CN102649895B - 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 for transfer film and its preparation method and application.
Background technology
UV oil polish, due to not with an organic solvent, does not have VOC discharge, and production efficiency is high, printable fabric is extensive, and film forming properties is excellent, becomes one of best protection film of ink ornament layer, in a lot of fields, is widely applied.UV gloss oil is applied to transfer film protective layer, can effectively improves the glossiness of pattern transferring, increase the performances such as the resistance of transfer film and wear resistance, increase aesthetics and the use value of product simultaneously.This films and has good plasticity-and stability for the protection of the gloss oil of pattern transferring with regard to requiring; guarantee that on the one hand pattern transferring can solidify with thorough in the abundant covering on three-dimensional body, guarantees that transfer film had stable performance before using on the other hand again.But traditional UV gloss oil is difficult to realize abundant extension protection and the after fixing at three-dimensional body conventionally; and current many supercoat for transfer film contain a large amount of organic solvents and the shelf time is shorter; if can not effectively use in the time; the quality of transfer film be can affect, the waste of enterprise and the pollution of environment also can be caused simultaneously.
Publication number CN101348620, discloses the patent application in day on November 10th, 2010, discloses a kind of coating of UV anaerobic double curing.This coating is comprised of prepolymer, reactive thinner, light trigger, auxiliary agent and anaerobic curing agent composition.This dual-cured coating mainly relies on UV-irradiation to solidify, and filming of not being mapped to by ultraviolet lighting is to utilize additional solidifying agent in coating and the component of hydroxyl to be cured.Mainly be applicable to the porous substrates such as timber, density board, paper, while having solved ultraviolet-curing paint for porous substrate, the coating infiltrating in space cannot be by the problem of fully solidifying and easily moving out human and environment is polluted.But this coating is only applicable to porous substrate, and be not suitable for use in the protective layer of transfer film pattern, can not under certain drying conditions, form the rete that is applicable to other ink printings, and through storage period of long period, other variations do not occur.
Publication number CN101412860, the patent application 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 comprised of ultraviolet light polymerization oligomer, thermofixation poly-hydroxy oligomer, solidifying agent, light trigger and auxiliary agent.In oligomer backbone structure in this coating, with tertiary amine group, greatly accelerated curing speed, can effectively solve that coating dash area solidifies not exclusively, filler hinders ultraviolet light polymerization not exclusively and oxygen inhibition causes the halfway problem of paint solidification in coating.But this dual-cured coating is only to provide, understands certainly oxygen inhibition and cause the halfway problem of paint solidification, and be not suitable for the protective layer printing of transfer film and carry out after fixing.
CN101245200, the patent application in open day on January 5th, 2011, discloses and a kind ofly can be imprinted in advance UV gloss oil on film and its production and use.This gloss oil is comprised of photo-curing epoxy resin, monomer diluent, photosensitizers, film coalescence aid and toner.This UV gloss oil can be imprinted in advance on film or on the film of photoengraving pattern, prepare UV and preprint decorating film, and UV is preprinted to decorating film for the packing of product, can increase the attractive in appearance and use value of product.But this UV gloss oil, for transfer film, is formed to the good rete of plasticity owing to can not carrying out Procuring, be difficult to realize pattern transferring in the complete docile of three-dimensional object surface, limited it and further used and promote.
CN101048474A, the patent application in open day on October 3rd, 2007, discloses a kind of ultraviolet ray (UV) post cure heat transfer label, making and use method.In the document, mentioned a kind of heat transfer printing ink that carries out UV-light after fixing.But in this ink, contain at least organic solvent VOC of 20%-70%, utilize the volatilization of organic solvent to form the dry of ink surface layer, when predrying, can form a large amount of VOC volatilizations, human body and environment are formed to huge harm, be unfavorable for promoting on a large scale and using.
Summary of the invention
The technical problem to be solved in the present invention is to provide 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 resistance 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, defoamer 1-10 part, base material wetting agent 1-10 part.Preferred resin composition 35-60 part, diluting monomer 10-40 part, light trigger 3-7 part, stopper 0.01-0.5 part, flow agent 1-3 part, defoamer 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 defoamers, 1 part of base material wetting agent.
Ultraviolet-heat dual cure gloss oil of the present invention, wherein preferred described resin combination is that the polyurethane acrylate resin [polyurethane acrylate resin (PUA) is known polymkeric substance, and what select in the present invention is the urethane acrylate that contains isocyanate group] that contains isocyanate group be take weight ratio as 1.6:1 ~ 1 with the resin that contains hydroxyl: 1 composition; The described polyurethane acrylate resin that contains isocyanate group is aliphatic urethane acrylate resin or aromatic urethane acrylate resin, preferred aliphat polyurethane acrylate resin; The resin of described hydroxyl is acrylic resin, Synolac or epoxy resin, preferred acrylic resins.
In the present invention, can to carry out the principle of ultraviolet light and heat dual cure be respectively the Raolical polymerizable that causes of UV-light (UV) and isocyanato (NCO) to above-mentioned resin combination and the reacting of hydroxyl (OH).Isocyanate group (NCO) carries out crosslinking reaction with hydroxyl (OH) under heating condition, realizes the thermofixation surface drying of resin combination, and reaches certain hardness.Design transfer to be printed to product after, gloss oil protective layer still has thermoplasticity and photocuring characteristic.Carry out after UV illumination; acrylic acid groups, unsaturated double-bond or epoxide group carry out 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 technique, obtain the excellent protective layers such as light, transparent, resistance, wear resistance.
Ultraviolet-heat dual cure gloss oil of the present invention, wherein preferred described diluting monomer is 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-HEMA phosphoric acid ester and propoxylation Viscoat 295.
Ultraviolet-heat dual cure gloss oil of the present invention; wherein preferred described light trigger is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-isopropyl thioxanthone, 2; 4; 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) one or both mixtures with arbitrary proportion in phenyl phosphine oxide.
Ultraviolet-heat dual cure gloss oil of the present invention, wherein preferred described 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; Described flow agent is selected from one or both mixtures with arbitrary proportion in Siloxane-Oxyalkylene Copolymers, methyl phenyl silicone, organosilicon-modified acrylate and Virahol; Described defoamer is polydimethylsiloxane, polydimethyl siloxane fluid or polyoxyethylene poly-oxygen propylene aether glycerine; Described base material wetting agent is selected from one or both mixtures with arbitrary proportion in modified polyorganosiloxane (as Siloxane-Oxyalkylene Copolymers, acroleic acid modified polysiloxane, epoxy-modified polysiloxane etc.) and organic silicon modified by polyether.
The method that the invention still further relates to the above-mentioned ultraviolet-heat dual cure gloss oil of preparation, it comprises the following steps:
(1) stir pre-dispersed: part diluting monomer is added in reaction vessel, slowly add light trigger, and carry out uniform stirring 20-30 minute, treat that light trigger adds flow agent after dissolving completely, continues to stir 20-30 minute, guarantee the abundant dissolving of flow agent, then add resin combination, 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, defoamer, base material wetting agent are joined in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 60-120 minute, heating and temperature control is at 30-40 ℃, stirring velocity is 800-1000r/min, last rewinding and get final product.
In aforesaid method, diluting monomer divides two portions to add, and add-on accounts for approximately 60% left and right of gross weight for the first time, and object is fully to dissolve light trigger.Because the viscosity of resin is larger, fully compatible for carrying out smoothly of can guaranteeing to stir and each component, first adopt partial monosomy that resin is diluted, reduce resin viscosity, pre-dispersed stirring, then fully stirs again, in the pre-dispersed stage, add flow agent simultaneously, so both can stir smoothly, guarantee the abundant consistency of each component, also guarantee levelling better effects if when gloss oil is used.
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, resistance, 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, first scribbling in the carrier film of release resin layer, be coated with above-mentioned ultraviolet-heat dual cure gloss oil of the present invention (thickness approximately 4 μ m), then the drying channel that is placed in 70-100 ℃ carries out the thermofixation of gloss oil, form the good rete of plasticity-, then on this rete, carry out the printing of other ink, finally apply transfer printing glue-line; Pattern transfer to be decorated to object after, the gloss oil protective layer on pattern transferring surface is applied to certain ultraviolet lighting, it is thoroughly solidified; Preferably, described UV-light, with the linear heat generation rate of 160W/cm, completed thoroughly solidifying of gloss oil layer 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, a kind of ultraviolet-heat dual cure gloss oil that is applicable to transfer film is proposed, dual cure composition, diluting monomer, light trigger and other auxiliary agents that this ultraviolet-heat dual cure gloss oil contains approrpiate wts proportioning.This gloss oil contains can carry out the group (isocyanate group and hydroxyl) of thermofixation and the group (unsaturated double-bond, acrylic acid groups or epoxide group) of ultraviolet light polymerization; can realize at a certain temperature one part heat curable crosslinked; form the good rete of plasticity-; and performance is comparatively stable within the longer time; design transfer to be transferred to article after; by applying certain UV-light; realize protective layer gloss oil in the abundant extension of three-dimensional object surface, form the good pattern transferring of glossiness.
The present invention, guaranteeing, under the prerequisite of gloss oil printability and glazing quality, to prepare a kind of ultraviolet-heat dual cure gloss oil that can be used for transfer film, increases the attractive in appearance and resistance of transfer film, extends the shelf time of protective layer photo-oil membrane simultaneously.For common UV gloss oil, be difficult to realize in the abundant extension protection of three-dimensional body and the problem of after fixing; the present invention is applied to transfer film industry by ultraviolet-heat dual cure gloss oil; after can effectively solving ornament layer transfer printing, ink degree is lower; surface ink layer resistance, the poor problem of wear resistance; increase the characteristic of gloss oil protective layer delay curing; realize protective layer gloss oil in the abundant extension of three-dimensional object surface, form the good pattern transferring of glossiness, extended work-ing life.
Compared with prior art, advantage is as follows in the present invention:
1. in gloss oil production and use procedure, there is no noxious solvent, process environment is friendly, VOC free discharge, environmental protection.
2. can carry out predrying (heating, drying); realize the partial cross-linked of gloss oil and solidify, form snappiness and the good rete of ductility, hardness can reach HB-1H; can after printing common ink, carry out rolling preservation, solve the problem that three-dimensional body is difficult to apply protective membrane.
3. after predrying film forming, performance is comparatively stable, and retention period is grown (under normal temperature, can keep in Dark Place 12 months).
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, to the present invention is above-mentioned, be described in more detail with other technical characterictic and advantage.
Embodiment 1
Prepare following feed composition:
Double cured resin composition 20g is that 3:2 forms by the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2396, Bayer resin) and hydroxyl polyacrylic resin (WB3011, Shanghai the Wenshui River chemical industry) by weight;
Diluting monomer 10g is that 2:3.5 forms by pentaerythritol triacrylate (PETA, Tianjin proud son of heaven chemical industry) with vinylformic acid caprolactone (AM2101, sharpening work is won in Shanghai) by weight;
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 Siloxane-Oxyalkylene Copolymers (enlightening is high by 432) and the Virahol weight ratio mixture that is 1:1.55; Defoamer 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 weighing up is positioned in beaker, slowly add light trigger, stir and dissolve completely to initiator for 20 minutes, then slowly add flow agent, continue to stir 20 minutes (guaranteeing that it fully dissolves), then add double cured resin composition, 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: by remainder diluting monomer 4g, stopper, defoamer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 75 minutes, heating and temperature control is at 30-40 ℃, stirring velocity is 1000r/min, each component of gloss oil is stirred, last rewinding and get final product.
Gloss oil viscosity prepared by the present embodiment is 0.3-0.9Pas(25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (according to < < GB-1720-79 film adhesive assay method > >, measuring); Rub resistance can reach 500 times/4 pounds; After thoroughly solidifying, hardness can reach 2H, is suitable for the protective layer of transfer film.
Adopt IGT gravure printing adaptive instrument to draw a design the dual cure gloss oil of above-mentioned preparation, be placed in the drying baker heat drying of 100 ℃, form the good predrying rete of plasticity-(hardness can reach 1H, measures according to < < GB6739-86 hardness of film pencil assay method > >); Then specimen page is placed in to ultraviolet light polymerization equipment and carries out photocuring dry (solidifying power is 160W/cm, and line speed is 25m/s) to complete the thoroughly curing time be 10s, the hardness after China ink layer thoroughly solidifies can reach 2H; By moulded products 45-degree-buckling angle, with visual inspection, whether it there is crackle; Moulded products is soaked in alcohol solvent to 24 hours, takes out with its surperficial changing conditions of visual inspection, 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 composition 70g is that 1:1 forms by the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2396, Bayer resin) and oh type Synolac (3616X60, Jiangsu Miki Group) by weight;
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 Siloxane-Oxyalkylene Copolymers (enlightening is high by 432) and the Virahol weight ratio mixture that is 1:1.55; Defoamer 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 weighing up is positioned in beaker, slowly add light trigger, stir and dissolve completely to initiator for 25 minutes, then slowly add flow agent, continue to stir 20 minutes, then add double cured resin composition, 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: by remainder diluting monomer 20g, stopper, defoamer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 120 minutes, heating and temperature control is at 30-40 ℃, stirring velocity is 1000r/min, each component of gloss oil is stirred, last rewinding and get final product.
Gloss oil viscosity prepared by the present embodiment is 0.3-0.9Pas(25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (according to < < GB-1720-79 film adhesive assay method > >, measuring); Rub resistance can reach 500 times/4 pounds; After thoroughly solidifying, hardness can reach 2H, is suitable for the protective layer of transfer film.
Adopt IGT gravure printing adaptive instrument to draw a design the dual cure gloss oil of above-mentioned preparation, be placed in the drying baker heat drying of 70-100 ℃, form the good predrying rete of plasticity-(hardness can reach 1H, measures according to < < GB6739-86 hardness of film pencil assay method > >); Then specimen page is placed in to ultraviolet light polymerization equipment and carries out photocuring dry (solidifying power is 160W/cm, and line speed is 25m/s), the thoroughly curing time that completes is 12s, and the hardness after China ink layer thoroughly solidifies can reach 2H; By moulded products 45-degree-buckling angle, with visual inspection, whether it there is crackle; Moulded products is soaked in alcohol solvent to 24 hours, takes out with its surperficial changing conditions of visual inspection, 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 composition 35g is that 6:5 forms by aromatic urethane acrylate resin and hydroxyl Synolac (WB101A, Huian, the north, Xi'an chemical industry) by weight;
Diluting monomer 10g is 2-HEMA phosphoric 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; Defoamer 1g is polydimethylsiloxane; Base material wetting agent 1g is organic silicon modified by polyether.
(1) stir pre-dispersed: the part diluting monomer 6g weighing up is positioned in beaker, slowly add light trigger, stir and dissolve completely to initiator for 20 minutes, then slowly add flow agent, continue to stir 25 minutes, then add double cured resin composition, 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: by remainder diluting monomer 4g, stopper, defoamer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 80 minutes, heating and temperature control is at 30-40 ℃, stirring velocity is 1000r/min, each component of gloss oil is stirred, last rewinding and get final product.
Gloss oil viscosity prepared by the present embodiment is 0.3-0.7Pas(25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (according to < < GB-1720-79 film adhesive assay method > >, measuring); Rub resistance can reach 400 times/4 pounds; After thoroughly solidifying, hardness can reach 2H, is suitable for the protective layer of transfer film.
Adopt IGT gravure printing adaptive instrument to draw a design the dual cure gloss oil of above-mentioned preparation, be placed in the drying baker heat drying of 70-100 ℃, form the good predrying rete of plasticity-(hardness can reach HB, measures according to < < GB6739-86 hardness of film pencil assay method > >); Then specimen page is placed in to ultraviolet light polymerization equipment and carries out photocuring dry (solidifying power is 160W/cm, and line speed is 25m/s), the thoroughly curing time that completes is 18s, and the hardness after China ink layer thoroughly solidifies can reach 2H; By moulded products 45-degree-buckling angle, with visual inspection, whether it there is crackle; Moulded products is soaked in alcohol solvent to 24 hours, takes out with its surperficial changing conditions of visual inspection, 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 composition 60g, by the polyacrylic resin (WB3011, Shanghai the Wenshui River chemical industry) of aromatic urethane acrylate resin and hydroxyl by weight being 7:5 composition;
Diluting monomer 40g is that 1:1 forms by propoxylation Viscoat 295 (Tianjin proud son of heaven chemical industry) with polyethyleneglycol diacrylate (SR344, the pretty color chemical industry in Shanghai) by weight;
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; Defoamer 3g is polydimethylsiloxane; Base material wetting agent 5g is organic silicon modified by polyether.
(1) stir pre-dispersed: the part diluting monomer 24g weighing up is positioned in beaker, slowly add light trigger, stir and dissolve completely to initiator for 30 minutes, then slowly add flow agent, continue to stir 20 minutes, then add double cured resin composition, 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: by remainder diluting monomer 16g, stopper, defoamer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 80 minutes, heating and temperature control is at 30-40 ℃, stirring velocity is 800r/min, each component of gloss oil is stirred, last rewinding and get final product.
Gloss oil viscosity prepared by the present embodiment is 0.3-0.9Pas(25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (according to < < GB-1720-79 film adhesive assay method > >, measuring); Rub resistance can reach 400 times/4 pounds; After thoroughly solidifying, hardness can reach 2H, is suitable for the protective layer of transfer film.
Adopt IGT gravure printing adaptive instrument to draw a design the dual cure gloss oil of above-mentioned preparation, be placed in the drying baker heat drying of 70-100 ℃, form the good predrying rete of plasticity-(hardness can reach 1H, measures according to < < GB6739-86 hardness of film pencil assay method > >); Completing the thoroughly curing time is 15s, and the hardness after China ink layer thoroughly solidifies can reach 2H; By moulded products 45-degree-buckling angle, with visual inspection, whether it there is crackle; Moulded products is soaked in alcohol solvent to 24 hours, takes out with its surperficial changing conditions of visual inspection, 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 composition 55g is that 3:2 forms by the aliphatic urethane acrylate resin that contains isocyanic ester (UAVPLS 2337, Bayer resin) with the Synolac (WB101A, Huian, the north, Xi'an chemical industry) of hydroxyl by weight;
Diluting monomer 32g is 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; Defoamer 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 weighing up is positioned in beaker, slowly add light trigger, stir and dissolve completely to initiator for 20 minutes, then slowly add flow agent, continue to stir 25 minutes, then add double cured resin composition, 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: by remainder diluting monomer 16g, stopper, defoamer, base material wetting agent join in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 100 minutes, heating and temperature control is at 30-40 ℃, stirring velocity is 1000r/min, each component of gloss oil is stirred, last rewinding and get final product.
Gloss oil viscosity prepared by the present embodiment is 0.4-0.9Pas(25 ℃); Glossiness is up to more than 95%; Sticking power can reach 100% and adhere to (according to < < GB-1720-79 film adhesive assay method > >, measuring); Rub resistance can reach 400 times/4 pounds; After thoroughly solidifying, hardness can reach 1H, is suitable for the protective layer of transfer film.
Adopt IGT gravure printing adaptive instrument to draw a design the dual cure gloss oil of above-mentioned preparation, be placed in the drying baker heat drying of 70-100 ℃, form the good predrying rete of plasticity-(hardness can reach HB, measures according to < < GB6739-86 hardness of film pencil assay method > >); Then specimen page is placed in to ultraviolet light polymerization equipment and carries out photocuring dry (solidifying power is 160W/cm, and curing speed is 25m/s), the thoroughly curing time that completes is 15 seconds, and the hardness after China ink layer thoroughly solidifies can reach 1H; By moulded products 45-degree-buckling angle, with visual inspection, whether it there is crackle; Moulded products is soaked in alcohol solvent to 24 hours, takes out with its surperficial changing conditions of visual inspection, 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 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, resistance, wear resistance, chemical resistance and the work-ing life (as shown in the test data in table 1) of transfer film.
First scribbling in the carrier film of release resin layer, the ultraviolet-heat dual cure gloss oil (thickness approximately 4 μ m) of coating above-described embodiment, then the drying channel that is placed in 70-100 ℃ carries out the thermofixation of gloss oil, form the good rete of plasticity-, then on this rete, carry out the printing [for example base gravure ink (Toyo Ink company)] of other ink, (this transfer printing glue-line can be the conventional hot melt adhesive in transfer printing field finally to apply transfer printing glue-line, transfer printing hot melt adhesive for example, safe parting agent hot melt adhesive factory of Dongguan unit); Pattern transfer to be decorated to object after, the gloss oil protective layer on pattern transferring surface is applied to the ultraviolet lighting of 160W/cm linear heat generation rate, make it in 20 seconds, complete thoroughly solidifying 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 is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing 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 the claims in the present invention book.
Claims (9)
1. a 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, defoamer 1-10 part, base material wetting agent 1-10 part;
Wherein, described resin combination is the composition of the polyurethane acrylate resin that contains isocyanate group and the resin that contains hydroxyl, and both weight ratios are 1.6:1～1:1; The described polyurethane acrylate resin that contains isocyanate group is aliphatic urethane acrylate resin or aromatic urethane acrylate resin; The resin of described hydroxyl is acrylic resin, Synolac or epoxy resin;
Wherein, described 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-HEMA phosphoric acid ester and propoxylation Viscoat 295;
Wherein, described 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; Described flow agent is selected from one or both mixtures with arbitrary proportion in Siloxane-Oxyalkylene Copolymers, methyl phenyl silicone, organosilicon-modified acrylate and Virahol; Described defoamer is polydimethylsiloxane, polydimethyl siloxane fluid or polyoxyethylene polyoxypropylene glyceryl ether; Described base material wetting agent is selected from one or both mixtures with arbitrary proportion in modified polyorganosiloxane and organic silicon modified by polyether.
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, defoamer 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 defoamers, 1 part of base material wetting agent.
4. according to the ultraviolet-heat dual cure gloss oil described in claim 1-3 any one, it is characterized in that: described in contain isocyanate group polyurethane acrylate resin be aliphatic urethane acrylate resin; The resin of described hydroxyl is acrylic resin.
5. according to the ultraviolet-heat dual cure gloss oil described in claim 1-3 any one; it is characterized in that: described light trigger is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-isopropyl thioxanthone, 2; 4; 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) one or both mixtures with arbitrary proportion in phenyl phosphine oxide.
6. the method for the ultraviolet-heat dual cure gloss oil described in preparation claim 1-3 any one, is characterized in that, comprises the following steps:
(1) stir pre-dispersed: part diluting monomer is added in reaction vessel, slowly add light trigger, and carry out uniform stirring 15-30 minute, treat that light trigger adds flow agent after dissolving completely, continue to stir flow agent fully to be dissolved in 15-30 minute, then add resin combination, 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, defoamer, base material wetting agent are joined in the pre-dispersed resin solution that step (1) obtains, continue heated and stirred 60-120 minute, heating and temperature control is at 30-40 ℃, stirring velocity is 800-1000r/min, last rewinding and get final product.
7. the application of the ultraviolet-heat dual cure gloss oil described in claim 1-3 any one, is characterized in that, uses it for the supercoat of transfer film, to increase glossiness, resistance, wear resistance, chemical resistance and the work-ing life of transfer film.
8. the application method of the ultraviolet-heat dual cure gloss oil described in claim 1-3 any one, it is characterized in that, first scribbling in the carrier film of release resin layer, ultraviolet-heat dual cure gloss oil described in coating claim 1-3 any one, then the drying channel that is placed in 70-100 ℃ carries out the thermofixation of gloss oil, form the good rete of plasticity-, then on this rete, carry out the printing of other ink, finally apply transfer printing glue-line; Design transfer to be decorated to object after, the protective layer gloss oil on pattern transferring surface is applied to ultraviolet lighting, it is thoroughly solidified.
9. application method as claimed in claim 8, is characterized in that UV-light is with the linear heat generation rate of 160W/cm, completes thoroughly solidifying of gloss oil layer in 20 seconds.
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