CN115477894A - Photo-curing composition and hardened film - Google Patents
Photo-curing composition and hardened film Download PDFInfo
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- CN115477894A CN115477894A CN202110665001.8A CN202110665001A CN115477894A CN 115477894 A CN115477894 A CN 115477894A CN 202110665001 A CN202110665001 A CN 202110665001A CN 115477894 A CN115477894 A CN 115477894A
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000000016 photochemical curing Methods 0.000 title abstract description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
- 239000004814 polyurethane Substances 0.000 claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000002519 antifouling agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 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 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 21
- 239000011247 coating layer Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920006289 polycarbonate film Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000006748 scratching Methods 0.000 description 5
- 230000002393 scratching effect Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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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
-
- 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
- C08J7/0427—Coating with only 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
- C08J7/046—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
- 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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- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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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Abstract
The present invention relates to a cured film, and more particularly to a photocurable composition and a cured film. The invention provides a photocuring composition and a hardened film, aiming at solving the problem that the existing hardened film cannot give consideration to both the stretching rate and the flexibility. The photo-curing composition comprises the following components: 20-40 parts of hexafunctionality polyurethane acrylate oligomer, 15-25 parts of polyurethane acrylate with OH, 5-15 parts of trifunctional fluorine-containing methyl acrylate, 10-20 parts of polyurethane acrylate with NCO groups, 0.7-1.4 parts of photoinitiator, 0.1-0.6 part of leveling agent, 0.5-2 parts of antifouling agent, 0.6-2.5 parts of nano silica particles and 20-25 parts of organic solvent. The photocuring composition provided by the invention forms a hard coating of a hardened film, so that the hardened film has the characteristics of good flexibility, high hardness, fingerprint resistance, high wear resistance and the like and high elongation.
Description
Technical Field
The present invention relates to a cured film, and more particularly to a photocurable composition and a cured film.
Background
The IML (In-mold Label) process is one of In-mold decoration (IMD) processes, and comprises the main processes of carrying out plane printing and drying on a cut film, then pasting the film, carrying out punching and thermoforming, and finally cutting and carrying out injection molding. After the injection molding is finished, the surface hardness of the product can generally reach 2H-3H and is divided into three layers, namely a base material, printing ink and a coating material. Transparent materials such as PC, PET, and PC + PMMA are often used; it is used for low-stretch products requiring windows and light-transmitting products. The single heat curing is adopted, the curing speed of the client is low, and the efficiency is low! The geometrical shape is complex, the uniform coating is difficult, the thickness is not uniform, and the curing is not uniform.
Polycarbonate is named polycarbonate for short PC, has high strength and rigidity, excellent shock resistance and creep resistance, small polarity, long-term use temperature of 120 ℃, low water absorption and excellent electrical property, and can keep good electrical property in a large temperature range. IMD needs the film to have high surface hardness and high wear resistance, and avoids product scratching; and simultaneously has good tensile property so as to realize 3D product modeling. At present, in order to solve the contradiction between high hardness and tensile property of the IMD hardened film, a dual-curing technology is adopted, and Ultraviolet (UV) curing or thermosetting is firstly utilized to dry the surface of the hardened film, so that the hardened film can be rolled and has good tensile property. After the hardened film is processed into a 3D shape, a second step of UV curing is performed to make the surface of the hardened film have high hardness. However, this technique has its limitation because the hardened film needs to be printed with various colors of ink on its back base film before it is processed into a 3D model to form a desired pattern. When printing dark color ink, especially black ink, the ink can absorb the energy of ultraviolet light, which results in incomplete UV curing in the second step and failure to achieve the required hardness.
Disclosure of Invention
The invention provides a photocuring composition and a hardened film, aiming at solving the problem that the conventional hardened film cannot give consideration to both the stretching rate and the flexibility. The photocuring composition provided by the invention forms a hard coating of a hardened film, so that the hardened film has the characteristics of good flexibility, high hardness, fingerprint resistance, high wear resistance and the like, and also has good formability, high tensile rate and excellent comprehensive performance.
In order to solve the technical problems, the invention adopts the following technical scheme.
The invention provides a photocuring composition, which comprises the following components: high functionality urethane acrylate oligomers, OH-bearing urethane acrylates, NCO-bearing urethane acrylates, and low functionality fluorochemical acrylate oligomers.
Further, the high functionality urethane acrylate oligomer is a hexa-functionality urethane acrylate oligomer.
Further, the OH-containing urethane acrylate is EBECRYL 8210 supplied by Zhan new resins (china) ltd.
Further, the urethane acrylate with NCO was CN1073NS provided by sartomer chemical limited.
Further, the low-functionality fluorine-containing acrylate oligomer is trifunctional fluorine-containing methyl acrylate.
Further, the photo-curing composition comprises the following components: hexafunctional urethane acrylate oligomer, urethane acrylate with OH, urethane acrylate with NCO groups, trifunctional fluorine-containing methyl acrylate, and nano silica particles.
Further, the photo-curing composition comprises the following components: hexafunctionality urethane acrylate oligomer, urethane acrylate with OH, urethane acrylate with NCO group, trifunctional fluorine-containing methyl acrylate, photoinitiator, and nano silica particles.
Further, the photo-curing composition comprises the following components: hexafunctionality polyurethane acrylate oligomer, polyurethane acrylate with OH, polyurethane acrylate with NCO group, trifunctional fluorine-containing methyl acrylate, photoinitiator, leveling agent, antifouling agent, nano silicon dioxide particles and organic solvent.
The invention provides a photocuring composition, which comprises the following components: 20-40 parts of hexafunctionality urethane acrylate oligomer, 15-25 parts of urethane acrylate with OH, 10-20 parts of urethane acrylate with NCO groups, 5-15 parts of trifunctional fluorine-containing methyl acrylate, 0.7-1.4 parts of photoinitiator, 0.1-0.6 part of leveling agent, 0.5-2 parts of antifouling agent, 0.6-2.5 parts of nano silica particles and 20-25 parts of organic solvent. The total parts of the components are 100 parts by weight.
Further, the photo-curing composition comprises the following components: 20-40 parts of hexafunctionality urethane acrylate oligomer RJ4217, 15-25 parts of urethane acrylate EBECRYL 8210 with OH (hydroxyl), 10-20 parts of urethane acrylate CN1073NS with NCO groups, 5-15 parts of trifunctional fluorine-containing methyl acrylate, 0.7-1.4 parts of photoinitiator 184,0.1-0.6 part of flatting agent BYK-333,0.5-2 parts of antifouling agent RS-90,0.6-2.5 parts of nano silica particles and 20-25 parts of organic solvent. The total parts of the components are 100 parts by weight.
Further, the organic solvent is selected from one or a combination of at least two of 4-methyl-2-pentanone, ethyl acetate or butyl acetate.
In another aspect, the present invention provides a hardened film comprising a substrate and a hard-coat layer attached to one surface of the substrate; the hard coat layer is formed from the photocurable composition of the present invention.
Compared with the prior art, the hardened film provided by the invention has high tensile rate (more than 100%); the method is suitable for complicated geometric shapes, small R angles and screen printing; therefore, the forming time is shortened, and the production efficiency of customers is greatly improved; moreover, the hardened film provided by the invention has good flexibility, high hardness, fingerprint resistance and high wear resistance.
Drawings
Fig. 1 is a schematic structural diagram of a hardened film provided by the present invention.
Detailed Description
For a better understanding of the present invention, its structure, and the functional features and advantages attained by its structure, reference is made to the following detailed description of the preferred embodiments taken in conjunction with the accompanying drawings, in which:
as shown in fig. 1, the hardened film provided by the present invention includes a base material layer 10 and a hard coat layer 20.
Further, the preparation method of the hardened film provided by the invention comprises the following steps: a photocurable composition was prepared, the photocurable composition was applied to a substrate, the formed coating was cured at 125 ℃ for 3 minutes, then aged at 80 ℃ for 30 minutes, and then the film was bent at different bend radii, and the dried coating was cured by ultraviolet rays of a high-pressure mercury lamp to obtain a cured film.
The properties of the hardened films provided in the examples of the present invention and the comparative examples were measured as follows:
(1) Haze, total luminous transmittance
Measured by the transmitted light method using a Japanese electrochromic NDH 2000N haze meter.
(2) Hardness of pencil
The pencil hardness of the article was measured using an Elcometer 3086 pencil hardness meter. Measurement technique: using Mitsubishi pencil with hardness of H-9H, 5 lines were drawn under a load of 500g, and then the presence or absence of scratches on the hardened film coating was observed and judged according to the following criteria.
Criteria for determination
Scratching 0-1 strip, and judging Pass; the highest hardness of the pencil recording "Pass" is the hardness of the hardened film.
Scratching 2-5 strips, and judging 'NG' (unqualified).
(3) Wear resistance
Using Kunzhijia instrument A20-339 steel wool tester at 500gf/cm 2 Under a load of 1kg, the hard coating surface was rubbed back and forth 1000 times with a #0000 steel wool, and the presence or absence of scratches was confirmed.
And (3) judging standard:
scratching 0 strips, and judging 'Pass' (qualified);
and (5) scratching more than or equal to 1, and judging NG (unqualified).
(4) Coating thickness test
And (3) testing the thickness of the transparent hardened coating (hard coating for short) by using a coating thickness tester ETA-SST thickness testing system and utilizing the light diffraction principle.
(5) Flexibility determination
Cutting the sample into: a strip having a length of 10cm by a width of 2cm was wound with a hard coat layer facing outward on a steel bar having a diameter of 1.5mm, and then unwound, and the surface of the hard coat layer was observed for the presence of fine cracks and evaluated according to the following criteria:
no cracks, and a rating of "excellent"; it shows excellent flexibility;
slight cracks appeared, no cracks were seen, and the results were reported as "Δ" (acceptable); the flexibility is qualified;
the appearance of cracks was marked by "X" (failure).
(6) Antifouling properties
The water contact angle of the hard coat layer was measured using a contact angle measuring instrument model JC2000D1, a digital technology equipment ltd, shanghai, midmorning. The larger the contact angle, the better the antifouling property.
(6) Elongation of stretching
The measurement is carried out by using Haida instrument HD-609B-S equipment according to the national standard GB 104092. The judgment basis is that no fracture occurs. The higher the elongation at break, the better the performance and the easier the 3D forming in the IML process.
Example 1
The invention provides a photocuring composition and a hardened film.
20 parts by weight of a hexafunctional urethane acrylate oligomer RJ4217, 24 parts by weight of an OH-containing urethane acrylate EBECRYL 8210 (supplied by Zhan New resins (China) Co., ltd.), 10 parts by weight of a trifunctional fluorine-containing methyl acrylate, 20 parts by weight of an NCO-group-containing urethane acrylate CN1073NS (supplied by Shadoma chemical Co., ltd.), 0.7 part by weight of a photoinitiator 184,0.1 parts by weight of a leveling agent BYK-333,0.6 parts by weight of an antifouling agent RS-90,0.6 parts by weight of nano silica particles, 14 parts by weight of a solvent butanone and 10 parts by weight of a solvent propylene glycol monomethyl ether were mixed to obtain a photocurable composition.
Will be at the topThe photocurable composition was applied to one surface of an optical grade polycarbonate film (manufactured by Corcisco, trade name; DE 1-1) having a thickness of 188 μm. The formed coating was dried at 125 ℃ for 3 minutes, and then aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coating layer or hardened layer) was 5 μm to obtain a hardened film.
Example 2
The photocurable composition and cured film provided in example 1.
25 parts by weight of hexafunctional urethane acrylate oligomer RJ4217, 18 parts by weight of OH-containing urethane acrylate EBECRYL 8210, 15 parts by weight of trifunctional fluorine-containing methyl acrylate, 12 parts by weight of NCO-group-containing urethane acrylate CN1073NS (supplied by Sandoma), 1.2 parts by weight of photoinitiator 184,0.3, leveling agent BYK-333,2, antifouling agent RS-90,1.5, nano silica particles, 20 parts by weight of solvent 4-methyl-2-pentanone and 5 parts by weight of solvent ethyl acetate are mixed to obtain the photocuring composition.
The photocurable composition was applied to one surface of a 188 μm thick optical-grade polycarbonate film (trade name, DE1-1, manufactured by Corseki Co., ltd.). After drying the formed coating at 125 ℃ for 3 minutes, it was aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Example 3
The photocurable composition and cured film provided in example 1.
40 parts by weight of hexafunctional urethane acrylate oligomer RJ4217, 15 parts by weight of OH-bearing urethane acrylate EBECRYL 8210,5, 10 parts by weight of NCO-bearing urethane acrylate CN1073NS (supplied by Sartomer), 0.7 part by weight of photoinitiator 184,0.5, leveling agent BYK-333,0.5, antifouling agent RS-90,2, nano silica particles and 25 parts by weight of solvent butyl acetate are mixed to obtain the photocuring composition.
The photocurable composition was applied to one surface of a 188 μm thick optical-grade polycarbonate film (trade name, DE1-1, manufactured by Corseki Co., ltd.). After drying the formed coating at 125 ℃ for 3 minutes, it was aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Example 4
The photocurable composition and cured film provided in example 1.
40 parts by weight of hexafunctional polyurethane acrylate oligomer RJ4217, 15 parts by weight of OH-bearing polyurethane acrylate EBECRYL 8210,5, 10 parts by weight of NCO-bearing polyurethane acrylate CN1073NS (supplied by Sartomer), 0.7 part by weight of photoinitiator 184,0.5, leveling agent BYK-333,0.5, antifouling agent RS-90,2, nano silica particles and 20 parts by weight of solvent methyl isobutyl ketone are mixed to obtain the photocuring composition.
The photocurable composition was applied to one surface of an optical-grade polycarbonate film (product of Corcisco, trade name; DE 1-1) having a thickness of 188 μm. The formed coating was dried at 125 ℃ for 3 minutes, and then aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Example 5
The photocurable composition and cured film provided in example 1.
30 parts by weight of hexafunctional urethane acrylate oligomer RJ4217, 25 parts by weight of OH-bearing urethane acrylate EBECRYL 8210,5, 14 parts by weight of NCO-bearing urethane acrylate CN1073NS (supplied by Sartomer), 1.4 parts by weight of photoinitiator 184,0.6, weight of leveling agent BYK-333,1.5, weight of antifouling agent RS-90,2.5, weight of nano silica particles, 10 parts by weight of solvent butanone and 10 parts by weight of solvent isopropanol are mixed to obtain the photocuring composition.
The photocurable composition was coated on one surface of a 125 μm thick optical-grade polyethylene terephthalate film (manufactured by Korea company, trade name; XG7PL 2). After drying the formed coating at 80-90 ℃ for 2 minutes, at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coating layer) was 5 μm, thereby obtaining a cured film.
Comparative example 1
A photocurable composition and a cured film are provided.
40 parts by weight of hexafunctionality polyurethane acrylate oligomer RJ4217, 10 parts by weight of trifunctional fluorine-containing methyl acrylate, 20 parts by weight of polyurethane acrylate CN1073NS (provided by sartomer) with NCO groups, 1 part by weight of photoinitiator 184,1, leveling agent BYK-333,3, antifouling agent RS-90,2, nano silica particles and 23 parts by weight of solvent butanone are mixed to obtain the photocuring composition.
The photocurable composition was applied to one surface of an optical-grade polycarbonate film (product of Corcisco, trade name; DE 1-1) having a thickness of 188 μm. After drying the formed coating at 125 ℃ for 3 minutes, it was aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Compared with the technical scheme provided by the invention, the difference of the photo-curing composition provided by the comparative example 1 is that polyurethane acrylate with OH groups is not added in the formula.
Comparative example 2
A photocurable composition and a cured film are provided.
35 parts by weight of hexafunctionality urethane acrylate oligomer RJ4217, 30 parts by weight of urethane acrylate EBECRYL 8210 with OH, 10 parts by weight of trifunctional fluorine-containing methyl acrylate, 1 part by weight of photoinitiator 184,1, leveling agent BYK-333,1, antifouling agent RS-90,2, nano silica particles and 20 parts by weight of solvent butanone are mixed to obtain the photocuring composition.
The photocurable composition was coated on one surface of a 188 μm thick optical-grade polyethylene terephthalate film (manufactured by Korea company, trade name; XG7PL 2). After drying the formed coating at 80-90 ℃ for 2 minutes, at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Compared with the technical scheme provided by the invention, the difference of the photo-curing composition provided by the comparative example 2 is that polyurethane acrylate with NCO groups is not added in the formula.
Comparative example 3
A photocurable composition and a cured film are provided.
25 parts by weight of nine-functional polyurethane acrylate oligomer INV-UV985, 20 parts by weight of OH-containing polyurethane acrylate EBECRYL 8210, 15 parts by weight of trifunctional fluorine-containing methyl acrylate, 10 parts by weight of NCO-containing polyurethane acrylate CN1073NS (supplied by Sartomer), 4 parts by weight of photoinitiator 184,1, leveling agent BYK-333,3, antifouling agent RS-90,2, nano silica particles, 10 parts by weight of solvent butanone and 10 parts by weight of solvent propylene glycol monomethyl ether are mixed to obtain the photocuring composition.
The photocurable composition was applied to one surface of an optical-grade polycarbonate film (product of Corcisco, trade name; DE 1-1) having a thickness of 188 μm. After drying the formed coating at 125 ℃ for 3 minutes, it was aged at 80 ℃ for 30 minutes at 800mJ/cm 2 The dried coating layer was cured by ultraviolet irradiation, and the thickness of the cured coating layer (i.e., hard coat layer) was 5 μm, thereby obtaining a cured film.
Compared with the technical scheme provided by the invention, the difference of the photo-curing composition provided by the comparative example 3 is that the coating liquid adopts polyurethane acrylate oligomer with too high functionality, so that high crosslinking density is formed, although the hardness is improved to 3H, good flexibility cannot be realized.
Table 1 results of performance test of the hardened films provided in examples 1 to 5 and comparative examples 1 to 3
The UV post-curing hardening film provided by the invention has good comprehensive performance, high hardness, high wear resistance and good flexibility. When a steel bar with the diameter of 1.5mm is selected to test the flexibility, the hard coatings provided by the comparative examples 1 and 2 can crack, and the hard coating provided by the comparative example 3 can not reach the low bending radius of 1.5mm.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.
Claims (10)
1. A photocurable composition comprising the following components: high functionality urethane acrylate oligomers, OH-bearing urethane acrylates, NCO-bearing urethane acrylates, and low functionality fluorochemical acrylate oligomers.
2. The photocurable composition of claim 1 wherein the high functionality urethane acrylate oligomer is a hexafunctionality urethane acrylate oligomer.
3. The photocurable composition of claim 1 wherein the OH-bearing urethane acrylate is EBECRYL 8210 available from Zhan New resins (China) Inc., and the NCO-bearing urethane acrylate is CN1073NS available from Sartomer Chemicals, inc.
4. The photocurable composition of claim 1 wherein the low functionality fluorochemical acrylate oligomer is a trifunctional fluorochemical methyl acrylate.
5. The photocurable composition of claim 1 wherein the photocurable composition comprises the following ingredients: hexafunctional urethane acrylate oligomer, urethane acrylate with OH, urethane acrylate with NCO groups, trifunctional fluorine-containing methyl acrylate, and nano silica particles.
6. The photocurable composition of claim 1 wherein the photocurable composition comprises the following components: hexafunctionality urethane acrylate oligomer, urethane acrylate with OH, urethane acrylate with NCO group, trifunctional fluorine-containing methyl acrylate, photoinitiator, and nano silica particles.
7. The photocurable composition of claim 1 wherein the photocurable composition comprises the following components: hexafunctionality polyurethane acrylate oligomer, polyurethane acrylate with OH, polyurethane acrylate with NCO group, trifunctional fluorine-containing methyl acrylate, photoinitiator, leveling agent, antifouling agent, nano silicon dioxide particles and organic solvent.
8. The photocurable composition of claim 1 wherein the photocurable composition comprises the following components: 20-40 parts by weight of hexafunctionality urethane acrylate oligomer, 15-25 parts by weight of urethane acrylate with OH, 5-15 parts by weight of trifunctional fluorine-containing methyl acrylate, 10-20 parts by weight of urethane acrylate with NCO groups, 0.7-1.4 parts by weight of photoinitiator, 0.1-0.6 part by weight of flatting agent, 0.5-2 parts by weight of antifouling agent, 0.6-2.5 parts by weight of nano silica particles and 20-25 parts by weight of organic solvent; the total parts of the components are 100 parts by weight.
9. The photocurable composition of claim 8 wherein the organic solvent is selected from one or a combination of at least two of 4-methyl-2-pentanone, ethyl acetate, or butyl acetate.
10. A hardened film characterized by comprising a base material and a hard coat layer attached to one surface of the base material; the hard coat layer is formed from the photocurable composition of any one of claims 1-9.
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