glycol classes such as triethylene glycol, polyethylene glycol, polypropylene glycol, DPG; Trimethylolpropane etc.They can use separately or two or more combination is used.
The content of above-mentioned plasticizer can suitably be set according to the rerum natura of target P VA class film, for example, with respect to resinoid total amount 100 weight portions of PVA, is generally below 5 weight portions, is preferably 0.05～4 weight portion.If the content of above-mentioned plasticizer is very few, then plasticization effect is low, has the tendency that causes gained PVA class film fracture, if content is too much, the poor dimensional stability during printed patterns on film surface then has and is difficult to carry out high-precision polychrome tendency.
In addition, except that above-mentioned PVA resinoid and the plasticizer, can cooperate various additives as required.
For example, in order to improve as the fissility between the metal surface of the rotating cylinder of the film forming apparatus of PVA class film and band etc. and the film processed, can the matching surface activating agent.As above-mentioned surfactant, for example can enumerate: polyoxyethylene alkyl amines such as polyoxyethylene nonylplenyl ether, polyoxyethylene octyl group nonyl ethers, polyoxyethylene dodecylphenyl ether, polyxyethylated allyl ether, polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene 20 sorbitan monopalmitate, polyoxyethylene 20 sorbitan monostearate, polyoxyethylene 20 sorbitan monooleate, polyoxyalkylene alkyl phosphate monoethanolamine salt, polyoxyethylene lauryl amine, polyoxyethylene stearyl acid amides etc.These surfactants can use separately or two or more combination is used.Wherein, consider, preferably use polyoxyalkylene alkyl phosphate monoethanolamine salt, polyoxyethylene alkyl amine, polyoxyethylene 20 sorbitan monolaurate from the fissility aspect.
The content of above-mentioned surfactant, preferred usually total amount 100 weight portions with respect to PVA resinoid and plasticizer are 0.01～5 weight portion, more preferably 0.03～4.5 weight portion.If the content of above-mentioned surfactant is very few; Thereby then there is the fissility of metal surface and the film of processing of the rotating cylinder, driving-belt etc. of film forming apparatus to reduce the tendency that is difficult to make; On the contrary, if content is too much, the tendency that is exuded to film surface and pattern printed layers is come off is arranged then.
In addition, also can in the PVA resinoid, cooperate crosslinking agent,,, for example can enumerate: K so long as get final product with the material of PVA resinoid generation cross-linking reaction as crosslinking agent
3C
6H
5O
7(citric acid tri potassium), boric acid, line borate, cobalt borate, Firebrake ZB (zinc tetraborate, zinc metaborate etc.), aluminium borate potassium, ammonium borate (ammonium metaborate, tetraboric acid ammonium, ammonium pentaborate, eight ammonium borates etc.), cadmium borate (ortho-boric acid cadmium, tetraboric acid cadmium etc.), potassium borate (potassium metaborate, dipotassium tetraborate, potassium pentaborate, six potassium borates, eight potassium borates etc.), boric acid silver (silver metaborate, silver tetraborate etc.), copper borate (copper borate, copper metaborate, tetraboric acid copper etc.), Boratex (kodalk, hypoboric acid sodium, sodium tetraborate, sodium pentaborate, six Boratexes, eight Boratexes etc.), lead borate (lead metaborate, six lead borates etc.), nickel borate (ortho-boric acid nickel, hypoboric acid nickel, tetraboric acid nickel, eight nickel borates etc.), barium borate (ortho-boric acid barium, barium metaborate, hypoboric acid barium, barium tetraborate etc.), bismuth boracic acid, antifungin (magnesium orthoborate, hypoboric acid magnesium, magnesium metaborate, tetraboric acid three magnesium, tetraboric acid five magnesium etc.), manganese borate (the inferior manganese of boric acid, metaboric acid manganese, tetraboric acid manganese etc.), lithium borate (lithium metaborate, lithium tetraborate, five lithium borates etc.) etc., and boron compounds such as borate mineral such as borax, kernite, inyoite, kotoite, suanite, boromagnesite etc.These crosslinking agents can use combination use more than a kind or 2 kinds, in the above-mentioned crosslinking agent, preferably use borax and boric acid.
Preferred resinoid total amount 100 weight portions of PVA relatively of the amount of crosslinking agent are 0.01～10 weight portion, more preferably 0.05～5 weight portion.
In addition; In the scope that does not hinder effect of the present invention; Can also add anti-oxidant (phenols, amine etc.), stabilizing agent (phosphoric acid ester etc.), colouring agent, spices, extender, antifoaming agent, antirust agent, ultra-violet absorber, inorganic powder, organic dust (starch, polymethyl methacrylate etc.), and other water-soluble high-molecular compound (Sodium Polyacrylate, PEO, PVP, dextrin, shitosan, chitin, methylcellulose, hydroxyethylcellulose etc.) etc.
The PVA class film that constitutes basement membrane of the present invention for example can be made as follows.At first, cooperate various raw materials such as above-mentioned PVA resinoid, plasticizer, surfactant, water with predetermined use level, the preparation film forms material.Then, from the T die, film is formed the material curtain coating on system film band or system film rotating cylinder, carry out drying, preferably further heat-treat, make the manufacturing of its filmization thus.As above-mentioned heat treated temperature conditions, be preferably set to 70～100 ℃.
The not special restriction of above-mentioned heat treatment method for example can be enumerated: methods such as hot-rolling (comprising felt wrapped roll), hot blast, far infrared, eddy-current heating.In addition, the face of heat-treating is preferably and the face of making the opposite side of face that film band or system film rotating cylinder contact, but also can be clipped in wherein.In addition, the moisture of implementing heat treated film is preferably about 4 weight %～about 8 weight % usually.In addition, the moisture of the film after the heat treatment is preferably 3～7 weight % usually.
More specifically, the first system film rotating cylinder of film from above-mentioned system film band or system film rotating cylinder peeled off the back till batch, preferably make film pass through the Heat treating roll of 70～100 ℃ of above surface temperatures.At this, above-mentioned system film band is meant to have the endless belt of between pair of rolls, setting up and moving, and carries out dry device in to the endless belt making the film that flows out from the T die form the material curtain coating.Above-mentioned endless belt for example preferably is made up of stainless steel, and its outer surface has been implemented minute surface fine finishining.
In addition, the above-mentioned first system film rotating cylinder is the rotating cylinder forming roll of instigating the film that flows out from the T die to form on the rotating cylinder forming roll of rotation more than the material curtain coating to and carrying out being positioned at the dry film-making machine upstream side.In addition; Peel off the back till batch from system film band or the first system film rotating cylinder; Represent following process: make from the film of the first-class discharge of T pattern and form material dry on the system film band or on the first system film rotating cylinder and become film like; Peel off from the system film band or the first system film rotating cylinder then, preferably pass through heat-treating machine, the process of batching with coiling machine.The above-mentioned heat treatment that utilizes heat-treating machine to carry out is preferably carried out under 70～100 ℃, more preferably under 75～98 ℃, carries out.That is,, then have the tendency that the swelling multiple of gained basement membrane becomes high, and have pattern elongation and cause the tendency of pattern property reduction before transfer printing if above-mentioned heat treatment temperature is low excessively.On the contrary, if heat treatment temperature is too high,, the damaged tendency of decorative pattern is arranged then for the moulding article that require following property.In addition, the needed time of above-mentioned heat treatment is depended on the surface temperature of Heat treating roll, but is preferably 0.5～60 second usually, is preferably 0.5～30 second especially, more preferably 0.5～15 second.If this time is too short, then have the inadequate tendency of heat treatment, if the time is long, then have the tendency that heat treatment is excessive or productivity ratio reduces.Above-mentioned heat treatment is right after usually after the dryer roll that is used for dry film is handled, and utilizes other Heat treating roll to carry out.
Thus, can access the PVA class film that constitutes basal membrane for hydraulic transfer printing of the present invention.
In addition, among the present invention, the water content of PVA class film is preferably 2～6 weight %, more preferably 3～5 weight %.If water content is too small, then film has curling tendency during transfer printing, if water content is excessive, diminishes though curl, and the tendency of unfavorable conditions such as generation printing position skew is arranged in practical applications such as printing.
In addition, the water content of PVA class film for example can be used Ka Er-Fei Xiu (Karl-Fisher) moisture teller (capital of a country Electronics Industry Company makes, and MKS-210) measures.
As the control method of the water content of above-mentioned PVA class film, for example can enumerate below shown in method.That is,, can be set at the water content of the PVA class film in the above-mentioned scope according to the control method of the water content shown in following.
(1) utilizing following method to carry out water content regulates: the drying machine temperature when making dope (dope) drying that is dissolved with PVA make film through rising or reduction, PVA class film is carried out humidification or dehumidifying.Because the temperature of dope is influential to drying efficiency, therefore, the temperature of above-mentioned dope is regulated in 70～98 ℃ scope.In addition, consider from the viewpoint that moisture is regulated, when dry, preferably between 150～50 ℃, more preferably had in two above air driers of thermograde dry 1～15 minute more preferably dry 1～12 minute between 145～60 ℃ at least.
If the gradient scope of above-mentioned baking temperature is excessive or drying time is long, dry excessive tendency is then arranged, on the contrary,, dry not enough tendency is arranged then if the gradient scope of baking temperature is too small or drying time is too short.
The said temperature gradient is between 150～50 ℃, to change baking temperature interimly; Usually; Following method is effective: when drying begins, temperature is raise gradually; Before reaching predetermined water content, make the high dry temperature in its baking temperature scope that temporarily reaches setting, then reduce baking temperature gradually, finally reach the target moisture content.This carries out for crystallization control property, fissility, productivity ratio etc.; For example can enumerate: 120 ℃-130 ℃-115 ℃-100 ℃, 130 ℃-120 ℃-110 ℃, 115 ℃-120 ℃ of-110 ℃ of-90 ℃ of isothermal gradients are set, and can suit to select to implement.
(2) make it through the damping groove before batching of PVA class film, thus PVA class film is carried out humidification, dehumidifying, thereby carry out the adjusting of water content.
(3) heat-treat before batching of PVA class film, thus PVA class film is dehumidified, thereby carry out the adjusting of water content.
In addition, the total light transmittance of above-mentioned PVA class film is generally more than 80%, is preferably 85～99%, is preferably 85～95% scope especially.This be because, if total light transmittance is low excessively, then have the tendency that printing the time is difficult to match colors.
In addition, the total light transmittance of PVA class film for example can use nephelometer (Japanese electric look industrial group makes, and NDH 2000) to measure.
The length of delay of above-mentioned PVA class film is preferably below the 40nm, more preferably below the 35nm.This length of delay representes with the birefringence of PVA class film and the product (birefringence * film thickness) of thickness, and above-mentioned birefringence is by the degree decision of the molecularly oriented of the film of giving in the thin film fabrication operation etc.If above-mentioned length of delay is too high, then have following tendency: membrane surface forms fold, hinders the formation of printed layers, stretches with uneven state when perhaps basement membrane floats on the surface, and makes the printed patterns distortion.Thus, be the method below the 40nm as making length of delay, for example can enumerate: make PVA class film fully dry on the rotating cylinder or on being with, after operation in batch the method for regulating thus with the mode that does not apply tension force.In addition, the lower limit of length of delay is generally 3nm.
In addition, as the elongation at break of above-mentioned PVA class film, under 23 ℃, 50%RH damping condition, be more than 150% preferably, more preferably more than 180%.This be because, if elongation at break is low excessively, have then that printing the time is ruptured or the tendency of the following property reduction during transfer printing.In addition, the upper limit of elongation at break is generally 300%.
In addition, the elongation at break of PVA class film is measured according to JIS K 7127 (1999).
The thickness of as above operating the PVA class film of making film and obtaining preferably sets in the scope of 20～50 μ m, and more preferably 23～47 μ m are preferably 25～45 μ m especially.If film thickness is thin excessively, the swelling that printing film then arranged is fast and be unfavorable for the tendency of transfer printing, if thickness is blocked up, then have film to remain on the transfer printing thing or in the transfer printing liquid the resinoid concentration of the PVA in the water rise fast and tendency that drainage load is increased.
The PVA class film (film rolling) that the system film obtains is for example preferred so that the mode that the water content of front explanation does not change has known water vapor proof barrier packaging processing now, and in 10～25 ℃ environment, preserves with suspension status.
Below, the hydraulic transfer printing method of using basement membrane of the present invention is described.
Liquid pressure transfer method as using basement membrane of the present invention can be applied to various liquid pressure transfer methods in the past, for example can enumerate: the liquid pressure transfer method of the liquid pressure transfer method of (1) continuation mode, (2) intermittent mode etc.
At first, the liquid pressure transfer method to above-mentioned (1) continuation mode describes.
That is the predetermined pattern of printing on the base film surface that as above obtains.Afterwards, on above-mentioned pattern printing surface, be coated with activating agent.Then, the width of above-mentioned basement membrane for example being limited in below 1.3 times with respect to flow direction, suction back basement membrane being stretched and pattern is fuzzy, serves as that the top makes basement membrane float on the liquid level and moves with the pattern printing surface that scribbles activating agent.Push from the above-mentioned basement membrane top of moving and to be transferred thing,, carry out hydraulic transfer printing thus being printed on pattern transfer on the base film surface to being transferred on the thing surface and fixing.And, after fixing,, make the figuratum fully drying of thing that is transferred of transfer printing through removing basement membrane, obtain target product.
On the other hand, the hydraulic transfer printing method to above-mentioned (2) intermittent mode describes.
That is the predetermined pattern of printing on the base film surface that as above obtains.Afterwards, on above-mentioned pattern printing surface, be coated with activating agent.Then, same with above-mentioned continuation mode, above-mentioned basement membrane is set the for example restriction in length and breadth below 1.3 times on all directions in length and breadth, suction back basement membrane is stretched and pattern is fuzzy, serve as that the top floats on the liquid level basement membrane with the pattern printing surface that scribbles activating agent.Then, under static state, push from above-mentioned basement membrane top and to be transferred thing,, carry out hydraulic transfer printing thus being printed on pattern transfer on the base film surface to being transferred on the thing and fully fixing.After fixing,, make the figuratum fully drying of thing that is transferred of transfer printing, obtain target product through removing basement membrane.
The activating agent that is coated with on the above-mentioned pattern printing surface is not special to be limited, and can use the material that obtains making the pattern that is printed on the base film surface add resin in the solvent of activation again etc., can also suitably add pigment, plasticizer, curing agent etc.For example, can use in butyl methacrylate hybrid pigment, plasticizer, acetate butyl cellulose ester, butyl carbitol acetate ester and the material that obtains.In addition, as the coating process of above-mentioned activating agent, can enumerate the coating process that uses gravure roll and sprayer.
In addition; Above-mentioned on the pattern printing surface operation of coating activating agent can basement membrane be carried out before floating on the liquid level; Also can basement membrane be carried out after floating on the liquid level, as long as carrying out then not special the qualification before being transferred thing from printing to push above the figuratum basement membrane.
In addition, except that the liquid pressure transfer method of above-mentioned continuation mode and intermittent mode, the liquid pressure transfer method that can be listed below (3).
Promptly; Can enumerate following liquid pressure transfer method: after printing on the base film surface that as above obtains becomes the predetermined pattern of drying regime; Coating contains the no-solvent type ultraviolet ray or the electron ray isoreactivity energy ray-curable resin combination of photopolymerization monomer, makes the pattern of above-mentioned drying regime moistening.Then, serve as that the top floats on the surface basement membrane with moistening pattern printing surface, push from above-mentioned basement membrane top and be transferred thing, with being printed on pattern transfer on the base film surface to being transferred on the thing surface.Then, be transferred on the thing irradiation ultraviolet radiation or electron ray isoreactivity energy-ray and hardening resin composition is solidified in that transfer printing is figuratum, will be transferred to the pattern that is transferred on the thing thus and fix.
In addition, as other liquid pressure transfer method, described liquid pressure transfer method (4) can be listed below.
That is, can enumerate following liquid pressure transfer method: prepare on the base film surface that as above obtains, to be formed with the hydrophobicity transfer printing layer (pattern) that dissolves in organic solvent, and the transfer film that preferably further obtains at the strippable stripping film of this transfer printing layer laminated.Then, peel off above-mentioned stripping film after, make basement membrane be positioned at the below and float on the surface, on above-mentioned transfer printing layer the coating activating agent make above-mentioned transfer printing layer activation.Then, will be transferred thing, and transfer printing layer is transferred to will be transferred on the thing surface, remove basement membrane then by being pressed on the above-mentioned transfer printing layer.Then, there is the thing that is transferred of above-mentioned transfer printing layer (pattern) to implement ultraviolet ray or the irradiation of electron ray isoreactivity energy-ray and add pine at least a, transfer printing layer (pattern) is solidified, fix thereby will be transferred to the pattern that is transferred on the thing to transfer printing.
At this; As above-mentioned organic solvent, for example can enumerate: toluene, xylenes, carbitol, carbitol acetate ester, butyl carbitol acetate ester, butyl cellulose, cellulose acetate ester, acetate butyl cellulose ester, methyl iso-butyl ketone (MIBK), ethyl acetate, acetate-3-methyl-3-methoxyl group butyl ester etc. and their mixture.
At this, transfer printing layer preferably has the curable resin layer, more preferably comprises being arranged on epilamellar curable resin layer and being arranged on the decorative layer with printing-ink tunicle or coating tunicle on this curable resin layer.
In addition, the curable resin layer preferably is made up of the active energy ray-curable resin that is selected from epoxy (methyl) acrylic acid ester that has (methyl) acryloyl group more than 3 in polyester (methyl) acrylic acid ester that has (methyl) acryloyl group more than 3 in polyurethane (methyl) acrylic acid ester that has (methyl) acryloyl group more than 3 in a part, a part and a part.
Basal membrane for hydraulic transfer printing of the present invention is in above-mentioned hydraulic transfer printing method, when particularly in liquid pressure transfer method (4), using; Not only has the film strength that be able to stand hydraulic transfer printing; Although formed hydrophobic curable resin layer, also can bring into play the dissolving or the dispersed good effect of basement membrane.
In addition, when shining above-mentioned active energy beam, for example, under ultraviolet situation, can use the existing known ultraviolet lamp of illuminators such as possessing high-pressure mercury-vapor lamp, metal halide lamp and irradiator (light source) to carry out.
In addition; Under situation about being cured through the irradiation active energy beam; The preferred Photoepolymerizationinitiater initiater that cooperates; This Photoepolymerizationinitiater initiater has light such as absorbing ultraviolet ray and the effect of initiated polymerization for example can be used: acetophenone compounds such as diethoxy acetophenone, 1-hydroxy-cyclohexyl-phenyl ketone; Benzophenone, o-benzoylbenzoic acid methyl-benzophenone cpds such as 4-phenyl benzophenone; Benzoin such as benzoin, benzoin iso-propylether compound; The acylphosphine oxide compounds; The thioxanthones compounds; The aminobenzophenone compound; Polyethers maleimide carbonate etc.Also can these compound combinations be used.
In the above-mentioned hardening resin composition, except that Photoepolymerizationinitiater initiater, according to additives such as necessary all right proper fit photopolymerization monomer, sensitizer, filler, inertia organic polymer, levelling agent, thixotropy imparting agent, thermal polymerization inhibitors.
Among the present invention, through hydraulic transfer printing method via above-mentioned operation, can be with being printed on pattern transfer on the base film surface to being transferred on the thing.In addition, above-mentioned not special qualification of pattern that is printed on the base film surface so long as the pattern that wood grain, various decorative pattern, image etc. can be printed, then can be pattern arbitrarily.
The material that is transferred thing in the hydraulic transfer printing method of the present invention is not special to be limited, and for example can use: inorganic formed bodys such as plastic shaped body, metal forming body, wooden formed body, glass.In addition, its shape is not special yet to be limited, and can be the plane, also can have various three-dimensional shapes.
Embodiment
Below, enumerate embodiment the present invention is explained more specifically, but the present invention is not limited to following embodiment in the scope that does not exceed its purport.
In addition, when not specifying, " % " in the example is meant weight basis.
[embodiment 1]
< preparation of basement membrane >
Making 85 part of 4 weight % viscosity in aqueous solution (20 ℃) is that the average viscosity (20 ℃) of the PVA (A1) of 88 moles of %, the 15 part of 4 weight % aqueous solution is that the PVA (A2) of 88 moles of %, 2 parts of glycerine, 6 parts of starch, 1.2 parts of surfactants (polyoxyethylene 20 sorbitan monolaurate) are dissolved in the water aqueous dispersions (dope) of preparation 18% (solid component concentration) for 5mPas, average saponification degree for 18mPas, average saponification degree.From the T die, this dope being discharged to surface temperature is adjusted on 80 ℃ the stainless steel endless belt of rotation; Speed casting film with 10m/ minute; Then heat-treat, obtain the PVA film of thickness 30 μ m, it is used basement membrane as hydraulic-transfer with the hot-rolling that is adjusted to 80 ℃.
< preparation of hardening resin composition >
Use make pentaerythrite 2 molar equivalents, hexamethylene diisocyanate 7 molar equivalents and hydroxyethyl methacrylate 6 molar equivalents 60 ℃ down average 6 officials that obtain of reaction can (Tg100 ℃ of the acrylic resin " Paraloid A-11 " of ammonia ester acrylic acid ester (UA1) 60 parts (quality mean molecule quantity 890), Rohm and Haas manufactured; The mixed solvent (mixed weight is than 1/1) of quality mean molecule quantity 125000) 40 parts, ethyl acetate and MEK, the hardening resin composition of preparation solid constituent 42%.
< preparation of decorating film (I) >
Use the un-stretched polypropylene film (being designated hereinafter simply as the PP film) of thickness 50 μ m that Japan spins manufactured as the fissility film; (trade name: the wood grain decorative pattern of print thickness 3 μ m ユ ニ PVC ア A) prepares decorative film (I) with polyurethane ink on this film with 4 look intaglio press.
< hydraulic-transfer is with the preparation of film (II) >
Be coated with above-mentioned hardening resin composition with lip formula coating machine (lip coater) in system film zone face one side of above-mentioned basement membrane; Making dried thickness is 20 μ m; Then following dry 2 minutes at 60 ℃; Preparation has the basement membrane of cured resin composition layer; The uniaxial tension polypropylene film (being designated hereinafter simply as the OPP film) that then manufactured is spun by cured resin composition layer and Japan of this film carries out lamination under 60 ℃, directly batch the film that lamination forms, and the preparation hydraulic-transfer is with film (II).
< hydraulic-transfer is with the preparation of film (III) >
After peeling off the OPP film from above-mentioned hydraulic-transfer with film (II), make the ink lay of cured resin composition layer and decorating film (I) under 60 ℃, carry out lamination relatively, directly batch the film that lamination forms once more, the preparation hydraulic-transfer is with film (III).
In addition, the hydraulic-transfer that obtains is peeled off the PP film with film (III) in use, at this moment, transfers on the cured resin composition layer of PVA film side the ink lay zero defect.
Hydraulic-transfer to obtaining carries out following evaluation with film (III).
< evaluation method >
After the above-mentioned hydraulic-transfer that obtains cut out the size into 3cm * 5cm with film (III), peel off the PP film, be fixed on below with the PVA film side being can anchor clamps with film and water surface secured in parallel on.Then; In 1 liter of beaker, add entry (1 liter); Keeping water temperature when using agitator to stir is 30 ℃, and sample is immersed in the water, makes the fixing height of sample be positioned at the graticule position of 600cc; Stirrer with 3cm stirs with the speed continuation of 400rpm, the dissolving situation of the PVA film of side below confirming simultaneously.
Confirmation method is: from water, take out sample through after the scheduled time, touch the PVA pellicular front, confirm to have or not mucus, estimate according to following benchmark.
Zero: mucus disappears in less than 5 minutes time.
*: do not disappear through 5 minutes mucus yet.
[embodiment 2～4, comparative example 1～3]
Except the composition that changes the PVA resin as shown in table 1ly, operate equally with embodiment 1, obtain the PVA film of thickness 30 μ m, it is used basement membrane as hydraulic-transfer.
The evaluation result of embodiment and comparative example is as shown in table 1.
Table 1
Can know by The above results, for and with 2 kinds of predetermined PVA as the resinoid embodiment of PVA, although single face is covered by hydrophobic cured resin composition layer; But dissolving or dispersiveness are still good; Relative therewith, do not cooperate the little PVA of molecular weight and only use the comparative example 1 of the PVA that uses in a kind of existing basement membrane, can not be dissolved fully or dispersed; And; And during with 2 kinds of PVA, if any one in the range of viscosities of 2 kinds of PVA outside the scope of the invention, then dissolving or bad dispersibility.Infer this be because, contain a small amount of PVA (A2) among the PVA (A1) through making, PVA (A1) thus become and decompose easily dissolving easily or disperse, when existing PVA (A1) is only arranged, thereby formation mucus is residual easily after the PVA swelling.
The specific embodiment of above reference specifies the present invention, but this area professional can know, can under the situation that does not break away from aim of the present invention and scope, carry out various changes and modification.
The application is based on the application of the Japanese patent application (the special 2008-307748 of hope) that proposed on December 2nd, 2008, and its content is introduced among the application as a reference.
Utilize possibility on the industry
Basal membrane for hydraulic transfer printing of the present invention can be widely used in the hydraulic transfer printing purposes of the internal and external ornament thing of automobile and the extraneous adornment of mobile phone, various electric equipment products, building materials, family, daily necessities etc.
Claims (7)
1. basal membrane for hydraulic transfer printing; Contain the polyvinyl alcohol film; It is characterized in that; Said polyvinyl alcohol film contains polyvinyl alcohol resin, said polyvinyl alcohol resin contain under 20 ℃, 4 weight % viscosity in aqueous solution be the polyvinyl alcohol resin A1 of 15～50mPas and under 20 ℃, 4 weight % viscosity in aqueous solution are the polyvinyl alcohol resin A2 of 1～10mPas.
2. basal membrane for hydraulic transfer printing as claimed in claim 1 is characterized in that, polyvinyl alcohol resin A2 under 20 ℃, 4 weight % viscosity in aqueous solution than polyvinyl alcohol resin A1 under 20 ℃, 4 weight % viscosity in aqueous solution are little by 5～50%.
3. basal membrane for hydraulic transfer printing as claimed in claim 1 is characterized in that, the use level of polyvinyl alcohol resin A2 is 10～50 weight portions with respect to the polyvinyl alcohol resin A1 of 100 weight portions.
4. basal membrane for hydraulic transfer printing as claimed in claim 1 is characterized in that, the average saponification degree of polyvinyl alcohol resin A1 is 70～98 moles of %, and the average saponification degree of polyvinyl alcohol resin A2 is 70～98 moles of %.
5. basal membrane for hydraulic transfer printing as claimed in claim 1 is characterized in that, the difference of the average saponification degree of polyvinyl alcohol resin A1 and the average saponification degree of polyvinyl alcohol resin A2 is 3 moles below the %.
6. basal membrane for hydraulic transfer printing as claimed in claim 1 is characterized in that, the thickness of polyvinyl alcohol film is 20～50 μ m.
7. like each described basal membrane for hydraulic transfer printing in the claim 1～6, be used for liquid pressure transfer method, in the said liquid pressure transfer method; Form in membrane surface and to dissolve in the hydrophobicity transfer printing layer of organic solvent, and then make basement membrane be positioned at the below and float on the surface, after the coating activating agent makes above-mentioned transfer printing layer activation on the above-mentioned transfer printing layer; To be transferred thing by being pressed on the above-mentioned transfer printing layer, and transfer printing layer will be transferred to be transferred the thing surface, remove basement membrane then; Then; The thing that is transferred through transfer printing there being above-mentioned transfer printing layer is implemented the active energy beam irradiation and is added pine at least a, and transfer printing layer is solidified, and fixes thereby will be transferred to the pattern that is transferred on the thing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008307748 | 2008-12-02 | ||
| JP2008-307748 | 2008-12-02 |
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| Publication Number | Publication Date |
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| CN101746168A CN101746168A (en) | 2010-06-23 |
| CN101746168B true CN101746168B (en) | 2012-10-10 |
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| CN2009102463967A Active CN101746168B (en) | 2008-12-02 | 2009-11-27 | Basal membrane for hydraulic transfer printing |
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| JP (1) | JP5557514B2 (en) |
| CN (1) | CN101746168B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201228831A (en) * | 2010-12-22 | 2012-07-16 | Nippon Synthetic Chem Ind | Transfer-printing laminated material |
| CN102093658B (en) * | 2010-12-23 | 2012-05-23 | 陕西科技大学 | Preparation method of water transfer glue |
| WO2012147530A1 (en) * | 2011-04-27 | 2012-11-01 | 株式会社タイカ | Fluid pressure transfer method |
| TWI540047B (en) * | 2011-05-24 | 2016-07-01 | Nippon Synthetic Chem Ind | A base film for transfer printing laminate, a transfer molding laminate, and a method for producing a base film |
| US9685678B2 (en) * | 2013-02-05 | 2017-06-20 | A123 Systems, LLC | Electrode materials with a synthetic solid electrolyte interface |
| CN103448455B (en) * | 2013-09-05 | 2015-12-02 | 王良利 | A kind of water pastes three-dimensional wall built-up technique |
| CN104589559B (en) * | 2014-12-01 | 2017-08-22 | 杭州绿兴环保材料有限公司 | A kind of ultra-thin polyurethane-hot melt gum resin film processing technology |
| KR102504426B1 (en) * | 2015-06-15 | 2023-02-27 | 주식회사 쿠라레 | Hydraulic transfer printing base film |
| CN107936431A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Polyvinyl alcohol water solubility casting films and preparation method thereof |
| CN113226687B (en) * | 2018-12-28 | 2023-09-29 | 株式会社可乐丽 | Water-soluble film, method for producing same, and package |
| CN110845747B (en) * | 2019-10-30 | 2022-11-11 | 中国石油化工股份有限公司 | PVA film with good flexibility and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6350518B1 (en) * | 1998-06-01 | 2002-02-26 | Kimberly-Clark Worldwide, Inc. | Methods of making blend compositions of an unmodified poly vinyl alcohol and a thermoplastic elastomer |
| EP1418196A1 (en) * | 2002-11-11 | 2004-05-12 | The Nippon Synthetic Chemical Industry Co., Ltd. | Water-soluble film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3824245B2 (en) * | 1997-08-26 | 2006-09-20 | 株式会社リコー | Transfer sheet and image forming method using the same |
| JP4464585B2 (en) * | 2001-07-04 | 2010-05-19 | 日本合成化学工業株式会社 | Base film for transfer printing |
| JP2005297429A (en) * | 2004-04-14 | 2005-10-27 | Dainippon Ink & Chem Inc | Film for hydraulic pressure transfer and hydraulic pressure transfer body |
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2009
- 2009-11-27 CN CN2009102463967A patent/CN101746168B/en active Active
- 2009-11-30 JP JP2009271368A patent/JP5557514B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350518B1 (en) * | 1998-06-01 | 2002-02-26 | Kimberly-Clark Worldwide, Inc. | Methods of making blend compositions of an unmodified poly vinyl alcohol and a thermoplastic elastomer |
| EP1418196A1 (en) * | 2002-11-11 | 2004-05-12 | The Nippon Synthetic Chemical Industry Co., Ltd. | Water-soluble film |
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| JP昭55-25330A 1980.02.23 |
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| JP5557514B2 (en) | 2014-07-23 |
| JP2010155453A (en) | 2010-07-15 |
| CN101746168A (en) | 2010-06-23 |
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Effective date of registration: 20190628 Address after: Tokyo, Japan Patentee after: Mitsubishi Kasei Corporation Address before: Osaka City, Osaka of Japan Patentee before: The Nippon Synthetic Chemical Industry Co., Ltd. |