Photo-curing composition and application
阅读说明：本技术 光固化组合物及应用 (Photo-curing composition and application ) 是由 钱彬 杨金梁 严春霞 于 2019-04-29 设计创作，主要内容包括：本发明提供了一种光固化组合物及应用。该光固化组合物包含：组分A,组分A包含一种或多种化合物a,化合物a的结构中含有环氧环己基；组分B,组分B包含一种或多种化合物b,化合物b的结构中含有氧杂环丁基和环氧基,且化合物b的分子量≤500；组分C,组分C包含一种或多种化合物c,化合物c的结构中含有氧杂环丁烷基和烷基；以及组分D,组分D为光致酸产生剂。该光固化组合物的固化产物能够持久保持优异的防雾防污性能,进而能有效延长所保护的产品的使用寿命。适宜在玻璃窗、浴室镜子等家具、汽车后视镜/反射镜、太阳能电池板、监控摄像头保护罩、镜片、照明灯保护罩、玻璃基材灯罩漆等表面进一步推广应用。(The invention provides a photocuring composition and application thereof. The photocurable composition comprises: the component A comprises one or more compounds a, and the structure of the compound a contains epoxy cyclohexyl; the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500; component C, component C comprises one or more compounds C, the structure of the compound C contains oxetanyl and alkyl; and a component D, the component D being a photoacid generator. The cured product of the photocuring composition can keep excellent antifogging and antifouling performance for a long time, and further can effectively prolong the service life of the protected product. The coating is suitable for further popularization and application on the surfaces of furniture such as glass windows, bathroom mirrors and the like, automobile rearview mirrors/reflectors, solar panels, monitoring camera protective covers, lenses, illuminating lamp protective covers, glass substrate lampshade paints and the like.)
1. A photocurable composition, wherein the photocurable composition comprises:
the component A comprises one or more compounds a, wherein the structure of the compound a contains epoxy cyclohexyl;
the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500;
a component C comprising one or more compounds C containing an oxetanyl group and an alkyl group in the structure; and
a component D, said component D being a photoacid generator.
2. The photocurable composition according to claim 1, wherein the compound a is a compound having 7 to 20 carbon atoms.
3. The photocurable composition according to claim 1, wherein the compound b is a compound having 5 to 23 carbon atoms.
4. The photocurable composition according to claim 1, wherein the compound c is a compound having 7 to 35 carbon atoms.
5. The photocurable composition according to claim 1 or 2, wherein the compound a is selected from any one of the following compounds:
6. the photocurable composition according to claim 1 or 3, wherein said compound b is selected from any one of the following compounds:
7. the photocurable composition of claim 1 or 4 wherein said compound c is selected from the group consisting of compounds of the following structural formula I:
R1is H or alkyl, R2Is alkyl or substituted alkyl.
8. The photocurable composition of claim 7, said R1Is alkyl, said R1Or the saidR2C of the alkyl group of (a) is substituted with oxygen, an ester group, a carbonyl group or an alkenyl group, preferably, the alkenyl group is a vinyl group; more preferably, the alkyl group is an alkyl group having 1 to 18 carbon atoms.
9. The photocurable composition of claim 6 wherein the compound c is selected from any one of the following compounds:
10. the photocurable composition of claim 1 wherein component D is: iodonium salts, sulfonium salts or arylferrocenium salts in which the negative ion is replaced by Al [ OC (CF) 3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other.
11. An anti-fog and anti-fouling application of the photocurable composition according to any one of claims 1 to 10 on the surface of a solid wood substrate, a metal substrate or a glass substrate.
12. A substrate having a photocurable film provided on a surface thereof, wherein the photocurable composition according to any one of claims 1 to 10 is cured to form the photocurable film.
13. The substrate according to claim 12, wherein the pure water contact angle of the photocurable film on the surface of the substrate is 95-150 °, preferably 110-130 °, and the hexadecane contact angle is 30-85 °, preferably 69-80 °.
14. The substrate according to claim 12 or 13, wherein the substrate is a solid wood substrate, a metal substrate or a glass substrate.
Technical Field
The invention relates to the field of antifogging and antifouling, and particularly relates to a photocuring composition and application thereof.
Background
Devices, parts and the like exposed to various environments for a long time are generally required to be protected from the surface by a certain protection means, so as to further improve the anti-fogging and anti-fouling properties of the devices, parts and the like, thereby improving the durability in use. As a protective means, generally, a coating of a structural member, a protective device, a protective film, or the like is used to achieve antifogging and antifouling properties, but there still remain problems such as: as the service life of the product is prolonged and the influence of factors such as external humidity and pollution is increased, water vapor or oil stains are likely to be gradually accumulated on the surfaces of devices, parts and the like, so that the existing product cannot exert the expected functions or performances.
The surfaces that need to be protected in practical applications include: protective covers for monitor lenses, protective covers for illumination lamps, reflectors, surface protective films for traffic signs, resin films, and the like, and when protective means are provided to protect these surfaces, it is necessary to take into consideration the problems of protection of devices, parts, and the like during long-term use, antifogging and antifouling properties, environmental costs during production, and the like.
The protective film on the surface in the prior art has the problem that the anti-fog and anti-fouling performance is difficult to be durably stable, so that the service life of a device or a part is influenced.
Disclosure of Invention
The invention mainly aims to provide a photocuring composition and application thereof, and aims to solve the problem that the antifogging and antifouling performance of a protective film cured by the photocuring composition in the prior art is difficult to last.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photocurable composition comprising: the component A comprises one or more compounds a, and the structure of the compound a contains epoxy cyclohexyl; the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500; component C, component C comprises one or more compounds C, the structure of the compound C contains oxetanyl and alkyl; and a component D, the component D being a photoacid generator.
Further, the compound a is a compound having 7 to 20 carbon atoms.
Further, the compound b is a compound having 5 to 23 carbon atoms.
Further, the compound c is a compound having 7 to 35 carbon atoms.
Further, the compound a is selected from any one of the following compounds:
further, compound b is selected from any one of the following compounds:
further, compound c is selected from compounds of the following structural formula I:
R1is H or alkyl, R2Is alkyl or substituted alkyl.
Further, R1Is alkyl, R1Or R2C of the alkyl group of (a) is substituted with oxygen, an ester group, a carbonyl group or an alkenyl group, preferably, the alkenyl group is a vinyl group; more preferably, the alkyl group is an alkyl group having 1 to 18 carbon atoms.
Further, the compound c is selected from any one of the following compounds:
further, the component D is: iodonium salt, sulfonium salt or arylferrocenium salt, wherein the anion in the iodonium salt, sulfonium salt or arylferrocenium salt is coated with Al [ OC (CF)3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other.
In order to achieve the above object, according to one aspect of the present invention, there is provided an antifogging and antifouling application of any one of the above photocurable compositions on a surface of a solid wood substrate, a surface of a metal substrate or a surface of a glass substrate.
According to another aspect of the present invention, there is provided a substrate having a photocurable film formed on a surface thereof, wherein the photocurable film is obtained by curing any one of the photocurable compositions.
Further, the pure water contact angle of the photo-cured film on the surface of the base material is 95 to 150 degrees, preferably 110 to 130 degrees, and the hexadecane contact angle is 30 to 85 degrees, preferably 69 to 80 degrees.
Further, the substrate is a solid wood substrate, a metal substrate or a glass substrate.
By applying the technical scheme of the invention, three components with specific structures are adopted as curing monomers, and the photocuring product formed by curing under the action of the photoacid generator has good stability and can permanently keep excellent antifogging and antifouling properties, so that the service life of the protected product can be effectively prolonged. The coating is suitable for further popularization and application on the surfaces of furniture such as glass windows, bathroom mirrors and the like, automobile rearview mirrors/reflectors, solar panels, monitoring camera protective covers, lenses, illuminating lamp protective covers, glass substrate lampshade paints and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background, the prior art protective films have the disadvantage of poor stability resulting in limited useful life of the devices or parts they protect, and in order to improve this situation in the prior art, in one exemplary embodiment of the present application, a photocurable composition is provided comprising: the component A comprises one or more compounds a, and the structure of the compound a contains epoxy cyclohexyl; the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500; component C, component C comprises one or more compounds C, the structure of the compound C contains oxetanyl and alkyl; and a component D, the component D being a photoacid generator.
The photocuring composition adopts the three components as curing monomers, and a cured product formed by curing under the action of the component D photoacid generator has good stability, can permanently maintain excellent antifogging and antifouling performances, and can effectively prolong the service life of a protected product. The coating is suitable for further popularization and application on the surfaces of furniture such as glass windows, bathroom mirrors and the like, automobile rearview mirrors/reflectors, solar panels, monitoring camera protective covers, lenses, illuminating lamp protective covers, glass substrate lampshade paints and the like.
In order to further increase the curing effect of the monomers in component A, in a preferred embodiment, compound a is a compound having 7 to 20 carbon atoms.
In a preferred embodiment, the compound b is a compound having 5 to 23 carbon atoms. In a preferred embodiment, the compound c is a compound having 7 to 35 carbon atoms.
In a more preferred embodiment of the present application, the compound a is selected from any one of the following compounds:
in a more preferred embodiment, compound b is selected from any one of the following compounds:
in a more preferred embodiment, compound c is selected from compounds of the following structural formula I:
R1is H or alkyl, R2Is alkyl or substituted alkyl.
In a preferred embodiment, R is as defined above1Is alkyl, R1Or R2C of the alkyl group of (a) is substituted with oxygen, an ester group, a carbonyl group or an alkenyl group, preferably, the alkenyl group is a vinyl group; more preferably, the alkyl group is an alkyl group having 1 to 18 carbon atoms.
In a more preferred embodiment, the compound c is selected from any one of the following compounds:
these compounds c have more excellent effects in terms of antifogging and antifouling after curing of the composition.
The compounds of components A, B and C are both photocurable monomers as curing monomers and are therefore curable to form polymers under the action of photoacid generators. The specific type of the specific photoacid generator can be reasonably selected according to different practical application scenes or requirements. Examples of such photoacid generators include onium salt compounds (e.g., sulfonium salts, iodonium salts) and arylferrocenium salt compounds. Based on the comprehensive consideration of cost and the effect of the matched use, such as photoinitiation efficiency, curing speed and the like, the component D can be a cationic photoinitiator, and further can be selected from the cationic photoacid generator disclosed in the application No. 201710035435.3.
In a preferred embodiment, component D is: iodonium salt, sulfonium salt or arylferrocenium salt, wherein the anion in the iodonium salt, sulfonium salt or arylferrocenium salt is coated with Al [ OC (CF)3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other. Photoacid generators of the above-mentioned kind have high ultraviolet sensitivity.
Commercially available cationic photoinitiators of the same type of structure may also be used in component D of the present invention, examples include, but are not limited to: PAG20001, PAG20001s, PAG20002s, PAG30201, PAG30101, etc., manufactured by Tronly, and Irgacure250, manufactured by BASF, etc.
The photo-curing composition has different dosage ratios of the components in the composition according to different requirements of practical application. In a preferred embodiment, the proportion of the above components in the composition is as follows: and (2) component A: 10-30 wt%; and (B) component: 20-58 wt%; and (3) component C: 30-60 wt%; and (3) component D: 2-5 wt%. Controlling the content of each component within the above content range can make the cured film have the beneficial effects of fog and stain resistance. In another preferred embodiment of the present application, the content ratio of the above components is further optimized, specifically, the ratio of component a: 15-25 wt%; and (B) component: 30-45 wt%; and (3) component C: 35-50 wt%; and (3) component D: 2.5-4.5 wt%.
It should be noted that, the above-mentioned photocurable composition of the present application may further comprise some optional auxiliary monomers, such as monofunctional compounds and monofunctional epoxy compounds and/or multifunctional epoxy compounds, examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1, 2-epoxybutane, 1, 3-butadiene monoxide, 1, 2-epoxydodecane, epichlorohydrin, 1, 2-epoxydecane, styrene oxide, epoxycyclohexane, 3-methacryloyloxymethyl cyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide, and the like.
Examples of the polyfunctional epoxy compound include bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol a diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol a diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4 '-epoxycyclohexylmethyl 3', 4 '-epoxycyclohexanecarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl 3', 4 '-epoxy-6' -methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3, 4-epoxycyclohexylmethyl) ether, ethylenebis (3, 4-epoxycyclohexanecarboxylate), dioctyl cyclohexylphthalate, di-2-ethylhexyl cyclohexylphthalate, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 13-tetradecane dioxide, limonene dioxide, 1,2,7, 8-diepoxyoctane and the like.
The content of the auxiliary monomer is 0 to 5% by weight, preferably 0 to 3% by weight, of the sum of the aforementioned components A, B and C.
The photocurable composition of the present invention may further comprise an auxiliary component E, wherein the auxiliary component E may be organic and/or inorganic auxiliary agents commonly used in the art, including but not limited to color materials, leveling agents, curing accelerators, light/heat acid generators, plasticizers, adhesion promoters, fillers, defoamers, surface modifiers, antioxidants, uv absorbers, dispersing aids, anti-agglomeration agents, catalysts, thickeners, sensitizers, coupling agents, crosslinking agents, etc.
As the coloring material, for example, a pigment, a dye, a natural pigment, and the like can be used, and these coloring materials may be used alone or in combination of two or more.
As an illustrative example of the Blue Pigment or cyan Pigment, Pigment Blue (Pigment Blue)1, 2, 3, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60; examples of the Green Pigment include Pigment Green (Pigment Green)7, 26, 36, and 50.
Examples of the Red Pigment or magenta Pigment include Pigment Red (Pigment Red)1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 19, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:2, 58:4, 63:1, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, iron oxide, and the like; examples of the Violet Pigment include Pigment Violet (Pigment Violet)3, 19, 23, 29, 30, 37, 50, 88; examples of orange pigments include pigment orange (pigment orange)13, 16, 20, and 36.
Examples of the Yellow Pigment include Pigment Yellow (Pigment Yellow)1, 2, 3, 4, 5, 6, 7, 10, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193.
Examples of the Black Pigment include Pigment Black (Pigment Black)7, 28, and 26, furnace Black, lamp Black, acetylene Black, and channel Black; mitsubishi chemical products NO.2300, NO.900, MCF88, NO.33, NO.40, NO.45, NO.52, MA7, MA8 and MA 100; carbon blacks such as Regal 400R, Regal 300R, Regal 660R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, and Monarch 1400 manufactured by Cabot Japan.
Examples of the White Pigment include Pigment White (Pigment White)6, 18, 21, and titanium oxide.
The content of the above color material is 0 to 40% by weight, preferably 5 to 40% by weight, based on the total mass of the components a + B + C + D in the photocurable composition of the present invention. The average particle size of the color material is not particularly limited and may be appropriately selected depending on the intended use.
For the dispersion of the color materials, there are optional dispersion apparatuses such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint stirrer, a kneader, a stirrer, a henschel mixer, a colloid mill, an ultrasonic homogenizer, a bead mill, a wet jet mill, or the like.
In the present invention, in order to stably disperse the color material in the photocurable composition of the present invention, it is preferable to add a dispersion monomer and/or a dispersion aid. The content of the dispersing aid in the photocurable composition of the present invention is 1 to 80 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the color material. When the dispersion aid is set within the above range, the color material is not easily aggregated or precipitated when used in the composition, and the composition has excellent storage stability and suitable viscosity.
As the dispersing aid usable in the present invention, a polymer dispersant is preferable. As an illustrative example, the polymer dispersant may be mentioned DISPERBYK-101/102/103/106/111/161/162/163/164/166/167/168/170/171/174/182 manufactured by BYK Chemie, etc.; EFKA4010/4046/4080/5010/5207/5244/6745/6750/7414/7462/7500/7570/7575/7580 prepared from EFKA additive; DISPERSE AID 6/8/15/9100 manufactured by San Nopco Limited, and the like; SOLSPERSE dispersants made by Avecia such as: SOLSPERSE3000/5000/9000/12000/13240/13940/17000/22000/24000/26000/28000/32000/36000/39000/41000/71000, etc.; ADEKA PLURONIC L31/F38/L42/L44/L61/L64/F68/L72/P95/F77/P84/F87/P94/L101/P103/F108/L121 manufactured by Adeka corporation, and the like.
The dispersion monomer used when the color material is dispersed in the above composition is not particularly limited, and for example, a polymerizable compound having a low molecular weight, preferably a low-viscosity polymerizable compound, may be used as the dispersion monomer. When the dispersing monomer, the color material and the dispersing auxiliary agent are preferentially mixed, the sum of the weight fraction of the dispersing monomer and the weight fraction of the color material is 100 percent.
The sensitizer is used for the purpose of improving the sensitivity of the ink, and particularly when the radiation source is an LED, the sensitizer may be a pyrazoline compound, an acridine compound, an anthracene compound, a thioxanthone compound, a naphthalene compound, a coumarin compound, a tertiary amine compound, or the like. As the anthracene-based sensitizer compound, the sensitizer content is 0-0.5 wt%, preferably 0.01-0.5 wt%, based on the total mass of the aforementioned components A + B + C + D, and may be selected from the sensitizers disclosed in patent 2017100354353, preferably one or more combinations selected from the following compounds:
in order to obtain a coating effect excellent in smoothness, the photocurable composition of the present invention may contain a leveling agent in an amount of 0 to 0.5 wt%, preferably 0.01 to 0.5 wt%, of the total of component a to component D.
In a second exemplary embodiment of the present application, an anti-fog and anti-fouling application of any one of the above-mentioned photocurable compositions on a solid wood substrate surface, a metal substrate surface or a glass substrate surface is provided. The three components A, B and C are used as curing monomers, and a photocuring film formed by curing under the action of the component D photoacid generator has good stability, can permanently maintain excellent antifogging and antifouling performances, and can effectively prolong the service life of a protected product. The coating is suitable for further popularization and application on the surfaces of furniture such as glass windows, bathroom mirrors and the like, automobile rearview mirrors/reflectors, solar panels, monitoring camera protective covers, lenses, illuminating lamp protective covers, glass substrate lampshade paints and the like.
In a third exemplary embodiment of the present application, there is provided a substrate having a photocurable film disposed on a surface thereof, wherein the photocurable film is formed by curing any one of the photocurable compositions described above. The photocuring film cured by the photocuring composition has good stability and excellent antifogging and antifouling performance, so that the service life of a corresponding base material can be effectively prolonged.
In a preferred embodiment, the pure water contact angle of the photo-cured film on the surface of the substrate is 95 to 150 °, and the hexadecane contact angle is 30 to 85 °. The surface of the photocured film prepared by the photocuring composition is not easy to adhere water-based stains such as ink, fingerprints, sweat and cosmetics or oil-based stains, and the water-based stains or oil-based stains can be easily removed by paper towels or the like when the stains are adhered, so that the antifogging and antifouling performance is recovered, and the surface with excellent antifogging and antifouling persistence is obtained.
The base material is not particularly limited, and may be appropriately selected depending on the purpose of use, and may be, for example: resin-based substrates, inorganic substrates, composite substrates, and the like. The resin-based substrate may be: polyester (TPEE), polyethylene terephthalate (PET), Polyamide (PA), aramid, Polyethylene (PE), polyacrylate, polypropylene (PP), polystyrene, polyvinyl chloride, polymethacrylate resin (PMMA), Polycarbonate (PC), epoxy resin, urea resin, polyurethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), and the like. The inorganic substrate may be: inorganic oxide substrates (quartz, sapphire, glass, etc.), metal substrates (iron-based, chromium-based, nickel-based, copper-based, titanium-based, aluminum-based, zinc-based, magnesium-based, etc.), and the like. The composite substrate may be: a substrate comprising glass and a resin material and compounded by mixing the glass and the resin material, a resin composite substrate obtained by kneading or bonding a plurality of resin materials, a composite substrate having a laminated structure obtained by laminating a plurality of materials, and the like.
In a preferred embodiment, the substrate may be a solid wood substrate, a metal substrate or a glass substrate.
The substrate preferably has transparency. The shape of the substrate is not particularly limited, and may be appropriately selected according to the purpose, and is preferably a film shape; and characters, patterns, images and the like can be printed on the surface of the base material.
When the photocurable composition is molded into a photocurable film, a pressure-sensitive adhesive layer may be provided on the surface of the substrate in order to improve the adhesion between the substrate and the molding material or to protect characters, patterns or images protected by the photocurable film from the material flow pressure during molding. The material of the adhesive layer may be selected from: acrylate series, polyurethane series, polyester series, polyamide series, ethyl acetate copolymer series, and the like.
The photocurable composition of the present invention can be used for photocuring molding by merely stirring and mixing it to be uniform, and specifically, it can be stirred and mixed to be uniform by using a stirrer, a disperser, a homogenizer, or the like. The specific coating method is appropriately selected depending on the purpose, and known methods such as coating methods using a bar, a wire bar, a blade, reverse roll coating, spray coating, microgravure, gravure, curtain, or spin coating can be used. The specific coating thickness of the photocurable composition of the present invention is not particularly limited, and may be suitably selected according to the purpose, and is generally 1 to 100. mu.m, preferably 4 to 50 μm. When the average thickness is within the above range, the anti-fogging and anti-fouling properties of the photocurable composition of the present invention are better.
In the present application, a specific curing method of the above-mentioned curable composition is a method of applying the photocurable composition to a substrate and curing the photocurable composition on the substrate by irradiation with active energy rays (for example, ultraviolet rays, electron beams, visible rays having a wavelength of 400nm to 500nm, and the like). Specifically, as the light source of ultraviolet rays and visible rays having a wavelength of 400nm to 500nm, an LED lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used.
The advantageous effects of the present application will be further described with reference to specific examples.
The starting materials used in the following examples are, unless otherwise indicated, all materials commonly used in the art and commercially available. The test methods used in the following examples and comparative examples are as follows:
the contact angle of pure water was measured by ellipsometry under the following conditions using DM-701 (manufactured by Kyowa Kagaku K.K.). The specific steps of the pure water contact angle test are as follows: distilled water was put into a plastic syringe, a stainless steel needle was attached to the tip of the syringe, 2. mu.L of distilled water was dropped on the evaluation surface, the measurement temperature was 25 ℃, contact angles after 4 seconds of dropping water were measured at 10 positions on the surface of the antifogging and antifouling layer, and the average value was taken as a contact angle of pure water.
The hexadecane contact angle was measured by ellipsometry under the following conditions using DM-701 (manufactured by Kyowa Kagaku K.K.). The specific steps of the hexadecane contact angle test are as follows: the hexadecane was put into a plastic syringe, a stainless steel needle coated with Teflon was attached to the tip thereof, 2. mu.L of hexadecane was dropped on the evaluation surface, the measurement temperature was 25 ℃, the contact angle after 4 seconds of dropping of hexadecane was measured at 10 positions on the surface of the antifogging and antifouling layer, and the average value was taken as the hexadecane contact angle.
The adhesion test refers to a GB/T13217.7-2009 adhesion fastness test method, an adhesive tape meeting the standard GB 7707 is stuck on a detection layer surface under the conditions of 25 +/-1 ℃ and 65% +/-5% humidity, and is rolled on a tape rolling machine for 3 times in a reciprocating mode. Placing for 5min, clamping the sample on disk A, fixing the tape with exposed head on disk B, starting machine, rotating disk A at speed of 0.6-1.0m/s to uncover the tape, and covering the uncovered part with semi-transparent millimeter paper with width of 20 mm. Counting the number of the lattices occupied by the detection layer and the number of the lattices occupied by the uncovered detection layer respectively, and calculating according to the following formula: a (%) [ a1/(a1+ a2) ] × 100%, where a represents the adhesion, a1 represents the number of squares of the test layer, and a2 represents the number of squares of the test layer that was peeled off. A.gtoreq.90 is understood to meet the performance criteria.
The pencil hardness test is determined by referring to GB/T6739-2006, and specifically comprises the following steps: a pencil (MITSU-BISHI/UNI test pencil) was inserted into the test instrument and held with a clamp so that the instrument was held horizontally, the tip of the pencil was placed on the paint film surface, then pushed at a speed of 0.5-1mm/s in a direction away from the operator for a distance of at least 10mm, and finally any debris of the pencil lead on the coating surface was wiped off with an eraser. The results were evaluated, and the coating hardness was represented by the highest hardness of a pencil used when no breakage occurred.
The test for breath antifogging property is: the surface was subjected to 1-time large-mouth exhalation at 25 ℃ and 37% RH from a distance of 5cm from the surface of the antifogging and antifouling layer in the normal direction, immediately thereafter, the surface was visually observed, and evaluated according to the following evaluation criteria: o: the surface of the antifogging antifouling layer is not changed in appearance at all; very good: white fog was observed on the surface of the antifogging antifouling layer; x: appearance changes such as water film formation were observed on the surface of the antifogging and antifouling layer.
The tests of the antifouling test were: the surface of the antifogging and antifouling layer was touched with a commercially available oil pen (a deli plate), and the ink state on the surface of the antifogging and antifouling layer was visually observed and evaluated according to the following evaluation criteria: o: > 50% area of ink was repelled; very good: ink is repelled in an area of less than or equal to 50%; x: > 50% area of ink adhesion.
The wipe test was: the surface of the antifogging and antifouling layer was touched with a commercially available oil pen (a force plate), and then the ink on the surface of the antifogging and antifouling layer was wiped with a paper towel (a commercially available fresh air coreless roll paper) 2 times in a circle-drawing manner, and the state after wiping was visually confirmed, after which a breath antifogging test was performed, and evaluation was performed according to the following evaluation criteria: o: the ink is wiped off, and the surface of the antifogging antifouling layer does not have appearance change after the expiration test; very good: the printing ink is wiped off, and white fog is formed on the surface of the antifogging antifouling layer after the expiration test; x: the ink was not wiped off, and/or the formation of a water film or the like was observed on the surface of the antifogging and antifouling layer.