Ultraviolet absorbing composition, ultraviolet absorbing resin, and method for producing the same

Abstract

To provide an ultraviolet-absorbing resin with a specific composition that efficiently absorbs ultraviolet rays, offers excellent visible light transmittance, and also exhibits high stability.SOLUTION: The present disclosure provides an ultraviolet-absorbing composition, including 35 to 45 wt.% of a fluorocarbon resin, 5 to 25 wt.% of an isocyanate curing agent, 1 to 5 wt.% of an ultraviolet absorbent, and the remainder as a solvent, based on total weight of the ultraviolet-absorbing composition. The present disclosure further provides an ultraviolet-absorbing resin, an ultraviolet-absorbing structure including the same, and a method for preparing the same.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates to an ultraviolet absorbing resin formed from a specific resin composition, including a fluorocarbon resin, an isocyanate curing agent, and an ultraviolet absorber, and also to an ultraviolet absorbing structure including multiple ultraviolet absorbing resin layers. [Background technology]

[0002] Since long-term exposure to ultraviolet rays can have adverse effects on devices, devices such as sensor elements, personal computers, communication products, consumer electronic products, and automotive products are usually equipped with elements capable of blocking ultraviolet rays, such as ultraviolet filters, which are widely used in optical devices. The ultraviolet filters used in optical devices are generally required to have a significant ultraviolet blocking effect and good transmittance for visible light.

[0003] The filtering effect of UV filters can deteriorate over time, so it is necessary to protect the UV absorber within the filter using a substrate to improve its UV resistance and stability. Previously, it was reported that the UV absorber could be protected by using epoxy resin and acrylic resin as the main resin layer. However, testing showed that this UV filter failed a 1,000-hour UV resistance test, and its performance needed to be improved. Meanwhile, the use of these resins requires high processing temperatures, so in coating applications, the substrate must also be able to withstand high temperatures, limiting substrate selection and limiting its widespread market application. Summary of the Invention

[0004] To address the above-mentioned problems, the present disclosure provides an ultraviolet absorbing composition that can be formed into an ultraviolet absorbing resin through processes such as drying and curing, and the ultraviolet absorbing composition includes a fluorocarbon resin having a protective function, an isocyanate curing agent, an ultraviolet absorber, and a solvent.

[0005] In the ultraviolet absorbing composition of the present disclosure, the fluorocarbon resin is 35 to 45 wt %, the isocyanate curing agent is 5 to 25 wt %, the ultraviolet absorber is 1 to 5 wt %, and the solvent is the remainder, based on the total weight of the ultraviolet absorbing composition.

[0006] In one embodiment, the fluorocarbon resin comprises fluorinated ethylene repeat units according to Formula 1: TIFF0007796170000001.tif5794In the formula, X1, X2, X3, and X4 each independently represent hydrogen, fluorine, or a substituted or unsubstituted C1-C 12 Alkyl groups, substituted or unsubstituted C3-C 12 Cycloalkyl groups, substituted or unsubstituted C6-C 12 an aryl group, n is any positive integer, and at least one of X1, X2, X3, and X4 is fluorine or a group substituted with fluorine.

[0007] In one embodiment, the fluorocarbon resin further comprises a second repeat unit different from the fluorinated ethylene repeat unit.

[0008] In one embodiment, the isocyanate curing agent is selected from the group consisting of hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), 12 At least one selected from the group consisting of methyl methyl diisocyanate (MDI), naphthalene diisocyanate (NDI), trimethylhexamethylene diisocyanate (TMDI), xylene diisocyanate (XDI), lysine diisocyanate (LDI), trimers of the above diisocyanates, triphenylmethane triisocyanate, toluol triisocyanate, and lysine triisocyanate.

[0009] In one embodiment, the ultraviolet absorber is at least one selected from the group consisting of azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, ketone compounds, and salicylic acid derivatives.

[0010] In one embodiment, the ultraviolet absorbing composition further comprises a solvent, hi another embodiment, the ultraviolet absorbing composition further comprises a light stabilizer.

[0011] In one embodiment, the ultraviolet absorbing composition includes a fluorocarbon resin, hexamethylene diisocyanate (HDI) as an isocyanate curing agent, a benzotriazole-based compound as an ultraviolet absorber, and xylene and butanone as a solvent.

[0012] In one embodiment, the ultraviolet absorbing composition includes 0.01 wt % to 2 wt % of a light stabilizer, a fluorocarbon resin, toluene diisocyanate (TDI) as an isocyanate curing agent, a benzotriazole-based compound as an ultraviolet absorber, and xylene as a solvent.

[0013] The present disclosure further provides an ultraviolet absorbing resin comprising the ultraviolet absorbing composition described herein.

[0014] In one embodiment, the ultraviolet absorbing resin comprises a fluorocarbon resin, an isocyanate curing agent, and an ultraviolet absorber.

[0015] In one embodiment, the fluorocarbon resin of the ultraviolet absorbing resin comprises a fluorinated ethylene repeat unit represented by Formula 1: TIFF0007796170000002.tif5794In the formula, X1, X2, X3, and X4 each independently represent hydrogen, fluorine, or a substituted or unsubstituted C1-C 12 Alkyl groups, substituted or unsubstituted C3-C 12 Cycloalkyl groups, substituted or unsubstituted C6-C 12an aryl group, n is any positive integer, and at least one of X1, X2, X3, and X4 is fluorine or a group substituted with fluorine.

[0016] In one embodiment, the isocyanate curing agent of the ultraviolet absorbing resin is hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), 12 At least one selected from the group consisting of methyl methyl diisocyanate (MDI), naphthalene diisocyanate (NDI), trimethylhexamethylene diisocyanate (TMDI), xylene diisocyanate (XDI), lysine diisocyanate (LDI), trimers of the above diisocyanates, triphenylmethane triisocyanate, toluol triisocyanate, and lysine triisocyanate.

[0017] In one embodiment, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays having a wavelength of 430 to 680 nm, and a maximum light transmittance of 1% or less for light rays having a wavelength of 380 to 410 nm, and an average transmittance of 1% or less.

[0018] In one embodiment, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays having a wavelength of 430 to 680 nm, and a maximum light transmittance of 1% or less and an average transmittance of 1% or less for light rays having a wavelength of 380 to 410 nm after a high-temperature, high-humidity test at 85°C and 85% humidity for 500 hours.

[0019] In one embodiment, after a high temperature and high humidity test at 85°C and 85% humidity for 1000 hours, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays having a wavelength of 430 to 680 nm, and a maximum light transmittance of 1% or less for light rays having a wavelength of 380 to 410 nm, and an average transmittance of 1% or less.

[0020] Furthermore, the present disclosure provides an ultraviolet-absorbing structure including a plurality of ultraviolet-absorbing resin layers, each of which contains an ultraviolet-absorbing resin described in the present disclosure, and the isocyanate curing agents of the ultraviolet-absorbing resins in each layer are different from each other.

[0021] In one embodiment, each UV absorbing resin layer of the UV absorbing structure is made from the UV absorbing composition described in this disclosure.

[0022] In one embodiment, the ultraviolet absorbing structure includes two ultraviolet absorbing resin layers, the isocyanate curing agent in the first ultraviolet absorbing resin layer is hexamethylene diisocyanate (HDI), and the isocyanate curing agent in the second ultraviolet absorbing resin layer is toluene diisocyanate (TDI).

[0023] In one embodiment, each ultraviolet absorbing resin layer of the ultraviolet absorbing structure has a thickness of 1 to 100 μm, hi another embodiment, the ultraviolet absorbing structure has a thickness of 2 to 200 μm.

[0024] The present disclosure also provides a method for producing an ultraviolet absorbing resin, the method comprising the steps of applying an ultraviolet absorbing composition described herein onto a surface of a substrate, and curing the ultraviolet absorbing composition to obtain an ultraviolet absorbing resin.

[0025] In one embodiment, the method for producing an ultraviolet absorbing resin further comprises the step of forming a plurality of ultraviolet absorbing resin layers by repeatedly applying and curing an ultraviolet absorbing composition to the ultraviolet absorbing resin layer.

[0026] In one embodiment, the isocyanate curing agent in the ultraviolet absorbing composition that is repeatedly applied and cured is different from the isocyanate curing agent in the ultraviolet absorbing composition that is applied onto the surface of the substrate.

[0027] In one embodiment, the substrate is glass or a triacetyl cellulose film.

[0028] In one embodiment, the coating is performed by spin coating, dip coating, cast coating, vinegar These are spray coating, bead coating, bar coating, doctor knife coating or slit coating.

[0029] In one embodiment, curing is carried out at a temperature of 100 to 150° C. for 10 to 60 minutes. [Brief explanation of the drawings]

[0030] [Figure 1A] FIG. 1A is a schematic diagram of the structure of a final product containing the ultraviolet absorbing resin of the present disclosure. [Figure 1B] FIG. 1B is a structural schematic diagram of another final product including the ultraviolet absorbing resin (ultraviolet absorbing structure) of the present disclosure. [Figure 2] Figure 2 shows the gloss retention rate of various base resins after irradiation with a QUV-A (Q-Lab ultraviolet accelerated) ultraviolet irradiation device. [Figure 3A] Figure 3A shows the transmittance curves of UV-absorbing resins containing various isocyanate curing agents in a UV resistance test. HDI: hexamethylene diisocyanate, IPDI: isophorone diisocyanate, XDI: xylene diisocyanate, TDI: toluene diisocyanate. TO: 0 hours of UV irradiation, T240: 240 hours of UV irradiation. [Figure 3B] Figure 3B shows the transmittance curves of UV-absorbing resins containing various isocyanate curing agents in a high temperature, high humidity (HTHH) weathering test. HDI: hexamethylene diisocyanate, IPDI: isophorone diisocyanate, XDI: xylene diisocyanate, TDI: toluene diisocyanate. TO: 0 hours of UV irradiation, T500: 500 hours of UV irradiation. [Figure 4A]4A is a transmittance curve diagram in an ultraviolet resistance test of the ultraviolet absorbing resins of Examples 1 and 2 and Comparative Example 3. T0: 0 hours of ultraviolet irradiation, T240: 240 hours of ultraviolet irradiation, T1000: 1000 hours of ultraviolet irradiation. [Figure 4B] 4B is a transmittance curve diagram in a high-temperature, high-humidity weather resistance test for the ultraviolet-absorbing resins of Examples 1 and 2 and Comparative Example 3. T0: 0 hours of ultraviolet irradiation, T500: 500 hours of ultraviolet irradiation. DETAILED DESCRIPTION OF THE INVENTION

[0031] Hereinafter, embodiments of the present disclosure will be described with reference to specific examples, but those skilled in the art can easily understand the scope and effects of the present disclosure from the contents described herein.

[0032] It should be noted that the structures, proportions, sizes, etc. shown in the drawings attached to this specification are all intended to be in accordance with the contents of the specification and to allow those skilled in the art to understand and read them, and are not intended to limit the conditions under which the present invention can be implemented, and have no substantial technical meaning. Any structural modification, change in proportional relationship, or adjustment in size is within the scope covered by the technical content disclosed in this specification, as long as it does not affect the effects and objectives achieved by the present invention. Furthermore, the terms "above," "first," "second," etc. used in this specification are intended to clarify the description, and are not intended to limit the scope of the present invention, and any change or adjustment of their relative relationship is considered to be within the scope of the present invention as long as it does not substantially change the technical content.

[0033] In this specification, when a particular feature is described as "comprising," "containing," or "having," unless otherwise specified, it may include other features such as elements, components, structures, regions, parts, devices, systems, steps, or connections, and does not exclude these other features.

[0034] As used herein, the singular forms "a," "an," and "the" include the plural forms, and "or" and "and / or" are used interchangeably, unless otherwise stated.

[0035] The numerical ranges described herein are inclusive and combinable, and any numerical value falling within a range recited herein can be used to derive subranges, etc., as a maximum or minimum value. For example, a numerical range of "5 to 25" should be understood to include any subrange between the endpoints 5 and 25, such as 5 to 15, 10 to 25, 10 to 15, etc. Additionally, any numerical value within each range described herein (e.g., between the maximum and minimum values) is considered to be within the scope of the present disclosure.

[0036] A first aspect of the present disclosure is an ultraviolet absorbing composition comprising a fluorocarbon resin, an isocyanate curing agent, an ultraviolet absorber, and a solvent.

[0037] The fluorocarbon resin mainly uses a base resin and protects the UV absorber therein. Exemplary fluorocarbon resins include, but are not limited to, fluorinated ethylene repeating units, such as monofluoroethylene, difluoroethylene, trifluoroethylene, and tetrafluoroethylene. Meanwhile, the fluorinated ethylene repeating units may be substituted with other groups in addition to being substituted with fluorine atoms, or may be modified, grafted, or otherwise modified to have diverse side chains. For example, the hydrogen atoms of fluorinated ethylene may be substituted with alkyl groups to form side chains, such as fluorinated propylene repeating units, fluorinated butene repeating units, and fluorinated styrene repeating units.

[0038] In one embodiment, the fluorocarbon resin comprises a fluorinated ethylene repeat unit represented by Formula 1: TIFF0007796170000003.tif5794In the formula, X1, X2, X3, and X4 each independently represent hydrogen, fluorine, or a substituted or unsubstituted C1-C 12 Alkyl groups, substituted or unsubstituted C3-C 12 Cycloalkyl groups, substituted or unsubstituted C6-C 12 an aryl group, n is any positive integer, and at least one of X1, X2, X3, and X4 is fluorine or a group substituted with fluorine.

[0039] Said C1-C 12 The alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a pentyl group. 12 The cycloalkyl group is, for example, a cyclopropyl group or a cyclobutyl group, and the C6-C 12 The aryl group is, for example, a phenyl group, a naphthyl group, etc. The substitution can be, for example, a hydrogen atom being replaced with a fluorine atom, a C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C6-C 12 It is substituted with a substituent such as an aryl group.

[0040] In one embodiment, the fluorocarbon resin further comprises a second repeat unit different from the fluorinated ethylene repeat unit.

[0041] In one embodiment, the fluorocarbon resin is polyfluoroethylene (PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylenetetrafluoroethylene (ETFE), perfluoroalkoxy polymer (PFA) or fluorinated ethylene propylene (FEP).

[0042] In one embodiment, the second repeating unit is an alkyl vinyl ether repeating unit. In yet another embodiment, the fluorocarbon resin is a perfluoroethyl vinyl ether (PEVE) type fluorocarbon resin, wherein X1, X2, and X3 in Formula 1 are fluorine, and X4 is a substituted or unsubstituted C1-C 12 Alkyl groups, substituted or unsubstituted C3-C 12 Cycloalkyl groups, substituted or unsubstituted C6-C 12 The repeating unit of the alkyl vinyl ether is -[CHR1-CHOR2]-, where R1 and R2 are hydrogen, substituted or unsubstituted C1-C 12 Alkyl groups, substituted or unsubstituted C3-C 12 It is a cycloalkyl group.

[0043] In the present disclosure, the isocyanate curing agent not only serves to cure the ultraviolet absorbing composition but also to impart light resistance and high temperature and humidity resistance to the resulting ultraviolet absorbing resin. The isocyanate curing agent may be hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), or the like. 12 At least one selected from the group consisting of hexamethylene diisocyanate (MDI), naphthalene diisocyanate (NDI), trimethylhexamethylene diisocyanate (TMDI), xylene diisocyanate (XDI), lysine diisocyanate (LDI), trimers of the above diisocyanates, triphenylmethane triisocyanate, toluene triisocyanate, and lysine triisocyanate can be used. In one embodiment, the isocyanate curing agent is hexamethylene diisocyanate (HDI). In another embodiment, the isocyanate curing agent is toluene diisocyanate (TDI).

[0044] In the present disclosure, the UV absorber primarily absorbs light with wavelengths of 380 to 410 nm and converts UV light energy into heat energy or other non-destructive longer wavelengths, thereby effectively protecting devices and preventing UV interference and damage. Applicable devices include, for example, sensor elements, personal computers, communication products, consumer electronics products, automotive products, and other devices exposed to UV light for long periods of time. The UV absorber can be at least one selected from the group consisting of azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, ketone compounds, and salicylic acid derivatives. In one embodiment, the UV absorber is a benzotriazole compound.

[0045] In one embodiment, the ultraviolet absorbing composition of the present disclosure may further include a light stabilizer that mainly repairs areas of photooxidative degradation caused by ultraviolet light in the ultraviolet absorbing composition of the present disclosure and assists the ultraviolet absorption. The light stabilizer may be a hindered amine light stabilizer (HALS), and specifically, a monomolecular hindered amine light stabilizer, a polymeric hindered amine light stabilizer, or a low-alkali hindered amine light stabilizer, such as a 2,2,6,6-tetramethylpiperidine derivative.

[0046] In the present disclosure, based on the total weight of the ultraviolet absorbing composition, the fluorocarbon resin is 35-45 wt%, the isocyanate curing agent is 5-25 wt%, the ultraviolet absorber is 1-5 wt%, and the remainder is solvent. In one embodiment, the weight of the fluorocarbon resin is 35-45 wt%, including, but not limited to, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, and / or 45 wt%. In one embodiment, the weight of the isocyanate curing agent is 5 to 25 wt%, including, but not limited to, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, and / or 25 wt%. In one embodiment, the weight of the UV absorber is 1 to 5 wt%, including, but not limited to, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, and / or 5 wt%.

[0047] In one embodiment, the solvent for the ultraviolet absorbing composition is not limited, and known solvents can be selected, including, but not limited to, water, alcohols, ketones, ethers, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, etc. Specific examples of the alcohols include methanol, ethanol, and propanol. Examples of the ketones include acetone and butanone. Examples of the esters include alkyl formate, alkyl acetate, alkyl propionate, alkyl butanoate, alkyl lactate, alkyl alkoxylate, alkyl 3-alkoxypropionate, alkyl 2-alkoxypropionate, alkyl 2-alkoxy-2-methylpropionate, alkyl acetonate, alkyl acetoacetate, and alkyl 2-oxobutanoate. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene. In one embodiment, the solvent is a mixed solvent of xylene and butanone. In another embodiment, the solvent is xylene.

[0048] In one embodiment, the weight of the solvent in the ultraviolet absorbing composition of the present disclosure is not limited, but for example, the weight of the solvent is 25 to 59 wt %, including but not limited to 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, and 59 wt %, based on the total weight of the ultraviolet absorbing composition. The solvent may be a single solvent or a mixed solvent. In one embodiment, the solvent is a mixed solvent, comprising a first solvent and a second solvent, wherein the first solvent is present in an amount of 15-25 wt%, including but not limited to 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, and / or 25 wt%, and the second solvent is present in an amount of 20-25 wt%, including but not limited to 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, and / or 25 wt%. In another embodiment, the solvent is a single solvent, and the amount by weight is 40-45 wt%, including but not limited to 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, and / or 45 wt%.

[0049] In one embodiment, the ultraviolet absorbing composition of the present disclosure includes a fluorocarbon resin, hexamethylene diisocyanate (HDI) as an isocyanate curing agent, a benzotriazole-based compound as an ultraviolet absorber, and xylene and butanone as a solvent. In another embodiment, the ultraviolet absorbing composition of the present disclosure includes a fluorocarbon resin, toluene diisocyanate (TDI) as an isocyanate curing agent, a benzotriazole-based compound as an ultraviolet absorber, and xylene as a solvent.

[0050] In one embodiment, the ultraviolet absorbing composition of the present disclosure can be in the form of a dispersion, and the ultraviolet absorber is uniformly dispersed in the ultraviolet absorbing composition, thereby avoiding deterioration of the ultraviolet blocking effect and haze due to aggregation.

[0051] A second aspect of the present disclosure is an ultraviolet-absorbing resin that can be formed from the ultraviolet-absorbing composition described herein. Specifically, the ultraviolet-absorbing resin includes a fluorocarbon resin, an isocyanate curing agent, and an ultraviolet absorber. Here, the types of the fluorocarbon resin, isocyanate curing agent, and ultraviolet absorber of the ultraviolet-absorbing resin are the same as those described in the first aspect of the present disclosure.

[0052] In one embodiment, the ultraviolet absorbing resin of the present disclosure is obtained from the ultraviolet absorbing composition of the first aspect of the present specification, for example, by drying and curing the ultraviolet absorbing composition to obtain the ultraviolet absorbing resin.

[0053] In one embodiment, the ultraviolet absorbing resin of the present disclosure includes a fluorocarbon resin, hexamethylene diisocyanate (HDI) as an isocyanate curing agent, and a benzotriazole-based ultraviolet absorber. In another embodiment, the ultraviolet absorbing resin of the present disclosure includes a fluorocarbon resin, toluene diisocyanate (TDI) as an isocyanate curing agent, and a benzotriazole-based ultraviolet absorber.

[0054] In one embodiment, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays in the wavelength range of incident light of 430 to 680 nm, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, and has a maximum light transmittance of 1% or less for light rays having a wavelength of 380 to 410 nm, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%, and the average transmittance is 1% or less, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%.

[0055] In one embodiment, after a high temperature and humidity test at 85°C and 85% humidity for 500 hours, the ultraviolet absorbing resin has an average transmittance of 85% or more for light having a wavelength of 430 to 680 nm, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, and a maximum light transmittance of 1% or less for light having a wavelength of 380 to 410 nm, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%, and an average transmittance of 1% or less, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%.

[0056] In one embodiment, after a high temperature and humidity test at 85°C and 85% humidity for 1000 hours, the ultraviolet absorbing resin has an average transmittance for light having a wavelength of 430 to 680 nm of 85% or more, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, and a maximum light transmittance for light having a wavelength of 380 to 410 nm of 1% or less, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%, and the average transmittance is 1% or less, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, or 0.5%.

[0057] A third aspect of the present disclosure is an ultraviolet absorbing structure including a plurality of ultraviolet absorbing resin layers, each of which includes the ultraviolet absorbing resin layer according to the second aspect of the present disclosure. In one embodiment, the isocyanate curing agents in the ultraviolet absorbing resins of each layer are different from each other.

[0058] In one embodiment, the multiple layers are, for example, two, three, four or more layers. In one example, the multiple layers are two layers. In yet another example, the multiple layers are two layers, and the isocyanate curing agent in the first ultraviolet-absorbing resin layer is hexamethylene diisocyanate (HDI), and the isocyanate curing agent in the second ultraviolet-absorbing resin layer is toluene diisocyanate (TDI).

[0059] In one embodiment, the thickness of each ultraviolet absorbing resin layer in the ultraviolet absorbing structure is 1 to 100 μm, including, but not limited to, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, and 100 μm. In one embodiment, the thickness of the ultraviolet absorbing structure is 2 to 200 μm, including, but not limited to, 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, and / or 200 μm.

[0060] A fourth aspect of the present disclosure is a method for producing an ultraviolet-absorbing resin, comprising the steps of applying an ultraviolet-absorbing composition described herein onto a surface of a substrate and curing the ultraviolet-absorbing composition to obtain an ultraviolet-absorbing resin. As shown in Figure 1A, the ultraviolet-absorbing composition is applied onto the surface of a substrate 10, and the ultraviolet-absorbing composition is cured to become an ultraviolet-absorbing resin 20, ultimately obtaining a final product 1 containing the ultraviolet-absorbing resin.

[0061] In one embodiment, the manufacturing method of the present disclosure further comprises mixing a fluorocarbon resin, an isocyanate curing agent, an ultraviolet absorber, and a solvent to form a composition, wherein the type and amount of each ingredient are as described herein.

[0062] The coating method is not limited as long as it can uniformly coat the composition on the surface of the substrate, and is included in the scope of the present disclosure. In one embodiment, the coating method is spin coating, dip coating, cast coating, spray coating, bead coating, bar coating, doctor knife coating, or slit coating.

[0063] The substrate is within the scope of the present disclosure and is not limited to any article having a surface that can be coated, including semi-finished and finished products. In one embodiment, the substrate is glass, triacetate cellulose (TAC) film, or a plastic film such as PET.

[0064] The curing method is not limited as long as it can cure the composition, and is within the scope of the present disclosure. In one embodiment, the curing is performed at a temperature of 100 to 150°C for 10 to 60 minutes, and the curing temperature includes, but is not limited to, 100°C, 110°C, 120°C, 130°C, 140°C, and 150°C, and the curing time includes, but is not limited to, 10, 15, 20, 30, 40, 50, and 60 minutes.

[0065] In one embodiment, the manufacturing method of the present disclosure further includes a step of forming multiple UV-absorbing resin layers by repeatedly applying and curing a UV-absorbing composition to the UV-absorbing resin layer. As shown in Figure 1B, a UV-absorbing composition is applied to the surface of substrate 10 and cured to form first UV-absorbing resin layer 21. Next, the above steps are repeated using the same or a different UV-absorbing composition to form second UV-absorbing resin layer 22, resulting in a final product comprising two UV-absorbing resin layers 21 and 22.

[0066] In one embodiment, the isocyanate curing agent in the ultraviolet absorbing composition that is repeatedly applied and cured is different from the isocyanate curing agent in the ultraviolet absorbing composition that is applied onto the surface of the substrate. [Example]

[0067] The present disclosure will be further described in detail with reference to the following specific examples and comparative examples, but these specific examples and comparative examples are not intended to limit the scope of the present invention.

[0068] Resin Selection Fluorinated vinyl ether (FEVE), polyester polyurethane, acrylic urethane, and siloxane resin were used as resin coating layers, and measurements were taken using a QUV-A ultraviolet irradiation device. The gloss retention rate of each resin coating layer after long-term exposure to ultraviolet light is shown in Figure 2. As can be seen from the results in Figure 2, the UV resistance of the resin coating layers is highest in the following order: FEVE > siloxane resin > acrylic urethane > polyester polyurethane. The UV resistance of the FEVE-type fluorocarbon resin coating layer is the best due to the fluorine-carbon bond in its structure, but this is not intended to be bound by theory.

[0069] Example 1 - UV-absorbing resin A UV-absorbing composition was prepared by mixing 40-50 wt% FEVE-type fluorocarbon resin (e.g., DS302 series resin, purchased from Yijin Technology; Lumiflon series resin, purchased from Asahi Technology; New Gamet-FEVE series resin, purchased from Deka Resin), 15-21% HDI, 1-5% benzotriazole-based UV absorber (Eversorb series dye, purchased from Yongguang Science), 15-20% xylene, and 20-25% butanone. The UV-absorbing composition was then spin-coated onto glass and cured by baking at 120°C for 30 minutes to obtain a UV-absorbing resin.

[0070] Examples 2 to 4 - UV-absorbing resin UV-absorbing resins were produced by replacing HDI in the UV-absorbing composition with IPDI, XDI, and TDI, respectively, based on Example 1. That is, Examples 1 to 4 use an HDI curing agent, an IPDI curing agent, an XDI curing agent, and a TDI curing agent, respectively.

[0071] The ultraviolet absorbing resins of Examples 1 to 4 were subjected to an ultraviolet resistance test to evaluate the influence of different curing agents. The ultraviolet resistance test was carried out after 0 and 240 hours of ultraviolet irradiation (UV wavelength: 420 nm, irradiation intensity: 2.4 W / M 2After the test, the transmittance curves of each UV-absorbing resin are shown in Figure 3A. According to Figure 3A, Example 1, which uses HDI curing agent, has the best resistance to UV rays. The order of UV resistance is Example 1 (HDI curing agent) > Example 4 (TDI curing agent) > Example 3 (XDI curing agent) > Example 2 (IPDI curing agent).

[0072] The UV-absorbing resins of Examples 1 to 4 were subjected to UV resistance tests in a high-temperature, high-humidity environment to evaluate the effects of different curing agents. The UV resistance tests were conducted at 0 and 500 hours of UV irradiation (UV wavelength: 420 nm, irradiation intensity: 2.4 W / M). 2 ). The transmittance curves of each UV-absorbing resin after the test are shown in Figure 3B. As shown in Figure 3B, Example 4, which uses a TDI curing agent, exhibits high resistance to UV rays in a high-temperature, high-humidity environment, has the best weather resistance, and can enhance protective effects. Furthermore, the order of highest resistance to UV rays in a high-temperature, high-humidity environment (weather resistance) is Example 4 (TDI curing agent) > Example 2 (IPDI curing agent) > Example 3 (XDI curing agent) > Example 1 (HDI curing agent).

[0073] In practical applications, the ultraviolet absorbing resin layer can be selected or combined according to the requirements based on the ultraviolet resistance, durability, and needs.

[0074] Comparative Example 1 Based on Example 1, an ultraviolet absorbing resin was produced by replacing the fluorocarbon resin in the ultraviolet absorbing composition with an acrylic resin.

[0075] The ultraviolet absorbing resins of Examples 1, 4, and Comparative Example 1 were subjected to an ultraviolet resistance test to evaluate the influence of different fluorocarbon resins. The ultraviolet resistance test was carried out at ultraviolet irradiation times of 0, 240, and 1000 hours (UV wavelength: 420 nm, irradiation intensity: 2.4 W / M 2) The transmittance curves of each ultraviolet-absorbing resin after the test are shown in Figure 4A. As shown in Figure 4A, the ultraviolet-absorbing resins of Examples 1 and 4 both passed the 1000-hour ultraviolet resistance test. However, the ultraviolet-absorbing resin of Comparative Example 1 deteriorated significantly after 240 hours of ultraviolet irradiation, and its transmittance for light with a wavelength of 380 to 410 nm was too high to meet the requirements, indicating that Comparative Example 1, which used an acrylic resin, simply had poor ultraviolet resistance.

[0076] The ultraviolet absorbing resins of Examples 1, 4, and Comparative Example 1 were subjected to an ultraviolet resistance test in a high-temperature, high-humidity environment to evaluate the influence of different fluorocarbon resins. The ultraviolet resistance test was carried out at 0 and 500 hours of ultraviolet irradiation (UV wavelength: 420 nm, irradiation intensity: 2.4 W / M). 2 The transmittance curves of each ultraviolet-absorbing resin after the test are shown in FIG. 4B. According to FIG. 4B, the ultraviolet-absorbing resins of Examples 1 and 4 and Comparative Example 1 exhibit excellent ultraviolet resistance even in a high-temperature, high-humidity environment, i.e., have excellent weather resistance.

[0077] The above embodiments and specific examples do not limit the present disclosure, and the listed technical features or solutions can be combined with each other, the present disclosure can be realized or applied in other different embodiments, and the details described in this specification can be variously modified or altered based on different perspectives and applications without departing from the gist of the present disclosure. [Explanation of symbols]

[0078] 1: Final products containing UV-absorbing resin 10: Base material 20: UV absorbing resin 21: First ultraviolet absorbing resin layer 22: Second ultraviolet absorbing resin layer

Claims

1. An ultraviolet absorbing structure comprising a plurality of ultraviolet absorbing resin layers, Each of the ultraviolet absorbing resin layers contains an ultraviolet absorbing resin made of an ultraviolet absorbing composition, The ultraviolet absorbing composition contains, based on the total weight of the ultraviolet absorbing composition, 35 to 45 wt % of a fluorocarbon resin, 5 to 25 wt % of an isocyanate curing agent, 1 to 5 wt % of an ultraviolet absorber, and the remainder being a solvent; The ultraviolet absorbing structure, wherein the isocyanate curing agents of the ultraviolet absorbing resins of the respective layers are different from each other.

2. 2. The ultraviolet absorbing structure of claim 1, wherein the fluorocarbon resin comprises a fluorinated ethylene repeat unit represented by Formula 1: [In the formula, X １ , X ２ , X ３ , and X ４ are each independently hydrogen, fluorine, substituted or unsubstituted C １ -C １２ alkyl group, substituted or unsubstituted C ３ -C １２ Cycloalkyl groups, substituted or unsubstituted C ６ -C １２ an aryl group, n is any positive integer, and １ , X ２ , X ３ , and X ４ At least one of is fluorine or a group substituted with fluorine.

3. The isocyanate curing agent may be hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (H １２ 2. The ultraviolet absorbing structure of claim 1, wherein the diisocyanate is at least one of the group consisting of methyl methyl diisocyanate (MDI), naphthalene diisocyanate (NDI), trimethylhexamethylene diisocyanate (TMDI), xylene diisocyanate (XDI), lysine diisocyanate (LDI), trimers of the above diisocyanates, triphenylmethane triisocyanate, toluol triisocyanate, and lysine triisocyanate.

4. 2. The ultraviolet absorbing structure according to claim 1, wherein the ultraviolet absorber is at least one selected from the group consisting of an azomethine compound, an indole compound, a benzotriazole compound, a triazine compound, a ketone compound, and a salicylic acid derivative.

5. The ultraviolet absorbing structure described in claim 1, wherein in one of the ultraviolet absorbing resin layers, the isocyanate curing agent is hexamethylene diisocyanate (HDI), the ultraviolet absorber is a benzotriazole-based compound, and the solvent is a mixed solvent of xylene and butanone.

6. The ultraviolet absorbing structure described in claim 1, wherein one of the ultraviolet absorbing resin layers further contains 0.01 wt% to 2 wt% of a light stabilizer, and the isocyanate curing agent is toluene diisocyanate (TDI), the ultraviolet absorber is a benzotriazole-based compound, and the solvent is xylene.

7. The ultraviolet absorbing structure described in claim 1, wherein the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays with wavelengths of 430 to 680 nm, a maximum light transmittance of 1% or less for light rays with wavelengths of 380 to 410 nm, and an average transmittance of 1% or less.

8. The ultraviolet absorbing structure described in claim 1, wherein after a 500-hour high-temperature, high-humidity test at 85°C and 85% humidity, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays with a wavelength of 430 to 680 nm, a maximum light transmittance of 1% or less for light rays with a wavelength of 380 to 410 nm, and an average transmittance of 1% or less.

9. The ultraviolet absorbing structure described in claim 1, wherein, after a 1000-hour high-temperature, high-humidity test at 85°C and 85% humidity, the ultraviolet absorbing resin has an average transmittance of 85% or more for light rays with a wavelength of 430 to 680 nm, a maximum light transmittance of 1% or less for light rays with a wavelength of 380 to 410 nm, and an average transmittance of 1% or less.

10. 2. The ultraviolet absorbing structure according to claim 1, comprising a first ultraviolet absorbing resin layer and a second ultraviolet absorbing resin layer, wherein the isocyanate curing agent in the first ultraviolet absorbing resin layer is hexamethylene diisocyanate (HDI), and the isocyanate curing agent in the second ultraviolet absorbing resin layer is toluene diisocyanate (TDI).

11. 2. The ultraviolet absorbing structure according to claim 1, wherein the thickness is 2 to 200 μm.

12. A step of applying the ultraviolet absorbing composition according to claim 1 onto a surface of a substrate; a step of curing the ultraviolet absorbing composition to obtain an ultraviolet absorbing resin; a step of forming a plurality of ultraviolet absorbing resin layers by repeatedly applying and curing an ultraviolet absorbing composition to the ultraviolet absorbing resin; A method for manufacturing the ultraviolet absorbing structure of claim 1, comprising:

13. 13. The method of claim 12, wherein the isocyanate curing agent in the ultraviolet absorbing composition that is repeatedly applied and cured is different from the isocyanate curing agent in the ultraviolet absorbing composition that is applied onto the surface of the substrate.

14. The method of claim 12, wherein the coating is spin coating, dip coating, cast coating, spray coating, bead coating, bar coating, doctor knife coating, or slit coating.

15. The method of claim 12, wherein the curing is carried out at a temperature of 100 to 150°C for 10 to 60 minutes.

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