CN102649895A - Ultraviolet light-heat dual-curing gloss oil, and preparation method and application thereof - Google Patents
Ultraviolet light-heat dual-curing gloss oil, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to ultraviolet light-heat dual-curing gloss oil for a transfer film, and a preparation method and application thereof. The ultraviolet light-heat dual-curing gloss oil comprises the following components by part by weight: 20 to 70 parts of resin composition, 10 to 50 parts of diluting monomer, 1 to 10 parts of photoinitiator, 0.01 to 5 parts of polymerization inhibitor, 1 to 10 parts of flatting agent, 1 to 10 parts of defoaming agent and 1 to 10 parts of base material wetting agent, wherein the resin composition is a composition of polyurethane acrylic ester resin containing isocyanate group and resin comprising hydroxyl group. The ultraviolet light-heat dual-curing gloss oil is applied to the transfer film industry, so that the problems of low glossiness of printing ink and low resistance and wear resistance of the surface ink layer are effectively solved, the delay curing characteristic of a gloss oil protective layer is improved, the protective layer gloss oil can be extended on the surface of a three-dimensional object completely to form a transfer pattern with good glossiness, the service life is prolonged, and the ultraviolet light-heat dual-curing gloss oil can be stored for 12 months under the conditions of normal temperature and dark place.
Description
Technical field
The present invention relates to a kind of dual cure gloss oil, particularly relate to a kind of ultraviolet-heat dual cure gloss oil that is used for transfer film.
Background technology
The UV oil polish because does not with an organic solvent have the VOC discharging, and production efficiency is high, printable fabric is extensive, and film forming properties is excellent, becomes one of best protection film of printing ink ornament layer, obtains widely applying in a lot of fields.The UV gloss oil is applied to the transfer film resist, can effectively improves the glossiness of pattern transferring, increase the performances such as resistency and wear resistance of transfer film, increase the aesthetics and the use value of product simultaneously.This films with regard to the gloss oil that requires to be used to protect pattern transferring and has good plasticity-and stability; Guarantee that on the one hand pattern transferring can solidify with thorough in the abundant covering on three-dimensional body, guarantees again that on the other hand transfer film had stable performance before using.But traditional UV gloss oil is difficult to be implemented in the abundant extension protection and the after fixing of three-dimensional body usually; And present many supercoat that are used for transfer film contain a large amount of organic solvents and the shelf time is shorter; If can not effectively use in the time; Then can influence the quality of transfer film, also can cause the waste of enterprise and the pollution of environment simultaneously.
Publication number CN101348620 discloses the patented claim in day on November 10th, 2010, discloses a kind of coating of UV anaerobic double curing.This coating is made up of prepolymer, reactive thinner, light trigger, auxiliary agent and anaerobic curing agent compsn.This dual-cured coating mainly relies on UV-irradiation to solidify, and is not to utilize the solidifying agent that adds and the component of hydroxyl in the coating to be cured by filming of being mapped to of ultraviolet lighting.Mainly be applicable to porous substrates such as timber, density board, paper, when having solved ultraviolet-curing paint and being used for porous substrate, infiltrate the problem that the coating in the space can't be moved out human and environment is polluted by abundant curing easily.But this coating only is applicable to porous substrate, is not suitable as the resist of transfer film pattern, can not under certain drying conditions, form the rete that is fit to other ink printings, and through storage period of long period other variations does not take place.
Publication number CN101412860, the patented claim in open day on February 16th, 2011 discloses ultraviolet-heat dual curing coating composite of a kind of antioxygen inhibition effect and preparation method thereof.This double curing coating composition is made up of ultraviolet light polymerization oligomer, thermofixation poly-hydroxy oligomer, solidifying agent, light trigger and auxiliary agent.Have tertiary amine group in the oligomer backbone structure in this coating, accelerated curing speed greatly, can solve effectively that the coating dash area solidifies not exclusively, in the coating filler hinder ultraviolet light polymerization not exclusively and oxygen inhibition cause the halfway problem of paint solidification.But this dual-cured coating only provides the oxygen inhibition of understand determining causes the halfway problem of paint solidification, and is not suitable for the resist printing of transfer film and carries out after fixing.
CN101245200, the patented claim in open day on January 5th, 2011 discloses a kind of UV gloss oil that can preprint on film.This gloss oil is made up of photo-curing epoxy resin, monomer diluent, photosensitizers, film coalescence aid and toner.This UV gloss oil can be preprinted at preparation UV on the film or on the film at photoengraving pattern and preprint decorating film, UV is preprinted decorating film be used for the packing of product, can increase the attractive in appearance and use value of product.But this UV gloss oil is used for transfer film, forms the good rete of plasticity, then be difficult to realize the fully subsides clothes of pattern transferring, limited it and further used and promote at three-dimensional object surface owing to can not carry out Procuring.
CN101048474A, the patented claim in open day on October 3rd, 2007 discloses a kind of ultraviolet ray (UV) post cure heat transfer label, making and use method.Mentioned a kind of heat transfer printing ink that carries out the UV-light after fixing in the document.But contain the organic solvent VOC of 20%-70% at least in this printing ink, utilize the volatilization of organic solvent to form the drying on printing ink top layer, when predrying, can form a large amount of VOC volatilizations,, be unfavorable for promoting on a large scale and using human body and environment formation huge harm.
Summary of the invention
The technical problem that the present invention will solve provides a kind of ultraviolet-heat dual cure gloss oil that can be used for protecting transfer film ornament layer pattern; This curing varnish can effectively increase glossiness, weathering resistance, chemical resistance, the resistency of transfer decorative figure layer, and has excellent environmental-protecting performance.
For reaching above-mentioned purpose, ultraviolet-heat dual cure gloss oil of the present invention comprises the component of following weight part: resin combination 20-70 part, diluting monomer 10-50 part, light trigger 1-10 part, stopper 0.01-5 part, flow agent 1-10 part, skimmer 1-10 part, base material wetting agent 1-10 part.Preferred resin compsn 35-60 part, diluting monomer 10-40 part, light trigger 3-7 part, stopper 0.01-0.5 part, flow agent 1-3 part, skimmer 1-3 part, base material wetting agent 1-5 part.More preferably 55 parts of resin combinations, 32 parts of diluting monomers, 5 parts of light triggers, 0.25 part of stopper, 1.5 parts of flow agents, 1.25 parts of skimmers, 1 part of base material wetting agent.
Ultraviolet-heat dual cure gloss oil of the present invention; Wherein preferred said resin combination is the polyurethane acrylate resin [polyurethane acrylate resin (PUA) is known polymkeric substance, and what select for use among the present invention is the urethane acrylate that contains NCO] that contains NCO and the resin that contains hydroxyl is the compsn of 1.6:1 ~ 1: 1 with the weight ratio; The said polyurethane acrylate resin that contains NCO is aliphatic urethane acrylate resin or aromatic urethane acrylate resin, the aliphatic polyurethane acrylate resin; The resin of said hydroxyl is vinyl resin, Synolac or epoxy resin, preferred acrylic resins.
Among the present invention above-mentioned resin combination can to carry out the principle of ultraviolet light and heat dual cure be respectively the Raolical polymerizable that causes of UV-light (UV) with isocyanato (NCO) and hydroxyl (reaction OH).Isocyanate group (NCO) (OH) carries out crosslinking reaction, realizes the thermofixation surface drying of resin combination, and reach certain rigidity with hydroxyl under heating condition.Design transfer to be printed to product after, the gloss oil resist still has thermoplasticity and photocuring characteristic.After carrying out UV illumination; Acrylic acid groups, unsaturated double-bond or epoxide group carry out the radically curing polyreaction under the effect of free radical photo-initiation; Form three-dimensional netted polymer architecture; Therefore can be used for UV after fixing technology, obtain excellent resists such as light, transparent, resistency, wear resistance.
Ultraviolet-heat dual cure gloss oil of the present invention, wherein preferred said diluting monomer are selected from the mixture of one or both arbitrary proportions in polyethyleneglycol diacrylate (a kind of monomer of low volatility), vinylformic acid caprolactone, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane triacrylate, three (2-hydroxyethyl) isocyanuric acid diacrylate, 2-hydroxyethyl methacrylic ester SULPHOSUCCINIC ACID ESTER and the propoxylation Viscoat 295.
Ultraviolet-heat dual cure gloss oil of the present invention; Wherein preferred said light trigger is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-isopropyl thioxanthone, 2; 4; One or both mixtures in 6-trimethylbenzoyl-diphenyl phosphine oxide, 2-methyl isophthalic acid-[4-methylthio group phenyl]-2-morpholinyl-1-acetone and two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxides with arbitrary proportion.
Ultraviolet-heat dual cure gloss oil of the present invention, wherein preferred said stopper is selected from Resorcinol, 2, and one or both of 6-di-t-butyl cresylol and MEHQ are with the mixture of arbitrary proportion; Said flow agent is selected from one or both mixtures with arbitrary proportion in polyether-modified ZGK 5, methyl phenyl silicone, organosilicon-modified acrylate and the Virahol; Said skimmer is YSR 3286, polydimethyl siloxane fluid or polyoxyethylene poly-oxygen propylene aether glycerine; Said base material wetting agent is selected from one or both mixtures with arbitrary proportion in modified polyorganosiloxane (like polyether-modified ZGK 5, acroleic acid modified polysiloxane, epoxy-modified polysiloxane etc.) and the organic silicon modified by polyether.
The invention still further relates to the method for the above-mentioned ultraviolet-heat dual cure gloss oil of preparation, it may further comprise the steps:
(1) stirring is pre-dispersed: the part diluting monomer is added in the reaction vessel, slowly add light trigger, and evenly stirred 20-30 minute; Treat that light trigger adds flow agent after dissolving fully, continue to stir 20-30 minute, guarantee the abundant dissolving of flow agent; Add resin combination then, heated and stirred is even, and wherein heating and temperature control is at 30-50 ℃; Churning time is 30-60 minute, and stirring velocity is 500-600r/min;
(2) fully stir: remainder diluting monomer, stopper, skimmer, base material wetting agent are joined in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 60-120 minute; Heating and temperature control is at 30-40 ℃; Stirring velocity is 800-1000r/min, and last rewinding promptly gets.
Diluting monomer divides two portions to add in the aforesaid method, and add-on accounts for the about about 60% of gross weight for the first time, and purpose is fully to dissolve light trigger.Because the viscosity of resin is bigger, carry out fully compatible with each component smoothly for what can guarantee stirring, at first adopt partial monosomy that resin is diluted; Reduce resin viscosity, promptly pre-dispersed stirring is then fully stirred again; Add flow agent in the pre-dispersed stage simultaneously; So both can stir smoothly, guarantee the abundant consistency of each component, also guarantee the levelling better effects if when gloss oil uses.
The invention still further relates to the application of above-mentioned ultraviolet-heat dual cure gloss oil, it can be used for the supercoat of transfer film, to increase glossiness, resistency, wear resistance, chemical resistance and the work-ing life of transfer film.
The application method of ultraviolet-heat dual cure gloss oil of the present invention; At first scribbling on the carrier film of release resin layer; Be coated with above-mentioned ultraviolet-heat dual cure gloss oil of the present invention (the about 4 μ m of thickness), place 70-100 ℃ drying channel to carry out the thermofixation of gloss oil then, form the good rete of plasticity-; In the printing of his printing ink of the enterprising Xingqi of this rete, apply the transfer printing glue-line at last then; Wait to decorate pattern transfer to object after, the gloss oil resist on pattern transferring surface is applied certain ultraviolet lighting, make its thorough curing; Preferably, said UV-light was accomplished the thorough curing of gloss oil layer with the linear heat generation rate of 160W/cm in 20 seconds.The rete that the two curing varnish of the present invention form can be preserved 12 months under normal temperature lucifuge condition.
The present invention is directed to common UV gloss oil and be difficult to use in the problem that transfer film is implemented after fixing; Propose a kind of ultraviolet-heat dual cure gloss oil that is applicable to transfer film, this ultraviolet-heat dual cure gloss oil contains dual cure composition, diluting monomer, light trigger and other auxiliary agents of approrpiate wts proportioning.This gloss oil contains the group (isocyanate group and hydroxyl) that can carry out thermofixation and the group (unsaturated double-bond, acrylic acid groups or epoxide group) of ultraviolet light polymerization; Implementation part thermofixation at a certain temperature is crosslinked; Form the good rete of plasticity-; And performance is comparatively stable in the long time, design transfer to be transferred to article after, through applying certain UV-light; Realize of the abundant extension of resist gloss oil, form the good pattern transferring of glossiness at three-dimensional object surface.
The present invention prepares a kind of ultraviolet-heat dual cure gloss oil that can be used for transfer film under the prerequisite that guarantees gloss oil printability and glazing quality, increase the attractive in appearance and resistency of transfer film, prolongs the shelf time of resist photo-oil membrane simultaneously.Be difficult to be implemented in the abundant extension protection of three-dimensional body and the problem of after fixing to common UV gloss oil; The present invention is applied to the transfer film industry with ultraviolet-heat dual cure gloss oil, can effectively solve the ornament layer transfer printing after the ink degree lower, surface ink layer resistency, the relatively poor problem of wear resistance; Increase gloss oil resist time-delay solidified characteristic; Realize of the abundant extension of resist gloss oil, form the good pattern transferring of glossiness, prolonged work-ing life at three-dimensional object surface.
The present invention compared with prior art, advantage is following:
1. do not have noxious solvent in gloss oil production and the use, process environment is friendly, VOC free discharging, environmental protection.
2. can carry out predrying (heating, drying); Realize the partial cross-linked curing of gloss oil, form snappiness and the good rete of ductility, hardness can reach HB-1H; Can behind the printing common ink, carry out rolling and preserve, solve the problem that three-dimensional body is difficult to apply protective membrane.
3. performance is comparatively stable after the predrying film forming, and retention period is grown (can keep in Dark Place 12 months under the normal temperature).
4. have wide range of applications, can be widely used in the stereo product that articles for daily use, toy, electrical equipment, building materials etc. need carry out flexography.
5. film forming properties is excellent, and printability is good.
Embodiment
Below in conjunction with embodiment and testing data, do more detailed explanation with other technical characterictic and advantage to the present invention is above-mentioned.
Embodiment 1
Prepare following feed composition:
Double cured resin compsn 20g, by the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2396, the Bayer resin) and hydroxyl WL 140 (WB3011, Shanghai the Wenshui River chemical industry) by weight being the 3:2 composition;
Diluting monomer 10g, by pentaerythritol triacrylate (PETA, Tianjin proud son of heaven chemical industry) and vinylformic acid caprolactone (AM2101, the sharpening worker is won in Shanghai) by weight being the 2:3.5 composition;
Light trigger 1g is 1-hydroxy-cyclohexyl phenyl ketone 184 (Beijing English power science and technology); Stopper 0.01g is Resorcinol (commercially available); Flow agent 1g is for polyether-modified ZGK 5 (enlightening is high by 432) is the mixture of 1:1.55 with the Virahol weight ratio; Skimmer 1g is polydimethyl siloxane fluid; Base material wetting agent 1g is modified polyorganosiloxane (enlightening is high by 245).
(1) stir pre-dispersed: the part diluting monomer 6g that will weigh up is positioned in the beaker, slowly adds light trigger, stirs to dissolve fully to initiator in 20 minutes; Slowly add flow agent then, continue to stir 20 minutes (guaranteeing that it fully dissolves), add the double cured resin compsn then; Heated and stirred is even; Wherein heating and temperature control is at 35-45 ℃, and stirring velocity is 500r/min, stirs 30 minutes.
(2) fully stir: remainder diluting monomer 4g; Stopper, skimmer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 75 minutes, heating and temperature control is at 30-40 ℃, and stirring velocity is 1000r/min; Each component of gloss oil is stirred, and last rewinding promptly gets.
The gloss oil viscosity of present embodiment preparation is 0.3-0.9Pas (25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (measuring according to " GB-1720-79 film adhesive assay method "); Rub resistance can reach 500 times/4 pounds; Thoroughly solidify back hardness and can reach 2H, be suitable for the resist of transfer film.
Adopt the right property appearance of IGT gravure printing to draw a design the dual cure gloss oil of above-mentioned preparation; Place 100 ℃ drying baker heat drying; Form the good predrying rete of plasticity-(hardness can reach 1H, measures according to " GB6739-86 hardness of film pencil assay method "); Placing ultraviolet light polymerization equipment to carry out photocuring drying (curing power is 160W/cm, and line speed is 25m/s) the thorough solidified time of completion specimen page then is 10s, and the hardness after the China ink layer thoroughly solidifies can reach 2H; Moulded products is bent 45, and whether it crackle occurs with visual inspection; Moulded products was soaked in the alcohol solvent 24 hours, takes out with its changes in surface situation of visual inspection, the The performance test results of this dual cure gloss oil is as shown in table 1.
Embodiment 2
Prepare following feed composition:
Double cured resin compsn 70g, by the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2396, the Bayer resin) and oh type Synolac (3616X60, Jiangsu Miki Group) by weight being the 1:1 composition;
Diluting monomer 50g, by propoxylation Viscoat 295 and pentaerythritol triacrylate by weight forming for 3:2;
Light trigger 10g is 1-hydroxy-cyclohexyl phenyl ketone 184 (Beijing English power science and technology); Stopper 5g is Resorcinol (commercially available); Flow agent 10g is for polyether-modified ZGK 5 (enlightening is high by 432) is the mixture of 1:1.55 with the Virahol weight ratio; Skimmer 10g is polydimethyl siloxane fluid; Base material wetting agent 10g is modified polyorganosiloxane (enlightening is high by 245).
(1) stir pre-dispersed: the part diluting monomer 30g that will weigh up is positioned in the beaker, slowly adds light trigger, stirs to dissolve fully to initiator in 25 minutes; Slowly add flow agent then, continue to stir 20 minutes, add the double cured resin compsn then; Heated and stirred is even; Wherein heating and temperature control is at 30-45 ℃, and stirring velocity is 500r/min, stirs 60 minutes.
(2) fully stir: remainder diluting monomer 20g; Stopper, skimmer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 120 minutes, heating and temperature control is at 30-40 ℃, and stirring velocity is 1000r/min; Each component of gloss oil is stirred, and last rewinding promptly gets.
The gloss oil viscosity of present embodiment preparation is 0.3-0.9Pas (25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (measuring according to " GB-1720-79 film adhesive assay method "); Rub resistance can reach 500 times/4 pounds; Thoroughly solidify back hardness and can reach 2H, be suitable for the resist of transfer film.
Adopt the right property appearance of IGT gravure printing to draw a design the dual cure gloss oil of above-mentioned preparation; Place 70-100 ℃ drying baker heat drying; Form the good predrying rete of plasticity-(hardness can reach 1H, measures according to " GB6739-86 hardness of film pencil assay method "); Place ultraviolet light polymerization equipment to carry out photocuring drying (curing power is 160W/cm, and line speed is 25m/s) specimen page then, accomplishing the thorough solidified time is 12s, and the hardness after the China ink layer thoroughly solidifies can reach 2H; Moulded products is bent 45, and whether it crackle occurs with visual inspection; Moulded products was soaked in the alcohol solvent 24 hours, takes out with its changes in surface situation of visual inspection, the The performance test results of this dual cure gloss oil is as shown in table 1.
Embodiment 3
Prepare following feed composition:
Double cured resin compsn 35g, by aromatic urethane acrylate resin and hydroxyl Synolac (WB101A, Huian, the north, Xi'an chemical industry) by weight being the 6:5 composition;
Diluting monomer 10g is 2-hydroxyethyl methacrylic ester SULPHOSUCCINIC ACID ESTER;
Light trigger 3g is 1-hydroxy-cyclohexyl phenyl ketone 184 (Beijing English power science and technology); Stopper 0.01g is Resorcinol (commercially available); Flow agent 1g is Virahol; Skimmer 1g is YSR 3286; Base material wetting agent 1g is organic silicon modified by polyether.
(1) stir pre-dispersed: the part diluting monomer 6g that will weigh up is positioned in the beaker, slowly adds light trigger, stirs to dissolve fully to initiator in 20 minutes; Slowly add flow agent then, continue to stir 25 minutes, add the double cured resin compsn then; Heated and stirred is even; Wherein heating and temperature control is at 45-50 ℃, and stirring velocity is 600r/min, stirs 40 minutes.
(2) fully stir: remainder diluting monomer 4g; Stopper, skimmer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 80 minutes, heating and temperature control is at 30-40 ℃, and stirring velocity is 1000r/min; Each component of gloss oil is stirred, and last rewinding promptly gets.
The gloss oil viscosity of present embodiment preparation is 0.3-0.7Pas (25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (measuring according to " GB-1720-79 film adhesive assay method "); Rub resistance can reach 400 times/4 pounds; Thoroughly solidify back hardness and can reach 2H, be suitable for the resist of transfer film.
Adopt the right property appearance of IGT gravure printing to draw a design the dual cure gloss oil of above-mentioned preparation; Place 70-100 ℃ drying baker heat drying; Form the good predrying rete of plasticity-(hardness can reach HB, measures according to " GB6739-86 hardness of film pencil assay method "); Place ultraviolet light polymerization equipment to carry out photocuring drying (curing power is 160W/cm, and line speed is 25m/s) specimen page then, accomplishing the thorough solidified time is 18s, and the hardness after the China ink layer thoroughly solidifies can reach 2H; Moulded products is bent 45, and whether it crackle occurs with visual inspection; Moulded products was soaked in the alcohol solvent 24 hours, takes out with its changes in surface situation of visual inspection, the The performance test results of this dual cure gloss oil is as shown in table 1.
Embodiment 4
Prepare following feed composition:
Double cured resin compsn 60g, by aromatic urethane acrylate resin and polypropylene provided with hydroxyl group acid resin (WB3011, Shanghai the Wenshui River chemical industry) by weight being that 7:5 forms;
Diluting monomer 40g, by propoxylation Viscoat 295 (Tianjin proud son of heaven chemical industry) and polyethyleneglycol diacrylate (SR344, the pretty color chemical industry in Shanghai) by weight being the 1:1 composition;
Light trigger 7g is 2-methyl isophthalic acid-[4-methylthio group phenyl]-2-morpholinyl-1-acetone; Stopper 0.5g is 2,6-di-t-butyl cresylol (commercially available); Flow agent 3g is Virahol; Skimmer 3g is YSR 3286; Base material wetting agent 5g is organic silicon modified by polyether.
(1) stir pre-dispersed: the part diluting monomer 24g that will weigh up is positioned in the beaker, slowly adds light trigger, stirs to dissolve fully to initiator in 30 minutes; Slowly add flow agent then, continue to stir 20 minutes, add the double cured resin compsn then; Heated and stirred is even; Wherein heating and temperature control is at 45-50 ℃, and stirring velocity is 600r/min, stirs 40 minutes.
(2) fully stir: remainder diluting monomer 16g; Stopper, skimmer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 80 minutes, heating and temperature control is at 30-40 ℃, and stirring velocity is 800r/min; Each component of gloss oil is stirred, and last rewinding promptly gets.
The gloss oil viscosity of present embodiment preparation is 0.3-0.9Pas (25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (measuring according to " GB-1720-79 film adhesive assay method "); Rub resistance can reach 400 times/4 pounds; Thoroughly solidify back hardness and can reach 2H, be suitable for the resist of transfer film.
Adopt the right property appearance of IGT gravure printing to draw a design the dual cure gloss oil of above-mentioned preparation; Place 70-100 ℃ drying baker heat drying; Form the good predrying rete of plasticity-(hardness can reach 1H, measures according to " GB6739-86 hardness of film pencil assay method "); Accomplishing the thorough solidified time is 15s, and the hardness after the China ink layer thoroughly solidifies can reach 2H; Moulded products is bent 45, and whether it crackle occurs with visual inspection; Moulded products was soaked in the alcohol solvent 24 hours, takes out with its changes in surface situation of visual inspection, the The performance test results of this dual cure gloss oil is as shown in table 1.
Embodiment 5
Prepare following feed composition:
Double cured resin compsn 55g, by the Synolac (WB101A, Huian, the north, Xi'an chemical industry) of the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2337, the Bayer resin) and hydroxyl by weight being the 3:2 composition;
Diluting monomer 32g is the propoxylation Viscoat 295;
Light trigger 5g is 1-hydroxy-cyclohexyl phenyl ketone 184 (Beijing English power science and technology); Stopper 0.25g is MEHQ (commercially available); Flow agent 1.5g is methyl phenyl silicone; Skimmer 1.25g is polyoxyethylene poly-oxygen propylene aether glycerine; Base material wetting agent 1g is organic silicon modified by polyether.
(1) stir pre-dispersed: the part diluting monomer 16g that will weigh up is positioned in the beaker, slowly adds light trigger, stirs to dissolve fully to initiator in 20 minutes; Slowly add flow agent then, continue to stir 25 minutes, add the double cured resin compsn then; Heated and stirred is even; Wherein heating and temperature control is at 40-50 ℃, and stirring velocity is 600r/min, stirs 35 minutes.
(2) fully stir: remainder diluting monomer 16g; Stopper, skimmer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 100 minutes, heating and temperature control is at 30-40 ℃, and stirring velocity is 1000r/min; Each component of gloss oil is stirred, and last rewinding promptly gets.
The gloss oil viscosity of present embodiment preparation is 0.4-0.9Pas (25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (measuring according to " GB-1720-79 film adhesive assay method "); Rub resistance can reach 400 times/4 pounds; Thoroughly solidify back hardness and can reach 1H, be suitable for the resist of transfer film.
Adopt the right property appearance of IGT gravure printing to draw a design the dual cure gloss oil of above-mentioned preparation; Place 70-100 ℃ drying baker heat drying; Form the good predrying rete of plasticity-(hardness can reach HB, measures according to " GB6739-86 hardness of film pencil assay method "); Place ultraviolet light polymerization equipment to carry out photocuring drying (curing power is 160W/cm, and curing speed is 25m/s) specimen page then, accomplishing the thorough solidified time is 15 seconds, and the hardness after the China ink layer thoroughly solidifies can reach 1H; Moulded products is bent 45, and whether it crackle occurs with visual inspection; Moulded products was soaked in the alcohol solvent 24 hours, takes out with its changes in surface situation of visual inspection, the The performance test results of this dual cure gloss oil is as shown in table 1.
The predrying rete that the two curing varnish of the present invention that embodiment 1-5 obtains form can be preserved 12 months under normal temperature lucifuge condition.
The The performance test results of table 1 ultraviolet-heat dual cure gloss oil
Application examples
Ultraviolet-heat dual cure gloss oil of the present invention can be used for the supercoat of transfer film, to increase glossiness, resistency, wear resistance, chemical resistance and the work-ing life (shown in the test data in the table 1) of transfer film.
At first scribbling on the carrier film of release resin layer; The ultraviolet-heat dual cure gloss oil (the about 4 μ m of thickness) of coating the foregoing description; Place 70-100 ℃ drying channel to carry out the thermofixation of gloss oil then; Form the good rete of plasticity-, then in the printing [for example base gravure ink (Toyo Ink company)] of his printing ink of the enterprising Xingqi of this rete, (this transfer printing glue-line can be transfer printing field hot melt adhesive commonly used to apply the transfer printing glue-line at last; Transfer printing hot melt adhesive for example, safe parting agent hot melt adhesive factory of Dongguan unit); Wait to decorate pattern transfer to object after, the gloss oil resist on pattern transferring surface is applied the ultraviolet lighting of 160W/cm linear heat generation rate, make it in 20 seconds, accomplish the thorough curing of gloss oil layer.The rete that the two curing varnish of the present invention form can be preserved 12 months under normal temperature lucifuge condition.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. ultraviolet-heat dual cure gloss oil is characterized in that it comprises the component of following weight part:
Resin combination 20-70 part, diluting monomer 10-50 part, light trigger 1-10 part, stopper 0.01-5 part, flow agent 1-10 part, skimmer 1-10 part, base material wetting agent 1-10 part.
2. ultraviolet-heat dual cure gloss oil according to claim 1; It is characterized in that it comprises the component of following weight part: resin combination 35-60 part, diluting monomer 10-40 part, light trigger 3-7 part, stopper 0.01-0.5 part, flow agent 1-3 part, skimmer 1-3 part, base material wetting agent 1-5 part.
3. ultraviolet-heat dual cure gloss oil according to claim 2; It is characterized in that it comprises the component of following weight part: 55 parts of resin combinations, 32 parts of diluting monomers, 5 parts of light triggers, 0.25 part of stopper, 1.5 parts of flow agents, 1.25 parts of skimmers, 1 part of base material wetting agent.
4. according to each described ultraviolet-heat dual cure gloss oil of claim 1-3; It is characterized in that: said resin combination is the polyurethane acrylate resin and the compsn that contains the resin of hydroxyl that contains NCO, and both weight ratios are 1.6:1 ~ 1:1; The said polyurethane acrylate resin that contains NCO is aliphatic urethane acrylate resin or aromatic urethane acrylate resin, the aliphatic polyurethane acrylate resin; The resin of said hydroxyl is vinyl resin, Synolac or epoxy resin, preferred acrylic resins.
5. according to each described ultraviolet-heat dual cure gloss oil of claim 1-3, it is characterized in that: said diluting monomer is selected from the mixture of one or both arbitrary proportions in polyethyleneglycol diacrylate, vinylformic acid caprolactone, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane triacrylate, three (2-hydroxyethyl) isocyanuric acid diacrylate, 2-hydroxyethyl methacrylic ester SULPHOSUCCINIC ACID ESTER and the propoxylation Viscoat 295.
6. according to each described ultraviolet-heat dual cure gloss oil of claim 1-3; It is characterized in that: said light trigger is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-isopropyl thioxanthone, 2; 4; One or both mixtures in 6-trimethylbenzoyl-diphenyl phosphine oxide, 2-methyl isophthalic acid-[4-methylthio group phenyl]-2-morpholinyl-1-acetone and two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxides with arbitrary proportion.
7. according to each described ultraviolet-heat dual cure gloss oil of claim 1-3, it is characterized in that: said stopper is selected from Resorcinol, 2, and one or both of 6-di-t-butyl cresylol and MEHQ are with the mixture of arbitrary proportion; Said flow agent is selected from one or both mixtures with arbitrary proportion in polyether-modified ZGK 5, methyl phenyl silicone, organosilicon-modified acrylate and the Virahol; Said skimmer is YSR 3286, polydimethyl siloxane fluid or polyoxyethylene polyoxypropylene glyceryl ether; Said base material wetting agent is selected from one or both mixtures with arbitrary proportion in modified polyorganosiloxane and the organic silicon modified by polyether.
8. prepare the method for each described ultraviolet-heat dual cure gloss oil of claim 1-3, it is characterized in that, may further comprise the steps:
(1) stirring is pre-dispersed: the part diluting monomer is added in the reaction vessel, slowly add light trigger, and evenly stirred 15-30 minute; Treat that light trigger adds flow agent after dissolving fully, continue to stir flow agent fully to be dissolved in 15-30 minute, add resin combination then; Heated and stirred is even; Wherein heating and temperature control is at 30-50 ℃, and churning time is 30-60 minute, and stirring velocity is 500-600r/min;
(2) fully stir: remainder diluting monomer, stopper, skimmer, base material wetting agent are joined in the pre-dispersed resin solution that step (1) obtains; Continued heated and stirred 60-120 minute; Heating and temperature control is at 30-40 ℃; Stirring velocity is 800-1000r/min, and last rewinding promptly gets.
9. the application of each described ultraviolet-heat dual cure gloss oil of claim 1-3 is characterized in that, uses it for the supercoat of transfer film, to increase glossiness, resistency, wear resistance, chemical resistance and the work-ing life of transfer film.
10. the application method of each described ultraviolet-heat dual cure gloss oil of claim 1-3; It is characterized in that, at first scribbling on the carrier film of release resin layer, each described ultraviolet-heat dual cure gloss oil of coating claim 1-3; Place 70-100 ℃ drying channel to carry out the thermofixation of gloss oil then; Form the good rete of plasticity-, in the printing of his printing ink of the enterprising Xingqi of this rete, apply the transfer printing glue-line at last then; Wait to decorate design transfer to object after, the resist gloss oil on pattern transferring surface is applied ultraviolet lighting, make its thorough curing; Preferably, said UV-light was accomplished the thorough curing of gloss oil layer with the linear heat generation rate of 160W/cm in 20 seconds.
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