CN113602032A - High-temperature-resistant holographic gold stamping film, gold stamping plastic part and preparation method - Google Patents
High-temperature-resistant holographic gold stamping film, gold stamping plastic part and preparation method Download PDFInfo
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- CN113602032A CN113602032A CN202110911623.4A CN202110911623A CN113602032A CN 113602032 A CN113602032 A CN 113602032A CN 202110911623 A CN202110911623 A CN 202110911623A CN 113602032 A CN113602032 A CN 113602032A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010931 gold Substances 0.000 title claims abstract description 73
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 73
- 229920003023 plastic Polymers 0.000 title claims abstract description 43
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 238000000576 coating method Methods 0.000 claims abstract description 95
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- 239000012948 isocyanate Substances 0.000 claims abstract description 54
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 54
- 239000011241 protective layer Substances 0.000 claims abstract description 45
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 42
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 42
- 238000003825 pressing Methods 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000011253 protective coating Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
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- 229920002799 BoPET Polymers 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
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- 239000011247 coating layer Substances 0.000 claims 1
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- 238000005034 decoration Methods 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000002585 base Substances 0.000 description 21
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 20
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 210000004243 sweat Anatomy 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1729—Hot stamping techniques
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/172—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The embodiment of the application provides a high-temperature-resistant holographic gold stamping film, a gold stamping plastic part and a preparation method, and relates to the field of gold stamping films. The high-temperature-resistant holographic gold-stamping film comprises a base film, a release layer, a protective layer, a mould pressing layer, a metal coating and a glue layer which are sequentially overlapped from bottom to top, wherein the surface of the mould pressing layer, which is close to the metal coating, is provided with a holographic pattern microstructure, the coatings corresponding to the protective layer and the mould pressing layer respectively contain polyhydroxy acrylic resin, amino resin and isocyanate, and the dosage ratio of the amino resin to the isocyanate in the coating corresponding to the protective layer is 2-4: 1, the dosage ratio of the amino resin to the isocyanate in the coating corresponding to the mould pressing layer is 0.5-1: 1. the high-temperature-resistant holographic gold stamping film has excellent physical and chemical resistance, can resist high-temperature hot stamping and die pressing, and meets higher decoration requirements in the field of plastic gold stamping.
Description
Technical Field
The application relates to the field of gold stamping films, in particular to a high-temperature-resistant holographic gold stamping film, a gold stamping plastic part and a preparation method.
Background
At present, some plastic surfaces are decorated by using gold stamping films, such as hot stamping character information, decorative strips and the like on a household electrical appliance shell, but the defects of low hot stamping temperature, insufficient physical and chemical resistance and insufficient brightness generally exist, and the gold stamping films mainly have the decoration effect of an alumite layer, cannot carry holographic patterns, have poor decoration effect and cannot meet higher decoration requirements of users.
The holographic bronzing film usually comprises a base film layer, a release layer, an imaging layer, a metal coating and an adhesive layer, and can be widely applied to the fields of cigarette and wine packaging, medical packaging, daily chemical product packaging and the like. The holographic gold stamping film in the fields of cigarette and wine packaging, medicine packaging and the like is mainly required to have good aesthetic property, good anti-counterfeiting property and good hot stamping property, and has no special requirement on the high temperature resistance of the gold stamping film; but for the field of plastic gold stamping, the common holographic gold stamping film cannot meet the requirements. The reason is that the hot stamping is carried out on the surface of the plastic part, the hot stamping temperature is generally higher, and the common holographic gold stamping film has the appearance abnormalities of gold stamping, whitening, fogging, color flooding and the like at the temperature of 200-; and the microstructure of the holographic pattern is damaged due to high-temperature mould pressing, so that the holographic pattern is distorted, and the decorative effect is greatly reduced.
Therefore, there is a need to develop a holographic bronzing film with high temperature hot stamping and die pressing resistance and excellent physical and chemical resistance to meet the higher decoration requirements in the plastic bronzing field.
Disclosure of Invention
An object of the embodiment of the application is to provide a high-temperature-resistant holographic gold stamping film, a gold stamping plastic part and a preparation method thereof, wherein the high-temperature-resistant holographic gold stamping film, the gold stamping plastic part and the preparation method have excellent physical and chemical resistance, can resist high-temperature hot stamping and mould pressing, and meet higher decoration requirements in the field of plastic gold stamping.
In a first aspect, an embodiment of the present application provides a high temperature resistant holographic gold stamping film, which includes a base film, a release layer, a protective layer, a mold pressing layer, a metal coating and a glue layer, which are sequentially stacked from bottom to top, wherein the surface of the mold pressing layer close to the metal coating has a holographic pattern microstructure, the coatings corresponding to the protective layer and the mold pressing layer both contain polyhydroxy acrylic resin, amino resin and isocyanate, and the usage ratio of the amino resin to the isocyanate in the coating corresponding to the protective layer is 2-4: 1, the dosage ratio of the amino resin to the isocyanate in the coating corresponding to the mould pressing layer is 0.5-1: 1.
in the implementation process, the coatings corresponding to the protective layer and the mould pressing layer adopt the matching of amino resin and isocyanate as curing agents, so that polyhydroxy acrylic resin is cured to form polyurethane resin with a cross-linked network, and the performance characteristics of the coating are adjusted by adjusting the proportion of the two curing agents of the amino resin and the isocyanate, so that different coatings can adapt to different use requirements. Particularly, the protective layer has excellent tolerance, which can ensure that the following structural layers are not damaged by the outside after use, and the tolerance can be divided into two aspects of physics and chemistry, wherein the physical tolerance comprises scratch resistance, wear resistance and the like, and the chemical tolerance comprises acid and alkali resistance, chemical reagent resistance, ultraviolet aging resistance and the like; the die pressing layer can form a holographic pattern microstructure through die pressing, and has good holographic effect and excellent physical and chemical resistance. Therefore, the high-temperature-resistant holographic gold stamping film disclosed by the embodiment of the application has excellent high temperature resistance and chemical resistance, a certain pressure is set for hot stamping in the gold stamping application on the surface of an actual plastic substrate, the hot stamping is finished at the highest energy under the condition of 300 ℃, the appearance abnormity such as gold stamping whitening, fogging and flooding cannot occur, meanwhile, the holographic pattern microstructure on the die pressing layer cannot be damaged, the holographic effect is still clear and visible, the integrity of the holographic pattern after heat transfer is ensured, and then the decorative effect of the gold stamping film is ensured.
In one possible implementation, the hydroxyl functionality of the polyhydroxyacrylic resin is between 1 and 3, and the molecular weight is between 10000-;
and/or the amino resin is methylated amino resin;
and/or the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 35 percent.
In the implementation process, the acrylic resin has good physical and mechanical properties, excellent weather resistance, chemical resistance and water resistance and high gloss and color retention, the hydroxyl functional group of the acrylic resin is increased, so that the acrylic resin can be matched with a curing agent for use to prepare the thermosetting acrylic resin with a cross-linked network, and the acrylic resin has more excellent wear resistance and scratch resistance besides the general properties (heat resistance, water resistance and solvent resistance) of the acrylic resin. The main curing agent comprises epoxy resin, amino resin and isocyanate; for the (exchange) reaction of hydroxyl acrylic resin and amino resin and the ether of alkoxy methyl on the hydroxyl and amino resin, the selected methylated amino resin has good compatibility with the hydroxyl acrylic resin, the reaction rate is general, high temperature or catalysis is needed to promote the reaction rate, and the formed thermosetting acrylic resin has high hardness, excellent temperature resistance and weather resistance; for hydroxyl acrylic resin and isocyanate, hydroxyl and isocyanate group react to produce carbamate, diphenylmethane diisocyanate is selected, the reaction rate is high, and the formed thermosetting acrylic resin has good light stability, weather resistance and mechanical property.
In one possible implementation, the base film is a PET film with a thickness of 10-25 μm;
and/or the release layer is made of water-based polyurethane wax and has the thickness of 0.5-1.5 mu m;
and/or the adhesive layer is made of acrylic resin and has a thickness of 0.5-3 μm.
In one possible implementation, the thickness of the protective layer is 0.5-1 μm;
and/or the thickness of the molding layer is 0.5-1 μm.
In one possible implementation, the metal plating layer is made of aluminum, magnesium, chromium or indium and has a thickness of 300-600 angstroms.
In a second aspect, an embodiment of the present application provides a method for preparing a high temperature resistant holographic bronzing film provided in the first aspect, which includes the following steps:
coating a coating corresponding to the protective layer on the surface of the base film with the release layer, and drying at 180-190 ℃ to form a protective coating;
coating a coating corresponding to the mold pressing layer on the surface of the protective coating, drying at the temperature of 140-;
and sequentially forming a metal coating and an adhesive layer on the surface of the mould pressing coating, curing to enable the protective coating to be cured to form a protective layer, and curing the mould pressing coating to form the mould pressing layer.
In the implementation process, the protective layer and the cured layer can be completely cured by controlling the proportion of the corresponding coating of the protective layer and the molded layer, and performing semi-curing, mold pressing and complete curing, so that the effect is good; the treatment process ensures the high temperature resistance of the whole finished film while the stamping film efficiently finishes the mould pressing procedure, and the stamping film finishes the stamping under the condition of 300 ℃ at the highest energy in the actual stamping application of the surface of the plastic substrate.
Specifically, in the process of preparing the high-temperature-resistant holographic bronzing film, by matching and using two curing agents, namely amino resin and isocyanate, rigid groups (mainly an amino resin highly etherified ring structure) are introduced into a cross-linked network of polyurethane formed by curing polyhydroxy acrylic resin, so that the heat resistance, physical resistance and chemical resistance of the polyurethane are improved; simultaneously, by adjusting the curing agent: the cross-linking state of polyurethane in different coatings is controlled by the proportion of the amino resin and the isocyanate, the coating performance stability of the coating is ensured, the processing feasibility of the subsequent mould pressing procedure is greatly improved, and finally the polyurethane is completely shaped by a post-curing mode, so that the bronzing film has two excellent characteristics of high temperature resistance and holographic pattern microstructure carrying.
In one possible implementation, the curing temperature is 60-120 ℃, and the curing time is 24-72 h.
In the implementation process, the protective layer and the mould pressing layer are completely solidified through curing at a certain temperature.
In a third aspect, an embodiment of the present application provides a gold stamping plastic part, which includes a release layer, a protective layer, a mold pressing layer, a metal plating layer, a glue layer, and a plastic substrate, which are sequentially stacked in the high temperature resistant holographic gold stamping film provided in the first aspect.
In the implementation process, the high-temperature-resistant holographic gold stamping film is thermoprinted on the plastic base material, so that the decoration effect is good.
In a fourth aspect, an embodiment of the present application provides a method for preparing a gold stamping plastic part, which is provided by the third aspect, the side of the high temperature resistant holographic gold stamping film with the glue layer is gold stamped on the plastic substrate, and then the base film is peeled off and removed.
In the implementation process, the high-temperature-resistant holographic gold stamping film is high-temperature-resistant, and is convenient for gold stamping to be applied to the surface of the plastic substrate.
In one possible implementation, the pressure for gold stamping is 0.5-0.8Mpa, and the temperature is 220-.
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 high-temperature-resistant holographic bronzing film provided in an embodiment of the present application;
fig. 2 is a schematic structural diagram of a bronzing element provided in an embodiment of the present application.
Icon: 100-high temperature resistant holographic gold stamping film; 110-a base film; 120-a release layer; 130-a protective layer; 140-a mold pressed layer; 141-holographic pattern microstructure; 150-metal plating; 160-glue layer; 170-plastic substrate; 200-gilding plastic piece.
Detailed Description
The inventor discovers that the mould pressing layer is generally a coating of a crosslinking system for forming polyurethane by polymerization of hydroxyl acrylic resin and curing agent isocyanate, has certain high temperature resistance and physical and chemical resistance, but the highest temperature resistance can only reach 180-plus-200 ℃, the hot stamping requirements under the hot stamping processes of 0.6Mpa and 220-plus-300 ℃ cannot be met during the hot stamping of the plastic surface, and the appearance abnormalities such as bronzing, blushing, flooding and the like are easy to appear; meanwhile, because the crosslinking reaction is difficult to control, the coating of a polyurethane crosslinking system is difficult to mold, the defects of weak holographic effect and low brightness are easy to occur when the crosslinking degree is too high, and the defects of plate sticking and peeling are easy to occur when the crosslinking degree is too low.
The high-temperature-resistant holographic gold stamping film provided by the embodiment of the application maintains the excellent tolerance of a reactive cross-linked material system, and simultaneously solves the problem that the gold stamping film is difficult to mold, so that the gold stamping film can have two excellent characteristics of high temperature resistance and holographic carrying. By matching and using the amino resin and the isocyanate curing agent, rigid groups are introduced into a cross-linked network of the polyurethane, so that the heat resistance, physical resistance and chemical resistance of the polyurethane are improved; meanwhile, the cross-linking state of polyurethane in different coatings is controlled by adjusting the proportion of the curing agent amino resin and the isocyanate, the coating performance stability of the coating is ensured, the feasibility of subsequent processing in a mould pressing procedure is greatly improved, and finally the polyurethane is completely shaped by a post-curing mode, so that the bronzing film has two excellent characteristics of high temperature resistance and holographic pattern carrying.
The technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, as presented in the figures, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present application, it should be noted that the terms "upper", "lower", "inner", "outer", and the like indicate orientations or positional relationships based on orientations or positional relationships shown in the drawings or orientations or positional relationships conventionally found in use of products of the application, and are used only for convenience in describing the present application and for simplification of description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present application.
In the description of the present application, it is also to be noted that, unless otherwise explicitly specified or limited, the term "disposed" is to be understood broadly, for example, as being fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
First embodiment
Referring to fig. 1, the high temperature resistant holographic bronzing film 100 provided in this embodiment includes a base film 110, a release layer 120, a protective layer 130, a mold pressing layer 140, a metal plating layer 150, and a glue layer 160, which are sequentially stacked from bottom to top, wherein the surface of the mold pressing layer 140 close to the metal plating layer 150 has a holographic pattern microstructure 141, and the holographic pattern microstructure 141 is formed on the mold pressing layer 140 by mold pressing.
In the embodiment of the present application, the base film 110 is a PET film having a thickness of 10 to 25 μm, and optionally 15 to 19 μm. In the present embodiment, the base film 110 is a high-brightness PET film having a thickness of 19 μm.
In the embodiment of the present application, the release layer 120 is made of water-based polyurethane wax, and the thickness is 0.5-1.5 μm. In this embodiment, the release layer 120 is formed by coating waterborne polyurethane, and the thickness is 0.8 μm.
In the embodiment of the present application, the coating corresponding to the protective layer 130 contains polyhydroxy acrylic resin, amino resin and isocyanate, the protective layer 130 is formed by coating a coating prepared from polyhydroxy acrylic resin, amino resin, isocyanate and other additives according to a certain ratio, wherein the ratio of the amount of the amino resin to the amount of the isocyanate is 2-4: 1. the paint corresponding to the protective layer 130 comprises the following components in parts by weight: 24-36 parts of polyhydroxy acrylic resin, 3-13.5 parts of amino resin, 3-13.5 parts of isocyanate, 0.01-0.02 part of ultraviolet absorbent, 0.01-0.02 part of catalyst, 0.01-0.04 part of flatting agent and 46-64 parts of solvent; the solvent comprises 16.1-22.4 parts of toluene, 6.9-9.6 parts of butanone, 3.3-4.6 parts of cyclohexanone and 19.7-27.4 parts of diacetone alcohol. Wherein, the hydroxyl functionality of the polyhydroxy acrylic resin is between 1 and 3, and the molecular weight is between 10000-; the amino resin is methylated amino resin; the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 35 percent; the auxiliary agent comprises an ultraviolet absorbent, a catalyst, a flatting agent and the like, wherein the ultraviolet absorbent is one or more of benzotriazole, and the catalyst is one or more of dibutyltin dilaurate or p-toluenesulfonic acid.
In this embodiment, the paint corresponding to the protective layer 130 includes, by weight: 30 parts of polyhydroxy acrylic resin, 11.25 parts of amino resin, 3.75 parts of isocyanate (the dosage ratio of the amino resin to the isocyanate is 3: 1), 0.02 part of ultraviolet absorber, 0.01 part of each of catalysts of dibutyltin dilaurate and p-toluenesulfonic acid, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 19.25 parts of toluene, 8.25 parts of butanone, 3.93 parts of cyclohexanone and 23.57 parts of diacetone alcohol. Wherein the hydroxyl functionality of the polyhydroxy acrylic resin is 1.5, and the molecular weight is 30000; the amino resin is methylated amino resin; the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 37 percent.
In the embodiment of the present application, the thickness of the protective layer 130 is 0.5 to 1 μm. In this embodiment, the thickness of the protection layer 130 is 0.5 μm.
In the embodiment of the present application, the coatings corresponding to the molded layer 140 all contain polyhydroxy acrylic resin, amino resin and isocyanate, the molded layer 140 is formed by coating a coating prepared from polyhydroxy acrylic resin, amino resin, isocyanate and other additives according to a certain ratio, wherein the ratio of the amount of the amino resin to the amount of the isocyanate is 0.5-1: 1. the coating corresponding to the mold pressing layer 140 comprises the following components in parts by weight: 24-36 parts of polyhydroxy acrylic resin, 3-13.5 parts of amino resin, 3-13.5 parts of isocyanate, 0.01-0.02 part of ultraviolet absorbent, 0.01-0.04 part of flatting agent and 46-64 parts of solvent; the solvent comprises 32.2 to 44.8 portions of toluene and 13.8 to 19.2 portions of butanone. Wherein, the hydroxyl functionality of the polyhydroxy acrylic resin is between 1 and 3, and the molecular weight is between 10000-; the amino resin is methylated amino resin; the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 35 percent; the auxiliary agent comprises an ultraviolet absorbent, a flatting agent and the like, and the ultraviolet absorbent is one or more of benzotriazoles.
In this embodiment, the coating corresponding to the mold pressing layer 140 includes, in parts by weight: 30 parts of polyhydroxy acrylic resin, 7.5 parts of amino resin, 7.5 parts of isocyanate (the dosage ratio of the amino resin to the isocyanate is 1: 1), 0.02 part of ultraviolet absorber, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 38.5 parts of toluene and 16.5 parts of butanone. Wherein the hydroxyl functionality of the polyhydroxy acrylic resin is 1.5, and the molecular weight is 30000; the amino resin is methylated amino resin with high imino; the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 37 percent.
In the embodiment of the present application, the thickness of the mold layer 140 is 0.5 to 1 μm. In this embodiment, the thickness of the mold layer 140 is 0.5 μm.
In the embodiment of the present application, the material of the metal plating layer 150 is one of aluminum, magnesium, chromium, indium, etc., and the thickness is 300-600 angstroms. In this embodiment, the metal plating layer 150 is made of aluminum and has a thickness of 400 ± 30 angstroms.
In the embodiment of the present application, the adhesive layer 160 is made of acrylic resin, and has a thickness of 0.5-5 μm, and optionally 1-3 μm. In this embodiment, the thickness of the glue layer 160 is 2 μm.
In addition, the embodiment of the application also provides a preparation method of the high-temperature-resistant holographic gold stamping film 100, which comprises the following steps:
(1) coating the coating corresponding to the protective layer 130 on the surface of the base film 110 with the release layer 120, and drying at 190 ℃ at the linear speed of 60-90m/min to form a high-toughness coating with high crosslinking degree, namely a protective coating.
(2) Coating the coating corresponding to the mold pressing layer 140 on the surface of the protective coating, and drying at the temperature of 140 ℃ and 150 ℃, wherein the linear speed during drying is between 60 and 90m/min, so as to form a prepolymer coating with lower crosslinking degree, and the curing degree is not high; and then the holographic pattern microstructure 141 is molded on the surface of the prepolymer coating at the temperature of 200-220 ℃, and the molding method is to mold by a molding press at the linear speed of 20-50m/min, and to obtain the molded coating while imprinting and curing.
(3) And sequentially forming a metal plating layer 150 and an adhesive layer 160 on the surface of the die-pressed coating, curing for 24-72h in a curing chamber at 60-120 ℃ to completely cure the protective coating to form a protective layer 130, and completely curing the die-pressed coating to form a die-pressed layer 140.
In the embodiment of the present application, the metal plating layer 150 may be formed first and then cured, or the metal plating layer 150 and the adhesive layer 160 may be formed after curing. As an embodiment, after the corresponding coating of the release layer 120, the protective layer 130, and the mold layer 140 is completed on the base film 110, molding is performed using a molding machine; transferring the semi-finished film into a curing chamber after the aluminum plating is finished; and after the curing is finished, coating the adhesive layer 160 on the semi-finished film on a high-speed coating machine to finally obtain the finished film.
Specifically, the embodiment provides a preparation method of the high-temperature-resistant holographic bronzing film 100, which includes the following steps:
s1, coating a layer of 0.8 μm aqueous polyurethane wax on the upper surface of the base film 110 to form the release layer 120.
S2, coating a layer of paint with the thickness of 0.5 mu m and prepared by polyhydroxy acrylic resin, amino resin, isocyanate and other auxiliary agents according to a certain proportion on the upper surface of the release layer 120, drying at 180 ℃ with the linear speed of 70m/min as a protective coating.
S3, coating a layer of paint with the thickness of 0.5 mu m and prepared by polyhydroxy acrylic resin, amino resin, isocyanate and other auxiliary agents according to a certain proportion on the upper surface of the protective coating, drying at 150 ℃ at the linear speed of 70m/min to be used as a prepolymer coating.
S4, die-pressing the holographic pattern microstructure 141 on the upper surface of the prepolymer coating, and die-pressing at 200 ℃ and a linear velocity of 30m/min by using a die press to obtain the die-pressed coating.
S5, evaporating a layer of aluminum with the thickness of 400 +/-30 angstroms on the upper surface of the die pressing coating to be used as the metal plating layer 150.
S6, baking the aluminized semi-finished film in a curing chamber at 60 ℃ for 48h, improving the crosslinking degree of a crosslinking system in the protective coating and the die pressing coating, forming the protective layer 130 and the die pressing layer 140, and improving the temperature resistance, physical resistance and chemical resistance of the protective layer 130 and the die pressing layer 140.
S7, coating an acrylic resin layer with a thickness of 1 μm on the upper surface of the metal plating layer 150 as the glue layer 160.
In the above preparation process, in the coating forming the protective layer 130, the amino resin and the isocyanate as the curing agent account for more amino resins in parts by mass, and the ratio is 3: 1, the coating is catalyzed by a catalyst and dried under the coating conditions of 180 ℃ and 70m/min linear speed, and the protective layer 130 is rapidly cured to form a protective coating (high-toughness coating) with higher crosslinking degree; in the coating forming the molded layer 140, the amino resin as the curing agent and the isocyanate are the same in parts by mass, and the ratio is 1: 1, drying the coating under the coating conditions of 150 ℃ and a linear speed of 70m/min to form a prepolymer coating with a lower crosslinking degree; in the subsequent die pressing process, a die pressing machine is used for die pressing under the process conditions of 200 ℃ and 30m/min, the holographic patterns on the plate shaft nickel plate are completely transferred onto the die pressing layer 140, and meanwhile, the cross-linking reaction of polyurethane in the die pressing layer 140 is further promoted, so that a die pressing coating (high-toughness coating) with a higher cross-linking degree is formed; finally, the crosslinking and curing are completed by curing for 48 hours in a curing chamber at 60 ℃.
The partial performance of the high-temperature resistant holographic bronzing film 100 of the first embodiment is tested, and the testing method, the determination rule and the testing result are shown in the following table 1:
TABLE 1 high temperature resistance holographic film Performance test and results summary of the first example
The test result shows that the high-temperature-resistant holographic gold stamping film 100 in the embodiment of the application has good physical and chemical resistance, the performance of each aspect can meet the test requirements of the existing manufacturers, and the requirements of products with long service cycles of plastic base materials 170 products can be completely met through more than ten resistance tests such as wear resistance, scratch resistance, high and low temperature impact resistance, salt water resistance, alcohol resistance, artificial sweat resistance, hydrochloric acid resistance, aging resistance and the like required by household appliance manufacturers, so that the high-temperature-resistant holographic gold stamping film 100 is suitable for gold stamping on the surface of the plastic base materials 170.
Comparative example 1
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the molded layer in this comparative example does not contain an amino resin, and specifically, the coating corresponding to the molded layer comprises, in parts by weight: 30 parts of polyhydroxy acrylic resin, 15 parts of isocyanate, 0.02 part of ultraviolet absorber, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 38.5 parts of toluene and 16.5 parts of butanone.
Comparative example 2
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the molded layer in this comparative example does not contain isocyanate, and specifically, the coating corresponding to the molded layer comprises, in parts by weight: 30 parts of polyhydroxy acrylic resin, 15 parts of amino resin, 0.02 part of ultraviolet absorbent, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 38.5 parts of toluene and 16.5 parts of butanone.
Comparative example 3
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the molded layer in the comparative example comprises the following components in parts by weight: 30 parts of polyhydroxy acrylic resin, 10 parts of amino resin, 5 parts of isocyanate (the dosage ratio of the amino resin to the isocyanate is 2: 1), 0.02 part of ultraviolet absorbent, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 38.5 parts of toluene and 16.5 parts of butanone.
TABLE 2 comparison of embossing Properties of holographic bronzing films of comparative examples
As can be seen from Table 2, if the molded layer is not used according to the coating corresponding to the molded layer in the embodiment of the present application, the molding effect of the corresponding product is poor.
Comparative example 4
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the protective layer in the comparative example does not contain an amino resin, and specifically, the coating corresponding to the protective layer comprises the following components in parts by weight: 30 parts of polyhydroxy acrylic resin, 15 parts of isocyanate, 0.02 part of ultraviolet absorbent, 0.01 part of each of catalysts of dibutyltin dilaurate and p-toluenesulfonic acid, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 19.25 parts of toluene, 8.25 parts of butanone, 3.93 parts of cyclohexanone and 23.57 parts of diacetone alcohol.
Comparative example 5
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the protective layer in the comparative example does not contain isocyanate, and specifically, the coating corresponding to the protective layer comprises the following components in parts by weight: 30 parts of polyhydroxy acrylic resin, 15 parts of amino resin, 0.02 part of ultraviolet absorbent, 0.01 part of each of catalysts dibutyltin dilaurate and p-toluenesulfonic acid, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 19.25 parts of toluene, 8.25 parts of butanone, 3.93 parts of cyclohexanone and 23.57 parts of diacetone alcohol.
Comparative example 6
This comparative example provides a holographic bronzing film that is substantially the same as the high temperature resistant holographic bronzing film 100 of the first example, except that: the coating corresponding to the protective layer in the comparative example comprises the following components in parts by weight: 30 parts of polyhydroxy acrylic resin, 7.5 parts of amino resin, 7.5 parts of isocyanate (the dosage ratio of the amino resin to the isocyanate is 1: 1), 0.02 part of ultraviolet absorber, 0.01 part of each of catalysts of dibutyltin dilaurate and p-toluenesulfonic acid, 0.02 part of flatting agent and 55 parts of solvent; the solvent comprises 19.25 parts of toluene, 8.25 parts of butanone, 3.93 parts of cyclohexanone and 23.57 parts of diacetone alcohol.
TABLE 3 comparison of the main Properties of the holographic bronzing film of the comparative example
As can be seen from Table 3, if the protective layer is not used according to the coating corresponding to the protective layer in the examples of the present application, the weather resistance, the temperature resistance and the salt water resistance of the corresponding product are poor.
Second embodiment
Referring to fig. 2, a gold stamping plastic part 200 provided in this embodiment includes a release layer 120, a protective layer 130, a stamping layer 140, a metal plating layer 150, a glue layer 160, and a plastic substrate 170, which are sequentially stacked in the high-temperature-resistant holographic gold stamping film 100 provided in the first embodiment. The plastic substrate 170 is made of one of PS, ABS, PP, PET, ASA, and the like. The gold stamping pattern layer composed of the release layer 120, the protective layer 130, the molding layer 140, the metal plating layer 150 and the adhesive layer 160 on the surface of the plastic substrate 170 has a decorative effect.
The embodiment of the application also provides a preparation method of the gold stamping plastic part 200, which comprises the steps of gold stamping the side, provided with the adhesive layer 160, of the high-temperature resistant holographic gold stamping film 100 on the plastic base material 170, and then peeling off and removing the base film 110. The gold stamping pressure is 0.5-0.8Mpa, and the temperature is 220-.
Specifically, the preparation method of the bronzing plastic part 200 of the embodiment is as follows:
firstly, setting technological parameters of an automatic stamping machine according to a stamping technological sheet, wherein the pressure and the temperature are respectively set to be 0.6Mpa and 260 ℃, fixing the plastic base material 170 at a preset position on the automatic stamping machine after an actual value reaches a set value, and finishing the stamping of the surface of the plastic base material 170 after a start button is pressed: separating the base film 110 from the release layer 120 in the high-temperature-resistant holographic gold stamping film 100, and thermally transferring other functional layers of the high-temperature-resistant holographic gold stamping film 100 except the base film 110 to the surface of the plastic base material 170 at 0.6Mpa and 260 ℃ to form the gold stamping plastic part 200.
Through the process, the high-temperature-resistant holographic gold stamping film 100 of the first embodiment can be hot stamped by using a silica gel stamping head under the pressure of 0.6MPa, the hot stamping can be completed at the highest temperature of 300 ℃, the appearance abnormalities such as bronzing, blushing, flooding and the like cannot occur, meanwhile, the holographic pattern microstructure 141 on the mould pressing layer 140 cannot be damaged, the holographic effect is still clear and visible, and the decorative effect of the gold stamping film is ensured. In the use process, the gold stamping pattern layer on the surface of the plastic substrate 170 can be used in a final use scene for a long time, the gold stamping pattern layer cannot be damaged, the long-term decoration effect is guaranteed, meanwhile, the appearance degree of the gold stamping pattern layer is improved due to the holographic pattern microstructure 141, and the grade and grade of the whole product are improved.
In summary, the high-temperature-resistant holographic gold stamping film, the gold stamping plastic part and the preparation method have excellent physical and chemical resistance, can resist high-temperature hot stamping and die pressing, and meet higher decoration requirements in the field of plastic gold stamping.
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 high-temperature-resistant holographic gold stamping film is characterized by comprising a base film, a release layer, a protective layer, a mould pressing layer, a metal coating and an adhesive layer which are sequentially overlapped from bottom to top, wherein the surface of the mould pressing layer close to the metal coating is provided with a holographic pattern microstructure, coatings corresponding to the protective layer and the mould pressing layer respectively contain polyhydroxy acrylic resin, amino resin and isocyanate, and the dosage ratio of the amino resin to the isocyanate in the coating corresponding to the protective layer is 2-4: 1, the dosage ratio of the amino resin to the isocyanate in the coating corresponding to the mould pressing layer is 0.5-1: 1.
2. the high temperature resistant holographic bronzing film of claim 1, wherein the hydroxyl functionality of the polyhydroxy acrylic resin is between 1 and 3, and the molecular weight is between 10000-;
and/or the amino resin is methylated amino resin;
and/or the isocyanate is diphenylmethane diisocyanate, and the mass fraction of the isocyanate is more than or equal to 35%.
3. The high-temperature-resistant holographic bronzing film according to claim 1, wherein the base film is a PET film with a thickness of 10-25 μm;
and/or the release layer is made of water-based polyurethane wax and has the thickness of 0.5-1.5 mu m;
and/or the adhesive layer is made of acrylic resin and has a thickness of 0.5-3 μm.
4. The high temperature resistant holographic bronzing film according to claim 1, wherein the thickness of the protective layer is 0.5-1 μm;
and/or the thickness of the moulding layer is 0.5-1 μm.
5. The high temperature resistant holographic gold stamping film as claimed in claim 1, wherein the metal plating layer is made of aluminum, magnesium, chromium or indium with a thickness of 300-600 angstroms.
6. The preparation method of the high-temperature-resistant holographic bronzing film according to claim 1, which comprises the following steps:
coating a coating corresponding to the protective layer on the surface of the base film with the release layer, and drying at 180-190 ℃ to form a protective coating;
coating a coating corresponding to the mold pressing layer on the surface of the protective coating, drying at the temperature of 140-;
and sequentially forming a metal coating and an adhesive layer on the surface of the mould pressing coating, curing to solidify the protective coating to form a protective layer, and solidifying the mould pressing coating to form a mould pressing layer.
7. The method for preparing the high-temperature-resistant holographic bronzing film according to claim 6, wherein the curing temperature is 60-120 ℃, and the curing time is 24-72 h.
8. A gold stamping plastic part, which is characterized by comprising the release layer, the protective layer, the stamping layer, the metal coating layer, the adhesive layer and a plastic substrate which are sequentially stacked in the high-temperature resistant holographic gold stamping film according to any one of claims 1 to 6.
9. The method for preparing a gold stamping plastic part according to claim 8, wherein the side of the high temperature resistant holographic gold stamping film with the glue layer is gold stamped on a plastic substrate, and then the base film is peeled off and removed.
10. The method of claim 9, wherein the pressure of the gold stamping is 0.5-0.8Mpa and the temperature is 220-300 ℃.
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