CN116410509A - Hardened film and preparation method thereof - Google Patents
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- CN116410509A CN116410509A CN202210079860.3A CN202210079860A CN116410509A CN 116410509 A CN116410509 A CN 116410509A CN 202210079860 A CN202210079860 A CN 202210079860A CN 116410509 A CN116410509 A CN 116410509A
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 31
- -1 acrylic polyol Chemical class 0.000 claims description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 19
- 150000002513 isocyanates Chemical class 0.000 claims description 19
- 229920005862 polyol Polymers 0.000 claims description 19
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000000016 photochemical curing Methods 0.000 claims description 13
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 3
- 238000010023 transfer printing Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 108
- 238000007639 printing Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to the technical field of in-mold transfer printing (IMR), in particular to a hardening film for IMR and a preparation method thereof. The invention provides a hardening film for in-mold transfer printing and a preparation method thereof, which aim to solve the problem that a hardening layer of the hardening film for in-mold transfer printing is difficult to peel off from a base material. The hardening film sequentially comprises a base material, a magnetron sputtering layer and a hardening layer. The hardening layer of the hardening film for in-mold transfer printing is easy to peel from the magnetron sputtering layer, so that the yield of products is greatly improved, and compared with the traditional process, the hardening film has the advantages that one layer of ink adhesion enhancing layer is omitted, and the production efficiency of the hardening film is improved.
Description
Technical Field
The invention relates to the technical field of in-mold transfer printing (IMR), in particular to a hardening film for IMR and a preparation method thereof.
Background
With the continuous development of surface treatment processes such as electroplating, paint spraying, real wood, thermal transfer printing, digital printing, electrophoresis, skin, water transfer printing and the like, people pay more attention to fashionable, environment-friendly and light design on the appearance design of industrial products. This has led to increasing attention to In-Mold transfer techniques (IMR) which can be integrally injection molded. The IMR technology is to print the pattern on the film, then place the film on the movable mold wall, then injection mold the plastic on the back ink layer of the film, finally tear the film off, transfer the pattern on the film to the surface of the plastic product, which is a technology for realizing the integrated molding of the decorative pattern and the plastic matrix.
The existing process for manufacturing the hardening film for in-mold transfer printing is complex, as shown in fig. 1, the hardening film is generally composed of a base film 01, a release layer 02, a hardening layer 03 and an ink adhesion enhancing layer 04, the release layer and the hardening layer are cured in a thermal reaction mode, the process is time-consuming and labor-consuming, the later sections are required to be subjected to processes such as ink printing, metal evaporation and the like, the process of heating for many times is carried out, the peeling force between the release layer and the hardening layer is increased due to heating, part of the hardening layer remains on the release layer when the hardening layer cannot be separated from the release layer or is peeled off, the product is scrapped, the later-section process of the IMR can be seriously influenced (seriously influencing the release layer to be generally coating a layer of silicone oil on the base film, the silicon content of the release layer is reduced due to many times of heating, and the peeling of the hardening layer is white in surface and poor in abrasion resistance), and the whole IMR membrane is finally influenced.
Disclosure of Invention
The invention provides a hardening film for in-mold transfer printing and a preparation method thereof, which aim to solve the problem that a hardening layer and a release layer of the existing hardening film for in-mold transfer printing are difficult to peel. The hardening layer of the hardening film for in-mold transfer printing is easy to peel from the magnetron sputtering layer, so that the yield of products is greatly improved, and compared with the traditional process, the hardening film has the advantages that one layer of ink adhesion enhancing layer is omitted, and the production efficiency of the hardening film is improved.
In order to solve the technical problems, the invention provides the following technical scheme.
The invention provides a hardening film which sequentially comprises a base material, a magnetron sputtering layer and a hardening layer.
Further, the magnetron sputtering layer is a silicon nitride layer or a silicon oxide layer.
The invention provides a hardening film which sequentially comprises a base material, a silicon nitride layer and a hardening layer.
The invention uses the magnetron sputtering layer to replace the traditional release layer, the magnetron sputtering layer does not improve the bonding force with the hardening layer due to the heating process, the stability of the stripping force between the base material and the hardening layer is enhanced, and meanwhile, the hardening layer does not have the condition of silicon transfer, so that the quality of the hardening film product is ensured.
Further, the hardened layer is formed of a photocurable composition.
Further, the photo-curing composition comprises 24-35 parts by weight of tetrafunctional polyurethane acrylate oligomer, 28-38 parts by weight of trimethylolpropane triacrylate, 7-10 parts by weight of acrylic polyol, 2-4 parts by weight of isocyanate, 0.3-0.7 part by weight of photoinitiator, 0.1-0.4 part by weight of flatting agent, 0.2-0.4 part by weight of nano silicon dioxide particles and 24-25 parts by weight of solvent butanone. The total parts by weight of the tetrafunctional urethane acrylate oligomer, trimethylolpropane triacrylate, acrylic polyol, isocyanate, photoinitiator, leveling agent, nano-silica particles, and solvent are 100 parts by weight.
The tetrafunctional urethane acrylate oligomer is the main resin. Trimethylolpropane triacrylate is the surface diluent. The acrylic polyol and the isocyanate are ink adhesion force increasing agents and are used for improving the adhesion force of the hardening layer and the ink layer. The nano silicon dioxide can enhance the hardness of the coating.
Further, the magnetron sputtering layer is a silicon nitride layer.
Further, the thickness of the magnetron sputtering layer is 30-70nm.
Further, the thickness of the hardened layer is 4-8 μm.
Further, the thickness of the substrate is 75-188 μm.
Further, the photo-curing composition comprises 28-30 parts by weight of tetrafunctional aliphatic polyurethane acrylate oligomer, 30-32 parts by weight of trimethylolpropane triacrylate, 10 parts by weight of acrylic polyol, 4 parts by weight of isocyanate, 0.5-0.6 parts by weight of photoinitiator, 0.1-0.2 parts by weight of flatting agent, 0.2-0.4 parts by weight of nano silicon dioxide particles and 25 parts by weight of solvent butanone. The total parts by weight of the tetrafunctional urethane acrylate oligomer, trimethylolpropane triacrylate, acrylic polyol, isocyanate, photoinitiator, leveling agent, nano-silica particles, and solvent are 100 parts by weight. The foregoing technical solutions include embodiment 1 and embodiment 4.
Further, the photocurable composition comprises 30 parts by weight of a tetrafunctional aliphatic polyurethane acrylate oligomer, 30 parts by weight of trimethylolpropane triacrylate, 10 parts by weight of an acrylic polyol, 4 parts by weight of isocyanate, 0.5 parts by weight of a photoinitiator, 0.1 parts by weight of a leveling agent, 0.4 parts by weight of nano silica particles, and 25 parts by weight of solvent butanone. The foregoing technical solutions include embodiment 1.
The preparation method of the hardened film provided by the invention comprises the following steps:
step one, magnetically sputtering a layer of silicon nitride coating on a substrate;
and step two, preparing a photo-curing composition, coating the photo-curing composition onto the magnetron sputtering layer, and drying and curing the coating to obtain a hardening layer.
Further, the preparation method of the hardening film for in-mold transfer printing provided by the invention comprises the following steps: step one, magnetically sputtering a layer of silicon nitride coating on a substrate; and secondly, preparing a photo-curing composition, coating the photo-curing composition onto the magnetron sputtering layer, drying the formed coating for 4 minutes at 80-90 ℃, and then curing the dried coating by ultraviolet rays of a high-pressure mercury lamp to obtain a hardening layer.
Compared with the prior art, the invention has the following advantages:
1. the invention simplifies the structure of the hardening film for IMR, which consists of a film layer (substrate layer, substrate for short), a magnetron sputtering layer and a hardening layer, does not contain an ink adhesion enhancement layer, reduces the membrane manufacturing process and improves the production efficiency;
2. the invention utilizes the characteristic of easy stripping between the magnetron sputtering layer and the hardening layer, the stripping force between the magnetron sputtering layer and the hardening layer is not influenced by the heating process, the yield of IMR products can be improved, and meanwhile, an auxiliary agent for improving the adhesive force of the printing ink (the auxiliary agent refers to acrylic polyol and isocyanate, the acrylic polyol reacts with the isocyanate, and the tail end contains isocyanate groups, which can react with hydroxyl groups in the printing ink to improve the adhesive force of the printing ink) is added into the hardening layer, so that the adhesive force of the hardening layer and the printing ink layer is enhanced.
Drawings
FIG. 1 is a schematic diagram of a conventional cured film;
fig. 2 is a schematic structural diagram of a cured film according to the present invention.
Detailed Description
The present invention will be specifically described with reference to the following specific examples and drawings, but the present invention is not limited thereto.
As shown in fig. 2, the hardened film provided by the present invention includes a base film (also referred to as a base material) 1, a magnetron sputtering layer 2, and a hardened layer 3.
The performance of the hardened film provided by the invention is tested according to the following method:
(1) Hardness of pencil
Sample pencil hardness was measured using an Elcometer 3086 pencil hardness tester. The measurement method comprises the following steps: using a mitsubishi pencil having a hardness of H to 9H, 5 lines were drawn under a load of 500g, and then the presence or absence of scratches on the cured coating was observed, and judged according to the following criteria.
Decision criterion
Scratch 0-1 strip, judge "Pass" (qualification);
2 to 5 strips are scratched, and the NG (unqualified) is judged.
(2) Wear resistance
A Kunshan fine instrument A20-339 was used with a steel wool tester at 500gf/cm 2 Under the load of #0000 steel wool, 1kg was loaded, and the surface of the hardened layer was rubbed back and forth 1000 times to confirm the presence or absence of scratches on the coating.
Determination criteria:
scratch 0 strip, judge "Pass" (qualification);
the scratch is more than or equal to 1, and the NG is judged (unqualified).
(3) Interlayer adhesion/peel force between hardened layer and magnetron sputtered layer
The tape was attached to the hardened layer and left at room temperature for 30 minutes, then peel test was performed at a speed of 300mm/min using a Haida International apparatus HD-B609B-S tensile machine at an angle of 180 °. The peel force between the hardened layer and the magnetron sputtering layer was recorded.
(3) Hardened layer peel integrity
And (3) attaching the adhesive tape to the hardening layer, standing for 30 minutes at normal temperature, then using a Haida International apparatus HD-B609B-S pulling machine to peel the hardening layer from the magnetron sputtering layer, and observing whether a part of hardening film remains on the magnetron sputtering layer or whether the hardening layer on the adhesive tape is cracked.
No residue and no cracking, and judging Pass (qualification);
residual or cracking, and "NG" (reject) was determined.
(4) Adhesion of ink
After the ink is coated on the hardened layer and cured completely, 11 intersecting straight lines are drawn on the ink layer by a hundred-grid method, so that one hundred grids with the size of 1 cm are formed, the 3MScotch 600 adhesive tape is used for testing, the printing ink layer is not dropped to be 100, if the printing ink layer is dropped, the number of the remaining grids is not dropped, for example, the number of the remaining grids is 5, and the number of the remaining grids is 5.
Example 1
The invention provides a hardening film and a preparation method thereof.
Silicon nitride was sputtered onto one surface of a 188 μm thick optical grade polyethylene terephthalate film (trade name; XG7PL2, manufactured by Korea Co.) by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 50nm.
The photo-curing composition is prepared by mixing 30 parts by weight of tetrafunctional aliphatic polyurethane acrylate oligomer, 30 parts by weight of trimethylolpropane triacrylate, 10 parts by weight of acrylic polyol, 4 parts by weight of isocyanate, 0.5 part by weight of photoinitiator 184,0.1 parts by weight of leveling agent BYK-333,0.4 parts by weight of nano silica particles and 25 parts by weight of solvent butanone.
The above-mentioned photocurable composition is applied to the surface of the magnetron sputtering layer. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 6. Mu.m.
Example 2
The photocurable composition and the cured film as provided in example 1.
Silicon oxide was sputtered onto one surface of a polyethylene terephthalate film (trade name; XG7PL2, manufactured by Korea Co.) having an optical grade of 100 μm in thickness by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 30nm.
The photo-curing composition was obtained by mixing 35 parts by weight of a tetrafunctional aliphatic urethane acrylate oligomer, 28 parts by weight of trimethylolpropane triacrylate, 9 parts by weight of an acrylic polyol, 3 parts by weight of isocyanate, 0.3 part by weight of a photoinitiator 184,0.4 parts by weight of a leveling agent BYK-333,0.3 parts by weight of nano silica particles, and 24 parts by weight of solvent butanone.
The above-mentioned photocurable composition is applied to the surface of the magnetron sputtering layer. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ +.cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 4. Mu.m.
Example 3
The photocurable composition and the cured film as provided in example 1.
Silicon nitride was sputtered onto one surface of a polyethylene terephthalate film (trade name; XG7LN8 manufactured by korean corporation) having an optical grade of 75 μm in thickness by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 70nm.
24 parts by weight of a tetrafunctional aliphatic polyurethane acrylate oligomer, 38 parts by weight of a polyfunctional reactive monomer trimethylolpropane triacrylate, 8 parts by weight of an acrylic polyol, 4 parts by weight of isocyanate, 0.7 part by weight of a photoinitiator 184,0.1 parts by weight of a leveling agent BYK-333,0.2 parts by weight of nano silica particles, and 25 parts by weight of solvent butanone are mixed to obtain a photocurable composition.
The above-mentioned photocurable composition is applied to the surface of the magnetron sputtering layer. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 8. Mu.m.
Example 4
The photocurable composition and the cured film as provided in example 1.
Silicon oxide was sputtered onto one surface of a polyethylene terephthalate film (trade name; XG7PL2, manufactured by Korea Co.) having an optical grade of 100 μm in thickness by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 40nm.
28 parts by weight of a tetrafunctional aliphatic polyurethane acrylate oligomer, 32 parts by weight of trimethylolpropane triacrylate, 10 parts by weight of acrylic polyol, 4 parts by weight of isocyanate, 0.6 part by weight of a photoinitiator 184,0.2 parts by weight of a leveling agent BYK-333,0.2 parts by weight of nano silica particles and 25 parts by weight of solvent butanone are mixed to obtain a photocurable composition.
Coating the above photo-curable compositionAnd covering the surface of the magnetron sputtering layer. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 7. Mu.m.
Example 5
The photocurable composition and the cured film as provided in example 1.
Silicon nitride was sputtered onto one surface of a polyethylene terephthalate film (trade name; XG7LN8 manufactured by korean corporation) having an optical grade of 75 μm in thickness by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 60nm.
The photo-curing composition was obtained by mixing 35 parts by weight of a tetrafunctional aliphatic urethane acrylate oligomer, 30 parts by weight of a polyfunctional reactive monomer trimethylolpropane triacrylate, 7 parts by weight of an acrylic polyol, 2 parts by weight of isocyanate, 0.4 part by weight of a photoinitiator 184,0.3 parts by weight of a leveling agent BYK-333,0.3 parts by weight of nano silica particles, and 25 parts by weight of solvent butanone.
The above-mentioned photocurable composition is applied to the surface of the magnetron sputtering layer. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 5. Mu.m.
Comparative example 1
Silicon nitride was sputtered onto one surface of a polyethylene terephthalate film (trade name; XG7PL2, manufactured by korean corporation) having an optical grade of 100 μm in thickness by means of magnetron sputtering to obtain a magnetron sputtered layer having a thickness of 60nm.
35 parts by weight of tetrafunctional aliphatic polyurethane acrylate oligomer, 40 parts by weight of trifunctional active monomer trimethylolpropane triacrylate, 0.5 part of photoinitiator 184,0.2 parts by weight of flatting agent BYK-333,0.3 parts of nano silica particles and 24 parts by weight of solvent butanone are mixed to obtain the photocuring composition.
Surface for applying the above-mentioned photocurable composition to magnetron sputtering layerOn the face. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 6. Mu.m.
Compared with the technical scheme provided by the invention, the difference of the comparative example 1 is that no acrylic polyol or isocyanate is added in the formula of the photo-curing composition.
Comparative example 2
A release layer was coated on one side of an optical grade polyethylene terephthalate film (trade name; XG7PL2, manufactured by Korean Co., ltd.) having a thickness of 188 μm, and the thickness of the release layer was 1. Mu.m.
The photocurable composition was obtained by mixing 25 parts by weight of a tetrafunctional aliphatic urethane acrylate oligomer, 35 parts by weight of a trifunctional reactive monomer trimethylolpropane triacrylate, 10 parts by weight of an acrylic polyol, 5 parts by weight of isocyanate, 0.6 part by weight of a photoinitiator 184,0.1 parts by weight of a leveling agent BYK-333,0.3 parts by weight of nano silica particles, and 24 parts by weight of solvent butanone.
The above-mentioned photocurable composition is applied to the release surface. After drying the formed coating at 80-90℃for 4 minutes, it was dried at 500mJ/cm 2 The dried coating layer is cured by ultraviolet irradiation to obtain a cured layer. The thickness of the hardened layer was 7. Mu.m.
Compared with the technical scheme provided by the invention, the difference of the comparative example 2 is that the IMR diaphragm structure is changed into a release layer from a magnetron sputtering layer.
TABLE 1 test results of Performance of the hardened films provided in examples 1-5 and comparative examples 1-2
The hardened film for IMR provided by the invention has good comprehensive performance, high hardness, high wear resistance, easy interlayer stripping, good ink adhesion and the like. Among them, the cured films provided in example 1 and example 4 had better overall properties: high hardness, low interlayer peeling force, qualified wear resistance, qualified peeling integrity of a hardened layer and high adhesive force of printing ink. In particular, the cured film provided in example 1 had the best overall properties.
It should be noted that the above description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made in accordance with the present invention are intended to be covered by the scope of the appended claims.
Claims (10)
1. The hardening film is characterized by sequentially comprising a base material, a magnetron sputtering layer and a hardening layer.
2. The cured film according to claim 1, wherein the magnetron sputtering layer is a silicon nitride layer or a silicon oxide layer.
3. The cured film of claim 1, wherein the cured layer is formed from a photocurable composition.
4. A hardened film according to claim 3, characterized in that the photocurable composition comprises 24-35 parts by weight of tetrafunctional urethane acrylate oligomer, 28-38 parts by weight of trimethylolpropane triacrylate, 7-10 parts by weight of acrylic polyol, 2-4 parts by weight of isocyanate, 0.3-0.7 parts by weight of photoinitiator, 0.1-0.4 parts by weight of leveling agent, 0.2-0.4 parts by weight of nano silica particles, 24-25 parts by weight of solvent butanone; the total parts by weight of the tetrafunctional urethane acrylate oligomer, trimethylolpropane triacrylate, acrylic polyol, isocyanate, photoinitiator, leveling agent, nano-silica particles, and solvent are 100 parts by weight.
5. The cured film of claim 4, wherein the magnetron sputtered layer is a silicon nitride layer.
6. The hardened film according to claim 1, characterized in that the thickness of the magnetron sputtering layer is 30-70nm.
7. The cured film according to claim 1, wherein the cured layer has a thickness of 4 to 8 μm.
8. The cured film of claim 1, wherein the substrate has a thickness of 75-188 μm.
9. A hardened film according to claim 3, characterized in that the photocurable composition comprises 28-30 parts by weight of tetrafunctional aliphatic urethane acrylate oligomer, 30-32 parts by weight of trimethylolpropane triacrylate, 10 parts by weight of acrylic polyol, 4 parts by weight of isocyanate, 0.5-0.6 parts by weight of photoinitiator, 0.1-0.2 parts by weight of leveling agent, 0.2-0.4 parts by weight of nano silica particles, 25 parts by weight of solvent butanone; the total parts by weight of the tetrafunctional urethane acrylate oligomer, trimethylolpropane triacrylate, acrylic polyol, isocyanate, photoinitiator, leveling agent, nano-silica particles, and solvent are 100 parts by weight.
10. A method for producing a cured film according to any one of claims 1 to 9, comprising the steps of:
step one: magnetron sputtering a magnetron sputtering layer on the substrate;
step two: preparing a photo-curing composition, coating the photo-curing composition onto the magnetron sputtering layer, and drying and curing the coating to obtain a hardening layer.
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JP2012013978A (en) * | 2010-07-01 | 2012-01-19 | Toppan Printing Co Ltd | Thin film pattern printing method |
CN106634462A (en) * | 2016-12-23 | 2017-05-10 | 合肥乐凯科技产业有限公司 | Hard coating film with high dyne value |
CN106750459A (en) * | 2016-12-14 | 2017-05-31 | 合肥乐凯科技产业有限公司 | One kind can print two-sided cured film |
CN107293627A (en) * | 2017-07-25 | 2017-10-24 | 中国南玻集团股份有限公司 | A kind of Obstruct membrane and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2012013978A (en) * | 2010-07-01 | 2012-01-19 | Toppan Printing Co Ltd | Thin film pattern printing method |
CN106750459A (en) * | 2016-12-14 | 2017-05-31 | 合肥乐凯科技产业有限公司 | One kind can print two-sided cured film |
CN106634462A (en) * | 2016-12-23 | 2017-05-10 | 合肥乐凯科技产业有限公司 | Hard coating film with high dyne value |
CN107293627A (en) * | 2017-07-25 | 2017-10-24 | 中国南玻集团股份有限公司 | A kind of Obstruct membrane and preparation method thereof |
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