Ultraviolet absorbing resin composition, ultraviolet absorbing resin and preparation method thereof

Abstract

An ultraviolet absorbing resin composition includes 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 balance of a solvent based on the total weight of the ultraviolet absorbing resin composition. The present disclosure further provides an ultraviolet absorbing resin, an ultraviolet absorbing structure including the same, and a method of preparing the same. According to the present invention, the ultraviolet ray absorbing resin having the specific composition is obtained through the specific resin composition formula, and the ultraviolet ray absorbing resin can efficiently absorb the ultraviolet ray, has excellent visible light transmittance, and has high stability.

Description

Technical Field

[0001] The present disclosure relates to an ultraviolet absorbing resin, which includes a fluorocarbon resin, an isocyanate curing agent, and an ultraviolet absorber. The ultraviolet absorbing resin is formed by a specific resin composition, and also relates to an ultraviolet absorbing structure including a plurality of ultraviolet absorbing resin layers. Background Art

[0002] Long-term exposure to ultraviolet rays has adverse effects on devices, so components that can filter out ultraviolet rays are usually installed in devices such as sensors, computers, communications products, consumer electronics, and automotive products. For example, ultraviolet filters are widely used in optical devices. Ultraviolet filters in optical devices are generally required to have a significant cutoff effect on ultraviolet rays and exhibit good transmittance for visible light.

[0003] The filtering effect of the UV filter may deteriorate with the increase of usage time, and it is necessary to protect the UV absorber therein through the substrate to improve the UV tolerance / stability. The prior art has reported the use of epoxy resin and acrylic resin as the main resin layer to protect the UV absorber therein. However, after testing, this UV filter cannot pass the 1000hr UV tolerance test, and its performance still needs to be improved. On the other hand, when using those resins, due to the high process temperature, the substrate during coating and film formation must also withstand high temperature, thereby limiting the selectivity of the substrate and failing to expand the application market. Summary of the invention

[0004] In view of the above problems, the present disclosure provides a UV absorbing resin composition, which can be formed into a UV absorbing resin after treatments such as drying and curing, wherein the UV absorbing resin composition includes a fluorocarbon resin with a protective function, an isocyanate curing agent, a UV absorber and a solvent.

[0005] In the ultraviolet absorbing resin composition disclosed herein, based on the total weight of the ultraviolet absorbing resin composition, the fluorocarbon resin accounts for 35 to 45 wt%, the isocyanate curing agent accounts for 5 to 25 wt%, the ultraviolet absorber accounts for 1 to 5 wt%, and the solvent accounts for the balance.

[0006] In one embodiment, the fluorocarbon resin comprises a fluorinated ethylene repeating unit as shown in Formula 1,

[0007]

[0008] wherein X1, X2, X3 and X4 are each independently hydrogen, fluorine, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C3-C 12Cycloalkyl, substituted or unsubstituted C6-C 12 Aryl, wherein n is any positive integer, and wherein at least one of X1, X2, X3 and X4 is fluorine or substituted with fluorine.

[0009] In one embodiment, the fluorocarbon resin further comprises a second repeating unit that is different from the fluorinated ethylene repeating unit.

[0010] In one embodiment, the isocyanate curing agent is selected from hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), 12 At least one of the group consisting of 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.

[0011] 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.

[0012] In one embodiment, the ultraviolet absorbing resin composition further includes a solvent. In another embodiment, the ultraviolet absorbing resin composition further includes a light stabilizer.

[0013] In one embodiment, the ultraviolet absorbing resin composition includes a fluorocarbon resin; hexamethylene diisocyanate (HDI) as an isocyanate curing agent; a benzotriazole compound as an ultraviolet absorber; and xylene and butanone as a solvent.

[0014] In one embodiment, the ultraviolet absorbing resin 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 compound as an ultraviolet absorber; and xylene as a solvent.

[0015] The present disclosure further provides an ultraviolet absorbing resin, which can be formed from the ultraviolet absorbing resin composition of the present disclosure.

[0016] In one embodiment, the ultraviolet absorbing resin includes a fluorocarbon resin, an isocyanate curing agent, and an ultraviolet absorber.

[0017] In one embodiment, the fluorocarbon resin of the ultraviolet absorbing resin comprises a fluorinated vinyl repeating unit as shown in Formula 1,

[0018]

[0019] wherein X1, X2, X3 and X4 are each independently hydrogen, fluorine, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C3-C 12 Cycloalkyl, substituted or unsubstituted C6-C 12 Aryl, wherein n is any positive integer, and wherein at least one of X1, X2, X3 and X4 is fluorine or substituted with fluorine.

[0020] In one embodiment, the isocyanate curing agent of the UV absorbing resin is selected from hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), and isophorone diisocyanate (IPDI). 12 At least one of the group consisting of 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.

[0021] In one embodiment, the ultraviolet absorbing resin has an average transmittance of 85% or more for light with 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 with a wavelength of 380 to 410 nm.

[0022] In one embodiment, after the ultraviolet absorbing resin is subjected to a high temperature and high humidity test at 85°C and 85% humidity for 500 hours, the average transmittance of light with a wavelength of 430 to 680 nm is greater than 85%; and the maximum light transmittance of light with a wavelength of 380 to 410 nm is less than 1% and the average transmittance is less than 1%.

[0023] In one embodiment, when the ultraviolet absorbing resin is subjected to a high temperature and high humidity test at 85°C and 85% humidity for 1000 hours, the average transmittance to light with a wavelength of 430 to 680 nm is greater than 85%; and the maximum light transmittance to light with a wavelength of 380 to 410 nm is less than 1% and the average transmittance is less than 1%.

[0024] The present disclosure also provides an ultraviolet absorbing structure, comprising a plurality of ultraviolet absorbing resin layers, wherein each of the ultraviolet absorbing resin layers comprises the ultraviolet absorbing resin described in the present disclosure, and the isocyanate curing agents of the ultraviolet absorbing resins of each layer are different from each other.

[0025] In one embodiment, each ultraviolet absorbing resin layer of the ultraviolet absorbing structure is prepared from the ultraviolet absorbing resin composition described in the present disclosure.

[0026] In one embodiment, the UV absorbing structure includes two UV absorbing resin layers, wherein the isocyanate curing agent of the first UV absorbing resin layer is hexamethylene diisocyanate (HDI) and the isocyanate curing agent of the second UV absorbing resin layer is toluene diisocyanate (TDI).

[0027] In one embodiment, each ultraviolet absorbing resin layer of the ultraviolet absorbing structure has a thickness of 1 to 100 μm. In another embodiment, the ultraviolet absorbing structure has a thickness of 2 to 200 μm.

[0028] The present disclosure also provides a method for preparing an ultraviolet absorbing resin, comprising coating the ultraviolet absorbing resin composition described herein on a surface of a substrate; and curing the ultraviolet absorbing resin composition to obtain the ultraviolet absorbing resin.

[0029] In one embodiment, the method for preparing the ultraviolet absorbing resin further includes repeatedly coating and curing the ultraviolet absorbing resin composition on the ultraviolet absorbing resin layer to form a plurality of ultraviolet absorbing resin layers.

[0030] In one embodiment, the isocyanate curing agent of the ultraviolet absorbing resin composition that is repeatedly coated and cured is different from the isocyanate curing agent of the ultraviolet absorbing resin composition coated on the surface of the substrate.

[0031] In one embodiment, the substrate is glass or triacetyl cellulose film.

[0032] In one embodiment, coating is spin coating, dip coating, cast coating, spray coating, bead coating, rod coating, blade coating, or slot coating.

[0033] In one embodiment, curing is performed at a temperature of 100° C. to 150° C. for 10 to 60 minutes. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1A The figure is a schematic diagram of the structure of a finished product including the ultraviolet absorbing resin disclosed in the present invention.

[0035] Figure 1B FIG. 4 is a schematic structural diagram of another finished product including the ultraviolet absorbing resin (ultraviolet absorbing structure) disclosed in the present invention.

[0036] Figure 2 It is the gloss retention rate of various base resins after being irradiated by QUV-A (Q-Lab ultraviolet accelerated) UV irradiator.

[0037] Figure 3A The transmittance curves of UV-absorbing resins containing various isocyanate curing agents under UV resistance test. HDI: Hexamethylene diisocyanate; IPDI: isophorone diisocyanate; XDI: xylene diisocyanate; and TDI: toluene diisocyanate. T0: 0 hours of UV irradiation; and T 240 : UV irradiation for 240 hours.

[0038] Figure 3B The transmittance curves of UV-absorbing resins containing various isocyanate curing agents under high temperature and high humidity (HTHH) weathering test. HDI: hexamethylene diisocyanate; IPDI: isophorone diisocyanate; XDI: xylene diisocyanate; TDI: toluene diisocyanate. T0: 0 hours of UV irradiation; and T 500 : UV irradiation 500 hours.

[0039] Figure 4A The transmittance curves of the ultraviolet absorbing resins of Example 1, Example 2 and Comparative Example 3 under ultraviolet tolerance test. T0: 0 hours of ultraviolet irradiation; T 240 : UV exposure for 240 hours; and T 1000 : UV irradiation 1000 hours.

[0040] Figure 4B The transmittance curves of the ultraviolet absorbing resins of Example 1, Example 2 and Comparative Example 3 in the high temperature and high humidity weather resistance test. T0: 0 hours of ultraviolet irradiation; and T 500 : UV irradiation 500 hours.

[0041] Wherein, the reference numerals are:

[0042] 1 Finished product including UV absorbing resin

[0043] 10 Base

[0044] 20 UV absorbing resin

[0045] 21 first ultraviolet absorbing resin layer

[0046] 22 Second ultraviolet absorbing resin layer. DETAILED DESCRIPTION

[0047] The following describes the embodiments of the present disclosure through specific embodiments. A person skilled in the art can easily understand the scope and effectiveness of the present disclosure based on the contents described herein.

[0048] It should be noted that the structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents described in the specification for people familiar with this technology to understand and read, and are not used to limit the limiting conditions for the implementation of the present invention, so they have no substantial technical significance. Any structural modification, change in proportional relationship or adjustment of size, without affecting the effects and purposes that can be achieved by the present invention, should still fall within the scope of the technical content described in the present invention. At the same time, the terms such as "upper", "first", "second", etc. cited in this specification are only for the convenience of description, and are not used to limit the scope of the implementation of the present invention. The change or adjustment of their relative relationship should also be regarded as the scope of the implementation of the present invention without substantially changing the technical content.

[0049] When “includes,” “comprising,” or “has” specific elements as described herein, unless otherwise stated, other elements, components, structures, regions, parts, devices, systems, steps, or connections may also be included, rather than excluding these other elements.

[0050] Unless clearly stated otherwise herein, the singular forms "a", "an" and "the" described herein also include plural forms, and "or" and "and / or" described herein are used interchangeably.

[0051] The numerical ranges described herein are inclusive and combinable, and any numerical value falling within the numerical range described herein can be used as the maximum value or the minimum value to derive its sub-range; for example, the numerical range of "5 to 25" should be understood to include any sub-range between endpoint 5 and endpoint 25, such as 5 to 15, 10 to 25, 10 to 15... and other sub-ranges; in addition, if a numerical value falls within the various ranges described herein (such as between the maximum value and the minimum value), it should be deemed to be included in the scope of the present disclosure.

[0052] A first aspect of the present disclosure is an ultraviolet absorbing resin composition including a fluorocarbon resin, an isocyanate curing agent, an ultraviolet absorber, and a solvent.

[0053] The fluorocarbon resin is mainly used as a base resin to protect the ultraviolet absorber therein. Exemplary fluorocarbon resins include, but are not limited to, fluorinated vinyl repeating units, such as monofluoroethylene, difluoroethylene, trifluoroethylene, and tetrafluoroethylene. On the other hand, in addition to being substituted with fluorine atoms, the fluorinated vinyl repeating units may also be substituted with other groups, or modified, grafted, etc., to have diversified side chains. For example, the hydrogen atoms of fluorinated vinyl are substituted with alkyl groups to have side chains, so that the fluorinated vinyl repeating units become fluorinated propylene repeating units, fluorinated butylene repeating units, fluorinated styrene repeating units, etc.

[0054] In one embodiment, the fluorocarbon resin comprises a fluorinated ethylene repeating unit as shown in Formula 1,

[0055]

[0056] wherein X1, X2, X3 and X4 are each independently hydrogen, fluorine, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C3-C 12 Cycloalkyl, substituted or unsubstituted C6-C 12 Aryl, wherein n is any positive integer, and wherein at least one of X1, X2, X3 and X4 is fluorine or substituted with fluorine.

[0057] C1-C 12 Alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl; C3-C 12 Cycloalkyl, for example, cyclopropyl, cyclobutyl; C6-C 12 Aryl, for example, phenyl, tolyl, naphthyl. Substitution, for example, hydrogen atoms are replaced by fluorine, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C6-C 12 The aryl group is substituted with a substituent such as an aryl group.

[0058] In one embodiment, the fluorocarbon resin further comprises a second repeating unit that is different from the fluorinated ethylene repeating unit.

[0059] In one embodiment, the fluorocarbon resin is polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene tetrafluoroethylene (ETFE), perfluoroalkoxy polymer (PFA) or fluorinated ethylene propylene (FEP).

[0060] In one embodiment, the second repeating unit is an alkyl vinyl ether repeating unit. In another embodiment, the fluorocarbon resin is a perfluoroethyl vinyl ether (PEVE) type fluorocarbon resin, X1, X2 and X3 of Formula 1 are fluorine, and X4 is a substituted or unsubstituted C1-C 12Alkyl, substituted or unsubstituted C3-C 12 Cycloalkyl, substituted or unsubstituted C6-C 12 The alkyl vinyl ether repeating unit is -[CHR1-CHOR2]-, R1 and R2 are hydrogen, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C3-C 12 Cycloalkyl.

[0061] In addition to the function of curing the ultraviolet absorbing resin composition in the present disclosure, the isocyanate curing agent also helps to provide the obtained ultraviolet absorbing resin with light resistance and high temperature and humidity resistance. The isocyanate curing agent can be selected from hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), methylene dicyclohexyl diisocyanate (HDI), and the like. 12 In one embodiment, the isocyanate curing agent is hexamethylene diisocyanate (HDI). In another embodiment, the isocyanate curing agent is toluene diisocyanate (TDI).

[0062] The ultraviolet absorber in the present disclosure mainly absorbs light with a wavelength of 380 to 410 nm, which can convert the light energy of ultraviolet rays into heat energy or other non-destructive longer wavelengths, thereby effectively protecting the device from interference and damage by ultraviolet rays. Applicable devices include sensor elements, computers, communication products, consumer electronic products and automotive products, as well as those devices that are exposed to ultraviolet rays for a long time. The ultraviolet absorber can use 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 ultraviolet absorber is a benzotriazole compound.

[0063] In one embodiment, the ultraviolet absorbing resin composition of the present invention may further include a light stabilizer, which is mainly used to repair the region of the ultraviolet absorbing resin composition of the present invention that is photo-oxidatively decomposed by ultraviolet rays to assist the ultraviolet absorber. The light stabilizer may use a hindered amine light stabilizer (HALS), specifically, a monomolecular hindered amine light stabilizer, a polymer hindered amine light stabilizer or a low-basic hindered amine light stabilizer, such as a 2,2,6,6-tetramethylpyridine derivative.

[0064] In the present disclosure, based on the total weight of the ultraviolet absorbing resin composition, 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 balance is the solvent. In one embodiment, the weight of the fluorocarbon resin is between 35 and 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 between 5 and 25wt%, including but not limited to 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt% and / or 25wt%. In one embodiment, the weight of the ultraviolet light absorber is between 1 and 5wt%, including but not limited to 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% and / or 5wt%.

[0065] In one embodiment, the solvent of the ultraviolet absorbing resin 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, cyclopentane, etc. Specifically, alcohols include methanol, ethanol, propanol, etc. Ketones include acetone, butanone, etc. Esters include alkyl formates, alkyl acetates, alkyl propionates, alkyl butyrates, alkyl lactates, alkyl alkoxy acetates, alkyl 3-alkoxy propionates, alkyl 2-alkoxy propionates, alkyl 2-alkoxy-2-methyl propionates, alkyl pyruvic acids, alkyl acetoacetates, alkyl 2-oxobutyrates, etc. Ethers include, for example, 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, propylene glycol monopropyl ether acetate, etc. Ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. Aromatic hydrocarbons include, for example, toluene, xylene, etc. In one embodiment, the solvent is a mixed solvent of xylene and butanone. In another embodiment, the solvent is xylene.

[0066] In one embodiment, the weight of the solvent in the ultraviolet absorbing resin composition of the present disclosure is not limited, however, as an example, based on the total weight of the ultraviolet absorbing resin composition, the weight of the solvent is between 25 and 59wt%, including but not limited to 25wt%, 30wt%, 35wt%, 40wt%, wt%, 45wt%, 50wt%, 55wt%, 59wt%. The solvent can be a single solvent or a mixed solvent. In one embodiment, the solvent is a mixed solvent, including a first solvent and a second solvent, and wherein the first solvent is 15 to 25wt%, including but not limited to 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt% and / or 25wt%, wherein the second solvent is 20 to 25wt%, including but not limited to 20wt%, 21wt%, 22wt%, 23wt%, 24wt% and / or 25wt%. In another embodiment, the solvent is a single solvent and the weight is 40 to 45 wt %, including but not limited to 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt % and / or 45 wt %.

[0067] In one embodiment, the ultraviolet absorbing resin composition of the present disclosure includes a fluorocarbon resin; hexamethylene diisocyanate (HDI) as an isocyanate curing agent; a benzotriazole compound as an ultraviolet absorber; and xylene and butanone as solvents. In another embodiment, the ultraviolet absorbing resin composition of the present disclosure includes a fluorocarbon resin; toluene diisocyanate (TDI) as an isocyanate curing agent; a benzotriazole compound as an ultraviolet absorber; and xylene as a solvent.

[0068] In one embodiment, the ultraviolet absorbing resin composition of the present disclosure may be in the form of a dispersion, wherein the ultraviolet absorber is uniformly dispersed in the ultraviolet absorbing resin composition to avoid deterioration of the ultraviolet cutoff effect and haze due to aggregation.

[0069] The second aspect of the present disclosure is a UV absorbing resin, which can be formed by the UV absorbing resin composition described in the present disclosure. Specifically, the UV absorbing resin includes a fluorocarbon resin, an isocyanate curing agent and a UV absorber. Here, the types of the fluorocarbon resin, the isocyanate curing agent and the UV absorber of the UV absorbing resin are those described in the first aspect of this article.

[0070] In one embodiment, the ultraviolet absorbing resin of the present disclosure can be obtained from the ultraviolet absorbing resin composition of the first aspect of the present disclosure, for example, by drying and curing the ultraviolet absorbing resin composition to obtain the ultraviolet absorbing resin.

[0071] 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 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 ultraviolet absorber.

[0072] In one embodiment, the ultraviolet absorbing resin has an average transmittance of 85% or more for incident light in the wavelength range of 430 to 680 nm, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%; the maximum light transmittance for light with a wavelength of 380 to 410 nm is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, and the average transmittance is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%.

[0073] In one embodiment, after the ultraviolet absorbing resin is subjected to a high temperature and high humidity test at 85°C and 85% humidity for 500 hours, the average transmittance of light with a wavelength of 430 to 680 nm is 85% or more, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%; the maximum light transmittance of light with a wavelength of 380 to 410 nm is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, and the average transmittance is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%.

[0074] In one embodiment, after the ultraviolet absorbing resin is subjected to a high temperature and high humidity test at 85°C and 85% humidity for 1000 hours, the average transmittance of light with a wavelength of 430 to 680 nm is 85% or more, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%; the maximum light transmittance of light with a wavelength of 380 to 410 nm is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, and the average transmittance is less than 1%, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%.

[0075] The third aspect of the present disclosure is a UV absorbing structure, comprising a plurality of UV absorbing resin layers, wherein each UV absorbing resin layer comprises the UV absorbing resin layer as described in the second aspect of the present disclosure. In one embodiment, the isocyanate curing agent of each layer of UV absorbing resin is different from each other.

[0076] In one embodiment, the multilayer is, for example, 2 layers, 3 layers, 4 layers or more. In one embodiment, the multilayer is 2 layers. In another embodiment, the multilayer is 2 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).

[0077] 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, 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.

[0078] The fourth aspect of the present disclosure is a method for preparing an ultraviolet absorbing resin, comprising coating the ultraviolet absorbing resin composition described herein on a surface of a substrate; and curing the ultraviolet absorbing resin composition to obtain the ultraviolet absorbing resin. Figure 1A As shown, the ultraviolet absorbing resin composition is coated on the surface of the substrate 10, and the ultraviolet absorbing resin composition is cured to become the ultraviolet absorbing resin 20, and finally a finished product 1 including the ultraviolet absorbing resin is obtained.

[0079] In one embodiment, the preparation 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. Here, the type and amount of each material are as described herein.

[0080] The coating is not limited, and any coating method that can evenly coat the composition on the surface of the substrate is included in the scope of the present disclosure. In one embodiment, the coating is spin coating, dip coating, cast coating, spray coating, bead coating, rod coating, blade coating or slot coating.

[0081] The substrate is not limited, and any article having a surface that can be coated is included in the scope of the present disclosure, including semi-finished products and finished products. In one embodiment, the substrate is glass, triacetatecellulose (TAC) film, or a plastic film such as PET.

[0082] The curing is also not limited, as long as the method that can cure the composition is included in the scope of the present disclosure. In one embodiment, the curing is thermal curing, light curing (such as ultraviolet curing), etc. In one embodiment, the curing is carried out at a temperature of 100°C 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, 150°C, and the curing time includes but is not limited to 10, 15, 20, 30, 40, 50, 60 minutes.

[0083] In one embodiment, the preparation method of the present disclosure further comprises the steps of repeatedly coating and curing the ultraviolet absorbing resin composition on the ultraviolet absorbing resin layer to form a plurality of ultraviolet absorbing resin layers. Figure 1B As shown, a UV absorbing resin composition is coated on the surface of a substrate 10, and the UV absorbing resin composition is cured to form a first UV absorbing resin layer 21. Then, the same or different UV absorbing resin composition is used and the above steps are repeated to obtain a second UV absorbing resin layer 22, and finally a finished product including two UV absorbing resin layers 21, 22 is obtained.

[0084] In one embodiment, the isocyanate curing agent in the ultraviolet absorbing resin composition that is repeatedly coated and cured is different from the isocyanate curing agent in the ultraviolet absorbing resin composition coated on the surface of the substrate.

[0085] The present disclosure will be described in further detail based on the following specific examples and comparative examples, which are however by no means intended to limit the scope of the present disclosure.

[0086] Resin selection

[0087] Fluorovinyl ether (FEVE), polyester urethane, acrylic urethane, and siloxane resin were used as resin coatings and tested by QUV-A ultraviolet irradiation instrument. The gloss retention rate of each resin coating after long-term ultraviolet irradiation is as follows: Figure 2 As shown. Figure 2The results show that the UV resistance of the resin coating is FEVE>silicone resin>acrylic urethane>polyester polyurethane from high to low. FEVE type fluorocarbon resin coating has the best UV resistance because of the fluorine-carbon bond in its structure, but it is not bound by theory.

[0088] Example 1 - UV absorbing resin

[0089] 40 to 50 wt% of FEVE type fluorocarbon resin (e.g., DS302 series resin, purchased from Yijin Technology; Lumiflon series resin, purchased from Xusheng Technology; New Gamet-FEVE series resin, purchased from Deya Resin), 15 to 21% of HDI, 1 to 5% of benzotriazole type ultraviolet absorber (Eversorb series dye, purchased from Everlight Chemical), 15 to 20% of xylene and 20 to 25% of butanone are mixed to form an ultraviolet absorbing resin composition. The ultraviolet absorbing resin composition is then formed on glass by spin coating and baked at 120° C. for 30 minutes to harden, thereby obtaining an ultraviolet absorbing resin.

[0090] Examples 2 to 4 - UV absorbing resin

[0091] The ultraviolet absorbing resin was prepared according to Example 1, but HDI in the ultraviolet absorbing resin composition was replaced with IPDI, XDI and TDI, respectively. That is, Examples 1 to 4 used HDI curing agent, TDI curing agent, XPDI curing agent and IPDI curing agent, respectively.

[0092] The UV absorbing resins of Examples 1 to 4 were subjected to UV tolerance tests to evaluate the effects of different curing agents. The UV tolerance tests were conducted with UV irradiation for 0 and 240 hours (UV wavelength: 420 nm, irradiation intensity 2.4 W / M 2 ). After the test, the transmittance curve of each UV absorbing resin is as follows Figure 3A As shown. Figure 3A , Example 1 using HDI curing agent has the best resistance to ultraviolet rays. The resistance to ultraviolet rays from high to low is respectively Example 1 (HDI curing agent)> Example 4 (TDI curing agent)> Example 3 (XDI curing agent)> Example 2 (IPDI curing agent).

[0093] The UV absorbing resins of Examples 1 to 4 were subjected to UV tolerance tests in a high temperature and high humidity environment to evaluate the effects of different curing agents. The UV tolerance tests were conducted with UV irradiation for 0 and 500 hours (UV wavelength: 420 nm, irradiation intensity 2.4 W / M 2 ). After the test, the transmittance curve of each UV absorbing resin is as follows Figure 3B As shown. Figure 3B , Example 4 using TDI curing agent exhibits high tolerance to ultraviolet rays under high temperature and high humidity environment, and its weather resistance is the best, which can enhance the protection effect. In addition, the tolerance to ultraviolet rays (weather resistance) under high temperature and high humidity environment is from high to low as follows: Example 4 (TDI curing agent) > Example 2 (IPDI curing agent) > Example 3 (XDI curing agent) > Example 1 (HDI curing agent).

[0094] In practical applications, the ultraviolet absorbing resin layer can be selected or used in combination according to the ultraviolet resistance and tolerance and as required.

[0095] Comparative Example 1

[0096] The ultraviolet absorbing resin was prepared according to Example 1, except that the fluorocarbon resin in the ultraviolet absorbing resin composition was replaced with an acrylic resin.

[0097] The ultraviolet absorbing resins of Example 1, Example 4 and Comparative Example 1 were subjected to ultraviolet tolerance tests to evaluate the effects of different fluorocarbon resins. The ultraviolet tolerance tests were conducted with ultraviolet irradiation for 0, 240 and 1000 hours (UV wavelength: 420 nm, irradiation intensity 2.4 W / M 2 ). After the test, the transmittance curve of each UV absorbing resin is as follows Figure 4A As shown. Figure 4A The ultraviolet absorbing resins of Examples 1 and 4 can both pass the 1000-hour ultraviolet tolerance test; however, the ultraviolet absorbing resin of Comparative Example 1 deteriorates significantly after being irradiated with ultraviolet rays for 240 hours, and its transmittance for light with a wavelength of 380 to 410 nm is too high to meet the requirements, indicating that Comparative Example 1 using acrylic resin has only poor ultraviolet tolerance.

[0098] The ultraviolet absorbing resins of Example 1, Example 4 and Comparative Example 1 were subjected to ultraviolet tolerance tests in a high temperature and high humidity environment to evaluate the effects of different fluorocarbon resins. The ultraviolet tolerance test was conducted with ultraviolet irradiation for 0 and 500 hours (UV wavelength: 420nm, irradiation intensity 2.4W / M 2 ). After the test, the transmittance curve of each UV absorbing resin is as follows Figure 4B As shown. Figure 4B The ultraviolet absorbing resins of Example 1, Example 4 and Comparative Example 1 can still exhibit excellent ultraviolet resistance even in a high temperature and high humidity environment, that is, have excellent weather resistance.

[0099] The above-mentioned implementation modes and specific examples are not intended to limit the present disclosure. The listed technical features or schemes can be combined with each other. The present disclosure can also be implemented or applied through other different implementation modes. The details recorded in this document can also be given different changes or modifications according to different viewpoints and applications without departing from the present disclosure.

Claims

1. A UV absorbing resin composition, characterized in that include: Based on the total weight of the ultraviolet absorbing resin composition, 35 to 45 wt% of fluorocarbon resin; 5 to 25 wt % of an isocyanate curing agent; 1 to 5 wt% of a UV absorber; and The remaining amount of solvent.

2. The ultraviolet absorbing resin composition according to claim 1, wherein The fluorocarbon resin comprises a fluorinated ethylene repeating unit as shown in Formula 1, wherein X1, X2, X3 and X4 are each independently hydrogen, fluorine, substituted or unsubstituted C1-C 12 Alkyl, substituted or unsubstituted C3-C 12 Cycloalkyl, substituted or unsubstituted C6-C 12 Aryl, n is any positive integer, and wherein at least one of X1, X2, X3 and X4 is fluorine or substituted by fluorine.

3. The ultraviolet absorbing resin composition according to claim 1, wherein The isocyanate curing agent is at least one selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, methylene dicyclohexyl diisocyanate, naphthalene diisocyanate, trimethyl hexamethylene diisocyanate, xylene diisocyanate, lysine diisocyanate, trimers of the above diisocyanates, triphenylmethane triisocyanate, toluene triisocyanate, and lysine triisocyanate.

4. The ultraviolet absorbing resin composition according to claim 1, wherein 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.

5. The ultraviolet absorbing resin composition according to claim 1, wherein The isocyanate curing agent is hexamethylene diisocyanate, the ultraviolet absorber is a benzotriazole compound, and the solvent is a mixed solvent of xylene and butanone. 6 . The ultraviolet absorbing resin composition according to claim 1 , further comprising 0.01 wt % to 2 wt % of a light stabilizer, wherein the isocyanate curing agent is toluene diisocyanate, the ultraviolet absorber is a benzotriazole compound, and the solvent is xylene.

7. An ultraviolet absorbing resin, characterized in that The invention is formed by the ultraviolet absorbing resin composition according to claim 1, comprising: a fluorocarbon resin, an isocyanate curing agent and an ultraviolet absorber, wherein the ultraviolet absorbing resin has an average transmittance of 85% or more for light with a wavelength of 430 to 680 nm, a maximum light transmittance of 1% or less and an average transmittance of 1% or less for light with a wavelength of 380 to 410 nm.

8. The ultraviolet absorbing resin according to claim 7, after being subjected to a high temperature and high humidity test at 85°C and 85% humidity for 500 hours, has an average transmittance of 85% or more for light with 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 with a wavelength of 380 to 410 nm.

9. The ultraviolet absorbing resin according to claim 7, after being subjected to a high temperature and high humidity test at 85°C and 85% humidity for 1000 hours, has an average transmittance of more than 85% for light with a wavelength of 430 to 680 nm, and a maximum light transmittance of less than 1% and an average transmittance of less than 1% for light with a wavelength of 380 to 410 nm.

10. An ultraviolet absorbing structure, characterized in that: A plurality of ultraviolet absorbing resin layers are included, wherein each of the ultraviolet absorbing resin layers contains the ultraviolet absorbing resin according to claim 7, and the isocyanate curing agent of the ultraviolet absorbing resin of each layer is different from each other.

11. The ultraviolet absorbing structure according to claim 10, 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).

12. The ultraviolet absorption structure according to claim 10, which has a thickness of 2 to 200 μm.

13. A method for preparing an ultraviolet absorbing resin, characterized in that: include: coating the ultraviolet absorbing resin composition according to claim 1 on the surface of a substrate; as well as The ultraviolet absorbing resin composition is cured to obtain an ultraviolet absorbing resin. 14 . The method according to claim 13 , further comprising repeatedly coating and curing the ultraviolet absorbing resin composition on the ultraviolet absorbing resin to form a plurality of ultraviolet absorbing resin layers.

15. The method according to claim 13, wherein: The isocyanate curing agent in the repeatedly coated and cured ultraviolet absorbing resin composition is different from the isocyanate curing agent in the ultraviolet absorbing resin composition coated on the surface of the substrate.

16. The method according to claim 13, wherein: The coating is spin coating, dip coating, cast coating, spray coating, bead coating, rod coating, blade coating or slot coating.

17. The method according to claim 13, wherein: The curing is performed at a temperature of 100° C. to 150° C. for 10 to 60 minutes.

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