CN103770492B - Method for manufacturing transfer film and transfer aluminum-plating paper - Google Patents
Method for manufacturing transfer film and transfer aluminum-plating paper Download PDFInfo
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- CN103770492B CN103770492B CN201410015153.3A CN201410015153A CN103770492B CN 103770492 B CN103770492 B CN 103770492B CN 201410015153 A CN201410015153 A CN 201410015153A CN 103770492 B CN103770492 B CN 103770492B
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Abstract
The invention discloses a method for manufacturing a transfer film. The method comprises the steps of (1) manufacturing a master die with Fresnel lens patterns and laser graph patterns, and then electroforming to form a die-pressing working plate; (2) mounting the die-pressing working plate on a die-pressing roller, coating a layer of ultraviolet curing embossed coating on a lower surface of a plastic film and enabling the ultraviolet curing embossed coating to be closely contacted with the die-pressing roller, and then curing the coating layer; (3) separating the ultraviolet curing embossed coating layer from the die-pressing working plate to obtain a transfer film. A method for manufacturing transfer aluminum-plating paper comprises the follow-up steps on the basis of the transfer film: (4) plating aluminum on the ultraviolet curing embossed coating layer to form an aluminum-plating layer; (5) coating a layer of oil paint on the aluminum-plating layer and then drying; (6) compounding the transfer film with printing paper, and then separating the ultraviolet curing embossed coating layer from the aluminum-plating layer to obtain the transfer aluminum-plating paper. According to the method, clear Fresnel lens patterns and laser graph patterns can be formed on the transfer film and the transfer aluminum-plating paper.
Description
Technical field
The present invention relates to typography, be specifically related to a kind of preparation method of transfer membrane, and a kind of preparation method of transfer aluminum plated paper.
Background technology
At present, the application scale of laser graphic packaging material expands gradually, and especially on the packaging such as tobacco bale, wine mark, its bright and colourful pattern makes people more and more like it.Fresnel Lenses (Fresnel Lens) is a kind of optical element of fine structure, its lens surface one side is light face, the ascending concentric circles of another side imprinting, always for fields such as Projection Display, vehicle light illumination, infrared acquisitions since its invention.If Fresnel Lenses is combined with laser graphic, the visual impact of laser graphic can be made stronger, improve the class of laser graphic packaging material.
Traditional laser graphic packaging material generally make in the steps below: the making of (1) transfer membrane: be coated with release mold pressing coating on a plastic film, form embossed plies, then mold pressing laser graphic in embossed plies, form the transfer membrane that mold pressing has laser graphic; Also by modified plastic film, realize without the need to being coated with embossed plies, directly mold pressing goes out laser graphic information on a plastic film, forms the transfer membrane that mold pressing has laser graphic; (2) aluminize: in above-mentioned embossed plies, plate aluminium lamination, or the one side being pressed with laser graphic at above-mentioned plastic sheeting patrix plates aluminium lamination; (3) laminating transfer: the transfer membrane being coated with aluminium lamination of rolling is placed on unwinding device, transfer membrane is by fitting with the stock (as paper) being coated with adhesive in advance during laminating apparatus, its aluminium lamination and adhesive bonds, then adhesive solidification is made, then by stripping off device, plastic sheeting is peeled off, the plastic sheeting stripped down is by wrap-up rolling, like this, aluminium lamination (or aluminium lamination and embossed plies) and laser graphic above thereof are just transferred on stock, thus achieve the laminating transfer of laser graphic, obtain transfer aluminum plated paper.
But, Fresnel Lenses lines is made up of concentric circles lines from small to large, the laser graphic lines that these concentric circles lines are more general has darker groove, traditional press moulding mode cannot be adopted to be formed, that is, traditional press moulding mode is adopted cannot to form Fresnel Lenses lines on transfer membrane.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method with the transfer membrane of Fresnel Lenses lines and laser graphic lines, and adopts this transfer membrane to make the method for transfer aluminum plated paper.The technical scheme adopted is as follows:
A preparation method for transfer membrane, is characterized in that comprising the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane.
After separation, the picture and text in die work version are transferred on the lower surface of ultraviolet light polymerization impression paint coatings, and this ultraviolet light polymerization impression paint coatings and plastic sheeting form transfer membrane jointly.
In above-mentioned steps (1), after electroforming, the lines on grand master pattern is copied in die work version, and accordingly, die work version has Fresnel Lenses lines and laser graphic lines.In addition, grand master pattern also can have other lines, as word lines.The printing important document of grand master pattern usually needed for client makes, and is stitched together by the printing important documents such as Fresnel Lenses, laser graphic, word.
Plastic sheeting in preferred steps (2) is PET film (i.e. pet film).The thickness of preferably plastic film is 15-35 micron (um).
In preferred steps (2), before coated UV curable impression coating, sided corona treatment is carried out to the lower surface of plastic sheeting (one side for coated UV curable impression coating), with the tack of reinforced plastics film lower surface, makes it to be easier to same ultraviolet light polymerization impression coating bonding.
In step (2), can adopt 150-250 object anilox roll coated UV curable impression coating on the lower surface of plastic sheeting, the transporting velocity of plastic sheeting is 25-60 m/min.The dry-coated amount of preferred ultraviolet light polymerization impression coating on plastic sheeting lower surface is 5-15 gram/m.
In preferred steps (2), on the lower surface of plastic sheeting after coated UV curable impression coating, make ultraviolet light polymerization impress paint coatings levelling by baking oven, then with the mold pressing roll close contact of die work version is housed.Temperature in preferred above-mentioned baking oven is 70-80 DEG C.
In step (2), ultraviolet light polymerization impression paint coatings instantaneous solidification (hardening time can be 0.5-1 second) under UV-irradiation.The uv fluorescent tube that power can be adopted to be more than or equal to 16 kilowatts irradiates ultraviolet light polymerization impression paint coatings.
A preparation method for transfer aluminum plated paper, is characterized in that comprising the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane;
(4) aluminize on the lower surface of ultraviolet light polymerization impression paint coatings, form aluminium coated;
(5) on the lower surface of aluminium coated, be coated with one deck oil paint, then make oil paint coating dry;
(6) coating binder on the lower surface of the oil paint coating of transfer membrane or on the upper surface of printing paper, then by transfer membrane and printing paper compound, after adhesive solidification, make ultraviolet light polymerization impress paint coatings be separated with aluminium coated, thus make aluminum transfer on printing paper, obtain transfer aluminum plated paper.
In the preparation method of transfer aluminum plated paper, step (1) is identical with the preparation method of above-mentioned transfer membrane to step (3).
Vacuum aluminizing method can be adopted to aluminize in step (4).Lines on aluminium coated upper surface is corresponding with the lines that ultraviolet light polymerization impresses on paint coatings lower surface.
In step (5), oil paint used is made up of the component of following weight proportioning: resin 20-30 part, solvent 60-80 part, auxiliary agent 1-5 part; Wherein resin is a kind of or wherein multiple combination in acrylic resin, polyurethane resin, nitrocotton resin, vinyl chloride-vinyl acetate resin and polyvinyl butyral resin.Solvent in preferred above-mentioned oil paint is a kind of or wherein multiple combination in butanone, butyl acetate, ethyl acetate, n-propyl acetate, ethanol, isopropyl alcohol and propylene glycol monomethyl ether.Auxiliary agent in above-mentioned oil paint can be a kind of in levelling agent and wear-resisting antiplastering aid or both combinations, wherein levelling agent is the siloxanes (byk 306, BYK333 as German BYK company) of polyether-modified siloxanes or polyester modification, and wear-resisting antiplastering aid can be modified polyethylene wax, polypropylene wax or polytetrafluoroethylene (PTFE) wax.After being equipped with resin, solvent and auxiliary agent by the weight proportion of resin 20-30 part, solvent 60-80 part, auxiliary agent 1-5 part, resin, solvent and auxiliary agent being mixed and stirs, can oil paint be obtained.
In preferred steps (5), the dry-coated amount of oil paint on aluminium coated lower surface is 1-1.5 gram/m.During coating, the viscosity of oil paint controls 18-25 second (being coated with 4-cup, 25 DEG C).150-200 object anilox roll can be adopted to be coated by oil paint on aluminium coated lower surface, and the transporting velocity of transfer membrane is 80-110 m/min.
In preferred steps (5), adopt the second baking oven to make oil paint coating dry, the temperature in the second baking oven is 80-130 DEG C.
In step (5), oil paint is in coating and dry run, solvent penetration wherein crosses aluminium coated, further reduction aluminium coated is to the adhesive force of ultraviolet light polymerization impression paint coatings, improve the film forming of aluminium coated, make aluminium coated and ultraviolet light polymerization in subsequent handling impress paint coatings more easily separated.
In step (6), aluminium coated is transferred on printing paper together with the lines on its upper surface.
In step (6), can dry when bake out temperature is 90-130 DEG C, make adhesive solidification; During oven dry, the transporting velocity of the composite of transfer membrane and printing paper is about 80 ms/min.
More preferably, after ultraviolet light polymerization impression paint coatings is separated with aluminium coated, on the upper surface of aluminium coated, last layer water varnish is coated with.Water varnish layer for the protection of the lines on aluminium coated upper surface from wearing and tearing.
In preferred version, above-mentioned ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 10-30 part, polyurethane resin 20-40 part, diluting monomer 40-60 part, light trigger 2-10 part, auxiliary agent 1-5 part.This ultraviolet light polymerization impression coating surface tension force is low, has fabulous adhesive force to plastic sheeting (as PET film), impresses and solidify easy and die work version afterwards to depart from, and the coating of solidification has fabulous heat resistance, pliability and solvent resistance.
A kind of preparation method of above-mentioned ultraviolet light polymerization impression coating, comprises the steps: successively by weight, is equipped with polyacrylic resin 10-30 part, polyurethane resin 20-40 part, diluting monomer 40-60 part, light trigger 2-10 part and auxiliary agent 1-5 part; Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (preferred mixing time is 10-20 minute) under the mixing speed of 200-300 rev/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 800-1200 rev/min, be stirred to light trigger dissolve completely (mixing time is generally 30-60 minute), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Above-mentioned diluting monomer can be Tetrahydrofurfuryl Methacrylate (THFFA), acrylate (POEA), 1, 6-hexanediyl ester (HDDA), neopentylglycol diacrylate (NPGDA), dipentaerythritol acrylate (DPHA), oxolane acrylate (THFA), acrylic acid DCPA (DCPA), acryloyl morpholine (ACMO), iso-bornyl acrylate (IBOA), ethoxyethoxyethyl acrylate (EOEOEA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), propenoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, a kind of or wherein multiple combination in propylene glycol diacrylate (DPGDA) and ethoxylated trimethylolpropane triacrylate (EO-TMPTA).
Above-mentioned light trigger can be benzoin, benzoin derivatives, 1-hydroxycyclohexyl phenyl ketone (light trigger 184), alpha-hydroxyalkyl benzophenone, benzophenone, benzophenone derivates, acylphosphine oxide is (as 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide, phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide), thioxanthone, thioxanthone derivative is (as isopropyl thioxanthone (ITX), 2-chlorothiaxanthenone (CTX), 1-chloro-4-propoxyl group thioxanthone (CPTX), 2, 4-diethyl thioxanthone (DETX)), 4-dimethyl ethyl aminobenzoate and N, a kind of or wherein multiple combination in the different monooctyl ester of N-dimethylaminobenzoic acid.
Above-mentioned auxiliary agent can be a kind of or wherein multiple combination in defoamer, levelling agent and coupling agent.Wherein, defoamer can prevent ultraviolet light polymerization from impressing coating and produce bubble when being coated with; The film effect that levelling agent can make ultraviolet light polymerization impression coating have when being coated with, and migrate to surface when version impresses, coating is effectively separated with version; Coupling agent can improve ultraviolet light polymerization impression paint coatings to the adhesive force of plastic sheeting (as PET film).Above-mentioned defoamer can be a kind of in dimethyl polysiloxane and aerosil or both mixtures, as 065,020 of 902,920, byk companies of German tego company.Above-mentioned levelling agent can be polysiloxane-polyether copolymer or silicone oil.Above-mentioned coupling agent can be silane coupler, as KH550, KH560, KH570, KH792, DL602, DL171.
In preferred version, the preparation method of above-mentioned polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 90-140 part, initator 0.5-4 part, acrylic or methacrylic acid 20-30 part, modified rosin resin 5-10 part, polymerization inhibitor A 0.1-1 part, catalyst A 0.1-1 part; Acrylate monomer 20-30 part containing hydroxyl acrylate monomer 20-30 part, band epoxy radicals in described 90-140 part acrylate monomer;
(2) in the reactor that thermometer, agitator and condenser are housed, add 15-30 part reflux solvent (by weight) and be warmed up to 110-130 DEG C, drip the mixture of acrylate monomer and initator again, react after 3-5 hour, obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 80-90 DEG C, then the mixture of polymerization inhibitor A, catalyst A, acrylic or methacrylic acid and modified rosin resin is dripped, react after 1-2 hour, be warmed up to 100-110 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin.
In step (3), usually make modified rosin resin be dissolved in acrylic or methacrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, and obtains the mixture of described polymerization inhibitor A, catalyst A, acrylic or methacrylic acid and modified rosin resin.
In the course of reaction of step (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 40-50 DEG C and discharging.
In preferred version, in aforesaid propylene acid ester monomer, hydroxyl acrylate monomer is a kind of or wherein multiple combination in hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxy-ethyl acrylate, acrylate monomer with epoxy radicals is a kind of in glycidyl acrylate and tertiary carbonic acid glycidyl ester or both combinations, and remaining acrylate monomer is a kind of or wherein multiple combination in butyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, isobornyl acrylate and EMA.Hydroxyl acrylate monomer introduces active oh group, improves PET tack.Acrylate monomer with epoxy radicals is the function monomer of reaction, introduces epoxide group by the acrylate monomer adding band epoxy radicals, then ring-opening reaction sour with acrylic or methacrylic, obtains polyacrylic resin.What all the other acrylate monomers were selected is soft acrylate monomer, and ultraviolet light polymerization is impressed, and coating bonding force is good, pliability is good.
Above-mentioned initator can be azodiisobutyronitrile, TBHP, benzoyl peroxide or two t-amyl peroxy compounds (DTAP).
In step (3), the epoxy radicals that polyacrylate long-chain contains and acrylic or methacrylic acid, modified rosin resin open loop addition, the obtained polyacrylic resin with unsaturated double-bond.
In step (3), by adding polymerization inhibitor A, make the unsaturated double-bond of acrylic resin reduce the possibility of autohemagglutination, the density of the reservation unsaturated double-bond of maximum possible, provides photo-crosslinking, makes polyacrylic resin have photolytic activity.Above-mentioned polymerization inhibitor A can be p methoxy phenol, hydroquinones or 2,6-toluene di-tert-butyl phenol.
In step (3), adding of catalyst A makes the easier open loop of epoxide group and acrylic or methacrylic acid addition.Above-mentioned catalyst A can be triphenyl phosphorus, triethylamine, tetraethylammonium bromide, N, N-dimethyl arylamine, antimony triphenyl or tetramethyl ammonium chloride.
In step (3), by introducing modified rosin resin, as the tackifying resin in polymer, mechanical strength can be improved, and improve the caking property of difficulty being glued to material, there is very big help to the cure shrinkage and the adhesive force of raising ultraviolet light polymerization impression coating to plastic sheeting (particularly PET film) reducing ultraviolet light polymerization impression coating.Above-mentioned modified rosin resin can be acrylic acid modified rosin ester or Foral.
Above-mentioned reflux solvent adopts toluene usually.
The polyurethane resin wearability that said method obtains is good, excellent physical mechanical property, ultraviolet light polymerization can be regulated to impress the curing rate of coating, and improve the pliability of coating.
The preparation method of preferred above-mentioned polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 30-50 part, polyisocyanates 30-60 part, catalyst B 0.05-1 part, end-capping reagent 10-30 part, polymerization inhibitor B 0.1-1 part;
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, at 50-60 DEG C, react 1-2 hour; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 60-70 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin.
Above-mentioned polyalcohol preferred molecular weight is the polyalcohol of 500-2000.Above-mentioned polyalcohol can be the acrylic polyol of PEPA, PPG, dimeric dibasic acid dihydroxylic alcohols, PolyTHF dihydroxylic alcohols or modification.Wherein PEPA can be polyneopentyl glycol adipate polyalcohol, PETG, poly-adipic acid hexylene glycol ester, polycaprolactone diols or PCDL.
Above-mentioned polyisocyanates can be IPDI, PPDI, 1,6 hexamethylene diisocyanates (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI) or XDI (XDI).
Above-mentioned catalyst B can be dibutyl tin laurate, stannous octoate or triethylamine.
Above-mentioned end-capping reagent can be hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, trimethylolpropane diacrylate (TMPDA) or pentaerythritol triacrylate (PETA).Add the above-mentioned end-capping reagent containing hydroxyl and can introduce double bond on polyurethane resin.
Above-mentioned polymerization inhibitor B can be hydroquinones or MEHQ.
The present invention's employing is carried out impressing and is made the mode that this ultraviolet light polymerization impression paint coatings solidifies under UV-irradiation on ultraviolet light polymerization impression paint coatings, ultraviolet light polymerization impression paint coatings forms Fresnel Lenses lines and laser graphic lines clearly, thus on transfer membrane and transfer aluminum plated paper, form Fresnel Lenses lines and laser graphic lines clearly, Fresnel Lenses combines with laser graphic, the visual impact of the laser graphic on transfer membrane and transfer aluminum plated paper can be made stronger, improve the class of laser graphic packaging material, antifalse effect is better.
Detailed description of the invention
The making of embodiment 1 transfer membrane and transfer aluminum plated paper
In the present embodiment, the preparation method of transfer membrane comprises the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
In step (1), after electroforming, the lines on grand master pattern is copied in die work version, and accordingly, die work version has Fresnel Lenses lines and laser graphic lines; Grand master pattern also can have other lines, as word lines.The printing important document of grand master pattern needed for client makes, and is stitched together by the printing important documents such as Fresnel Lenses, laser graphic, word.
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
In step (2), plastic sheeting adopts PET film, and the thickness of plastic sheeting is 25 microns; Before coated UV curable impression coating, sided corona treatment is carried out to the lower surface (one side for coated UV curable impression coating) of plastic sheeting; Adopt 200 object anilox roll coated UV curable impression coating on the lower surface of plastic sheeting, the transporting velocity of plastic sheeting is 40 ms/min, and the dry-coated amount of ultraviolet light polymerization impression coating on plastic sheeting lower surface is 10 grams/m; On the lower surface of plastic sheeting coated UV curable impression coating after, by baking oven make ultraviolet light polymerization impress paint coatings levelling (temperature in baking oven is 75 DEG C), then with the mold pressing roll close contact of die work version is housed; Employing power is that the uv fluorescent tube of 16 kilowatts irradiates ultraviolet light polymerization impression paint coatings, makes ultraviolet light polymerization impress paint coatings solidification.
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane.After separation, the picture and text in die work version are transferred on the lower surface of ultraviolet light polymerization impression paint coatings, and this ultraviolet light polymerization impression paint coatings and plastic sheeting form transfer membrane jointly.
On the basis of above-mentioned transfer membrane, continue to carry out following step successively, make transfer aluminum plated paper:
(4) aluminize on the lower surface of ultraviolet light polymerization impression paint coatings, form aluminium coated;
Vacuum aluminizing method is adopted to aluminize in step (4).
(5) on the lower surface of aluminium coated, be coated with one deck oil paint, then make oil paint coating dry;
In step (5), oil paint used is made up of the component of following weight proportioning: resin 25 parts, solvent 70 parts, auxiliary agent 3 parts; Wherein resin is acrylic resin, and solvent is butanone, and auxiliary agent is made up of 2 parts of levelling agents (being polyether-modified siloxanes) and 1 part of wear-resisting antiplastering aid (being polytetrafluoroethylene (PTFE) wax).After being equipped with resin, solvent and auxiliary agent by above-mentioned weight proportion, resin, solvent and auxiliary agent being mixed and stirs, can oil paint be obtained.
In step (5), adopt 180 object anilox roll to be coated by oil paint on aluminium coated lower surface, the transporting velocity of transfer membrane is 100 ms/min, and the dry-coated amount of oil paint on aluminium coated lower surface is 1.2 grams/m; During coating, the viscosity of oil paint is 20 seconds (being coated with 4-cup, 25 DEG C).
In step (5), adopt the second baking oven to make oil paint coating dry, the temperature in the second baking oven is 110 DEG C.
(6) coating binder on the lower surface of the oil paint coating of transfer membrane or on the upper surface of printing paper, then by transfer membrane and printing paper compound, after adhesive solidification, make ultraviolet light polymerization impress paint coatings be separated with aluminium coated, thus make aluminum transfer to (aluminium coated is transferred on printing paper together with the lines on its upper surface) on printing paper, obtain transfer aluminum plated paper.
In step (6), dry when bake out temperature is 110 DEG C, make adhesive solidification; During oven dry, the transporting velocity of the composite of transfer membrane and printing paper is 80 ms/min.
After ultraviolet light polymerization impression paint coatings is separated with aluminium coated, on the upper surface of aluminium coated, be coated with last layer water varnish, water varnish layer for the protection of the lines on aluminium coated upper surface from wearing and tearing.
The making of embodiment 2 transfer membrane and transfer aluminum plated paper
In the present embodiment, the preparation method of transfer membrane comprises the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
In step (1), after electroforming, the lines on grand master pattern is copied in die work version, and accordingly, die work version has Fresnel Lenses lines and laser graphic lines; Grand master pattern also can have other lines, as word lines.The printing important document of grand master pattern needed for client makes, and is stitched together by the printing important documents such as Fresnel Lenses, laser graphic, word.
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
In step (2), plastic sheeting adopts PET film, and the thickness of plastic sheeting is 35 microns; Before coated UV curable impression coating, sided corona treatment is carried out to the lower surface (one side for coated UV curable impression coating) of plastic sheeting; Adopt 150 object anilox roll coated UV curable impression coating on the lower surface of plastic sheeting, the transporting velocity of plastic sheeting is 30 ms/min, and the dry-coated amount of ultraviolet light polymerization impression coating on plastic sheeting lower surface is 15 grams/m; On the lower surface of plastic sheeting coated UV curable impression coating after, by baking oven make ultraviolet light polymerization impress paint coatings levelling (temperature in baking oven is 80 DEG C), then with the mold pressing roll close contact of die work version is housed; Employing power is that the uv fluorescent tube of 18 kilowatts irradiates ultraviolet light polymerization impression paint coatings, makes ultraviolet light polymerization impress paint coatings solidification.
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane.After separation, the picture and text in die work version are transferred on the lower surface of ultraviolet light polymerization impression paint coatings, and this ultraviolet light polymerization impression paint coatings and plastic sheeting form transfer membrane jointly.
On the basis of above-mentioned transfer membrane, continue to carry out following step successively, make transfer aluminum plated paper:
(4) aluminize on the lower surface of ultraviolet light polymerization impression paint coatings, form aluminium coated;
Vacuum aluminizing method is adopted to aluminize in step (4).
(5) on the lower surface of aluminium coated, be coated with one deck oil paint, then make oil paint coating dry;
In step (5), oil paint used is made up of the component of following weight proportioning: resin 30 parts, solvent 60 parts, auxiliary agent 5 parts; Wherein resin is made up of 15 parts of polyurethane resins and 15 parts of nitrocotton resins, and solvent is ethyl acetate, and auxiliary agent is made up of 3 parts of levelling agents (being the siloxanes of polyester modification) and 2 parts of wear-resisting antiplastering aids (being polypropylene wax).After being equipped with resin, solvent and auxiliary agent by above-mentioned weight proportion, resin, solvent and auxiliary agent being mixed and stirs, can oil paint be obtained.
In step (5), adopt 200 object anilox roll to be coated by oil paint on aluminium coated lower surface, the transporting velocity of transfer membrane is 80 ms/min, and the dry-coated amount of oil paint on aluminium coated lower surface is 1 gram/m; During coating, the viscosity of oil paint controls 25 seconds (being coated with 4-cup, 25 DEG C).
In step (5), adopt the second baking oven to make oil paint coating dry, the temperature in the second baking oven is 85 DEG C.
(6) coating binder on the lower surface of the oil paint coating of transfer membrane or on the upper surface of printing paper, then by transfer membrane and printing paper compound, after adhesive solidification, make ultraviolet light polymerization impress paint coatings be separated with aluminium coated, thus make aluminum transfer to (aluminium coated is transferred on printing paper together with the lines on its upper surface) on printing paper, obtain transfer aluminum plated paper.
In step (6), dry when bake out temperature is 90 DEG C, make adhesive solidification; During oven dry, the transporting velocity of the composite of transfer membrane and printing paper is 80 ms/min.
After ultraviolet light polymerization impression paint coatings is separated with aluminium coated, on the upper surface of aluminium coated, be coated with last layer water varnish, water varnish layer for the protection of the lines on aluminium coated upper surface from wearing and tearing.
The making of embodiment 3 transfer membrane and transfer aluminum plated paper
In the present embodiment, the preparation method of transfer membrane comprises the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
In step (1), after electroforming, the lines on grand master pattern is copied in die work version, and accordingly, die work version has Fresnel Lenses lines and laser graphic lines; Grand master pattern also can have other lines, as word lines.The printing important document of grand master pattern needed for client makes, and is stitched together by the printing important documents such as Fresnel Lenses, laser graphic, word.
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
In step (2), plastic sheeting can adopt PET film, and the thickness of plastic sheeting is 15 microns; Before coated UV curable impression coating, sided corona treatment is carried out to the lower surface (one side for coated UV curable impression coating) of plastic sheeting; Adopt 250 object anilox roll coated UV curable impression coating on the lower surface of plastic sheeting, the transporting velocity of plastic sheeting is 60 ms/min, and the dry-coated amount of ultraviolet light polymerization impression coating on plastic sheeting lower surface is 5 grams/m; On the lower surface of plastic sheeting coated UV curable impression coating after, by baking oven make ultraviolet light polymerization impress paint coatings levelling (temperature in baking oven is 70 DEG C), then with the mold pressing roll close contact of die work version is housed; Employing power is that the uv fluorescent tube of 17 kilowatts irradiates ultraviolet light polymerization impression paint coatings, makes ultraviolet light polymerization impress paint coatings solidification.
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane.After separation, the picture and text in die work version are transferred on the lower surface of ultraviolet light polymerization impression paint coatings, and this ultraviolet light polymerization impression paint coatings and plastic sheeting form transfer membrane jointly.
On the basis of above-mentioned transfer membrane, continue to carry out following step successively, make transfer aluminum plated paper:
(4) aluminize on the lower surface of ultraviolet light polymerization impression paint coatings, form aluminium coated;
Vacuum aluminizing method is adopted to aluminize in step (4).
(5) on the lower surface of aluminium coated, be coated with one deck oil paint, then make oil paint coating dry;
In step (5), oil paint used is made up of the component of following weight proportioning: resin 20 parts, solvent 80 parts, auxiliary agent 1 part; Wherein resin is vinyl chloride-vinyl acetate resin, and solvent is ethanol, and auxiliary agent is levelling agent (being the siloxanes of polyester modification).After being equipped with resin, solvent and auxiliary agent by above-mentioned weight proportion, resin, solvent and auxiliary agent being mixed and stirs, can oil paint be obtained.
In step (5), adopt 150 object anilox roll to be coated by oil paint on aluminium coated lower surface, the transporting velocity of transfer membrane is 110 ms/min, and the dry-coated amount of oil paint on aluminium coated lower surface is 1.5 grams/m; During coating, the viscosity of oil paint controls 18 seconds (being coated with 4-cup, 25 DEG C).
In step (5), adopt the second baking oven to make oil paint coating dry, the temperature in the second baking oven is 130 DEG C.
(6) coating binder on the lower surface of the oil paint coating of transfer membrane or on the upper surface of printing paper, then by transfer membrane and printing paper compound, after adhesive solidification, make ultraviolet light polymerization impress paint coatings be separated with aluminium coated, thus make aluminum transfer to (aluminium coated is transferred on printing paper together with the lines on its upper surface) on printing paper, obtain transfer aluminum plated paper.
In step (6), dry when bake out temperature is 130 DEG C, make adhesive solidification; During oven dry, the transporting velocity of the composite of transfer membrane and printing paper is 80 ms/min.
After ultraviolet light polymerization impression paint coatings is separated with aluminium coated, on the upper surface of aluminium coated, be coated with last layer water varnish, water varnish layer for the protection of the lines on aluminium coated upper surface from wearing and tearing.
The ultraviolet light polymerization impression coating used in above-described embodiment 1-3, can be selected from any one of the ultraviolet light polymerization impression coating that following examples 4-8 obtains.
The preparation of embodiment 4 ultraviolet light polymerization impression coating
In the present embodiment, first prepare polyacrylic resin and polyurethane resin.
The preparation method of polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 120 parts, initator 2 parts (being benzoyl peroxide), 25 parts, acrylic acid, modified rosin resin 8 parts (being Foral), polymerization inhibitor A 0.5 part (being p methoxy phenol), catalyst A 0.6 part (being triphenyl phosphorus); Containing hydroxy-ethyl acrylate 25 parts, glycidyl acrylate 25 parts, butyl acrylate 30 parts, butyl methacrylate 40 parts in described 120 parts of acrylate monomers;
(2) in the reactor that thermometer, agitator and condenser are housed, add 20 parts of (by weight) reflux solvents (being toluene) and be warmed up to 120 DEG C, drip the mixture of acrylate monomer and initator again, react after 4 hours and (react at 120 DEG C), obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 85 DEG C, then the mixture dripping polymerization inhibitor A, catalyst A, acrylic acid and modified rosin resin (makes modified rosin resin be dissolved in acrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, obtain this mixture), react after 1.5 hours, be warmed up to 105 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin, for subsequent use.
In the course of reaction of above-mentioned steps (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 45 DEG C and dischargings.
The preparation method of polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 40 parts (being the polyneopentyl glycol adipate polyalcohol that molecular weight is 1000), polyisocyanates 50 parts (being IPDI), catalyst B 0.08 part (being dibutyl tin laurate), end-capping reagent 20 parts (being hydroxyethyl methacrylate), polymerization inhibitor B 0.6 part (being hydroquinones);
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, and reacts 1.5 hours at 55 DEG C; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 65 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin, for subsequent use.
Then above-mentioned polyacrylic resin for subsequent use and polyurethane resin is utilized to prepare ultraviolet light polymerization impression coating.
The preparation method of above-mentioned ultraviolet light polymerization impression coating comprises the steps: by weight successively, is equipped with polyacrylic resin 25 parts, polyurethane resin 30 parts, diluting monomer 50 parts (wherein trimethylolpropane triacrylate 30 parts, acryloyl morpholine 20 parts), light trigger 6 parts (being 1-hydroxycyclohexyl phenyl ketone) and auxiliary agent 3 parts (wherein defoamer dimethyl polysiloxane 1 part, levelling agent polysiloxane-polyether copolymer 1 part, silane coupler 1 part); Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (mixing time is 15 minutes) under the mixing speed of 250 revs/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 1000 revs/min, be stirred to light trigger dissolve completely (mixing time is 50 minutes), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Obtained ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 25 parts, polyurethane resin 30 parts, diluting monomer 50 parts (wherein trimethylolpropane triacrylate 30 parts, acryloyl morpholine 20 parts), light trigger 6 parts (being 1-hydroxycyclohexyl phenyl ketone), auxiliary agent 3 parts (wherein defoamer dimethyl polysiloxane 1 part, levelling agent polysiloxane-polyether copolymer 1 part, silane coupler 1 part).
The performance of obtained ultraviolet light polymerization impression coating is as follows: viscosity: 46 seconds (being coated with-4 glasss, 25 DEG C); Hardness >=2H; Pliability: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines with the speed of 40 ms/min, doubling flawless; Adhesive force: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, draws without coming off with 3M adhesive tape with the speed of 40 ms/min; Upper machine adaptability: normally produce without gum deposit conditions of streaking; Heat-resisting hot: to coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, aluminizes and puts the baking of 140 DEG C, baking oven with the speed of 40 ms/min, without growing dim general color loss of gloss.Solvent resistant MEK tests: close to dripping MEK agent, wipe dry after putting 5 minutes, and surface is without fading phenomenon.
The preparation of embodiment 5 ultraviolet light polymerization impression coating
In the present embodiment, first prepare polyacrylic resin and polyurethane resin.
The preparation method of polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 95 parts, initator 0.5 part (being two t-amyl peroxy compounds), 20 parts, acrylic acid, modified rosin resin 10 parts (being acrylic acid modified rosin ester), polymerization inhibitor A 0.1 part (being p methoxy phenol), catalyst A 1 part (being triphenyl phosphorus); Containing hydroxy-ethyl acrylate 20 parts, glycidyl acrylate 20 parts, butyl acrylate 30 parts, butyl methacrylate 15 parts, isobornyl acrylate 10 parts in described 95 parts of acrylate monomers;
(2) in the reactor that thermometer, agitator and condenser are housed, add 15 parts of (by weight) reflux solvents (being toluene) and be warmed up to 130 DEG C, drip the mixture of acrylate monomer and initator again, react after 3 hours and (react at 130 DEG C), obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 90 DEG C, then the mixture dripping polymerization inhibitor A, catalyst A, acrylic acid and modified rosin resin (makes modified rosin resin be dissolved in acrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, obtain this mixture), react after 1 hour, be warmed up to 110 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin, for subsequent use.
In the course of reaction of step (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 50 DEG C and dischargings.
The preparation method of polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 50 parts (being the polycaprolactone diols that molecular weight is 500), polyisocyanates 30 parts (being PPDI), catalyst B 0.05 part (being dibutyl tin laurate), end-capping reagent 24 parts (being pentaerythritol triacrylate), polymerization inhibitor B 0.1 part (being MEHQ);
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, and reacts 2 hours at 50 DEG C; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 70 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin, for subsequent use.
Then, above-mentioned polyacrylic resin for subsequent use and polyurethane resin is utilized to prepare ultraviolet light polymerization impression coating.
The preparation method of above-mentioned ultraviolet light polymerization impression coating comprises the steps: by weight successively, be equipped with polyacrylic resin 30 parts, polyurethane resin 20 parts, diluting monomer 40 parts (wherein propylene glycol diacrylate 20 parts, ethoxylated trimethylolpropane triacrylate 20 parts), light trigger 8 parts (wherein benzophenone 6 parts, 2,4,6-trimethylbenzoy-dipheny phosphine oxide 2 parts) and auxiliary agent 4 parts (wherein defoamer aerosil 2 parts, levelling agent silicone oil 1 part, silane coupler 1 part); Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (mixing time is 10 minutes) under the mixing speed of 300 revs/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 1200 revs/min, be stirred to light trigger dissolve completely (mixing time is 30 minutes), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Obtained ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 30 parts; polyurethane resin 20 parts; diluting monomer 40 parts (wherein propylene glycol diacrylate 20 parts, ethoxylated trimethylolpropane triacrylate 20 parts); light trigger 8 parts (wherein benzophenone 6 parts, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide 2 parts), auxiliary agent 4 parts (wherein defoamer aerosil 2 parts, levelling agent silicone oil 1 part, silane coupler 1 part).
The performance of obtained ultraviolet light polymerization impression coating is as follows: viscosity: 38 seconds (being coated with-4 glasss, 25 DEG C); Hardness >=2H; Pliability: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines with the speed of 40 ms/min, doubling flawless; Adhesive force: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, draws without coming off with 3M adhesive tape with the speed of 40 ms/min; Upper machine adaptability: normally produce without gum deposit conditions of streaking; Heat-resisting hot: to coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, aluminizes and puts the baking of 140 DEG C, baking oven without growing dim general color loss of gloss with the speed of 40 ms/min; Solvent resistant MEK tests: close to dripping MEK agent, wipe dry after putting 5 minutes, and surface is without fading phenomenon.
The preparation of embodiment 6 ultraviolet light polymerization impression coating
In the present embodiment, first prepare polyacrylic resin and polyurethane resin.
The preparation method of polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 140 parts, initator 4 parts (being TBHP), methacrylic acid 30 parts, modified rosin resin 5 parts (being Foral), polymerization inhibitor A 1 part (is 2,6-toluene di-tert-butyl phenol), catalyst A 0.1 part (being triethylamine); Containing hydroxypropyl acrylate 15 parts, hydroxy-ethyl acrylate 15 parts, glycidyl acrylate 20 parts, tertiary carbonic acid glycidyl ester 10 parts, butyl acrylate 50 parts, ethyl acrylate 30 parts in described 140 parts of acrylate monomers;
(2) in the reactor that thermometer, agitator and condenser are housed, add 30 parts of (by weight) reflux solvents (being toluene) and be warmed up to 110 DEG C, drip the mixture of acrylate monomer and initator again, react after 5 hours and (react at 110 DEG C), obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 80 DEG C, then the mixture dripping polymerization inhibitor A, catalyst A, methacrylic acid and modified rosin resin (makes modified rosin resin be dissolved in methacrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, obtain this mixture), react after 2 hours, be warmed up to 100 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin, for subsequent use.
In the course of reaction of step (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 40 DEG C and dischargings.
The preparation method of polyurethane resin comprises the following steps:
(1 '), following weight proportion was equipped with raw material: polyalcohol 30 parts (being poly-adipic acid hexylene glycol ester), polyisocyanates 60 parts (is 1,6 hexamethylene diisocyanates), catalyst B 1 part (being stannous octoate), end-capping reagent 10 parts (being hydroxy-ethyl acrylate), polymerization inhibitor B 1 part (being hydroquinones);
(2 ') is equipped with in the reactor of thermometer, agitator and condenser and adds polyalcohol, polyisocyanates and catalyst B, reacts 1 hour at 60 DEG C; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 65 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin, for subsequent use.
Then above-mentioned polyacrylic resin for subsequent use and polyurethane resin is utilized to prepare ultraviolet light polymerization impression coating.
The preparation method of above-mentioned ultraviolet light polymerization impression coating comprises the steps: by weight successively, be equipped with polyacrylic resin 10 parts, polyurethane resin 40 parts, diluting monomer 40 parts (wherein pentaerythritol triacrylate 10 parts, 1,6-hexanediyl ester 10 parts, oxolane acrylate 20 parts), light trigger 2 parts (benzophenone 1 part, 2,4,6-trimethylbenzoy-dipheny phosphine oxide 1 part) and auxiliary agent 1 part (being silane coupler); Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (mixing time is 20 minutes) under the mixing speed of 200 revs/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 800 revs/min, be stirred to light trigger dissolve completely (mixing time is 60 minutes), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Obtained ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 10 parts; polyurethane resin 40 parts; diluting monomer 40 parts (wherein pentaerythritol triacrylate 10 parts, 1; 6-hexanediyl ester 10 parts, oxolane acrylate 20 parts); light trigger 2 parts (benzophenone 1 part, 2; 4,6-trimethylbenzoy-dipheny phosphine oxide 1 part), auxiliary agent 1 part (being silane coupler).
The performance of obtained ultraviolet light polymerization impression coating is as follows: viscosity: 56 seconds (being coated with-4 glasss, 25 DEG C); Hardness >=2H; Pliability: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines with the speed of 40 ms/min, doubling flawless; Adhesive force: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, draws without coming off with 3M adhesive tape with the speed of 40 ms/min; Upper machine adaptability: normally produce without gum deposit conditions of streaking; Heat-resisting hot: to coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, aluminizes and puts the baking of 140 DEG C, baking oven with the speed of 40 ms/min, without growing dim general color loss of gloss.Solvent resistant MEK tests: close to dripping MEK agent, wipe dry after putting 5 minutes, and surface is without fading phenomenon.
The preparation of embodiment 7 ultraviolet light polymerization impression coating
In the present embodiment, first prepare polyacrylic resin and polyurethane resin.
The preparation method of polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 120 parts, initator 1 part (being azodiisobutyronitrile), methacrylic acid 28 parts, modified rosin resin 6 parts (being Foral), polymerization inhibitor A 0.4 part (being p methoxy phenol), catalyst A 0.5 part (being tetraethylammonium bromide); Containing hydroxypropyl acrylate 25 parts, glycidyl acrylate 25 parts, ethyl acrylate 40 parts, isobornyl acrylate 30 parts in described 120 parts of acrylate monomers;
(2) in the reactor that thermometer, agitator and condenser are housed, add 20 parts of (by weight) reflux solvents (being toluene) and be warmed up to 115 DEG C, drip the mixture of acrylate monomer and initator again, react after 4.5 hours and (react at 115 DEG C), obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 82 DEG C, then the mixture dripping polymerization inhibitor A, catalyst A, methacrylic acid and modified rosin resin (makes modified rosin resin be dissolved in methacrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, obtain this mixture), react after 2 hours, be warmed up to 102 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin, for subsequent use.
In the course of reaction of step (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 42 DEG C and dischargings.
The preparation method of polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 45 parts (being PolyTHF dihydroxylic alcohols), polyisocyanates 50 parts (being dicyclohexyl methyl hydride diisocyanate), catalyst B 0.08 part (being triethylamine), end-capping reagent 25 parts (being hydroxy propyl methacrylate), polymerization inhibitor B 0.8 part (being hydroquinones);
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, and reacts 1.5 hours at 58 DEG C; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 68 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin, for subsequent use.
Then above-mentioned polyacrylic resin for subsequent use and polyurethane resin is utilized to prepare ultraviolet light polymerization impression coating.
The preparation method of above-mentioned ultraviolet light polymerization impression coating comprises the steps: by weight successively, be equipped with polyacrylic resin 30 parts, polyurethane resin 40 parts, diluting monomer 60 parts (being acrylic acid DCPA), light trigger 6 parts (wherein 2,4-diethyl thioxanthone 3 parts, 4-dimethyl ethyl aminobenzoate 3 parts), auxiliary agent 2 parts (wherein defoamer dimethyl polysiloxane 1 part, levelling agent polysiloxane-polyether copolymer 1 part); Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (mixing time is 14 minutes) under the mixing speed of 280 revs/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 900 revs/min, be stirred to light trigger dissolve completely (mixing time is 50 minutes), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Obtained ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 30 parts, polyurethane resin 40 parts, diluting monomer 60 parts (being acrylic acid DCPA), light trigger 6 parts (wherein 2,4-diethyl thioxanthone 3 parts, 4-dimethyl ethyl aminobenzoate 3 parts), auxiliary agent 2 parts (wherein defoamer dimethyl polysiloxane 1 part, levelling agent polysiloxane-polyether copolymer 1 part).
The performance of obtained ultraviolet light polymerization impression coating is as follows: viscosity: 43 seconds (being coated with-4 glasss, 25 DEG C); Hardness >=2H; Pliability: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines with the speed of 40 ms/min, doubling flawless; Adhesive force: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, draws without coming off with 3M adhesive tape with the speed of 40 ms/min; Upper machine adaptability: normally produce without gum deposit conditions of streaking; Heat-resisting hot: to coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, aluminizes and puts the baking of 140 DEG C, baking oven with the speed of 40 ms/min, without growing dim general color loss of gloss.Solvent resistant MEK tests: close to dripping MEK agent, wipe dry after putting 5 minutes, and surface is without fading phenomenon.
The preparation of embodiment 8 ultraviolet light polymerization impression coating
In the present embodiment, first prepare polyacrylic resin and polyurethane resin.
The preparation method of polyacrylic resin comprises the following steps:
(1) raw material is equipped with by following weight proportion: acrylate monomer 100 parts, initator 3 parts (being TBHP), 28 parts, acrylic acid, modified rosin resin 8 parts (being acrylic acid modified rosin ester), polymerization inhibitor A 0.4 part (being p methoxy phenol), catalyst A 0.8 part (being antimony triphenyl); Containing hydroxypropyl acrylate 14 parts, hydroxy-ethyl acrylate 14 parts, glycidyl acrylate 22 parts, butyl acrylate 30 parts, isobornyl acrylate 20 parts in described 100 parts of acrylate monomers;
(2) in the reactor that thermometer, agitator and condenser are housed, add 25 parts of (by weight) reflux solvents (being toluene) and be warmed up to 125 DEG C, drip the mixture of acrylate monomer and initator again, react after 4 hours and (react at 125 DEG C), obtain hydroxyl and acrylic resin that is epoxy radicals;
(3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 85 DEG C, then the mixture dripping polymerization inhibitor A, catalyst A, acrylic acid and modified rosin resin (makes modified rosin resin be dissolved in acrylic acid, and make polymerization inhibitor A, catalyst A is uniformly dispersed, obtain this mixture), react after 2 hours, be warmed up to 105 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin, for subsequent use.
In the course of reaction of step (3), sampling detecting acid number, to follow the tracks of extent of reaction; When judging to react completely when acid number is down to 10mgKOH/g.React completely and after removing reflux solvent, the polyacrylic resin obtained be cooled to 45 DEG C and dischargings.
The preparation method of polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 50 parts (being PolyTHF dihydroxylic alcohols), polyisocyanates 50 parts (being IPDI), catalyst B 0.08 part (being dibutyl tin laurate), end-capping reagent 25 parts (being trimethylolpropane diacrylate), polymerization inhibitor B 0.8 part (being MEHQ);
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, and reacts 2 hours at 55 DEG C; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 65 DEG C and being less than 0.5% to NCO group content (i.e. isocyanate content), obtaining polyurethane resin, for subsequent use.
Then above-mentioned polyacrylic resin for subsequent use and polyurethane resin is utilized to prepare ultraviolet light polymerization impression coating.
The preparation method of above-mentioned ultraviolet light polymerization impression coating comprises the steps: by weight successively, is equipped with polyacrylic resin 25 parts, polyurethane resin 35 parts, diluting monomer 50 parts (wherein neopentylglycol diacrylate 30 parts, pentaerythritol triacrylate 10 parts, tripropylene glycol diacrylate 10 parts), light trigger 8 parts (wherein thioxanthone 4 parts, 4-dimethyl ethyl aminobenzoate 4 parts) and auxiliary agent 5 parts (wherein defoamer aerosil 2 parts, levelling agent silicone oil 2 parts, silane coupler 1 part); Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and carry out stirring (mixing time is 18 minutes) under the mixing speed of 250 revs/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 1100 revs/min, be stirred to light trigger dissolve completely (mixing time is 40 minutes), obtain ultraviolet light polymerization impression coating.The obtained qualified rear packaging warehouse-in of ultraviolet light polymerization impression coating tested viscosity.
Obtained ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 25 parts, polyurethane resin 35 parts, diluting monomer 50 parts (wherein neopentylglycol diacrylate 30 parts, pentaerythritol triacrylate 10 parts, tripropylene glycol diacrylate 10 parts), light trigger 8 parts (wherein thioxanthone 4 parts, 4-dimethyl ethyl aminobenzoate 4 parts) and auxiliary agent 5 parts (wherein defoamer aerosil 2 parts, levelling agent silicone oil 2 parts, silane coupler 1 part).
The performance of obtained ultraviolet light polymerization impression coating is as follows: viscosity: 67 seconds (being coated with-4 glasss, 25 DEG C); Hardness >=2H; Pliability: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines with the speed of 40 ms/min, doubling flawless; Adhesive force: coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, draws without coming off with 3M adhesive tape with the speed of 40 ms/min; Upper machine adaptability: normally produce without gum deposit conditions of streaking; Heat-resisting hot: to coat PET film, coating layer thickness is 10um, after crossing the drying of 8 kilowatts of uv machines, aluminizes and puts the baking of 140 DEG C, baking oven with the speed of 40 ms/min, without growing dim general color loss of gloss.Solvent resistant MEK tests: close to dripping MEK agent, wipe dry after putting 5 minutes, and surface is without fading phenomenon.
Claims (11)
1. a preparation method for transfer membrane, is characterized in that comprising the steps: successively
(1) make the grand master pattern with Fresnel Lenses lines and laser graphic lines, then carry out electroforming, form die work version;
(2) die work version is arranged in mold pressing roll; The lower surface of plastic sheeting is coated with one deck ultraviolet light polymerization impression coating, then ultraviolet light polymerization is made to impress paint coatings and the mold pressing roll close contact that die work version is housed, make ultraviolet light polymerization impress coating and fill up groove in die work version under the effect of the pressure, under UV-irradiation, then make ultraviolet light polymerization impress paint coatings solidification;
(3) under the traction of deflector roll, make ultraviolet light polymerization impress paint coatings and be separated with die work version, obtain transfer membrane.
2. the preparation method of transfer membrane according to claim 1, it is characterized in that: described ultraviolet light polymerization impression coating comprises the component of following weight proportioning: polyacrylic resin 10-30 part, polyurethane resin 20-40 part, diluting monomer 40-60 part, light trigger 2-10 part, auxiliary agent 1-5 part.
3. the preparation method of transfer membrane according to claim 2, it is characterized in that: described diluting monomer is Tetrahydrofurfuryl Methacrylate, acrylate, 1, 6-hexanediyl ester, neopentylglycol diacrylate, dipentaerythritol acrylate, oxolane acrylate, acrylic acid DCPA, acryloyl morpholine, iso-bornyl acrylate, ethoxyethoxyethyl acrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, propenoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, a kind of or wherein multiple combination in propylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, described light trigger is a kind of or wherein multiple combination in benzoin, benzoin derivatives, 1-hydroxycyclohexyl phenyl ketone, alpha-hydroxyalkyl benzophenone, benzophenone, benzophenone derivates, acylphosphine oxide, thioxanthone, thioxanthone derivative, 4-dimethyl ethyl aminobenzoate and the different monooctyl ester of N, N-dimethylaminobenzoic acid, described auxiliary agent is a kind of or wherein multiple combination in defoamer, levelling agent and coupling agent, defoamer is a kind of in dimethyl polysiloxane and aerosil or both mixtures, and levelling agent is polysiloxane-polyether copolymer or silicone oil, and coupling agent is silane coupler.
4. the preparation method of transfer membrane according to claim 2, is characterized in that: the preparation method of described polyacrylic resin comprises the following steps:
(2-1) raw material is equipped with by following weight proportion: acrylate monomer 90-140 part, initator 0.5-4 part, acrylic or methacrylic acid 20-30 part, modified rosin resin 5-10 part, polymerization inhibitor A 0.1-1 part, catalyst A 0.1-1 part; Acrylate monomer 20-30 part containing hydroxyl acrylate monomer 20-30 part, band epoxy radicals in described 90-140 part acrylate monomer;
(2-2) in the reactor that thermometer, agitator and condenser are housed, add 15-30 part reflux solvent and be warmed up to 110-130 DEG C, drip the mixture of acrylate monomer and initator again, react after 3-5 hour, obtain hydroxyl and acrylic resin that is epoxy radicals;
(2-3) acrylic resin of the hydroxyl and epoxy radicals in aforesaid reaction vessel is cooled to 80-90 DEG C, then the mixture of polymerization inhibitor A, catalyst A, acrylic or methacrylic acid and modified rosin resin is dripped, react after 1-2 hour, be warmed up to 100-110 DEG C gradually, make to react completely, then remove reflux solvent, obtain polyacrylic resin.
5. the preparation method of transfer membrane according to claim 4, it is characterized in that: in described acrylate monomer, hydroxyl acrylate monomer is hydroxyethyl methacrylate, a kind of or wherein multiple combination in hydroxypropyl acrylate and hydroxy-ethyl acrylate, acrylate monomer with epoxy radicals is a kind of in glycidyl acrylate and tertiary carbonic acid glycidyl ester or both combinations, remaining acrylate monomer is butyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, a kind of or wherein multiple combination in isobornyl acrylate and EMA, described initator is azodiisobutyronitrile, TBHP, benzoyl peroxide or two t-amyl peroxy compounds, described polymerization inhibitor A is p methoxy phenol, hydroquinones or 2,6-toluene di-tert-butyl phenol, described catalyst A is triphenyl phosphorus, triethylamine, tetraethylammonium bromide, N, N-dimethyl arylamine, antimony triphenyl or tetramethyl ammonium chloride, described modified rosin resin is acrylic acid modified rosin ester or Foral.
6. the preparation method of transfer membrane according to claim 2, is characterized in that: the preparation method of described polyurethane resin comprises the following steps:
(1 ') is equipped with raw material by following weight proportion: polyalcohol 30-50 part, polyisocyanates 30-60 part, catalyst B 0.05-1 part, end-capping reagent 10-30 part, polymerization inhibitor B 0.1-1 part;
(2 ') adds polyalcohol, polyisocyanates and catalyst B in the reactor that thermometer, agitator and condenser be housed, at 50-60 DEG C, react 1-2 hour; Then adding end-capping reagent and polymerization inhibitor B when stirring, reacting at 60-70 DEG C and being less than 0.5% to NCO group content, obtaining polyurethane resin.
7. the preparation method of transfer membrane according to claim 6, is characterized in that: described polyalcohol is the acrylic polyol of PEPA, PPG, dimeric dibasic acid dihydroxylic alcohols, PolyTHF dihydroxylic alcohols or modification; Described polyisocyanates is IPDI, PPDI, 1,6 hexamethylene diisocyanates, dicyclohexyl methyl hydride diisocyanate or XDI; Described catalyst B is dibutyl tin laurate, stannous octoate or triethylamine; Described end-capping reagent is hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate; Described polymerization inhibitor B is hydroquinones or MEHQ.
8. the preparation method of transfer membrane according to claim 2, it is characterized in that: the preparation method of described ultraviolet light polymerization impression coating comprises the steps: by weight successively, is equipped with polyacrylic resin 10-30 part, polyurethane resin 20-40 part, diluting monomer 40-60 part, light trigger 2-10 part and auxiliary agent 1-5 part; Then polyacrylic resin and polyurethane resin are joined in the reaction vessel with agitator, and stir under the mixing speed of 200-300 rev/min, polyacrylic resin is mixed with polyurethane resin; Then diluting monomer, light trigger and auxiliary agent are joined in above-mentioned reaction vessel, and under the mixing speed of 800-1200 rev/min, be stirred to light trigger dissolve completely, obtain ultraviolet light polymerization impression coating.
9. a preparation method for transfer aluminum plated paper, is characterized in that, on the basis of the preparation method of the arbitrary described transfer membrane at claim 1-8, also comprising the steps: successively
(4) aluminize on the lower surface of ultraviolet light polymerization impression paint coatings, form aluminium coated;
(5) on the lower surface of aluminium coated, be coated with one deck oil paint, then make oil paint coating dry;
(6) coating binder on the lower surface of the oil paint coating of transfer membrane or on the upper surface of printing paper, then by transfer membrane and printing paper compound, after adhesive solidification, make ultraviolet light polymerization impress paint coatings be separated with aluminium coated, thus make aluminum transfer on printing paper, obtain transfer aluminum plated paper.
10. the preparation method of transfer aluminum plated paper according to claim 9, is characterized in that: in step (5), oil paint used is made up of the component of following weight proportioning: resin 20-30 part, solvent 60-80 part, auxiliary agent 1-5 part; Wherein resin is a kind of or wherein multiple combination in acrylic resin, polyurethane resin, nitrocotton resin, vinyl chloride-vinyl acetate resin and polyvinyl butyral resin.
The preparation method of 11. transfer aluminum plated papers according to claim 10, is characterized in that: the solvent in described oil paint is a kind of or wherein multiple combination in butanone, butyl acetate, ethyl acetate, n-propyl acetate, ethanol, isopropyl alcohol and propylene glycol monomethyl ether; Auxiliary agent in oil paint is a kind of in levelling agent and wear-resisting antiplastering aid or both combinations, and wherein levelling agent is polyether-modified siloxanes or the siloxanes of polyester modification, and wear-resisting antiplastering aid is modified polyethylene wax, polypropylene wax or polytetrafluoroethylene (PTFE) wax.
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