CN114085558A - Staged photocuring coating, heat transfer film, decorative device and preparation method - Google Patents

Staged photocuring coating, heat transfer film, decorative device and preparation method Download PDF

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Publication number
CN114085558A
CN114085558A CN202111577513.5A CN202111577513A CN114085558A CN 114085558 A CN114085558 A CN 114085558A CN 202111577513 A CN202111577513 A CN 202111577513A CN 114085558 A CN114085558 A CN 114085558A
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layer
parts
coating
functional layer
chemical
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CN202111577513.5A
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申政
石建行
肖烜
杨志方
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Shanghai Huagong Aimar New Material Co ltd
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Shanghai Huagong Aimar New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes

Abstract

The embodiment of the application provides a staged photocuring coating, a heat transfer film, a decoration device and a preparation method, and relates to the technical field of transfer materials. The staged photocureable coating comprises the following components in parts by weight: 40-70 parts of macromolecular compound, 30-60 parts of acrylic resin, 5-10 parts of monofunctional monomer, 5-10 parts of polyfunctional monomer and 1-10 parts of photoinitiator. And coating a staged light-cured coating on the release layer of the heat transfer film, and performing UV curing to form a semi-cured functional layer. The heat transfer method is that the surface of the heat transfer film with the adhesion layer is pasted on the device, and certain temperature and pressure are applied to make the adhesion layer adhere to the device, thus completing the transfer printing; and coating a transparent PE protective layer on the transferred device, and then carrying out UV curing to completely cure the semi-cured functional layer to form the functional layer. The coating formed by the coating can be cured by stages, has high stretchability and good wear resistance, and can meet the requirements of various transfer printing devices.

Description

Staged photocuring coating, heat transfer film, decorative device and preparation method
Technical Field
The application relates to the technical field of transfer printing materials, in particular to a staged photocuring coating, a heat transfer printing film, a decoration device and a preparation method.
Background
The heat transfer film is used for printing or coating the pattern information on a carrier film, then peeling the pattern information from the carrier film through the bonding action of thermosol under the action of certain temperature and pressure by professional equipment, and transferring the pattern information to a corresponding device, so that the heat transfer film has certain functions and certain decorative effect. With the development of technology and the advancement of technology, the competition of consumer electronics and automobile market is in the stage of getting hotter, and consumers have made higher demands on the performance of related products, such that the products are not only required to be beautiful, but also required to be durable.
The traditional heat transfer film has single functionality and cannot meet the requirements of sweat resistance, oil stain resistance, wear resistance and the like. Chinese patent CN 202319328U discloses a three-dimensional grain heat transfer film, which can diversify the appearance style of the product, and increase the diversity of the heat transfer process; and a UV photocuring layer is introduced into the heat transfer film structure, so that the wear resistance is improved. However, the heat transfer film has no stretchability, and cannot meet the surface decoration of a device with a special shape and the market demand.
Disclosure of Invention
The embodiment of the application aims to provide the staged photocuring coating, the thermal transfer film, the decoration device and the preparation method, and the coating formed by the coating can be cured in stages, has high stretchability and good wear resistance, and can meet the requirements of various transfer devices.
In a first aspect, an embodiment of the present application provides a staged photo-curing coating, which includes, by weight: 40-70 parts of macromolecular compound, 30-60 parts of acrylic resin, 5-10 parts of monofunctional monomer, 5-10 parts of polyfunctional monomer and 1-10 parts of photoinitiator;
wherein the macromolecular compound has a molecular weight of 5 × 104-10×104The high polymer of (a); the acrylic resin has a molecular weight of 0.5 × 104-2×104An oligomer of (a); the monofunctional monomer is at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, 2, 2-trifluoroethyl methacrylate, butyl methacrylate, vinyl acetate and acrylamide; the multifunctional monomer is at least one of tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and trimethoxy silane methacrylate.
In the technical scheme, the staged photocureable coating comprises a high polymer, an oligomer, a monofunctional monomer, a polyfunctional monomer and a photoinitiator, and during the photocuring process, the staged photocuring is realized by controlling the illumination condition and the environment: in the first stage: because oxygen exists in the environment, the coating can only reach a semi-cured state and cannot be completely cured under the action of oxygen inhibition, so that the high stretchability of the film layer is ensured; the second stage is as follows: after oxygen is blocked, the oxygen inhibition is relieved, the coating can be completely cured, and the wear resistance of the film layer is ensured.
In one possible implementation, the macromolecular compound is at least one of xiamenweilin chemical UV3540, xiamenweilin chemical UV3542, dongguan xinyue electronic material SY-5213, dongguan xinyue electronic material SY-5231, changxing chemical 6071 and changxing chemical 6072;
and/or the acrylic resin is at least one of Xingxing chemical 4220, Xingxing chemical 3508, Xingxing chemical EM231, Xingxing chemical EM221, south China fine chemical G21, south China fine chemical U010 and south China fine chemical C11;
and/or the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide.
In the technical scheme, the oxygen inhibition effect is good, the molecular crosslinking degree is low, and the curing degree of the coating is 40-80%, so that the high stretchability of the coating is ensured; the curing agent can be completely cured by removing oxygen inhibition, the molecular crosslinking degree is increased, and the functional layer formed by curing has good wear resistance.
In a possible implementation mode, the antifouling auxiliary agent also comprises 1-10 parts by weight of the antifouling auxiliary agent, and the antifouling auxiliary agent is a fluorocarbon siloxane compound containing acrylic acid functional groups or a fluorine-containing acrylic acid compound.
In the technical scheme, the addition of the fluorine-containing antifouling auxiliary agent can reduce the surface tension of the coating after coating to enable the coating to be better spread, and can endow the coating with the antifouling property, particularly the properties of sweat resistance, oil resistance and the like.
In a second aspect, an embodiment of the present application provides a thermal transfer film, which includes a base film layer, a release layer, a semi-cured functional layer, an image-text layer, and a bonding layer, which are sequentially stacked from top to bottom, where the semi-cured functional layer is formed by applying and photocuring the phased photocuring coating provided in the first aspect, and a curing rate of the semi-cured functional layer is 40% to 80%.
In the technical scheme, the curing rate of the semi-cured functional layer does not reach 100%, the flexibility and the stretchability are good, the semi-cured functional layer is combined with other functional layers as a main layer, the heat transfer film with good flexibility and stretchability can be formed, and the heat transfer film is suitable for the requirements of various transfer devices, particularly the heat transfer film can be formed on the devices with large surface radian.
In one possible implementation mode, the base film layer is a PET film, a PC film, a PVC film, an ABS film or a PMMA film, and the thickness of the base film layer is 12-60 mu m;
and/or the material of the release layer is at least one of water-based release wax, solvent-based release wax, silicone release agent and fluorine release agent, and the thickness of the release layer is 1-10 mu m;
and/or the thickness of the semi-curing functional layer is 2-15 mu m.
In the technical scheme, the semi-cured functional layer is combined with other functional layers as a main layer, so that the heat transfer film with good flexibility and stretchability can be formed.
In one possible implementation, the adhesive corresponding to the adhesion layer comprises, in parts by weight: 50-90 parts of silicon rubber, 20-40 parts of MQ silicon resin, 3-15 parts of hydrogen-containing silicone oil, 5-10 parts of platinum catalyst and 100-300 parts of solvent.
In the technical scheme, the adhesive has good adhesion with a plastic material, so that the edge of the transfer printing film is not easy to warp, the adhesive is an organic silicon material, the formed bonding layer has good aging resistance and yellowing resistance, the service life is long, and the phenomena of degumming and yellowing are avoided; the problems that the service life of a heat transfer film product on the market is not long enough, and the heat transfer film product is easy to fall off from the surface of a decorated device after being used for a long time, and the market demand cannot be met are solved.
In one possible embodiment, the silicone rubber is a vinyl-containing silicone rubber having a vinyl content of 0.2 to 0.8g/mol and a molecular weight of 10X 104-20×104；
And/or, the MQ silicon resin is MQ silicon resin containing methyl and has a molecular weight of 0.2 multiplied by 104-0.8×104；
And/or, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%, and the molecular weight is 100-1000;
and/or, the platinum catalyst is PT 4000;
and/or the solvent is at least one of toluene, ethyl acetate, butyl acetate, ethanol, n-butyl alcohol and butanone.
In a third aspect, an embodiment of the present application provides a method for manufacturing a thermal transfer film according to the second aspect, including the following steps:
forming a release layer on the base film layer;
coating a staged photocuring coating on the release layer, and irradiating and curing for 10-60s by adopting a UV mercury lamp with the power of 40-120W/cm to form a semi-cured functional layer;
and sequentially forming an image-text layer and a bonding layer on the semi-solidified functional layer.
In the technical scheme, the coating formed by the staged photocuring coating is cured for 10-60s under the irradiation of a UV mercury lamp with the power of 40-120W/cm, and the curing rate of the coating is 40-80% due to the action of oxygen inhibition.
In a fourth aspect, an embodiment of the present application provides a decoration device, which includes a device, and an adhesion layer, a graphics layer, and a functional layer that are adhered to a surface of the device, where the adhesion layer, the graphics layer, and the functional layer are derived from the thermal transfer film provided in the second aspect, and the functional layer is formed by photo-curing a semi-cured functional layer.
In the technical scheme, after the semi-cured functional layer is subjected to photocuring, the semi-cured functional layer is further crosslinked, so that the crosslinking density is improved, and the stain resistance and the wear resistance of the decorative film layer are further improved.
In a fifth aspect, embodiments of the present application provide a method for preparing a decorative device provided in the fourth aspect, which includes the following steps:
attaching the surface of the thermal transfer film with the adhesion layer on a device, applying certain temperature and pressure to adhere the adhesion layer on the device, and stripping off the base film layer and the release layer to finish transfer printing;
wrapping a transparent PE protective layer on the device, and then using radiation energy of 600mJ/cm2And irradiating the device by the UV lamp to completely cure the semi-cured functional layer, and stripping off and removing the PE protective layer.
According to the technical scheme, the PE protective layer is covered on the heat transfer film, on one hand, the incompletely cured semi-cured functional layer can be protected from being scratched, on the other hand, oxygen can be blocked, the oxygen inhibition effect is relieved, and the semi-cured functional layer can be further photo-cured to be completely cured.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a thermal transfer film according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of a decorative device provided in an embodiment of the present application during a manufacturing process.
Icon: 100-heat transfer film; 110-a base film layer; 120-a release layer; 130-a semi-cured functional layer; 140-a graphic layer; 150-an adhesion layer; 200-a decorative device; 210-a device; 220-a functional layer; 230-PE protective layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The staged photo-curable coating, the thermal transfer film, the decoration device and the preparation method according to the embodiment of the present application will be described in detail below.
The embodiment of the application provides a staged photo-curing coating, which comprises the following components in parts by weight: 40-70 parts of macromolecular compound, 30-60 parts of acrylic resin, 5-10 parts of monofunctional monomer, 5-10 parts of polyfunctional monomer, 1-10 parts of photoinitiator and 1-10 parts of antifouling auxiliary agent.
Wherein the macromolecular compound has a molecular weight of 5 × 104-10×104The macromolecular compound is at least one of xiamenweilin chemical UV3540, xiamenweilin chemical UV3542, dongguan xinyue electronic material SY-5213, dongguan xinyue electronic material SY-5231, changxing chemical 6071 and changxing chemical 6072.
Wherein the acrylic resin has a molecular weight of 0.5 × 104-2×104An oligomer of (a); illustratively, the acrylic resin is at least one of chang chemical 4220, chang chemical 3508, chang chemical EM231, chang chemical EM221, south china fine chemical G21, south china fine chemical U010, and south china fine chemical C11.
Wherein the single-function monomer is at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, 2, 2-trifluoroethyl methacrylate, butyl methacrylate, vinyl acetate and acrylamide.
Wherein the polyfunctional monomer is at least one of tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and trimethoxy silane methacrylate.
Wherein the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide.
Wherein, the antifouling auxiliary agent is a fluorocarbon siloxane compound containing acrylic acid functional groups or a fluorine-containing acrylic acid compound; illustratively, the anti-fouling aid is at least one of the following chemical industries, namely, shin-Ethery UV-300, shin-Ethery UV-250, shin-Ethery UV-370, Large gold fluorinating chemical OPTOOL DAC-HP, and Meiwei chemical KY-1203.
The preparation method of the staged photocureable coating provided by the embodiment of the application is to uniformly stir the macromolecular compound, the acrylic resin, the monofunctional monomer, the polyfunctional monomer, the photoinitiator and the antifouling auxiliary agent at room temperature to obtain the coating.
Referring to fig. 1, an embodiment of the present application further provides a thermal transfer film 100, which includes a base film layer 110, a release layer 120, a semi-cured functional layer 130, an image-text layer 140, and an adhesion layer 150, which are sequentially stacked from top to bottom. Wherein, the base film layer 110 is a PET film, a PC film, a PVC film, an ABS film or a PMMA film, and the thickness of the base film layer 110 is 12-60 μm. The material of the release layer 120 is at least one of water-based release wax, solvent-based release wax, silicone release agent and fluorine release agent, and the thickness of the release layer 120 is 1-10 μm. The semi-cured functional layer 130 is formed by coating and photocuring the staged photocureable coating, the curing rate of the semi-cured functional layer 130 is 40% -80%, and the thickness of the semi-cured functional layer 130 is 2-15 μm. The graphics layer 140 is a printing ink layer.
The adhesive layer 150 is an adhesive layer, and the corresponding adhesive comprises the following components in parts by weight: 50-90 parts of silicon rubber, 20-40 parts of MQ silicon resin, 3-15 parts of hydrogen-containing silicone oil, 5-10 parts of platinum catalyst and 100-300 parts of solvent.
Wherein the silicone rubber is vinyl-containing silicone rubber with vinyl content of 0.2-0.8g/mol and molecular weight of 10 × 104-20×104(ii) a Illustratively, the silicone rubber is at least one of 110 silicone rubber in New chemical industry, vinyl silicone oil in New chemical industry, 110 silicone rubber in Runzhu chemical industry, 110 silicone rubber in Dongju of Nanjing, and the like.
The MQ silicon resin is MQ silicon resin containing methyl, and has molecular weight of 0.2 × 104-0.8×104(ii) a Illustratively, the MQ silicone resin is at least one of a Runshu chemical MQ silicone resin, a Dayi chemical MQ silicone resin, a Jipeng MQ silicone resin, and the like.
The hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2 percent, and the molecular weight is 100-1000; illustratively, the hydrogen-containing silicone oil is at least one of hydrogen-containing silicone oil DY-H2101, DY-2102 in chemical industry, RH-H518 and RH-DH07 in chemical industry of Runshe rice.
The platinum catalyst was PT 4000.
The solvent is at least one of toluene, ethyl acetate, butyl acetate, ethanol, n-butanol and butanone.
As an embodiment, the preparation method of the adhesive comprises the following steps: adding a certain amount of silicon rubber, MQ silicon resin and a solvent into a container, carrying out pre-reaction at the temperature of 120-180 ℃ for 0.5-2h, then cooling the reaction solution to room temperature, adding a certain amount of hydrogen-containing silicon oil and a platinum catalyst into the container, and uniformly stirring at room temperature to obtain the catalyst.
The embodiment of the present application further provides a method for manufacturing the thermal transfer film 100, which includes the following steps:
(1) and coating a release layer 120 coating on the base film layer 110, and naturally curing to form the release layer 120.
(2) Coating a staged photo-curing coating on the release layer 120, and irradiating and curing for 10-60s by adopting a UV mercury lamp with the power of 40-120W/cm to form the semi-cured functional layer 130, wherein the curing rate of the semi-cured functional layer 130 is 40% -80%.
(3) Printing ink on the semi-cured functional layer 130 to form an image-text layer 140.
(4) The image-text layer 140 is coated with an adhesive and naturally cured to form the adhesive layer 150.
Referring to fig. 1 and fig. 2, an embodiment of the present application further provides a decoration device 200, which includes a device 210, and an adhesion layer 150, an image-text layer 140, and a functional layer 220 adhered to a surface of the device 210, where the adhesion layer 150, the image-text layer 140, and the functional layer 220 are derived from the thermal transfer film 100, the functional layer 220 is formed by photo-curing a semi-cured functional layer 130, and a curing rate of the functional layer 220 is 100%. The surface of the device 210 may be made of plastic materials such as PC, PMMA, ABS, PVC, etc., and the adhesion layer 150 can be firmly adhered to the surface.
The embodiment of the present application further provides a method for manufacturing the decoration device 200, which includes the following steps:
(1) attaching the surface of the thermal transfer film 100 with the adhesive layer 150 to the device 210, applying a certain temperature and pressure to adhere the adhesive layer 150 to the device 210, and peeling off the base film layer 110 and the release layer 120 to complete the transfer.
(2) A transparent PE protective layer 230 is wrapped on the transferred device 210, and then irradiated with energy of 600mJ/cm2The UV lamp irradiates the device 210 to completely cure the semi-cured functional layer 130 to form the functional layer 220, and the PE protective layer 230 is peeled off and removed.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a thermal transfer film, which is composed of a base film layer, a release layer, a functional layer, an image-text layer and an adhesion layer, which are sequentially stacked from top to bottom, and the preparation process is as follows:
(1) a solvent-based release wax was coated on the 15 μm PET base film layer to form a 2 μm thick release layer.
(2) Preparing a staged photocureable coating: weighing 25 parts of Xiamen chemical UV3540, 25 parts of SY-5213 from Xinyue electronic materials Co., Ltd, 50 parts of Changxing chemical 4220, 5 parts of methyl acrylate, 8 parts of tripropylene glycol diacrylate, 1 part of 2-hydroxy-2-methyl-1-phenyl acetone and 3 parts of Fluere UV-300 in parts by weight, and uniformly stirring all the raw materials at room temperature to obtain the Xiameningwei flame retardant.
And coating a staged photocuring coating on the release layer to form a coating, and carrying out UV curing for 30s under the illumination condition of a UV mercury lamp with the power of 40-120W/cm, wherein the curing rate is 50 percent, so as to form a semi-cured functional layer with the thickness of 3 microns.
(3) Printing ink on the semi-solidified functional layer to form an image-text layer.
(4) Preparing an adhesive: adding 60 parts by weight of 110 silicone rubber in the new safety chemical industry, 25 parts by weight of MQ silicone resin in the lubricating chemical industry and 150 parts by weight of toluene solvent into a container, pre-reacting at the high temperature of 150 ℃ for 1 hour, then cooling the reaction solution to the room temperature, adding 10 parts by weight of DY-H2101 in the large easy chemical industry and 5 parts by weight of PT4000 into the container, and uniformly stirring at the room temperature to obtain the high-temperature-resistant silicone rubber.
The image-text layer was coated with an adhesive to form a 2 μm thick adhesive layer.
Example 2
The embodiment provides a thermal transfer film, which is composed of a base film layer, a release layer, a functional layer, an image-text layer and an adhesion layer, which are sequentially stacked from top to bottom, and the preparation process is as follows:
(1) a solvent-based release wax was coated on the 23 μm PET base film layer to form a 5 μm thick release layer.
(2) Preparing a staged photocureable coating: weighing 30 parts of Xiamen chemical UV3542, 30 parts of Changxing chemical 6071, 20 parts of Changxing chemical 3508, 20 parts of south China fine chemical G21, 8 parts of methacrylic acid-2, 2, 2-trifluoroethyl ester, 4 parts of pentaerythritol triacrylate, 2 parts of 1-hydroxycyclohexyl benzophenone and 4 parts of Dajinflurane chemical OPTOOL DAC-HP in parts by weight, and uniformly stirring all the raw materials at room temperature to obtain the product.
And coating a staged photocuring coating on the release layer to form a coating, and carrying out UV curing for 40s under the illumination condition of a UV mercury lamp with the power of 40-120W/cm, wherein the curing rate is 60 percent, so as to form a 6-micron-thick semi-cured functional layer.
(3) Printing ink on the semi-solidified functional layer to form an image-text layer.
(4) Preparing an adhesive: adding 70 parts by weight of 110 silicone oil in the new safety chemical industry, 20 parts by weight of MQ silicone resin in the grain-moistening chemical industry and 150 parts by weight of toluene solvent into a container, pre-reacting at the high temperature of 150 ℃ for 1 hour, then cooling the reaction solution to the room temperature, adding 7 parts by weight of RH-H518 in the grain-moistening chemical industry and 3 parts by weight of PT4000 into the container, and uniformly stirring at the room temperature to obtain the composite material.
The image-text layer was coated with an adhesive to form a 4 μm thick adhesive layer.
Example 3
The embodiment provides a thermal transfer film, which is composed of a base film layer, a release layer, a functional layer, an image-text layer and an adhesion layer, which are sequentially stacked from top to bottom, and the preparation process is as follows:
(1) a solvent-based release wax was coated on a 50 μm PET base film layer to form a 7 μm thick release layer.
(2) Preparing a staged photocureable coating: according to parts by weight, 60 parts of SY-5231, 15 parts of Changxing chemical EM231, 15 parts of Changxing chemical EM221, 10 parts of south China fine chemical C11, 5 parts of acrylamide, 8 parts of methacrylic trimethoxy silane, 1 part of 2-hydroxy-2 methyl-1-phenyl acetone and 3 parts of Xinyue chemical Fluere UV-370 are weighed, and all raw materials are uniformly stirred at room temperature to obtain the product.
And coating a staged photocuring coating on the release layer to form a coating, and carrying out UV curing for 50s under the illumination condition of a UV mercury lamp with the power of 40-120W/cm, wherein the curing rate is 70%, so as to form a 9-micron-thick semi-cured functional layer.
(3) Printing ink on the semi-solidified functional layer to form an image-text layer.
(4) Preparing an adhesive: weighing 80 parts by weight of Nanjing Dongjue 110 silicone rubber, 10 parts by weight of Dayi chemical MQ silicone resin and 150 parts by weight of toluene solvent, adding into a container, pre-reacting at a high temperature of 150 ℃ for 1H, cooling the reaction solution to room temperature, adding 5 parts by weight of Dayi chemical DY-H2102 and 5 parts by weight of PT4000 into the container, and uniformly stirring at room temperature to obtain the nano silicon rubber.
The image-text layer was coated with an adhesive to form a 6 μm thick adhesive layer.
Comparative example 1
The present comparative example provides a thermal transfer film, which is different from example 1 in that: the functional layer of the comparative example is formed by photocuring a UV curing coating, wherein the UV curing coating is as follows: 75 parts of Xinyue electronic material SY-5231 (macromolecular compound) from Dongguan city, 17 parts of butyl methacrylate (monofunctional monomer), 2 parts of 1-hydroxycyclohexyl benzophenone (photoinitiator), and 6 parts of polyfluorinated OPTOOL DAC-HP (antifouling aid).
Comparative example 2
The present comparative example provides a thermal transfer film, which is different from example 1 in that: the functional layer of the comparative example was formed by thermal curing using a dual-cure coating requiring thermal curing and UV curing, the dual-cure coating being: 35 parts of Xiamen chemical UV3542 (macromolecular compound), 35 parts of Changxing chemical 6071 (acrylic resin), 10 parts of pentaerythritol triacrylate (polyfunctional monomer), 8 parts of benzoyl peroxide, 4 parts of 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiator), 8 parts of polyfluorinated chemical OPTOOL DAC-HP (antifouling aid); the heat curing conditions were: baking at 140 deg.C for 1 min.
Comparative example 3
The present comparative example provides a thermal transfer film, which is different from example 1 in that: the adhesive of this comparative example was: 40 parts of castor oil, 15 parts of toluene diisocyanate, 42 parts of styrene, 3 parts of dibenzoyl peroxide and 300 parts of ethyl acetate.
Procedure of experiment
First, the heat transfer films of examples 1 to 3 and comparative examples 1 to 3 were subjected to tensile strength tests, respectively. The test method comprises the following steps: according to the national standard of tensile strength test, cutting the thermal transfer film into a standard I shape, placing the I shape sample piece into a fixture of a tensile machine for testing, and recording the elongation at break. The test results are shown in Table 1.
Table 1 results of elongation at break test of different heat transfer films
Heat transfer film Elongation at break
Example 1 230％
Example 2 220％
Example 3 240％
Comparative example 1 40％
Comparative example 2 85％
Comparative example 3 Can not be transferred
Secondly, respectively transferring the heat transfer films of the embodiments 1 to 3 and the comparative examples 1 to 3 to a plastic device through the adhesion of the adhesive layer under the action of certain temperature and pressure, and stripping off the base film layer; wrapping a layer of transparent PE film on the device, and placing the device with transferred image-text information at 600mJ/cm2And (5) curing for 1min under the UV lamp to obtain the decorative device.
The decorative devices after UV curing were tested for abrasion resistance. Abrasion resistance test method: for 1cm3The 0000# steel wool of (1) was subjected to a load of 200g, reciprocated 200 times per second and a moving distance of 2cm on the surface of the cured heat transfer film, and the degree of surface abrasion was observed and judged with the naked eye. The test results are shown in Table 2.
TABLE 2 abrasion resistance test results of various decorative devices
Decorative device Wear resistance
Example 1 No scratch
Example 2 Slight scratch
Example 3 No scratch
Comparative example 1 Slight scratch
Comparative example 2 Severe scratch
Comparative example 3 Can not be transferred
And thirdly, testing the water drop angle on the surface of the decorative device after the UV curing. Water drop angle test method: a water drop is dropped on the surface of the sample by a syringe, the angle is measured by a water drop angle tester, and the test data are shown in Table 3.
TABLE 3 Water drop Angle test results for various decorative devices
Examples Angle of water drop (°)
Example 1 115
Example 2 113
Example 3 118
Comparative example 1 110
Comparative example 2 108
Comparative example 3 Can not be transferred
As can be seen from the results in tables 1 to 3, the thermal transfer film of the embodiment of the present application has not only good tensile properties, but also good wear resistance and stain resistance, and is suitable for the requirements of various transfer devices.
In summary, the coating formed by the staged photocuring coating of the embodiment of the application can be cured in stages, has high stretchability and good wear resistance, and can be suitable for the requirements of various transfer printing devices.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. The staged photocureable coating is characterized by comprising the following components in parts by weight: 40-70 parts of macromolecular compound, 30-60 parts of acrylic resin, 5-10 parts of monofunctional monomer, 5-10 parts of polyfunctional monomer and 1-10 parts of photoinitiator;
wherein the macromolecular compound has a molecular weight of 5 × 104-10×104The high polymer of (a); the acrylic resin has a molecular weight of 0.5 × 104-2×104An oligomer of (a); the monofunctional monomer is at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, 2, 2-trifluoroethyl methacrylate, butyl methacrylate, vinyl acetate and acrylamide; the multifunctional monomer is at least one of tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and trimethoxy silane methacrylate.
2. A staged photo-curing coating according to claim 1, wherein said macromolecular compound is at least one of xiamenweilian chemical UV3540, xiamenweilian chemical UV3542, guan xinyue electronic material SY-5213, guan xinyue electronic material SY-5231, changxing chemical 6071 and changxing chemical 6072;
and/or the acrylic resin is at least one of Xingxing chemical 4220, Xingxing chemical 3508, Xingxing chemical EM231, Xingxing chemical EM221, south China fine chemical G21, south China fine chemical U010 and south China fine chemical C11;
and/or the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide.
3. The staged photo-curable coating according to claim 1, further comprising 1-10 parts by weight of an anti-fouling auxiliary agent, wherein the anti-fouling auxiliary agent is a fluorocarbon siloxane compound containing acrylic functional groups or a fluoroacrylic compound.
4. The heat transfer film is characterized by comprising a base film layer, a release layer, a semi-cured functional layer, an image-text layer and a bonding layer which are sequentially stacked from top to bottom, wherein the semi-cured functional layer is formed by coating and photocuring the stage-by-stage photocuring coating according to any one of claims 1 to 3, and the curing rate of the semi-cured functional layer is 40-80%.
5. The heat transfer film according to claim 4, wherein the base film layer is a PET film, a PC film, a PVC film, an ABS film, or a PMMA film, and the thickness of the base film layer is 12 to 60 μm;
and/or the release layer is made of at least one of water-based release wax, solvent-based release wax, silicone release agent and fluorine release agent, and the thickness of the release layer is 1-10 mu m;
and/or the thickness of the semi-solidified functional layer is 2-15 mu m.
6. The thermal transfer film according to claim 4, wherein the adhesive corresponding to the adhesion layer comprises, in parts by weight: 50-90 parts of silicon rubber, 20-40 parts of MQ silicon resin, 3-15 parts of hydrogen-containing silicone oil, 5-10 parts of platinum catalyst and 100-300 parts of solvent.
7. The heat transfer film according to claim 6, wherein the silicone rubber is a silicone rubber containing a vinyl group, the vinyl group content is 0.2 to 0.8g/mol, and the molecular weight is 10 x 104-20×104；
And/or the MQ silicon resin is MQ silicon resin containing methyl and has the molecular weight of 0.2 multiplied by 104-0.8×104；
And/or, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%, and the molecular weight is 100-1000;
and/or, the platinum catalyst is PT 4000;
and/or the solvent is at least one of toluene, ethyl acetate, butyl acetate, ethanol, n-butyl alcohol and butanone.
8. The method for manufacturing the thermal transfer film according to any one of claims 4 to 7, comprising the steps of:
forming a release layer on the base film layer;
coating a staged photocuring coating on the release layer, and irradiating and curing for 10-60s by adopting a UV mercury lamp with the power of 40-120W/cm to form a semi-cured functional layer;
and sequentially forming an image-text layer and a bonding layer on the semi-solidified functional layer.
9. A decorative device, comprising a device, and an adhesion layer, a graphic layer and a functional layer adhered to the surface of the device, wherein the adhesion layer, the graphic layer and the functional layer are derived from the thermal transfer film according to any one of claims 4 to 8, and the functional layer is formed by photocuring the semi-cured functional layer.
10. A method for preparing a decorative device according to claim 9, characterized in that it comprises the following steps:
attaching the surface of the thermal transfer film with the adhesion layer to the device, applying certain temperature and pressure to adhere the adhesion layer to the device, and stripping off the base film layer and the release layer to finish transfer printing;
coating a transparent PE protective layer on the transferred device, and then using radiation energy of 600mJ/cm2And irradiating the device by the UV lamp to completely cure the semi-cured functional layer to form the functional layer, and stripping off and removing the PE protective layer.
CN202111577513.5A 2021-12-22 2021-12-22 Staged photocuring coating, heat transfer film, decorative device and preparation method Pending CN114085558A (en)

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