Composition and cured product formed therefrom

Abstract

Compositions are provided that include a wavelength converting compound that absorbs a wavelength A and emits a wavelength B different from the wavelength A, a crosslinkable monomer, a polymeric monomer, a filler, and a photoinitiator. A cured product formed from the composition is also provided.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and all benefits derived from Korean Patent Application No. 10-2023-0150276 filed in the Korean Intellectual Property Office on November 2, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] One or more embodiments are directed to compositions and cured products formed from the compositions. Background Art

[0004] A cured product for blocking ambient light is generated by ultraviolet (UV) light curing the composition, and the cured product for blocking ambient light may have a high optical density value.

[0005] At the same time, when compositions comprising fillers are concerned, it is difficult to achieve a satisfactory depth of cure because fillers absorb UV light.

[0006] Considering the amount of processing time, it is desirable to obtain a cured product having a high optical density and a satisfactory depth of cure by performing curing for a short time. Summary of the invention

[0007] One or more embodiments include a composition for forming a cured product having a satisfactory cure depth and a satisfactory optical density, and a cured product formed from the composition.

[0008] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0009] According to one or more embodiments, the composition includes a wavelength conversion compound that absorbs wavelength A and emits wavelength B different from wavelength A, a crosslinkable monomer, and a photoinitiator.

[0010] According to one or more embodiments, there is provided a cured product formed by using an ultraviolet light curing composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The above and other aspects, features and advantages of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings,

[0012] Figure 1 : is a diagram schematically depicting an absorption spectrum and an emission spectrum of a wavelength conversion compound included in a composition according to an embodiment, the wavelength conversion compound absorbing a wavelength A and emitting a wavelength B different from the wavelength A. DETAILED DESCRIPTION

[0013] Now will be referred to in detail embodiment, the example of described embodiment is illustrated in the accompanying drawings, wherein the same reference numerals refer to the same elements throughout. In this regard, the present embodiment can have different forms and should not be construed as being limited to the description set forth herein. Therefore, the following only describes the embodiment with reference to the accompanying drawings to explain the aspects of the current description. As used herein, the term "and / or" includes any combination and all combinations of one or more than one of the related listed items. Throughout the disclosure, the expression "at least one (kind) of a, b and c" means only a, only b, only c, both a and b, both a and c, both b and c, all a, b and c, or its variant.

[0014] In order to block ambient light, the optical density of the cured product needs to be 2 or more (for example, at a thickness of 30 μm).

[0015] In order to increase the optical density, a curing depth of 200 μm or more is required.

[0016] A cured product can be produced by curing the composition with UV light, and the cured product may contain a filler to achieve a satisfactory optical density and light blocking level. However, since the filler absorbs UV, it is difficult to obtain a satisfactory depth of cure.

[0017] Furthermore, considering processing time, a cured product formed by short-time (eg, 2 seconds or less) curing needs to have a curing depth of 200 μm or more and an optical density (eg, at a thickness of 30 μm) value of 2 or more.

[0018] The composition according to one aspect may include a wavelength conversion compound that absorbs wavelength A and emits wavelength B different from wavelength A, a cross-linkable monomer, a polymerizable monomer, a filler, and a photoinitiator.

[0019] According to an embodiment, the length of wavelength B may be longer than the length of wavelength A. For example, wavelength A may be a wavelength in the ultraviolet region, and wavelength B may be a wavelength in the visible region. For example, the wavelength conversion compound may include a compound that absorbs light of wavelength A of about 250 nm to about 470 nm and emits light of wavelength A of about 380 nm to about 700 nm.

[0020] According to an embodiment, the wavelength conversion compound includes perylene, CdS, CdSe, CdTe, ZnS, perovskite, [Tb(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3- 、[Eu(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3-or a combination thereof. For example, the wavelength conversion compound includes perylene, CdS, CdSe, CdSe / CdS, CdSe / CdS / CdTe, CdSe / ZnS, perovskite, [Tb(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3- 、[Eu(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3- or a combination thereof.

[0021] Figure 1 is a diagram schematically showing an absorption spectrum and an emission spectrum of perylene contained in a composition according to an embodiment. Figure 1 , it can be seen that perylene absorbs light in the ultraviolet region and emits light in the visible region.

[0022] [Tb(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3- It can absorb light having a wavelength of 254 nm and emit light having a wavelength of about 492 nm to about 622 nm. [Eu(pyridine-2,6-pyridinedicarboxylic acid) 3 ] 3- It is possible to absorb light having a wavelength of 254 nm and emit light having a wavelength of about 594 nm to about 695 nm.

[0023] According to an embodiment, the cross-linkable monomer and the polymerizable monomer may each independently include an acryl-based monomer, a diisocyanate-based monomer, or a combination thereof.

[0024] According to an embodiment, the acryl-based monomer may include C 1 -C 20 Alkyl group, C 3 -C 10 A cycloalkyl group, -NCO, -OH or a combination thereof.

[0025] According to an embodiment, the crosslinkable monomer may include an ultraviolet light crosslinkable monomer, a visible light crosslinkable monomer, a crosslinkable monomer crosslinkable at low temperature, or a combination thereof. For example, the low temperature may be a temperature of 80°C or below, such as about 25°C to about 80°C, about 30°C to about 80°C, about 40°C to about 80°C, about 50°C to about 80°C, about 60°C to about 80°C, or about 70°C to about 80°C.

[0026] According to an embodiment, the crosslinkable monomer may include isobornyl acrylate, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl (meth)acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, or a combination thereof.

[0027] According to an embodiment, the polymerizable monomer may include 2-isocyanoethyl acrylate, 2,4-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2-hydroxyethyl methacrylate, glycol methacrylate, glycol monomethacrylate, ethylene glycol methacrylate, 2-(methacryloyloxy)ethanol, or a combination thereof.

[0028] According to an embodiment, the photoinitiator may include a single initiator that reacts with each of ultraviolet light and visible light. In this regard, the photoinitiator refers to a compound in which not only free radicals generated by decomposition of visible light can initiate polymerization of monomers, but also free radicals generated by decomposition of ultraviolet light can initiate polymerization of monomers.

[0029] According to embodiments, the photoinitiator may include an ultraviolet photoinitiator and a visible light initiator.

[0030] According to an embodiment, the photoinitiator may include Irgacure 784 (Irgacure 784 contains 1-hydroxycyclohexyl phenyl ketone), Irgacure 819 (Irgacure 819 contains 2-hydroxy-2-methyl-1-phenyl-propan-1-one), Irgacure 651 (Irgacure 651 contains benzoin methyl ether), Irgacure 184 (Irgacure 184 contains 1-hydroxycyclohexyl phenyl ketone), [ethoxy(phenyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone (TPO-L) or a combination thereof.

[0031] Irgacure 784, Irgacure 819, Irgacure 651 and Irgacure 184 are product names of commercially available compounds.

[0032] For example, Irgacure 784 can be decomposed by ultraviolet light to generate free radicals to initiate the polymerization reaction of the monomer, and can also be decomposed by visible light to generate free radicals to initiate the polymerization reaction of the monomer.

[0033] For example, the wavelength of visible light is longer than that of ultraviolet light. Therefore, when ultraviolet light is irradiated to the composition according to the embodiment, the wavelength conversion compound absorbs the ultraviolet light and emits visible light. The longer wavelength visible light can reach deeper and decompose the additional initiator (e.g., Irgacure 784) to generate free radicals, thereby initiating the polymerization reaction of the monomer.

[0034] Therefore, when the composition according to the embodiment is cross-linked with ultraviolet light, the curing depth is relatively deep and the optical density increases.

[0035] In some embodiments, since the crosslinkable monomer in the composition according to the embodiment has a reactive functional group (e.g., a double bond), the crosslinkable monomer can be directly crosslinked by ultraviolet light or visible light, and the free radicals generated by the decomposition of the initiator that absorbs ultraviolet light at a relatively low depth (e.g., the depth that ultraviolet light can reach) can initiate the polymerization reaction of the monomer. For example, isobornyl acrylate is a monomer that can directly undergo a curing reaction by visible light without an initiator.

[0036] According to an embodiment, the composition may further include a thermal catalyst. The term "thermal catalyst" as used herein may refer to a compound that catalyzes a polymerization reaction (eg, a polymerization reaction that produces a urethane bond) by heat generated in the reaction.

[0037] According to an embodiment, the thermal catalyst may include dibutyltin dilaurate, tin tetrachloride, butyltin trichloride, a diorganotin ester, and dibutyltin oxide, or a combination thereof.

[0038] When the composition according to the embodiment further comprises a thermal catalyst and the composition is irradiated with ultraviolet light, the thermal catalyst catalyzes the polymerization reaction (e.g., a polymerization reaction that produces a urethane bond) by the heat generated in the polymerization reaction described above. Therefore, a wider range of curing can be performed in a shorter period of time, the curing depth can be relatively deep, and the curing density can be further increased.

[0039] For example, the thermal catalyst may catalyze the polymerization reaction (eg, polymerization reaction producing urethane bonds) of low temperature polymerization monomers (eg, 2-isocyanoethyl acrylate and 2-hydroxyethyl methacrylate) at a temperature of 80°C or less.

[0040] According to an embodiment, the composition may further include a filler. For example, the filler may include carbon black, tungsten oxide, lanthanum oxide, titanium oxide, cobalt, graphite, graphene oxide, or a combination thereof.

[0041] Meanwhile, the carbon black may not be perylene black. Perylene black is a pigment and is not suitable for use as a filler.

[0042] According to an embodiment, based on the total weight of 100wt% of the composition, the content of the wavelength conversion compound can be about 0.1wt% to about 2wt%, for example, about 0.5wt% to about 2wt%, about 0.8wt% to about 2wt%, about 1.0wt% to about 2wt%, about 1.5wt% to about 2wt%, or about 1.8wt% to about 2wt%, and the content of the photoinitiator can be about 5wt% to about 20wt%, for example, about 8wt% to about 20wt%, about 10wt% to about 20wt%, about 15wt% to about 20wt%, or about 18wt% to about 20wt%.

[0043] When the content of the wavelength conversion compound exceeds 2 wt %, the wavelength conversion compound may act as fine particles and inhibit curing. When the content of the wavelength conversion compound is less than 0.1 wt %, the curing depth and optical density of the formed cured product may be unsatisfactory.

[0044] The content of the photoinitiator may be 5wt% or more, and in this case, the photoinitiator may act as an initiator by visible light. When the content of the photoinitiator exceeds 20wt%, the physical properties of the formed cured product may be poor. Meanwhile, when the photoinitiator includes an ultraviolet light initiator and a visible light initiator, the content of the photoinitiator may refer to the total content of the ultraviolet light initiator and the visible light initiator. In this regard, the weight ratio of the ultraviolet light initiator to the visible light initiator may be 9:1 to 1:9, such as 9:2 to 2:9, 9:3 to 3:9, 9:4 to 4:9, 9:5 to 5:9, 9:6 to 6:9, or 9:8 to 8:9. For example, the weight ratio of the ultraviolet light initiator to the visible light initiator may be 6:4 to 4:6.

[0045] For example, based on 100wt% of the total weight of the composition, the content of the thermal catalyst can be about 0.05wt% to about 1wt%, such as about 0.1wt% to about 1wt%, about 0.2wt% to about 1wt%, about 0.4wt% to about 1wt%, about 0.6wt% to about 1wt%, or about 0.8wt% to about 1wt%. Within the content range, the curing depth and optical density of the cured product are satisfactory.

[0046] For example, based on 100wt% of the total weight of the composition, the content of the filler can be about 3wt% to about 7wt%, such as about 4wt% to about 7wt%, about 5wt% to about 7wt%, or about 6wt% to about 7wt%. The physical properties (e.g., strength) of the cured product formed within this content range are satisfactory.

[0047] For example, the crosslinkable monomer may further include other monomers in addition to the monomers. For example, the crosslinkable monomer may further include N,N-dimethylacrylamide.

[0048] For example, the composition may further comprise an oligomer. For example, the composition may further comprise polypropylene glycol.

[0049] For example, the composition may include other additives. For example, the composition may include trace amounts of antioxidants. For example, the composition may contain trace amounts of 2,6-bis(1,1-dimethylethyl)-4-methylphenol.

[0050] For example, the remainder of the contents of the composition may be crosslinkable monomers or polymerizable monomers.

[0051] A cured product according to another aspect may be formed by curing the composition with ultraviolet light.

[0052] For example, the cured product according to the embodiment can be formed by curing the composition with ultraviolet light for about 0.1 seconds to about 3 seconds. For example, the cured product according to the embodiment can be formed by curing the composition with ultraviolet light for about 0.5 seconds to about 2 seconds.

[0053] According to the embodiment, the cured product may have a cured depth of 200 μm or more.

[0054] According to the embodiment, the cured material may have an optical density value of 2 or more at a thickness of 50 μm or less. For example, the cured product may have an optical density of 2 to 7 at a thickness of 30 μm.

[0055] Optical density, often abbreviated as OD, is a measure of how much light a substance absorbs or transmits. It is commonly used in a variety of fields such as chemistry, physics, biology, and environmental science.

[0056] Calculate the optical density using the following equation:

[0057] OD = log 10 (I 0 / I)

[0058] in:

[0059] OD is optical density; I 0 is the intensity of incident light; and I is the intensity of transmitted light. The higher the optical density value, the more light the material absorbs and the less light is transmitted through it. Conversely, a lower optical density indicates less light absorption and more light transmission.

[0060] [Definition of terms]

[0061] As used herein, the term "C 1 -C 20The “alkyl group” refers to a straight or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms (e.g., 1 to 15, 1 to 10, or 1 to 5 carbon atoms), and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, and the like.

[0062] As used herein, the term "C 3 -C 10 The cycloalkyl group refers to a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group (or a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group and a bicyclo[2.2.2]octyl group.

[0063] The numbers of carbon atoms indicated when defining substituents are examples.

[0064] Spatially relative terms such as "under", "below", "lower", "above", "upper", etc. are used to easily describe the correlation between a single term or element and other terms or elements, as shown in the figure. Spatially relative terms should be understood as terms that include different directions of elements in addition to the directions shown in the figure during use or operation. For example, when the elements shown in the figure are turned over, an element described as being "under" or "below" another element can be placed "above" the other element. Therefore, the exemplary term "downward" can include both a downward direction and an upward direction. Elements can also be oriented in other directions, so spatially relative terms can be interpreted based on the orientation.

[0065] Hereinafter, the composition according to the embodiment will be described in more detail through examples.

[0066] [Example]

[0067] Composition preparation

[0068] Example 1

[0069] The examples demonstrate the manufacture of the composition. A composition was prepared by mixing 1 wt% perylene, 10 wt% Irgacure 784, 0.07 wt% dibutyltin dilaurate, 6.5 wt% carbon black, 6 wt% 2-isocyanoethyl acrylate, 6 wt% 2-hydroxyethyl methacrylate and the remainder isobornyl acrylate.

[0070] Example 2

[0071] A composition was prepared in the same manner as Example 1, but containing 8 wt% carbon black.

[0072] Comparative Example 1

[0073] A composition was prepared in the same manner as in Example 1, except that perylene was not mixed.

[0074] The compositions prepared in Examples and Comparative Examples were each applied to a substrate to a thickness of 300 μm, and then exposed to 365 nm ultraviolet light for 2 seconds. The curing depth of each cured product was measured. The results are shown in Table 1.

[0075] In addition, the optical density of each cured product formed under these conditions was measured except that the compositions prepared in Examples and Comparative Examples were applied to a substrate to a thickness of 30 μm. The results are shown in Table 1.

[0076] The curing depth was determined as follows: after the sample was made, the uncured portion was removed and the back of the cured surface was measured using Fourier transform infrared spectroscopy (FT-IR) (Bruker, ALPHA2 model), and the thickness at a curing rate of more than 90% was measured. The transmittance from 400 nm to 700 nm was measured using a spectrometer (Dongil Shimazu Co., Ltd., Uv-2600 model), and the optical density was calculated using the following equation 1.

[0077] [Table 1]

[0078] Curing depth (μm) Optical density Example 1 290 2.2 Example 2 210 3.0 Comparative Example 1 70 1.9

[0079] [Equation 1]

[0080] Optical density = -logT

[0081] %T = 100 × T (T: transmittance)

[0082] According to an embodiment, the composition comprises a light-down conversion compound, a crosslinkable monomer, a polymerizable monomer, a filler, a photoinitiator and a thermal catalyst, and the short-time process [short curing time] product of the composition is determined to have a curing depth of 200 μm or more and an optical density of 2 or more at a thickness of 30 μm. The light-down conversion compound means a compound that absorbs short-wavelength light (energy) and emits long-wavelength light (energy). According to an embodiment, the light-down conversion compound may be perylene.

[0083] The cured product obtained by ultraviolet light curing using the composition according to the embodiment has a deep curing depth and a high optical density.

[0084] It should be understood that the embodiments described herein should be considered in a descriptive sense only, and not for limiting purposes. The description of the features or aspects in each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Although one or more than one embodiment has been described with reference to the accompanying drawings, it should be understood by those of ordinary skill in the art that various changes in form and detail may be made herein without departing from the subject matter and scope defined by the appended claims.

Claims

1. A composition comprising: a wavelength conversion compound that absorbs wavelength A and emits wavelength B different from wavelength A; a crosslinkable monomer; a polymerizable monomer; a filler; and a photoinitiator.

2. The composition of claim 1, wherein the length of the wavelength B is longer than the length of the wavelength A.

3. The composition of claim 1, wherein the wavelength A is a wavelength in the ultraviolet region, and the wavelength B is a wavelength in the visible region.

4. The composition of claim 1, wherein the wavelength conversion compound comprises perylene, CdS, CdSe, CdTe, ZnS, perovskite, [Tb(pyridine-2,6-pyridinedicarboxylic acid)3] 3- 、[Eu(pyridine-2,6-pyridinedicarboxylic acid)3] 3- or a combination thereof. 5 . The composition of claim 1 , wherein the crosslinkable monomer and the polymerizable monomer each independently comprise an acryl-based monomer, a diisocyanate-based monomer, or a combination thereof.

6. The composition of claim 5, wherein the acryl-based monomer comprises C1-C 20 Alkyl groups, C3-C 10 A cycloalkyl group, -NCO, -OH or a combination thereof.

7. The composition of claim 1, wherein the crosslinkable monomer comprises an ultraviolet light crosslinkable monomer, a visible light crosslinkable monomer, a crosslinkable monomer crosslinkable at a low temperature, or a combination thereof.

8. The composition of claim 7, wherein the low temperature is a temperature at or below 80°C.

9. The composition of claim 1, wherein The crosslinkable monomer includes isobornyl acrylate, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl (meth)acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate or a combination thereof, and The polymerizable monomer includes 2-isocyanoethyl acrylate, 2,4-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2-hydroxyethyl methacrylate, diol methacrylate, diol monomethacrylate, ethylene glycol methacrylate, 2-(methacryloyloxy)ethanol or a combination thereof.

10. The composition of claim 1, wherein the photoinitiator comprises a single initiator that reacts with each of ultraviolet light and visible light.

11. The composition of claim 1, wherein the photoinitiator comprises an ultraviolet photoinitiator and a visible light photoinitiator.

12. The composition of claim 1, wherein the photoinitiator comprises 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzoin methyl ether, [ethoxy(phenyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone, or a combination thereof.

13. The composition of claim 1, further comprising a thermal catalyst.

14. The composition of claim 13, wherein the thermal catalyst comprises dibutyltin dilaurate, tin tetrachloride, butyltin trichloride, a diorganotin ester, and dibutyltin oxide, or a combination thereof.

15. The composition of claim 1, wherein the filler comprises carbon black, tungsten oxide, lanthanum oxide, titanium oxide, cobalt, graphite, graphene oxide, or a combination thereof. 16 . The composition of claim 1 , wherein the wavelength conversion compound is present in an amount of about 0.1 wt % to about 2 wt %, and the photoinitiator is present in an amount of about 5 wt % to about 20 wt %, based on 100 wt % of the total weight of the composition.

17. A cured product formed by photocuring the composition according to any one of claims 1 to 16. 18 . The cured product according to claim 17 , wherein the cured product has a curing depth of 200 μm or more. 19 . The cured product of claim 17 , wherein the cured product has an optical density value of 2 or more at a thickness of 50 μm or less.

20. A composition comprising: Photoconversion compounds, Crosslinkable monomers, Polymerization monomers, Fillers, Photoinitiator, and A thermal catalyst, wherein a cured product of the composition has a cure depth of 200 μm or more and an optical density of 2 or more at a thickness of 30 μm.

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