CN106867442B - UV curing adhesive composition, flexible mold and transfer printing method - Google Patents
UV curing adhesive composition, flexible mold and transfer printing method Download PDFInfo
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- CN106867442B CN106867442B CN201710026345.8A CN201710026345A CN106867442B CN 106867442 B CN106867442 B CN 106867442B CN 201710026345 A CN201710026345 A CN 201710026345A CN 106867442 B CN106867442 B CN 106867442B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- B41M5/382—Contact thermal transfer or sublimation processes
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a UV curing adhesive composition, a soft mold and a transfer printing method. The UV curing adhesive composition comprises, by weight, 15-35 parts of a urethane acrylate oligomer, 5-20 parts of a silicon modified resin, 30-50 parts of a first monomer and 2-8 parts of a first photoinitiator. The UV curing adhesive composition comprises the polyurethane acrylate oligomer and the silicon modified resin with the above dosage, so that the surface dyne value of the UV curing adhesive composition is controllable by curing under UV irradiation, when the UV curing adhesive composition is used as a soft mold, the difference between the surface dyne value of the UV curing adhesive composition and the surface dyne value of a decorative film formed by curing is controlled to be larger, the purpose that the UV curing adhesive composition and the decorative film are easy to separate can be realized, and the problem that the soft mold is difficult to demold is solved.
Description
Technical Field
The invention relates to the field of transfer printing, in particular to a UV curing adhesive composition, a soft mold and a transfer printing method.
Background
With the rapid development of social economy, the living standard of people is continuously improved, so the demand on ornaments is also increasingly high, and the requirement is also increasingly high. In the glass for decoration, the main methods for making the pattern structure on the glass comprise mechanical carving and thermal transfer printing, and the mechanical carving method is labor-consuming and time-consuming and has high requirements on the glass; the pattern film is transferred to the glass by a thermal transfer printing method, so that the process is simplified, but the cost is high, the pattern film is easily influenced by the environment or easily falls off during cleaning, and the service life is short.
The 201510443701.7 patent application discloses a glass transfer process comprising: coating a layer of UV glue on the glass; pasting a transfer printing film with required patterns on one surface coated with the UV glue, and scraping; irradiating for 10-30 s by using an ultraviolet lamp; and (5) cooling, taking down the transfer printing film, and obtaining the required patterns on the glass. However, most UV curable glues have poor adhesion to glass, and generally require a primer to improve adhesion.
The patent application with the application number of 201610031144.2 discloses an ultraviolet curing transfer adhesive, and a preparation method and application thereof, wherein the prepared ultraviolet curing transfer adhesive has excellent adhesive force to glass and can replace the traditional hot melt adhesive type transfer adhesive. However, the transfer film needs to be prepared with a pattern structure on a soft base material, and then the back surface of the transfer film is coated with transfer glue and then is attached to glass. The whole process has more working procedures, more material cost and higher cost.
Patent application with application number 200710092834.X discloses a manufacturing method of a glass craft picture, which comprises the following steps: manufacturing a glass substrate, pasting a paper adhesive tape on the periphery of the glass, mixing the epoxy resin adhesive and the curing agent in proportion, and coating the mixture on the surface of the glass for leveling; manufacturing a template, namely carving patterns on the immediately-pasted facial tissue, pasting the immediately-pasted facial tissue on a plastic film, tearing off the pattern part, and putting a pattern module on the double-sided adhesive to manufacture the template; and (3) making a craft picture on the glass substrate, when the epoxy resin adhesive reaches 40-70% of curing degree, placing the template on the epoxy resin adhesive, downwards extruding the pattern module to form a three-dimensional pattern, after the epoxy resin adhesive is cured, taking off the template, and coating colors to obtain the glass craft picture. However, this method requires a large amount of manual work and is not suitable for mechanized production.
In the above method for attaching the pattern structure to the glass by thermal transfer printing, the used hot melt adhesive generally has some problems: the adhesive has low heat resistance, low bonding strength and poor chemical resistance, also contains a small amount of Volatile Organic Compounds (VOC), and is also required to be provided with a special hot melting gun and the like during operation; most of the UV curing glue has poor adhesion to glass. In addition, since the hard mold cannot be molded on glass, the soft mold generally has problems of poor mold releasability, low recycling rate, and the like.
Disclosure of Invention
The invention mainly aims to provide a UV curing adhesive composition, a flexible mold and a transfer printing method, so as to solve the problem of poor mold release performance of the thermal transfer printing method in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a UV curable adhesive composition including, in parts by weight: 15-35 parts of a polyurethane acrylate oligomer; 5-20 parts of silicon modified resin; 30-50 parts of a first monomer; and 2-8 parts of a first photoinitiator.
Further, the urethane acrylate oligomer is a mixture of one or more of the group consisting of a double bond 583-1, cyanotex EB8465, cyanotex EB264, Changxing DR-U025, Changxing 6158B-80, Changxing DR-U029 and Kenmett EO-2238.
Further, the silicon modified resin is a mixture formed by one or more of the group consisting of Meiyuan SIU2400, Cyanote EB1360 and Changxing DR-U188C.
Further, the first monomer is one or more selected from the group consisting of trimethylolpropane triacrylate, tetrahydrofurfuryl acrylate, ethoxylated trimethylolpropane trimethacrylate and 1, 6-hexanediol diacrylate.
Further, the first photoinitiator is an α -hydroxyalkanone photoinitiator or an acyl oxide photoinitiator.
Further, the UV curing adhesive composition also comprises a first auxiliary agent with the weight part of less than or equal to 2, preferably the first auxiliary agent is polyether modified organic silicon, and more preferably the polyether modified organic silicon is a mixture formed by one or more of BYK-333, BYK-UV3500 and BYK-UV 3505.
According to another aspect of the present invention, there is provided a flexible mold cured by a UV curable adhesive, wherein the UV curable adhesive is cured by any one of the UV curable adhesive compositions.
Further, the surface dyne value of the flexible mold is less than 30.
According to another aspect of the present invention, there is provided a transfer method including: step S1, preparing a soft mold by adopting any one of the UV curing adhesive compositions; step S2, glue for manufacturing the decorative film is arranged on the base material; step S3, modeling the glue by using a soft mold to obtain a modeled glue layer; and step S4, curing the molding glue layer to obtain the decorative film.
Further, the surface dyne value of the flexible mold is less than 30.
Further, the step S1 includes: disposing a mixture of the UV curable adhesive composition on a metal mold; arranging a soft base material on the mixture, and rolling the soft base material; solidifying the rolled mixture to obtain a solidified layer; and removing the metal mold, and performing UV curing on the cured layer to obtain a soft mold.
Further, the UV energy used for the UV curing is 20000-100000 mj/cm2。
Further, the surface dyne value of the decorative film is more than 40, and the UV energy adopted for curing in the step S4 is preferably 10-100 mj/cm2。
Further, the transfer printing method also comprises a process of carrying out heat curing on the decorative film.
Further, the glue comprises the following components in parts by weight: 45-70 parts of oligomer, 10-30 parts of second monomer, 2-8 parts of second photoinitiator and 0-5 parts of second auxiliary agent, wherein the oligomer is preferably polyurethane acrylate or pure acrylate; preferably, the second monomer is a mixture formed by one or more of the group consisting of isobornyl acrylate, Changxing chemical 2-hydroxyethyl methacrylate phosphate and tetrahydrofurfuryl acrylate; preferably, the second photoinitiator is an alpha-hydroxyalkanone photoinitiator or an acyl oxide photoinitiator; preferably, the second auxiliary agent is polyether modified acrylate or organic silicon modified acrylate.
Further, the substrate is glass.
The UV curing adhesive composition comprises the polyurethane acrylate oligomer and the silicon modified resin in the above dosage, so that the surface dyne value of the UV curing adhesive composition is controllable through curing under UV irradiation, when the UV curing adhesive composition is used as a soft mold, the difference between the surface dyne value of the UV curing adhesive composition and the surface dyne value of a decorative film formed through curing is controlled to be large, the purpose that the UV curing adhesive composition and the decorative film are easy to separate can be realized, and the problem that the soft mold is difficult to demold is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram illustrating a glue layer modeled by a flexible mold according to a preferred embodiment of the present invention; and
fig. 2 is a schematic view illustrating a method for manufacturing a flexible mold using a metal mold according to a preferred embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a metal mold; 20. a flexible mold; 30. and (6) molding the adhesive layer.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the prior art has various improvements on the transfer printing process, wherein the advantages of the flexible mold transfer printing are obvious, but the problem of difficult demoulding still exists when the flexible mold transfer printing is adopted, and in order to solve the problem, the application provides a UV curing adhesive composition, a flexible mold and a transfer printing method.
In an exemplary embodiment of the present application, there is provided a UV curable adhesive composition including, in parts by weight: 15-35 parts of a polyurethane acrylate oligomer; 5-20 parts of silicon modified resin; 30-50 parts of a first monomer; and 2-8 parts of a first photoinitiator.
The UV curing adhesive composition comprises the polyurethane acrylate oligomer and the silicon modified resin in the above dosage, so that the surface dyne value of the UV curing adhesive composition is controllable through curing under UV irradiation, when the UV curing adhesive composition is used as a soft mold, the difference between the surface dyne value of the UV curing adhesive composition and the surface dyne value of a decorative film formed through curing is controlled to be large, the purpose that the UV curing adhesive composition and the decorative film are easy to separate can be realized, and the problem that the soft mold is difficult to demold is solved.
The urethane acrylate oligomer may be selected from the group of oligomers commonly used in the art, and preferably the urethane acrylate oligomer comprises a mixture of one or more of the group consisting of double bonds 583-1, cyanoter EB8465, cyanoter EB264, Changxing DR-U025, Changxing 6158B-80, Changxing DR-U029 and Kelmett EO-2238.
Further, it is preferable that the silicon-modified resin includes at least one of Meiyuan SIU2400, Cyanote EB1360, and Changxing DR-U188C. The surface dyne value adjustability of a soft mold formed by the UV curing adhesive composition is further controlled by using the silicon modified resin and the polyurethane acrylic acid oligomer for matching.
The first monomer may be a mixture of one or more selected from the group consisting of trimethylolpropane triacrylate, tetrahydrofurfuryl acrylate, ethoxylated trimethylolpropane trimethacrylate and 1, 6-hexanediol diacrylate, and may be referred to a monomer commonly used for UV curable adhesives in the prior art, and is preferably used for better blending with urethane acrylate oligomer. Such as johnson chemistry EM231(TMPTA), johnson chemistry EM214(THFA), johnson chemistry EM2382(TMP9EOTMA) and/or johnson chemistry EM221 (HDDA).
In order to accelerate the curing rate, it is preferable that the first photoinitiator is an α -hydroxyalkanone type photoinitiator or an acyl oxide type photoinitiator. Such as Doublecure (Doublecy chemical trade Co., Ltd.) TPO, Doublecure 184, Doublecure 1173, and/or Doublecure 369.
In a preferred embodiment of the present application, the UV curable adhesive composition further includes a first auxiliary agent in an amount of 2 parts by weight or less, preferably the first auxiliary agent is a polyether modified silicone, and more preferably the polyether modified silicone is a mixture of one or more selected from the group consisting of BYK-333, BYK-UV3500 and BYK-UV 3505. The surface dyne value adjustable performance of a soft mould formed by the UV curing glue composition is further improved by utilizing the first auxiliary agent.
In another exemplary embodiment of the present application, a flexible mold is provided, which is formed by curing a UV curable adhesive using any one of the UV curable adhesive compositions.
The surface dyne value of the soft mould formed by the UV curing adhesive composition is controllable under UV irradiation, and when the soft mould is used for transfer printing, the surface dyne value of the soft mould and the surface dyne value of a decorative film formed by curing are adjusted to form a larger difference value, so that the purpose that the soft mould and the decorative film are easy to separate can be realized, and the problem of difficult demoulding of the soft mould is solved.
In order to allow the flexible mold of the present application to be used with a plurality of decorative films, it is preferable that the flexible mold has a surface dyne value of less than 30.
In still another exemplary embodiment of the present application, there is provided a transfer method including: step S1, preparing a soft mold by adopting any one of the UV curing adhesive compositions; step S2, glue for manufacturing the decorative film is arranged on the base material; step S3, modeling the glue by using the flexible mold 20 to obtain a molding glue layer 30 (refer to fig. 1); and step S4, curing the molding glue layer to obtain the decorative film.
Because the surface dyne value is controllable when the soft mould of this application is under UV irradiation, when the mould when will be used for the rendition uses, adjust the surface dyne value and the surface dyne value of the decorative film that the solidification formed and form great difference, can realize the purpose that the two easily breaks away from, and then solved the difficult problem of soft mould drawing of patterns.
Further, it is preferable to control the surface dyne value of the flexible mold to be less than 30, so that the problem of difficulty in releasing the flexible mold can be solved and the stain resistance of the flexible mold can be improved.
In another preferred embodiment of the present application, there is provided a method for manufacturing a flexible mold, wherein the step S1 preferably includes: disposing a mixture of a UV curable adhesive composition on a metal mold 10; arranging a soft base material on the mixture, and rolling the soft base material; solidifying the rolled mixture to obtain a solidified layer; and removing the metal mold and UV curing the cured layer to obtain a flexible mold 20 (refer to fig. 2).
The method of curing first and then curing enables both the hardness and the surface dyne value of the soft template to be flexibly controlled, for example, in order to control the surface dyne value to be less than 30, the UV energy adopted by the UV curing is preferably 20000-100000 mj/cm2. In addition, the surface dyne value is beneficial to improving the pollution resistance of the flexible moldAnd (4) sex. On one hand, after the strong UV curing, the soft film glue can fully react to achieve higher hardness, and the surface structure is not easy to deform. On the other hand, the auxiliary agent can be transferred to the surface after strong UV curing, so that the surface smoothness is improved, and the demolding is easy.
In addition, in order to improve recoatability and facilitate surface inking or other coating, it is preferable that the decorative film has a surface dyne value of more than 40, and the surface dyne value matches the surface dyne value of the soft template, which is more advantageous for removal of the soft mold. Further preferably, the UV energy for curing in the step S4 is 10 to 100mj/cm2And curing the molding adhesive layer by low-energy UV irradiation to partially cure and dry the surface of the molding adhesive layer, so that the flexible mold is easy to demould. The soft mold is made of organic materials, and partial unreacted double bonds exist in the soft mold, so that chemical reaction is generated between the molding glue layer and the surface of the soft mold due to overhigh UV energy, the adhesive force is enhanced, and demolding is not facilitated.
When the decorative film of the present application is required to be applied to an environment where the requirement for hardness is high, it is preferable that the above-mentioned transfer method further includes a process of heat curing the decorative film. The decorative film is cured by heat energy, so that the hardness of the decorative film is further improved.
The above glue for forming the decorative film can refer to the forming raw material of the decorative film in the prior art, and in order to adapt to the transfer printing method and the matching with the flexible mold, the glue preferably comprises the following components in parts by weight: 45-70 parts of oligomer, 10-30 parts of second monomer, 2-8 parts of second photoinitiator and 0-5 parts of second auxiliary agent, wherein the oligomer is preferably polyurethane acrylate or pure acrylate; preferably the second monomer is a mixture of one or more of the group consisting of isobornyl acrylate, johnson chemical EM39(HEMAP) 2-hydroxyethyl methacrylate phosphate, tetrahydrofurfuryl acrylate; preferably, the second photoinitiator is an alpha-hydroxyalkanone photoinitiator or an acyl oxide photoinitiator; preferably, the second auxiliary agent is polyether modified acrylate or organic silicon modified acrylate. The polyether modified acrylate or the organic silicon modified acrylate is used as a second auxiliary agent, and the surface dyne value of the decorative film is improved.
The transfer printing method is suitable for transfer printing of the decorative film on various substrates, particularly glass substrates such as common glass or toughened glass, and the thickness of the glass substrates is preferably 0.5-5 cm.
The soft base material used in the process of forming the soft mold can be a plastic base material with certain flexibility such as PET, PMMA or PC, and the thickness of the soft base material is preferably 25-250 μm for easy removal.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
Preparation of decorative films
(1) 20 parts of urethane acrylate EO-2238, 10 parts of urethane acrylate 6158B-80, 15 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 30 parts of monomer EM221, 4 parts of initiator 184 and 1 part of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
(2) 40 parts of polyurethane acrylate EB8210, 10 parts of polyurethane acrylate XP2765, 17 parts of pure acrylate 353L, 10 parts of monomer EM39, 15 parts of monomer EM214, 4 parts of initiator 184, 1 part of initiator TPO and 3 parts of auxiliary agent BYK-3560 are mixed and stirred for 30min to obtain the decorative film adhesive.
(3) Selecting 188 mu m thick PET as a soft base material, arranging master mould glue on a metal mould, arranging the soft base material on the master mould glue, and rolling the soft base material by using a roller to ensure that the master mould glue is uniform; curing the rolled master mold adhesive by adopting ultraviolet light to obtain a soft mold sheet, and using 50000mj/cm for the soft mold sheet before use2The energy of (3) to cure.
(4) Selecting 0.5 cm-thick toughened glass as a substrate, coating the decorative film adhesive on the substrate, modeling the decorative film adhesive by using a soft die sheet, and then adopting 50mj/cm2The energy of the ultraviolet light curing decorative film adhesive is torn off the soft mold sheet, and the decorative film of the embodiment 1 can be obtained.
Example 2
Preparation of decorative films
(1) 20 parts of urethane acrylate EO-2238, 10 parts of urethane acrylate 6158B-80, 15 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 30 parts of monomer EM221, 4 parts of initiator 184 and 1 part of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
(2) 40 parts of polyurethane acrylate EB8210, 10 parts of polyurethane acrylate XP2765, 17 parts of pure acrylate 353L, 10 parts of monomer EM39, 15 parts of monomer EM214, 4 parts of initiator 184, 1 part of initiator TPO and 3 parts of auxiliary agent BYK-3560 are mixed and stirred for 30min to obtain the decorative film adhesive.
(3) Selecting 188 mu m thick PET as a soft base material, arranging master mould glue on a metal mould, arranging the soft base material on the master mould glue, and rolling the soft base material by using a roller to ensure that the master mould glue is uniform; curing the rolled master mold adhesive by adopting ultraviolet light to obtain a soft mold sheet, and using 50000mj/cm for the soft mold sheet before use2The energy of (3) to cure.
(4) Selecting 0.5 cm-thick toughened glass as a base material, coating the decorative film adhesive on the base material, modeling the decorative film adhesive by using a soft die sheet, and then adopting 100mj/cm2The energy of the ultraviolet light curing decorative film adhesive is torn off the soft mold sheet, and the decorative film of the embodiment 2 can be obtained.
Example 3
Preparation of decorative films
(1) 20 parts of urethane acrylate EO-2238, 10 parts of urethane acrylate 6158B-80, 15 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 30 parts of monomer EM221, 4 parts of initiator 184 and 1 part of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
(2) 40 parts of polyurethane acrylate EB8210, 10 parts of polyurethane acrylate XP2765, 17 parts of pure acrylate 353L, 10 parts of monomer EM39, 15 parts of monomer EM214, 4 parts of initiator 184, 1 part of initiator TPO and 3 parts of auxiliary agent BYK-3560 are mixed and stirred for 30min to obtain the decorative film adhesive.
(3) Selecting 188-micron-thick PET as a base material, arranging master mold glue on a metal mold, arranging a soft base material on the master mold glue, and rolling the soft base material by using a roller to ensure that the master mold glue is uniform; curing the rolled master mold adhesive by adopting ultraviolet light to obtain a soft mold sheet, and using 50000mj/cm for the soft mold sheet before use2The energy of (3) to cure.
(4) Selecting 0.5 cm-thick toughened glass as a substrate, coating the decorative film adhesive on the substrate, modeling the decorative film adhesive by using a soft die sheet, and then adopting 500mj/cm2The ultraviolet light of energy solidifies the decorative film adhesive, tears off the soft mould sheet, can obtain the decorative film of example 3.
Example 4
(1) 20 parts of urethane acrylate EO-2238, 10 parts of urethane acrylate 6158B-80, 15 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 30 parts of monomer EM221, 4 parts of initiator 184 and 1 part of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
(2) Mixing and stirring 40 parts of polyurethane acrylate EB8210, 10 parts of polyurethane acrylate XP2765, 20 parts of pure acrylate 353L, 10 parts of monomer EM39, 15 parts of monomer EM214, 4 parts of initiator 184 and 1 part of initiator TPO for 30min to obtain the decorative film adhesive.
(3) Selecting 188 mu m thick PET as a soft base material, arranging master mould glue on a metal mould, arranging the soft base material on the master mould glue, and rolling the soft base material by using a roller to ensure that the master mould glue is uniform; curing the rolled master mold adhesive by adopting ultraviolet light to obtain a soft mold sheet, and using 50000mj/cm for the soft mold sheet before use2The energy of (3) to cure.
(4) Selecting 0.5 cm-thick toughened glass as a substrate, coating the decorative film adhesive on the substrate, modeling the decorative film adhesive by using a soft die sheet, and then adopting 50mj/cm2The ultraviolet light of energy solidifies the decorative film adhesive, tears off the soft mould sheet, can obtain the decorative film of example 4.
Example 5
The difference from example 1 is that 20000mj/cm is used for the soft mold sheet2The energy of (3) to cure.
Example 6
The difference from example 1 is that 100000mj/cm was used for the soft mold sheet2The energy of (3) to cure.
Example 7
The difference from example 1 is that 10000mj/cm is used for the soft mold sheet2The energy of (3) to cure.
Example 8
The difference from example 1 is that 110000mj/cm is used for the soft mold sheet2The energy of (3) to cure.
Example 9
The difference from example 1 is that 200mj/cm is used2Energy ultraviolet light is used for curing the decorative film adhesive.
Example 10
The difference from example 1 is that 10mj/cm is used2Energy ultraviolet light is used for curing the decorative film adhesive.
Example 11
The difference from example 1 is that:
20 parts of urethane acrylate EO-2238, 5 parts of urethane acrylate 6158B-80, 5 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 20 parts of monomer EM221 and 8 parts of initiator 184 are mixed and stirred for 30min to obtain the master mould adhesive.
20 parts of urethane acrylate EB8210, 15 parts of urethane acrylate XP2765, 10 parts of pure acrylate 353L, 20 parts of monomer EM39, 10 parts of monomer EM214, 4 parts of initiator 184, 4 parts of initiator TPO and 3 parts of auxiliary agent BYK-3560 are mixed and stirred for 30min to obtain the decorative film adhesive.
Example 12
The difference from example 1 is that:
10 parts of urethane acrylate EO-2238, 5 parts of urethane acrylate 6158B-80, 20 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 10 parts of monomer EM221, 2 parts of initiator 184 and 2 parts of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
Mixing and stirring 40 parts of polyurethane acrylate EB8210, 10 parts of polyurethane acrylate XP2765, 10 parts of pure acrylate 353L, 5 parts of monomer EM39, 5 parts of monomer EM214, 1 part of initiator 184, 1 part of initiator TPO and 5 parts of auxiliary agent BYK-3560 for 30min to obtain the decorative film adhesive.
Comparative example 1
The difference from example 1 is that 20 parts of urethane acrylate EO-2238, 20 parts of urethane acrylate 6158B-80, 2 parts of silicon modified resin SIU2400, 20 parts of monomer EM214, 20 parts of monomer EM221 and 4 parts of initiator 184 are mixed and stirred for 30min to obtain a master batch.
Comparative example 2
The difference from the example 1 is that 20 parts of urethane acrylate EO-2238, 10 parts of urethane acrylate 6158B-80, 25 parts of silicon modified resin SIU2400, 10 parts of monomer EM214, 10 parts of monomer EM221, 4 parts of initiator 184 and 1 part of auxiliary agent BYK-UV3505 are mixed and stirred for 30min to obtain the master mould adhesive.
The preparation processes and the comprehensive evaluation of the performance of the decorative film are carried out in the examples 1-12 and the comparative examples 1-2, wherein the dyne value is determined by a German arcotest dyne pen. The average distribution is drawn, the largest Dain pen without any bead point within 3 seconds is the Dain value test, the hardness is tested by a pencil hardness tester according to GB/T6739-.
TABLE 1
As can be seen from the comparison between the examples and the comparative examples, the surface dyne value of the flexible mold formed by curing the UV-curable adhesive composition of the present application varies with the curing energy, but all of them can be controlled below 30, and the flexible mold can be easily separated from the decorative adhesive film.
In addition, according to the comparison of examples 1, 2, 3, 9 and 10, it can be seen that the hardness of the decorative adhesive film is increased with the increase of the curing energy of the decorative adhesive film, but the excessively high UV energy causes the decorative adhesive film to chemically react with the surface of the decorative adhesive film, resulting in the increase of the adhesion force, so that the difficulty of demolding is increased, but there is still a significant advantage over the demolding of the comparative example.
According to the proportion of the embodiment 1 and the embodiments 5 to 8, the hardness of the UV curing adhesive composition is improved along with the improvement of curing energy of the soft mold, the surface structure of the decorative film is not easy to deform, and on the other hand, the auxiliary agent can be migrated to the surface after strong UV curing, so that the surface smoothness is improved, and the demolding is easy.
Meanwhile, as can be seen from the comparison between example 1 and example 4, the surface dyne value of the decorative adhesive film is obviously reduced due to the removal of the surface-improving additive, and therefore, the recoatability of the surface of the decorative adhesive film is affected.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the UV curing adhesive composition comprises the polyurethane acrylate oligomer and the silicon modified resin in the above dosage, so that the surface dyne value of the UV curing adhesive composition is controllable through curing under UV irradiation, when the UV curing adhesive composition is used as a soft mold, the difference between the surface dyne value of the UV curing adhesive composition and the surface dyne value of a decorative film formed through curing is controlled to be large, the purpose that the UV curing adhesive composition and the decorative film are easy to separate can be realized, and the problem that the soft mold is difficult to demold is solved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A transfer method, characterized by comprising:
step S1, preparing a soft mold by adopting the UV curing adhesive composition;
step S2, glue for manufacturing the decorative film is arranged on the base material;
step S3, modeling the glue by using the soft mold to obtain a modeled glue layer; and
step S4, curing the molding glue layer to obtain the decorative film,
the UV curable adhesive composition includes:
15-35 parts of a polyurethane acrylate oligomer;
5-20 parts of silicon modified resin;
30-50 parts of a first monomer; and
2-8 parts of a first light initiator,
the polyurethane acrylate oligomer is a mixture formed by one or more of the group consisting of double bonds 583-1, cyanotex EB8465, cyanotex EB264, Changxing DR-U025, Changxing 6158B-80 and Changxing DR-U029; the silicon modified resin is a mixture formed by one or more of the group consisting of Meiyuan SIU2400, Cyanote EB1360 and Changxing DR-U188C; the first monomer is one or a mixture of more of trimethylolpropane triacrylate, tetrahydrofurfuryl acrylate, ethoxylated trimethylolpropane trimethacrylate and 1, 6-hexanediol diacrylate; the first photoinitiator is alpha-hydroxyalkanone photoinitiator or acyl oxide photoinitiator,
the glue comprises the following components in parts by weight: 45-70 parts of oligomer, 10-30 parts of second monomer, 2-8 parts of second photoinitiator and 0-5 parts of second auxiliary agent, wherein the oligomer is polyurethane acrylate or pure acrylate; the second monomer is a mixture formed by one or more of isobornyl acrylate, Changxing chemical 2-hydroxyethyl methacrylate phosphate and tetrahydrofurfuryl acrylate; the second photoinitiator is an alpha-hydroxyalkanone photoinitiator or an acyl oxide photoinitiator; the second auxiliary agent is polyether modified acrylate or organic silicon modified acrylate,
the surface dyne value of the flexible mold is less than 30, and the surface dyne value of the decorative film is more than 40.
2. The transfer method according to claim 1, wherein the step S1 includes:
disposing a mixture of the UV curable adhesive composition on a metal mold;
arranging a soft base material on the mixture, and rolling the soft base material;
solidifying the rolled mixture to obtain a solidified layer; and
and removing the metal mold, and carrying out UV curing on the cured layer to obtain the flexible mold.
3. The transfer printing method according to claim 2, wherein the UV energy used for the UV curing is 20000 to 100000mj/cm2。
4. The transfer method according to claim 1, wherein the curing of step S4 is performed with UV energy of 10-100 mj/cm2。
5. The transfer method according to claim 1, further comprising a process of heat curing the decoration film.
6. The transfer printing method according to claim 1, wherein the substrate is glass.
7. The transfer printing method according to claim 1, wherein the UV-curable adhesive composition further comprises a first auxiliary agent in an amount of 2 parts by weight or less, and the first auxiliary agent is polyether modified silicone.
8. The transfer method according to claim 7, wherein the polyether modified silicone is a mixture of one or more selected from the group consisting of BYK-333, BYK-UV3500 and BYK-UV 3505.
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| CN107571656A (en) * | 2017-08-25 | 2018-01-12 | 苏州安江源光电科技有限公司 | A kind of method for rupture pressure disc UV transfer textures |
| CN109575864A (en) * | 2017-09-28 | 2019-04-05 | 比亚迪股份有限公司 | Ultraviolet cured adhesive composition, transfer method, transfer pattern and shell |
| CN107936904A (en) * | 2017-11-23 | 2018-04-20 | 苏州创佳电子材料有限公司 | The application of heat-resistant adhesive |
| CN109988540B (en) * | 2017-12-29 | 2020-12-25 | 比亚迪股份有限公司 | LED light-cured adhesive composition, transfer-printed curing adhesive and preparation method |
| CN112521872B (en) * | 2019-09-18 | 2022-08-09 | 苏州苏大维格科技集团股份有限公司 | Manufacturing method and application of transfer film |
| CN113980628B (en) * | 2021-11-30 | 2023-06-23 | 福建省安元光学科技有限公司 | UV adhesive formula suitable for vulcanization demolding of silica gel |
| CN115122811A (en) * | 2022-06-22 | 2022-09-30 | 广东普赛尔新材料有限公司 | Production method of special-shaped structure decorative face shell and special-shaped structure decorative face shell |
| CN115946463A (en) * | 2023-01-30 | 2023-04-11 | 歌尔股份有限公司 | UV rendition technology and UV rendition frock |
| CN117624689A (en) * | 2023-12-01 | 2024-03-01 | 江苏怡丽科姆新材料股份有限公司 | High-wear-resistance fingerprint-proof antiglare film and preparation method thereof |
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